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Sample records for resonance raman investigation

  1. [Effect on Fermi Resonance by Some External Fields: Investigation of Fermi Resonance According to Raman Spectra].

    Science.gov (United States)

    Jiang, Xiu-lan; Sun, Cheng-lin; Zhou, Mi; Li, Dong-fei; Men, Zhi-wei; Li, Zuo-wei; Gao, Shu-qin

    2015-03-01

    Fermi resonance is a phenomenon of molecular vibrational coupling and energy transfer occurred between different groups of a single molecule or neighboring molecules. Many properties of Fermi resonance under different external fields, the investigation method of Raman spectroscopy as well as the application of Fermi resonance, etc need to be developed and extended further. In this article the research results and development about Fermi resonance obtained by Raman spectral technique were introduced systematically according to our work and the results by other researchers. Especially, the results of the behaviors of intramolecular and intermolecular Fermi resonance of some molecules under some external fields such as molecular field, pressure field and temperature field, etc were investigated and demonstrated in detail according to the Raman spectra obtained by high pressure DAC technique, temperature variation technique as well as the methods we planed originally in our group such as solution concentration variation method and LCOF resonance Raman spectroscopic technique, and some novel properties of Fermi resonance were found firstly. Concretely, (1) Under molecular field. a. The Raman spectra of C5H5 N in CH3 OH and H2O indicates that solvent effect can influence Fermi resonance distinctly; b. The phenomena of the asymmetric movement of the Fermi resonance doublets as well as the fundamental involved is tuned by the Fermi resonance which had not been found by other methods were found firstly by our variation solution concentration method; c. The Fermi resonance properties can be influenced distinctly by the molecular group reorganization induced by the hydrogen bond and anti-hydrogen bond in solution; d. Fermi resonance can occurred between C7 H8 and m-C8H10, and the Fermi resonance properties behave quite differently with the solution concentration; (2) Under pressure field. a. The spectral lines shift towards high wavenumber with increasing pressure, and

  2. UV resonance Raman investigation of the aqueous solvation dependence of primary amide vibrations.

    Science.gov (United States)

    Punihaole, David; Jakubek, Ryan S; Dahlburg, Elizabeth M; Hong, Zhenmin; Myshakina, Nataliya S; Geib, Steven; Asher, Sanford A

    2015-03-12

    We investigated the normal mode composition and the aqueous solvation dependence of the primary amide vibrations of propanamide. Infrared, normal Raman, and UV resonance Raman (UVRR) spectroscopy were applied in conjunction with density functional theory (DFT) to assign the vibrations of crystalline propanamide. We examined the aqueous solvation dependence of the primary amide UVRR bands by measuring spectra in different acetonitrile/water mixtures. As previously observed in the UVRR spectra of N-methylacetamide, all of the resonance enhanced primary amide bands, except for the Amide I (AmI), show increased UVRR cross sections as the solvent becomes water-rich. These spectral trends are rationalized by a model wherein the hydrogen bonding and the high dielectric constant of water stabilizes the ground state dipolar (-)O-C═NH2(+) resonance structure over the neutral O═C-NH2 resonance structure. Thus, vibrations with large C-N stretching show increased UVRR cross sections because the C-N displacement between the electronic ground and excited state increases along the C-N bond. In contrast, vibrations dominated by C═O stretching, such as the AmI, show a decreased displacement between the electronic ground and excited state, which result in a decreased UVRR cross section upon aqueous solvation. The UVRR primary amide vibrations can be used as sensitive spectroscopic markers to study the local dielectric constant and hydrogen bonding environments of the primary amide side chains of glutamine (Gln) and asparagine (Asn).

  3. Resonance Raman investigation of the radical cation of 1,3,5-hexatriene

    DEFF Research Database (Denmark)

    Keszhelyi, T.; Wilbrandt, R.; Cave, R.J.;

    1994-01-01

    of more than one rotamer has to be assumed to account for all the observed resonance Raman bands. The bands are assigned to a mixture of the two rotamers, calculated at lowest energy, the ttt and tct rotamers, on the basis of ab initio ROHF/6-31G calculated harmonic frequencies. The spectrum indicates...

  4. Resonance Raman and theoretical investigation of the photodissociation dynamics of benzamide in S3 state.

    Science.gov (United States)

    Pei, Ke-Mei; Ma, Yufang; Zheng, Xuming

    2008-06-14

    Resonance Raman spectra were obtained for benzamide in methanol and acetonitrile solutions with excitation wavelengths in resonance with the S(3) state. These spectra indicate that the Franck-Condon region photodissociation dynamics have multidimensional character with the motions mainly along the benzene ring C[Double Bond]C stretch nu(9), the Ph-CO-NH(2) and ring benzene stretch nu(14), the CCH in plane bend nu(17), the Ph-CO-NH(2) stretch and NH(2) rock nu(19), the ring trigonal bend nu(23), and the ring deformation and Ph-CO-NH(2) stretch nu(29). A preliminary resonance Raman intensity analysis was done, and the results were compared to those previously reported for acetophenone to examine the substituent effect. Solvent effect on the short-time photodissociation dynamics of benzamide was also examined. A conical intersection point S(2)S(3) between S(3) and S(2) potential energy surfaces of benzamide was determined by using a complete active space self-consistent field theory computations. The structural differences and similarities between S(3)S(2) point and S(0) were examined, and the results were used to correlate to the Franck-Condon photodissociation dynamics of benzamide in S(3) state.

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

    Science.gov (United States)

    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.

  6. Triplet State Resonance Raman Spectroscopy

    DEFF Research Database (Denmark)

    Wilbrandt, Robert Walter; Jensen, N. H.; Pagsberg, Palle Bjørn

    1978-01-01

    Makes the first report on the resonance Raman spectrum of a molecule in its triplet state generated by pulse radiolysis. A solution of 0.01 mol dm-3 of p-terphenyl in benzene was studied......Makes the first report on the resonance Raman spectrum of a molecule in its triplet state generated by pulse radiolysis. A solution of 0.01 mol dm-3 of p-terphenyl in benzene was studied...

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

    Science.gov (United States)

    Guthmuller, Julien; Champagne, Benoît

    2007-10-28

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

  8. Ultraviolet Resonant Raman Enhancements in the Detection of Explosives

    Energy Technology Data Exchange (ETDEWEB)

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

    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.

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

    CERN Document Server

    Guddala, Sriram; Ramakrishna, S Anantha

    2016-01-01

    A tri-layer metamaterial perfect absorber of light, consisting of (Al/ZnS/Al) films with the top aluminium layer patterned as an array of circular disk nanoantennas, is investigated for resonantly enhancing Raman scattering from C-60 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 from C60 on metamaterials with off-resonant absorption bands peaked 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...

  10. A polyene chain of canthaxanthin investigated by temperature-dependent resonance Raman spectra and density functional theory (DFT) calculations

    Institute of Scientific and Technical Information of China (English)

    Chen Yuan-Zheng; Li Shuo; Zhou Mi; Li Zuo-Wei; Sun Cheng-Lin

    2013-01-01

    We report on a temperature-dependent resonance Raman spectral characterization of the polyene chain of canthaxanthin.It is observed that all vibrational intensities of the polyene chain are inversely proportional to temperature,which is analyzed by the resonance Raman effect and the coherent weakly damped electron/lattice vibrations.The increase in intensity of the CC overtone/combination relative to the fundamental with temperature decreasing is detected and discussed in terms of electron/phonon coupling and the activation energy Uop.Moreover,the polyene chain studies using the density functional theory B3LYP/6-31G* level reveal a prominent peak at 1525 cm-1 consisting of two closely spaced modes that are both dominated by C=C stretching coordinates of the polyene chain.

  11. Second order resonant Raman scattering

    Energy Technology Data Exchange (ETDEWEB)

    Garcia-Cristobal, A.; Catarero, A. [Valencia Univ. (Spain). Dept. de Fisica Aplicada; Trallero-Giner, C. [Instituto Politecnico Nacional, Mexico City (Mexico). Centro de Investigacion y de Estudios Avanzados

    1996-03-01

    A theoretical model for resonant Raman scattering by two optical phonons in zincblende-type semiconductors is presented. The effect of Coulomb interaction between electrons and holes is taken into account by introducing discrete and continuous excitonic intermediate states. The model can be applied for laser frequencies below and above the band gap. We consider deformation potential and Froehlich interaction for the electron-one-phonon coupling. The absolute value of the scattering efficiency is evaluated for the L-O-phonons, TO-plus LO-phonon and two-TO-photons Raman processes, around the E{sub o} absorption edge of II-VI compound semiconductors. Comparison with the electron-hole uncorrelated theory and experimental data emphasizes the role if the excitonic effects. (author). 10 refs., 2 figs.

  12. Investigation of the electronic structure of CuO by means of resonant X-ray Raman scattering

    CERN Document Server

    Doering, G

    2001-01-01

    excited state. By means of a perturbation theoretical treatment of the Coulomb interaction between the core-hole and the 3d-electrons an expression for the cross-section of the shakeup-process is derived. Thereby the observed excitation energy dependence of the shakeup-satellite's intensity and its position in the energy loss spectrum can be explained. Furthermore, its intensity shows a strong dependence on the scattering angle in certain scattering geometries. By means of a model calculation this dependence is attributed to a polarisation-effect. In this thesis the electronic structure of CuO is investigated utilizing resonant X-ray Raman Scattering. The special properties of this transition metal oxide are emphasized and the potential of the method is shown. First it is explained how one can draw conclusions about the unoccupied density of states of CuO and its symmetry from measurements of the copper K-alpha fluorescence by using an excitation energy of a few eV below the absorption threshold. By this mean...

  13. Effect of TiO2 particles on normal and resonance Raman spectra of coumarin 343: a theoretical investigation.

    Science.gov (United States)

    Yang, Linzhi; Wu, Wenpeng; Zhao, Yi

    2015-04-28

    It is well known that interfacial structures and charge transfer in dye-sensitized solar cells are extremely important for the enhancement of cell efficiency. Here, the normal Raman spectra (NRS) and resonance Raman spectra (RRS) of a C343-sensitized TiO2 cluster (Ti9O18) are theoretically predicted from combined electronic structure calculations and a vibrationally-resolved spectral method to reveal the relationship between interfacial geometries and excited-state dynamics. The results show that although the NRS of free C343 and the C343-TiO2 cluster correspond to the vibrational motions of C343 in a high frequency domain, their mode frequencies show obvious differences due to the interaction of the TiO2 cluster on C343, and several new Raman active fingerprint modes, such as bidentate chelating bonding modes, can be used to determine interfacial geometries. However, the resonance Raman activities of low-frequency modes are significantly enhanced and several modes from the TiO2 cluster can be observed, consistent with experimental measurements. Furthermore, the RRS from a locally excited state and a charge transfer state of C343-TiO2 are dramatically different, for instance, new Raman active modes with 1212 cm(-1), 1560 cm(-1) and 1602 cm(-1), corresponding to the motions of CH2 rocking, C=C/C-N/C=O stretching and C=O/C=C stretching, appear from the charge transfer state. The obtained information on mode-specific reorganization energies from these excited states is greatly helpful to understand and control interfacial electron transfer.

  14. Investigation of resonant Raman scattering in type II GaAs/AlAs superlattices

    CERN Document Server

    Choi, H

    2001-01-01

    GAMMA-related Type I outgoing RR spectra within several theoretical models. Thereby, the mechanisms of the Type II RR scattering, the origins of the RR lineshape and the polarisation dependence, are fully explained, clarifying the spectral features observed in the GaAs zone-centre optic phonon region. The Type II resonance also allows the observation of zone boundary (X-point) phonons from intervalley (IV) scattering. A model of the IV electron-phonon interaction involving X conduction band electrons and zone boundary phonons in Type II SLs is presented. With the predicted SL selection rules for IV scattering, the simultaneous observation of both the zone-boundary longitudinal acoustic and optic phonons can be understood and the spectral features quantitatively explained. As a consequence of the band alignment in GaAs/AIAs superlattices (SLs) and the indirect nature of bulk AIAs, quantum confinement can be used to engineer a Type II system. This produces an electron population in the AIAs longitudinal (X sub ...

  15. A new combined nuclear magnetic resonance and Raman spectroscopic probe applied to in situ investigations of catalysts and catalytic processes

    Energy Technology Data Exchange (ETDEWEB)

    Camp, Jules C. J.; Mantle, Michael D. [Department of Chemical Engineering and Biotechnology, University of Cambridge, Pembroke Street, Cambridge CB2 3RA (United Kingdom); York, Andrew P. E. [Johnson Matthey Technology Centre, Blounts Court, Sonning Common, Reading RG4 9NH (United Kingdom); McGregor, James, E-mail: james.mcgregor@sheffield.ac.uk [Department of Chemical and Biological Engineering, University of Sheffield, Mappin Street, Sheffield S1 3JD (United Kingdom)

    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.

  16. Resonance Raman study of benzyl radical

    DEFF Research Database (Denmark)

    Langkilde, F.W.; Bajdor, K.; Wilbrandt, R.

    1992-01-01

    Time-resolved resonance Raman spectra are obtained of benzyl radicals created by laser flash photolysis of benzylchloride and diphenylacetone in solution. The spectra are obtained in resonance with the intense 2 2A2-1 B-2(2) transition of benzyl. The strong Raman bands are assigned to totally...... symmetric a1 modes. The remaining observed bands are tentatively assigned to fundamental modes of b1, a2, and b2 symmetry, and to overtones and combinations. The resonance Raman spectra are found to be quite different from previous fluorescence spectra of benzyl, and the origins of these differences...

  17. Resonance Raman spectroscopic investigation of the light-harvesting chromophore in escherichia coli photolyase and Vibrio cholerae cryptochrome-1.

    Science.gov (United States)

    Sokolova, Olga; Cecala, Christine; Gopal, Anand; Cortazar, Frank; McDowell-Buchanan, Carla; Sancar, Aziz; Gindt, Yvonne M; Schelvis, Johannes P M

    2007-03-27

    Photolyases and cryptochromes are flavoproteins that belong to the class of blue-light photoreceptors. They usually bind two chromophores: flavin adenine dinucleotide (FAD), which forms the active site, and a light-harvesting pigment, which is a 5,10-methenyltetrahydrofolate polyglutamate (MTHF) in most cases. In Escherichia coli photolyase (EcPhr), the MTHF cofactor is present in substoichiometric amounts after purification, while in Vibrio cholerae cryptochrome-1 (VcCry1) the MTHF cofactor is bound more strongly and is present at stoichiometric levels after purification. In this paper, we have used resonance Raman spectroscopy to monitor the effect of loss of MTHF on the protein-FAD interactions in EcPhr and to probe the protein-MTHF interactions in both EcPhr and VcCry1. We find that removal of MTHF does not perturb protein-FAD interactions, suggesting that it may not affect the physicochemical properties of FAD in EcPhr. Our data demonstrate that the pteridine ring of MTHF in EcPhr has different interactions with the protein matrix than that of MTHF in VcCry1. Comparison to solution resonance Raman spectra of MTHF suggests that the carbonyl of its pteridine ring in EcPhr experiences stronger hydrogen bonding and a more polar environment than in VcCry1, but that hydrogen bonding to the pteridine ring amine hydrogens is stronger in VcCry-1. These differences in hydrogen bonding may account for the higher binding affinity of MTHF in VcCry1 compared to EcPhr.

  18. Resonance Raman Optical Activity and Surface Enhanced Resonance Raman Optical Activity analysis of Cytochrome C

    DEFF Research Database (Denmark)

    Johannessen, Christian; Abdali, Salim; White, Peter C.

    2007-01-01

    High quality Resonance Raman (RR) and resonance Raman Optical Activity (ROA) spectra of cytochrome c were obtained in order to perform full assignment of spectral features of the resonance ROA spectrum. The resonance ROA spectrum of cytochrome c revealed a distinct spectral signature pattern due...... to resonance enhanced skeletal porphyrin vibrations, more pronounced than any contribution from the protein back-bone. Combining the intrinsic resonance enhancement of cytochrome c with surface plasmon enhancement by colloidal silver particles, the Surface Enhanced Resonance Raman Scattering (SERRS) and Chiral...... Enhanced Raman Spectroscopy (ChERS) spectra of the protein were successfully obtained at very low concentration (as low as 1 µM). The assignment of spectral features was based on the information obtained from the RR and resonance ROA spectra. Excellent agreement between RR and SERRS spectra is reported...

  19. A resonance Raman spectroscopic and CASSCF investigation of the Franck-Condon region structural dynamics and conical intersections of thiophene.

    Science.gov (United States)

    Wu, Xian-Fang; Zheng, Xuming; Wang, Hui-Gang; Zhao, Yan-Yin; Guan, Xiangguo; Phillips, David Lee; Chen, Xuebo; Fang, Weihai

    2010-10-07

    Resonance Raman spectra were acquired for thiophene in cyclohexane solution with 239.5 and 266 nm excitation wavelengths that were in resonance with ∼240 nm first intense absorption band. The spectra indicate that the Franck-Condon region photodissociation dynamics have multidimensional character with motion mostly along the reaction coordinates of six totally symmetry modes and three nontotally symmetry modes. The appearance of the nontotally symmetry modes, the C-S antisymmetry stretch +C-C=C bend mode ν(21)(B(2)) at 754 cm(-1) and the H(7)C(3)-C(4)H(8) twist ν(9)(A(2)) at 906 cm(-1), suggests the existence of two different types of vibronic-couplings or curve-crossings among the excited states in the Franck-Condon region. The electronic transition energies, the excited state structures, and the conical intersection points (1)B(1)/(1)A(1) and (1)B(2)/(1)A(1) between 2 (1)A(1) and 1 (1)B(2) or 1 (1)B(1) potential energy surfaces of thiophene were determined by using complete active space self-consistent field theory computations. These computational results were correlated with the Franck-Condon region structural dynamics of thiophene. The ring opening photodissociation reaction pathway through cleavage of one of the C-S bonds and via the conical intersection point (1)B(1)/(1)A(1) was revealed to be the predominant ultrafast reaction channel for thiophene in the lowest singlet excited state potential energy hypersurface, while the internal conversion pathway via the conical intersection point (1)B(2)/(1)A(1) was found to be the minor decay channel in the lowest singlet excited state potential energy hypersurface.

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

    Science.gov (United States)

    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.

  1. Chemical state speciation by resonant Raman scattering

    CERN Document Server

    Karydas, A G; Zarkadas, C; Paradelis, T; Kallithrakas-Kontos, N

    2002-01-01

    In the resonant Raman scattering (RRS) process the emitted photon exhibits a continuous energy distribution with a high energy cutoff limit. This cutoff energy depends on the chemical state of the element under examination. In the present work, the possibility of identifying the chemical state of V atoms by employing RRS spectroscopy with a semiconductor Si(Li) detector is investigated. A proton induced Cr K alpha x-ray beam was used as the incident radiation, having a fixed energy lower than the V K-absorption edge. The net RRS distributions extracted from the energy dispersive spectra of metallic V and its compound targets were simulated by an appropriate theoretical model. The results showed the possibility of employing RRS spectroscopy with a semiconductor detector for chemical speciation studies.

  2. Transmission resonance Raman spectroscopy: experimental results versus theoretical model calculations.

    Science.gov (United States)

    Gonzálvez, Alicia G; González Ureña, Ángel

    2012-10-01

    A laser spectroscopic technique is described that combines transmission and resonance-enhanced Raman inelastic scattering together with low laser power (view, a model for the Raman signal dependence on the sample thickness is also presented. Essentially, the model considers the sample to be homogeneous and describes the underlying physics using only three parameters: the Raman cross-section, the laser-radiation attenuation cross-section, and the Raman signal attenuation cross-section. The model was applied successfully to describe the sample-size dependence of the Raman signal in both β-carotene standards and carrot roots. The present technique could be useful for direct, fast, and nondestructive investigations in food quality control and analytical or physiological studies of animal and human tissues.

  3. Investigation of magnetic field enriched surface enhanced resonance Raman scattering performance using Fe3O4@Ag nanoparticles for malaria diagnosis

    Science.gov (United States)

    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.

  4. Resonance raman studies of phenylcyclopropane radical cations

    NARCIS (Netherlands)

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

    2000-01-01

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

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

    Science.gov (United States)

    Rösch, P.; Popp, J.; Kiefer, W.

    1999-05-01

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

  6. Proliferation detection using a remote resonance Raman chemical sensor

    Energy Technology Data Exchange (ETDEWEB)

    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.

  7. Resonance Raman studies of the purple membrane.

    Science.gov (United States)

    Aton, B; Doukas, A G; Callender, R H; Becher, B; Ebrey, T G

    1977-06-28

    The individual resonance Raman spectra of the PM568 and M412 forms of light-adapted purple membrane from Halobacterium halobium have been measured using the newly developed flow technique. For comparison purposes, the Raman spectra of the model chromophores, all-trans- and 13-cis retinal n-butylamine, both as protonated and unprotonated Schiff bases, have also been obtained. In agreement with previous work, the Raman data indicate that the retinal chromophore is linked to the purple membrane protein via a protonated. Schiff base in the case of the PM568 and an unprotonated Schiff base for the M412 form. The basic mechanism for color regulation in both forms appears to be electron delocalization. The spectral features of the two forms are different from each other and different from the model compound spectra.

  8. Perspective: Two-dimensional resonance Raman spectroscopy

    Science.gov (United States)

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

    2016-11-01

    Two-dimensional resonance Raman (2DRR) spectroscopy has been developed for studies of photochemical reaction mechanisms and structural heterogeneity in complex systems. The 2DRR method can leverage electronic resonance enhancement to selectively probe chromophores embedded in complex environments (e.g., a cofactor in a protein). In addition, correlations between the two dimensions of the 2DRR spectrum reveal information that is not available in traditional Raman techniques. For example, distributions of reactant and product geometries can be correlated in systems that undergo chemical reactions on the femtosecond time scale. Structural heterogeneity in an ensemble may also be reflected in the 2D spectroscopic line shapes of both reactive and non-reactive systems. In this perspective article, these capabilities of 2DRR spectroscopy are discussed in the context of recent applications to the photodissociation reactions of triiodide and myoglobin. We also address key differences between the signal generation mechanisms for 2DRR and off-resonant 2D Raman spectroscopies. Most notably, it has been shown that these two techniques are subject to a tradeoff between sensitivity to anharmonicity and susceptibility to artifacts. Overall, recent experimental developments and applications of the 2DRR method suggest great potential for the future of the technique.

  9. Raman microscopy investigation of beryllium materials

    Science.gov (United States)

    Pardanaud, C.; Rusu, M. I.; Giacometti, G.; Martin, C.; Addab, Y.; Roubin, P.; Lungu, C. P.; Porosnicu, C.; Jepu, I.; Dinca, P.; Lungu, M.; Pompilian, O. G.; Mateus, R.; Alves, E.; Rubel, M.; contributors, JET

    2016-02-01

    We report for the first time on the ability of Raman microscopy to give information on the structure and composition of Be related samples mimicking plasma facing materials that will be found in ITER. For that purpose, we investigate two types of material. First: Be, W, Be1W9, and Be5W5 deposits containing a few percents of D or N, and second: a Mo mirror exposed to plasma in the main JET chamber (in the framework of the first mirror test in JET with ITER-like wall). We performed atomic quantifications using ion beam analysis for the first samples. We also did atomic force microscopy. We found defect induced Raman bands in Be, Be1W9, and Be5W5 deposits. Molybdenum oxide has been identified showing an enhancement due to a resonance effect in the UV domain.

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

    Institute of Scientific and Technical Information of China (English)

    Abdelsalam Mohammed; Yu-Ping Sun; Quan Miao; Hans (A)gren; Faris Gel'mukhanov

    2012-01-01

    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.

  11. Resonance Raman of BCC and normal skin

    Science.gov (United States)

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

    2017-02-01

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

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

    Science.gov (United States)

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

    2008-12-11

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

  13. The Role of Fermi Resonance in Formation of Valence Band of Water Raman Scattering

    Directory of Open Access Journals (Sweden)

    Sergey A. Burikov

    2008-01-01

    Full Text Available The role of Fermi resonance in formation of valence band of water Raman scattering was investigated. Simultaneous measurement of characteristics of bending and valence bands of water in D2O solutions, KBr, and KCl and using genetic algorithms in conjunction with variation methods allowed increasing accuracy of estimation of Fermi resonance coupling constant and of Fermi resonance contribution into formation of water Raman valence band.

  14. Preventing Raman Lasing in High-Q WGM Resonators

    Science.gov (United States)

    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.

  15. Time-resolved resonance Raman and computational investigation of the influence of 4-acetamido and 4-N-methylacetamido substituents on the chemistry of phenylnitrene.

    Science.gov (United States)

    Xue, Jiadan; Vyas, Shubham; Du, Yong; Luk, Hoi Ling; Chuang, Yung Ping; But, Tracy Yuen Sze; Toy, Patrick H; Wang, Jin; Winter, Arthur H; Phillips, David Lee; Hadad, Christopher M; Platz, Matthew S

    2011-07-07

    A time-resolved resonance Raman (TR(3)) and computational investigation of the photochemistry of 4-acetamidophenyl azide and 4-N-methylacetamidophenyl azide in acetonitrile is presented. Photolysis of 4-acetamidophenyl azide appears to initially produce singlet 4-acetamidophenylnitrene which undergoes fast intersystem crossing (ISC) to form triplet 4-acetamidophenylnitrene. The latter species formally produces 4,4'-bisacetamidoazobenzene. RI-CC2/TZVP and TD-B3LYP/TZVP calculations predict the formation of the singlet nitrene from the photogenerated S(1) surface of the azide excited state. The triplet 4-acetamidophenylnitrene and 4,4'-bisacetamidoazobenzene species are both clearly observed on the nanosecond to microsecond time-scale in TR(3) experiments. In contrast, only one species can be observed in analogous TR(3) experiments after photolysis of 4-N-methylacetamidophenyl azide in acetonitrile, and this species is tentatively assigned to the compound resulting from dimerization of a 1,2-didehydroazepine. The different photochemical reaction outcomes for the photolysis of 4-acetamidophenyl azide and 4-N-methylacetamidophenyl azide molecules indicate that the 4-acetamido group has a substantial influence on the ISC rate of the corresponding substituted singlet phenylnitrene, but the 4-N-methylacetamido group does not. CASSCF analyses predict that both singlet nitrenes have open-shell electronic configurations and concluded that the dissimilarity in the photochemistry is probably due to differential geometrical distortions between the states. We briefly discuss the probable implications of this intriguing substitution effect on the photochemistry of phenyl azides and the chemistry of the related nitrenes.

  16. Time Resolved Resonance Raman Conference Royal Institution, London United Kingdom,

    Science.gov (United States)

    1983-01-01

    polar molecules. The rejection of fluorescence which is practically inherent _s most if not all resonance Raman experiments was discussed is great ...presented may be devided into two sections. 1) chemical processes presented in the rorninq and 2) biological in the afternoon. The resonance Raman spectra

  17. Fast Resonance Raman Spectroscopy of Short-Lived Radicals

    DEFF Research Database (Denmark)

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

    1976-01-01

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

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

    DEFF Research Database (Denmark)

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

    1984-01-01

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

  19. Role of multipolar plasmon resonances during surface-enhanced Raman spectroscopy on Au micro-patches

    DEFF Research Database (Denmark)

    Dowd, Annette; Geisler, Mathias; Zhu, Shaoli;

    2016-01-01

    The enhancement of a Raman signal by multipolar plasmon resonances – as opposed to the more common practice of using dipolar resonances – is investigated. A wide range of gold stars, triangles, circles and squares with multipolar resonances in the visible region were designed and then produced...

  20. Resonance Raman excitation profiles of lycopene

    Science.gov (United States)

    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.

  1. Brain metastasis detection by resonant Raman optical biopsy method

    Science.gov (United States)

    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.

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

    DEFF Research Database (Denmark)

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

    1998-01-01

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

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

    Science.gov (United States)

    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.

  4. Insights into Protein Structure and Dynamics by Ultraviolet and Visible Resonance Raman Spectroscopy.

    Science.gov (United States)

    López-Peña, Ignacio; Leigh, Brian S; Schlamadinger, Diana E; Kim, Judy E

    2015-08-11

    Raman spectroscopy is a form of vibrational spectroscopy based on inelastic scattering of light. In resonance Raman spectroscopy, the wavelength of the incident light falls within an absorption band of a chromophore, and this overlap of excitation and absorption energy greatly enhances the Raman scattering efficiency of the absorbing species. The ability to probe vibrational spectra of select chromophores within a complex mixture of molecules makes resonance Raman spectroscopy an excellent tool for studies of biomolecules. In this Current Topic, we discuss the type of molecular insights obtained from steady-state and time-resolved resonance Raman studies of a prototypical photoactive protein, rhodopsin. We also review recent efforts in ultraviolet resonance Raman investigations of soluble and membrane-associated biomolecules, including integral membrane proteins and antimicrobial peptides. These examples illustrate that resonance Raman is a sensitive, selective, and practical method for studying the structures of biological molecules, and the molecular bonding, geometry, and environments of protein cofactors, the backbone, and side chains.

  5. Resonant Raman scattering in GaSe and GaS/sub x/Se/sub 1-x/

    Energy Technology Data Exchange (ETDEWEB)

    Chiang, T.C.; Camassel, J.; Voitchovsky, J.P.; Shen, Y.R.

    1976-07-01

    Multiphonon resonant Raman scattering up to four phonons in GaSe and one and two phonon resonant Raman scattering in the mixed GaS/sub x/Se/sub 1 - x/ crystals with x less than or equal to 0.23 were investigated. The results can be explained by a simple theory in which the dispersion of the resonance behavior is mainly dominated by resonances with the 1s direct exciton state.

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

    Energy Technology Data Exchange (ETDEWEB)

    Rahn, L.A. [Sandia National Laboratories, Livermore, CA (United States)

    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).

  7. Human brain cancer studied by resonance Raman spectroscopy

    Science.gov (United States)

    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.

  8. Periodontitis diagnostics using resonance Raman spectroscopy on saliva

    Science.gov (United States)

    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.

  9. Resonance Raman Spectroscopy of Free Radicals Produced by Ionizing Radiation

    DEFF Research Database (Denmark)

    Wilbrandt, Robert Walter

    1984-01-01

    Applications of time-resolved resonance Raman spectroscopy to the study of short-lived free radicals produced by ionizing radiation are briefly reviewed. Potential advantages and limitations of this technique are discussed in the light of given examples. The reduction of p-nitrobenzylchloride and......Applications of time-resolved resonance Raman spectroscopy to the study of short-lived free radicals produced by ionizing radiation are briefly reviewed. Potential advantages and limitations of this technique are discussed in the light of given examples. The reduction of p......-nitrobenzylchloride and subsequent formation of the p-nitrobenzyl radical and the reaction of p-nitrotoluene with O– are studied by resonance Raman and optical absorption spectroscopy....

  10. Resonance Raman spectra of black soap film containing dye molecule

    Institute of Scientific and Technical Information of China (English)

    梁映秋; 张韫宏

    1995-01-01

    Dye molecule brilliant yellow (BY) has been used as an acid-base probe in the study of the resonance Raman spectra of three kinds of microenvironments of the black soap film (BSF) containing BY, the BY-CTAB micellar solution, and the aqueous BY solution under various pH conditions. It has been revealed that BY bound to the sandwich interface of the BSF and that to the micellar interface show similar spectral changes, but the former owns the character of coexistence of acidic and basic structures in a relatively large range of pH values (neutral to basic). Further investigations have demonstrated that BSF exhibits the buffer effect that the pH value of the aqueous core is insensitive to the pH change of the bulk solution.

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

    CERN Document Server

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

    2016-01-01

    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 much stronger effect on the scattering than electric modes of the same order. We demonstrate experimentally a 140-fold enhancement of Raman signal from individual silicon spherical nanoparticles at the magnetic dipole resonance. Our results confirm the importance of the optically-induced magnetic response of subwavelength dielectric nanoparticles for enhancing light-matter interactions.

  12. Origin invariance in vibrational resonance Raman optical activity

    Energy Technology Data Exchange (ETDEWEB)

    Vidal, Luciano N., E-mail: lnvidal@utfpr.edu.br; Cappelli, Chiara, E-mail: chiara.cappelli@unipi.it [Dipartimento di Chimica e Chimica Industriale, Università di Pisa, Via Moruzzi 3, 56124 Pisa (Italy); Egidi, Franco [Department of Chemistry, University of Washington, Seattle, Washington 98195 (United States); Barone, Vincenzo [Scuola Normale Superiore, Piazza dei Cavalieri 7, 56126 Pisa (Italy)

    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.

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

    Science.gov (United States)

    Argade, Pramod Vasant

    lysine residue 41. Several methods of kinetic resonance Raman scattering were developed to monitor the spectral changes during the photocycle. This involved using a rotating cell and extensively utilizing computer control for data aquisition. By finding the Voigt profiles of these spectra, the spectral changes were quantitatively analyzed. In particular, the existence of the controversial "X" intermediate was investigated.

  14. Resonance Raman spectroscopy in one-dimensional carbon materials

    Directory of Open Access Journals (Sweden)

    Dresselhaus Mildred S.

    2006-01-01

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

  15. UV resonance Raman analysis of trishomocubane and diamondoid dimers

    Energy Technology Data Exchange (ETDEWEB)

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

    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.

  16. Fast Resonance Raman Spectroscopy of a Free Radical

    DEFF Research Database (Denmark)

    Wilbrandt, Robert Walter; Pagsberg, Palle Bjørn; Hansen, K. B.

    1975-01-01

    The resonance Raman spectrum of a 10−3 molar solution of the stable diphenyl-pikryl-hydrazyl radical in benzene was obtained using a single laser pulse of 10 mJ energy and 600 ns duration from a flashlamp pumped tunable dye laser. Spectra were recorded using an image intensifier coupled to a TV...

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

    Energy Technology Data Exchange (ETDEWEB)

    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.

  18. Investigating the lignocellulosic composition during delignification using confocal raman spectroscopy, cross-polarization magic angle spinning carbon 13 - nuclear magnetic resonance (CP/MAS 13C- NMR) spectroscopy and atomic force microscopy

    CSIR Research Space (South Africa)

    Chunilall, Viren

    2012-03-01

    Full Text Available spectroscopy, Cross-Polarization Magic Angle Spinning Carbon 13 - Nuclear Magnetic Resonance (CP/MAS 13C-NMR) spectroscopy and Atomic Force Microscopy (AFM) in conjunction with image analysis. The confocal Raman results showed that there were differences...

  19. Ultraviolet resonant Raman spectroscopy of nucleic acid components.

    Science.gov (United States)

    Blazej, D C; Peticolas, W L

    1977-07-01

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

  20. Multiphonon Resonance Raman Scattering in InGaN

    Energy Technology Data Exchange (ETDEWEB)

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

    2005-06-28

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

  1. Resonance electronic Raman scattering in rare earth crystals

    Energy Technology Data Exchange (ETDEWEB)

    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.

  2. Atmospheric absorption versus deep ultraviolet (pre-)resonance in Raman lidar measurements

    Science.gov (United States)

    Hallen, Hans D.; Willitsford, Adam H.; Neely, Ryan R.; Chadwick, C. Todd; Philbrick, C. Russell

    2016-05-01

    The Raman scattering of several liquids and solid materials has been investigated near the deep ultraviolet absorption features corresponding to the electron energy states of the chemical species present. It is found to provide significant enhancement, but is always accompanied by absorption due to that or other species along the path. We investigate this trade-off for water vapor, although the results for liquid water and ice will be quantitatively very similar. An optical parametric oscillator (OPO) was pumped by the third harmonic of a Nd:YAG laser, and the output frequency doubled to generate a tunable excitation beam in the 215-600 nm range. We use the tunable laser excitation beam to investigate pre-resonance and resonance Raman spectroscopy near an absorption band of ice. A significant enhancement in the Raman signal was observed. The A-term of the Raman scattering tensor, which describes the pre-resonant enhancement of the spectra, is also used to find the primary observed intensities as a function of incident beam energy, although a wide resonance structure near the final-state-effect related absorption in ice is also found. The results suggest that use of pre-resonant or resonant Raman LIDAR could increase the sensitivity to improve spatial and temporal resolution of atmospheric water vapor measurements. However, these shorter wavelengths also exhibit higher ozone absorption. These opposing effects are modeled using MODTRAN for several configurations relevant for studies of boundary layer water and in the vicinity of clouds. Such data could be used in studies of the measurement of energy flow at the water-air and cloud-air interface, and may help with understanding some of the major uncertainties in current global climate models.

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

    CERN Document Server

    Milián, Carles; Taki, Majid; Yulin, Alexey V; Skryabin, Dmitry V

    2015-01-01

    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 can not exist and, instead, a rich dynamics characterized by generation of self-frequency shift- ing solitons and dispersive waves is observed. A mechanism of broadening of the Cherenkov radiation through Hopf instability of the frequency locked solitons is also reported.

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

    Science.gov (United States)

    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.

  5. Guided-mode-resonance coupled localized surface plasmons for dually resonance enhanced Raman scattering sensing

    Science.gov (United States)

    Wang, Zheng; Liu, Chao; Li, Erwen; Chakravarty, Swapnajit; Xu, Xiaochuan; Wang, Alan X.; Fan, D. L.; Chen, Ray T.

    2017-02-01

    Raman scattering spectroscopy is a unique tool to probe vibrational, rotational, and other low-frequency modes of a molecular system and therefore could be utilized to identify chemistry and quantity of molecules. However, the ultralow efficient Raman scattering, which is only 1/109 1/1014 of the excitation light due to the small Raman scattering cross-sections of molecules, have significantly hindered its development in practical sensing applications. The discovery of surface-enhanced Raman scattering (SERS) in the 1970s and the significant progress in nanofabrication technique, provide a promising solution to overcome the inherent issues of Raman spectroscopy. It is found that In the vicinity of nanoparticles and their junctions, the Raman signals of molecules can be significantly improved by an enhancement factor as high as 1010, due to the ultrahigh electric field generated by the localized surface plasmons resonance (LSPR), where the intensity of Raman scattering is proportional to the |E|4. In this work, we propose and demonstrate a new approach combining LSPR from nanocapsules with densely assembled silver nanoparticles (NC-AgNPs) and guidemode- resonance (GMR) from dielectric photonic crystal slabs (PCSs) for SERS substrates with robustly high performance.

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

    OpenAIRE

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

    2001-01-01

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

  7. Resonance Raman scattering and excitonic spectra in TlInS{sub 2} crystals

    Energy Technology Data Exchange (ETDEWEB)

    Zalamai, V.V. [Institute of Applied Physics, Academy of Sciences of Moldova, 5 Academy Street, 2028 Chisinau, Republic of Moldova (Moldova, Republic of); Stamov, I.G. [T.G. Shevchenko State University of Pridnestrovie, 25 Oktyabrya Street 107, 3300 Tiraspol, Republic of Moldova (Moldova, Republic of); Syrbu, N.N., E-mail: sirbunn@yahoo.com [Technical University of Moldova, 168 Stefan cel Mare Avenue, 2004 Chisinau, Republic of Moldova (Moldova, Republic of); Ursaki, V.V. [Institute of Applied Physics, Academy of Sciences of Moldova, 5 Academy Street, 2028 Chisinau, Republic of Moldova (Moldova, Republic of); Dorogan, V. [Technical University of Moldova, 168 Stefan cel Mare Avenue, 2004 Chisinau, Republic of Moldova (Moldova, Republic of)

    2015-04-15

    The excitons ground and excited states for E∥a and E∥b polarizations in absorption and reflection spectra of TlInS{sub 2} crystals were detected. The fundamental parameters of excitons and bands were determined at k=0. The resonance Raman spectra were investigated in the region of excitons transitions. The resonance Raman scattering spectra with participation of optical phonons that are active at the center of Brillouin zone were identified. The Raman scattering in Y(YX)Z and Y(ZX)Z geometries at 10 K with excitation by He–Ne laser was researched. Energies of phonons with A{sub g} and B{sub g} symmetries were determined. It was shown that the number of modes at 10 K was two times lower than expected according to theoretical calculations. - Highlights: • The resonance Raman scattering in geometry Y(YX)Z and Y(ZX)Z at 10 K was investigated. • Energies of phonons with A{sub g} and B{sub g} symmetries were determined. • The experimental and theoretical calculations completely conform if crystals are described by symmetry group D{sub 4h}{sup 15}. • The main parameters of excitons and bands were determined. • The model of electron transitions in k=0 was suggested.

  8. Effect of atomic diffusion on the Raman-Ramsey CPT resonances

    CERN Document Server

    Kuchina, Elena; Novikova, Irina

    2015-01-01

    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.

  9. A Theoretical Distinction Between Time-Resolved Resonance Raman andResonance Fluorescence

    Institute of Scientific and Technical Information of China (English)

    LU Jing; DU Si-De; FAN Kang-Nian; Lee Soo-Ying

    2000-01-01

    Based on the time-dependent theory, an analysis of the distinction between resonance Raman (RR) and resonance fluorescence (RF) with pulse excitation was presented. The real population of the intermediate state gives two optical components-the independent time evolution of intermediate ket and bra states generates RR while RF originates from the phase coherent between ket and bra states. In cw limit, the transition probability of spontaneous emission with pulse excitation can be reduced to the classical theory.

  10. Resonance-Enhanced Raman Spectroscopy on Explosives Vapor at Standoff Distances

    Directory of Open Access Journals (Sweden)

    Anneli Ehlerding

    2012-01-01

    Full Text Available Resonance-enhanced Raman spectroscopy has been used to perform standoff measurements on nitromethane (NM, 2,4-DNT, and 2,4,6-TNT in vapor phase. The Raman cross sections for NM, DNT, and TNT in vapor phase have been measured in the wavelength range 210–300 nm under laboratory conditions, in order to estimate how large resonance enhancement factors can be achieved for these explosives. The results show that the signal is enhanced up to 250,000 times for 2,4-DNT and up to 60,000 times for 2,4,6-TNT compared to the nonresonant signal at 532 nm. Realistic outdoor measurements on NM in vapor phase at 13 m distance were also performed, which indicate a potential for resonance Raman spectroscopy as a standoff technique for detection of vapor phase explosives. In addition, the Raman spectra of acetone, ethanol, and methanol were measured at the same wavelengths, and their influence on the spectrum from NM was investigated.

  11. Determination of resonance Raman cross-sections for use in biological SERS sensing with femtosecond stimulated Raman spectroscopy.

    Science.gov (United States)

    Silva, W Ruchira; Keller, Emily L; Frontiera, Renee R

    2014-08-05

    Surface-enhanced Raman spectroscopy (SERS) is a promising technique for in vivo bioanalyte detection, but accurate characterization of SERS biosensors can be challenging due to difficulties in differentiating resonance and surface enhancement contributions to the Raman signal. Here, we quantitate the resonance Raman cross-sections for a commonly used near-infrared SERS dye, 3,3'-diethylthiatricarbocyanine (DTTC). It is typically challenging to measure resonance Raman cross-sections for fluorescent dye molecules due to the overwhelming isoenergetic fluorescence signal. To overcome this issue, we used etalon-based femtosecond stimulated Raman spectroscopy, which is intrinsically designed to acquire a stimulated Raman signal without strong fluorescence or interference from signals resulting from other four-wave mixing pathways. Using this technique, we found that the cross-sections for most of the resonantly enhanced modes in DTTC exceed 10(-25) cm(2)/molecule. These cross-sections lead to high signal magnitude SERS signals from even weakly enhancing SERS substrates, as much of what appears to be a SERS signal is actually coming from the intrinsically strong resonance Raman signal. Our work will lead to a more accurate determination of SERS enhancement factors and SERS substrate characterization in the biologically relevant near-infrared region, ultimately leading to a more widespread use of SERS for biosensing and bioimaging applications.

  12. Absolute determination of cross sections for resonant Raman scattering on silicon

    Science.gov (United States)

    Müller, Matthias; Beckhoff, Burkhard; Ulm, Gerhard; Kanngießer, Birgit

    2006-07-01

    We studied the resonant Raman scattering of x rays in the vicinity of the K absorption edge of silicon. The investigation was carried out at the plane grating monochromator beamline for undulator radiation of the PTB laboratory at BESSY II in Berlin. Cross sections were determined absolutely for a wide energy range of incident photons with small relative uncertainties employing calibrated instrumentation avoiding any reference samples. The experimentally determined values differ clearly from the theoretical ones found in the literature.

  13. Quantum State Absorptions Coupled To Resonance Raman Spectroscopy Could Result In A General Explanation of TERS

    CERN Document Server

    Schultz, Zachary D; Dekhter, Rimma; Anestopoulos, Dimitris; Grammatikopoulos, Spyridon; Papagelis, Kostantinos; Marr, James M; Lewis, David; Galiotis, Costas; Lev, Dimtry; Lewis, Aaron

    2016-01-01

    Tip enhanced Raman scattering (TERS) amplifies the intensity of vibrational Raman scattering by employing the tip of a probe interacting, in ultra close proximity, with a surface. Although a general understanding of the TERS process is still to be fully elucidated, scanning tunneling microscopy (STM) feedback is often applied with success in TERS to keep a noble metal probe in intimate proximity with a noble metal substrate. Since such STM TERS is a common modality, the possible implications of plasmonic fields that may be induced by the tunneling process are investigated and reported. In addition, TERS of a 2D resonant molecular system, a MoS2 bilayer crystal and a 2D non-resonant, lipid molecular bilayer is compared. Data with multiple excitation wavelengths and surfaces for the resonant system in the near- (TERS) and far-field regimes are reported. An interpretation based on weak coupling interactions within the framework of conventional resonance Raman scattering can explain the observed TERS enhancements...

  14. La spectrométrie Raman de résonance résolue dans le temps : une puissante méthode d'investigation en temps réel de la réactivité photochimique Time Resolved Resonance Raman Spectrometry: a Powerful Method for the Real-Time Investigation of Photochemical Reactivity

    Directory of Open Access Journals (Sweden)

    Buntinx G.

    2006-11-01

    Full Text Available La spectroscopie Raman de résonance résolue dans le temps est une technique récente particulièrement bien adaptée à la caractérisation des intermédiaires réactionnels mis en jeu dans les réactions photochimiques (états excités, radicaux, paires d'ions, . . . . Elle permet de visualiser finement les variations de géométrie et de distribution électronique des espèces transitoires tout au long du chemin réactionnel. Nous présentons dans cet article une compilation des résultats obtenus dans notre laboratoire sur des molécules aromatiques dérivées du biphényle. Ces résultats constituent une bonne illustration des potentialités de cette technique à apporter des informations sur la réactivité de cette famille de composés. Après une partie consacrée à la description du dispositif expérimental utilisé dans de telles expériences, nous abordons l'étude structurale par spectrométrie Raman de résonance résolue dans le temps des radicaux cations et des états triplets de dérivés du biphényle. La dernière partie de cet article est consacrée à l'étude de la réactivité photochimique de dérivés de la pyridine (4,4'-bipyridine, 2,2'-bipyridine, 4-phénylpyridine, 2--phénylpyridine dans les solvants organiques par spectrométrie Raman de résonance résolue dans le temps. Time resolved resonance Raman spectroscopy is a recent technique that is particularly well suited for characterizing reaction intermediates involved in photochemical reactions (excited states, radicals, ion pair, etc. . It can finely visualize variations in geometry and electron distribution of transient species along the entire reaction path. This article describes a compilation of the results obtained in our laboratory on aromatic molecules derived from biphenyl. These results are a good illustration of the potentialities of this technique for providing information on the reactivity of this family of compounds. After a section devoted to

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

    Science.gov (United States)

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

    1989-05-01

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

  16. Unusual Raman spectra of para-nitroaniline by sequential Fermi resonances.

    Science.gov (United States)

    Xia, Jiarui; Zhu, Ling; Feng, Yanting; Li, Yongqing; Zhang, Zhenglong; Xia, Lixin; Liu, Liwei; Ma, Fengcai

    2014-01-01

    In this communication, we report the unusual Raman spectra of para-nitroaniline (PNA) by sequential Fermi resonances. The combinational mode 1292 cm(-1) in the experimental Raman spectrum indirectly gains the initial spectral weight at 1392 cm(-1) by three sequential Fermi resonances. These Fermi resonances result in the strong interaction between the donor group of NH2 and the acceptor group of NO2. Our theoretical calculations provide reasonable interpretation for the abnormal Raman spectra of PNA. Experimental surface enhanced Raman scattering (SERS) spectrum of PNA further confirmed our conclusion, where the strongest Raman peak at 1292 cm(-1) is very weak, while the Raman peak at 1392 cm(-1) becoming the strongest Raman peak, which is consistent with the theoretical simulations.

  17. Investigation of biomineralization by Raman spectroscopy

    Science.gov (United States)

    Fatscher, Robert William

    implants. These implants are designed to osteointegrate with the native healthy tissues in order to create a functionally stable and structural interface. Biomaterials such as hydroxyapatite and titania are known to increase the rate of bone regeneration in vivo.1 By accelerating the early response of bone forming cells to these implants, better fixation is achieved between the implant and the bone, shortening recovery times and increasing the viability of these implants. In the last part of this research an investigation of osteoblasts cultured at 14 days on five different heat-treated titania substrates was investigated by Raman spectroscopy, in order to observe the initial cellular response to the titania substrates. The heat-treatment of titania changes the amount of oxygen on it's surface which in turn effects the surface energy. A change in the surface energy of a material will affect the cellular response, by culturing cells on various heat-treated titania substrates a relationship between the surface energy and cellular response can be investigated. A faster cellular response would lead to an increased rate of bone regeneration shortening healing times and allowing for better fixation of the implant.

  18. Resonance Raman Scattering Studies of Gallium - - Aluminum-Arsenide Superlattices.

    Science.gov (United States)

    Gant, Thomas Andrew

    We have made resonance Raman scattering studies of folded LA phonons and quantized LO phonons in several GaAs-AlAs superlattices. The motivation for this work was to study the electronic structure and the electron -phonon interaction in these structures. The samples were not intentionally doped. The Raman spectra of optic phonons were usually taken at a temperature of 10 K or less. The folded acoustic phonon work was taken at temperatures ranging from 200-300 K in order to enhance the scattering by the thermal factor. Two samples in particular have received very close attention: sample 2292 (50 A GaAs- 20 A AlAs) and sample 3250 (20 A GaAs- 50 A AlAs). In sample 2292 we have made resonance studies of the folded LA phonons and the GaAs -like confined LO_2 mode near the second heavy hole exciton. The results on the folded acoustic phonons show a very strong resonance enhancement for the second order folded phonons, but very little for the first order. An interference between two different scattering channels (the n = 1 light hole and the n = 2 heavy hole subbands) seems to be responsible for this effect. The resonance profile for the LO_2 confined optic phonon in sample 2292 shows 4 peaks in the region from 1.8 eV to 2.05 eV. We have studied the dependence of this resonance profile on the power density. A higher power density was achieved by using the same laser power with a tighter focus. At the higher power density the peak at 1.93 eV (formerly the strongest peak present) vanished. This "bleaching" effect is related to screening due to the higher carrier density. In sample 3250 we have studied the polarization dependence of the resonance profiles of four peaks (LO _2, LO_4, LO_6, and an interface mode) near the lowest direct gap. The A_1 symmetry confined LO modes are seen in both polarized and depolarized geometries, in violation of the usual selection rule (polarized). A mechanism is proposed to explain this result, which has been previously observed by other

  19. Resonance Raman detection of carotenoid antioxidants in living human tissue

    Science.gov (United States)

    Ermakov, Igor V.; Sharifzadeh, M.; Ermakova, Maia; Gellermann, W.

    2011-01-01

    Increasing evidence points to the beneficial effects of carotenoid antioxidants in the human body. Several studies, for example, support the protective role of lutein and zeaxanthin in the prevention of age-related eye diseases. If present in high concentrations in the macular region of the retina, lutein and zeaxanthin provide pigmentation in this most light sensitive retinal spot, and as a result of light filtering and/or antioxidant action, delay the onset of macular degeneration with increasing age. Other carotenoids, such as lycopene and beta-carotene, play an important role as well in the protection of skin from UV and short-wavelength visible radiation. Lutein and lycopene may also have protective function for cardiovascular health, and lycopene may play a role in the prevention of prostate cancer. Motivated by the growing importance of carotenoids in health and disease, and recognizing the lack of any accepted noninvasive technology for the detection of carotenoids in living human tissue, we explore resonance Raman spectroscopy as a novel approach for noninvasive, laser optical carotenoid detection. We review the main results achieved recently with the Raman detection approach. Initially we applied the method to the detection of macular carotenoid pigments, and more recently to the detection of carotenoids in human skin and mucosal tissues. Using skin carotenoid Raman instruments, we measure the carotenoid response from the stratum corneum layer of the palm of the hand for a population of 1375 subjects and develope a portable skin Raman scanner for field studies. These experiments reveal that carotenoids are a good indicator of antioxidant status. They show that people with high oxidative stress, like smokers, and subjects with high sunlight exposure, in general, have reduced skin carotenoid levels, independent of their dietary carotenoid consumption. We find the Raman technique to be precise, specific, sensitive, and well suitable for clinical as well as

  20. Raman spectroscopic investigation of blood and related materials

    Science.gov (United States)

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

    2015-03-01

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

  1. Elucidation of Chemical Reactions by Two-Dimensional Resonance Raman Spectroscopy

    Science.gov (United States)

    Moran, Andrew

    Two-dimensional (2D) Raman spectroscopies were proposed by Mukamel and Loring in1985 as a method for resolving line broadening mechanisms of vibrational motions in liquids. Significant technical issues challenged the development of both five- and seven-pulse 2D Raman spectroscopies. For this reason, 2D Raman experiments were largely abandoned in 2002 following the first demonstrations of 2D infrared spectroscopies (i.e., an alternate approach for obtaining similar information). We have recently shown that 2D Raman experiments conducted under electronically resonant conditions are much less susceptible to the problems encountered in the earlier 2D Raman work, which was carried out off-resonance. In effect, Franck-Condon activity obviates the problematic selection rules encountered under electronically off-resonant conditions. In this presentation, I will discuss applications of 2D resonance Raman spectroscopies to photodissocation reactions of triiodide and myoglobin. It will be shown that vibrational resonances of the reactants and products can be displayed in separate dimensions of a 2D resonance Raman spectrum when the photo-dissociation reaction is fast compared to the vibrational period. Such 2D spectra expose correlations between the nonequilibrium geometry of the reactant and the distribution of vibrational quanta in the product, thereby yielding insight in the photo-dissociation mechanism. Our results suggest that the ability of 2D resonance Raman spectroscopy to detect correlations between reactants and products will generalize to other ultrafast processes such as electron transfer and energy transfer.

  2. Single-Molecule Surface-Enhanced Raman Scattering Spectrum of Non-Resonant Aromatic Amine Showing Raman Forbidden Bands

    CERN Document Server

    Yamamoto, Yuko S; Ozaki, Yukihiro; Zhang, Zhenglong; Kozu, Tomomi; Itoh, Tamitake; Nakanishi, Shunsuke

    2016-01-01

    We present the experimentally obtained single-molecule (SM) surface-enhanced Raman scattering (SERS) spectrum of 4-aminibenzenethiol (4-ABT), also known as para-aminothiophenol (PATP). Measured at a 4-ABT concentration of 8 * 10^-10 M, the spectra show Raman forbidden modes. The SM-SERS spectrum of 4-ABT obtained using a non-resonant visible laser is different from the previously reported SERS spectra of 4-ABT, and could not be reconstructed using quantum mechanical calculations. Careful classical assignments (not based on quantum-mechanical calculations) are reported, and indicate that differences in the reported spectra of 4-ABT are mainly due to the appearance of Raman forbidden bands. The presence of Raman forbidden bands can be explained by the charge-transfer (CT) effect of 4-ABT adsorbed on the silver nanostructures, indicating a breakdown of Raman selection rules at the SERS hotspot.

  3. Resonant-Raman Intensities of N-layer Transition Metal Dichalcogenides from First Principles

    Science.gov (United States)

    Miranda, Henrique; Froehlicher, Guillaume; Lorchat, Ettienne; Fernique, François; Molina-Sánchez, Alejandro; Berciaud, Stéphane; Wirtz, Ludger

    Transition metal dichalcogenides (TMDs) have interesting optical and electronic properties that make them good candidates for nano-engineering applications. Raman spectroscopy provides information about the vibrational modes and optical spectrum at the same time: when the laser energy is close to an electronic transition, the intensity is increased due to resonance. We investigate these effects combining different ab initio methods: we obtain ground-state and vibrational properties from density functional theory and the optical absorption spectrum using GW corrections and the Bethe-Salpeter equation to account for the excitonic effects which are known to play an important role in TMDs. Using a quasi-static finite differences approach, we calculate the dielectric susceptibility for different light polarizations and different phonon modes in order to determine the Raman tensor of TMDs, in particular of multi-layer and bulk MoTe2. We explain recent experimental results for the splitting of high-frequency modes and deviations from the non-resonant Raman model. We also give a brief outlook on possible improvements of the methodology.

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

    Science.gov (United States)

    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.

  5. Rapidly reconfigurable slow-light system based on off-resonant Raman absorption

    Science.gov (United States)

    Vudyasetu, Praveen K.; Camacho, Ryan M.; Howell, John C.

    2010-11-01

    We present a slow-light system based on dual Raman absorption resonances in warm rubidium vapor. Each Raman absorption resonance is produced by a control beam in an off-resonant Λ system. This system combines all optical control of the Raman absorption and the low-dispersion broadening properties of the double Lorentzian absorption slow light. The bandwidth, group delay, and central frequency of the slow-light system can all be tuned dynamically by changing the properties of the control beam. We demonstrate multiple pulse delays with low distortion and show that such a system has fast switching dynamics and thus fast reconfiguration rates.

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

    Science.gov (United States)

    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.

  7. Resonant femtosecond stimulated Raman spectroscopy with an intense actinic pump pulse: Application to conical intersections

    Science.gov (United States)

    Rao, B. Jayachander; Gelin, Maxim F.; Domcke, Wolfgang

    2017-02-01

    We theoretically investigate the feasibility of characterizing conical intersections with time-resolved resonant femtosecond stimulated Raman spectroscopy (FSRS) using an intense actinic pump pulse. We perform nonperturbative numerical simulations of FSRS signals for a three-electronic-state two-vibrational-mode model, which is inspired by the S 2 ( π π * )- S 1 ( n π * ) conical intersection in pyrazine. Our results show that moderately strong actinic pulses increase the intensity of vibrational fingerprint lines in FSRS transients. They facilitate the extraction of useful spectroscopic information by enhancing peaks revealing the coupling and tuning modes of the conical intersection.

  8. Investigation of SOI Raman Lasers for Mid-Infrared Gas Sensing

    Science.gov (United States)

    Passaro, Vittorio M.N.; De Leonardis, Francesco

    2009-01-01

    In this paper, the investigation and detailed modeling of a cascaded Raman laser, operating in the midwave infrared region, is described. The device is based on silicon-on-insulator optical waveguides and a coupled resonant microcavity. Theoretical results are compared with recent experiments, demonstrating a very good agreement. Design criteria are derived for cascaded Raman lasers working as continuous wave light sources to simultaneously sense two types of gases, namely C2H6 and CO2, at a moderate power level of 130 mW. PMID:22408481

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

    Science.gov (United States)

    Stufkens, D. J.

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

  10. Semi-analytical model of Raman generation in silicon-on-insulator rib waveguide with DBR/F-P resonator

    National Research Council Canada - National Science Library

    Tyszka-Zawadzka, A; Szczepański, P; Mossakowska-Wyszyńska, A; Karpierz, M; Bugaj, M

    2013-01-01

    An approximate method of modelling of Raman generation in silicon-on-insulator (SOI) rib waveguide with DBR/F-P resonator including spatial field distribution and nonlinear effects such as Raman amplification and two photon absorption...

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

    Science.gov (United States)

    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.

  12. Strong overtones and combination bands in ultraviolet resonance Raman spectroscopy.

    Science.gov (United States)

    Efremov, Evtim V; Ariese, Freek; Mank, Arjan J G; Gooijer, Cees

    2006-05-01

    Ultraviolet resonance Raman spectroscopy is carried out using a continuous wave frequency-doubled argon ion laser operated at 229, 244, and 257 nm in order to characterize the overtones and combination bands for several classes of organic compounds in liquid solutions. Contrary to what is generally anticipated, for molecules such as pyrene and anthracene, strong overtones and combination bands can show up; it is demonstrated that their intensity depends critically on the applied laser wavelength. If the excitation wavelength corresponds with a purely electronic transition--this applies to a good approximation for 244-nm excitation in the case of pyrene and for 257-nm excitation in the case of anthracene--mostly fundamental vibrations (up to 1700 cm(-1)) are observed. Overtones and combination bands are detected but are rather weak. However, if the laser overlaps with the vibronic region--as holds for 229- and 257-nm excitation for pyrene and 244-nm excitation for anthracene--very strong bands are found in the region 1700-3400 cm(-1). As illustrated for pyrene at 257 nm, all these bands can be assigned to first overtones or binary combinations of fundamental vibrations. Their intensity distribution can roughly be simulated by multiplying the relative intensities of the fundamental bands. Significant bands can also be found in the region 3400-5000 cm(-1), corresponding with second overtones and ternary combinations. It is shown that these findings are not restricted to planar and rigid molecules with high symmetry. Substituted pyrenes exhibit similar effects, and relatively strong overtones are also observed for adenosine monophosphate and for abietic acid. The reasons for these observations are discussed, as well as the potential applicability for analytical purposes.

  13. Signal enhancement of surface enhanced Raman scattering and surface enhanced resonance Raman scattering using in situ colloidal synthesis in microfluidics.

    Science.gov (United States)

    Wilson, Rab; Bowden, Stephen A; Parnell, John; Cooper, Jonathan M

    2010-03-01

    We demonstrate the enhanced analytical sensitivity of both surface enhanced Raman scattering (SERS) and surface enhanced resonance Raman scattering (SERRS) responses, resulting from the in situ synthesis of silver colloid in a microfluidic flow structure, where both mixing and optical interrogation were integrated on-chip. The chip-based sensor was characterized with a model Raman active label, rhodamine-6G (R6G), and had a limit of detection (LOD) of ca. 50 fM (equivalent to single molecule detection). The device was also used for the determination of the natural pigment, scytonemin, from cyanobacteria (as an analogue for extraterrestrial life existing in extreme environments). The observed LOD of approximately 10 pM (ca. microfluidic system than those measured using the same experimental parameters, with colloid synthesized off-chip, under quiescent conditions.

  14. Raman spectroscopy investigations of chemically derived zigzag edge graphene nanoribbons

    Directory of Open Access Journals (Sweden)

    R. Nishinakagawa

    2013-09-01

    Full Text Available We fabricated graphene nanoribbons (GNRs chemically derived from expandable graphite. All GNRs exhibit atomically smooth edges that extended over their entire length. We investigated four of the fabricated GNRs using Raman spectroscopy. Two of the investigated GNRs show Raman spectra with a missing D-band peak, while D-band peaks can be clearly observed for the other two GNRs. The two GNRs which do not show the D-band peak are GNRs with zigzag edges, and the two other GNRs which show clearly the D-band peaks are possibly GNRs with armchair edges.

  15. Resonance Raman and quantum chemical studies of short polyene radical cations

    DEFF Research Database (Denmark)

    Keszthelyi, T.; Wilbrandt, R.; Bally, T.

    1997-01-01

    The results of our investigations of the geometric and vibrational structures of some short conjugated polyene radical cations are reported. The radical cations of 1,3-butadiene and three of its deuterated isotopomers, trans- and cis-1,3-pentadiene, 2-methyl-1,3-butadiene, and E- and Z-1,3,5-hexa......The results of our investigations of the geometric and vibrational structures of some short conjugated polyene radical cations are reported. The radical cations of 1,3-butadiene and three of its deuterated isotopomers, trans- and cis-1,3-pentadiene, 2-methyl-1,3-butadiene, and E- and Z-1...... and to assist assignment of the resonance Raman spectra. A new and improved scaled quantum mechanical force field for the butadiene radical cation was also determined. The presence of more than one rotamer was observed in all the polyene radical cations we investigated. (C) 1997 Elsevier Science B.V....

  16. Resonance Raman kinetic spectroscopy of bacteriorhodopsin on the microsecond time scale

    Energy Technology Data Exchange (ETDEWEB)

    Campion, A.; El-Sayed, M.A.; Terner, J.

    1977-12-01

    Using a rotating disk with a slit of variable width, a continuous wave argon ion laser, and an Optical Multichanel Analyzer for detection, a new technique is reported which should, in principle, be capable of recording resonance Raman spectra with time resolution of 100 ns. The resonance Raman spectra of the intermediates of the photosynthetic cycle of bacteriorhodopsin are recorded on the microsecond time scale. Both the kinetic results and the resonance enhancement profile suggest that deprotonation results in an intermediate preceding bM/sub 412/ that has an optical absorption maximum at a wavelength longer than that of bM/sub 412/.

  17. Resonance Raman Spectroscopy of human brain metastasis of lung cancer analyzed by blind source separation

    Science.gov (United States)

    Zhou, Yan; Liu, Cheng-Hui; Pu, Yang; Cheng, Gangge; Yu, Xinguang; Zhou, Lixin; Lin, Dongmei; Zhu, Ke; Alfano, Robert R.

    2017-02-01

    Resonance Raman (RR) spectroscopy offers a novel Optical Biopsy method in cancer discrimination by a means of enhancement in Raman scattering. It is widely acknowledged that the RR spectrum of tissue is a superposition of spectra of various key building block molecules. In this study, the Resonance Raman (RR) spectra of human metastasis of lung cancerous and normal brain tissues excited by a visible selected wavelength at 532 nm are used to explore spectral changes caused by the tumor evolution. The potential application of RR spectra human brain metastasis of lung cancer was investigated by Blind Source Separation such as Principal Component Analysis (PCA). PCA is a statistical procedure that uses an orthogonal transformation to convert a set of observations of possibly correlated variables into a set of values of linearly uncorrelated variables called principal components (PCs). The results show significant RR spectra difference between human metastasis of lung cancerous and normal brain tissues analyzed by PCA. To evaluate the efficacy of for cancer detection, a linear discriminant analysis (LDA) classifier is utilized to calculate the sensitivity, and specificity and the receiver operating characteristic (ROC) curves are used to evaluate the performance of this criterion. Excellent sensitivity of 0.97, specificity (close to 1.00) and the Area Under ROC Curve (AUC) of 0.99 values are achieved under best optimal circumstance. This research demonstrates that RR spectroscopy is effective for detecting changes of tissues due to the development of brain metastasis of lung cancer. RR spectroscopy analyzed by blind source separation may have potential to be a new armamentarium.

  18. Chemical Enhancement on Surface-Enhanced Resonance Raman Scattering of Au3-1,4-BenzenedithioI-Au3 Junction

    Institute of Scientific and Technical Information of China (English)

    Xiu-rning Zhao; Xiao-rui Tian; Sha-sha Liu; Yuan-zuo Lia; Mao-du Chen

    2011-01-01

    Surface-enhanced Raman scattering (SERS) and surface-enhanced resonance Raman scattering (SERRS) spectra of the 1,4-benzenedithiol molecule in the junction of two Au3 clusters have been calculated using density functional theory (DFT) and time-dependent DFT method.In order to investigate the contribution of charge transfer (CT) enhancement,the wavelengths of incident light are chosen to be at resonance with four representative excited states,which correspond to CT in four different forms.Compared with SERS spectrum,SERRS spectra are enhanced enormously with distinct enhancement factors,which can be attributed to CT resonance in different forms.

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

    DEFF Research Database (Denmark)

    Liu, Chuan; Berg, Rolf W.

    2013-01-01

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

  20. Communication: Significant contributions of Albrecht's $A$ term to non-resonant Raman scattering processes

    CERN Document Server

    Duan, Sai; Luo, Yi

    2015-01-01

    The Raman intensity can be well described by the famous Albrecht equation that consists of $A$ and $B$ terms. It has become a textbook knowledge that the contribution from Albrecht's $A$ term can be neglected without loss of accuracy for non-resonant Raman scattering processes. However, as demonstrated in this study, we have found that this widely accepted long-standing assumption fails drastically for totally symmetric vibration modes of molecules. Perturbed first principles calculations for water molecule show that strong constructive interference between the $A$ and $B$ terms occurs for the Raman intensity of the symmetric O-H stretching mode, which can account for about 40% of the total intensity. Meanwhile, a minor destructive interference is found for the angle bending mode. The state to state mapping between the Albrecht's theory and the perturbation theory allows us to verify the accuracy of the widely employed perturbation method for the dynamic/resonant Raman intensities. The model calculations show...

  1. Scanning angle Raman spectroscopy: Investigation of Raman scatter enhancement techniques for chemical analysis

    Energy Technology Data Exchange (ETDEWEB)

    Meyer, Matthew W. [Iowa State Univ., Ames, IA (United States)

    2013-01-01

    This thesis outlines advancements in Raman scatter enhancement techniques by applying evanescent fields, standing-waves (waveguides) and surface enhancements to increase the generated mean square electric field, which is directly related to the intensity of Raman scattering. These techniques are accomplished by employing scanning angle Raman spectroscopy and surface enhanced Raman spectroscopy. A 1064 nm multichannel Raman spectrometer is discussed for chemical analysis of lignin. Extending dispersive multichannel Raman spectroscopy to 1064 nm reduces the fluorescence interference that can mask the weaker Raman scattering. Overall, these techniques help address the major obstacles in Raman spectroscopy for chemical analysis, which include the inherently weak Raman cross section and susceptibility to fluorescence interference.

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

    Science.gov (United States)

    Ham, Byoung S

    2008-09-01

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

  3. Boosting the Amount of Molecular Information Through Polarized Resolved Resonance Raman Scattering

    DEFF Research Database (Denmark)

    Hassing, Søren

    2017-01-01

    and near-infrared absorption spectroscopy, i.e. only the spectral distribution is analysed. The goal of the present chapter is to demonstrate that the amount of molecular information (also for solutions and powders) can be increased considerably by analysing also the polarization of the Raman and resonance......Vibrational Raman spectroscopy, one of the experimental techniques available, is applied for characterization and analysis of molecular samples in different areas such as medical, food and environmental analysis. Application of the Raman technique is mostly similar to the application of infrared...

  4. Surface-enhanced resonance Raman spectroscopy of copper chlorophyllin on silver and gold colloids

    Energy Technology Data Exchange (ETDEWEB)

    Hildebrandt, P.; Spiro, T.G.

    1988-06-16

    Surface-enhanced resonance Raman spectra (SERRS) are reported for copper chlorophyllin a (CuChl) adsorbed on silver and gold colloids. The surface species are shown to be monomeric, by comparison with solution resonance Raman (RR) spectra, although lowering the pH of the gold colloid to 2.0 induces spectral changes suggestive of surface aggregation. The similarity of CuChl monomer RR and SERRS spectra is consistent with electromagnetic enhancement of the RR spectra via the metal particles, with no indication of a chemical interaction that would perturb the electronic states. The SERRS spectra change markedly with excitation wavelength in ways that can be explained on the basis of the different Raman enhancement pattern expected for resonance with the different chlorin excited states. The SERRS spectra are highly resolved and are useful in suggesting new assignments for chlorin vibrational modes.

  5. Multiwavelength Resonance Raman Characterization of the Effect of Growth Phase and Culture Medium on Bacteria.

    Science.gov (United States)

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

    2015-08-01

    We examine the use of multiwavelength ultraviolet (UV) resonance-Raman signatures to identify the effects of growth phase and growth medium on gram-positive and gram-negative bacteria. Escherichia coli (E. coli), Citrobacter koseri (C. koseri), Citrobacter braakii (C. braakii), and Bacillus cereus (B. cereus) were grown to logarithmic and stationary phases in nutrient broth and brain heart infusion broth. Resonance Raman spectra of bacteria were obtained at multiple wavelengths between 220 and 260 nm; a range that encompasses the resonance frequencies of cellular constituents. We find that spectra of the same bacterial species exhibit differences due to both growth condition and growth phase, but the larger differences reflect changes due to growth phase. The differences in the Raman spectra correlate with genetic differences among the species. Using a Pearson correlation based algorithm, we achieve successful identification of these bacteria in 83% of the cases.

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

    Science.gov (United States)

    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.

  7. NONLINEAR OPTICS: Stimulated resonant hyper-Raman scattering of light by polaritons in alkali metal vapors

    Science.gov (United States)

    Galaĭchuk, Yu A.; Yashkir, Yu N.

    1989-12-01

    A theory is developed for the calculation of the gain g due to stimulated resonant hyper-Raman scattering of light by polaritons in gaseous media. It is shown that throughout the tuning range of the pump frequency (including one- and two-photon resonances) a maximum of g corresponds to a dispersion curve of polaritons plotted ignoring attenuation. Theoretical results are used to analyze characteristics of hyper-Raman scattering in sodium vapor. It is shown that under normal experimental conditions the splitting of polariton branches is considerable (amounting to tens of reciprocal centimeters on the frequency scale and several angular degrees). The value of g is estimated for two-photon resonances in the case when the pump frequency is tunable in a wide range. The optimal conditions for stimulated hyper-Raman scattering are identified.

  8. Resonance Raman measurements of carotenoids using light emitting diodes

    CERN Document Server

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

    2008-01-01

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

  9. Harmonic-seeded resonant Raman amplification in strong-field ionized nitrogen molecules

    CERN Document Server

    Yao, Jinping; Tian, Chuanshan; Li, Ziting; Wang, Zhanshan; Cheng, Ya

    2016-01-01

    Generation of free-space laser-like emissions of high spatiotemporal coherence and narrow bandwidth in atmosphere opens promising opportunities for remote spectroscopic sensing. Here, we report on generation of such laser-like emissions, which results from the combined contributions of perturbative and non-perturbative nonlinear optical effects in nitrogen molecules exposed to intense mid-infrared laser fields. We systematically investigate the dependence of the generated free-space laser spectrum on wavelength and power of the driver laser. It is revealed that the free-space laser is produced by resonant Raman amplification of the fifth harmonic of the driver pulses in rotational wavepacket of the molecular nitrogen ions.

  10. 13C Solid State Nuclear Magnetic Resonance and µ-Raman Spectroscopic Characterization of Sicilian Amber.

    Science.gov (United States)

    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.

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

    Science.gov (United States)

    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.

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

    Science.gov (United States)

    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.

  13. An investigation on wind turbine resonant vibrations

    DEFF Research Database (Denmark)

    Tibaldi, Carlo; Kim, Taeseong; Larsen, Torben J.

    2016-01-01

    Wind turbine resonant vibrations are investigated based on aeroelastic simulations both in frequency and time domain. The investigation focuses on three different aspects: the need of a precise modeling when a wind turbine is operating close to resonant conditions; the importance of estimating wi...

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

    Science.gov (United States)

    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

    Energy Technology Data Exchange (ETDEWEB)

    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

    Energy Technology Data Exchange (ETDEWEB)

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

    Science.gov (United States)

    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

  18. Dielectric square resonator investigated with microwave experiments.

    Science.gov (United States)

    Bittner, S; Bogomolny, E; Dietz, B; Miski-Oglu, M; Richter, A

    2014-11-01

    We present a detailed experimental study of the symmetry properties and the momentum space representation of the field distributions of a dielectric square resonator as well as the comparison with a semiclassical model. The experiments have been performed with a flat ceramic microwave resonator. Both the resonance spectra and the field distributions were measured. The momentum space representations of the latter evidenced that the resonant states are each related to a specific classical torus, leading to the regular structure of the spectrum. Furthermore, they allow for a precise determination of the refractive index. Measurements with different arrangements of the emitting and the receiving antennas were performed and their influence on the symmetry properties of the field distributions was investigated in detail, showing that resonances with specific symmetries can be selected purposefully. In addition, the length spectrum deduced from the measured resonance spectra and the trace formula for the dielectric square resonator are discussed in the framework of the semiclassical model.

  19. Molecular structure and vibrational spectra of spin-crossover complexes in solution and colloidal media: resonance Raman and time-resolved resonance Raman studies.

    Science.gov (United States)

    Brady, Clare; Callaghan, Philip L; Ciunik, Zbigniew; Coates, Colin G; Døssing, Anders; Hazell, Alan; McGarvey, John J; Schenker, Sabine; Toftlund, Hans; Trautwein, Alfred X; Winkler, Heiner; Wolny, Juliusz A

    2004-07-12

    The spin-crossover system [Fe(btpa)](PF(6))(2) (btpa = N,N,N',N'-tetrakis(2-pyridylmethyl)-6,6'-bis(aminomethyl)-2,2'-bipyridine) and the predominantly low-spin species [Fe(b(bdpa))](PF(6))(2) ((b(bdpa) = N,N'-bis(benzyl)-N,N'-bis(2-pyridylmethyl)-6,6'-bis(aminomethyl)-2,2'-bipyridine) have been characterized by means of X-ray diffraction. The unit cell of [Fe(btpa)](PF(6))(2) contains two crystallographically independent molecules revealing octahedral low-spin and quasi-seven-coordinated high-spin structures. The unit cell of [Fe(b(bdpa))](PF(6))(2) contains two crystallographically independent molecules one of which corresponds to a low-spin structure, while the other reveals a disordering. On the basis of magnetic susceptibility and Mössbauer measurements, it has been proposed that this disorder involves low-spin and high-spin six-coordinated molecules. The structures of [Zn(btpa)](PF(6))(2) and [Ru(btpa)](PF(6))(2) have been determined also. Pulsed laser photoperturbation, coupled here with time-resolved resonance Raman spectroscopy (TR(3)), has been used to investigate, for the first time by this technique, the relaxation dynamics in solution on nanosecond and picosecond time scales of low-spin, LS ((1)A) --> high-spin, HS ((5)T) electronic spin-state crossover in these Fe(II) complexes. For the nanosecond experiments, use of a probe wavelength at 321 nm, falling within the pi-pi transition of the polypyridyl backbone of the ligands, enabled the investigation of vibrational modes of both LS and HS isomers, through coupling to spin-state-dependent angle changes of the backbone. Supplementary investigations of the spin-crossover (SCO) equilibrium in homogeneous solution and in colloidal media assisted the assignment of prominent features in the Raman spectra of the LS and HS isomers. The relaxation data from the nanosecond studies confirm and extend earlier spectrophotometric findings, (Schenker, S.; Stein, P. C.; Wolny, J. A.; Brady, C.; McGarvey, J. J

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

    Energy Technology Data Exchange (ETDEWEB)

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

    1999-12-09

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

  1. Resonance Raman and UV-visible spectroscopy of black dyes on textiles.

    Science.gov (United States)

    Abbott, Laurence C; Batchelor, Stephen N; Smith, John R Lindsay; Moore, John N

    2010-10-10

    Resonance Raman and UV-visible diffuse reflectance spectra were recorded from samples of cotton, viscose, polyester, nylon, and acrylic textile swatches dyed black with one of seven single dyes, a mixture of two dyes, or one of seven mixtures of three dyes. The samples generally gave characteristic Raman spectra of the dyes, demonstrating that the technique is applicable for the forensic analysis of dyed black textiles. Survey studies of the widely used dye Reactive Black 5 show that essentially the same Raman spectrum is obtained on bulk sampling from the dye in solution, on viscose, on cotton at different uptakes, and on microscope sampling from the dye in cotton threads and single fibres. The effects of laser irradiation on the Raman bands and emission backgrounds from textile samples with and without dye are also reported. Copyright © 2010 Elsevier Ireland Ltd. All rights reserved.

  2. Boosting the Amount of Molecular Information Through Polarized Resolved Resonance Raman Scattering

    DEFF Research Database (Denmark)

    Hassing, Søren

    2017-01-01

    Ramanscattered light. The goal is achieved through: (1) a discussion of the basic properties of Raman scattering with special focus on polarization and polarization dispersion. The discussion includes the rotational invariants of Raman tensors, the non-commuting generator approach to molecular symmetry as a tool...... and near-infrared absorption spectroscopy, i.e. only the spectral distribution is analysed. The goal of the present chapter is to demonstrate that the amount of molecular information (also for solutions and powders) can be increased considerably by analysing also the polarization of the Raman and resonance...... for construction of state and Raman tensors for single molecules and dimers and higher aggregates and thereby predict the polarization; (2) a discussion of two illustrative case studies: Case study 1: Aggregation of haemoglobin in red blood cells (RBC); and Case study 2: In vitro polarization resolved RRS study...

  3. Investigation of L(+)-Ascorbic Acid with Raman Spectroscopy in Visible and UV Light

    DEFF Research Database (Denmark)

    Berg, Rolf W.

    2015-01-01

    Abstract: Raman spectroscopy investigations of l(+)-ascorbic acid and its mono- and di-deprotonated anions (AH(-) and A(2-)) are reviewed and new measurements reported with several wavelengths, 229, 244, 266, 488, and 532nm. Results are interpreted, assisted by new DFT/B3LYP quantum chemical calc......). Relatively weak preresonance enhancement was seen for A(2-) when excitation was done with 229nm UV light, allowing water bands to become observable as for normal visible light Raman spectra....... calculations with 6-311++G(d,p) basis sets for several conformations of ascorbic acid and the anions. Raman spectra were measured during titration with NaOH base in an oxygen-poor environment to avoid fluorescence when solutions were alkaline. The ultraviolet (UV) absorption band for ascorbic acid in aqueous......cm(-1). Finally, for the ascorbate di-anion, absorption was found at similar to 298.4nm with molar absorptivity of similar to 7,000 L mol(-1) cm(-1) and below similar to 220nm. With UV light (244 and 266nm), strongly basic solutions gave pronounced Raman resonance enhancement at similar to 1556cm(-1...

  4. Continuous Flow-Resonance Raman Spectroscopy of an Intermediate Redox State of Cytochrome-C

    DEFF Research Database (Denmark)

    Forster, M.; Hester, R. E.; Cartling, B.

    1982-01-01

    An intermediate redox state of cytochrome c at alkaline pH, generated upon rapid reduction by sodium dithionite, has been observed by resonance Raman (RR) spectroscopy in combination with the continuous flow technique. The RR spectrum of the intermediate state is reported for excitation both...

  5. Electro-Optical Multichannel Spectrometer for Transient Resonance Raman and Absorption Spectroscopy

    DEFF Research Database (Denmark)

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

    1979-01-01

    An optical multichannel system is described, used for time‐dependent absorption measurements in the gas phase and the liquid phase and for resonance Raman spectroscopy of short‐lived transient species in the liquid phase in pulse radiolysis. It consists of either an image converter streak unit or...

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

    Science.gov (United States)

    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…

  7. Resonance Raman Spectra of the Transient Cl2 and Br2 Radical Anions

    DEFF Research Database (Denmark)

    Wilbrandt, Robert Walter; Jensen, Niels-Henrik; Sillesen, Alfred Hegaard

    1984-01-01

    The resonance Raman spectra of the short-lived radical anions ClImage 2− and BrImage − in aqueous solution are reported. The observed wavenumbers of 279 cm−1 for ClImage − and 177 cm−1 for BrImage − are about 10% higher than those published for the corresponding species isolated in solid argon...

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

    Science.gov (United States)

    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.

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

    DEFF Research Database (Denmark)

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

    1985-01-01

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

  10. Calculation of optical absorption and resonance Raman correlators using time-dependent recursion relationships

    DEFF Research Database (Denmark)

    Svendsen, Christian; Mortensen, O. Sonnich; Henriksen, Niels Engholm

    1996-01-01

    Time-dependent recursion relationships are derived for optical absorption and resonance Raman correlators in the multidimensional harmonic case using a second-quantization formalism. Furthermore, a procedure is given for the calculation of correlators involving a general analytic coordinate depen...... dependence of the transition dipole moment....

  11. Protein Interactions Investigated by the Raman Spectroscopy for Biosensor Applications

    Directory of Open Access Journals (Sweden)

    R. P. Kengne-Momo

    2012-01-01

    Full Text Available Interaction and surface binding characteristics of staphylococcal protein A (SpA and an anti-Escherichia coli immunoglobulin G (IgG were studied using the Raman spectroscopy. The tyrosine amino acid residues present in the α-helix structure of SpA were found to be involved in interaction with IgG. In bulk interaction condition the native structure of proteins was almost preserved where interaction-related changes were observed in the overall secondary structure (α-helix of SpA. In the adsorbed state, the protein structure was largely modified, which allowed the identification of tyrosine amino acids involved in SpA and IgG interaction. This study constitutes a direct Raman spectroscopic investigation of SpA and IgG (receptor-antibody interaction mechanism in the goal of a future biosensor application for detection of pathogenic microorganisms.

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

    Science.gov (United States)

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

    2014-09-01

    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.

  13. Resonance Raman Spectroscopic and Theoretical Study of Geometry Distortion of Thiourea in 21A State

    Institute of Scientific and Technical Information of China (English)

    Hai-bo Zhang; Yan-ying Zhao; Xu-ming Zheng

    2012-01-01

    The A-band resonance Raman spectra of thiourea were obtained in water and acetonitrile solution.B3LYP/6-311++G(3df,3pd) and RCIS/6-311++G(3df,3pd) calculations were done to elucidate the ultraviolet electronic transitions,the distorted geometry structure and the saddle point of thiourea in 21A excited state,respectively.The resonance Raman spectra were assigned.The absorption spectrum and resonance Raman intensities were modeled using Heller's time-dependent wavepacket approach to resonance Raman scattering.The results indicate that largest change in the displacement takes place with the C=S stretch mode v6 (|Δ|=0.95) and noticeable changes appear in the HsN3H6+H8N4H7 wag v5 (|Δ|=0.19),NCN symmetric stretch+C=S stretch+N3H6+H8N4 wag v4 (|Δ|=0.18),while the moderate intensities of 2v15 and 4v15 are mostly due to the large excited state frequency changes of v15,but not due to its significant change in the normal mode displacement.The mechanism of the appearance of even overtones of the S=CN2 out of plane deformation is explored.The results indicate that a Franck-Condon region saddle point is the driving force for the quadric phonon mechanism within the standard A-term of resonance Raman scattering,which leads to the pyramidalization of the carbon center and the geometry distortion of thiourea molecule in 21A excited state.

  14. Raman scattering enhancement in photon-plasmon resonance mediated metal-dielectric microcavity

    Science.gov (United States)

    Guddala, Sriram; Dwivedi, Vindesh K.; Vijaya Prakash, G.; Narayana Rao, D.

    2013-12-01

    Here, we report the photon-plasmon interaction scheme and enhanced field strengths resulted into the amplification of phonon in a novel microcavity. A metal-dielectric microcavity, with unified cavity photonic mode and localized surface plasmon resonances, is visualized by impregnating the gold nanoparticles into the deep see-through nano-sized pores of porous silicon microcavity. The intense optical field strengths resulting from the photon-plasmon interactions are probed by both resonant and non-resonant Raman scattering experiments. Due to photon-plasmon-phonon interaction mechanism, several orders of enhancement in the intensity of scattered Raman Stokes photon (at 500 cm-1) are observed. Our metal nanoparticle-microcavity hybrid system shows the potential to improve the sensing figure of merit as well as the applications of plasmonics for optoelectronics, photovoltaics, and related technologies.

  15. Raman scattering enhancement in photon-plasmon resonance mediated metal-dielectric microcavity

    Energy Technology Data Exchange (ETDEWEB)

    Guddala, Sriram; Narayana Rao, D., E-mail: dnr.laserlab@gmail.com, E-mail: dnrsp@uohyd.ernet.in [School of Physics, University of Hyderabad, Hyderabad 500 046 (India); Dwivedi, Vindesh K.; Vijaya Prakash, G. [Nanophotonics Laboratory, Department of Physics, IIT Delhi, New Delhi 110 016 (India)

    2013-12-14

    Here, we report the photon-plasmon interaction scheme and enhanced field strengths resulted into the amplification of phonon in a novel microcavity. A metal-dielectric microcavity, with unified cavity photonic mode and localized surface plasmon resonances, is visualized by impregnating the gold nanoparticles into the deep see-through nano-sized pores of porous silicon microcavity. The intense optical field strengths resulting from the photon-plasmon interactions are probed by both resonant and non-resonant Raman scattering experiments. Due to photon-plasmon-phonon interaction mechanism, several orders of enhancement in the intensity of scattered Raman Stokes photon (at 500 cm{sup −1}) are observed. Our metal nanoparticle-microcavity hybrid system shows the potential to improve the sensing figure of merit as well as the applications of plasmonics for optoelectronics, photovoltaics, and related technologies.

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

    Science.gov (United States)

    Sension, Roseanne J.; Hudson, Bruce S.

    1989-02-01

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

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

    Institute of Scientific and Technical Information of China (English)

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

    2012-01-01

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

  18. Development of a fiber based Raman probe compatible with interventional magnetic resonance imaging

    Science.gov (United States)

    Ashok, Praveen C.; Praveen, Bavishna B.; Rube, Martin; Cox, Benjamin; Melzer, Andreas; Dholakia, Kishan

    2014-02-01

    Raman spectroscopy has proven to be a powerful tool for discriminating between normal and abnormal tissue types. Fiber based Raman probes have demonstrated its potential for in vivo disease diagnostics. Combining Raman spectroscopy with Magnetic Resonance Imaging (MRI) opens up new avenues for MR guided minimally invasive optical biopsy. Although Raman probes are commercially available, they are not compatible with a MRI environment due to the metallic components which are used to align the micro-optic components such as filters and lenses at the probe head. Additionally they are not mechanically compatible with a typical surgical environment as factors such as sterility and length of the probe are not addressed in those designs. We have developed an MRI compatible fiber Raman probe with a disposable probe head hence maintaining sterility. The probe head was specially designed to avoid any material that would cause MR imaging artefacts. The probe head that goes into patient's body had a diameter biopsy needles and catheters. The probe has been tested in MR environment and has been proven to be capable of obtaining Raman signal while the probe is under real-time MR guidance.

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

    Science.gov (United States)

    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.

  20. Photobleaching of the resonance Raman lines of cytochromes in living yeast cells.

    Science.gov (United States)

    Okotrub, Konstantin A; Surovtsev, Nikolay V

    2014-12-01

    The photobleaching of the resonance cytochrome Raman lines in living Saccharomyces cerevisiae cells was studied. The photobleaching rate versus the irradiation power was described by square function plus a constant in contrast to the linear dependence of the photoinjury rate. This difference distinguishes the cytochrome photooxidation from other processes of the cell photodamage. The square dependence is associated with the reaction involving two photogenerated intermediates while the constant with the dark redox balance rates. This work demonstrates a potential of Raman spectroscopy to characterize the native cytochrome reaction rates and to study the cell photodamage precursors. Copyright © 2014 Elsevier B.V. All rights reserved.

  1. One phonon resonant Raman scattering in semiconductor quantum wires: Magnetic field effect

    Energy Technology Data Exchange (ETDEWEB)

    Betancourt-Riera, Re., E-mail: rbriera@posgrado.cifus.uson.mx [Instituto Tecnologico de Hermosillo, Avenida Tecnologico S/N, Colonia Sahuaro, C.P. 83170, Hermosillo, Sonor, (Mexico); Departamento de Investigacion en Fisica, Universidad de Sonora, Apartado Postal 5-088, C.P. 83190, Hermosillo, Sonora (Mexico); Betancourt-Riera, Ri. [Instituto Tecnologico de Hermosillo, Avenida Tecnologico S/N, Colonia Sahuaro, C.P. 83170, Hermosillo, Sonora (Mexico); Nieto Jalil, J.M. [Tecnologico de Monterrey-Campus Sonora Norte, Bulevar Enrique Mazon Lopez No. 965, C.P. 83000, Hermosillo, Sonora (Mexico); Riera, R. [Departamento de Investigacion en Fisica, Universidad de Sonora, Apartado Postal 5-088, C.P. 83190, Hermosillo, Sonora (Mexico)

    2013-02-01

    We have developed a theory of one phonon resonant Raman scattering in a semiconductor quantum wire of cylindrical geometry in the presence of an external magnetic field distribution, parallel to the cylinder axis. The effect of the magnetic field in the electron and hole states, and in the Raman scattering efficiency, is determinate. We consider the electron-phonon interaction using a Froehlich-type Hamiltonian, deduced for the case of complete confinement phonon modes by Comas and his collaborators. We also assume T=0 K, a single parabolic conduction and valence bands. The spectra are discussed for different magnetic field values and the selection rules for the processes are also studied.

  2. Demonstration of resonant backward Raman amplification in high-density gas-jet plasma

    Science.gov (United States)

    Wu, Z. H.; Zhou, K. N.; Zheng, X. M.; Wei, X. F.; Zhu, Q. H.; Su, J. Q.; Xie, N.; Jiao, Z. H.; Peng, H.; Wang, X. D.; Sun, L.; Li, Q.; Huang, Z.; Zuo, Y. L.

    2016-10-01

    Backward Raman amplification was observed in a 0.7 mm-long high-density gas jet plasma. The 800 nm 30 fs seed pulse was amplified by a factor  ∼28, with an output energy of 2.8 mJ. The output spectra showed that the waveband around 800 nm was significantly amplified. The experimental result demonstrated that the resonant Raman amplification can be realized in high-density plasma against strong plasma instability.

  3. Raman and non Raman EIT resonances in a degenerate four level system

    CERN Document Server

    Ahmedov, Haji

    2013-01-01

    Interference effects in a degenerate four level system subjected to two optical and one radio frequency (rf) fields are studied. The degeneracy of a metastable level (which is common for the rf field and one of the optical field) leads to EIT resonances properties of which depend not only on the optical field frequency and the rf field amplitude, but also on the geometry of polarizations of the optical and the rf fields. The properties of these resonances can be manipulated to design a desired atomic response.

  4. Surface-enhanced Raman spectroscopy on a surface plasmon resonance biosensor platform for gene diagnostics

    Science.gov (United States)

    Yuan, W.; Ho, H. P.; Suen, Y. K.; Kong, S. K.; Lin, Chinlon; Prasad, Paras N.; Li, J.; Ong, Daniel H. C.

    2008-02-01

    We propose to integrate the surface-enhanced Raman spectroscopy (SERS) detection capability with a surface plasmon resonance (SPR) biosensor platform. As a demonstration setup, the experimental scheme is built from a Total Internal Reflection Fluorescence (TIRF) microscope. The sample surface is a gold-coated plasmonic crystal substrate. Two oligonucleotide (ODN) probes that have been labeled with two different Raman active dyes are used to achieve a sandwich assay of target ODNs or polynucleotide. Upon complementary hybridizations between the target and probe ODNs, the target can be identified by detecting the narrow-band spectroscopic fingerprints of the Raman tags. This concept has high potential for achieving multiplexed detection of ODN targets because a very large number of probes can be incorporated to the plasmonic crystal substrate, which may find applications in gene based diseases diagnostics. We also explored the detection of single molecules and achieved some preliminary results.

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

    Science.gov (United States)

    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

  6. Raman spectroscopy as a tool for investigating lipid protein interactions

    DEFF Research Database (Denmark)

    Petersen, Frederic Nicolas Rønne; Helix Nielsen, Claus

    2009-01-01

    Raman spectroscopy is a very well-established technique for noninvasive probing of chemical compounds. The fad that Raman scattering is an inherently weak effect has prompted many new developments in sample signal enhancement and techniques (such as surface-enhancement Raman spectroscopy [SERS]) ...... to study using noninvasive vibrational spectroscopy....

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

    Science.gov (United States)

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

    2010-04-01

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

  8. Determination of Temperature-Dependent Stress State in Thin AlGaN Layer of AlGaN/GaN HEMT Heterostructures by Near-Resonant Raman Scattering

    Directory of Open Access Journals (Sweden)

    Yanli Liu

    2015-01-01

    Full Text Available The temperature-dependent stress state in the AlGaN barrier layer of AlGaN/GaN heterostructure grown on sapphire substrate was investigated by ultraviolet (UV near-resonant Raman scattering. Strong scattering peak resulting from the A1(LO phonon mode of AlGaN is observed under near-resonance condition, which allows for the accurate measurement of Raman shifts with temperature. The temperature-dependent stress in the AlGaN layer determined by the resonance Raman spectra is consistent with the theoretical calculation result, taking lattice mismatch and thermal mismatch into account together. This good agreement indicates that the UV near-resonant Raman scattering can be a direct and effective method to characterize the stress state in thin AlGaN barrier layer of AlGaN/GaN HEMT heterostructures.

  9. Resonant Raman scattering theory for Kitaev models and their Majorana fermion boundary modes

    Science.gov (United States)

    Perreault, Brent; Knolle, Johannes; Perkins, Natalia B.; Burnell, F. J.

    2016-09-01

    We study the inelastic light scattering response in two- (2D) and three-dimensional (3D) Kitaev spin-liquid models with Majorana spinon band structures in the symmetry classes BDI and D leading to protected gapless surface modes. We present a detailed calculation of the resonant Raman/Brillouin scattering vertex relevant to iridate and ruthenate compounds whose low-energy physics is believed to be proximate to these spin-liquid phases. In the symmetry class BDI, we find that while the resonant scattering on thin films can detect the gapless boundary modes of spin liquids, the nonresonant processes do not couple to them. For the symmetry class D, however, we find that the coupling between both types of light-scattering processes and the low-energy surface states is strongly suppressed. Additionally, we describe the effect of weak time-reversal symmetry breaking perturbations on the bulk Raman response of these systems.

  10. Nonadiabaticity in a Jahn-Teller system probed by absorption and resonance Raman scattering.

    Science.gov (United States)

    Pae, K; Hizhnyakov, V

    2013-03-14

    A theory of absorption and resonance Raman scattering of impurity centers in crystals with E⊗e-type Jahn-Teller effect in the excited state is presented. The vibronic interaction with non-totally symmetric local or pseudolocal modes and with a continuum of bath modes (phonons) is considered. A number of specific quantum effects, such as the nonadiabaticity-induced enhancement of the Raman scattering at high-energy excitation, the size effect of the final state, the interference of different channels of scattering, the Fermi resonances in the conical intersection, and others, were shown to become apparent in the calculated spectra. The vibronic interaction with phonons essentially determines the structure of the spectra.

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

    Science.gov (United States)

    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.

  12. Raman Theory for a Molecule in a Vibrating Microcavity Oscillating in Fundamental Resonance

    Institute of Scientific and Technical Information of China (English)

    YANG XiaoXue; WU Ying

    2001-01-01

    We propose a model to describe the energy structure and dynamics of a system of a molecule interacting with infinite photon modes in a vibrating microcavity whose boundary oscillates in the fundamental resonance. By constructing an so(2,1) Lie algebra for the infinite photon modes, we obtain analytical expressions of the energy eigenstates, energy eigenvalues and the system's evolution operator for this Raman model under certain conditions.``

  13. Anisotropy of electron-phonon interaction in nanoscale CdSe platelets as seen via off-resonant and resonant Raman spectroscopy

    Science.gov (United States)

    Cherevkov, S. A.; Fedorov, A. V.; Artemyev, M. V.; Prudnikau, A. V.; Baranov, A. V.

    2013-07-01

    The off-resonant and resonant Raman spectra of optical phonons in colloidal CdSe nanoplatelets (NPLs) with the thickness of 4, 5, and 6 CdSe monolayers are analyzed. These spectra are dominated by SO and LO phonon bands of CdSe whose frequencies are thickness independent in the off-resonant Raman but demonstrate evident thickness dependence similar to that observed for confined optical phonons in CdSe quantum dots in the resonant Raman. The results show that conventional optical phonons propagating along the NPL lateral planes contribute mainly to the off-resonant Raman while confined optical phonons propagating in the perpendicular direction dominate the Raman spectra excited in the resonance with confined exciton transitions of CdSe NPLs. An anisotropic electron-phonon interaction is proposed to be responsible for this effect in the CdSe NPLs. A formation of Cd-S monolayer on the surface of CdSe NPLs treated by thiol-containing ligands is also detected in Raman spectra.

  14. Electronic Raman scattering and the Fano resonance in metallic carbon nanotubes

    Science.gov (United States)

    Hasdeo, Eddwi H.; Nugraha, Ahmad R. T.; Sato, Kentaro; Dresselhaus, Mildred S.; Saito, Riichiro

    2013-09-01

    The Fano resonance spectra for the G band in metallic carbon nanotubes are calculated as a function of laser excitation energy, in which the origin of the resonance is given by an interference between the continuous electronic Raman spectra and the discrete phonon spectra. We found that the second-order scattering process of the q≠0 electron-electron interaction is more relevant to the continuous spectra rather than the q=0 first-order process because the q=0 direct Coulomb interaction vanishes due to the symmetry of the two sublattices of a carbon nanotube.

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

    Energy Technology Data Exchange (ETDEWEB)

    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.

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

    Energy Technology Data Exchange (ETDEWEB)

    Zheng, Junwei [Iowa State Univ., Ames, IA (United States)

    1999-11-08

    Surface plasmon resonance was utilized to enhance the electron transfer at silver/solution interfaces. Photoelectrochemical reductions of nitrite, nitrate, and CO2 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 CO2, large photoelectrocatalytic effect for the reduction of CO2 was observed in the presence of surface adsorbed methylviologen, which functions as a mediator for the photoexcited electron transfer from silver metal to CO2 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.

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

    Energy Technology Data Exchange (ETDEWEB)

    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).

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

    Energy Technology Data Exchange (ETDEWEB)

    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).

  19. Resonance Raman examination of the wavelength regulation mechanism in human visual pigments.

    Science.gov (United States)

    Kochendoerfer, G G; Wang, Z; Oprian, D D; Mathies, R A

    1997-06-03

    Resonance Raman spectra of recombinant human green and red cone pigments have been obtained to examine the molecular mechanism of color recognition by visual pigments. Spectra were acquired using a 77 K resonance Raman microprobe or preresonance Raman spectroscopy. The vibrational bands were assigned by comparison to the spectra of bovine rhodopsin and model compounds. The C=NH stretching frequencies of rhodopsin, the green cone pigment, and the red cone pigment in H2O (D2O) are found at 1656 (1623), 1640 (1618), and 1644 cm(-1), respectively. Together with previous resonance Raman studies on iodopsin [Lin, S. W., Imamoto, Y., Fukada, Y., Shichida, Y., Yoshizawa, T., & Mathies, R. A. (1994) Biochemistry 33, 2151-2160], these values suggest that red and green pigments have very similar Schiff base environments, while the Schiff base group in rhodopsin is more strongly hydrogen-bonded to its protein environment. The absence of significant frequency and intensity differences of modes in the fingerprint and the hydrogen out-of-plane wagging regions for all these pigments does not support the hypothesis that local chromophore interactions with charged protein residues and/or chromophore planarization are crucial for the absorption differences among these pigments. However, our data are consistent with the idea that the Schiff base group in blue visual pigments is stabilized by protein and water dipoles and that the removal of this dipolar field shifts the absorption maximum from blue to green. A further red shift of the lambda(max) from the green to the red pigment is successfully modeled by the addition of hydroxyl-bearing amino acids (Ser164, Tyr261, and Thr269) close to the ionone ring that lower the transition energy by interacting with the change of dipole moment of the chromophore upon excitation. The increased hydrogen bonding of the protonated Schiff base group in rhodopsin is predicted to account for the 30 nm blue shift of its absorption maximum compared to

  20. Resonance Raman spectra of phthalocyanine monolayers on different supports. A normal mode analysis of zinc phthalocyanine by means of the MNDO method

    NARCIS (Netherlands)

    Palys, Barbara J.; Ham, van den Dirk M.W.; Briels, Wim; Feil, Dirk

    1995-01-01

    Resonance Raman spectra of monolayers of transition metal phthalocyanines reveal specific interaction with the support. To elucidate its mechanism, Raman spectra of zinc phthalocyanine monolayers were studied. The analysis was based largely on the results of MNDO calculations. Calculated wavenumbers

  1. Resonance Raman spectra of phthalocyanine monolayers on different supports. A normal mode analysis of zinc phthalocyanine by means of the MNDO method

    NARCIS (Netherlands)

    Palys, Barbara J.; van den Ham, Dirk M.W.; van den Ham, D.M.W.; Briels, Willem J.; Feil, D.; Feil, Dirk

    1995-01-01

    Resonance Raman spectra of monolayers of transition metal phthalocyanines reveal specific interaction with the support. To elucidate its mechanism, Raman spectra of zinc phthalocyanine monolayers were studied. The analysis was based largely on the results of MNDO calculations. Calculated wavenumbers

  2. Raman spectroscopy as a tool for investigating lipid protein interactions

    DEFF Research Database (Denmark)

    Petersen, Frederic Nicolas Rønne; Helix Nielsen, Claus

    2009-01-01

    Raman spectroscopy is a very well-established technique for noninvasive probing of chemical compounds. The fad that Raman scattering is an inherently weak effect has prompted many new developments in sample signal enhancement and techniques (such as surface-enhancement Raman spectroscopy [SERS......]) as well as improved technical equipment for signal capture (such as improved sensitivity of charge-coupled devices [CCDs]). Combined, these technological advances have brought Raman spectroscopy into a new era in which hitherto inaccessible or hardly accessible research areas now are becoming possible...... to study using noninvasive vibrational spectroscopy....

  3. Applicability of surface-enhanced resonance Raman scattering for the direct discrimination of ballpoint pen inks.

    Science.gov (United States)

    Seifar, R M; Verheul, J M; Ariese, F; Brinkman, U A; Gooijer, C

    2001-08-01

    In situ surface-enhanced resonance Raman spectroscopy (SERRS) with excitation at 685 nm is suitable for the direct discrimination of blue and black ballpoint pen inks on paper. For black inks, shorter excitation wavelengths can also be used. For blue inks, SERRS at 514.5 and 457.9 nm does not provide adequate discriminative power. At these excitation wavelengths, the SERRS signals of the Methyl Violet derivatives present in inks easily dominate the overall spectrum because of resonance enhancement and preferential interaction with silver sol particles. At 685 nm, this problem is not encountered as the Methyl Violet derivatives do not show resonance enhancement, while other components may still exhibit resonance. Thirteen blue and thirteen black ink lines were examined. For the blue and black inks, on the basis of the 685 nm SERR spectra, eight and six groups of spectra, respectively, could be distinguished. This discrimination largely agrees with information from thin layer chromatography (TLC) experiments, although some differences in group compositions are found. The in situ SERR spectra show good repeatability with regard to the Raman frequencies, band shapes and relative intensities of the spectral bands. However, absolute intensities cannot be used for discrimination purposes.

  4. Analysis of structure-function relationships in cytochrome c oxidase and its biomimetic analogs via resonance Raman and surface enhanced resonance Raman spectroscopies.

    Science.gov (United States)

    Weidinger, Inez M

    2015-01-01

    Cytochrome c oxidase (CcO) catalyzes the four electron reduction of molecular oxygen to water while avoiding the formation of toxic peroxide; a quality that is of high relevance for the development of oxygen-reducing catalysts. Resonance Raman spectroscopy has been used since many years as a technique to identify electron transfer pathways in cytochrome c oxidase and to identify the key intermediates in the catalytic cycle. This information can be compared to artificial systems such as modified heme-copper enzymes, molecular heme-copper catalysts or CcO/electrode complexes in order to shed light into the reaction mechanism of these non-natural systems. Understanding the structural commonalities and differences of CcO with its non-natural analogs is of great value for designing efficient oxygen-reducing catalysts. In this review therefore Raman spectroscopic measurements on artificial heme-copper enzymes and model complexes are summarized and compared to the natural enzyme cytochrome c oxidase. This article is part of a Special Issue entitled: Vibrational spectroscopies and bioenergetic systems.

  5. Normal mode analysis of pyrococcus furiosus rubredoxin via nuclear resonance vibrational spectroscopy (NRVS) and resonance raman spectroscopy.

    Energy Technology Data Exchange (ETDEWEB)

    Xiao, Y.; Wang, H.; George, S.J.; Smith, M.C.; Adams, M.W.W.; Jenney, F.E., Jr.; Sturhahn, W.; Alp, E.E.; Zhao, J.; Yoda, Y.; Dey, A.; Solomon, E.I.; Cramer, S.P.; Experimental Facilities Division (APS); Univ. of California; LBNL; Stanford Univ.; Univ. of Georgia; SPring-8

    2005-10-26

    We have used {sup 57}Fe nuclear resonance vibrational spectroscopy (NRVS) to study the Fe(S{sub cys})4 site in reduced and oxidized rubredoxin (Rd) from Pyrococcus furiosus (Pf). The oxidized form has also been investigated by resonance Raman spectroscopy. In the oxidized Rd NRVS, strong asymmetric Fe-S stretching modes are observed between 355 and 375 cm{sup -1}; upon reduction these modes shift to 300-320 cm{sup -1}. This is the first observation of Fe-S stretching modes in a reduced Rd. The peak in S-Fe-S bend mode intensity is at {approx}150 cm{sup -1} for the oxidized protein and only slightly lower in the reduced case. A third band occurs near 70 cm{sup -1} for both samples; this is assigned primarily as a collective motion of entire cysteine residues with respect to the central Fe. The {sup 57}Fe partial vibrational density of states (PVDOS) were interpreted by normal mode analysis with optimization of Urey-Bradley force fields. The three main bands were qualitatively reproduced using a D{sub 2d} Fe(SC){sub 4} model. A C{sub 1} Fe(SCC){sub 4} model based on crystallographic coordinates was then used to simulate the splitting of the asymmetric stretching band into at least 3 components. Finally, a model employing complete cysteines and 2 additional neighboring atoms was used to reproduce the detailed structure of the PVDOS in the Fe-S stretch region. These results confirm the delocalization of the dynamic properties of the redox-active Fe site. Depending on the molecular model employed, the force constant KFe-S for Fe-S stretching modes ranged from 1.24 to 1.32 mdyn/Angstrom. KFe-S is clearly diminished in reduced Rd; values from {approx}0.89 to 1.00 mdyn/Angstrom were derived from different models. In contrast, in the final models the force constants for S-Fe-S bending motion, HS-Fe-S, were 0.18 mdyn/Angstrom for oxidized Rd and 0.15 mdyn/Angstrom for reduced Rd. The NRVS technique demonstrates great promise for the observation and quantitative

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

    Science.gov (United States)

    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.

  7. Understanding double-resonant Raman scattering in chiral carbon nanotubes: Diameter and energy dependence of the D mode

    Science.gov (United States)

    Herziger, Felix; Vierck, Asmus; Laudenbach, Jan; Maultzsch, Janina

    2015-12-01

    We present a theoretical model to describe the double-resonant scattering process in arbitrary carbon nanotubes (CNTs). We use this approach to investigate the defect-induced D mode in CNTs and unravel the dependence of the D -mode frequency on the CNT diameter and on the energy of the resonant optical transition. Our approach is based on the symmetry of the hexagonal lattice and geometric considerations; hence the method is independent of the exact model that is chosen to describe the electronic band structure or the phonon dispersion. We finally clarify the diameter dependence of this Raman mode that has been under discussion in the past and demonstrate that, depending on the experimental conditions, in general two different dependencies can be measured. We also prove that CNTs with an arbitrary chiral index can exhibit a D mode in their Raman spectrum, in contrast to previous symmetry-based arguments. Furthermore, we give a direct quantification of the curvature-induced phonon frequency corrections of the D mode in CNTs with respect to graphite.

  8. Surface-enhanced resonance Raman scattering spectroscopy of single R6G molecules

    Institute of Scientific and Technical Information of China (English)

    Zhou Zeng-Hui; Liu Li; Wang Gui-Ying; Xu Zhi-Zhan

    2006-01-01

    Surface-enhanced resonance Raman scattering (SERRS) of Rhodamine 6G (R6G) adsorbed on colloidal silver clusters has been studied. Based on the great enhancement of the Raman signal and the quench of the fluorescence, the SERRS spectra of R6G were recorded for the samples of dye colloidal solution with different concentrations. Spectral inhomogeneity behaviours from single molecules in the dried sample films were observed with complementary evidences, such as spectral polarization, spectral diffusion, intensity fluctuation of vibrational lines and even "breathing" of the molecules. Sequential spectra observed from a liquid sample with an average of 0.3 dye molecules in the probed volume exhibited the expected Poisson distribution for actually measuring 0, 1 or 2 molecules. Difference between the SERRS spectra of R6G excited by linearly and circularly polarized light were experimentally measured.

  9. Experimental and theoretical study of red-shifted solitonic resonant radiation in photonic crystal fibers and generation of radiation seeded Raman solitons

    CERN Document Server

    Bose, Surajit; Chattopadhyay, Rik; Pal, Mrinmay; Bhadra, Shyamal K

    2015-01-01

    The red shifted solitonic resonant radiation is a fascinating phase matching phenomenon that occurs when an optical pulse, launched in the normal dispersion regime of photonic crystal fiber, radiates across the zero dispersion wavelength. The formation of such phase-matched radiation is independent of the generation of any optical soliton and mainly governed by the leading edge of input pump which forms a shock front. The radiation is generated at the anomalous dispersion regime and found to be confined both in time and frequency domain. We experimentally investigate the formation of such radiations in photonic crystal fibers with detailed theoretical analysis. Our theoretical predictions corroborate well with experimental results. Further we extend our study for long length fiber and investigate the interplay between red-shifted solitonic resonant radiation and intrapulse Raman scattering (IPRS). It is observed that series of radiation-seeded Raman solitons are generated in anomalous dispersion regime.

  10. Resonance Raman study on distorted symmetry of porphyrin in nickel octaethyl porphyrin

    Indian Academy of Sciences (India)

    S Tewari; R Das; A Chakraborty; Ramendu Bhattacharjee

    2004-11-01

    The resonance Raman (RR) spectra of nickel octaethyl porphyrin, Ni(OEP), in CH2Cl2 (solvent) at different excitations such as 514.5, 488.0, 441.6 and 406.7 nm are recorded and analysed. The results of the theory of distortion-induced RR intensity is applied to the observed spectra to determine the excited electronic state symmetry of porphyrin in Ni(OEP). It is concluded that the porphyrin molecule (D4h structure) attains a non-polar distorted structure of D2 symmetry rather than S4 symmetry in CH2Cl2 solution.

  11. Measurements of vitamin B12 in human blood serum using resonance Raman spectroscopy

    Science.gov (United States)

    Tsiminis, G.; Schartner, E. P.; Brooks, J. L.; Hutchinson, M. R.

    2016-12-01

    Vitamin B12 (cobalamin and its derivatives) deficiency has been identified as a potential modifiable risk factor for dementia and Alzheimer's disease. Chronic deficiency of vitamin B12 has been significantly associated with an increased risk of cognitive decline. An effective and efficient method for measuring vitamin B12 concentration in human blood would enable ongoing tracking and assessment of this potential modifiable risk factor. In this work we present an optical sensor based on resonance Raman spectroscopy for rapid measurements of vitamin B12 in human blood serum. The measurement takes less than a minute and requires minimum preparation (centrifuging) of the collected blood samples.

  12. Resonance Raman Spectrum of the Transient (SCN)2 Free Radical Anion

    DEFF Research Database (Denmark)

    Wilbrandt, Robert Walter; Jensen, N. H.; Pagsberg, Palle Bjørn

    1979-01-01

    The resonance Raman spectrum of the transient species (λmax = 475 nm, τ½ = 1.6 μs) formed by pulse radiolysis of aqueous solutions of thiocyanate, SCN2−, is reported. The spectrum is discussed in terms of the previous assignment of this transient to the radical anion, (SCN)−2. The observed...... vibrational frequencies of the radical anion are consistent with substantial weakening of the S---S and the Ctriple bond; length as m-dashN bonds are compared with neutral thiocyanogen....

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

    Science.gov (United States)

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

    2013-10-03

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

  14. Spatially resolved confocal resonant Raman microscopic analysis of anode-grown Geobacter sulfurreducens biofilms.

    Science.gov (United States)

    Lebedev, Nikolai; Strycharz-Glaven, Sarah M; Tender, Leonard M

    2014-02-03

    When grown on the surface of an anode electrode, Geobacter sulfurreducens forms a multi-cell thick biofilm in which all cells appear to couple the oxidation of acetate with electron transport to the anode, which serves as the terminal metabolic electron acceptor. Just how electrons are transported through such a biofilm from cells to the underlying anode surface over distances that can exceed 20 microns remains unresolved. Current evidence suggests it may occur by electron hopping through a proposed network of redox cofactors composed of immobile outer membrane and/or extracellular multi-heme c-type cytochromes. In the present work, we perform a spatially resolved confocal resonant Raman (CRR) microscopic analysis to investigate anode-grown Geobacter biofilms. The results confirm the presence of an intra-biofilm redox gradient whereby the probability that a heme is in the reduced state increases with increasing distance from the anode surface. Such a gradient is required to drive electron transport toward the anode surface by electron hopping via cytochromes. The results also indicate that at open circuit, when electrons are expected to accumulate in redox cofactors involved in electron transport due to the inability of the anode to accept electrons, nearly all c-type cytochrome hemes detected in the biofilm are oxidized. The same outcome occurs when a comparable potential to that measured at open circuit (-0.30 V vs. SHE) is applied to the anode, whereas nearly all hemes are reduced when an exceedingly negative potential (-0.50 V vs. SHE) is applied to the anode. These results suggest that nearly all c-type cytochrome hemes detected in the biofilm can be electrochemically accessed by the electrode, but most have oxidation potentials too negative to transport electrons originating from acetate metabolism. The results also reveal a lateral heterogeneity (x-y dimensions) in the type of c-type cytochromes within the biofilm that may affect electron transport to the

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

    Science.gov (United States)

    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.

  16. Molecular-level investigation on electrochemical interfaces by Raman spectroscopy

    Institute of Scientific and Technical Information of China (English)

    TIAN, Zhong-Qun; REN, Bin

    2000-01-01

    The structure and dynamics of electrode/liquid interfaces play an increasingly important role in electrochemistry. Raman spectroscopy is capable of providing detailed structural information at molecular level and new insight into the interfacial structure, adsorption, reaction, electrocatalysis and corrosion. In this account we will summarize some progresses of surface Raman spectroscopy in the study of electrochemical interfaces, mainly based on our group's work, laying emphasis on the detection sensitivity, spectral resolution, time resolution and spatial resolution as well as the hyphenated technique.

  17. Raman spectroscopic investigation of thorium dioxide-uranium dioxide (ThO₂-UO₂) fuel materials.

    Science.gov (United States)

    Rao, Rekha; Bhagat, R K; Salke, Nilesh P; Kumar, Arun

    2014-01-01

    Raman spectroscopic investigations were carried out on proposed nuclear fuel thorium dioxide-uranium dioxide (ThO2-UO2) solid solutions and simulated fuels based on ThO2-UO2. Raman spectra of ThO2-UO2 solid solutions exhibited two-mode behavior in the entire composition range. Variations in mode frequencies and relative intensities of Raman modes enabled estimation of composition, defects, and oxygen stoichiometry in these compounds that are essential for their application. The present study shows that Raman spectroscopy is a simple, promising analytical tool for nondestructive characterization of this important class of nuclear fuel materials.

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

    Science.gov (United States)

    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(1)*; S1 state) and the shorter (1π-π(1)*; S2 state) wavelength band undergoes a hypsochromic and bathochromic shift due to intermolecular hydrogen bond weakening and strengthening, respectively. It also indicates that hydrogen bonding plays a major role in the differential solvation of the S2 state relative to the ground state. Raman excitation profiles of PQ (400-1800 cm(-1)) in various solvents followed their corresponding absorption spectra therefore the enhancements on resonant excitation are from single-state rather than mixed states. The hyperchromism of the longer wavelength band is attributed to intensity borrowing from the nearby allowed electronic transition through vibronic coupling. Computational calculation with C2ν symmetry constraint on the S2 state resulted in an imaginary frequency along the low-frequency out-of-plane torsional modes involving the C=O site and therefore, we hypothesize that this mode could be involved in the vibronic coupling.

  19. Resonance Raman study on indoleamine 2,3-dioxygenase: Control of reactivity by substrate-binding

    Energy Technology Data Exchange (ETDEWEB)

    Yanagisawa, Sachiko; Hara, Masayuki [Graduate School of Life Science and Picobiology Institute, University of Hyogo, Koto 3-2-1, Kamigori-cho, Ako-gun, Hyogo 678-1297 (Japan); Sugimoto, Hiroshi; Shiro, Yoshitsugu [Biometal Science Laboratory, RIKEN SPring-8 Center, Harima Institute, Koto 1-1-1, Sayo-cho, Sayo-gun, Hyogo 679-5198 (Japan); Ogura, Takashi, E-mail: ogura@sci.u-hyogo.ac.jp [Graduate School of Life Science and Picobiology Institute, University of Hyogo, Koto 3-2-1, Kamigori-cho, Ako-gun, Hyogo 678-1297 (Japan)

    2013-06-20

    Highlights: • Indoleamine 2,3-dioygenase has been studied by resonance Raman spectroscopy. • Trp-binding to the enzyme induces high frequency shift of the Fe–His stretching mode. • Increased imidazolate character of histidine promotes the O–O bond cleavage step. • A fine-tuning of the reactivity of the O–O bond cleavage reaction is identified. • The results are consistent with the sequential oxygen-atom-transfer mechanism. - Abstract: Resonance Raman spectra of ligand-bound complexes including the 4-phenylimidazole complex and of free and L-Trp-bound forms of indoleamine 2, 3-dioxygenase in the ferric state were examined. Effects on the vinyl and propionate substituent groups of the heme were detected in a ligand-dependent fashion. The effects of phenyl group of 4-phenylimidazole on the vinyl and propionate Raman bands were evident when compared with the case of imidazole ligand. Substrate binding to the ferrous protein caused an upshift of the iron–histidine stretching mode by 3 cm{sup −1}, indicating an increase in negativity of the imidazole ring, which favors the O–O bond cleavage. The substrate binding event is likely to be communicated from the heme distal side to the iron–histidine bond through heme substituent groups and the hydrogen-bond network which includes water molecules, as identified in an X-ray structure of a 4-phenylimidazole complex. The results provide evidence for fine-tuning of the reactivity of O–O bond cleavage by the oxygenated heme upon binding of L-Trp.

  20. 1064nm FT-Raman spectroscopy for investigations of plant cell walls and other biomass materials

    Science.gov (United States)

    Umesh P. Agarwal

    2014-01-01

    Raman spectroscopy with its various special techniques and methods has been applied to study plant biomass for about 30 years. Such investigations have been performed at both macro- and micro-levels. However, with the availability of the Near Infrared (NIR) (1064 nm) Fourier Transform (FT)-Raman instruments where, in most materials, successful fluorescence suppression...

  1. Dynamics of Rhodobacter capsulatus [2Fe-2S] Ferredoxin VI and Aquifex aeolicus Ferredoxin 5 Via Nuclear Resonance Vibrational Spectroscopy (NRVS) and Resonance Raman Spectroscopy.

    Energy Technology Data Exchange (ETDEWEB)

    Xiao, Yuming; Tan, Ming-Liang; Ichiye, Toshiko; Wang, Hongxin; Guo, Yisong; Smith, Matt C.; Meyer, Jacques; Sturhahn, Wolfgang; Alp, E. E.; Zhao, Jiyong; Yoda, Yoshitaka; Cramer, Stephen P.

    2008-06-24

    We have used (57)Fe nuclear resonance vibrational spectroscopy (NRVS) to study the Fe(2)S(2)(Cys)(4) sites in oxidized and reduced [2Fe-2S] ferredoxins from Rhodobacter capsulatus (Rc FdVI) and Aquifex aeolicus (Aa Fd5). In the oxidized forms, nearly identical NRVS patterns are observed, with strong bands from Fe-S stretching modes peaking around 335 cm(-1), and additional features observed as high as the B(2u) mode at approximately 421 cm(-1). Both forms of Rc FdVI have also been investigated by resonance Raman (RR) spectroscopy. There is good correspondence between NRVS and Raman frequencies, but because of different selection rules, intensities vary dramatically between the two kinds of spectra. For example, the B(3u) mode at approximately 288 cm(-1), attributed to an asymmetric combination of the two FeS(4) breathing modes, is often the strongest resonance Raman feature. In contrast, it is nearly invisible in the NRVS, as there is almost no Fe motion in such FeS(4) breathing. NRVS and RR analysis of isotope shifts with (36)S-substituted into bridging S(2-) ions in Rc FdVI allowed quantitation of S(2-) motion in different normal modes. We observed the symmetric Fe-Fe stretching mode at approximately 190 cm(-1) in both NRVS and RR spectra. At still lower energies, the NRVS presents a complex envelope of bending, torsion, and protein modes, with a maximum at 78 cm(-1). The (57)Fe partial vibrational densities of states (PVDOS) were interpreted by normal-mode analysis with optimization of Urey-Bradley force fields. Progressively more complex D(2h) Fe(2)S(2)S'(4), C(2h) Fe(2)S(2)(SCC)(4), and C(1) Fe(2)S(2)(Cys)(4) models were optimized by comparison with the experimental spectra. After modification of the CHARMM22 all-atom force field by the addition of refined Fe-S force constants, a simulation employing the complete protein structure was used to reproduce the PVDOS, with better results in the low frequency protein mode region. This process was then repeated

  2. UV-vis and Raman spectroelectrochemical investigation of the redox behavior of poly(5-cyanoindole) in acidic aqueous solutions

    Science.gov (United States)

    Talbi, H.; Billaud, D.; Louarn, G.; Pron, A.

    2000-03-01

    Spectroelectrochemical properties of conducting poly(5-cyanoindole) films deposited on indium tin oxide (ITO) and platinum electrodes are investigated using UV-vis and resonant Raman spectroscopies. The transitions from undoped to semi-conducting state of P5CN require the partial oxidation of the polymer to create radical-cations by insertion of charge-neutralizing anions into the polymer. In order to obtain detailed structural information from the vibrational spectra, it is necessary to know the vibrational modes of oxidation-sensitive bands. Vibrational assignments were made on the basis of the results obtained on polyindole and P5CN in acetonitrile solution. The drastic changes in optical absorption and Raman spectra observed at various stage of oxidation were explained by the conversions between at least three different structures. On the basis of the Raman spectra, we have identified the vibrational modes associated with neutral and polaronic segments. The perturbation associated with the coexistence of these polaronic segments has been described as a quinoid structure growing on the expense of the benzoid one. The results obtained indicate that the molecular properties of the conducting polymers at various stages of an oxidation are better revealed by in-situ Raman spectra than by ex-situ studies.

  3. Vibrational techniques applied to photosynthesis: Resonance Raman and fluorescence line-narrowing.

    Science.gov (United States)

    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.

  4. In situ monitoring of polymer redox states by resonance µRaman spectroscopy and its applications in polymer modified microfluidic channels

    NARCIS (Netherlands)

    Logtenberg, Hella; Jellema, Laurens-Jan C.; Lopez-Martinez, Maria J.; Areephong, Jetsuda; Verpoorte, Elisabeth; Feringa, Ben L.; Browne, Wesley R.

    2012-01-01

    We report the application of multi-wavelength resonance Raman (rR) spectroscopy for the characterisation of vinyl-bridged polysexithiophene films formed by electropolymerisation on gold electrodes. Resonance Raman spectroscopy of the neutral, polaronic and bipolaronic states of the polymer were dete

  5. A study on the Fermi resonance of phenol under the effects of pressure and temperature by Raman spectroscopy.

    Science.gov (United States)

    Li, DongFei; Hua, Zhong; Liu, ChengZhi; Fan, Cunbo; Sun, ChengLin; Li, ZuoWei; Chen, WanJin

    2015-02-05

    The ν1-ν18a Fermi resonance (FR) of phenol were investigated by pressure-dependent Raman spectroscopy from atmospheric up to P=15.2GPa and temperature-dependent Raman spectroscopy from 40 down to T=-180°C, respectively. In the case of pressure, we found the Fermi coupling coefficient W, which were calculated based on the FR theory, exposed a value turnover between 1.912 and 2.244GPa in the process of increasing the pressure. This turnover phenomenon of the Fermi coupling coefficient W has been ascribed to the crystal structure of phenol evolving towards a more symmetric structure with pressure, from a structure like a pseudo-threefold helical chain at ambient pressure to like a ribbon arrangement at 1.912GPa, then to adopt a herringbone arrangement at much higher pressure. On the other hand, we also found the Fermi coupling coefficient W exhibited monotonic reduction without turnover points appearing by decreasing the temperature. The tendencies of the Fermi coupling coefficient W with temperature were in good agreement with the pressure dependence of the Fermi coupling coefficient W in the region of ambient to 1.912GPa, indicating that the effect of pressure and temperature on the FR of phenol in this region might be the same. A conformation evolving induced by pressure and temperature on the ν1 and ν18a FR of phenol have been analyzed.

  6. Arsenic speciation by X-ray spectroscopy using resonant Raman Scattering

    Energy Technology Data Exchange (ETDEWEB)

    Sanchez, H.J.; Leani, J.J. [Universidad Nacional de Cordoba, Cba (Argentina); Perez, C.A. [Laboratorio Nacional de Luz Sincrotron (LNLS), Campinas, SP (Brazil)

    2012-07-01

    Full text: The toxicity of arsenic species is widely known. A realistic evaluation of the risk posed by As depends on accurate determination of As speciation, because its toxicity and mobility varies with oxidation state and chemical environment. The most toxic species are inorganic As (III) and As (V) called respectively arsenite or trivalent arsenic, and arsenate or pentavalent arsenic. Recently, x-ray Resonant Raman Scattering spectroscopy has been successfully employed to determine the oxidation state of metals. In this work we use RRS spectroscopy to perform arsenic speciation. The measurements were carried out in XRF station of the D09B-XRF beamline at the Brazilian synchrotron facility (LNLS, Campinas). Mineral samples of As in different oxidation states (As(III) and AS(V)), and two biological forms of arsenic (monomethylarsonic acid (MMA(V) and dimethylarsinic acid DMA(V)) were analysed. The samples were diluted, deposited on silicon wafers and allowed to dry. The amount of liquid deposited on the reflector before evaporation was 20 microliters for all the specimens. These samples were irradiated with monochromatic photons of 11816 eV, i.e., below the K-edge of arsenic in order to inspect the Raman emissions. The measuring lifetime was 3600 sec for each sample. Spectra were analysed with specific programs for spectrum analysis using non-conventional functions for data fitting, i.e., modified Voight functions (for Compton peaks), Gaussian functions for fluorescent and for low intensity peaks (such as escape peaks and other contributions), and polynomial functions for the background. Raman peaks were fitted using specific functions. In this work we have shown that resonant Raman scattering spectroscopy can be used to analyse arsenic species. The method is very simple and reliable. The most important feature of this method relies in the possibility of using the same spectrometer of XRF analysis or TXRF analysis. In this way, practically in the same experiment

  7. Tip-enhanced Raman spectroscopy with silver-coated optical fiber probe in reflection mode for investigating multiwall carbon nanotubes.

    Science.gov (United States)

    Wang, Rui; Wang, Jia; Hao, Fenghuan; Zhang, Mingqian; Tian, Qian

    2010-04-01

    We developed a tip-enhanced Raman spectrometer (TERS) with reflection mode. The instrument, with a scanning shear-force microscope (ShFM) and a side-illumination Raman spectroscope, can overcome the diffraction limit and has high sensitivity. A chemical method to fabricate optical fiber probes with Ag coating is proposed. The local electromagnetic responses of the silver-coated optical fiber probe are numerically analyzed by the finite-difference time-domain method, and the excitation wavelength is optimized to resonate with the localized surface plasmons (LSP) of the probe tip. The instrument is applied to investigate a single multiwall carbon nanotube. The experiment results indicate that our TERS instrument has a spatial resolution better than 70 nm, and the enhancement factor is about 5 x 10(3).

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

    Science.gov (United States)

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

    2012-08-02

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

  9. In Vitro Polarized Resonance Raman Study of N719 and N719-TBP in Dye Sensitized Solar Cells

    DEFF Research Database (Denmark)

    Hassig, Søren; Jernshøj, Kit; Phuong, Nguyen Tuyet;

    2016-01-01

    The working efficiency of dye-sensitized solar cells (DSCs) depends on the long-term stability of the dye itself and on the microscopic structure of the dye-semiconductor interface. Previous experimental studies of DSCs based on ruthenium dye with bipyridine ligands (N719) adsorbed to the TiO2......substrate applied FTIR,un-polarized Raman (RS) and un-polarized resonance Raman (RRS) spectroscopy. In the un-polarized RRS studies of N719/TiO2 – DSCs the discussion of the adsorption of N719 was based on the rather weak carbonyl or carboxyl group stretching vibrations and on minor spectral changes...... of overlapping Raman modes, whereas conclusions about the dye-stability was based on the observation that fresh and aged DSCs had almost identical RRS spectra. In the present paper we address the problems mentioned above, by utilizing the unique property of Raman scattering that the polarization of the scattered...

  10. Stimulated Raman spectroscopy and nanoscopy of molecules using near field photon induced forces without resonant electronic enhancement gain

    Science.gov (United States)

    Tamma, Venkata Ananth; Huang, Fei; Nowak, Derek; Kumar Wickramasinghe, H.

    2016-06-01

    We report on stimulated Raman spectroscopy and nanoscopy of molecules, excited without resonant electronic enhancement gain, and recorded using near field photon induced forces. Photon-induced interaction forces between the sharp metal coated silicon tip of an Atomic Force Microscope (AFM) and a sample resulting from stimulated Raman excitation were detected. We controlled the tip to sample spacing using the higher order flexural eigenmodes of the AFM cantilever, enabling the tip to come very close to the sample. As a result, the detection sensitivity was increased compared with previous work on Raman force microscopy. Raman vibrational spectra of azobenzene thiol and l-phenylalanine were measured and found to agree well with published results. Near-field force detection eliminates the need for far-field optical spectrometer detection. Recorded images show spatial resolution far below the optical diffraction limit. Further optimization and use of ultrafast pulsed lasers could push the detection sensitivity towards the single molecule limit.

  11. Gold split-ring resonators (SRRs) as substrates for surface-enhanced raman scattering

    KAUST Repository

    Yue, Weisheng

    2013-10-24

    We used gold split ring resonators (SRRs) as substrates for surface-enhanced Raman scattering (SERS). The arrays of SRRs were fabricated by electron-beam lithography in combination with plasma etching. In the detection of rhodamine 6G (R6G) molecules, SERS enhancement factors of the order of 105 was achieved. This SERS enhancement increased as the size of the split gap decrease as a consequence of the matching between the resonance wavelength of the SRRs and the excitation wavelength of SERS. As the size of the split gap decreased, the localized surface plasmon resonance shifted to near the excitation wavelength and, thus, resulted in the increase in the electric field on the nanostructures. We used finite integration method (FIT) to simulate numerically the electromagnetic properties of the SRRs. The results of the simulation agreed well with our experimental observations. We anticipate this work will provide an approach to manipulate the SERS enhancement by modulating the size of split gap with SRRs without affecting the area and structural arrangement. © 2013 American Chemical Society.

  12. A time-resolved resonance Raman study of chlorine dioxide photochemistry in water and acetonitrile

    Energy Technology Data Exchange (ETDEWEB)

    Hayes, S.C.; Philpott, M.P.; Mayer, S.G.; Reid, P.J. [Univ. of Washington, Seattle, WA (United States). Dept. of Chemistry

    1999-07-15

    The photochemistry of chlorine dioxide (OClO) has attracted much interest due to its participation in the atmospheric chlorine reservoir as well as its potential role in stratospheric ozone depletion. Since the environmental impact of OClO arises from its ability to produce atomic chlorine, understanding this phase-dependent reactivity is essential if models capable of predicting the environmental impact of OClO in both homogeneous and heterogeneous settings are to be obtained. The photochemistry of chlorine dioxide (OClO) in water and acetonitrile is investigated using time-resolved resonance Raman spectroscopy. Stokes and anti-Stokes spectra are measured as a function of time following photoexcitation using degenerate pump and probe wavelengths of 390 nm. For aqueous OClO, the time-dependent Stokes intensities are found to be consistent with the re-formation of ground-state OClO by subpicosecond geminate recombination of the primary ClO and O photofragments. This represents the first unequivocal demonstration of primary-photoproduct geminate recombination in the condensed-phase photochemistry of OClO. Anti-Stokes intensity corresponding to the OClO symmetric stretch is observed demonstrating that, following geminate recombination, excess vibrational energy is deposited along this coordinate. Analysis of the anti-Stokes decay kinetics demonstrates that, in water, intermolecular vibrational relaxation occurs with a time constant of {approximately}9 ps. For OClO dissolved in acetonitrile, the Stokes scattering intensities are consistent with a significant reduction in the geminate-recombination quantum yield relative to water. Comparison of the OClO anti-Stokes decay kinetics in acetonitrile and water demonstrates that the rate of intermolecular vibrational relaxation is {approximately}4 times smaller in acetonitrile. Finally, in both solvents the appearance of symmetric-stretch anti-Stokes intensity is significantly delayed relative to geminate recombination. This

  13. Identification of metalloporphyrins with high sensitivity using graphene-enhanced resonance Raman scattering.

    Science.gov (United States)

    Kim, Bo-Hyun; Kim, Daechul; Song, Sungho; Park, DongHyuk; Kang, Il-Suk; Jeong, Dae Hong; Jeon, Seokwoo

    2014-03-18

    Graphene-enhanced resonance Raman scattering (GERRS) was performed for the detection of three different metallo-octaethylporphyrins (M-OEPs; M = 2H, FeCl, and Pt) homogeneously thermal vapor deposited on a graphene surface. GERRS of M-OEPs were measured using three different excitation wavelengths, λ(ex) = 405, 532, and 633 nm, and characterized detail vibrational bands for the identification of M-OEPs. The GERRS spectra of Pt-OEP at λ(ex) = 532 nm showed ~29 and ~162 times signal enhancement ratio on graphene and on graphene with Ag nanoclusters, respectively, compared to the spectra from bare SiO2 substrate. This enhancement ratio, however, was varied with M-OEPs and excitation wavelengths. The characteristic peaks and band shapes of GERRS for each M-OEP were measured with high sensitivity (100 pmol of thermal vapor deposited Pt-OEP), and these facilitate the selectively recognition of molecules. Also, the peaks shift and broadening provide the evidence of the interaction between graphene and M-OEPs through the charge transfer and π-orbital interaction. The increase of graphene layer induced the decrease of signal intensity and GERRS effect was almost not observed on the thick graphite flakes. Further experiments with various substrates demonstrated that the interaction of single layer of graphene with molecule is the origin of the Raman signal enhancement of M-OEPs. In this experiment, we proved the graphene is a good alternative substrate of Raman spectroscopy for the selective detection of various metalloporphyrins with high sensitivity.

  14. Experimental Raman and infrared investigation of phenobarbital febarabamate, difebarbamate and tetrabamate

    Science.gov (United States)

    Buchet, R.; Bill, H.; Siegfried, B.

    The results of a Raman and an i.r. investigation show that the tetrabamate molecule is formed by the hydrogen bonded constituants phenobarbital, febarbamate. Detailed spectroscopic results are given on these four molecules.

  15. Status of miniature integrated UV resonance fluorescence and Raman sensors for detection and identification of biochemical warfare agents

    Science.gov (United States)

    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.

  16. [Raman spectroscopic investigation of hydrogen storage in nitrogen gas hydrates].

    Science.gov (United States)

    Meng, Qing-guo; Liu, Chang-ling; Ye, Yu-guang; Li, Cheng-feng

    2012-08-01

    Recently, hydrogen storage using clathrate hydrate as a medium has become a hotspot of hydrogen storage research In the present paper, the laser Raman spectroscopy was used to study the hydrogen storage in nitrogen hydrate. The synthetic nitrogen hydrate was reacted with hydrogen gas under relatively mild conditions (e.g., 15 MPa, -18 degrees C). The Raman spectra of the reaction products show that the hydrogen molecules have enclathrated the cavities of the nitrogen hydrate, with multiple hydrogen cage occupancies in the clathrate cavities. The reaction time is an important factor affecting the hydrogen storage in nitrogen hydrate. The experimental results suggest that nitrogen hydrates are expected to be an effective media for hydrogen storage.

  17. Raman Mapping for the Investigation of Nano-phased Materials

    Science.gov (United States)

    Gouadec, G.; Bellot-Gurlet, L.; Baron, D.; Colomban, Ph.

    Nanosized and nanophased materials exhibit special properties. First they offer a good compromise between the high density of chemical bonds by unit volume, needed for good mechanical properties and the homogeneity of amorphous materials that prevents crack initiation. Second, interfaces are in very high concentration and they have a strong influence on many electrical and redox properties. The analysis of nanophased, low crystallinity materials is not straigtforward. The recording of Raman spectra with a geometric resolution close to 0.5 \\upmu {text{ m}^3} and the deep understanding of the Raman signature allow to locate the different nanophases and to predict the properties of the material. Case studies are discussed: advanced polymer fibres, ceramic fibres and composites, textured piezoelectric ceramics and corroded (ancient) steel.

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

    Energy Technology Data Exchange (ETDEWEB)

    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. Low skin carotenoid concentration measured by resonance Raman spectroscopy is associated with metabolic syndrome in adults.

    Science.gov (United States)

    Holt, Edward W; Wei, Esther K; Bennett, Nancy; Zhang, Laura M

    2014-10-01

    Oxidative stress is increased in patients with metabolic syndrome (MS). Antioxidants, including carotenoids, are decreased in MS. We hypothesized that a low skin carotenoid score (SCS), calculated using resonance Raman spectroscopy, would correlate with the presence of MS. We retrospectively reviewed consecutive patients referred for dietary assessment between 2010 and 2012. For each patient, a nutrition history, medical history, and SCS were recorded. χ(2) and Student t test were used to determine factors associated with MS. Multivariate logistic regression was used to identify factors associated with MS. One hundred fifty-five patients were included. The mean age was 54.1 ± 13.1 years, and the mean body mass index was 28.3 ± 6.1 kg/m(2). Metabolic syndrome was present in 43.9% of patients. The mean SCS was 28 084 ± 14 006 Raman counts (RC), including 23 058 ± 9812 RC for patients with MS and 32 011 ± 15 514 RC for patients without MS (P = .0001). In a multivariate analysis, SCS less than 25 000 RC (odds ratio, 3.71; 95% confidence interval, 1.36-10.7; P = .01) was independently associated with MS. A higher number of MS components was associated with a progressively lower SCS (P = .004). In a consecutive sample of patients referred for dietary assessment, a noninvasively measured SCS was lower among patients with MS.

  20. a Study of the Hydroxycyclohexadienyl Radical Absorption Using Time-Resolved Resonance Raman Spectroscopy

    Science.gov (United States)

    O'Donnell, Deanna M.; Tripathi, G. N. R.; Brinkmann, Nicole R.

    2009-06-01

    Thus far there has been little understanding of the vibrational spectra, structure and electronic absorption of hydroxycyclohexadienyl radicals in water. They are primary chemical species formed on interaction of radiation with aqueous solutions containing aromatic molecules. We have applied time- resolved resonance Raman (TR-RR) spectroscopy to structurally identify isomers of cyclohexadienyl radicals formed in the pulse radiolysis, using aqueous benzoate solutions as a model system. An early ESR study ((Eiben, K; Fessenden, R.W.; J. Phys. Chem. 1971, 75, 1186-1201) has shown that a mixture of three benzoate hydroxycyclohexadienyl radical isomers: ortho-, meta- and para- are formed upon electron irradiation of N_{2}O saturated benzoate solution. Their collective transient absorption is believed to exhibit a single broad band in the near UV region (λ_{max} = 330 nm, ɛ_{330} = 3800 M^{-1}cm^{-1}). To extract the single isomeric contribution to this collective absorption, we applied TR-RR at various wavelengths within the broad transient absorption range looking for the characteristic indication of each individual isomer. Raman signals of various para-substituted benzoates were also collected to aid in the vibrational studies of the aforementioned benzoate hydroxycyclohexadienyl radicals.

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

    Science.gov (United States)

    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…

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

    Science.gov (United States)

    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…

  3. In situ resonant Raman scattering and reversible photoinduced structural change in YBa2Cu3O6+x

    DEFF Research Database (Denmark)

    Osada, M.; Käll, M.; Bäckström, J.;

    2005-01-01

    or absence of a specific Raman scattering resonance. A comparison of the spectral efficiencies for this photoswitching with analogous data for the persistent photoconductivity and photoconductivity quenching effects suggests that the two phenomena have the same microscopic origin. We argue that the effects...

  4. Potential energy surfaces of short polyenes in the state T1 : analysis of time resolved resonance Raman spectra

    NARCIS (Netherlands)

    Orlandi, G.; Negri, F.; Wilbrandt, R.; Langkilde, F.W.; Brouwer, A.M.

    1993-01-01

    The analysis of T1 resonance Raman spectra of some conjugated compounds is discussed making use of semiempirical quantum chemical calculations. Information obtained about T1 potential energy curve indicates that in short polyenes the perpendicular form is roughly degenerate with the trans isomer. Pr

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

    Directory of Open Access Journals (Sweden)

    M. Durga Prasad

    2002-05-01

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

  6. Freely designable optical frequency conversion in Raman-resonant four-wave-mixing process

    Science.gov (United States)

    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

  7. Operational electrochemical stability of thiophene-thiazole copolymers probed by resonant Raman spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Wade, Jessica; Wood, Sebastian; Kim, Ji-Seon, E-mail: ji-seon.kim@imperial.ac.uk [Department of Physics and Centre for Plastic Electronics, Imperial College London, London SW7 2AZ (United Kingdom); Beatrup, Daniel; Hurhangee, Michael; McCulloch, Iain; Durrant, James R. [Department of Chemistry and Centre for Plastic Electronics, Imperial College London, London SW7 2AY (United Kingdom); Bronstein, Hugo [Department of Chemistry and Centre for Plastic Electronics, Imperial College London, London SW7 2AY (United Kingdom); Department of Chemistry, University College London, London WC1H 0AJ (United Kingdom)

    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.

  8. Theoretical and experimental investigation of microstrip rhombic resonators

    Science.gov (United States)

    Al-Charchafchi, S. H.; Boulkos, J.

    1990-06-01

    The resonant behavior of a novel microstrip rhombic resonator is investigated by analyzing an equivalent circuit based on transmission line modeling. Design curves showing the dependence of resonator performance on its parameters, as well as the substrate parameters, are presented. Experiments carried out showed a significant reduction in insertion loss when the rhombic resonator is dielectrically shielded. The resonator could be used as a microwave bandpass filter or a stabilization circuit for microwave oscillators in both hybrid and monolithic integrated circuits.

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

    Science.gov (United States)

    Oshokoya, Olayinka O; JiJi, Renee D

    2015-09-10

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

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

    Energy Technology Data Exchange (ETDEWEB)

    Ravi Kumar, Venkatraman; Rajkumar, Nagappan; Umapathy, Siva, E-mail: umapathy@ipc.iisc.ernet.in

    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.

  11. (17)O NMR and Raman Spectroscopies of Green Tea Infusion with Nanomaterial to Investigate Their Properties.

    Science.gov (United States)

    Zhou, Changyan; Zhang, Huiping; Yan, Ying; Zhang, Xinya

    2016-09-01

    (17)O NMR and Raman spectrograms of green tea infusions with nanomaterial were investigated. Different green tea infusions were prepared by steeping tea powder with different concentrations of nanomaterial aqueous solution. The tea infusions were tested with (17)O NMR and Raman spectroscopies. The (17)O NMR results showed that line width increased to 90 in the tea infusions after nanomaterial was added as a result of the effects of the self-association of Ca(2+) and tea polyphenol. The results of Raman spectroscopy showed that, in tea infusions, the enhancement of C─C and C─O stretching vibrations suggest an increase in the number of effective components in water.

  12. Investigation of drug distribution in tablets using surface enhanced Raman chemical imaging.

    Science.gov (United States)

    Firkala, Tamás; Farkas, Attila; Vajna, Balázs; Farkas, István; Marosi, György

    2013-03-25

    This paper reports the first application of surface enhanced Raman chemical imaging on pharmaceutical tablets containing the active ingredient (API) in very low concentrations. Taking advantage of the extremely intensive Raman signals in the presence of silver colloids, image aquisition time was radically decreased. Moreover, the investigation of drug distribution below the detection limit of regular micro-Raman spectrometry was made feasible. The characteristics of different manufacturing technologies could be revealed at very low API concentrations by using chemometric methods for processing and evaluating the large number of varying spectra provided with this imaging method.

  13. Interactions of water-soluble porphyrins with hexadeoxyribonucleotides: resonance raman, UV-visible and 1H NMR studies.

    Science.gov (United States)

    Bütje, K; Schneider, J H; Kim, J J; Wang, Y; Ikuta, S; Nakamoto, K

    1989-10-01

    The interactions of the water-soluble porphyrins M(TMpy-P4) [M = H2, Cu(II), Ni(II), and Co(III); TMpy-P4 = tetrakis(4-N-methylpyridyl)porphyrinato ion], with the hexadeoxyribonucleotides d(CGTACG)2, d(TACGTA)2, d(GCATGC)2, d(TGTGCA)2, and d(CTATAG)2 have been investigated by resonance Raman and/or UV-visible spectroscopy. The results indicate that all hexamers containing the 5'CG3' as well as the 5'GC3' site, and also the mismatched hexamer d(TGTGCA)2, are capable of intercalating the H2, Cu(II) and Ni(II) porphyrins. 1H nuclear magnetic resonance spectra of d(CGTACG)2 mixed with Cu(TMpy-P4) have provided further evidence for the intercalation. For the other cases, outside binding by localized electrostatic interaction is suggested. There is no evidence of groove binding to any of the hexamers. Possible reasons for different binding properties of long and short helices are discussed.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2009-01-01

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

  15. Structural characterization of titania by X-ray diffraction, photoacoustic, Raman spectroscopy and electron paramagnetic resonance spectroscopy.

    Science.gov (United States)

    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.

  16. Raman microspectroscopy investigation of Ag ion-exchanged glass layers.

    Science.gov (United States)

    Rahman, A; Giarola, M; Cattaruzza, E; Gonella, F; Mardegan, M; Trave, E; Quaranta, A; Mariotto, G

    2012-11-01

    The ion-exchange process is widely used to dope silicate glass layers with silver, aimed at controlling the Ag state in view of possible applications, ranging from light waveguide fabrication to nanostructured composite glass synthesis. The silver doped glass structure as well as its prescribed properties depend on both the preparation parameters and the subsequent treatments. Several structural aspects are still open with regard either to the modification of the glass incorporating the dopant, or to clustering phenomena silver undergoes as a function of its local concentration and state, which are in turn strongly dependent on the preparation route. Systematic characterizations of these systems are mandatory to address the role of the various synthesis parameters in giving rise to the observed features, thus pointing out the effective methodologies for the fabrication of silicate glass layers with the desired properties. In this work, the results of micro-Raman, optical absorption and photoluminescence characterizations are presented for soda-lime glass slides doped with silver by Ag(+)-Na+ exchange and subsequent thermal treatments in air. In particular, a cross-section profiling analysis by Raman micro-spectroscopy was performed on Ag ion-exchanged samples after treatment at some different temperatures. The experimental findings allow to elucidate the role of the treatment temperature in the clustering process related to the local Ag concentration inside the exchanged glass layer.

  17. Investigation of Surface-Enhanced Raman Spectra of Human Gallstones on Colloidal Silver

    Institute of Scientific and Technical Information of China (English)

    2000-01-01

    The surface-enhanced Raman scatterihg (SERS) spectra of human gallstones is investigated. Complicated Raman bands were due to multiple components that include bilirubin, bilirubinate salts, cholesterol, fatty salts and proteins. The results suggest that besides bilirubin and cholesterol, fatty salts and proteins may play an important role in the formation of gallstone. The experimental data supply an useful information for the research of the formation mechanism of gallstones.

  18. Raman investigation of ro-vibrational modes of interstitial H2 in Si

    Science.gov (United States)

    Koch, S. G.; Lavrov, E. V.; Weber, J.

    2012-08-01

    A Raman scattering study of ro-vibrational transitions Q(J) of the interstitial H2 in Si is presented. It is shown that the Q(2) mode of para hydrogen is coupled to the TAX phonon of Si. The mode appears in the spectra at temperatures above 200 K. The results presented also suggest that the Q(3) transition of ortho hydrogen is resonantly coupled to the OΓ phonon.

  19. Raman investigation of ro-vibrational modes of interstitial H{sub 2} in Si

    Energy Technology Data Exchange (ETDEWEB)

    Koch, S.G., E-mail: sandro.koch@physik.tu-dresden.de [Technische Universitaet Dresden, 01062 Dresden (Germany); Lavrov, E.V.; Weber, J. [Technische Universitaet Dresden, 01062 Dresden (Germany)

    2012-08-01

    A Raman scattering study of ro-vibrational transitions Q(J) of the interstitial H{sub 2} in Si is presented. It is shown that the Q(2) mode of para hydrogen is coupled to the TA{sub X} phonon of Si. The mode appears in the spectra at temperatures above 200 K. The results presented also suggest that the Q(3) transition of ortho hydrogen is resonantly coupled to the O{sub {Gamma}} phonon.

  20. Investigation of skin cancer treatment efficiency by raman spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Lee, M. S.; Kim, D. W. [Kyungpook National University, Taegu (Korea)

    2000-04-01

    From the successful perform of the molecular structures of various kinds of human skin cancer. We can predict the types of cancer when a small abnormal change change occurs on skin by raman spectrum. When we applied the cancer causing chemicals, bezopyrene, to nude mouse, it did not develop to cancer. But we had radiated UV light after developed to skin cancer in a few days. We can deduce the development of human skin cancer from the result of nude mouse skin cancer, because the two skin are structurally very similar to each other. From the results of own research we could conform the UV light is essential for the development of skin cancer. The results of own research can be directly apply to early detection and proper treatment of skin cancer in hospital. 32 refs., 40 figs., 16 tabs. (Author)

  1. Resonance Raman spectroscopic measurements delineate the structural changes that occur during tau fibril formation.

    Science.gov (United States)

    Ramachandran, Gayathri; Milán-Garcés, Erix A; Udgaonkar, Jayant B; Puranik, Mrinalini

    2014-10-21

    The aggregation of the microtubule-associated protein, tau, into amyloid fibrils is a hallmark of neurodegenerative diseases such as the tauopathies and Alzheimer's disease. Since monomeric tau is an intrinsically disordered protein and the polymeric fibrils possess an ordered cross-β core, the aggregation process is known to involve substantial conformational conversion besides growth. The aggregation mechanism of tau in the presence of inducers such as heparin, deciphered using probes such as thioflavin T/S fluorescence, light scattering, and electron microscopy assays, has been shown to conform to ligand-induced nucleation-dependent polymerization. These probes do not, however, distinguish between the processes of conformational conversion and fibril growth. In this study, UV resonance Raman spectroscopy is employed to look directly at signatures of changes in secondary structure and side-chain packing during fibril formation by the four repeat functional domain of tau in the presence of the inducer heparin, at pH 7 and at 37 °C. Changes in the positions and intensities of the amide Raman bands are shown to occur in two distinct stages during the fibril formation process. The first stage of UVRR spectral changes corresponds to the transformation of monomer into early fibrillar aggregates. The second stage corresponds to the transformation of these early fibrillar aggregates into the final, ordered, mature fibrils and during this stage; the processes of conformational conversion and the consolidation of the fibril core occur simultaneously. Delineation of these secondary structural changes accompanying the formation of tau fibrils holds significance for the understanding of generic and tau-specific principles of amyloid assembly.

  2. Probing the photoreaction mechanism of phytochrome through analysis of resonance Raman vibrational spectra of recombinant analogues.

    Science.gov (United States)

    Andel, F; Murphy, J T; Haas, J A; McDowell, M T; van der Hoef, I; Lugtenburg, J; Lagarias, J C; Mathies, R A

    2000-03-14

    Resonance Raman spectra of native and recombinant analogues of oat phytochrome have been obtained and analyzed in conjunction with normal mode calculations. On the basis of frequency shifts observed upon methine bridge deuteration and vinyl and C(15)-methine bridge saturation of the chromophore, intense Raman lines at 805 and 814 cm(-)(1) in P(r) and P(fr), respectively, are assigned as C(15)-hydrogen out-of-plane (HOOP) wags, lines at 665 cm(-)(1) in P(r) and at 672 and 654 cm(-)(1) in P(fr) are assigned as coupled C=C and C-C torsions and in-plane ring twisting modes, and modes at approximately 1300 cm(-)(1) in P(r) are coupled N-H and C-H rocking modes. The empirical assignments and normal mode calculations support proposals that the chromophore structures in P(r) and P(fr) are C(15)-Z,syn and C(15)-E,anti, respectively. The intensities of the C(15)-hydrogen out-of-plane, C=C and C-C torsional, and in-plane ring modes in both P(r) and P(fr) suggest that the initial photochemistry involves simultaneous bond rotations at the C(15)-methine bridge coupled to C(15)-H wagging and D-ring rotation. The strong nonbonded interactions of the C- and D-ring methyl groups in the C(15)-E,anti P(fr) chromophore structure indicated by the intense 814 cm(-1) C(15) HOOP mode suggest that the excited state of P(fr) and its photoproduct states are strongly coupled.

  3. FTIR, FT-Raman, FT-NMR, UV-visible and quantum chemical investigations of 2-amino-4-methylbenzothiazole.

    Science.gov (United States)

    Arjunan, V; Sakiladevi, S; Rani, T; Mythili, C V; Mohan, S

    2012-03-01

    The FT-IR (4000-400 cm(-1)) and FT-Raman (4000-100 cm(-1)) spectral measurements and complete assignments of the observed spectra of 2-amino-4-methylbenzothiazole (2A4MBT) have been proposed. Ab initio and DFT calculations have been performed and the structural parameters of the compound were determined from the optimised geometry with 6-31G(d,p), 6-311++G(d,p) and cc-pVDZ basis sets and giving energies, harmonic vibrational frequencies, depolarisation ratios, IR intensities and Raman activities. (1)H and (13)C NMR spectra were recorded and (1)H and (13)C nuclear magnetic resonance chemical shifts of the molecule were calculated using the gauge independent atomic orbital (GIAO) method. UV-visible spectrum of the compound was also recorded and the electronic properties, such as HOMO, LUMO and band gap energies were measured by time-dependent DFT (TD-DFT) approach. The geometric parameters, energies, harmonic vibrational frequencies, IR intensities, Raman activities chemical shifts and absorption wavelengths were compared with the available experimental data of the molecule. The influences of methyl and amino groups on the skeletal modes and on the proton chemical shifts have been investigated. Copyright © 2011 Elsevier B.V. All rights reserved.

  4. Raman Mapping in the Scientific Investigations of Works of Art

    Science.gov (United States)

    Ropret, Polonca; Miliani, Costanza; Centeno, Silvia A.

    Raman mapping in works of art has traditionally been performed using a motorized xy stage that moves a small artwork or a sample taken from the object in a step-by-step manner in two directions under the microscope objective. This configuration allows to obtain important information about the objects in a non-invasive manner and, in the case of samples, on the stratigraphy and the composition of all layers. Three case studies are presented to discuss the capabilities and limitations of this approach. In the first case, the distribution of crystalline and amorphous phases in a sample from a historical glaze were mapped and the resulting composition was related to the production technology of the decoration. In the second case, Raman mapping was performed non-destructively in a ceramic fragment to contribute to elucidate the complex process involved in the lustre decoration formation. And in the third case, the composition of the different paint layers in a sample cross-section removed from a polychromed wooden sculpture was mapped in order to help differentiate original paint layers from those resulting from restoration interventions. Among the limitations of the mapping approach using a motorized xy stage are the impossibility to use it with art objects that do not fit on the stage, under the microscope objective, and the time required for the automatic optimization of the focus distance at each point. Examples of in situ non-invasive mapping experiments in two contemporary paintings using a novel configuration in which a set of mirrors is placed in the horizontal exit of the microscope attached to the spectrometer are discussed. The advantages of this system are, in addition to allowing to map larger objects, its full confocality and the possibility to work with multiple laser excitations. The limitations of this approach are also discussed.

  5. Resonance Raman mapping as a tool to monitor and manipulate Si nanocrystals in Si-SiO{sub 2} nanocomposite

    Energy Technology Data Exchange (ETDEWEB)

    Rani, Ekta; Ingale, Alka A., E-mail: alka@rrcat.gov.in [Laser Physics Applications Section, Raja Ramanna Centre for Advanced Technology, Indore-452013 (India); Homi Bhabha National Institute, Raja Ramanna Centre for Advanced Technology, Indore-452013 (India); Chaturvedi, A. [Laser Material Processing Division, Raja Ramanna Centre for Advanced Technology, Indore-452013 (India); Joshi, M. P.; Kukreja, L. M. [Homi Bhabha National Institute, Raja Ramanna Centre for Advanced Technology, Indore-452013 (India); Laser Material Processing Division, Raja Ramanna Centre for Advanced Technology, Indore-452013 (India)

    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.

  6. A magnetic-field enriched surface-enhanced resonance Raman spectroscopy strategy towards the early diagnosis of malaria

    Science.gov (United States)

    Yuen, Clement; Liu, Quan

    2012-03-01

    Early malaria diagnosis is important because malaria disease can develop into fatal illness within hours upon the appearance of the first symptom. The low concentration of the diagnosis biomarker, hemozoin, at the early stage of malaria disease makes early diagnosis difficult. In this paper, we present a magnetic field-enriched surface-enhanced resonance Raman spectroscopy (SERRS) strategy for the sensitive detection of β - hematin crystals, which is equivalent to hemozoin in the characteristics of Raman spectrum, by using magnetic nanoparticles. We observe several orders of magnitude enhancement in the SERRS signal of enriched β - hematin in comparison to the Raman signal of β - hematin in the cases of SERRS alone or magnetic enrichment alone, showing the great potential of this method towards early malaria diagnosis.

  7. Elucidating photoinduced structural changes in phytochromes by the combined application of resonance Raman spectroscopy and theoretical methods

    Science.gov (United States)

    Mroginski, M. A.; von Stetten, D.; Kaminski, S.; Escobar, F. Velazquez; Michael, N.; Daminelli-Widany, G.; Hildebrandt, P.

    2011-05-01

    Phytochromes constitute a family of red-light sensing photoreceptors in plants and microorganisms. The photoactive cofactor is an open-chain methine-bridged tetrapyrrole that, upon light absorption, undergoes a double bond isomerisation followed by series thermal relaxation processes which eventually lead to the functional structural change of the protein. Resonance Raman spectroscopy has contributed significantly to the understanding of the molecular functioning of these proteins although both the experiments and the interpretation of the spectra represent a considerable challenge. This account is dedicated to describe achievements, potential and limitations of combined resonance Raman spectroscopic and theoretical approaches for elucidating cofactor structures in phytochromes. Experimental approaches are discussed paying specific attention on strategies to overcome unwanted photochemical and photophysical processes when probing the various states of the photoinduced reaction cycle of phytochromes. The most comprehensive set of experimental data on phytochromes, including engineered protein variants and adducts formed with isotopically labelled tetrapyrroles, has been obtained by resonance Raman spectroscopy with near-infrared excitation that also allows probing phytochrome crystals without photo-induced destruction. Quantum mechanical calculations of Raman spectra of model compounds represent a first approximation for determining the methine bridge geometry of the protein-bound tetrapyrroles and constitute the basis for the identification of marker bands for specific structural properties such as the protonation state of the cofactor. Drawbacks of this theoretical method that inevitably neglects the protein environment have become evident with the first determinations of three-dimensional structures of phytochromes. These structural models can now be used for employing hybrid methods that combine quantum mechanical and molecular mechanics calculations of the

  8. Investigation of thermostability of Mo6S3I6 nanowires using Raman spectroscopy

    Directory of Open Access Journals (Sweden)

    Todorović Jelena M.

    2009-01-01

    Full Text Available The thermostability (phase stability of Mo6S3I6 nanowires was investigated by Raman spectroscopy, varying the incident laser power (1-9 mW or by gradual heating of the sample from room temperature to 600°C. We have noticed 18 Raman modes in the room temperature Raman spectra, which is in good agreement with the factor group analysis prediction for P1 space group. We confirmed that the vibrations of Mo6S8 clusters dominate in vibrational properties of the Mo6S3I6 nanostructure, since nanowires Raman spectra are similar to Chevrel phase Raman spectra. During the temperature treatment, it was established that in the temperature range between 300 and 400°C a new Raman mode appeares. This mode can be ascribed to molybdenum oxide (MoO3. With further temperature increase, the intensity of this mode increases, drawing a conclusion that at temperature above 300°C the phase separation takes place in this system followed by a formation of oxide layer.

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

    Science.gov (United States)

    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.

  10. Resonance Raman imaging as a tool to assess the atmospheric pollution level: carotenoids in Lecanoraceae lichens as bioindicators.

    Science.gov (United States)

    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.

  11. Real-time magnetic resonance imaging investigation of resonance tuning in soprano singing

    OpenAIRE

    Bresch, Erik; Narayanan, Shrikanth

    2010-01-01

    This article investigates using real-time magnetic resonance imaging the vocal tract shaping of 5 soprano singers during the production of two-octave scales of sung vowels. A systematic shift of the first vocal tract resonance frequency with respect to the fundamental is shown to exist for high vowels across all subjects. No consistent systematic effect on the vocal tract resonance could be shown across all of the subjects for other vowels or for the second vocal tract resonance.

  12. Application of Raman spectroscopy in forensic investigation of questioned documents involving stamp inks.

    Science.gov (United States)

    Raza, Ali; Saha, Basudeb

    2013-09-01

    Stamp pad inks from different manufacturers across India have been analyzed to investigate the feasibility of Raman scattering as a tool for forensic analysis of questioned documents involving stamp inks. Nine different stamping inks were analyzed by both Raman spectroscopic and HPTLC methods. The results demonstrate the effectiveness of these methods in classifying the investigated stamping inks based on their spectral pattern and HPTLC chromatogram. Raman scattering tool was able to determine the sequence of heterogeneous intersection strokes involving a blue stamp pad ink and other writing instruments, such as ballpoint pen ink (red and black), pencil and laser printer toner. However, this method was unable to resolve the exact sequencing for the intersection strokes involving investigated stamp ink and blue ballpoint ink or gel pen ink (all colors).

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

    Science.gov (United States)

    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.

  14. Resonance Raman Analysis of the Mechanism of Energy Storage and Chromophore Distortion in the Primary Visual Photoproduct†

    OpenAIRE

    Yan, Elsa C. Y.; Ganim, Ziad; Kazmi, Manija A; Chang, Belinda S. W.; Sakmar, Thomas P.; Mathies, Richard A.

    2004-01-01

    The vibrational structure of the chromophore in the primary photoproduct of vision, bathorhodopsin, is examined to determine the cause of the anomalously decoupled and intense C11=C12 hydrogen-out-of-plane (HOOP) wagging modes and their relation to energy storage in the primary photoproduct. Low-temperature (77 K) resonance Raman spectra of Glu181 and Ser186 mutants of bovine rhodopsin reveal only mild mutagenic perturbations of the photoproduct spectrum suggesting that dipolar, electrostatic...

  15. High resolution AFM and single cell resonance Raman spectroscopy of Geobacter sulfurreducens biofilms early in growth.

    Directory of Open Access Journals (Sweden)

    Nikolai eLebedev

    2014-08-01

    Full Text Available AFM and confocal resonance Raman microscopy (CRRM of single-cells were used to study the transition of anode-grown Geobacter sulfurreducens biofilms from lag phase (initial period of low current to exponential phase (subsequent period of rapidly increasing current. Results reveal that lag phase biofilms consist of lone cells and tightly packed single-cell thick clusters crisscrossed with extracellular linear structures that appear to be comprised of nodules approximately 20 nm in diameter aligned end to end. By early exponential phase cell clusters expand laterally and a second layer of closely packed cells begins to form on top of the first. Abundance of c-type cytochromes (c-Cyt is > 3-fold greater in 2-cell thick regions than in 1-cell thick regions. The results indicate that early biofilm growth involves two transformations. The first is from lone cells to 2-dimensionally associated cells during lag phase when current remains low. This is accompanied by formation of extracellular linear structures. The second is from 2- to 3-dimensionally associated cells during early exponential phase when current begins to increases rapidly. This is accompanied by a dramatic increase in c-Cyt abundance.

  16. Molecular effects of high-pressure processing on food studied by resonance Raman.

    Science.gov (United States)

    Tintchev, Filip; Wackerbarth, Hainer; Kuhlmann, Uwe; Toepfl, Stefan; Knorr, Dietrich; Hildebrandt, Peter; Heinz, Volker

    2010-02-01

    Pressurization may cause unwanted side effects including color or texture changes of fish and meat. The color changes of poultry, pork, and smoked salmon were studied by CIE L*, a*, b* system, and resonance Raman (RR). High-pressure processing (HPP) of pork and chicken meat resulted in significant color modification at pressures higher than 270 and 280 MPa, respectively. RR spectra were taken after a high-pressure treatment of pork meat. According to the RR-data, deoxymyoglobin is the dominating myoglobin species in pork meat. High-pressure treatment causes conformational changes resulting in a stabile nonnative ferrous myoglobin species while the ferrous myoglobin state is maintained. High-pressure treatment causes a decrease of the relative RR intensities of astaxanthin by salmon as probed with 514 nm. RR spectra excited at 413 nm revealed a heterogeneous broadening of astaxanthin bands accompanied by the formation of deoxymyoglobin or deoxyhemoglobin. The broadening is interpreted as the degradation products of astaxanthin. Obviously, the high-pressure treatment of smoked salmon triggers redox processes of astaxanthin and the heme protein.

  17. Combining fibre optic Raman spectroscopy and tactile resonance measurement for tissue characterization

    Science.gov (United States)

    Candefjord, Stefan; Nyberg, Morgan; Jalkanen, Ville; Ramser, Kerstin; Lindahl, Olof A.

    2010-12-01

    Tissue characterization is fundamental for identification of pathological conditions. Raman spectroscopy (RS) and tactile resonance measurement (TRM) are two promising techniques that measure biochemical content and stiffness, respectively. They have potential to complement the golden standard--histological analysis. By combining RS and TRM, complementary information about tissue content can be obtained and specific drawbacks can be avoided. The aim of this study was to develop a multivariate approach to compare RS and TRM information. The approach was evaluated on measurements at the same points on porcine abdominal tissue. The measurement points were divided into five groups by multivariate analysis of the RS data. A regression analysis was performed and receiver operating characteristic (ROC) curves were used to compare the RS and TRM data. TRM identified one group efficiently (area under ROC curve 0.99). The RS data showed that the proportion of saturated fat was high in this group. The regression analysis showed that stiffness was mainly determined by the amount of fat and its composition. We concluded that RS provided additional, important information for tissue identification that was not provided by TRM alone. The results are promising for development of a method combining RS and TRM for intraoperative tissue characterization.

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

    Science.gov (United States)

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

    2013-11-15

    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.

  19. Accurate Simulation of Resonance-Raman Spectra of Flexible Molecules: An Internal Coordinates Approach.

    Science.gov (United States)

    Baiardi, Alberto; Bloino, Julien; Barone, Vincenzo

    2015-07-14

    The interpretation and analysis of experimental resonance-Raman (RR) spectra can be significantly facilitated by vibronic computations based on reliable quantum-mechanical (QM) methods. With the aim of improving the description of large and flexible molecules, our recent time-dependent formulation to compute vibrationally resolved electronic spectra, based on Cartesian coordinates, has been extended to support internal coordinates. A set of nonredundant delocalized coordinates is automatically generated from the molecular connectivity thanks to a new general and robust procedure. In order to validate our implementation, a series of molecules has been used as test cases. Among them, rigid systems show that normal modes based on Cartesian and delocalized internal coordinates provide equivalent results, but the latter set is much more convenient and reliable for systems characterized by strong geometric deformations associated with the electronic transition. The so-called Z-matrix internal coordinates, which perform well for chain molecules, are also shown to be poorly suited in the presence of cycles or nonstandard structures.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2013-08-31

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

  1. Absorption and resonance Raman study of the {sup 2}B{sub 1}(X)-{sup 2}A{sub 2}(A) transition of chlorine dioxide in the gas phase

    Energy Technology Data Exchange (ETDEWEB)

    Esposito, A.P.; Stedl, T.; Jonsson, H.; Reid, P.J. [Univ. of Washington, Seattle, WA (United States). Dept. of Chemistry; Peterson, K.A. [Washington State Univ., Pullman, WA (United States). Dept. of Chemistry

    1999-03-25

    The photochemical reaction dynamics of chlorine dioxide (OClO) are investigated using absorption and resonance Raman spectroscopy. The first Raman spectra of gaseous OClO obtained directly on resonance with the {sup 2}B{sub 1}-{sup 2}A{sub 2} electronic transition are reported. Significant scattering intensity is observed for all vibrational degrees of freedom (the symmetric stretch, bend, and asymmetric stretch), demonstrating that structural evolution occurs along all three normal coordinates following photoexcitation. The experimentally measured absorption and resonance Raman intensities are compared to the intensities predicted using both empirical and ab initio models for the optically active {sup 2}A{sub 2} surface. Comparison of the experimental and theoretical absorption spectra demonstrates that the frequencies and intensities of transitions involving the asymmetric stretch are well reproduced by the empirical model characterized by a double-minimum along the asymmetric stretch. However, the ab initio model is also found to reproduce a subset of the experimental intensities. In addition, the extremely large resonance Raman intensity of the asymmetric stretch overtone transition is predicted by both models. The results presented here taken in combination with the model for the {sup 2}A{sub 2} surface in condensed environments suggest that the phase-dependent photochemical reactivity of OClO is due to environment-dependent excited-state structural evolution along the asymmetric stretch coordinate.

  2. Long-range surface plasmon resonance and surface-enhanced Raman scattering on X-shaped gold plasmonic nanohole arrays.

    Science.gov (United States)

    Hou, Chao; Galvan, Daniel David; Meng, Guowen; Yu, Qiuming

    2017-09-13

    A multilayered architecture including a thin Au film supporting an X-shaped nanohole array and a thick continuous Au film separated by a Cytop dielectric layer is reported in this work. Long-range surface plasmon resonance (LR-SPR) was generated at the top Au/water interface, which also resulted in a long-range surface-enhanced Raman scattering (LR-SERS) effect. LR-SPR originates from the coupling of surface plasmons (SPs) propagating along the opposite sides of the thin Au film embedded in a symmetric refractive index environment with Cytop (n = 1.34) and water (n = 1.33). The finite-difference time-domain (FDTD) simulation method was used to investigate the optimal dimensions of the substrate by studying the reflectance spectra and electric field profiles. The calculated optimal structure was then fabricated via electron beam lithography, and its LR-SERS performance was demonstrated by detecting rhodamine 6G and 4-mercaptobenzoic acid in the refractive index-matched environment. We believe that this structure as a LR-SPR or LR-SERS substrate can have broad applications in biosensing.

  3. Resonance Raman analysis of the mechanism of energy storage and chromophore distortion in the primary visual photoproduct.

    Science.gov (United States)

    Yan, Elsa C Y; Ganim, Ziad; Kazmi, Manija A; Chang, Belinda S W; Sakmar, Thomas P; Mathies, Richard A

    2004-08-31

    The vibrational structure of the chromophore in the primary photoproduct of vision, bathorhodopsin, is examined to determine the cause of the anomalously decoupled and intense C(11)=C(12) hydrogen-out-of-plane (HOOP) wagging modes and their relation to energy storage in the primary photoproduct. Low-temperature (77 K) resonance Raman spectra of Glu181 and Ser186 mutants of bovine rhodopsin reveal only mild mutagenic perturbations of the photoproduct spectrum suggesting that dipolar, electrostatic, or steric interactions with these residues do not cause the HOOP mode frequencies and intensities. Density functional theory calculations are performed to investigate the effect of geometric distortion on the HOOP coupling. The decoupled HOOP modes can be simulated by imposing approximately 40 degrees twists in the same direction about the C(11)=C(12) and C(12)-C(13) bonds. Sequence comparison and examination of the binding site suggests that these distortions are caused by three constraints consisting of an electrostatic anchor between the protonated Schiff base and the Glu113 counterion, as well as steric interactions of the 9- and 13-methyl groups with surrounding residues. This distortion stores light energy that is used to drive the subsequent protein conformational changes that activate rhodopsin.

  4. Resonance Raman Analysis of the Mechanism of Energy Storage and Chromophore Distortion in the Primary Visual Photoproduct†

    Science.gov (United States)

    Yan, Elsa C. Y.; Ganim, Ziad; Kazmi, Manija A.; Chang, Belinda S. W.; Sakmar, Thomas P.; Mathies, Richard A.

    2005-01-01

    The vibrational structure of the chromophore in the primary photoproduct of vision, bathorhodopsin, is examined to determine the cause of the anomalously decoupled and intense C11=C12 hydrogen-out-of-plane (HOOP) wagging modes and their relation to energy storage in the primary photoproduct. Low-temperature (77 K) resonance Raman spectra of Glu181 and Ser186 mutants of bovine rhodopsin reveal only mild mutagenic perturbations of the photoproduct spectrum suggesting that dipolar, electrostatic, or steric interactions with these residues do ded by NIHnot cause the HOOP mode frequencies and intensities. Density functional theory calculations are performed to investigate the effect of geometric distortion on the HOOP coupling. The decoupled HOOP modes can be simulated by imposing ∼40° twists in the same direction about the C11=C12 and C12-C13 bonds. Sequence comparison and examination of the binding site suggests that these distortions are caused by three constraints consisting of an electrostatic anchor between the protonated Schiff base and the Glu113 counterion, as well as steric interactions of the 9- and 13-methyl groups with surrounding residues. This distortion stores light energy that is used to drive the subsequent protein conformational changes that activate rhodopsin. PMID:15323547

  5. Determination of retinal chromophore structure in bacteriorhodopsin with resonance Raman spectroscopy.

    Science.gov (United States)

    Smith, S O; Lugtenburg, J; Mathies, R A

    1985-01-01

    The analysis of the vibrational spectrum of the retinal chromophore in bacteriorhodopsin with isotopic derivatives provides a powerful "structural dictionary" for the translation of vibrational frequencies and intensities into structural information. Of importance for the proton-pumping mechanism is the unambiguous determination of the configuration about the C13=C14 and C=N bonds, and the protonation state of the Schiff base nitrogen. Vibrational studies have shown that in light-adapted BR568 the Schiff base nitrogen is protonated and both the C13=C14 and C=N bonds are in a trans geometry. The formation of K625 involves the photochemical isomerization about only the C13=C14 bond which displaces the Schiff base proton into a different protein environment. Subsequent Schiff base deprotonation produces the M412 intermediate. Thermal reisomerization of the C13=C14 bond and reprotonation of the Schiff base occur in the M412------O640 transition, resetting the proton-pumping mechanism. The vibrational spectra can also be used to examine the conformation about the C--C single bonds. The frequency of the C14--C15 stretching vibration in BR568, K625, L550 and O640 argues that the C14--C15 conformation in these intermediates is s-trans. Conformational distortions of the chromophore have been identified in K625 and O640 through the observation of intense hydrogen out-of-plane wagging vibrations in the Raman spectra (see Fig. 2). These two intermediates are the direct products of chromophore isomerization. Thus it appears that following isomerization in a tight protein binding pocket, the chromophore cannot easily relax to a planar geometry. The analogous observation of intense hydrogen out-of-plane modes in the primary photoproduct in vision (Eyring et al., 1982) suggests that this may be a general phenomenon in protein-bound isomerizations. Future resonance Raman studies should provide even more details on how bacterio-opsin and retinal act in concert to produce an

  6. DOSY-NMR and raman investigations on the self-aggregation and cyclodextrin complexation of vanillin.

    Science.gov (United States)

    Ferrazza, Ruggero; Rossi, Barbara; Guella, Graziano

    2014-06-26

    Vanillin (4-hydroxy-3-methoxybenzaldehyde) is a phenolic aldehyde with limited solubility in water; in this work, we investigate its self-aggregation, as well as its complexation equilibria with β-cyclodextrin by using nuclear magnetic resonance (NMR) and vibrational spectroscopy. In particular, diffusion-ordered NMR (DOSY) measurements allowing to detect diffusional changes caused by aggregation/inclusion phenomena lead to a reliable estimate of the equilibrium constants of these processes, while Raman spectroscopy was used to further characterize some structural details of vanillin self-aggregates and inclusion complexes. Although the self-association binding constant of vanillin in water was found to be low (K(a) ∼10), dimeric species are not negligible within the investigated range of concentration (3-65 mM); on the other hand, formation of β-cyclodextrin self-aggregates was not detected by DOSY measurements on aqueous solutions of β-cyclodextrin at different concentrations (2-12 mM). Finally, the binding of vanillin with β-cyclodextrin, as measured by the DOSY technique within a narrow range of concentrations (2-15 mM) by assuming the existence of only the monomeric 1:1 vanillin/β-CD complex, was about an order of magnitude higher (K(c) ∼ 90) than self-aggregation. However, the value of the equilibrium constant for this complexation was found to be significantly affected by the analytical concentrations of the host and guest system, thus indicating that K(c) is an "apparent" equilibrium constant.

  7. Water in the hydration shell of halide ions has significantly reduced Fermi resonance and moderately enhanced Raman cross section in the OH stretch regions.

    Science.gov (United States)

    Ahmed, Mohammed; Singh, Ajay K; Mondal, Jahur A; Sarkar, Sisir K

    2013-08-22

    Water in the presence of electrolytes plays an important role in biological and industrial processes. The properties of water, such as the intermolecular coupling, Fermi resonance (FR), hydrogen-bonding, and Raman cross section were investigated by measuring the Raman spectra in the OD and OH stretch regions in presence of alkali halides (NaX; X = F, Cl, Br, I). It is observed that the changes in spectral characteristics by the addition of NaX in D2O are similar to those obtained by the addition of H2O in D2O. The spectral width decreases significantly by the addition of NaX in D2O (H2O) than that in the isotopically diluted water. Quantitative estimation, on the basis of integrated Raman intensity, revealed that the relative Raman cross section, σ(H)/σ(b) (σ(H) and σ(b) are the average Raman cross section of water in the first hydration shell of X(-) and in bulk, respectively), in D2O and H2O is higher than those in the respective isotopically diluted water. These results suggest that water in the hydration shell has reduced FR and intermolecular coupling compared to those in bulk. In the isotopically diluted water, the relative Raman cross section increases with increase in size of the halide ions (σ(H)/σ(b) = 0.6, 1.1, 1.5, and 1.9 for F(-), Cl(-), Br(-), and I(-), respectively), which is assignable to the enhancement of Raman cross section by charge transfer from halide ions to the hydrating water. Nevertheless, the experimentally determined σ(H)/σ(b) is lower than the calculated values obtained on the basis of the energy of the charge transfer state of water. The weak enhancement of σ(H)/σ(b) signifies that the charge transfer transition in the hydration shell of halide ions causes little change in the OD (OH) bond lengths of hydrating water.

  8. Raman spectroscopic and mass spectrometric investigations of the hydrogen isotopes and isotopically labelled methane

    Energy Technology Data Exchange (ETDEWEB)

    Jewett, J.R., Fluor Daniel Hanford

    1997-02-24

    Suitable analytical methods must be tested and developed for monitoring the individual process steps within the fuel cycle of a fusion reactor and for tritium accountability. The utility of laser-Raman spectroscopy accompanied by mass spectrometry with an Omegatron was investigated using the analysis of all hydrogen isotopes and isotopically labeled methanes as an example. The Omegatron is useful for analyzing all hydrogen isotopes mixed with the stable helium isotopes. The application of this mass spectrometer were demonstrated by analyzing mixtures of deuterated methanes. In addition, it was employed to study the radiochemical Witzbach exchange reaction between tritium and methanes. A laser-Raman spectrometer was designed for analysis of tritium-containing gases and was built from individual components. A tritium-compatible, metal-sealed Raman cuvette having windows with good optical properties and additional means for measuring the stray light was first used successfully in this work. The Raman spectra of the hydrogen isotopes were acquired in the pure rotation mode and in the rotation-vibration mode and were used for on. The deuterated methanes were measured by Raman spectroscopy, the wavenumbers determined were assigned to the corresponding vibrations, and the wavenumbers for the rotational fine-structure were summarized in tables. The fundamental Vibrations of the deuterated methanes produced Witzbach reactions were detected and assigned. The fundamental vibrations of the molecules were obtained with Raman spectroscopy for the first time in this work. The @-Raman spectrometer assembled is well suited for the analysis of tritium- containing gases and is practical in combination with mass spectrometry using an Omegatron, for studying gases used in fusion.

  9. Raman scattering investigation of VOCs in interaction with ice particles

    Science.gov (United States)

    Facq, Sébastien; Oancea, Adriana; Focsa, Cristian; Chazallon, Bertrand

    2010-05-01

    Cirrus clouds that form in the Earth's upper troposphere (UT) are known to play a significant role in the radiation budget and climate [1]. These clouds that cover about 35% of the Earth's surface [2] are mainly composed of small ice particles that can provide surfaces for trace gas interactions [3]. Volatile Organic Compounds (VOCs) are present in relative high abundance in the UT [4][5]. They promote substantial sources of free OH radicals that are responsible for driving photochemical cycles in the atmosphere. Their presence can both influence the oxidizing capacity and the ozone budget of the atmosphere. VOCs can interact with ice particles via different trapping processes (adsorption, diffusion, freezing, and co-deposition, i.e., incorporation of trace gases during growing ice conditions) which can result in the perturbation of the chemistry and photochemistry of the UT. Knowledge of the incorporation processes of VOCs in ice particles is important in order to understand and predict their impact on the ice particles structure and reactivity and more generally on the cirrus cloud formation. This proceeds via the in-situ characterization of the ice condensed phase in a pressure and temperature range of the UT. An important mechanism of UT cirrus cloud formation is the heterogeneous ice freezing process. In this study, we examine and characterize the interaction of a VOC, i.e., ethanol (EtOH) with ice particles during freezing. Vibrational spectra of water O-H and EtOH C-H spectral regions are analysed using confocal micro-Raman spectroscopy. Information at the molecular level on the surface structure can be derived from accompanying changes observed in band shapes and vibrational mode frequencies. Depending of the EtOH content, different crystalline phases have been identified and compared to hydrates previously reported for the EtOH-water system. Particular attention is paid on the effect of EtOH aqueous solutions cooling rate and droplet sizes on the phases

  10. Investigation on Clarified Fruit Juice Composition by Using Visible Light Micro-Raman Spectroscopy

    Directory of Open Access Journals (Sweden)

    Maria Lepore

    2007-10-01

    Full Text Available Liquid samples of clarified apple and apricot juices at different productionstages were investigated using visible light micro-Raman spectroscopy in order to assessits potential in monitoring fruit juice production. As is well-known, pectin plays a strategicrole in the production of clarified juice and the possibility of using Raman for its detectionduring production was therefore evaluated. The data analysis has enabled the clearidentification of pectin. In particular, Raman spectra of apple juice samples from washedand crushed fruits revealed a peak at 845 cm-1 (typical of pectin which disappears in theRaman spectra of depectinised samples. The fructose content was also revealed by thepresence of four peaks at 823 cm-1, 872 cm-1, 918 cm-1 and 975 cm-1. In the case of apricotjuice, several Raman fingerprints of β-carotene at 1008, 1159 and 1520 cm-1 were alsohighlighted. Present results resulted interesting for the exclusive use of optical methods forthe quantitative determination of the above-mentioned substances in place of thebiochemical assays generally used for this purpose, which are time consuming and requiredifferent chemical reagents for each of them.

  11. Investigation of pre-pulse pumping laser for preserving temporal waveform of stimulated Raman scattering

    Science.gov (United States)

    Chen, Junchi; Su, Hongpeng; Peng, Yujie; Guo, Xiaoyang; Wang, Zhanshan; Leng, Yuxin

    2017-01-01

    A modified polarized beam combination technique is proposed for preserving the temporal waveforms of stimulated Raman scattering. 1064 nm pre-pulse pumping lasers prior to the main pumping laser with a delay time are generated and injected into a Ba(NO3)2 Raman medium to excite the crystal firstly. The influences of pre-pulse lasers with various energy levels on the temporal shapes of Raman lasers are investigated, and it is demonstrated that the temporal waveforms of the Raman laser are distorted once the energies of the pre-pulse are below and above the required energy for preserving the temporal shapes of Stokes radiation. It is also discovered that the temporal shape of the 1197 nm Raman laser cannot be perfectly preserved if the energy of the 1064 nm main laser is too low or the relative delay time is too large. Moreover, the optical conversion efficiency and Stokes laser energy obtained under pumping lasers with single and double intensity peaks are compared.

  12. Optimization of Fe3O4@Ag nanoshells in magnetic field-enriched surface-enhanced resonance Raman scattering for malaria diagnosis.

    Science.gov (United States)

    Yuen, Clement; Liu, Quan

    2013-11-07

    The great potential of magnetic field enriched surface enhanced resonance Raman spectroscopy (SERRS) for early malaria diagnosis has been demonstrated previously. This technique is able to detect β-hematin, which is equivalent to a malaria biomarker (hemozoin) in Raman features, at a concentration of 5 nM. In this study, we present the optimization of nanoparticles used in the magnetic field enriched SERRS by tuning the core size and shell thickness of nanoparticles with an iron oxide core and a silver shell (Fe3O4@Ag). The discrete dipole approximation (DDA) model was introduced to investigate the localized electromagnetic field distributions and extinction efficiencies of the aggregate of Fe3O4@Ag and β-hematin, in correlation with their magnetic field enriched SERRS performance. We find that the optimal core-shell size of Fe3O4@Ag leading to the effective aggregation of Fe3O4@Ag and β-hematin under an external magnetic field with superior extinction efficiencies is the key to realize highly augmented Raman signals in this strategy. Furthermore, it is noted that the optimized result differs from the case without the external magnetic field to that with the external magnetic field. Therefore, this work demonstrates experimentally and theoretically the potential of tuning the core-shell Fe3O4@Ag for achieving the efficient magnetic field-enriched SERRS detection of β-hematin for early malaria diagnosis.

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

    Institute of Scientific and Technical Information of China (English)

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

    2008-01-01

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

  14. Glass transition of polystyrene (PS) studied by Raman spectroscopic investigation of its phenyl functional groups

    Science.gov (United States)

    Bertoldo Menezes, D.; Reyer, A.; Marletta, A.; Musso, M.

    2017-01-01

    In polymeric materials the glass transition (GT) is a well-known and very important relaxation process related to movements of functional groups in the polymeric chain. In this work, we show the potential of Raman spectroscopy for exploring the GT process in the polymer polystyrene. We collected Raman spectra during a step-by-step heating process of the sample, which allowed us to collect signatures of the GT process from peak parameters of specific vibrational modes, and to verify the GT temperature. Results of the latter were in accordance with published values obtained via other methods. We identified the aromatic ring vibrational modes of the phenyl functional groups to be those which, due to steric hindrance, suffer the largest influence during the GT process. This confirms that Raman spectroscopy can be used as a complementary technique to perform GT investigations in polymeric materials due to its sensitivity to small intermolecular changes affecting vibrational properties of relevant functional side groups.

  15. A raman microprobe investigation of the molecular architecture of loblolly pine tracheids

    Science.gov (United States)

    James S. Bond; Rajai H. Atalla

    1999-01-01

    Our understanding of the molecular architecture of intact, native plant cell walls is very limited. Traditional methods of investigation disturb the tissue to varying degrees and conclusions based on these methods may be intimately related to the technique used. A promising new technique to study native-state organization is polarized Raman spectroscopy. In this...

  16. Theoretical investigation of resonant frequencies of unstrapped magnetron with arbitrary side resonators

    Energy Technology Data Exchange (ETDEWEB)

    Yue, Song, E-mail: yuessd@163.com [Key Laboratory of High Power Microwave Sources and Technologies, Institute of Electronics, Chinese Academy of Sciences, Beijing 100190 (China); University of Chinese Academy of Sciences, Beijing 100049 (China); Zhang, Zhao-chuan; Gao, Dong-ping [Key Laboratory of High Power Microwave Sources and Technologies, Institute of Electronics, Chinese Academy of Sciences, Beijing 100190 (China)

    2015-04-15

    In this paper, a sector steps approximation method is proposed to investigate the resonant frequencies of magnetrons with arbitrary side resonators. The arbitrary side resonator is substituted with a series of sector steps, in which the spatial harmonics of electromagnetic field are also considered. By using the method of admittance matching between adjacent steps, as well as field continuity conditions between side resonators and interaction regions, the dispersion equation of magnetron with arbitrary side resonators is derived. Resonant frequencies of magnetrons with five common kinds of side resonators are calculated with sector steps approximation method and computer simulation softwares, in which the results have a good agreement. The relative error is less than 2%, which verifies the validity of sector steps approximation method.

  17. Resonance Raman study of the active site of Coprinus cinereus peroxidase.

    Science.gov (United States)

    Smulevich, G; Feis, A; Focardi, C; Tams, J; Welinder, K G

    1994-12-27

    Resonance Raman (RR) spectra for the resting state ferric and the reduced ferrous forms of recombinant Coprinus cinereus peroxidase (CIP), obtained with different excitation wavelengths and in polarized light, are reported. The spectra are compared with those obtained previously for cytochrome c peroxidase expressed in Escherichia coli [(CCP(MI)] and horseradish peroxidase (HRP-C). Although the enzymic properties of CIP and HRP-C are similar, the RR data show that, in terms of the heme cavity structures, CIP and CCP(MI) are much more closely related to each other than to HRP-C. The ferric state of CIP at neutral pH is characteristic mainly of a five-coordinate high spin heme. However, the lower frequency of the v2 mode and a higher frequency of the v(C = C) vinyl stretching modes for CIP as compared to CCP, indicate a higher degree of vibrational coupling between the two modes in CIP. In addition, CIP is rather unstable under low laser power irradiation as an irreversible transition to a six-coordinate high spin heme followed by a second transition to a six-coordinate low spin heme is observed. This instability of CIP as compared to CCP(MI) is proposed to be a consequence of the presence of a distal Phe54 in CIP rather than the homologous Trp51 in CCP, as Trp51 is hydrogen-bonded to a distal water molecule located above the heme Fe thereby preventing its coordination in CCP. In CIP the FeII-His RR band has two components with frequencies at 230 and 211 cm-1.(ABSTRACT TRUNCATED AT 250 WORDS)

  18. Resonance Raman analysis of the Pr and Pfr forms of phytochrome.

    Science.gov (United States)

    Fodor, S P; Lagarias, J C; Mathies, R A

    1990-12-18

    Resonance Raman vibrational spectra of the Pr and Pfr forms of oat phytochrome have been obtained at room temperature. When Pr is converted to Pfr, new bands appear in the C = C and C = N stretching region at 1622, 1599, and 1552 cm-1, indicating that a major structural change of the chromophore has occurred. The Pr to Pfr conversion results in an 11 cm-1 lowering of the N-H rocking band from 1323 to 1312 cm-1. Normal mode calculations correlate this frequency drop with a Z----E isomerization about the C15 = C16 bond. A line at 803 cm-1 in Pr is replaced by an unusually intense mode at 814 cm-1 in Pfr. Calculations on model tetrapyrrole chromophores suggest that these low-wavenumber modes are hydrogen out-of-plane (HOOP) wagging vibrations of the bridging C15 methine hydrogen and that both the intensity and frequency of the C15 HOOP mode are sensitive to the geometry around the C14-C15 and C15 = C16 bonds. The large intensity of the 814-cm-1 mode in Pfr indicates that the chromophore is highly distorted from planarity around the C15 methine bridge. If the Pr----Pfr conversion does involve a C15 = C16 Z----E isomerization, then the intensity of the C15 HOOP mode in Pfr argues that the chromophore has an E,anti conformation. On the basis of a comparison with the vibrational calculations, the low frequency (803 cm-1) and the reduced intensity of the C15 HOOP mode in Pr suggest that the chromophore in Pr adopts the C15-Z,syn conformation.

  19. Single-molecule surface-enhanced Raman scattering of R6G in aqueous environment under non-resonance conditions

    Institute of Scientific and Technical Information of China (English)

    Enzhong Tan; Penggang Yin; Lidong Li; Lin Guo

    2011-01-01

    The single-molecule surface-enhanced Raman scattering (SERS) spectra of Rhodamine 6G (R6G) in an aqueous environment under non-resonance conditions are studied. Series of spectra are recorded in time-mapping mode, and intensity fluctuations of SERS signals and spectral diffusion are observed. The correlations between the presence frequency of SERS spectra and number of hot spots as well as the quantity of molecules in scattering volume are examined thoroughly. The results indicate that only molecules located at hot spots produce good signal-to-noise ratio Raman spectra and the origin of fluctuating SERS signals are mainly ascribed to the movement of hot spots.%@@ The single-molecule surface-enhanced Raman scattering(SERS) spectra of Rhodamine 6G(R6G) in anaqueous environment under non-resonance conditions are studied.Series of spectra are recorded in timemapping mode,and intensity fluctuations of SERS signals and spectral diffusion are observed.The correlations between the presence frequency of SERS spectra and number of hot spots as well as the quantity of molecules in scattering volume are examined thoroughly.

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

    Science.gov (United States)

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

    2016-02-15

    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. Copyright © 2015 Elsevier B.V. All rights reserved.

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

    Science.gov (United States)

    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.

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

    Science.gov (United States)

    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.

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

    Science.gov (United States)

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

    2015-02-05

    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.

  4. Chemotaxonomic Raman Spectroscopy Investigation of Ascomycetes and Zygomycetes

    Energy Technology Data Exchange (ETDEWEB)

    Lee, Cheol Min [Hanyang Univ., Seoul (Korea, Republic of); Cho, Eunmin; Yang, Sung Ik [Kyung Hee Univ., Yongin (Korea, Republic of); Ochir, Erdeneganbold; Dembereldorj, Uuriintuya [Soongsil Univ., Seoul (Korea, Republic of)

    2013-04-15

    Enormous diversity exists in fungi, which cause epidemic diseases and infections by producing mycotoxins. Conventional fungal identification methods involve elaborate observations and time-consuming measurements of macroscopic and microscopic morphologies. The drawbacks with these methods include the need for an experienced investigator and the length of time taken to process the data. More recently, bioinformatic methods based on sequencing parts of the genome have been used to analyze fungi or fungal extracts by introducing chemotaxonomical markers. It is necessary to introduce a novel monitoring method that can accurately and efficiently identify fungal species. Spectroscopic analysis, which requires little sample preparation procedures, would meet the purpose of rapid analysis or identification of fungi.

  5. An Electrochemical and Raman Spectroelectrochemical Investigation of Underpotentially Deposited Silver on a Gold Substrate.

    Science.gov (United States)

    1986-07-30

    Raman Spectroelectrochemical Investigation of Underpotentially Deposited Silver on a Gold Substrate By Stanley Pons. J. Li, J. Liang DTIC S ELECTE APR 14...ACCCSSIONd 14U. 3. i4CCipIa.ti rs CATALOG. PiumnRi - 4. ITL (sa~utfie) . TYPE Of REPORT a PCI3ioo covEuiv Investigation of Underpotentially Deposited ...spectroelectrochemical data indicate that underpotentially * deposited silver adatoms on gold substrates are photolyzed to form silver meta clusters. *DD

  6. Resonant Raman scattering in superconducting Ba1-xKxBiO3

    NARCIS (Netherlands)

    Menushenkov, AP; Troyan, IA; Eremets, MI

    2003-01-01

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

  7. Investigation of stratigraphic mapping in paintings using micro-Raman spectroscopy

    Science.gov (United States)

    Karagiannis, Georgios Th.; Apostolidis, Georgios K.

    2016-04-01

    In this work, microRaman spectroscopy is used to investigate the stratigraphic mapping in paintings. The objective of mapping imaging is to segment the dataset, here spectra, into clusters each of which consisting spectra that have similar characteristics; hence, similar chemical composition. The spatial distribution of such clusters can be illustrated in pseudocolor images, in which each pixel of image is colored according to its cluster membership. Such mapping images convey information about the spatial distribution of the chemical substances in an object. Moreover, the laser light source that is used has excitation in 1064 nm, i.e., near infrared (NIR), allowing the penetration of the radiation in deeper layers. Thus, the mapping images that are produced by clustering the acquired spectra (specifying specific bands of Raman shifts) can provide stratigraphic information in the mapping images, i.e., images that convey information of the distribution of substances from deeper, as well. To cluster the spectra, unsupervised machine learning algorithms are applied, e.g., hierarchical clustering. Furthermore, the optical microscopy camera (×50), where the Raman probe (B and WTek iRaman EX) is plugged in, is attached to a computerized numerical control (CNC) system which is driven by a software that is specially developed for Raman mapping. This software except for the conventional CNC operation allows the user to parameterize the spectrometer and check each and every measurement to ensure proper acquisition. This facility is important in painting investigation because some materials are vulnerable to such specific parameterization that other materials demand. The technique is tested on a portable experimental overpainted icon of a known stratigraphy. Specifically, the under icon, i.e., the wavy hair of "Saint James", can be separated from upper icon, i.e., the halo of Mother of God in the "Descent of the Cross".

  8. Raman E sub 1 , E sub 1 + DELTA sub 1 resonance in nonstressed quantum dots of germanium

    CERN Document Server

    Talochkin, A B; Efanov, A V; Kozhemyako, I G; Shumskij, V N

    2001-01-01

    The Raman light scattering on the optical phonons in the nonstressed Ge quantum dots, obtained in the GaAs/ZnSe/Ge/ZnSe structures is studied through the molecular-beam epitaxy. The E sub 1 , E sub 1 + DELTA sub 1 resonance energy shift, connected with quantization of the electron and hole states spectrum in the quantum dots is observed. Application of the simplest localization model with an account of the Ge electron states spectrum made it possible to explain the observed peculiarities

  9. Raman investigation of GaP–Si interfaces grown by molecular beam epitaxy

    Energy Technology Data Exchange (ETDEWEB)

    Bondi, A.; Cornet, C.; Boyer, S.; Nguyen Thanh, T.; Létoublon, A.; Pedesseau, L.; Durand, O. [Université Européenne de Bretagne, INSA, FOTON, UMR CNRS 6082, 20 Avenue des Buttes de Coësmes, F-35708 Rennes (France); Moreac, A. [Institut de Physique de Rennes, UMR-CNRS n°6251, Université Rennes1, Campus de Beaulieu — 35042 Rennes cedex (France); Ponchet, A. [CEMES, UPR CNRS 8011, F-31055 Toulouse (France); Le Corre, A. [Université Européenne de Bretagne, INSA, FOTON, UMR CNRS 6082, 20 Avenue des Buttes de Coësmes, F-35708 Rennes (France); Even, J., E-mail: jacky.even@insa.rennes.fr [Université Européenne de Bretagne, INSA, FOTON, UMR CNRS 6082, 20 Avenue des Buttes de Coësmes, F-35708 Rennes (France)

    2013-08-31

    Raman spectroscopy was used to investigate the residual strain in thin GaP layers deposited on Si substrates by molecular beam epitaxy. Different growth conditions were used to obtain a clean GaP–Si interface, including migration enhanced epitaxy. The strain induced Raman shifts of the longitudinal and the transverse optical GaP lattice modes were analyzed. The effects of crystalline defects are discussed, supported by high resolution transmission electron microscopy and X-ray scattering studies. Finally, Raman Spectroscopy reveals the presence of disorder (or surface)-activated optical phonons. This result is discussed in the light of surface morphology analyses. - Highlights: ► GaP thin layers grown by molecular beam epitaxy on Si substrates. ► Strain-induced Raman shifts of the optical GaP modes are analyzed. ► Simulation of optical GaP modes by density functional perturbation theory. ► Comparison with X-ray diffraction and electron and scanning probe microscopy data.

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

    Science.gov (United States)

    Craig, Norman C.

    2015-06-01

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

  11. Quantitative Raman imaging investigations of mixing phenomena in high-pressure cryogenic jets.

    Science.gov (United States)

    Decker, M; Schik, A; Meier, U E; Stricker, W

    1998-08-20

    A two-dimensional Raman technique was used to investigate mixing phenomena of cryogenic jets under both supercritical and transcritical conditions. The aim of this study was to enlarge the experimental data basis for modeling purposes and to provide quantitative information to help to improve the design of injectors for high-pressure rocket engine combustion chambers. Cryogenic nitrogen, which served as substitute for liquid O(2), was injected into N(2) at room temperature at pressures up to 6.0 MPa. The liquid N(2) jet could be atomized by a coaxial H(2) flow. Raman scattering was generated with a XeF excimer laser. The resulting signal images were discriminated against background by spectral filtering and preferential detection of light with a polarization corresponding to the polarization of the laser, thus making use of the conserved polarization of the Raman-scattered light. The Raman images were converted into density distributions of N(2) and H(2), respectively, as well as into temperature distributions for a variety of experimental conditions.

  12. Raman mapping investigation of chemical vapor deposition-fabricated twisted bilayer graphene with irregular grains.

    Science.gov (United States)

    Chen, Yuming; Meng, Lijuan; Zhao, Weiwei; Liang, Zheng; Wu, Xing; Nan, Haiyan; Wu, Zhangting; Huang, Shan; Sun, Litao; Wang, Jinlan; Ni, Zhenhua

    2014-10-21

    Bilayer graphene as a prototype of two-dimensional stacked material has recently attracted great attention. The twist angle between graphene layers adds another dimension to control its properties. In this study, we used Raman mapping to investigate the twist angle dependence of properties of twisted bilayer graphene (TBG) with irregular grains that was fabricated by chemical vapor deposition (CVD). Different Raman parameters including intensity, width, and position of G and 2D peaks were used to distinguish TBG with different twist angles. The statistical results from Raman imaging on the distribution of twist angle are consistent with the results from selected area election diffraction (SAED). Finally, the Raman peak at approximately 1347 cm(-1) for TBG with a large twist angle was assigned to the D-like peak, although it has similar excitation energy dependence of frequency as the defect-induced D peak. Theoretical calculation further confirmed that vacancy-like defect is not favored in the formation energy for TBG with a large twist angle as compared to monolayer graphene or TBG with other twist angles. These results will help to advance the understanding of TBG properties, especially for CVD samples with irregular grains.

  13. X-ray radiation-induced effects in human mammary epithelial cells investigated by Raman microspectroscopy

    Science.gov (United States)

    Risi, R.; Manti, L.; Perna, G.; Lasalvia, M.; Capozzi, V.; Delfino, I.; Lepore, M.

    2012-06-01

    Micro-Raman technique can be particularly useful to investigate the chemical changes induced in structure, protein, nucleic acid, lipid, and carbohydrate contents of cells. The aim of this work is to inspect the possibility to employ Raman microspectroscopy to detect biochemical modifications in human mammary epithelial cells after exposure to different Xray doses. The samples consisted of cells cultured on polylysine-coated glass coverslips. After the exposition, control and treated cells were washed in phosphate-buffered saline (PBS) and then fixed in paraformaldehyde 3.7%. They were examined using a confocal micro-Raman system equipped with a He-Ne laser (λ = 632.8 nm; power on the sample= 3.5mW). Differences in the intensity ratio of specific Raman vibrational markers commonly assigned to phenylalanine and tyrosine amino acids (at 1000, 1030, 1618 cm-1), DNA bases (787, 1090, 1305 cm-1), and amide III (1237, and 1265 cm-1) with respect a reference peak (the one of lipids at 1450 cm-1) were evidenced between control and exposed cells. These differences may be indicative of damage in exposed cells as the fragmentation of individual amino acids and DNA bases, crosslink effects in molecular structure of DNA and protein conformational change that especially tend to "unwind" the protein due to the breaking of hydrogen bonds between peptide chains.

  14. Raman spectroscopic investigation of spinal cord injury in a rat model

    Science.gov (United States)

    Saxena, Tarun; Deng, Bin; Stelzner, Dennis; Hasenwinkel, Julie; Chaiken, Joseph

    2011-02-01

    Raman spectroscopy was used to study temporal molecular changes associated with spinal cord injury (SCI) in a rat model. Raman spectra of saline-perfused, injured, and healthy rat spinal cords were obtained and compared. Two injury models, a lateral hemisection and a moderate contusion were investigated. The net fluorescence and the Raman spectra showed clear differences between the injured and healthy spinal cords. Based on extensive histological and biochemical characterization of SCI available in the literature, these differences were hypothesized to be due to cell death, demyelination, and changes in the extracellular matrix composition, such as increased expression of proteoglycans and hyaluronic acid, at the site of injury where the glial scar forms. Further, analysis of difference spectra indicated the presence of carbonyl containing compounds, hypothesized to be products of lipid peroxidation and acid catalyzed hydrolysis of glycosaminoglycan moieties. These results compared well with in vitro experiments conducted on chondroitin sulfate sugars. Since the glial scar is thought to be a potent biochemical barrier to nerve regeneration, this observation suggests the possibility of using near infrared Raman spectroscopy to study injury progression and explore potential treatments ex vivo, and ultimately monitor potential remedial treatments within the spinal cord in vivo.

  15. X-ray absorption and resonance raman spectroscopy of human myeloperoxidase at neutral and acid pH.

    Science.gov (United States)

    Yue, K T; Taylor, K L; Kinkade, J M; Sinclair, R B; Powers, L S

    1997-04-01

    Myeloperoxidase (MPO), an important enzyme in the oxygen-dependent host defense system of human polymorphonuclear leukocytes, utilizes hydrogen peroxide to catalyze the production of hypochlorous acid, an oxidizing bactericidal agent. While MPO shows significant sequence homology with other peroxidases and this homology is particularly striking among the active-site residues, MPO exhibits unusual spectral features and the unique ability to catalyze the oxidation of chloride ions. We have investigated the MPO active-site with X-ray absorption (XAS) and resonance Raman (RRS) spectroscopies at neutral pH and also at the physiological acidic pH (pH approximately 3) and have compared these results with those of horseradish peroxidase (HRP). At pH 7.5, XAS results show that the iron heme active site is 6-coordinate where the distal ligand is likely nitrogen or oxygen, but not sulfur. The heme is distorted compared to HRP, other peroxidases, and heme compounds, but at pH approximately 3, the distal ligand is lost and the heme is less distorted. RRS results under identical pH conditions show that the skeletal core-size sensitive modes and v3 are shifted to higher frequency at pH approximately 3 indicating a 6- to 5-coordination change of high spin ferric heme. In addition, a new band at 270 cm(-1) is observed at pH approximately 3 which is consistent with the loss of the sixth ligand. The higher symmetry of the heme at pH approximately 3 is reflected by a single v4 mode in the (RRS) spectrum. HRP also loses its loosely associated distal water at this pH, but little change in heme distortion is observed. This change suggests that loss of the distal ligand in MPO releases stress on the heme which may facilitate binding of chloride ion.

  16. Investigation of burn effect on skin using simultaneous Raman-Brillouin spectroscopy, and fluorescence microspectroscopy

    Science.gov (United States)

    Coker, Zachary; Meng, Zhaokai; Troyanova-Wood, Maria; Traverso, Andrew; Ballmann, Charles; Petrov, Georgi; Ibey, Bennett L.; Yakovlev, Vladislav

    2017-02-01

    Burns are thermal injuries that can completely damage or at least compromise the protective function of skin, and affect the ability of tissues to manage moisture. Burn-damaged tissues exhibit lower elasticity than healthy tissues, due to significantly reduced water concentrations and plasma retention. Current methods for determining burn intensity are limited to visual inspection, and potential hospital x-ray examination. We present a unique confocal microscope capable of measuring Raman and Brillouin spectra simultaneously, with concurrent fluorescence investigation from a single spatial location, and demonstrate application by investigating and characterizing the properties of burn-afflicted tissue on chicken skin model. Raman and Brillouin scattering offer complementary information about a material's chemical and mechanical structure, while fluorescence can serve as a useful diagnostic indicator and imaging tool. The developed instrument has the potential for very diverse analytical applications in basic biomedical science and biomedical diagnostics and imaging.

  17. Negative pressure effects in SrTiO 3 nanoparticles investigated by Raman spectroscopy

    Science.gov (United States)

    Wu, XueWei; Wu, DaJian; Liu, XiaoJun

    2008-02-01

    The size effects on SrTiO 3 nanoparticles have been investigated by means of Raman spectroscopy with changing the grain size in the range 10-80 nm. The intensities of the first-order polar TO 2 and TO 4 modes increase as the grain size reduces, suggesting the enhanced interaction of the surface-defect dipoles on the grain boundary. By contrast, the intensities for the first-order nonpolar TO 3 mode decrease with reducing the grain size. Further we have found that the Raman frequencies of the vibration modes are very sensitive to the variation of the grain size. The softening of the TO 2 and TO 3 modes with decreasing the grain size indicates the increase of the Ti-O bond length, which is consistent with the lattice expansion investigated by XRD. We have ascribed the size effects to the negative pressure effects due to the enhanced interaction of the surface-defect dipoles.

  18. Luminescence and micro-Raman investigations on inclusions of unusual habit in chrysoprase from Turkey

    Energy Technology Data Exchange (ETDEWEB)

    Ayvac Latin-Small-Letter-Dotless-I kl Latin-Small-Letter-Dotless-I , M., E-mail: mayvacikli@yahoo.com [Celal Bayar University, Faculty of Arts and Sciences, Department of Physics, 45010 Muradiye-Manisa (Turkey); Garcia-Guinea, J.; Jorge, A. [Museo Nacional Ciencias Naturales, Jose Gutierrez Abascal 2, Madrid 28006 (Spain); Akal Latin-Small-Letter-Dotless-I n, I.; Kotan, Z. [Celal Bayar University, Faculty of Arts and Sciences, Department of Physics, 45010 Muradiye-Manisa (Turkey); Can, N., E-mail: cannurdogan@yahoo.com [Celal Bayar University, Faculty of Arts and Sciences, Department of Physics, 45010 Muradiye-Manisa (Turkey)

    2012-07-15

    Chemical analyses performed on chrysoprase from Turkey have shown many trace elements as well as rare earth impurities. Quantitative chemical analyses of inclusions in minerals can improve our understanding of the chemistry of surface. The environmental scanning electron microscope (ESEM) with an attached X-ray energy dispersive system (EDS) is capable of producing rapid and accurate major element chemical analyses of individual inclusions in crystals larger than about 30 {mu}m in diameter. The samples were examined with lifetime-resolved and spatially-resolved cathodoluminescence (CL), and inductively coupled plasma-atomic emission spectrometry (ICP-AES). Spatially resolved CL results at room temperature were recorded for two different areas. Bulk area displays with low CL emission and pores contain iron phases such as chromite, hematite and anatase which cause the green color. For the raw data in the lifetime resolved CL spectrum, at least three broad emission bands were detected in a yellow band of the highest intensity at about 550 nm, a weaker orange band at about 650 nm, and a red band at 720 nm. It is assumed that there are links between the CL emissions and the presence of some transition metal and REE elements, but it is obvious that all trace elements do not play a direct role. Micro-Raman measurements were performed on chrysoprase and these showed a characteristic intensive Raman band peaked at 464 cm{sup -1} which can be inferred to {nu}{sub 2} doubly symmetric bending mode of [SiO{sub 4}/M] centers. Raman spectrum of all inclusions found in the material are also given and discussed in detail. - Highlights: Black-Right-Pointing-Pointer Luminescence and Raman investigations of Chrysoprase. Black-Right-Pointing-Pointer Characteristic intensive Raman band peaked at 464 cm{sup -1}. Black-Right-Pointing-Pointer Ironed phases such as chromite, hematite and anatase.

  19. Optical pathology of human brain metastasis of lung cancer using combined resonance Raman and spatial frequency spectroscopies

    Science.gov (United States)

    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.

  20. DNA-wrapped carbon nanotubes aligned in stretched gelatin films: Polarized resonance Raman and absorption spectroscopy study

    Science.gov (United States)

    Glamazda, A. Yu.; Plokhotnichenko, A. M.; Leontiev, V. S.; Karachevtsev, V. A.

    2017-09-01

    We present the study of DNA-wrapped single-walled carbon nanotubes (SWNTs) embedded in the stretched gelatin film by the polarized resonance Raman spectroscopy and visible-NIR optical absorption. The polarized dependent absorption spectra taken along and normal to the stretching direction demonstrate a comparatively high degree of the alignment of isolated SWNTs in the gelatin matrix. The analysis of Raman spectra of isolated SWNTs in the gelatin stretched films showed that the degree of the alignment of carbon nanotubes along the stretching direction is about 62%. The dependence of the peak position of G+-band in Raman spectra on the polarization angle θ between the polarization of the incident light and the direction of the stretching of films was revealed. This shift is explained by the different polarization dependence of the most intensive A and E1 symmetry modes within the G+-band. The performed studies of embedded DNA-wrapped nanotubes in the gelatin film show the simple method for obtaining the controlled ordered biocompatible nanotubes inside a polymer matrix. It can be used for manufacturing sizable flexible self-transparent films with integrated nanoelectrodes.

  1. Klimt artwork: material investigation by backscattering Fe-57 Mössbauer and Raman spectroscopy

    Science.gov (United States)

    Costa, B. F. O.; Blumers, M.; Sansano, A.; Klingelhöfer, G.; Rull, F.; Lehmann, R.; Renz, F.

    2014-04-01

    The long lost painting "Trumpeting Putto" was discovered and now is not only in the focus of art historian, but has also scientific interest too. We underwent this rare case of an inorganic layered artwork a non-destructive material investigation by employing Raman and MIMOSII Fe-57 Mössbauer spectroscopy. First results indicate several layers, where two layers of different pigments are on an inorganic background layer stabilised by a metallic wire within a wooden frame structure

  2. Investigation of Vertical Spiral Resonators for Low Frequency Metamaterial Design

    CERN Document Server

    Zhu, Jiwen; Stevens, Christopher J; Edwards, David J

    2008-01-01

    This paper thoroughly explores the characteristics of vertical spiral resonators (VSR). They exhibit rela-tively high Q factors and sizes around a few percent of the free space wavelength, which make them ideal candi-dates for assembling metamaterial devices. A quasistatic model of VSR is obtained from simple analytical ex-pressions, and the effects of certain geometrical parameters on the resonant frequency are investigated.

  3. Investigations of ionomers by electron spin resonance

    CERN Document Server

    Sueleymanoglu, N

    1999-01-01

    through direct diffusion and ligand making manner. Cu''+ sup + and Mn''+''+ ion adsorption properties of Polyn (N-vinyl-2 pyrrolidone/Itaconic acid) P(VP/IA) hydrogels that were prepared to be used to remove some environmental agents from water were investigated and teh similarity of the structure which was formed by the adsorption of metal ions by hydrogels with so called ionomers was examined. For this purpose, the hydrogels that were formed with 2ml vinyl pyrrolidone (VP) aqueous solutions of 0.06, 0.09, 0.12, 0.18, 0.24g itaconic acid with 1 ml of distilled water and exposed to 6''0''Co gamma source were used. The adsorbed quantity of Cu''+''+ ions in hydrogels was determined with UV-Visible absorption spectroscopy and adsorption isotherms of hydrogels were formed. The shapes of the lines showed that the adsorption of metal ions by hydrogels was in accordance with the multilayer physical adsorption isoterms. Same isotherms were also obtained by the relative intensity values ESR spectra. DSC study was carr...

  4. The electron–phonon coupling of fundamental, overtone, and combination modes and its effects on the resonance Raman spectra

    Energy Technology Data Exchange (ETDEWEB)

    Li, Shuo [State Key Laboratory of Superhard Materials, Jilin University, Changchun 130012 (China); College of Physics, Jilin University, Changchun 130012 (China); Li, Zhanlong; Wang, Shenghan; Gao, Shuqin [College of Physics, Jilin University, Changchun 130012 (China); Sun, Chenglin, E-mail: chenglin@jlu.edu.cn [State Key Laboratory of Superhard Materials, Jilin University, Changchun 130012 (China); College of Physics, Jilin University, Changchun 130012 (China); Li, Zuowei [College of Physics, Jilin University, Changchun 130012 (China)

    2015-12-15

    Highlights: • The Huang–Rhys factors and electron–phonon coupling constants are calculated. • The changes of overtone mode are larger than those of fundamental mode. • The variation pattern of electron–phonon coupling well interprets the changes of spectra. - Abstract: External field plays a very important role in the interaction between the π-electron transition and atomic vibration of polyenes. It has significant effects on both the Huang–Rhys factor and the electron–phonon coupling. In this paper, the visible absorption and resonance Raman spectra of all-trans-β-carotene are measured in the 345–295 K temperature range and it is found that the changes of the 0–1 and 0–2 vibration bands of the absorption spectra with the temperature lead to the different electron–phonon coupling of fundamental, overtone, and combination modes. The electron-phonon coupling constants of all the modes are calculated and analyzed under different temperatures. The variation law of the electron–phonon coupling with the temperature well interprets the changes of the resonance Raman spectra, such as the shift, intensity and line width of the overtone and combination modes, which are all greater than those of the fundamental modes.

  5. The effect of the Fermi resonance on the Raman scattering cross sections of the Fermi doublet ν1 and 2ν2 of liquid carbon disulfide in benzene.

    Science.gov (United States)

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

    2012-04-01

    The effect of the Fermi resonance (FR) on the Raman scattering cross sections (RSCSs) of the Fermi doublet ν1, 2ν2 of liquid CS2 in C6H6 using the method of changing the volume concentration of the solution is investigated. We have calculated the RSCSs of the Fermi doublet ν1, 2ν2 using Onsager's theory with the 992 cm(-1) Raman line of C6H6 as the internal standard. The result shows that the RSCS of the ν1 line decreases with decreasing the volume concentration of CS2, while that of the 2ν2 line unexpectedly increases. With decreasing the volume concentration of CS2, two main effects of the solvent effect (SE) and the FR in binary solution that can make the ν1, 2ν2 RSCSs change: the SE, as calculated, reduces both the ν1 and 2ν2 RSCSs; the FR plays a significant role in reducing the ν1 RSCS and enhancing the 2ν2 RSCS. In comparison with our previous investigation [J. Raman Spectrosc. 41 (2010) 776-779], it was found that the stronger the FR is, the more the RSCS of the ν1 decreases and the 2ν2 increases. Thus, we proposed that the result can be best explained by taking into account the effect of the FR on the RSCSs of the Fermi doublet. In addition, this paper also gives an explanation to the experimental results deviating from the theoretical results of the scattering coefficients of CS2 in solvent C6H6 as mentioned in Fini's paper.

  6. Avoiding Ethanol Presence in DNA Samples Enhances the Performance of Ultraviolet Resonance Raman Spectroscopy Analysis.

    Science.gov (United States)

    Cammisuli, Francesca; Pascolo, Lorella; Morgutti, Marcello; Gessini, Alessandro; Masciovecchio, Claudio; D'Amico, Francesco

    2017-01-01

    Ethanol is an essential chemical reagent in DNA preparation as its use increases the yield of extraction. All methodologies for DNA isolation involve the use of ethanol in order to prevent DNA dissolution in water and to optimize the binding of DNA to chromatographic membranes. In this note, we show how the presence of ethanol traces in DNA aqueous solution affects ultraviolet Raman spectra, leading to possible misinterpretations. We report a simple method to remove the ethanol Raman features from the spectra, based on heating the DNA sample at 80 ℃, followed by a slow cooling procedure.

  7. The molecular interaction of a protein in highly concentrated solution investigated by Raman spectroscopy.

    Science.gov (United States)

    Ota, Chikashi; Noguchi, Shintaro; Tsumoto, Kouhei

    2015-04-01

    We used Raman spectroscopy to investigate the structure and interactions of lysozyme molecules in solution over a wide range of concentrations (2.5-300 mg ml(-1)). No changes in the amide-I band were observed as the concentration was increased, but the width of the Trp band at 1555 cm(-1) and the ratios of the intensities of the Tyr bands at 856 and 837 cm(-1), the Trp bands at 870 and 877 cm(-1), and the bands at 2940 (CH stretching) and 3420 cm(-1) (OH stretching) changed as the concentration was changed. These results reveal that although the distance between lysozyme molecules changed by more than an order of magnitude over the tested concentration range, the secondary structure of the protein did not change. The changes in the molecular interactions occurred in a stepwise process as the order of magnitude of the distance between molecules changed. These results suggest that Raman bands can be used as markers to investigate the behavior of high-concentration solutions of proteins and that the use of Raman spectroscopy will lead to progress in our understanding not only of the basic science of protein behavior under concentrated (i.e., crowded) conditions but also of practical processes involving proteins, such as in the field of biopharmaceuticals. © 2014 Wiley Periodicals, Inc.

  8. Non-invasive determination of the CO contents in tuna fish using polarization resolved resonance Raman scattering and/or Rayleigh spectroscopy

    DEFF Research Database (Denmark)

    Hassing, Søren

    Carbon monoxide (CO) is used for Modified Atmosphere Packaging of fresh fish and meat. CO is added because it binds to the Myoglobin of the muscle tissue with high affinity resulting in a bright, cherry-red colored carboxy-Myoglobin complex. The product will because of the red color appear...... to be more fresh and attractive for longer periods of time and thus mask the aging of the product. In the present project it is investigated whether the small wavenumber shift in the visible absorption spectrum of carboxy-Myoglobin relative to the visible absorption of Oxy-Myoglobin in combination...... with polarization resolved resonance Raman spectra of these molecules, can form the basis of the development of a fast and non-invasive method for the screening of the presence of CO in tuna fish and meat....

  9. Raman Spectra of High-κ Dielectric Layers Investigated with Micro-Raman Spectroscopy Comparison with Silicon Dioxide

    Directory of Open Access Journals (Sweden)

    P. Borowicz

    2013-01-01

    Full Text Available Three samples with dielectric layers from high-κ dielectrics, hafnium oxide, gadolinium-silicon oxide, and lanthanum-lutetium oxide on silicon substrate were studied by Raman spectroscopy. The results obtained for high-κ dielectrics were compared with spectra recorded for silicon dioxide. Raman spectra suggest the similarity of gadolinium-silicon oxide and lanthanum-lutetium oxide to the bulk nondensified silicon dioxide. The temperature treatment of hafnium oxide shows the evolution of the structure of this material. Raman spectra recorded for as-deposited hafnium oxide are similar to the results obtained for silicon dioxide layer. After thermal treatment especially at higher temperatures (600°C and above, the structure of hafnium oxide becomes similar to the bulk non-densified silicon dioxide.

  10. Remote Raman - laser induced breakdown spectroscopy (LIBS) geochemical investigation under Venus atmospheric conditions

    Energy Technology Data Exchange (ETDEWEB)

    Clegg, Sanuel M [Los Alamos National Laboratory; Barefield, James E [Los Alamos National Laboratory; Humphries, Seth D [Los Alamos National Laboratory; Wiens, Roger C [Los Alamos National Laboratory; Vaniman, D. T. [Los Alamos National Laboratory; Sharma, S. K. [UNIV OF HAWAII; Misra, A. K. [UNIV OF HAWAII; Dyar, M. D. [MT. HOLYOKE COLLEGE; Smrekar, S. E. [JET PROPULSION LAB.

    2010-12-13

    The extreme Venus surface temperatures ({approx}740 K) and atmospheric pressures ({approx}93 atm) create a challenging environment for surface missions. Scientific investigations capable of Venus geochemical observations must be completed within hours of landing before the lander will be overcome by the harsh atmosphere. A combined remote Raman - LIBS (Laser Induced Breakdown Spectroscopy) instrument is capable of accomplishing the geochemical science goals without the risks associated with collecting samples and bringing them into the lander. Wiens et al. and Sharma et al. demonstrated that both analytical techniques can be integrated into a single instrument capable of planetary missions. The focus of this paper is to explore the capability to probe geologic samples with Raman - LIBS and demonstrate quantitative analysis under Venus surface conditions. Raman and LIBS are highly complementary analytical techniques capable of detecting both the mineralogical and geochemical composition of Venus surface materials. These techniques have the potential to profoundly increase our knowledge of the Venus surface composition, which is currently limited to geochemical data from Soviet Venera and VEGA landers that collectively suggest a surface composition that is primarily tholeiitic basaltic with some potentially more evolved compositions and, in some locations, K-rich trachyandesite. These landers were not equipped to probe the surface mineralogy as can be accomplished with Raman spectroscopy. Based on the observed compositional differences and recognizing the imprecise nature of the existing data, 15 samples were chosen to constitute a Venus-analog suite for this study, including five basalts, two each of andesites, dacites, and sulfates, and single samples of a foidite, trachyandesite, rhyolite, and basaltic trachyandesite under Venus conditions. LIBS data reduction involved generating a partial least squares (PLS) model with a subset of the rock powder standards to

  11. Silver Nanoparticle-Enhanced Resonance Raman Sensor of Chromium(III) in Seawater Samples.

    Science.gov (United States)

    Ly, Nguyễn Hoàng; Joo, Sang-Woo

    2015-04-29

    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 mM 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.

  12. Raman spectroscopy based investigation of molecular changes associated with an early stage of dengue virus infection

    Science.gov (United States)

    Bilal, Maria; Bilal, Muhammad; Saleem, Muhammad; Khurram, Muhammad; Khan, Saranjam; Ullah, Rahat; Ali, Hina; Ahmed, Mushtaq; Shahzada, Shaista; Ullah Khan, Ehsan

    2017-04-01

    Raman spectroscopy based investigations of the molecular changes associated with an early stage of dengue virus infection (DENV) using a partial least squares (PLS) regression model is presented. This study is based on non-structural protein 1 (NS1) which appears after three days of DENV infection. In total, 39 blood sera samples were collected and divided into two groups. The control group contained samples which were the negative for NS1 and antibodies and the positive group contained those samples in which NS1 is positive and antibodies were negative. Out of 39 samples, 29 Raman spectra were used for the model development while the remaining 10 were kept hidden for blind testing of the model. PLS regression yielded a vector of regression coefficients as a function of Raman shift, which were analyzed. Cytokines in the region 775–875 cm‑1, lectins at 1003, 1238, 1340, 1449 and 1672 cm‑1, DNA in the region 1040–1140 cm‑1 and alpha and beta structures of proteins in the region 933–967 cm‑1 have been identified in the regression vector for their role in an early stage of DENV infection. Validity of the model was established by its R-square value of 0.891. Sensitivity, specificity and accuracy were 100% each and the area under the receiver operator characteristic curve was found to be 1.

  13. Applications of Raman Spectroscopy to Virology and Microbial Analysis

    Science.gov (United States)

    Harz, Michaela; Stöckel, Stephan; Ciobotă, Valerian; Cialla, Dana; Rösch, Petra; Popp, Jürgen

    This chapter reports from the utilization of Raman spectroscopic techniques like Raman microscopy, Raman optical activity (ROA), UV-resonance Raman (UVRR)-spectroscopy, surface enhanced Raman spectroscopy (SERS), and tip-enhanced Raman spectroscopy (TERS) for the investigation of viruses and microorganisms, especially bacteria and yeasts for medical and pharmaceutical applications. The application of these Raman techniques allows for the analysis of chemical components of cells and subcellular regions, as well as the monitoring of chemical differences occurring as a result of the growth of microorganisms. In addition, the interaction of microorganisms with active pharmaceutical agents can be investigated. In combination with chemometric methods Raman spectroscopy can also be applied to identify microorganisms both in micro colonies and even on single cells.

  14. 瞬态吸收和共振拉曼光谱研究硝基对联苯氮宾、氮宾离子反应活性的影响%Investigation of the Influence of Nitro-Substitution on the Reaction of Biphenyl-Nitrene and Nitrenium Ion by Transient Absorption and Resonance Raman Spectroscopic Techniques

    Institute of Scientific and Technical Information of China (English)

    李亚芳; 程博文; 沈超; 郑旭明; 薛佳丹; 杜勇; 汤文建

    2016-01-01

    利用光解芳基叠氮化合物得到单重态氮宾,运用纳秒瞬态吸收光谱、瞬态共振拉曼光谱实验手段,辅以密度泛函理论(DFT)计算,研究了4′-硝基-4-联苯氮宾在乙腈和水溶液中的光化学反应中间体。实验结果表明,在非质子溶剂中,4′-硝基-4-联苯氮宾发生系间窜越反应生成三线态氮宾;在质子溶剂中,单重态氮宾可被质子化产生氮宾离子。与4-联苯氮宾和氮宾离子相比,硝基对单重态氮宾系间窜越反应路径影响很小;降低了氮宾离子与水和叠氮阴离子的反应活性,却提高了其与鸟苷的反应活性。%Arylnitrenes and arylnitrenium ions are both short-lived intermediates that are highly reactive. In this work, nanosecond transient absorption and transient resonance Raman spectroscopic measurements were used to detect and identify the intermediates generated from the singlet 4′-nitro-4-biphenylnitrene after photolysis of the corresponding aryl azide in acetonitrile and aqueous solution. Combined with the density functional theory (DFT) simulation results, the structural and electronic characteristics of the above experimental intermediates were specified. The spectral results indicate that in aprotic solvents (such as acetonitrile), the singlet 4′-nitro-4-biphenylnitrene undergoes intersystem crossing (ISC) to the triplet nitrene. In contrast, in a protic solvent (such as the mixed aqueous solution used in this work), the singlet 4′-nitro-4-biphenylnitrene can be protonated to produce the nitrenium ion. Compared with its un-substituted counterpart, the nitro substitution has little influence on the ISC reaction pathway of the singlet 4-biphenylnitrene. With regard to the un-substituted nitrenium ion, the nitro group decreases its reactivity towards water and azide anion, while accelerating its reaction rate towards 2′-deoxyguanosine based on the different quench reaction rates between the nitrenium ion and

  15. UV resonance Raman spectroscopic studies of protein structure and dynamics (Conference Presentation)

    Science.gov (United States)

    Asher, Sanford A.; Punihaole, David; Dahlburg, Elizabeth M.; Jakubek, Ryan S.; Hong, Zhenmin

    2016-09-01

    UV Raman excitation into the 200 nm peptide bond electronic transitions enhance peptide bond amide vibrations of the backbone. A particular band (the amide III3) reports on the Ramachandran psi angle and peptide bond hydrogen bonding. This band is Raman scattered independently by each peptide bond with insignificant coupling between adjacent peptide bonds. Isotope editing of a peptide bond (by replacing the Calpha- H with Calpha- D) allows us to determine the frequency of individual peptide bonds within a peptide or protein to yield their psi angles. Consideration of the Boltzmann equilibria allows us to determine the psi angle Gibbs free energy landscape along the psi (un)folding coordinate that connects secondary structure conformations. The psi angle coordinate is the most important reaction coordinate necessary to understand mechanism(s) of protein folding. We have also discovered an analogous correlation for the primary amide sidechain of Gln. This allows us to monitor the hydrogen bonding and structure of this sidechain. We examine the details of peptide folding conformation dynamics with laser T-jumps where the water temperature is elevated by an 1.9 mM IR nsec laser pulse and we monitor the 200 nm UV Raman spectrum as a function of time. These spectra show the time evolution of conformation. We will discuss the role of salts on stabilizing conformations in solution

  16. The double-resonance enhancement of stimulated low-frequency Raman scattering in silver-capped nanodiamonds

    Science.gov (United States)

    Baranov, A. N.; Butsen, A. V.; Ionin, A. A.; Ivanova, A. K.; Kuchmizhak, A. A.; Kudryashov, S. I.; Kudryavtseva, A. D.; Levchenko, A. O.; Rudenko, A. A.; Saraeva, I. N.; Strokov, M. A.; Tcherniega, N. V.; Zayarny, D. A.

    2017-09-01

    Hybrid plasmonic-dielectric nano- and (sub)microparticles exhibit magnetic and electrical dipolar Mie-resonances, which makes them useful as efficient basic elements in surface-enhanced spectroscopy, non-linear light conversion and nanoscale light control. We report the stimulated low-frequency Raman scattering (SLFRS) of a nanosecond ruby laser radiation (central wavelength λ = 694.3 nm (full-width at half-maximum ≈ 0.015 cm-1), gaussian 1/e-intensity pulsewidth τ ≈ 20 ns, TEM00-mode pulse energy Emax ≈ 0.3 J) in nanodiamond (R ≈ 120 nm) hydrosols, induced via optomechanical coherent excitation of fundamental breathing eigen-modes, and the two-fold enhancement of SLFRS in Ag-decorated nanodiamonds, characterized by hybrid dipolar resonances of electrical (silver) and magnetic (diamond) nature. Hybrid metal-dielectric particles were prepared by means of nanosecond IR-laser ablation of solid silver target in diamond hydrosols with consecutive Ag-capping of diamonds, and were characterized by scanning electron microscopy, UV-vis, photoluminescence and energy-dispersive X-ray spectroscopy. Intensities of the SLFR-scattered components and their size-dependent spectral shifts were measured in the highly sensitive stimulated scattering regime, indicating the high (≈ 30%) SLFRS conversion efficiency and the resonant character of the scattering species.

  17. Fluorescence rejection in resonance Raman spectroscopy using a picosecond-gated intensified charge-coupled device camera.

    Science.gov (United States)

    Efremov, Evtim V; Buijs, Joost B; Gooijer, Cees; Ariese, Freek

    2007-06-01

    A Raman instrument was assembled and tested that rejects typically 98-99% of background fluorescence. Use is made of short (picosecond) laser pulses and time-gated detection in order to record the Raman signals during the pulse while blocking most of the fluorescence. Our approach uses an ultrafast-gated intensified charge-coupled device (ICCD) camera as a simple and straightforward alternative to ps Kerr gating. The fluorescence rejection efficiency depends mainly on the fluorescence lifetime and on the closing speed of the gate (which is about 80 ps in our setup). A formula to calculate this rejection factor is presented. The gated intensifier can be operated at 80 MHz, so high repetition rates and low pulse energies can be used, thus minimizing photodegradation. For excitation we use a frequency-tripled or -doubled Ti : sapphire laser with a pulse width of 3 ps; it should not be shorter in view of the required spectral resolution. Other critical aspects tested include intensifier efficiency as a function of gate width, uniformity of the gate pulse across the spectrum, and spectral resolution in comparison with ungated detection. The total instrumental resolution is 7 cm(-1) in the blue and 15 cm(-1) in the ultraviolet (UV) region. The setup allows one to use resonance Raman spectroscopy (RRS) for extra sensitivity and selectivity, even in the case of strong background fluorescence. Excitation wavelengths in the visible or UV range no longer have to be avoided. The effectiveness of this setup is demonstrated on a test system: pyrene in the presence of toluene fluorescence (lambda(exc) = 257 nm). Furthermore, good time-gated RRS spectra are shown for a strongly fluorescent flavoprotein (lambda(exc) = 405 nm). Advantages and disadvantages of this approach for RRS are discussed.

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

    Energy Technology Data Exchange (ETDEWEB)

    Sivadasan, A. K., E-mail: sivankondazhy@gmail.com; Patsha, Avinash; Dhara, Sandip, E-mail: dhara@igcar.gov.in [Surface and Nanoscience Division, Indira Gandhi Centre for Atomic Research, Kalpakkam 603102 (India)

    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.

  19. Light-induced change of configuration of the LHCII-bound xanthophyll (tentatively assigned to violaxanthin): a resonance Raman study.

    Science.gov (United States)

    Gruszecki, Wiesław I; Gospodarek, Małgorzata; Grudziński, Wojciech; Mazur, Radosław; Gieczewska, Katarzyna; Garstka, Maciej

    2009-02-26

    Raman scattering spectra of light-harvesting complex LHCII isolated from spinach were recorded with an argon laser, tuned to excite the most red-absorbing LHCII-bound xanthophylls (514.5 nm). The intensity of the nu(4) band (at ca. 950 cm-1) corresponding to the out-of-plane wagging modes of the C-H groups in the resonance Raman spectra of carotenoids appears to be inversely dependent on the probing laser power density. This observation can be interpreted in terms of excitation-induced change of configuration of the protein-bound xanthophyll owing to the fact that the intensity of this particular band is diagnostic of a chromophore twisting resulting from its binding to the protein environment. The comparison of the shape of the nu(4) band of a xanthophyll involved in the light-induced spectral changes with the shape of the nu(4) band of the xanthophylls present in LHCII, reported in the literature, lets us conclude that, most probably, violaxanthin is a pigment that undergoes light-driven changes of molecular configuration but also the involvement of lutein may not be excluded. Possible physical mechanisms responsible for the configuration changes and physiological importance of the effect observed are discussed.

  20. Empirical Equation Based Chirality (n, m Assignment of Semiconducting Single Wall Carbon Nanotubes from Resonant Raman Scattering Data

    Directory of Open Access Journals (Sweden)

    Md Shamsul Arefin

    2012-12-01

    Full Text Available This work presents a technique for the chirality (n, m assignment of semiconducting single wall carbon nanotubes by solving a set of empirical equations of the tight binding model parameters. The empirical equations of the nearest neighbor hopping parameters, relating the term (2n, m with the first and second optical transition energies of the semiconducting single wall carbon nanotubes, are also proposed. They provide almost the same level of accuracy for lower and higher diameter nanotubes. An algorithm is presented to determine the chiral index (n, m of any unknown semiconducting tube by solving these empirical equations using values of radial breathing mode frequency and the first or second optical transition energy from resonant Raman spectroscopy. In this paper, the chirality of 55 semiconducting nanotubes is assigned using the first and second optical transition energies. Unlike the existing methods of chirality assignment, this technique does not require graphical comparison or pattern recognition between existing experimental and theoretical Kataura plot.

  1. Detection and imaging of quorum sensing in Pseudomonas aeruginosa biofilm communities by surface-enhanced resonance Raman scattering

    Science.gov (United States)

    Bodelón, Gustavo; Montes-García, Verónica; López-Puente, Vanesa; Hill, Eric H.; Hamon, Cyrille; Sanz-Ortiz, Marta N.; Rodal-Cedeira, Sergio; Costas, Celina; Celiksoy, Sirin; Pérez-Juste, Ignacio; Scarabelli, Leonardo; La Porta, Andrea; Pérez-Juste, Jorge; Pastoriza-Santos, Isabel; Liz-Marzán, Luis M.

    2016-11-01

    Most bacteria in nature exist as biofilms, which support intercellular signalling processes such as quorum sensing (QS), a cell-to-cell communication mechanism that allows bacteria to monitor and respond to cell density and changes in the environment. As QS and biofilms are involved in the ability of bacteria to cause disease, there is a need for the development of methods for the non-invasive analysis of QS in natural bacterial populations. Here, by using surface-enhanced resonance Raman scattering spectroscopy, we report rationally designed nanostructured plasmonic substrates for the in situ, label-free detection of a QS signalling metabolite in growing Pseudomonas aeruginosa biofilms and microcolonies. The in situ, non-invasive plasmonic imaging of QS in biofilms provides a powerful analytical approach for studying intercellular communication on the basis of secreted molecules as signals.

  2. Empirical Equation Based Chirality (n, m) Assignment of Semiconducting Single Wall Carbon Nanotubes from Resonant Raman Scattering Data

    Science.gov (United States)

    Arefin, Md Shamsul

    2012-01-01

    This work presents a technique for the chirality (n, m) assignment of semiconducting single wall carbon nanotubes by solving a set of empirical equations of the tight binding model parameters. The empirical equations of the nearest neighbor hopping parameters, relating the term (2n− m) with the first and second optical transition energies of the semiconducting single wall carbon nanotubes, are also proposed. They provide almost the same level of accuracy for lower and higher diameter nanotubes. An algorithm is presented to determine the chiral index (n, m) of any unknown semiconducting tube by solving these empirical equations using values of radial breathing mode frequency and the first or second optical transition energy from resonant Raman spectroscopy. In this paper, the chirality of 55 semiconducting nanotubes is assigned using the first and second optical transition energies. Unlike the existing methods of chirality assignment, this technique does not require graphical comparison or pattern recognition between existing experimental and theoretical Kataura plot.

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

    Science.gov (United States)

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

    2013-08-14

    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 a(2g) 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 () 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 equal to 24.2 nm, while at pH = 8 and 9, a dissociation process starts to take place resulting in = 9 nm. At pH = 10, only large aggregates of fragmented Hbl Hb with 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.

  4. Experimental Investigation of 2:1 and 3:1 Internal Resonances in Nonlinear MEMS Arch Resonators

    KAUST Repository

    Ramini, Abdallah

    2016-12-05

    We demonstrate experimentally internal resonances in MEMS resonators. The investigation is conducted on in-plane MEMS arch resonators fabricated with a highly doped silicon. The resonators are actuated electrostatically and their stiffness are tuned by electrothermal loading by passing an electrical current though the microstructures. We show that through this tuning, the ratio of the various resonance frequencies can be varied and set at certain ratios. Particularly, we adjust the resonance frequencies of two different vibrational modes to 2:1 and 3:1. Finally, we validate the internal resonances at these ratios through frequency-response curves and FFTs.

  5. In situ Raman investigation of electrolyte solutions in the vicinity of graphite negative electrodes.

    Science.gov (United States)

    Song, Hee-Youb; Fukutsuka, Tomokazu; Miyazaki, Kohei; Abe, Takeshi

    2016-10-05

    The structure of electrolyte solutions plays an important role in the lithium-ion intercalation reaction at graphite negative electrodes. The solvation structure of an electrolyte solution in bulk has been investigated previously. However, the structure of an electrolyte solution at the graphite negative electrode/electrolyte solution interface, where the lithium-ion intercalation reaction occurs is more important. In this study, the structure of electrolyte solutions in the vicinity of a graphite negative electrode was investigated using in situ Raman spectroscopy during the 1st reduction process in 1 mol dm(-3) LiClO4/ethylene carbonate (EC) + diethyl carbonate (DEC) (1 : 1 volume ratio), 1 mol dm(-3) LiCF3SO3/propylene carbonate (PC), and 1 mol dm(-3) LiCF3SO3/PC + tetraethylene glycol dimethyl ether (tetraglyme) (20 : 1 volume ratio). As a result, in the electrolyte solutions in which the lithium-ion intercalation reaction can occur (LiClO4/EC + DEC and LiCF3SO3/PC + tetraglyme), the Raman spectra of free solvent molecules (EC or PC) and anions showed a positive vibrational frequency shift during the co-intercalation reaction, and these shifts returned to their original positions during the lithium-ion intercalation reaction. On the other hand, there is no vibrational frequency shift in LiCF3SO3/PC, an electrolyte in which the lithium-ion intercalation reaction cannot occur. Based on our results, the relationship between the Raman shift and the solid electrolyte interphase (SEI) formation process was discussed.

  6. Resonance investigation of pump-turbine during startup process

    Science.gov (United States)

    He, L. Y.; Wang, Z. W.; Kurosawa, S.; Nakahara, Y.

    2014-12-01

    The causes of resonance of a certain model pump-turbine unit during startup process were investigated in this article. A three-dimensional full flow path analysis model which contains spiral case, stay vanes, guide vanes, runner, gaps outside the runner crown and band, and draft tube was constructed. The transient hydraulic excitation force of full flow path was analyzed under five conditions near the resonance region. Based on one-way fluid- structure interaction (FSI) analysis model, the dynamic stress characteristics of the pump-turbine runner was investigated. The results of pressure pulsation, vibration mode and dynamic stress obtained from simulation were consistent with the test results. The study indicated that the hydraulic excitation frequency (Zg*fn) Hz due to rotor-stator interference corresponding to the natural frequency of 2ND+4ND runner mode is the main cause of resonance. The relationship among pressure pulsation, vibration mode and dynamic stress was discussed in this paper. The results revealed the underlying causes of the resonance phenomenon.

  7. Raman spectroscopy of white wines.

    Science.gov (United States)

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

    2015-08-15

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

  8. Investigating hadronic resonances in pp interactions with HADES

    Directory of Open Access Journals (Sweden)

    Przygoda Witold

    2015-01-01

    Full Text Available In this paper we report on the investigation of baryonic resonance production in proton-proton collisions at the kinetic energies of 1.25 GeV and 3.5 GeV, based on data measured with HADES. Exclusive channels npπ+ and ppπ0 as well as ppe+e− were studied simultaneously in the framework of a one-boson exchange model. The resonance cross sections were determined from the one-pion channels for Δ(1232 and N(1440 (1.25 GeV as well as further Δ and N* resonances up to 2 GeV/c2 for the 3.5 GeV data. The data at 1.25 GeV energy were also analysed within the framework of the partial wave analysis together with the set of several other measurements at lower energies. The obtained solutions provided the evolution of resonance production with the beam energy, showing a sizeable non-resonant contribution but with still dominating contribution of Δ(1232P33. In the case of 3.5 GeV data, the study of the ppe+e− channel gave the insight on the Dalitz decays of the baryon resonances and, in particular, on the electromagnetic transition form-factors in the time-like region. We show that the assumption of a constant electromagnetic transition form-factors leads to underestimation of the yield in the dielectron invariant mass spectrum below the vector mesons pole. On the other hand, a comparison with various transport models shows the important role of intermediate ρ production, though with a large model dependency. The exclusive channels analysis done by the HADES collaboration provides new stringent restrictions on the parameterizations used in the models.

  9. Separation of multiple-quantum signals with different orders along with frequency axis in Raman magnetic resonance spectroscopy in heteronuclear systems

    Institute of Scientific and Technical Information of China (English)

    缪希茄; 卢广; 叶朝辉

    1997-01-01

    One-dimensional multiple-quantum spectroscopy with Raman magnetic resonance (RMR) in het-eronuclear systems was described by the product operator formalism in detail.The effects of the field strength and the frequency offset of the irradiation introduced during the detection period on the intensities and the resonant frequencies of the multiple-quantum signals in RMR spectra were investigated extensively by this product operator formalism.The results predicted by the formalism showed that the multiple-quantum signals in RMR spectroscopy had a higher sensitivity when a smaller frequency offset of irradiation field was employed.However,this situation would complicate the assignment and the separation of the multiple-quantum signals in different orders along the frequency axis in RMR spectra.On the other hand,a larger strength of the irradiation field would result in decoupling and therefore would obscure the detection of the multiple-quantum signals.In the meantime,a much weaker RF field might greatly dec

  10. In Situ Resonance Raman Spectra of Organic Pigments in Momo Coral

    Institute of Scientific and Technical Information of China (English)

    Fan Luwei; Yang Mingxing

    2008-01-01

    In this study, Raman scattering measurements were obtained for momo corals covering their typical range of colors. Three different excitation wavelengths (785, 633, 514 nm) are used for the same samples at the same points. All the samples show the two major Raman features of polyenic compounds assigned to double carbon-carbon (C=C) stretching vibration at approximately 1 500 cm-1 and single carbon-carbon (C--C) stretching vibration at approximately 1 130 cm-1 bond stretching mode. These peaks are not detected in the corresponding white parts of momo corals. However, somechanges in intensities, shape, and position of C=C stretching vibrations of the same point are observed by using different excitation wavelengths. The exact position of C-C stretching vibration of polyenic molecules depends strongly on the number of double bonds contained in their polyenic chain. In addition, the number of double bonds contained in the polyenic chains shows that different colors of the red momo coral are caused by different mixtures of polyenic compounds.

  11. Raman and photoelectron spectroscopic investigation of high-purity niobium materials: Oxides, hydrides, and hydrocarbons

    Science.gov (United States)

    Singh, Nageshwar; Deo, M. N.; Nand, Mangla; Jha, S. N.; Roy, S. B.

    2016-09-01

    We present investigations of the presence of oxides, hydrides, and hydrocarbons in high-purity (residual resistivity ratio, ˜300) niobium (Nb) materials used in fabrication of superconducting radio frequency (SRF) cavities for particle accelerators. Raman spectroscopy of Nb materials (as-received from the vendor as well as after surface chemical- and thermal processing) revealed numerous peaks, which evidently show the presence of oxides (550 cm-1), hydrides (1277 and 1385 cm-1: ˜80 K temperature), and groups of hydrocarbons (1096, 2330, 2710, 2830, 2868, and 3080 cm-1). The present work provides direct spectroscopic evidence of hydrides in the electropolished Nb materials typically used in SRF cavities. Raman spectroscopy thus can provide vital information about the near-surface chemical species in niobium materials and will help in identifying the cause for the performance degradation of SRF cavities. Furthermore, photoelectron spectroscopy was performed on the Nb samples to complement the Raman spectroscopy study. This study reveals the presence of C and O in the Nb samples. Core level spectra of Nb (doublet 3d5/2 and 3d3/2) show peaks near 206.6 and 209.4 eV, which can be attributed to the Nb5+ oxidation state. The core level spectra of C 1 s of the samples are dominated by graphitic carbon (binding energy, 284.6 eV), while the spectra of O 1 s are asymmetrically peaked near binding energy of ˜529 eV, and that indicates the presence of metal-oxide Nb2O5. The valence-band spectra of the Nb samples are dominated by a broad peak similar to O 2p states, but after sputtering (for 10 min) a peak appears at ˜1 eV, which is a feature of the elemental Nb atom.

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

    Science.gov (United States)

    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.

  13. Analytical investigation into the resonance frequencies of a curling probe

    Science.gov (United States)

    Arshadi, Ali; Brinkmann, Ralf Peter

    2016-08-01

    The term ‘active plasma resonance spectroscopy’ (APRS) denotes a class of closely related plasma diagnostic methods which utilize the natural ability of plasmas to resonate on or near the electron plasma frequency {ω\\text{pe}} ; an electrical radio frequency signal (in the GHz range) is coupled into the plasma via an antenna or a probe, the spectral response is recorded and a mathematical model is employed to determine plasma parameters such as the plasma density and the electron temperature. The curling probe, recently invented by Liang et al (2011 Appl. Phys. Express 4 066101), is a novel realization of the APRS concept which has many practical advantages. In particular, it can be miniaturized and flatly embedded into the chamber wall, thus allowing the monitoring of plasma processes without contamination nor disturbance. Physically, the curling probe can be understood as a ‘coiled’ form of the hairpin probe (Stenzel 1976 Rev. Sci. Instrum. 47 603). Assuming that the spiralization of the probe has little electrical effect, this paper investigates the characteristcs of a ‘straightened’ curling probe by modeling it as an infinite slot-type resonator that is in direct contact with the plasma. The diffraction of an incident plane wave at the slot is calculated by solving the cold plasma model and Maxwell’s equations simultaneously. The resonance frequencies of the probe are derived and are found to be in good agreement with the numerical results of the probe inventors.

  14. Investigating Nanoscale Electrochemistry with Surface- and Tip-Enhanced Raman Spectroscopy.

    Science.gov (United States)

    Zaleski, Stephanie; Wilson, Andrew J; Mattei, Michael; Chen, Xu; Goubert, Guillaume; Cardinal, M Fernanda; Willets, Katherine A; Van Duyne, Richard P

    2016-09-20

    The chemical sensitivity of surface-enhanced Raman spectroscopy (SERS) methodologies allows for the investigation of heterogeneous chemical reactions with high sensitivity. Specifically, SERS methodologies are well-suited to study electron transfer (ET) reactions, which lie at the heart of numerous fundamental processes: electrocatalysis, solar energy conversion, energy storage in batteries, and biological events such as photosynthesis. Heterogeneous ET reactions are commonly monitored by electrochemical methods such as cyclic voltammetry, observing billions of electrochemical events per second. Since the first proof of detecting single molecules by redox cycling, there has been growing interest in examining electrochemistry at the nanoscale and single-molecule levels. Doing so unravels details that would otherwise be obscured by an ensemble experiment. The use of optical spectroscopies, such as SERS, to elucidate nanoscale electrochemical behavior is an attractive alternative to traditional approaches such as scanning electrochemical microscopy (SECM). While techniques such as single-molecule fluorescence or electrogenerated chemiluminescence have been used to optically monitor electrochemical events, SERS methodologies, in particular, have shown great promise for exploring electrochemistry at the nanoscale. SERS is ideally suited to study nanoscale electrochemistry because the Raman-enhancing metallic, nanoscale substrate duly serves as the working electrode material. Moreover, SERS has the ability to directly probe single molecules without redox cycling and can achieve nanoscale spatial resolution in combination with super-resolution or scanning probe microscopies. This Account summarizes the latest progress from the Van Duyne and Willets groups toward understanding nanoelectrochemistry using Raman spectroscopic methodologies. The first half of this Account highlights three techniques that have been recently used to probe few- or single-molecule electrochemical

  15. A Study of the Cis—Trans Isomers of β—Apo—12′—Carotenal By Resonance Raman Spectroscopy at Low Temperature

    Institute of Scientific and Technical Information of China (English)

    YingHu; TadashiMizoguchi; 等

    1995-01-01

    Resonance Raman spectroscopy is a powerful technique to study the cis-trans configurations and the intermolecular interactions of carotenoids bound to pigmentprotein complexes[1,2].In the present invertigation,we studied a set of cis-trans isomers of β-Apo-12′-carotenal,the conjugated chain of which has a length in -between those of β-carotene and retinal,to examine whether the configurational key Raman lines which have been established for β-carotene are still valid for β-Apo-12′-caotenal[3

  16. Dissecting X-Ray Raman Resonances Using Four-Wave Mixing

    Energy Technology Data Exchange (ETDEWEB)

    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).

  17. Dissecting X-Ray Raman Resonances Using Four-Wave Mixing

    Directory of Open Access Journals (Sweden)

    Govind Niranjan

    2013-03-01

    Full Text Available 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.

  18. Evidence of the Fano resonance in a temperature dependent Raman study of CaCu3Ti4O12 and SrCu3Ti4O12.

    Science.gov (United States)

    Mishra, Dileep K; Sathe, V G

    2012-06-27

    Phononic excitations have been investigated using Raman scattering studies on CaCu(3)Ti(4)O(12) and SrCu(3)Ti(4)O(12) compounds as a function of temperature down to 10 K. Evidence of the Fano resonance effect is found in the A(g)(1) mode with an asymmetric phonon line shape that occurs because of composite electron-phonon scattering due to the onset of metallic fractions in the system. The evolution of the Fano line shape with temperature affirms the existence of nanoscale phase separation and the prominence of orbitally disrupted metallic regions above 100 K. Anomalies in the evolution of the line width of the A(g)(1) Raman mode with temperature are observed around 100 K where these compounds show an orbital order/disorder transition. These anomalies manifest mutual coupling of orbital degrees of freedom to lattice degrees of freedom.

  19. An investigation of FT-Raman spectroscopy for quantification of additives to milk

    Science.gov (United States)

    Cheng, Yuche; Qin, Jianwei; Lim, Jongguk; Chan, Diane E.; Kim, Moon S.; Chao, Kuanglin

    2012-05-01

    In this research, four chemicals, urea, ammonium sulfate, dicyandiamide, and melamine, were mixed into liquid nonfat milk at concentrations starting from 0.1% to a maximum concentration determined for each chemical according to its maximum solubility, and two Raman spectrometers-a commercial Nicolet Raman system and an in-house Raman Chemical Imaging (RCI) system-were used to acquire Raman shift spectra for these mixture samples. These chemicals are potential adulterants that could be used to artificially elevate protein measurements of milk products evaluated by the Kjeldahl method. Baseline subtraction was employed to eliminate milk intensity, and the normalized Raman intensity was calculated from the specific Raman shift from the spectrum of solid chemical. Linear relationships were found to exist between the normalized Raman intensity and chemical concentrations. The linear regression coefficients (R2) ranged from 0.9111 to 0.998. Although slightly higher R2 values were calculated for regressions using spectral intensities measured by the Nicolet system compared to those using measurements from the RCI system, the results from the two systems were similar and comparable. A very low concentration of melamine (400 ppm) in milk was also found to be detectable by both systems. Raman sensitivity of Nicolet Raman system was estimated from normalized Raman intensity and slope of regression line in this study. Chemicals (0.2%) were dissolved in milk and detected the normalized Raman intensity. Melamine was found to have the highest Raman sensitivity, with the highest values for normalized Raman intensity (0.09) and regression line slope (57.04).

  20. Coherent anti-Stokes Raman spectroscopy in the presence of strong resonant signal from background molecules

    CERN Document Server

    Bitter, Martin

    2012-01-01

    Optical spectroscopy with broadband femtosecond laser pulses often involves simultaneous excitation of multiple molecular species with close resonance frequencies. Interpreting the collective optical response from molecular mixtures typically requires Fourier analysis of the detected time-resolved signal. We propose an alternative method of separating coherent optical responses from two molecular species with neighboring excitation resonances (here, vibrational modes of oxygen and carbon dioxide). We utilize ro-vibrational coupling as a mechanism of suppressing the strong vibrational response from the dominating molecular species (O$_{2}$). Coherent ro-vibrational dynamics lead to long "silence windows" of zero signal from oxygen molecules. In these silence windows, the detected signal stems solely from the minority species (CO$_{2}$) enabling background-free detection and characterization of the O$_2$/CO$_2$ mixing ratio. In comparison to a Fourier analysis, our technique does not require femtosecond time re...

  1. Femtosecond laser irradiation of indium phosphide in air: Raman spectroscopic and atomic force microscopic investigations

    Energy Technology Data Exchange (ETDEWEB)

    Bonse, J.; Wrobel, J.M.; Brzezinka, K.-W.; Esser, N.; Kautek, W

    2002-12-30

    Surface modification and ablation of crystalline indium phosphide was performed with single and double 130 fs pulses from a Ti:sapphire laser. The morphological features resulting from laser processing, have been investigated by means of micro Raman spectroscopy as well as by optical, atomic force and scanning electron microscopy. The studies indicate amorphous, ablated and recrystallized zones on the processed surface. In the single-pulse irradiation experimentsveral different threshold fluences could be assigned to the processes of melting, ablation and polycrystalline resolidification. Residual stress has been detected within the irradiated areas. Double-pulse exposure experiments have been analyzed in order to clarify the effect of cumulative damage in the ablation process of indium phosphide.

  2. The effect of chemical variations on the structural polarity of relaxor ferroelectrics studied by resonance Raman spectroscopy.

    Science.gov (United States)

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

    2016-11-30

    Resonance Raman spectroscopy was applied to doped PbSc0.5Ta0.5O3 and PbSc0.5Nb0.5O3 relaxor ferroelectrics, to better understand the effect of composition disorder on the mesoscopic-scale polar order in complex perovskite-type (ABO3) ferroelectrics. The excitation photon energy used was 3.8 eV, which is slightly above the energy gap and corresponds to the maximum of the optical dielectric permittivity. Group-theory analysis reveals that the resonance Raman scattering (RRS) observed under these conditions is allowed only in polar crystal classes. Therefore, RRS is dominated by the atomic dynamics of nanoregions with coherent polar distortions, which considerably facilitates the comparison of polar order in various compounds. The results show that A-site doping (Ba(2+), Sr(2+), La(3+), Bi(3+)) has significantly stronger effect on the structural polarity than the introduction of a third element at the B site (Nb(5+) or Sn(4+) doped in PbSc0.5Ta0.5O3). The A-site substitution by cations that in contrast to Pb(2+) have isotropic outermost electron shells disturbs the system of lone-pair electrons, thus reducing the correlation length of coupled polar distortions and the strength of the electric field associated with the mean polarization of polar nanoregions. A-site doping with larger cations (Ba(2+)) augments the polar deformation of the individual BO6 octahedra due to local elastic fields. As a result, such A-site doping intensifies the initial structural polarity at high temperatures and prevails the enlargement of the polar fraction at low temperatures. A-site doping with smaller cations (Sr(2+), La(3+)), regardless if they are isovalent or aliovalent to Pb(2+), increases the correlation length of antiferrodistortive order (BO6 tilts), which in turn assists the development of double-perovskite structure with coherent local polar distortions. A-site doping with aliovalent cations (Bi(3+)) having the same outermost electron shell and ionic radius as the host A

  3. The effect of chemical variations on the structural polarity of relaxor ferroelectrics studied by resonance Raman spectroscopy

    Science.gov (United States)

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

    2016-11-01

    Resonance Raman spectroscopy was applied to doped PbSc0.5Ta0.5O3 and PbSc0.5Nb0.5O3 relaxor ferroelectrics, to better understand the effect of composition disorder on the mesoscopic-scale polar order in complex perovskite-type (ABO3) ferroelectrics. The excitation photon energy used was 3.8 eV, which is slightly above the energy gap and corresponds to the maximum of the optical dielectric permittivity. Group-theory analysis reveals that the resonance Raman scattering (RRS) observed under these conditions is allowed only in polar crystal classes. Therefore, RRS is dominated by the atomic dynamics of nanoregions with coherent polar distortions, which considerably facilitates the comparison of polar order in various compounds. The results show that A-site doping (Ba2+, Sr2+, La3+, Bi3+) has significantly stronger effect on the structural polarity than the introduction of a third element at the B site (Nb5+ or Sn4+ doped in PbSc0.5Ta0.5O3). The A-site substitution by cations that in contrast to Pb2+ have isotropic outermost electron shells disturbs the system of lone-pair electrons, thus reducing the correlation length of coupled polar distortions and the strength of the electric field associated with the mean polarization of polar nanoregions. A-site doping with larger cations (Ba2+) augments the polar deformation of the individual BO6 octahedra due to local elastic fields. As a result, such A-site doping intensifies the initial structural polarity at high temperatures and prevails the enlargement of the polar fraction at low temperatures. A-site doping with smaller cations (Sr2+, La3+), regardless if they are isovalent or aliovalent to Pb2+, increases the correlation length of antiferrodistortive order (BO6 tilts), which in turn assists the development of double-perovskite structure with coherent local polar distortions. A-site doping with aliovalent cations (Bi3+) having the same outermost electron shell and ionic radius as the host A-site Pb2+ cations leads to

  4. Protonation state and structural changes of the tetrapyrrole chromophore during the Pr --> Pfr phototransformation of phytochrome: a resonance Raman spectroscopic study.

    Science.gov (United States)

    Kneip, C; Hildebrandt, P; Schlamann, W; Braslavsky, S E; Mark, F; Schaffner, K

    1999-11-16

    The photoconversion of phytochrome (phytochrome A from Avena satina) from the inactive (Pr) to the physiologically active form (Pfr) was studied by near-infrared Fourier transform resonance Raman spectroscopy at cryogenic temperatures, which allow us to trap the intermediate states. Nondeuterated and deuterated buffer solutions were used to determine the effect of H/D exchange on the resonance Raman spectra. For the first time, reliable spectra of the "bleached" intermediates meta-R(A) and meta-R(C) were obtained. The vibrational bands in the region 1300-1700 cm(-)(1), which is particularly indicative of structural changes in tetrapyrroles, were assigned on the basis of recent calculations of the Raman spectra of the chromophore in C-phycocyanin and model compounds [Kneip, C., Hildebrandt, P., Németh, K., Mark, F., Schaffner, K. (1999) Chem. Phys. Lett. 311, 479-485]. The experimental resonance Raman spectra Pr are compatible with the Raman spectra calculated for the protonated ZZZasa configuration, which hence is suggested to be the chromophore structure in this parent state of phytochrome. Furthermore, marker bands could be identified that are of high diagnostic value for monitoring structural changes in individual parts of the chromophore. Specifically, it could be shown that not only in the parent states Pr and Pfr but also in all intermediates the chromophore is protonated at the pyrroleninic nitrogen. The spectral changes observed for lumi-R confirm the view that the photoreaction of Pr is a Z --> E isomerization of the CD methine bridge. The subsequent thermal decay reaction to meta-R(A) includes relaxations of the CD methine bridge double bond, whereas the formation of meta-R(C) is accompanied by structural adaptations of the pyrrole rings B and C in the protein pocket. The far-reaching similarities between the chromophores of meta-R(A) and Pfr suggest that in the step meta-R(A) --> Pfr the ultimate structural changes of the protein matrix occur.

  5. Resonance Raman, electron paramagnetic resonance, and density functional theory calculations of a phenolate-bound iron porphyrin complex: electrostatic versus covalent contribution to bonding.

    Science.gov (United States)

    Das, Pradip Kumar; Dey, Abhishek

    2014-07-21

    Resonance Raman (rR), electron paramagnetic resonance (EPR), and density functional theory (DFT) calculations of a phenolate-bound iron porphyrin complex are reported. The complex is found to exist in a five-coordinate high-spin state in a noncoordinating solvent and in a six-coordinate low-spin state in a coordinating solvent. The vibrations originating from the iron phenolate-bound chromophores reproduced those reported for heme tyrosine active sites in nature. The EPR parameters and iron-pyrrole (Fe-Npyr) vibrations of phenolate, thiolate, and imidazole ligated iron porphyrin complexes indicate that the phenolate axial ligand acts as a π anisotropic ligand, which is more covalent than a neutral imidazole ligand but less covalent than a thiolate axial ligand. While the Fe(III/II) potential of the phenolate compound in a noncoordinating solvent is 500 mV more negative than that of the imidazole-bound complex, it is also 110 mV more negative than that of the thiolate-bound complex. DFT calculations reproduce the geometry and vibrational frequencies and show that while both phenolate and thiolate axial ligands bear π and σ interaction with the ferric center, the former is significantly less covalent than the thiolate. The higher covalency of the thiolate ligand is responsible for the lower Fe-Npyr vibration and higher V/λ (from EPR) of the thiolate-bound complexes relative to those of the phenolate-bound complex, whereas the greater electrostatic stabilization of the Fe(III)-OPh bond is responsible for lowering the Fe(III/II) E° of the phenolate-bound complex relative to that of the thiolate-bound complex in a medium having a reasonable dielectric constant.

  6. Ultraviolet Resonance Raman spectroscopy used to study formulations of salmon calcitonin, a starch-peptide conjugate and TGF-β3.

    Science.gov (United States)

    Patois, E; Larmour, I A; Bell, S E J; Palais, C; Capelle, M A H; Gurny, R; Arvinte, T

    2012-06-01

    Ultraviolet Resonance Raman (UVRR) spectroscopy with excitation at 244 nm was investigated here as a possible useful tool for fast characterization of biopharmaceuticals. Studies were performed on three protein drugs: salmon calcitonin (sCT), starch-peptide conjugate, and transforming growth factor-β3 (TGF-β3) adsorbed onto solid granules of tricalcium phosphate (TCP). Secondary structure of sCT was investigated for solutions of 0.5mg/mL up to 200mg/mL, regardless of the turbidity or aggregation states. An increase in β-sheet content was detected when sCT solutions aggregated. UVRR spectroscopy also detected a small amount of residual organic solvent in a starch-peptide conjugate solution containing only 40 μg/mL of peptide. UVRR spectroscopy was then used to characterize a protein, TGF-β3, adsorbed onto solid granules of TCP at 50 and 250 μg/cm(3). This study shows that UVRR is suitable to characterize the protein formulations in a broad range of concentrations, in liquid, aggregated, and solid states.

  7. An investigation of the feasibility of applying Raman microscopy for exploring stained glass.

    Science.gov (United States)

    Bouchard, Michel; Smith, David C; Carabatos-Nédelec, Constantin

    2007-12-15

    Raman microscopy (RM) is widely used in archaeometrical studies of pigments, geomaterials and biomaterials in the Cultural Heritage, but one domain has received relatively less attention: the colouring of stained glass. This feasibility study investigates the advantages and disadvantages of employing RM alone in this field by means of a study of modern commercial glasses, modern commercial pigments, and a few archaeological stained glasses, but especially by an experimental project whereby the authors created stained glass. The different kinds of possible unreacted or reacted material are rigorously established. The distinction between Na, K, Ca glasses was explored, as well as the red colouring of an industrial glass which was proved to be due to the presence of (Zn, Cd)S(x)Se(1-x). Yellow, green, blue and maroon pigments were studied before and after an initial firing and then after heating on glass. The quality of the Raman spectra varied enormously and was sometimes disappointing. Nevertheless RM successfully identified various coloured products such as bindheimite, crocoite, cobalt aluminate, haematite; relict reactants such as corundum, eskolaite and oxides of Co or Pb; and provided indications of other phases such as maghemite or Co-olivine. One conclusion is that the amount of chemical reaction between the pigments and the glass is small compared to the amount in between the pigments. Comments are made on the potential for dating archaeological glass from the known age of synthesis of the pigments, and of the dangers of this approach. Overall it has been shown that RM can be useful for studying stained glass, especially for remote in situ analytical operations with mobile RM, but one must expect some problems either with fluorescence or weak spectra.

  8. Single v. multiple measures of skin carotenoids by resonance Raman spectroscopy as a biomarker of usual carotenoid status

    Science.gov (United States)

    Scarmo, Stephanie; Cartmel, Brenda; Lin, Haiqun; Leffell, David J.; Ermakov, Igor V.; Gellermann, Werner; Bernstein, Paul S.; Mayne, Susan T.

    2013-01-01

    Resonance Raman spectroscopy (RRS) is a non-invasive method of assessing carotenoid status in the skin, which has been suggested as an objective indicator of fruit/vegetable intake. The present study assessed agreement and identified predictors of single v. multiple RRS measures of skin carotenoid status. A total of seventy-four participants had their skin carotenoid status measured in the palm of the hand by RRS at six time points over 6 months. Questionnaires were administered to collect information on demographic, lifestyle and dietary data. Mean age of the participants was 36.6 years, 62.2% were female, 83.8% Caucasian and 85.1% were non-smoking at baseline. There was a good agreement between a single measure of skin carotenoids by RRS and multiple measures (weighted κ = 0.80; 95% CI 0.72, 0.88). The same variables were significantly associated with carotenoid status based on single or multiple measures, including a positive association with intake of total carotenoids (Pseason of measurement (P≤0.05). The exception was recent sun exposure, which emerged as a significant predictor of lower carotenoid status only when using multiple RRS measures (P≤0.01). A single RRS measure was reasonably accurate at classifying usual skin carotenoid status. Researchers using RRS may want to take into account other factors that are associated with the biomarker, including season of measurement and recent sun exposure. PMID:23351238

  9. Microanalysis of organic pigments and glazes in polychrome works of art by surface-enhanced resonance Raman scattering.

    Science.gov (United States)

    Leona, Marco

    2009-09-01

    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 microm 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).

  10. Single v. multiple measures of skin carotenoids by resonance Raman spectroscopy as a biomarker of usual carotenoid status.

    Science.gov (United States)

    Scarmo, Stephanie; Cartmel, Brenda; Lin, Haiqun; Leffell, David J; Ermakov, Igor V; Gellermann, Werner; Bernstein, Paul S; Mayne, Susan T

    2013-09-14

    Resonance Raman spectroscopy (RRS) is a non-invasive method of assessing carotenoid status in the skin, which has been suggested as an objective indicator of fruit/vegetable intake. The present study assessed agreement and identified predictors of single v. multiple RRS measures of skin carotenoid status. A total of seventy-four participants had their skin carotenoid status measured in the palm of the hand by RRS at six time points over 6 months. Questionnaires were administered to collect information on demographic, lifestyle and dietary data. Mean age of the participants was 36.6 years, 62.2% were female, 83.8% Caucasian and 85.1% were non-smoking at baseline. There was a good agreement between a single measure of skin carotenoids by RRS and multiple measures (weighted κ = 0.80; 95% CI 0.72, 0.88). The same variables were significantly associated with carotenoid status based on single or multiple measures, including a positive association with intake of total carotenoids (Pcarotenoid status only when using multiple RRS measures (P≤ 0.01). A single RRS measure was reasonably accurate at classifying usual skin carotenoid status. Researchers using RRS may want to take into account other factors that are associated with the biomarker, including season of measurement and recent sun exposure.

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

    Science.gov (United States)

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

    2016-10-01

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

  12. Vibrational Relaxation of the Backbone and Base Modes in LacDNA Complexes by UV Resonance Raman Spectroscopy.

    Science.gov (United States)

    Muntean, Cristina M; Bratu, Ioan; Hernanz, Antonio

    2017-07-20

    Vibrational band shape analysis through time correlation function concept is widely used to obtain experimental information on the molecular dynamics of medium-size molecules in different environments. Interesting details are revealed by extending this technique to biomolecules such as functional groups of the nucleic acids in media approaching the physiological conditions. In this work a study into the UV resonance Raman (UVRR) vibrational half bandwidths of functional groups in LacDNA, upon lowering the pH (pH 6.4, pH 3.45) and in the presence of Mn(2+) and Ca(2+) ions, respectively, was of interest. The corresponding global relaxation times have been derived. Also, the 793 cm(-1) UVRR band, corresponding to ν (backbone O-P-O, dT) oscillator of LacDNA in aqueous solutions, was selected for band shape-analysis. Vibrational relaxation appears as the dominant relaxation process for this mode, with vibrational dephasing being the most efficient for this oscillator. Current theories developed for vibrational dephasing have been applied to this profile, and relevant relaxation parameters have been obtained and discussed. To our knowledge this is the first study on DNA oligomers vibrational band shape analysis through time correlation function concept.

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

    Energy Technology Data Exchange (ETDEWEB)

    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.

  14. [Application of Raman spectroscopic technique to the identification and investigation of Chinese ancient jades and jade artifacts].

    Science.gov (United States)

    Zhao, Hong-Xia; Gan, Fu-Xi

    2009-11-01

    Laser Raman spectroscopic technique is one of the essential methods in scientific archaeological research, which belongs to the nondestructive analysis. As a very good nondestructive analysis approach, it has not been widely applied in the research of the Chinese ancient jade artifacts. First of all in the present paper the fundamentals of laser Raman spectroscopic technique and the new research progress in this field were reviewed. Secondly, the Raman spectra of five familiar jades including nephrite (mainly composed of tremolite), Xiuyan Jade (mainly composed of serpentine), Dushan Jade (mainly composed of anorthite and Zoisite), turquoise and lapis lazuli were summarized respectively. As for an example, the Raman spectra of the four Chinese ancient jade artifacts excavated from Liangzhu Site of Zhejiang Province and Yinxu Site of Anyang in Henan Province were compared with that of the nephrite sample in Hetian of Xinjiang Province. It was shown that the Raman spectroscopic technique is a good nondestructive approach to the identification and investigation of the structures and mineral composition of Chinese ancient jade artifacts. Finally, the limitations and the foreground of this technique were discussed.

  15. Raman spectroscopic investigation of the chemopreventive response of naringenin and its nanoparticles in DMBA-induced oral carcinogenesis

    Science.gov (United States)

    Krishnakumar, N.; Sulfikkarali, N. K.; Manoharan, S.; Venkatachalam, P.

    2013-11-01

    Raman spectroscopy is a vibrational spectroscopic technique that can be used to optically probe the biomolecular changes associated with tumor progression. The aim of the present study is to investigate the biomolecular changes in chemopreventive response of prepared naringenin-loaded nanoparticles (NARNPs) relative to efficacy of free naringenin (NAR) during 7,12-dimethyl benz(a)anthracene (DMBA)-induced oral carcinogenesis by Fourier Transform Raman (FT-Raman) spectroscopy. Oral squamous cell carcinoma (OSCC) was developed in the buccal pouch of golden Syrian hamsters by painting with 0.5% DMBA in liquid paraffin three times a week for 14 weeks. Raman spectra differed significantly between the control and tumor tissues, with tumors showing higher percentage signals for nucleic acids, phenylalanine and tryptophan and a lower in the percentage of phospholipids. Moreover, oral administration of free NAR and NARNPs significantly increased phospholipids and decreased the levels of tryptophan, phenylalanine and nucleic acid contents. On a comparative basis, NARNPs was found to have a more potent antitumor effect than free NAR in completely preventing the formation of squamous cell carcinoma and in improving the biochemical status to a normal range in DMBA-induced oral carcinogenesis. The present study further suggest that Raman spectroscopy could be a valuable tool for rapid and sensitive detection of specific biomolecular changes in response to chemopreventive agents.

  16. Defect-induced Raman spectroscopy in single-layer graphene with boron and nitrogen substitutional defects by theoretical investigation

    Science.gov (United States)

    Jiang, Jie; Pachter, Ruth; Islam, Ahmad E.; Maruyama, Benji; Boeckl, John J.

    2016-10-01

    Although advances in heteroatom incorporation into the single-layer graphene lattice resulted in films with large carrier densities, careful characterization by Raman spectroscopy is important for assessment of the material's quality. We investigated theoretically I(D)/I(D‧) Raman intensity ratios induced by B- and N- substitutional doping, demonstrated to be consistent with measurements. Calculated Fermi level shifts showed that for a moderate doping density results are comparable to electrolyte gating, while analytical analysis of the electron-defect scattering provided insight into changes of cross-sections. Effects of doping density on the D band intensity and broadening were quantified, and will assist in graphene characterization.

  17. Raman mapping investigation of single-walled carbon nanotube bending in bottom-contact field-effect-transistor devices

    Science.gov (United States)

    Setiadi, Agung; Akai-Kasaya, Megumi; Kuwahara, Yuji

    2016-09-01

    We investigated the bending of single-walled carbon nanotubes (SWNTs) in bottom-contact SWNT devices using Raman mapping measurements. The height difference between the metal electrodes and the substrate caused the SWNTs to bend, down-shifting the G+ and G- bands of the bent SWNTs. No shifting of the G+ and G- bands was observed when flat electrodes were used. Shifting of the G+ and G- bands in SWNTs is strongly correlated to modulation of the Fermi level. We confirmed this effect by measuring the transport properties of the SWNT devices, which were in good agreement with the Raman measurement results.

  18. Acquisition of pro-oxidant activity of fALS-linked SOD1 mutants as revealed using circular dichroism and UV-resonance Raman spectroscopy

    Science.gov (United States)

    Fujimaki, Nobuhiro; Nishiya, Ken; Miura, Takashi; Nakabayashi, Takakazu

    2016-11-01

    The acquisition of pro-oxidant activity of the mutated form of human Cu, Zn-superoxide dismutase (SOD1) has been investigated to clarify the relationship between mutations in SOD1 and the pathogenesis of amyotrophic lateral sclerosis (ALS). Ala4 → Val (A4V) and Gly93 → Ala (G93A) mutants, which are representative ALS-linked SOD1 mutants, have been found to exhibit both the denaturation and the gain of pro-oxidant activity after incubation in the apo-form at a physiological condition of 37 °C and pH 7.4 and the rebinding of Cu2+. These characteristics are similar to those previously reported for the His43 → Arg (H43R) mutant. UV-resonance Raman spectra indicated that the coordination structure of the Cu-binding site catalyzing the oxidation reaction is the same among the denatured A4V, G93A, and H43R. Since wild-type SOD1 does not exhibit the denaturation in its apo-form at 37 °C and pH 7.4, the instability of the protein structure due to mutation can be considered as a significant factor that induces the denaturation and the subsequent pro-oxidant activity.

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

    Science.gov (United States)

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

    1999-01-19

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

  20. Investigation of porous media combustion by coherent anti-Stokes Raman spectroscopy

    Science.gov (United States)

    Weikl, M. C.; Tedder, S. A.; Seeger, T.; Leipertz, A.

    2010-10-01

    High efficiency, marginal pollutant emissions and low fuel consumption are desirable standards for modern combustion devices. The porous burner technology is a modern type of energy conversion with a strong potential to achieve these standards. However, due to the solid ceramic framework investigation of the thermodynamic properties of combustion, for example temperature, is difficult. The combustion process inside the ceramic structure of a porous burner was experimentally investigated by coherent anti-Stokes Raman spectroscopy (CARS). In this work, we present measurements using dual-pump dual-broadband CARS (DP-DBB-CARS) of temperature and species concentrations inside the reaction and flue gas zone of a porous media burner. Improvements to the setup and data evaluation procedure in contrast to previous measurements are discussed in detail. The results at varied thermal power and stoichiometry are presented. In addition, measurements at a range of radial positions inside a pore are conducted and correlated with the solid structure of the porous foam, which was determined by X-ray computer tomography.

  1. Raman Investigations to Identify Corallium rubrum in Iron Age Jewelry and Ornaments

    Directory of Open Access Journals (Sweden)

    Sebastian Fürst

    2016-06-01

    Full Text Available During the Central European Iron Age, more specifically between 600 and 100 BC, red precious corals (Corallium rubrum became very popular in many regions, often associated with the so-called (early Celts. Red corals are ideally suited to investigate several key questions of Iron Age research, like trade patterns or social and economic structures. While it is fairly easy to distinguish modern C. rubrum from bone, ivory or shells, archaeologists are confronted with ancient, hence altered, artifacts. Due to ageing processes, archaeological corals lose their intensive red color and shiny surface and can easily be confused with these other light colored materials. We propose a non-destructive multi-stage approach to identify archaeological corals amongst other biominerals used as ornament during the central European Iron Age with emphasis on optical examination and mobile Raman spectroscopy. Our investigations suggest that the noticeably high amount of misidentifications or at least uncertain material declarations existing in museums or even in the literature (around 15% could be overcome by the proposed approach. Furthermore, the range of different materials is higher than previously expected in archaeological research. This finding has implications for contemporary concepts of social structures and distribution networks during the Iron Age.

  2. Raman, SEM-EDS and XRPD investigations on pre-Columbian Central America "estucado" pottery

    Science.gov (United States)

    Casanova Municchia, Annalaura; Micheli, Mario; Ricci, Maria Antonietta; Toledo, Michelle; Bellatreccia, Fabio; Lo Mastro, Sergio; Sodo, Armida

    2016-03-01

    Seventeen different colored fragments from six selected pre-Columbian estucado ceramics from El Salvador have been investigated by Raman spectroscopy, scanning electron microscope coupled to an energy dispersive spectrometer (SEM/EDS) and X-ray powder diffraction (XRPD). The peculiarity of this kind of ceramics consist of the unusual presence of a white engobe, traditionally termed stucco, between the ceramic body and the decoration elements, hence the name estucado ceramics. The aim of this work was to study the unusual manufacturing technique and to identify the chemical composition of the engobe and of the pigment palette. The results showed that the stucco layer is made of clay (kaolinite) with traces of titanium oxide (anatase). Remarkably, this is the same composition of the white pigments used for the decoration layer, thus excluding an early use of natural titanium oxide as a white pigment in the estucado productions as suggested in previous investigations. Moreover, the presence of kaolinite and anatase both in the stucco and in the decoration layer suggests a cold-working or low temperature technique. The red, yellow and green decorations were realized by the use of natural ochre, while in all the blue and gray decorations Maya blue pigment was identified. Finally, an amorphous carbon pigment of vegetal origin and manganese oxide were used to obtain black pigments.

  3. Investigation of Subcombination Internal Resonances in Cantilever Beams

    Directory of Open Access Journals (Sweden)

    Haider N. Arafat

    1998-01-01

    Full Text Available Activation of subcombination internal resonances in transversely excited cantilever beams is investigated. The effect of geometric and inertia nonlinearities, which are cubic in the governing equation of motion, is considered. The method of time-averaged Lagrangian and virtual work is used to determine six nonlinear ordinary-differential equations governing the amplitudes and phases of the three interacting modes. Frequency- and force-response curves are generated for the case ω ≈ ω4 ≈ 1/2(ω2 + ω5. There are two possible responses: single-mode and three-mode responses. The single-mode periodic response is found to undergo supercritical and subcritical pitchfork bifurcations, which result in three-mode interactions. In the case of three-mode responses, there are conditions where the low-frequency mode dominates the response, resulting in high-amplitude quasiperiodic oscillations.

  4. Investigation of Relativistic Electron Resonance with EMIC Waves

    Science.gov (United States)

    Woodger, L. A.; Millan, R. M.; Denton, R. E.

    2008-12-01

    Wave-particle interaction of relativistic electrons with EMIC waves has been proposed as an important loss mechanism for radiation belt electrons (e.g. Thorne and Andreoli, 1980). Lorentzen et al (2000) and Millan et al (2002) suggested this mechanism to be responsible for dusk side relativistic electron precipitation (REP) detected by balloon borne instrumentation. This study will use the linear electromagnetic dispersion code WHAMP to investigate the effects of density, magnetic field, anisotropy, and heavy ions on the minimum resonance energy for relativistic electrons with EMIC waves. Results will be compared with observations of REP during the MAXIS balloon campaign on Jan. 19, 2000 and the MINIS balloon campaign on Jan. 21, 2005.

  5. Electron magnetic resonance investigation of chromium diffusion in yttria powders

    Energy Technology Data Exchange (ETDEWEB)

    Biasi, R.S. de, E-mail: rsbiasi@ime.eb.b [Secao de Engenharia Mecanica e de Materiais, Instituto Militar de Engenharia, Pr. General Tiburcio, 80, 22290-270 Rio de Janeiro, RJ (Brazil); Grillo, M.L.N., E-mail: mluciag@uerj.b [Instituto de Fisica, Universidade do Estado do Rio de Janeiro, 20550-013 Rio de Janeiro, RJ (Brazil)

    2010-03-01

    The electron magnetic resonance (EMR) technique was used to investigate the diffusion of chromium in yttria (Y{sub 2}O{sub 3}) powders. The EMR absorption intensity was measured for several annealing times and three different temperatures of isothermal annealing: 1273, 1323 and 1373 K. The activation temperature for diffusion, calculated from the experimental data using a theoretical model based on the Fick equation, was found to be E{sub A}=342+-5 kJ mol{sup -1}. This value is larger than the activation energy for the diffusion of chromium in rutile (TiO{sub 2}), periclase (MgO) and cobalt monoxide (CoO) and smaller than the activation energy for the diffusion of chromium in chrysoberyl (BeAl{sub 2}O{sub 4}).

  6. Investigating Effects of Proteasome Inhibitor on Multiple Myeloma Cells Using Confocal Raman Microscopy

    Directory of Open Access Journals (Sweden)

    Jeon Woong Kang

    2016-12-01

    Full Text Available Due to its label-free and non-destructive nature, applications of Raman spectroscopic imaging in monitoring therapeutic responses at the cellular level are growing. We have recently developed a high-speed confocal Raman microscopy system to image living biological specimens with high spatial resolution and sensitivity. In the present study, we have applied this system to monitor the effects of Bortezomib, a proteasome inhibitor drug, on multiple myeloma cells. Cluster imaging followed by spectral profiling suggest major differences in the nuclear and cytoplasmic contents of cells due to drug treatment that can be monitored with Raman spectroscopy. Spectra were also acquired from group of cells and feasibility of discrimination among treated and untreated cells using principal component analysis (PCA was accessed. Findings support the feasibility of Raman technologies as an alternate, novel method for monitoring live cell dynamics with minimal external perturbation.

  7. In-situ investigation of the calcination process of mixed oxide xerogels with Raman spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Panitz, J.C. [Paul Scherrer Inst. (PSI), Villigen (Switzerland)

    1997-06-01

    The controlled calcination of materials derived by sol-gel reactions is important for the evolution of the final structure. Raman spectroscopy is an ideal tool for the identification of surface species under in-situ conditions, as demonstrated in the following for the example of a molybdenum oxide-silica xerogel. Raman spectra of this particular sample were recorded at temperatures as high as 1173 K, and compared with those of a reference material.(author) 3 figs., 4 refs.

  8. Investigation of the thermal stability of phosphotungstic Wells-Dawson heteropoly-acid through in situ Raman spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Matkovic, Silvana Raquel, E-mail: matkovic@quimica.unlp.edu.ar [Centro de Investigacion y Desarrollo en Ciencias Aplicadas-Dr. Jorge J. Ronco. U.N.L.P., CONICET, CCT La Plata. Calle 47 N 257, B1900AJK La Plata, Buenos Aires (Argentina); Briand, Laura Estefania [Centro de Investigacion y Desarrollo en Ciencias Aplicadas-Dr. Jorge J. Ronco. U.N.L.P., CONICET, CCT La Plata. Calle 47 N 257, B1900AJK La Plata, Buenos Aires (Argentina); Banares, Miguel Angel [Laboratorio de Espectroscopia Catalitica, Instituto de Catalisis y Petroleoquimica, CSIC. Marie Curie 2, Cantoblanco, E-28049 Madrid (Spain)

    2011-11-15

    Highlights: {yields} Insitu Raman is used to monitor the thermal stability of Wells Dawson heteropolyacid. {yields} TP-Raman follows the gradual dehydration and the effect on the secondary structure. {yields} Wells-Dawson heteropolyacid does not decompose into Keggin and WO{sub 3} units below 600{sup o}C -- Abstract: The present investigation applies laser Raman spectroscopy under in situ conditions to obtain insights on the effect of the temperature on the molecular structure of the bulk phosphotungstic Wells-Dawson heteropoly-acid H{sub 6}P{sub 2}W{sub 18}O{sub 62}.xH{sub 2}O (HPA). The in situ temperature-programmed studies followed the evolution of phosphotungstic Wells-Dawson and Keggin heteropoly-acids along with tungsten trioxide under controlled atmosphere and temperature. The spectroscopic investigation of the Wells-Dawson HPA demonstrated that in situ Raman spectroscopy is a suitable technique to follow the effect of a gradual dehydration on the secondary structure of such a complex structure. Moreover, the absence of the signals belonging either to the Keggin or WO{sub 3} phases provides further evidence that the phosphotungstic heteropolyanion does not decomposes towards those materials at temperatures below 600 {sup o}C.

  9. FT-IR, Raman and thermoluminescence investigation of P 2O 5-BaO-Li 2O glass system

    Science.gov (United States)

    Ivascu, C.; Timar Gabor, A.; Cozar, O.; Daraban, L.; Ardelean, I.

    2011-05-01

    The 0.5P 2O 5· xBaO·(0.5- x) Li 2O glass system (0 ⩽ x ⩽ 0.5 mol%) is investigated by FT-IR, Raman and thermoluminescence as a possible dosimetic material. FT-IR and Raman spectra show structural network modifications with the composition variations of the studied glasses. The predominant absorption band from IR spectra is attributed to the symmetric stretching vibrations of P = O double bonds. Raman spectra of the studied glasses contain also typical phosphate glasses bands. Thus the band at ˜700 cm -1 is assigned to symmetric stretching vibrations of P-O-P groups and that from ˜1158 cm -1 is attributed to symmetric stretching motions of the non-bridging oxygen (NBO) atoms bonded to phosphorous atoms (PO 2) in phosphate tetrahedron. Finally FT-IR and Raman spectroscopies revealed a local network structure mainly based on Q 2 and Q 3 tetrahedrons connected by P-O-P linkages. Luminescence investigations show that by adding modifier oxides to phosphate glass dose dependent TL signals result upon irradiation. Thus P 2O 5-BaO-Li 2O glass system is a possible candidate material for dosimetry in the high dose range (>10 Gy).

  10. Suppression of resonance Raman scattering via ground state depletion towards sub-diffraction-limited label-free microscopy

    NARCIS (Netherlands)

    Rieger, S.; Fischedick, M.; Boller, K-J.; Fallnich, C.

    2016-01-01

    We report on the first experimental demonstration of the suppression of spontaneous Raman scattering via ground state depletion. The concept of Raman suppression can be used to achieve sub-diffraction-limited resolution in label-free microscopy by exploiting spatially selective signal suppression wh

  11. In situ noninvasive Raman microspectroscopic investigation of polychrome plasterworks in the Alhambra.

    Science.gov (United States)

    Dominguez-Vidal, Ana; de la Torre-Lopez, Maria Jose; Rubio-Domene, Ramon; Ayora-Cañada, Maria Jose

    2012-12-21

    A totally non-invasive in situ investigation in one of the main halls of the Palace of the Lions in the Alhambra (Granada, Spain) has been carried out. Analyses were made with a fiber-optic portable Raman microspectrometer placed on scaffolding platforms at a height of ca. 12 m above the ground level during the period of conservation works. The objects of this study are the decorated plasterworks in the seven vaults of the Hall of the Kings. Together with the results, the different practical problems related to the positioning of the instrumental setup and the influence of the local environment during the analysis are discussed. In general, high quality spectra were obtained despite difficulties for micro-probe head positioning and sometimes the vibrations of the corresponding scaffold. Different typical antiquity pigments have been identified: cinnabar, minium, carbon black and lapis lazuli. Furthermore, the luminescence pattern from lapis lazuli found in most blue decorations has allowed the establishment of the natural origin and provenance of the pigment. Apart from this natural lapis lazuli, synthetic ultramarine blue was also found in one of the vaults showing up a recent restoration. In addition, some degradation products of cinnabar and minium were identified, with the major advantage of providing real-time information to the conservators during their work.

  12. Investigation of Chinese archaic jade by PIXE and {mu}Raman spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Chen, T.H. [UMR 171 du CNRS, Centre de Recherche et de Restauration des Musees de France, Palais du Louvre, Porte des Lions, 14 Quai Francois Mitterrand, 75001, Paris (France); Ecole Doctorale MMRMM, Universite de Versailles - St Quentin en Yvelines, 45 Avenue des Etats Unis, 78035, Versailles Cedex (France); Calligaro, T.; Pages-Camagna, S.; Menu, M. [UMR 171 du CNRS, Centre de Recherche et de Restauration des Musees de France, Palais du Louvre, Porte des Lions, 14 Quai Francois Mitterrand, 75001, Paris (France)

    2004-07-01

    External-beam particle-induced X-ray emission (PIXE) and {mu}Raman spectrometry were used for elemental and structural studies of Chinese archaic nephrite jades of the Guimet Asian Museum in Paris in a non-destructive way. Nephrite is a variety of tremolite-actinolite of the amphibole group, with variable iron and magnesium contents. In the present work, in addition to identification of materials, the cation distribution in nephrite was investigated. Cation order-disorder is related to thermodynamic properties of minerals, and hence associated with geological conditions of the mineral formation. Besides, it plays an important role in the mechanism of coloration. So far, little work has been done on the cation distribution in nephrite. We thus initiated this research expecting to answer open questions concerning art and archaeological issues such as jade provenance and colour. The OH stretching vibration band of nephrite, depending on the electronegativity of the bonded cations, presents a fine structure. The study of this fine structure, together with the total cation content obtained by PIXE, allows estimation of the cation distribution in nephrite. In this study, six jade artefacts, dated from the Neolithic period to the Han dynasty (about 3000 BC to 220 AD), with diverse colours including white, yellow-green, green, dark green and black, were analysed. The data obtained permits establishing a geological database for determination of nephrite provenance and explaining the correlation between colour and cation distribution. (orig.)

  13. Investigation of Chinese archaic jade by PIXE and μRaman spectrometry

    Science.gov (United States)

    Chen, T.-H.; Calligaro, T.; Pagès-Camagna, S.; Menu, M.

    External-beam particle-induced X-ray emission (PIXE) and μRaman spectrometry were used for elemental and structural studies of Chinese archaic nephrite jades of the Guimet Asian Museum in Paris in a non-destructive way. Nephrite is a variety of tremolite-actinolite of the amphibole group, with variable iron and magnesium contents. In the present work, in addition to identification of materials, the cation distribution in nephrite was investigated. Cation order-disorder is related to thermodynamic properties of minerals, and hence associated with geological conditions of the mineral formation. Besides, it plays an important role in the mechanism of coloration. So far, little work has been done on the cation distribution in nephrite. We thus initiated this research expecting to answer open questions concerning art and archaeological issues such as jade provenance and colour. The OH stretching vibration band of nephrite, depending on the electronegativity of the bonded cations, presents a fine structure. The study of this fine structure, together with the total cation content obtained by PIXE, allows estimation of the cation distribution in nephrite. In this study, six jade artefacts, dated from the Neolithic period to the Han dynasty (about 3000 BC to 220 AD), with diverse colours including white, yellow-green, green, dark green and black, were analysed. The data obtained permits establishing a geological database for determination of nephrite provenance and explaining the correlation between colour and cation distribution.

  14. Internal structure changes in bleached black human hair resulting from chemical treatments: A Raman spectroscopic investigation

    Science.gov (United States)

    Kuzuhara, Akio

    2014-11-01

    In order to investigate in detail the influence of chemical treatments (reduction, hydrolyzed eggwhite protein (HEWP) treatment, and oxidation) on damaged hair keratin fibers, the structure of cross-sections at various depths of excessively bleached (damaged) black human hair resulting from a permanent waving process was directly analyzed using Raman spectroscopy. It was found that L-cysteine (CYS) largely reacted with the gauche-gauche-gauche (GGG) conformation of disulfide (-SS-) groups (while CYS did not react with the trans-gauche-trans (TGT) conformation). In particular, not only the GGG content, but also the cysteic acid content existing throughout the cortex region of the excessively bleached human hair remarkably decreased by performing the oxidation process after reduction. On the other hand, the GGG content of the excessively bleached black human hair increased, while the TGT content decreased by performing the oxidation process after reduction and then HEWP treatment processes. From these experiments, the authors concluded that some of the keratin associated protein (KAP), which has a rich -SS- content and cysteic acid content was eluted from the cortex region along with the disconnection of -SS- groups, thereby leading to the remarkable reduction in the reconnection of -SS- groups of the excessively bleached black human hair after the permanent waving process (the reduction and oxidation processes). Also, the authors concluded that the HEWP treatment process in the permanent waving process caused the reconstruction of the KAP, thereby contributing to the acceleration of the reconnection of -SS- groups during the oxidation process.

  15. Color change of Ruby investigated by Raman and UV-vis

    Science.gov (United States)

    Breckling, Sean; Zou, Ying; Ray, Shishir; Buroker, Larry; Sen, Somaditya; Williamsen, Mark; Guptasarma, Prasenjit

    2009-03-01

    The origin of a distinctive red color in Ruby (Al2O3:Cr^3+) continues to be a fundamental unsolved question [1]. We report the synthesis of a series of samples of 2% Cr2O3 by solid state reaction [2] at temperatures varying between 900^o and 1300^oC. We observe a visible change in color at every stage, from light green, to grey, and to pink, indicating progressive incorportation of Cr^3+ ions into the Al2O3 lattice. We report further investigations of x-ray diffraction analysis, Raman and UV-visible spectroscopy, and correlate the observed color changes with the evolution of vibration modes of the cage around CrO6 and band-gap states resulting from Cr incorporation. We also plan to report results from single crystals grown using a floating zone. [1]J.M. Garcia-Lastra, M.T. Barriuso, J.A. Aramburu and M. Moreno, Phys. Rev. B 72(2005)113104 [2]L.W. Finger and R.M. Hazen, J. Appl. Phys. 49(1978)5823

  16. Investigation of a CO2 round jet using an integrated Raman-LDA system

    Science.gov (United States)

    Ballal, D. R.; Chen, T. H.

    1987-01-01

    An experimental investigation of a CO2 round jet spreading into a low-turbulence, coflowing airstream has been performed. Velocity and concentration properties in axial (x/D up to 20) and radial (r/D up to + or - 2.5) planes have been measured using an integrated Raman-LDA optical diagnostic system. These properties include mean value, fluctuating intensity, Reynolds shear stress, skewness, kurtosis, turbulent kinetic energy, joint pdfs, turbulent scalar fluxes and turbulent Schmidt number. From these quantitative measurements, and available flow visualization evidence, a three-region description of the jet structure is developed. It is found that: (1) in the instability dominated region, circumferential vortex rings are formed around the jet boundary; (2) in the near-field region, pairing, growth, coalescence and stretching processes are important; and (3) these processes ultimately produce the small-scale turbulence of the far-field region. Furthermore, measured peak values of turbulent fluctuations confirm the coalescence and streching of vortices, skewness and kurtosis data highlight the production of small-scale turbulence, and measurements of joint pdfs suggest that radial flow transports the jet concentration outward. Finally, concentration spreads faster than velocity, resulting in a turbulent Schmidt number below unity. A comparison of these results with those of other workers is made and the outcome is discussed.

  17. Resonance Raman Spectra of Five-Coordinate Heme-Nitrosyl Cytochromes c': Effect of the Proximal Heme-NO Environment.

    Science.gov (United States)

    Servid, Amy E; McKay, Alison L; Davis, Cherry A; Garton, Elizabeth M; Manole, Andreea; Dobbin, Paul S; Hough, Michael A; Andrew, Colin R

    2015-06-02

    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.

  18. Probing the pigment binding sites in LHCII with resonance Raman spectroscopy: The effect of mutations at S123.

    Science.gov (United States)

    Kish, Elizabeth; Wang, Ke; Llansola-Portoles, Manuel J; Ilioaia, Cristian; Pascal, Andrew A; Robert, Bruno; Yang, Chunhong

    2016-09-01

    Resonance Raman spectroscopy was used to evaluate the structure of light-harvesting chlorophyll (Chl) a/b complexes of photosystem II (LHCII), reconstituted from wild-type (WT) and mutant apoproteins over-expressed in Escherichia coli. The point mutations involved residue S123, exchanged for either P (S123P) or G (S123G). In all reconstituted proteins, lutein 2 displayed a distorted conformation, as it does in purified LHCII trimers. Reconstituted WT and S123G also exhibited a conformation of bound neoxanthin (Nx) molecules identical to the native protein, while the S123P mutation was found to induce a change in Nx conformation. This structural change of neoxanthin is accompanied by a blue shift of the absorption of this carotenoid molecule. The interactions assumed by (and thus the structure of the binding sites of) the bound Chls b were found identical in all the reconstituted proteins, and only marginally perturbed as compared to purified LHCII. The interactions assumed by bound Chls a were also identical in purified LHCII and the reconstituted WT. However, the keto carbonyl group of one Chl a, originally free-from-interactions in WT LHCII, becomes involved in a strong H-bond with its environment in LHCII reconstituted from the S123P apoprotein. As the absorption in the Qy region of this protein is identical to that of the LHCII reconstituted from the WT apoprotein, we conclude that the interaction state of the keto carbonyl of Chl a does not play a significant role in tuning the binding site energy of these molecules.

  19. A resonance Raman enhancement mechanism for axial vibrational modes in the pyridine adduct of myoglobin proximal cavity mutant (H93G).

    Science.gov (United States)

    Franzen, Stefan; Brown, Derek; Gaff, John; Delley, B

    2012-09-06

    The proximal cavity mutant of myoglobin consists of a mutation of the proximal histidine to glycine (H93G), which permits exogenous ligands to bind to the heme iron. A non-native pyridine ligand can ligate to the heme to yield a five-coordinate adduct, H93G(Pyr), that cannot be formed freely in solution since the six-coordinate bis-pyridine adduct is more stable than the five-coordinate adduct. We have used resonance Raman spectroscopy in the Soret band region of the heme to study the enhancement of axial vibrations of bound pyridine in the H93G(Pyr) adduct. The observation that the pyridine ring breathing mode (ν(1)) and the symmetric ring stretching (ν(3)) modes are enhanced under these conditions is explained by a computational approach that shows that coupling of the π-system of the heme with the p-orbitals of the pyridine is analogous to π-backbonding in diatomic ligand adducts of heme proteins. The result has the broader significance that it suggests that the resonance enhancement of pyridine modes could be an important aspect of Raman scattering of pyridine on conducting surfaces such as those studied in surface enhanced Raman scattering experiments.

  20. Dynamics of the [4Fe-4S] cluster in Pyrococcus furiosus D14C ferredoxin via nuclear resonance vibrational and resonance Raman spectroscopies, force field simulations, and density functional theory calculations.

    Science.gov (United States)

    Mitra, Devrani; Pelmenschikov, Vladimir; Guo, Yisong; Case, David A; Wang, Hongxin; Dong, Weibing; Tan, Ming-Liang; Ichiye, Toshiko; Jenney, Francis E; Adams, Michael W W; Yoda, Yoshitaka; Zhao, Jiyong; Cramer, Stephen P

    2011-06-14

    We have used (57)Fe nuclear resonance vibrational spectroscopy (NRVS) to study oxidized and reduced forms of the [4Fe-4S] cluster in the D14C variant ferredoxin from Pyrococcus furiosus (Pf D14C Fd). To assist the normal-mode assignments, we conducted NRVS with D14C ferredoxin samples with (36)S substituted into the [4Fe-4S] cluster bridging sulfide positions, and a model compound without ligand side chains, (Ph(4)P)(2)[Fe(4)S(4)Cl(4)]. Several distinct regions of NRVS intensity are identified, ranging from "protein" and torsional modes below 100 cm(-1), through bending and breathing modes near 150 cm(-1), to strong bands from Fe-S stretching modes between 250 and ∼400 cm(-1). The oxidized ferredoxin samples were also investigated by resonance Raman (RR) spectroscopy. We found good agreement between NRVS and RR frequencies, but because of different selection rules, the intensities vary dramatically between the two types of spectra. The (57)Fe partial vibrational densities of states for the oxidized samples were interpreted by normal-mode analysis with optimization of Urey-Bradley force fields for local models of the [4Fe-4S] clusters. Full protein model calculations were also conducted using a supplemented CHARMM force field, and these calculations revealed low-frequency modes that may be relevant to electron transfer with Pf Fd partners. Density functional theory (DFT) calculations complemented these empirical analyses, and DFT was used to estimate the reorganization energy associated with the [Fe(4)S(4)](2+/+) redox cycle. Overall, the NRVS technique demonstrates great promise for the observation and quantitative interpretation of the dynamical properties of Fe-S proteins.

  1. Dynamics of the [4Fe-4S] Cluster in Pyrococcus furiosus D14C Ferredoxin via Nuclear Resonance Vibrational and Resonance Raman Spectroscopies, Force Field Simulations, and Density Functional Theory Calculations

    Science.gov (United States)

    Mitra, Devrani; Pelmenschikov, Vladimir; Guo, Yisong; Case, David A.; Wang, Hongxin; Dong, Weibing; Tan, Ming-Liang; Ichiye, Toshiko; Jenney, Francis E.; Adams, Michael W. W.; Yoda, Yoshitaka; Zhao, Jiyong; Cramer, Stephen P.

    2011-01-01

    We have used 57Fe nuclear resonance vibrational spectroscopy (NRVS) to study oxidized and reduced forms of the [4Fe-4S] cluster in the D14C variant ferredoxin from Pyrococcus furiosus (Pf D14C Fd). To assist the normal mode assignments, we recorded the NRVS of D14C ferredoxin samples with 36S substituted into the [4Fe-4S] cluster bridging sulfide positions, and a model compound without ligand side chains: (Ph4P)2[Fe4S4Cl4]. Several distinct regions of NRVS intensity are identified, ranging from `protein' and torsional modes below 100 cm−1, through bending and breathing modes near 150 cm−1, to strong bands from Fe-S stretching modes between 250 cm−1 and ~400 cm−1. The oxidized ferredoxin samples were also investigated by resonance Raman (RR) spectroscopy. We found good agreement between NRVS and RR frequencies, but because of different selection rules, the intensities vary dramatically between the two types of spectra. The 57Fe partial vibrational densities of states (PVDOS) for the oxidized samples were interpreted by normal mode analysis with optimization of Urey-Bradley force fields for local models of the [4Fe-4S] clusters. Full protein model calculations were also conducted using a supplemented CHARMM force field, and these calculations revealed low frequency modes that may be relevant to electron transfer with Pf Fd partners. Density functional theory (DFT) calculations complemented these empirical analyses, and DFT was used to estimate the reorganization energy associated with the [Fe4S4]2+/1+ redox cycle. Overall, the NRVS technique demonstrates great promise for the observation and quantitative interpretation of the dynamical properties of Fe-S proteins. PMID:21500788

  2. Magnetic resonance imaging (MRI): A review of genetic damage investigations.

    Science.gov (United States)

    Vijayalaxmi; Fatahi, Mahsa; Speck, Oliver

    2015-01-01

    Magnetic resonance imaging (MRI) is a powerful, non-invasive diagnostic medical imaging technique widely used to acquire detailed information about anatomy and function of different organs in the body, in both health and disease. It utilizes electromagnetic fields of three different frequency bands: static magnetic field (SMF), time-varying gradient magnetic fields (GMF) in the kHz range and pulsed radiofrequency fields (RF) in the MHz range. There have been some investigations examining the extent of genetic damage following exposure of bacterial and human cells to all three frequency bands of electromagnetic fields, as used during MRI: the rationale for these studies is the well documented evidence of positive correlation between significantly increased genetic damage and carcinogenesis. Overall, the published data were not sufficiently informative and useful because of the small sample size, inappropriate comparison of experimental groups, etc. Besides, when an increased damage was observed in MRI-exposed cells, the fate of such lesions was not further explored from multiple 'down-stream' events. This review provides: (i) information on the basic principles used in MRI technology, (ii) detailed experimental protocols, results and critical comments on the genetic damage investigations thus far conducted using MRI equipment and, (iii) a discussion on several gaps in knowledge in the current scientific literature on MRI. Comprehensive, international, multi-centered collaborative studies, using a common and widely used MRI exposure protocol (cardiac or brain scan) incorporating several genetic/epigenetic damage end-points as well as epidemiological investigations, in large number of individuals/patients are warranted to reduce and perhaps, eliminate uncertainties raised in genetic damage investigations in cells exposed in vitro and in vivo to MRI.

  3. Raman investigation on the behavior of parasibirskite CaHBO3 at high pressure

    Science.gov (United States)

    Goryainov, S. V.; Pan, Y.; Smirnov, M. B.; Sun, W.; Mi, J.-X.

    2017-02-01

    Knowledge about the stability of hydrous borates and borosilicates at high pressures are of critical importance to our understanding on the boron geochemical cycle. Raman spectroscopic measurements of parasibirskite CaHBO3, containing the [BO2(OH)] groups, have been made to pressures up to 5.4 GPa. The Raman data show that a progressive structural evolution from ambient pressure to 5.4 GPa can be accounted for by the same monoclinic phase P21/m, where the splitting of several Raman bands observed at some pressures is interpreted as the effect of the complex disordering in the H-bond network that has bifurcated H-bonds and ½-occupied H sites. There is no unambiguous evidence for phase transition to the ordered P21 monoclinic phase predicted by first-principles calculations at T = 0 K (W. Sun et al., Can. Miner., 2011). On the contrary, the disordering of parasibirskite, evidenced by the widening and attenuating Raman spectra, increases markedly at high pressures above 4.5 GPa that results in incipient amorphization. Comparison of theoretical (lattice-dynamical) and experimental Raman spectra allows the reliable interpretation of almost all observed bands. The strongest symmetric B-O stretching band v1 at the wavenumber 908 cm- 1, which is split into a doublet at high pressures, exhibits a shift rate of 4.22 cm- 1/GPa for the main component.

  4. Experimental and theoretical investigation of pressure-dependent Raman spectra of triaminotrinitrobenzene (TATB) at high pressures

    Science.gov (United States)

    Landerville, Aaron C.; Crowhurst, Jonathan C.; Grant, Christian D.; Zaug, Joseph M.; Oleynik, Ivan

    2017-01-01

    The experimental pressure dependent Raman spectra of triamino-trinitrobenzene (TATB) are determined up to 24.5 GPa, and compared with those obtained using density functional theory (DFT) up to 27 GPa. The density functional theory calculations include the Grimme empirical van der Waals correction, as well as corrections for both thermal and zero-point energy contributions to pressure. DFT-predicted crystal structure of TATB at ambient conditions, the equation of state, and Raman spectra up to 24.5 GPa are in good agreement with experiment. Pressure-dependence of specific vibrational modes is discussed in detail. Further, the comparison of experimental and calculated Raman spectra of TATB offers evidence that no first-order polymorphic phase transition occurs at least up to 27 GPa.

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

    Energy Technology Data Exchange (ETDEWEB)

    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. Heart valve disease: investigation by cardiovascular magnetic resonance

    Directory of Open Access Journals (Sweden)

    Myerson Saul G

    2012-01-01

    Full Text Available Abstract Cardiovascular magnetic resonance (CMR has become a valuable investigative tool in many areas of cardiac medicine. Its value in heart valve disease is less well appreciated however, particularly as echocardiography is a powerful and widely available technique in valve disease. This review highlights the added value that CMR can bring in valve disease, complementing echocardiography in many areas, but it has also become the first-line investigation in some, such as pulmonary valve disease and assessing the right ventricle. CMR has many advantages, including the ability to image in any plane, which allows full visualisation of valves and their inflow/outflow tracts, direct measurement of valve area (particularly for stenotic valves, and characterisation of the associated great vessel anatomy (e.g. the aortic root and arch in aortic valve disease. A particular strength is the ability to quantify flow, which allows accurate measurement of regurgitation, cardiac shunt volumes/ratios and differential flow volumes (e.g. left and right pulmonary arteries. Quantification of ventricular volumes and mass is vital for determining the impact of valve disease on the heart, and CMR is the 'Gold standard' for this. Limitations of the technique include partial volume effects due to image slice thickness, and a low ability to identify small, highly mobile objects (such as vegetations due to the need to acquire images over several cardiac cycles. The review examines the advantages and disadvantages of each imaging aspect in detail, and considers how CMR can be used optimally for each valve lesion.

  7. A micro-Raman spectroscopic investigation of leukemic U-937 cells in aged cultures

    Science.gov (United States)

    Fazio, Enza; Trusso, Sebastiano; Franco, Domenico; Nicolò, Marco Sebastiano; Allegra, Alessandro; Neri, Fortunato; Musolino, Caterina; Guglielmino, Salvatore P. P.

    2016-04-01

    Recently it has been shown that micro-Raman spectroscopy combined with multivariate analysis is able to discriminate among different types of tissues and tumoral cells by the detection of significant alterations and/or reorganizations of complex biological molecules, such as nucleic acids, lipids and proteins. Moreover, its use, being in principle a non-invasive technique, appears an interesting clinical tool for the evaluation of the therapeutical effects and of the disease progression. In this work we analyzed molecular changes in aged cultures of leukemia model U937 cells with respect to fresh cultures of the same cell line. In fact, structural variations of individual neoplastic cells on aging may lead to a heterogeneous data set, therefore falsifying confidence intervals, increasing error levels of analysis and consequently limiting the use of Raman spectroscopy analysis. We found that the observed morphological changes of U937 cells corresponded to well defined modifications of the Raman contributions in selected spectral regions, where markers of specific functional groups, useful to characterize the cell state, are present. A detailed subcellular analysis showed a change in cellular organization as a function of time, and correlated to a significant increase of apoptosis levels. Besides the aforementioned study, Raman spectra were used as input for principal component analysis (PCA) in order to detect and classify spectral changes among U937 cells.

  8. Investigation of Raman chemical imaging for detection of Lycopene changes in tomatoes during postharvest ripening

    Science.gov (United States)

    Lycopene is a major carotenoid in tomatoes and detecting changes in lycopene content can be used to monitor the ripening of tomatoes. Raman chemical imaging is a new technique that shows promise for mapping constituents of interest in complex food matrices. In this study, a benchtop point-scanning...

  9. An investigation of different Raman amplification configurations in 160 Gbit/s transmission

    DEFF Research Database (Denmark)

    Xu, Zhenbo; Rottwitt, Karsten; Jeppesen, Palle

    2003-01-01

    In this paper, different Raman pumping schemes are numerically simulated with newly developed super large core area fiber (SLA) at 160 Gbit/s single channel. We find that the optimal scheme is inverse dispersion fiber pump scheme. Transmission distance of 1700 km is predicted and shorter pulse...

  10. In operando Raman spectroscopy as a tool for investigation of solid oxide electrodes

    DEFF Research Database (Denmark)

    Traulsen, Marie Lund; Holtappels, Peter; Walker, Robert

    potential of combining in operando Raman spectroscopy with electrochemical characterisation, DTU Energy Conversion decided in 2014 to invest in a set-up dedicated to this purpose, At the end of the talk a short description will be given of this set-up, and the future plans will be described for combined...

  11. Raman spectroscopic investigations on the interactions of gastric cancer cells with 5-fluorouracil

    Institute of Scientific and Technical Information of China (English)

    Jianyu Guo; Weiying Cai; Jipeng Yang; Zhenrong Sun

    2008-01-01

    To study the efficacy and side effects of antitumor drug by the method of Raman spectroscopy, the cancerous (SGC-7901) and normal (GES-1) gastric cells were treated with 0, 25-, 100-, and 200-mg/L 5-fluorouracil (5-Fu) for 24 h, respectively, then Raman spectra of cells were recorded. The excitation wavelength was 514.5 nm and the Raman spectra in the region of 500 - 1800 cm-1 were recorded. For the gastric cancer cells, as the concentration of 5-Fu increases, the band at 1094 cm-1 attributed to the symmetric stretching vibration mode of PO2- in the DNA backbone gradually decreases, and the intensity ratio of the band at 1315 cm-1 to that at 1340 cm-1 (I1315/I1340) shows the ascending trend, and the ratio of the band area at 1655 cm-1 to that at 1450 cm-1 (A1655/A1450) shows the slight ascending trend. For the normal gastric cells, these peaks also appear changes, however, the changes are weaker than those for the cancer cells. In SGC-7901 cells, 5-Fu can interfere with the DNA synthesis and result in the reduction of the DNA content. Besides, it can affect the unsaturation degree of the hydrocarbon chains and alter the external environment of guanine and adenine residues in cancer cells. The changes of Raman spectra for normal gastric cells reveal the side effect of 5-Fu.

  12. Investigation of surface enhanced Raman spectroscopy for hemozoin detection in malaria diagnosis

    Science.gov (United States)

    Chen, Keren; Xiong, Aoli; Yuen, Clement; Preiser, Peter; Liu, Quan

    2016-03-01

    We report two methods of surface enhanced Raman spectroscopy (SERS) for hemozoin detection in malaria infected human blood. In the first method, silver nanoparticles were synthesized separately and then mixed with lysed blood; while in the second method, silver nanoparticles were synthesized directly inside the parasites of Plasmodium falciparum.

  13. The effect of an anti-hydrogen bond on Fermi resonance:A Raman spectroscopic study of the Fermi doublet v1-v12 of liquid pyridine

    Institute of Scientific and Technical Information of China (English)

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

    2012-01-01

    The effects of an anti-hydrogen bond on the v1-v12 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 v1 and triangle mode v12 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 thev1-v12 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 v1-v12 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 v1 - v12 FR of pyridine is given.

  14. Investigation of a delayed feedback controller of MEMS resonators

    KAUST Repository

    Masri, Karim M.

    2013-08-04

    Controlling mechanical systems is an important branch of mechanical engineering. Several techniques have been used to control Microelectromechanical systems (MEMS) resonators. In this paper, we study the effect of a delayed feedback controller on stabilizing MEMS resonators. A delayed feedback velocity controller is implemented through modifying the parallel plate electrostatic force used to excite the resonator into motion. A nonlinear single degree of freedom model is used to simulate the resonator response. Long time integration is used first. Then, a finite deference technique to capture periodic motion combined with the Floquet theory is used to capture the stable and unstable periodic responses. We show that applying a suitable positive gain can stabilize the MEMS resonator near or inside the instability dynamic pull in band. We also study the stability of the resonator by tracking its basins of attraction while sweeping the controller gain and the frequency of excitations. For positive delayed gains, we notice significant enhancement in the safe area of the basins of attraction. Copyright © 2013 by ASME.

  15. Hydration of human nails investigated by NIR-FT-Raman spectroscopy.

    Science.gov (United States)

    Wessel, S; Gniadecka, M; Jemec, G B; Wulf, H C

    1999-08-17

    The human nail, although it is usually stable against outer influences, becomes soft and flexible after soaking in water. Frequent washing increases brittleness of nails. Hydration of nails is thought to be the most important factor influencing the physical properties of nails and possibly acts through changes in keratin structure. Here NIR-FT-Raman has been used to examine molecular structural changes of intact moisten nails. Raman spectra were obtained both in vitro from nail samples and in vivo before and after soaking in water. The water uptake of normal nail samples during the first 15 min was reflected in the increasing intensity ratio of the nu(OH)/nu(CH(2)) bands. A saturating effect appeared soon after 10 min which is explained by a defined water holding capacity. R(nu) representation of the low frequency range of the Raman spectra showed that mainly bound water is found both in dry and in wet nails. This implies water-protein interaction. Protein backbone vibration at 932 cm(-1) indicating alpha-helical proteins increased in intensity in the wet nails. The nu(S-S) which is sensitive to changes in conformation of proteins showed a 4% higher intensity. Additional protein-water interactions could lead to a slight change of the dihedral angle of the C-S-S-C bonds and to geometric changes in coiling behavior of the alpha-helical protein. Suggesting a separation between matrix proteins and fiber proteins giving them a greater freedom of flexibility. The in vivo spectra detected from the distal part of the nail resembled spectra in vitro. Raman spectra of the proximal part of the nail showed that it was fully saturated with water. The proximal part of the nail did not show changes in water content and protein structure during nail moisturizing in the Raman spectra. Our results suggest that the softening of the nail following hydration may be due to changed matrix protein molecular structure induced by water.

  16. Raman spectra investigation of the defects of chemical vapor deposited multilayer graphene and modified by oxygen plasma treatment

    Science.gov (United States)

    Li, Zongyao; Xu, Yu; Cao, Bing; Qi, Lin; He, Shunyu; Wang, Chinhua; Zhang, Jicai; Wang, Jianfeng; Xu, Ke

    2016-11-01

    Graphene, a two dimensional material, can be modified its properties by defects engineering. Here, we present Raman spectra studies of the multilayer graphene (MLG) fabricated by low-pressure chemical vapor deposition over copper foil, and report that the defects of MLG can be controlled by adjusting methane concentration. Moreover, MLG can be changed from metallic to semiconductoring properties by using oxygen plasma treatment, and we investigate the defects evolution of the graphene after exposing to oxygen plasma by Raman spectra. Our results indicate that the amount of defects in graphene can be changed by regulating the methane concentration and oxygen plasma exposure times, but the primary type of defect in MLG is still boundary-like defect. It is valuable for understanding the physics of defects evolution through artificially generated defects, and such defect engineering will greatly open up the future application of the novel material.

  17. The investigation on the pressure-induced phase transition in linoleic acid by in situ Raman spectroscopy

    Science.gov (United States)

    Ya, Fan; Jing, Zhou; Da-Peng, Xu

    2014-08-01

    With diamond anvil cell as a high-pressure apparatus, the in situ Raman spectra of linoleic acid from normal pressure to 1.29 GPa were measured to investigate the effect of pressure on the structural changes. In the pressure ranges of 0.07-0.12 GPa and 0.31-0.53 GPa, the significant changes in Raman spectra show that linoleic acid undergoes two pressure-induced phase transitions. Spectral analysis indicates that the polymethylene chain of linoleic acid molecule transforms from the disordered gauche conformation to the ordered trans conformation in the range of 0.07-0.12 GPa. And the polymethylene chain of linoleic acid molecule remains the ordered trans conformation whereas the conformation of the olefin group significantly changes and the degree of conformational order increases in the range of 0.31-0.53 GPa. The pressure-induced phase transitions in linoleic acid are reversible.

  18. Investigating the structural changes of β-amyloid peptide aggregation using attenuated-total-reflection surface-enhanced Raman spectroscopy

    Science.gov (United States)

    Chiu, K.-C.; Yu, L.-Y.; Yih, J.-N.; Chen, S.-J.

    2007-02-01

    This study utilizes a surface-enhanced Raman spectroscopy (SERS) based on the attenuated-total-reflection (ATR) method to investigate that the structural information of the biomolecular monolayer on sensing surface can be dynamically observed with a higher signal-to-noise ratio signal. The secondary structures of long oligonucleotides and their influence on the DNA hybridization on the sensing surface are investigated. The SERS spectrum provides the structural information of the oligonucleotides with the help of a silver colloidal nanoparticle monolayer by control of the size and distribution of the nanoparticles adapted as a Raman active substrate. It is found that the ring-breathing modes of adenine, thymine, guanine, and cytosine in Raman fingerprint associated with three 60mer oligonucleotides with prominent secondary structures are lower than those observed for the two oligonucleotides with no obvious secondary structures. It is also determined that increasing the DNA hybridization temperature from 35°C to 45°C reduces secondary structure effects. The ATR-SERS biosensing technique will be used to provide valuable structural information regarding the short-term reversible interactions and long-term polymerization events in the Aβ aggregates on the sensing surface.

  19. Indirect exciton luminescense and Raman scattering in CdI 2

    Science.gov (United States)

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

    1981-06-01

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

  20. Efficiency Investigation of Subwoofer Driven Around Resonance Frequency

    DEFF Research Database (Denmark)

    Thydal, Tobias; Iversen, Niels Elkjær; Knott, Arnold

    2017-01-01

    The need for efficient portable speaker systems has increased tremendously over the past 10 years. The batteries, amplifiers and filtering has all seen great improvements in efficiency leaving the speakers units as the most inefficient part of the system, mainly due to the large amounts of current...... drawn that ends up being dissipated as heat in the voice coil. This paper will look at how you can design a speaker system to take advantage of the resonance of a speaker unit, since that is where the unit is most efficient and draws the least current. A subwoofer speaker system will be designed...... with focus on only driving the speaker units near their resonance frequency. The tests found that with modern DSP it was rather simple to design a speaker system that operate in a very narrow frequency band around the speaker units’ resonance frequencies, which in turn ensured a very small current draw...

  1. Experimental Investigation of 'Transonic Resonance' with Convergent-Divergent Nozzles

    Science.gov (United States)

    Zaman, K. B. M. Q.; Dahl, M. D.; Bencic, T. J.; Zaman, Khairul (Technical Monitor)

    2001-01-01

    Convergent-divergent nozzles, when run at pressure ratios lower than the design value, often undergo a flow resonance accompanied by the emission of acoustic tones. The phenomenon, different in characteristics from conventional 'screech' tones, has been studied experimentally. Unlike screech, the frequency increases with increasing supply pressure. There is a 'staging' behavior; 'odd harmonic' stages resonate at lower pressures while the fundamental occurs in a range of higher pressures corresponding to a fully expanded Mach number (M(sub j)) around unity. The frequency (f(sub N)) variation with M(sub j) depends on the half angle-of-divergence (theta) of the nozzle. At smaller theta, the slope of f(sub N) versus M(sub j) curve becomes steeper. The resonance involves standing waves and is driven by unsteady shock/boundary layer interaction. The distance between the foot of the shock and the nozzle exit imposes the lengthscale (L'). The fundamental corresponds to a quarterwave resonance, the next stage at a lower supply pressure corresponds to a three-quarter-wave resonance, and so on. The principal trends in the frequency variation are explained simply from the characteristic variation of the length-scale L'. Based on the data, correlation equations are provided for the prediction of f(sub N). A striking feature is that tripping of the boundary layer near the nozzle's throat tends to suppress the resonance. In a practical nozzle a tendency for the occurrence of the phenomenon is thought to be a source of 'internal noise'; thus, there is a potential for noise benefit simply by appropriate boundary layer tripping near the nozzle's throat.

  2. Raman scattering investigation of the quasi-one-dimensional superconductor Ta₄Pd₃Te₁₆.

    Science.gov (United States)

    Chen, D; Richard, P; Song, Z-D; Zhang, W-L; Wu, S-F; Jiao, W H; Fang, Z; Cao, G-H; Ding, H

    2015-12-16

    We have performed polarized Raman scattering measurements on the newly discovered superconductor Ta4Pd3Te16 (T(c) = 4.6 K). We observe 28 out of 33 Raman active modes, with frequencies in good accordance with first-principles calculations. Although most of the phonons observed vary only slightly with temperature and do not exhibit any asymmetric profile that would suggest strong electron-phonon coupling, the linewidth of the A(g) phonon mode at 89.9 cm(-1) shows an unconventional increase with temperature decreasing, which is possibly due to a charge-density-wave transition or the emergence of charge-density-wave fluctuations below a temperature estimated to fall in the 140-200 K range.

  3. Investigating the Microstructure of Slenderized Wool Fibers at Different Stretching Ratios by Raman Spectroscopy

    Institute of Scientific and Technical Information of China (English)

    LIU Hong-ling; YU Wei-dong; ZHANG Yue-ting

    2005-01-01

    The molecular conformation and the microstructure of the slenderized wool fibers have been studied by the Raman spectroscopy. The typical bands analyzed in this paper include the amideⅠand amide Ⅲ regions, the C-C skeletal vibration region, and the S-S and C-S bond vibration regions. The experimental results show that ⅰ) the Raman spectroscopy can reveal the secondary structural transformation from α-helical to β-pleated sheet begin at the early stage of stretching; ⅱ) the stretching mechanism of wool fibers can be divided into two different mechanisms, I.e. The secondary structural transformation and the slippage of the polypeptide chain; and ⅲ) the stretching leads to the increasing of the amount of the disordered conformation and the decreasing of the amount of S-S bonds.

  4. Raman and terahertz spectroscopical investigation of cocrystal formation process of piracetam and 3-hydroxybenzoic acid

    Science.gov (United States)

    Du, Yong; Zhang, Huili; Xue, Jiadan; Fang, Hongxia; Zhang, Qi; Xia, Yi; Li, Yafang; Hong, Zhi

    2015-03-01

    Cocrystallization can improve physical and chemical properties of active pharmaceutical ingredient, and this feature has great potential in pharmaceutical development. In this study, the cocrystal of piracetam and 3-hydroxybenzoic acid under grinding condition has been characterized by Raman and terahertz spectroscopical techniques. The major vibrational modes of individual starting components and cocrystal are obtained and assigned. Spectral results show that the vibrational modes of the cocrystal are different from those of the corresponding parent materials. The dynamic process of such pharmaceutical cocrystal formation has also been monitored directly with Raman and THz spectra. The formation rate is pretty fast in first several 20 min grinding time, and then it becomes slow. After ∼35 min, such process has been almost completed. These results offer us the unique means and benchmark for characterizing the cocrystal conformation from molecule-level and also provide us rich information about the reaction dynamic during cocrystal formation process in pharmaceutical fields.

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

    Science.gov (United States)

    Teimoory, Faranak; Loppnow, Glen R

    2016-05-04

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

  6. Predictive value of the surface-enhanced resonance Raman scattering-based MTT assay: a rapid and ultrasensitive method for cell viability in situ.

    Science.gov (United States)

    Mao, Zhu; Liu, Zhuo; Chen, Lei; Yang, Jin; Zhao, Bing; Jung, Young Mee; Wang, Xu; Zhao, Chun

    2013-08-06

    SERRS (surface-enhanced resonance Raman scattering) has been used to develop and optimize a novel and quantitative MTT assay for living cell viability. This highly sensitive method derives from two factors for formazan signal enhancing: the addition of Au nanoparticles and the resonance effect by 632.8 nm of excitation. The results show that the background elements, such as excessive MTT residues, serum, and the drug, did not interfere with the detection of formazan. Moreover, the detection limit of formazan is as low as 1 ng/mL. With the use of this method to quantify metabolically viable cells, dose-response curves of treated and untreated cells with the drug were constructed on the human lung cancer cell A549. The results also show that the Raman signal generated is dependent on the degree of activation of the cells. In comparison to the traditional method, the main advantages of this method are its rapidity (30 min), high-selectivity, high-precision, and cost-effectiveness (0.1 mg/mL MTT) without time-consuming steps and any modifying or labeling procedure. This work reports on an improved research tool that may help researchers apply this method for in situ cell assays.

  7. Spectroscopic ellipsometric and Raman spectroscopic investigations of pulsed laser treated glassy carbon surfaces

    Energy Technology Data Exchange (ETDEWEB)

    Csontos, J., E-mail: jcsontos@titan.physx.u-szeged.hu [University of Szeged, Department of Optics and Quantum Electronics, Dóm tér 9, H-6720 Szeged (Hungary); Pápa, Z.; Gárdián, A. [University of Szeged, Department of Optics and Quantum Electronics, Dóm tér 9, H-6720 Szeged (Hungary); Füle, M. [University of Szeged, Department of Experimental Physics, Dóm tér 9, H-6720 Szeged (Hungary); Budai, J. [University of Szeged, Department of Optics and Quantum Electronics, Dóm tér 9, H-6720 Szeged (Hungary); Toth, Z. [University of Szeged, Department of Optics and Quantum Electronics, Dóm tér 9, H-6720 Szeged (Hungary); University of Szeged, Department of Oral Biology and Experimental Dental Research, Tisza Lajos krt. 64, H-6720 Szeged (Hungary)

    2015-05-01

    Highlights: • Laser treatment modifies the top layer of glassy carbon as shown by ellipsometry. • Raman signal is composed from signals of the layer and the glassy carbon substrate. • Using volumetric fluence allows to compare the effects of different lasers. • Melting effects of glassy carbon was observed in case of Nd:YAG laser treatment. - Abstract: In this study spectroscopic ellipsometry (SE) and Raman spectroscopy are applied to study structural modification of glassy carbon, due to high intensity laser ablation. Two KrF lasers with different pulse durations (480 fs and 18 ns), an ArF (20 ns), and a frequency doubled Nd:YAG laser (8 ns) were applied to irradiate the surface of glassy carbon targets. The main characteristics of the different laser treatments are compared by introducing the volumetric fluence which takes into account the different absorption values at different wavelengths. SE showed the appearance of a modified layer on the ablated surfaces. In the case of the ns lasers the thickness of this layer was in the range of 10–60 nm, while in the case of fs laser it was less than 20 nm. In all cases the average refractive index (n) of the modified layers slightly decreased compared to the refractive index of glassy carbon. Increase in extinction coefficient (k) was observed in the cases of ArF and fs KrF laser treatment, while the k values decreased significantly in the cases of nanosecond pulse duration KrF and Nd:YAG laser treatments. In the Raman spectra of the ablated areas the characteristic D and G peaks were widened due to appearance of an amorphous phase. Both Raman spectroscopy and SE indicate that the irradiated areas show carbon nanoparticle formation in all cases.

  8. Investigation of organo-carbonate associations in carbonaceous chondrites by Raman spectroscopy

    Science.gov (United States)

    Chan, Queenie H. S.; Zolensky, Michael E.; Bodnar, Robert J.; Farley, Charles; Cheung, Jacob C. H.

    2017-03-01

    Carbonates record information regarding the timing, nature and conditions of the fluids circulating through asteroid parent bodies during aqueous alteration events. Determining carbonate abundances and their relationships with organic matter improves our understanding of the genesis of major carbonaceous components in chondritic materials. In this study, five CM2 carbonaceous chondrites (CM2.2 Nogoya, CM2.3 Jbilet Winselwan, CM2.5 Murchison, CM2 Santa Cruz, and CM2TII Wisconsin Range 91600) were studied with Raman spectroscopy. Carbonates were identified in these meteorite samples by the distinctive Raman band in the ∼1100 cm-1 region, representing the symmetric stretching vibration mode (ν1) of the (CO3)2- anion. Carbonates identified in the meteorite samples are all calcite, with the exception of a single dolomite grain in Nogoya. The v1 positions of the CM calcites are 2-3 cm-1 higher than in pure calcite, which suggests that they contain significant impurity cations. Typical graphitic first-order D and G bands were identified in the meteorite matrix as well as in ∼25% of the analyzed carbonate grains. From the Raman results, we postulate that the carbonates might not have formed under equilibrium conditions from a single fluid. The first generation of carbonate is interpreted to have formed from highly oxidized fluids that led to the oxidation of organic matter (OM) and produced carbonates that are OM-barren. The second generation of carbonate was formed from a more evolved aqueous fluid with the presence of OM. The Raman parameters of the organics in carbonates clearly deviate from the matrix OM which suggests that the carbonate organics contain very different carbonaceous components that are distinct from the typical amorphous OM of the CM matrix. The occurrence of different generations of carbonate in close proximity may be partly responsible for the wide range in estimated ages of carbonates in carbonaceous chondrites reported in previous studies.

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

    Energy Technology Data Exchange (ETDEWEB)

    Ouyang, Bing, E-mail: ouyangbing.zj@foxmail.com; Xue, Jia-Dan, E-mail: jenniexue@126.com; Zheng, Xuming, E-mail: zhengxuming126@126.com, E-mail: zxm@zstu.edu.cn, E-mail: fangwh@dnu.edu.cn [Department of Chemistry, Zhejiang Sci-Tech University, Hangzhou 310018 (China); Fang, Wei-Hai, E-mail: zxm@zstu.edu.cn, E-mail: fangwh@dnu.edu.cn, E-mail: fangwh@dnu.edu.cn [Department of Chemistry, Beijing Normal University, Beijing 100875 (China)

    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.

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

    Science.gov (United States)

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

    2014-05-21

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

  11. High-pressure Raman investigations of phase transformations in pentaerythritol (C(CH sub 2 OH) sub 4)

    CERN Document Server

    Bhattacharya, T

    2002-01-01

    Our high-pressure Raman scattering experiments on pentaerythritol (C(CH sub 2 OH) sub 4) show that this compound undergoes at least three phase transformations up to 25 GPa. Splitting of various modes at approx 6.3, approx 8.2 and 10 GPa suggests that these phase transformations result in lowering of crystalline symmetry. A very small discontinuous change in slope of most of the Raman-active modes is observed at 0.3 GPa. However, no other signature of a phase transition was observed at this pressure. The observed correlation of the pressures for the onset of the two phase transformations with the limiting values of the distances between various non-bonded atoms in the parent phase suggests that the molecular rearrangements across the phase transformations are not very drastic. In addition, our earlier Fourier transform infrared and present Raman investigations indicate that high-pressure compression leads to increase in strength of the hydrogen bond present in this compound.

  12. Investigating resonances above and below the threshold in nuclear reactions of astrophysical interest and beyond

    Energy Technology Data Exchange (ETDEWEB)

    La Cognata, M., E-mail: lacognata@lns.infn.it [Laboratori Nazionali del Sud - INFN, Catania (Italy); Kiss, G. G. [ATOMKI, Debrecen (Hungary); Mukhamedzhanov, A. M. [Cyclotron Institute, Texas A& M University, College Station, Texas (United States); Spitaleri, C. [Laboratori Nazionali del Sud - INFN, Catania (Italy); Department of Physics and Astronomy, University of Catania, Catania (Italy); Trippella, O. [Sezione di Perugia - INFN, Perugia (Italy)

    2015-10-15

    Resonances in nuclear cross sections dramatically change their trends. Therefore, the presence of unexpected resonances might lead to unpredicted consequences on astrophysics and nuclear physics. In nuclear physics, resonances allow one to study states in the intermediate compound systems, to evaluate their cluster structure, for instance, especially in the energy regions approaching particle decay thresholds. In astrophysics, resonances might lead to changes in the nucleosynthesis flow, determining different isotopic compositions of the nuclear burning ashes. For these reasons, the Trojan Horse method has been modified to investigate resonant reactions. Thanks to this novel approach, for the first time normalization to direct data might be avoided. Moreover, in the case of sub threshold resonances, the Trojan Horse method modified to investigate resonances allows one to deduce the asymptotic normalization coefficient, showing the close connection between the two indirect approaches.

  13. Raman investigation of few-layer graphene on different substrate structures

    Energy Technology Data Exchange (ETDEWEB)

    Lee, Jong-Kwon; Kim, Do-Hyun; Kim, Gyu-Tae; Dettlaff-Weglikowska, Urszula; Roth, Siegmar [WCU Flexible Nano-systems, School of Electrical Engineering, Korea University, Seoul 136-713 (Korea, Republic of); Yamazaki, Shiro [Institute of Applied Physics and INCH, University of Hamburg, Jungiusstrasse 9-11, 20355 Hamburg (Germany)

    2012-12-15

    We report Raman analysis of few-layer graphene (FLG) transferred on flat and patterned substrate structures. These different surface structures created by patterning an area of a Si-substrate produce differences in the interaction between FLG and the substrate surface. The topography measurement performed by scanning tunneling potentiometry shows that the FLG on the patterned substrate was deformed periodically with 3-4 nm depth variation. Raman spectroscopy reveals that two important features related to the G- and 2D-modes in graphitic structures show different sensitivity to the interaction with the substrate for single-layer graphene (SLG), FLG, and graphite. Whereas SLG and FLG placed on the patterned substrate demonstrate a strong shift of both 2D- and G-peaks to lower frequencies with respect to the flat part, the multilayer graphene in a graphite flake shows almost no difference between patterned and non-patterned substrates. We identified the origin of the observed changes in the Raman spectra of SLG and FLG as effects created by the underlying substrate. Especially, substrate induced periodic strain and surface interaction were taken into account to interpret the results. (Copyright copyright 2012 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  14. Raman microprobe investigation of molecular structure and organization in the native state of woody tissue

    Energy Technology Data Exchange (ETDEWEB)

    Atalla, R.H.

    1989-08-01

    Although the primary emphasis of our program has remained with the application of Raman spectroscopy to the study of native tissue, the scope of the work has been expanded to include a number of complementary approaches. These have included Solid State 13C NMR, autoradiography of radiolabeled woody tissue sections, and the generation of biomimetic tertiary aggregates which simulate states of aggregation characteristic of cell walls. Our Raman spectroscopic studies have resulted in progress in the areas of interpretation of the spectral features, and confirmation of the variability of the patterns of orientation of lignin reported earlier. We have assembled and made operational our new microprobe and spectrometer systems acquired under the DOE-URIP program. We have also demonstrated that, operating with gated detection and pulsed laser excitation, we can discriminate against the laser-excited fluorescence characteristic of most woody tissue. Our studies of celluloses, which combine Raman spectroscopy and 13C NMR have shown that all native celluloses are composites of two forms which have the same secondary structure but different tertiary structures.

  15. Raman and Luminescence Investigation of Rare Earth Doped Laser-Induced Crystals-in-Glass

    Science.gov (United States)

    Knorr, Brian; Stone, Adam; Jain, Himanshu; Dierolf, Volkmar

    2015-03-01

    Laser induced crystallization of glasses is a highly spatially selective process which has the potential to produce compact, integrated optics within a glass matrix. In LaBGeO5 low temperature Combined Excitation Emission Spectroscopy (CEES) revealed that erbium incorporates into both glass-ceramics and laser-induced crystals-in-glass in predominantly one type of environment (site). The energy levels of this site were quantified. The fluorescence characteristics of the erbium ions in any site in the laser-induced crystals were found to be only weakly influenced by the irradiation conditions during growth. On the other hand, a hidden parameter, potentially boron deficiency-related defects, resulted in a significant change in the incorporation behavior of the erbium ions. Scanning confocal Raman and fluorescence spectroscopy showed that the energies of the Raman modes are shifted and the erbium fluorescence intensity is inhomgeneously distributed, despite the host glass being homogeneously doped, across the cross-sections of laser-induced crystals in glass. These fluctuations within the Raman and fluorescence are spatially correlated, implying that different erbium sites form preferentially at different locations in the crystal cross-section.

  16. Nondestructive Raman investigation on wall paintings at Sala Vaccarini in Catania (Sicily)

    Science.gov (United States)

    Barone, Germana; Bersani, Danilo; Coccato, Alessia; Lauwers, Debbie; Mazzoleni, Paolo; Raneri, Simona; Vandenabeele, Peter; Manzini, Davide; Agostino, Giuseppe; Neri, Nicola Francesco

    2016-09-01

    In this work, the results of a Raman campaign for studying seventeenth-century Sicilian frescoes, by using two portable Raman systems, equipped with different excitation sources (785 and 1064 nm), are proposed. The measurements were performed with the aim to provide an in situ diagnostic analysis of the wall paintings (in terms of colorants and preparation layer) and to support the conservators in the framework of the ongoing restoration. The combined use of the two Raman spectrometers has given a complete overview on the artist palette and on the state of preservation of frescoes, also informing us about the technique employed by the painter. Natural pigments as hematite, vermillion, goethite, lead red, lead white and carbon-based black pigments have been identified. Additionally, the application of a transitional Romanesque-Renaissance frescoes method has been noticed by the systematic combined presence of calcite and gypsum in the substrate. Finally, the analyses have highlighted the presence of degradation products, mainly related to alteration of lead-based pigments.

  17. A XANES and Raman investigation of sulfur speciation and structural order in Murchison and Allende meteorites

    Science.gov (United States)

    Bose, M.; Root, R. A.; Pizzarello, S.

    2017-03-01

    Insoluble organic matter (IOM) and hydrothermally treated IOM extracted from two carbonaceous chondrites, Murchison and Allende, was studied using sulfur K-edge XANES (X-ray absorption near edge structure) and μ-Raman spectroscopy, with the aim to understand their IOM's sulfur speciation and structural order, and how aqueous alteration or thermal metamorphism may have transformed these materials. We found that the sulfur-functional group chemistry of both the Murchison IOM and hydrothermally treated IOM samples have a large chemical variability ranging from oxidation states of S-2 to S+6, and exhibit a transformation in their oxidation state after the hydrothermal treatment (HT) to produce thiophenes and thiol compounds. Sulfoxide and sulfite peaks are also present in Murchison. Sulfates considered intrinsic to Murchison are most likely preaccretionary in nature, and not a result of reactions with water at high temperatures on the asteroid parent body. We argue that the reduced sulfides may have formed in the CM parent body, while the thiophenes and thiol compounds are a result of the HT. Micro-Raman spectra show the presence of aliphatic and aromatic moieties in Murchison's material as observed previously, which exhibits no change after HT. Because the Murchison IOM was modified, as seen by XANES analysis, absence of a change observed using micro-Raman indicated that although the alkyl carbons of IOM were cleaved, the aromatic network was not largely modified after HT. By contrast, Allende IOM contains primarily disulfide and elemental sulfur, no organic sulfur, and shows no transformation after HT. This nontransformation of Allende IOM after HT would indicate that parent body alteration of sulfide to sulfate is not feasible up to temperatures of 300°C. The reduced sulfur products indicate extreme secondary chemical processing from the precursor compounds in its parent body at temperatures as high as 624°C, as estimated from μ-Raman D band parameters. The

  18. Raman scattering excitation spectroscopy of monolayer WS2.

    Science.gov (United States)

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

    2017-07-11

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

  19. Abnormal Raman spectral phenomenon of silicon nanowires

    Institute of Scientific and Technical Information of China (English)

    2000-01-01

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

  20. Visible-IR and Raman micro-spectroscopic investigation of three Itokawa particles collected by Hayabusa

    Science.gov (United States)

    Brunetto, R.; Bonal, L.; Beck, P.; Dartois, E.; Dionnet, Z.; Djouadi, Z.; Füri, E.; Kakazu, Y.; Oudayer, P.; Quirico, E.; Engrand, C.

    2014-07-01

    HAYABUSA grains offer a unique perspective to better understand the link between asteroids and cosmomaterials available in the laboratory and to get an insight on the early stages of surface space weathering. The scientific objectives of our consortium are threefold: (i) the characterization of asteroidal surface processes (e.g., space weathering alteration); (ii) the assessment of parent-body alteration processes; (iii) the search for a possible association between S-type asteroids and micrometeorites. To this aim, our strategy is based on a combination of analytical techniques. Here we report a first series of results obtained through Visible-Infrared and Raman spectroscopy of three Itokawa particles (RA-QD02-0163, -0174, and -0213) collected by the Hayabusa spacecraft and provided by JAXA for our consortium. In a first step, our main objective was to collect maximum information without altering the particles. Reported results were thus obtained on the raw particles, both (i) in their original containers, and (ii) deposited on diamond windows. Raman and IR confocal spectra were acquired at the SMIS beamline of the French national synchrotron facility SOLEIL and at the Lyon Raman national facility using spots of 2 μ m for the Raman, and 10--20 μ m for the IR analyses. Point analyses and automatic mapping were performed. Analytical parameters (e.g., laser power on the sample) were optimized to prevent any damage. Diffuse reflectance spectra (i=45°, e=0°) in the visible and near-IR wavelengths were obtained with an IAS-CSNSM in-home system coupling a fiber spectrometer to an optical microscope, providing a 20-μ m spot on sample. In the case of particle -0163, Raman and IR results reveal a heterogeneous mixing of minerals, mostly olivine (Fo76), and Ca-rich (En50, Wo50) and Ca-poor (En85) pyroxenes. The modal distribution of these minerals is determined based on the spectral maps. The mineral compositions of -0163 are consistent with those previously reported on

  1. Particle-in-cell investigation on the resonant absorption of a plasma surface wave

    Institute of Scientific and Technical Information of China (English)

    Lan Chao-Hui; Hu Xi-Wei

    2011-01-01

    The resonant absorption of a plasma surface wave is supposed to be an important and efficient mechanism of power deposition for a surface wave plasma source.In this paper,by using the particle-in-cell method and Monte Carlo simulation,the resonance absorption mechanism is investigated.Simulation results demonstrate the existence of surface wave resonance and show the high efficiency of heating electrons.The positions of resonant points,the resonance width and the spatio-temporal evolution of the resonant electric field are presented,which accord well with the theoretical results.The paper also discusses the effect of pressure on the resonance electric field and the plasma density.

  2. The micro-distribution of carbonaceous matter in the Murchison meteorite as investigated by Raman imaging

    Science.gov (United States)

    Amri, Chahrazade El; Maurel, Marie-Christine; Sagon, Gérard; Baron, Marie-Hélène

    2005-07-01

    The carbonaceous Murchison chondrite is one of the most studied meteorites. It is considered to be an astrobiology standard for detection of extraterrestrial organic matter. Considerable work has been done to resolve the elemental composition of this meteorite. Raman spectroscopy is a very suitable technique for non-destructive rapid in situ analyses to establish the spatial distribution of carbonaceous matter. This report demonstrates that Raman cartography at a resolution of 1 μm 2 can be performed. Two-dimensional distribution of graphitised carbon, amorphous carbonaceous matter and minerals were obtained on 100 μm 2 maps. Maps of the surface of native stones and of a powdered sample are compared. Graphitic and amorphous carbonaceous domains are found to be highly overlapping in all tested areas at the surface of the meteorite and in its interior as well. Pyroxene, olivine and iron oxide grains are embedded into this mixed carbonaceous material. The results show that every mineral grain with a size of less than a few μm 2 is encased in a thin carbonaceous matrix, which accounts for only 2.5 wt.%. This interstitial matter sticks together isolated mineral crystallites or concretions, including only very few individualized graphitised grains. Grinding separates the mineral particles but most of them retain their carbonaceous coating. This Raman study complements recent findings deduced from other spatial analyses performed by microprobe laser-desorption laser-ionisation mass spectrometry (μL 2MS), transmission electron microscopy (TEM) and scanning transmission X-ray microscopy (STXM).

  3. Full investigation of the resonant frequency servo loop for resonator fiber-optic gyro.

    Science.gov (United States)

    Ma, Huilian; Lu, Xiao; Yao, Linzhi; Yu, Xuhui; Jin, Zhonghe

    2012-07-20

    Resonator fiber-optic gyro (RFOG) is a high-accuracy inertial rotation sensor based on the Sagnac effect. A high-accuracy resonant frequency servo loop is indispensable for a high-performance RFOG. It is composed of a frequency discriminator, a loop filter, and a laser actuator. Influences of the loop parameters are fully developed. Optimized loop parameters are obtained by considering the noise reduction and wide dynamic performance of the RFOG. As a result, with the integration time of 10 s, the accuracy of the resonant frequency loop is increased to 0.02 Hz (1σ). It is equivalent to a rotation rate of 0.067°/h, which is close to the shot noise limit for the RFOG, while a minimum rotation of ±0.05°/s has been carried out simultaneously. These are the best results reported to date, to the best of our knowledge, for an RFOG using the miniature semiconductor laser that benefits from the optimization of the resonant frequency servo-loop parameters.

  4. Local stress determination in chromia-former thanks to micro-Raman spectroscopy: A way to investigate spontaneous delamination processes

    Science.gov (United States)

    Guerain, M.; Goudeau, P.; Panicaud, B.; Grosseau-Poussard, J. L.

    2013-02-01

    Spontaneous delamination process for α-Cr2O3 thermal oxide films growing on NiCr-30 alloys is studied thanks to micro Raman spectroscopy. In particular, stress maps are performed through and around buckles developed on chromia films. Depending on the cooling rate at the end of the oxidation process, different buckle types appear which are investigated. Associated residual stress distribution clearly evidences the stress release field. In addition, geometrical features are determined for the different buckle types, and from comparison with modelling describing buckle formation and propagation, it is possible to get the interface toughness distribution.

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

    Science.gov (United States)

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

    2015-09-01

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

  6. Raman investigations on nitrogen ion implantation effects on semi-insulating InP

    CERN Document Server

    Santhakumar, K; Kesavamoorthy, R; Magudapathy, P; Nair, K G M; Ravichandran, V

    2002-01-01

    Raman scattering measurements on liquid-encapsulated Czochralski-grown Fe-doped semi-insulating InP(1 0 0) single crystal substrates have been carried out before and after 120 keV N sup + implantation for various doses from 10 sup 1 sup 3 to 10 sup 1 sup 5 cm sup - sup 2 and also after post-implantation rapid thermal annealing of these samples. It is observed that LO phonon mode frequency decreases and full width at half maximum (FWHM) increases with fluence due to implantation-induced lattice damage. Forbidden Raman TO mode in (1 0 0) cut InP is observed at the doses of 5x10 sup 1 sup 3 and 5x10 sup 1 sup 4 cm sup - sup 2. This might have appeared due to the polycrystalline and/or misoriented regions created during implantation. TO mode is not observed for high doses in as-implanted samples due to excessive lattice damage induced by the implantation. On rapid thermal annealing at 573 K for 30 s, the implanted samples show a partial recovery of LO phonon mode frequency and FWHM due to partial annealing of the...

  7. Protein dynamics in an intermediate state of myoglobin: optical absorption, resonance Raman spectroscopy, and x-ray structure analysis.

    OpenAIRE

    N. Engler; Ostermann, A; Gassmann, A.; Lamb, D C; Prusakov, V E; J. Schott; Schweitzer-Stenner, R; Parak, F. G.

    2000-01-01

    A metastable state of myoglobin is produced by reduction of metmyoglobin at low temperatures. This is done either by irradiation with x-rays at 80 K or by electron transfer from photoexcited tris(2, 2'-bipyridine)-ruthenium(II) at 20 K. At temperatures above 150 K, the conformational transition toward the equilibrium deoxymyoglobin is observed. X-ray crystallography, Raman spectroscopy, and temperature-dependent optical absorption spectroscopy show that the metastable state has a six-ligated ...

  8. Rational Design of a Chalcogenopyrylium-Based Surface-Enhanced Resonance Raman Scattering-Nanoprobe with Attomolar Sensitivity

    Science.gov (United States)

    Wall, Matthew A.; Huang, Ruimin; Detty, Michael R.; Kircher, Moritz F.

    2015-01-01

    High sensitivity and specificity are two desirable features in biomedical imaging. Raman imaging has surfaced as a promising optical modality that offers both. Here, we report the design and synthesis of a group of near infrared absorbing 2-thienyl-substituted chalcogenopyrylium dyes tailored to have high affinity for gold. When adsorbed onto gold nanoparticles, these dyes produce biocompatible SERRS-nanoprobes with attomolar limits of detection amenable to ultrasensitive in vivo multiplexed tumor and disease marker detection. PMID:25800697

  9. Rational design of a chalcogenopyrylium-based surface-enhanced resonance Raman scattering nanoprobe with attomolar sensitivity

    Science.gov (United States)

    Harmsen, Stefan; Bedics, Matthew A.; Wall, Matthew A.; Huang, Ruimin; Detty, Michael R.; Kircher, Moritz F.

    2015-03-01

    High sensitivity and specificity are two desirable features in biomedical imaging. Raman imaging has surfaced as a promising optical modality that offers both. Here we report the design and synthesis of a group of near-infrared absorbing 2-thienyl-substituted chalcogenopyrylium dyes tailored to have high affinity for gold. When adsorbed onto gold nanoparticles, these dyes produce biocompatible SERRS nanoprobes with attomolar limits of detection amenable to ultrasensitive in vivo multiplexed tumour and disease marker detection.

  10. Structure and reactivity of thiazolium azo dyes: UV-visible, resonance Raman, NMR, and computational studies of the reaction mechanism in alkaline solution.

    Science.gov (United States)

    Abbott, Laurence C; Batchelor, Stephen N; Moore, John N

    2013-03-07

    UV-visible absorption, resonance Raman, and (1)H NMR spectroscopy, allied with density functional theory (DFT) calculations, have been used to study the structure, bonding, and alkaline hydrolysis mechanism of the cationic thiazloium azo dye, 2-[2-[4-(diethylamino)phenyl]diazenyl]-3-methyl-thiazolium (1a), along with a series of six related dyes with different 4-dialkylamino groups and/or other phenyl ring substituents (2a-c, 3a-c) and the related isothiazolium azo dye, 5-[2-[4-(dimethylamino)phenyl]diazenyl]-2-methyl-isothiazolium (4). These diazahemicyanine dyes are calculated to have a similar low-energy structure that is cis, trans at the (iso)thiazolium-azo group, and for which the calculated Raman spectra provide a good match with the experimental data; the calculations on these structures are used to assign and discuss the transitions giving rise to the experimental spectra, and to consider the bonding and its variation between the dyes. UV-visible, Raman, and NMR spectra recorded from minutes to several weeks after raising the pH of an aqueous solution of 1a to ca. 11.5 show that the dominant initial step in the reaction is loss of diethylamine to produce a quinonimine (ca. hours), with subsequent reactions occurring on longer time scales (ca. days to weeks); kinetic analyses give a rate constant of 2.6 × 10(-2) dm(3) mol(-1) s(-1) for reaction of 1a with OH(-). UV-visible spectra recorded on raising the pH of the other dyes in solution show similar changes that are attributed to the same general reaction mechanism, but with different rate constants for which the dependence on structure is discussed.

  11. Enhanced Raman scattering of graphene on Ag nanoislands

    Institute of Scientific and Technical Information of China (English)

    HU Wei; HUANG ZhiYi; ZHOU YingHui; CAI WeiWei; KANG JunYong

    2014-01-01

    The effect of Ag nanoislands on the Raman of graphene was investigated in this work.Compared with that on the bare silicon wafer,Raman enhancement was observed in the graphene film that covered on Ag/Si surface with nanoscale Ag islands,which would be induced by the localized plasmon resonance in Ag nanostructures.The interaction between the graphene sheet and Ag/Si substrate was further studied.The peak shift and line shape of Raman spectroscopy indicated a nonuniform strain distribution in the Ag/Si supported graphene film.

  12. Raman spectroscopic investigation of 13CO 2 labeling and leaf dark respiration of Fagus sylvatica L. (European beech).

    Science.gov (United States)

    Keiner, Robert; Gruselle, Marie-Cécile; Michalzik, Beate; Popp, Jürgen; Frosch, Torsten

    2015-03-01

    An important issue, in times of climate change and more extreme weather events, is the investigation of forest ecosystem reactions to these events. Longer drought periods stress the vitality of trees and promote mass insect outbreaks, which strongly affect ecosystem processes and services. Cavity-enhanced Raman gas spectrometry was applied for online multi-gas analysis of the gas exchange rates of O2 and CO2 and the labeling of Fagus sylvatica L. (European beech) seedlings with (13)CO2. The rapid monitoring of all these gases simultaneously allowed for the separation of photosynthetic uptake of CO2 by the beech seedlings and a constant (12)CO2 efflux via respiration and thus for a correction of the measured (12)CO2 concentrations in course of the labeling experiment. The effects of aphid infestation with the woolly beech aphid (Phyllaphis fagi L.) as well as the effect of a drought period on the respirational gas exchange were investigated. A slightly decreased respirational activity of drought-stressed seedlings in comparison to normally watered seedlings was found already for a low drought intensity. Cavity-enhanced Raman gas monitoring of O2, (12)CO2, and (13)CO2 was proven to be a powerful new tool for studying the effect of drought stress and aphid infestation on the respirational activity of European beech seedlings as an example of important forest species in Central Europe.

  13. Investigation of coatings of natural organic matter on silver nanoparticles under environmentally relevant conditions by surface-enhanced Raman scattering.

    Science.gov (United States)

    Kühn, Melanie; Ivleva, Natalia P; Klitzke, Sondra; Niessner, Reinhard; Baumann, Thomas

    2015-12-01

    The widespread use of engineered inorganic nanoparticles (EINP) leads to a growing risk for an unintended release into the environment. Despite the good characterization of EINP in regard to their function scale and the application areas, there is still a gap of knowledge concerning their behaviour in the different environmental compartments. Due to their high surface to volume ratio, surface properties and existence or development of a coating are of high importance for their stability and transport behaviour. However, analytical methods to investigate organic coatings on nanoparticles in aqueous media are scarce. We used Raman microspectroscopy in combination with surface-enhanced Raman scattering (SERS) to investigate humic acid coatings on silver nanoparticles under environmentally relevant conditions and in real world samples. This setup is more challenging than previous mechanistic studies using SERS to characterize the humic acids in tailored settings where only one type of organic matter is present and the concentrations of the nanoparticles can be easily adjusted to the experimental needs. SERS offers the unique opportunity to work with little sample preparation directly with liquid samples, thus significantly reducing artefacts. SERS spectra of different natural organic matter brought into contact with silver nanoparticles indicate humic acid in close proximity to the nanoparticles. This coating was also present after several washing steps by centrifugation and resuspension in deionized water and after an increase in ionic strength.

  14. Resonance Raman and absorption spectroscopy of the lowest triplet state of 1,3,5-hexatriene and deuteriated derivatives at 183 K : molecular structure in the T1 state

    NARCIS (Netherlands)

    Langkilde, F.W.; Wilbrandt, R.; M?ller, S.; Brouwer, A.M.; Negri, F.; Orlandi, G.

    1991-01-01

    Time-resolved resonance Raman (RR) spectra of the lowest excited triplet state T1 of (E)-1,3,5-hexatriene, (E)-3-deuterio-1,3,5-hexatriene, and (E)-1,1-dideuterio-1,3,5-hexatriene are obtained at 183 K. The T1 potential energy surface (PES), determining energy minima, equilibrium geometries, frequen

  15. Theoretical investigation on Raman induced Kerr effect spectroscopy in nonlinear confocal microscopy

    Institute of Scientific and Technical Information of China (English)

    Gun LiNa; TANG ZhiLie; XING Da

    2008-01-01

    The imaging theory of Raman induced Kerr effect spectroscopy (RIKES) in nonlinear confocal microscopy is presented in this paper. Three-dimensional point spread function (3D-PSF) of RIKES nonlinear confocal microscopy in isotropic media is derived with Fourier imaging theory and RIKES theory. The impact of nonlinear property of RIKES on the spatial resolution and imaging properties of confocal microscopy have been analyzed in detail. It is proved that RIKES nonlinear confocal microscopy can simultaneously provide more information than twophoton confocal microscopy concerning molecular vibration mode, vibration orientation and optically induced molecular reorientation, etc. It is shown that RIKES nonlinear confocal microscopy significantly enhances the spatial resolution and imaging quality of confocal microscopy and achieves much higher resolution than that of two-photon confocal microscopy.

  16. Molecular structure and spectral (FT-IR, Raman) investigations of 3-aminocoumarin

    Science.gov (United States)

    Dereli, Ömer

    2016-05-01

    The molecular structure of 3-Aminocoumarin was determined by conformational analysis. Conformational space was scanned by conformer distribution option of Spartan 08 program package using Merck Molecular Force Field (MMFF) method. Then obtained conformers were optimized by B3LYP/6-311++ G( d, p) and B3LYP/6-311 G( d, p) levels of Density Functional Theory. As a result of these calculations, only one conformer was determined. Vibrational frequencies of this conformer were calculated by Gaussian 03 program package using the same levels of geometry optimizations. The FT-IR and Raman spectra of 3-Aminocoumarin were recorded and compared with the calculated values. Consequently, a good agreement between experimental and the calculated values were founded. Molecular electrostatic potentials (MEPs), HOMO-LUMO energies, thermodynamic properties and Mulliken atomic charges were also covered in this study.

  17. Theoretical investigation on Raman induced Kerr effect spectroscopy in nonlinear confocal microscopy

    Institute of Scientific and Technical Information of China (English)

    2008-01-01

    The imaging theory of Raman induced Kerr effect spectroscopy (RIKES) in nonlinear confocal microscopy is presented in this paper. Three-dimensional point spread function (3D-PSF) of RIKES nonlinear confocal microscopy in isotropic media is derived with Fourier imaging theory and RIKES theory. The impact of nonlinear property of RIKES on the spatial resolution and imaging properties of confocal microscopy have been analyzed in detail. It is proved that RIKES nonlinear confocal microscopy can simultaneously provide more information than two-photon confocal microscopy concerning molecular vibration mode, vibration orientation and optically induced molecular reorientation, etc. It is shown that RIKES nonlinear confocal microscopy significantly enhances the spatial resolution and imaging quality of confocal microscopy and achieves much higher resolution than that of two-photon confocal microscopy.

  18. Experimental investigation of resonance self-shielding and the Doppler effect in uranium and tantalum

    Science.gov (United States)

    Byoun, T. Y.; Block, R. C.; Semler, T. T.

    1972-01-01

    A series of average transmission and average self-indication ratio measurements were performed in order to investigate the temperature dependence of the resonance self-shielding effect in the unresolved resonance region of depleted uranium and tantalum. The measurements were carried out at 77 K, 295 K and approximately 1000 K with sample thicknesses varying from approximately 0.1 to 1.0 mean free path. The average resonance parameters as well as the temperature dependence were determined by using an analytical model which directly integrates over the resonance parameter distribution functions.

  19. Article ID:1007-0206(2001)03-0129-09Investigation on the Gain of Multi-wavelength Pumping Broadband Raman Amplifier

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    The Stokes spectrum in the stimulated Raman scattering (SRS) is very complicated. In this article, we use both Gaussian and Lorentz approximation to investigate the gain properties of multi-pumping broadband Raman amplifier, and present some schemes for flattening the gain. All the results show that the flatness of the gain spectrum is closely related to the pumping frequency grid. By researching the gain properties of Raman amplifiers of such ITU-T fibers as G.652, G.653, G.655 and large effective area non-zero dispersion flattening fiber, we find that the Raman gain is associated with the fiber type and its transmission characteristics, especially it decreases with the increase of the effective core area.

  20. High-pressure investigation of CaTiO3 up to 60 GPa using x-ray diffraction and Raman spectroscopy

    Science.gov (United States)

    Guennou, Mael; Bouvier, Pierre; Krikler, Benjamin; Kreisel, Jens; Haumont, Raphaël; Garbarino, Gaston

    2010-10-01

    In this work, we investigate calcium titanate [CaTiO3(CTO)] using x-ray diffraction and Raman spectroscopy up to 60 GPa and 55 GPa, respectively. Both experiments show that the orthorhombic Pnma structure remains stable up to the highest pressures measured, in contradiction to ab initio predictions. A fit of the compression data with a second-order Birch-Murnaghan equation of state yields a bulk modulus K0 of 181.0(6) GPa. The orthorhombic distortion is found to increase slightly with pressure, in agreement with previous experiments at lower pressures and the general rules for the evolution of perovskites under pressure. High-pressure polarized Raman spectra also enable us to clarify the Raman mode assignment of CTO and identify the modes corresponding to rigid rotation of the octahedra, A -cation shifts, and Ti-O bond stretching. The Raman signature is then discussed in terms of compression mechanisms.

  1. Towards combined electrochemistry and surface-enhanced resonance Raman of heme proteins: Improvement of diffusion electrochemistry of cytochrome c at silver electrodes chemically modified with 4-mercaptopyridine.

    Science.gov (United States)

    Millo, Diego; Ranieri, Antonio; Koot, Wynanda; Gooijer, Cees; van der Zwan, Gert

    2006-08-01

    To date, a successful combination of surface-enhanced resonance Raman spectroscopy (SERRS) and electrochemistry to study heme proteins is inhibited by the problems raised by the prerequisite to use silver as electrode metal. This paper indicates an approach to overcome these problems. It describes a quick and reproducible procedure to prepare silver electrodes chemically modified with 4-mercaptopyridine suitable to perform diffusion electrochemistry of cytochrome c (cyt c). The method involves the employment of a mechanical and a chemical treatment and avoids the use of alumina slurries and any electrochemical pretreatment. Cyclic voltammetry (CV) was used to test the electrochemical response of cyt c, and the CV signals were found identical with those obtained on gold electrodes under the same experimental conditions. Compared to previous literature, a significant improvement of the CV signal of cyt c at silver electrodes was achieved. Preliminary results show that this treatment can be also successfully employed for the preparation of SERRS-active electrodes.

  2. Non-invasive determination of the CO contents in tuna fish using polarization resolved resonance Raman scattering and/or Rayleigh spectroscopy

    DEFF Research Database (Denmark)

    Hassing, Søren

    2016-01-01

    Carbon monoxide (CO) is used for Modified Atmosphere Packaging of fresh fish and meat. CO is added because it binds to the Myoglobin of the muscle tissue with high affinity resulting in a bright, cherry-red colored carboxy-Myoglobin complex. The product will because of the red color appear to be ...... with polarization resolved resonance Raman spectra of these molecules, can form the basis of the development of a fast and non-invasive method for the screening of the presence of CO in tuna fish and meat.......Carbon monoxide (CO) is used for Modified Atmosphere Packaging of fresh fish and meat. CO is added because it binds to the Myoglobin of the muscle tissue with high affinity resulting in a bright, cherry-red colored carboxy-Myoglobin complex. The product will because of the red color appear...

  3. Fourier Transform Infrared (FTIR) Spectroscopy, Ultraviolet Resonance Raman (UVRR) Spectroscopy, and Atomic Force Microscopy (AFM) for Study of the Kinetics of Formation and Structural Characterization of Tau Fibrils.

    Science.gov (United States)

    Ramachandran, Gayathri

    2017-01-01

    Kinetic studies of tau fibril formation in vitro most commonly employ spectroscopic probes such as thioflavinT fluorescence and laser light scattering or negative stain transmission electron microscopy. Here, I describe the use of Fourier transform infrared (FTIR) spectroscopy, ultraviolet resonance Raman (UVRR) spectroscopy, and atomic force microscopy (AFM) as complementary probes for studies of tau aggregation. The sensitivity of vibrational spectroscopic techniques (FTIR and UVRR) to secondary structure content allows for measurement of conformational changes that occur when the intrinsically disordered protein tau transforms into cross-β-core containing fibrils. AFM imaging serves as a gentle probe of structures populated over the time course of tau fibrillization. Together, these assays help further elucidate the structural and mechanistic complexity inherent in tau fibril formation.

  4. Effective approach to strengthen plasmon resonance localized on top surfaces of Ag nanoparticles and application in surface-enhanced Raman spectroscopy

    Science.gov (United States)

    Zhan, Zhibing; Xu, Rui; Zheng, Xianzheng; Fu, Qun; Wu, Minghong; Lei, Yong

    2016-11-01

    The spatial distribution of localized surface plasmon resonance (LSPR) plays a key role in many plasmonic applications. Based on the thermal stability of alumina templates, this work reports a novel approach to manipulate the distribution of LSPR and exhibits its significance for an important plasmonic application, the surface-enhanced Raman spectroscopy (SERS). A suitable thermal annealing sharpens the edges in top surfaces (far from the substrates) of Ag nanoparticles, which significantly strengthens the distal mode (DM) with the LSPR excited on the top surfaces. Because the top surface is the major place to adsorb probe molecules, this manipulation greatly improves the detection sensitivity of SERS. Our research provides a new way to improve the sensitivity of SERS, which also indicates that great care has to be taken on special LSPR mode which is largely responsible for a certain plasmonic application (e.g., the DM for SERS although it is not the major mode).

  5. Magnetic resonance techniques for investigation of multiple sclerosis

    Science.gov (United States)

    MacKay, Alex; Laule, Cornelia; Li, David K. B.; Meyers, Sandra M.; Russell-Schulz, Bretta; Vavasour, Irene M.

    2014-11-01

    Multiple sclerosis (MS) is a common neurological disease which can cause loss of vision and balance, muscle weakness, impaired speech, fatigue, cognitive dysfunction and even paralysis. The key pathological processes in MS are inflammation, edema, myelin loss, axonal loss and gliosis. Unfortunately, the cause of MS is still not understood and there is currently no cure. Magnetic resonance imaging (MRI) is an important clinical and research tool for MS. 'Conventional' MRI images of MS brain reveal bright lesions, or plaques, which demark regions of severe tissue damage. Conventional MRI has been extremely valuable for the diagnosis and management of people who have MS and also for the assessment of therapies designed to reduce inflammation and promote repair. While conventional MRI is clearly valuable, it lack pathological specificity and, in some cases, sensitivity to non-lesional pathology. Advanced MR techniques have been developed to provide information that is more sensitive and specific than what is available with clinical scanning. Diffusion tensor imaging and magnetization transfer provide a general but non-specific measure of the pathological state of brain tissue. MR spectroscopy provides concentrations of brain metabolites which can be related to specific pathologies. Myelin water imaging was designed to assess brain myelination and has proved useful for measuring myelin loss in MS. To combat MS, it is crucial that the pharmaceutical industry finds therapies which can reverse the neurodegenerative processes which occur in the disease. The challenge for magnetic resonance researchers is to design imaging techniques which can provide detailed pathological information relating to the mechanisms of MS therapies. This paper briefly describes the pathologies of MS and demonstrates how MS-associated pathologies can be followed using both conventional and advanced MR imaging protocols.

  6. Real-time measurements of the redox states of c-type cytochromes in electroactive biofilms: a confocal resonance Raman Microscopy study.

    Science.gov (United States)

    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.

  7. Real-time measurements of the redox states of c-type cytochromes in electroactive biofilms: a confocal resonance Raman Microscopy study.

    Directory of Open Access Journals (Sweden)

    Bernardino Virdis

    Full Text Available 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.

  8. Spectroscopic (FTIR, FT-Raman, UV and NMR) investigation and NLO, HOMO-LUMO, NBO analysis of 2-Benzylpyridine based on quantum chemical calculations.

    Science.gov (United States)

    Mathammal, R; Sudha, N; Guru Prasad, L; Ganga, N; Krishnakumar, V

    2015-02-25

    In this work, the vibrational characteristics of 2-Benzylpyridine have been investigated. The structure of the molecule has been optimized and the structural characteristics of the molecule have been determined by density functional theory B3LYP method with 6-31G(d,p) basis set. The infrared and Raman spectra have been simulated from calculated intensities. Both the experimental and theoretical vibrational data confirms the presence of functional groups in the title compound. The (1)H and (13)C NMR spectra were recorded and (1)H and (13)C nuclear magnetic resonance chemical shifts of the molecule were calculated using the gauge independent atomic orbital method. UV-Visible spectrum of the title compound was recorded in the region 190-1100 nm and the electronic properties HOMO and LUMO energies were calculated by CIS approach. Nonlinear optical and thermodynamic properties were interpreted. All the calculated results were compared with the available experimental data of the title molecule. Copyright © 2014 Elsevier B.V. All rights reserved.

  9. Investigation of oxygen vacancies in Ce coupled TiO2 nanocomposites by Raman and PL spectra

    Science.gov (United States)

    Dhanalakshmi, J.; Iyyapushpam, S.; Nishanthi, S. T.; Malligavathy, M.; Pathinettam Padiyan, D.

    2017-03-01

    CeO2–TiO2 nanocomposites with different Ce weight percentages (2, 4, 6 and 8%) were synthesized by sol-gel method. The influence of cerium inclusion on the structural, morphological, optical properties and elemental composition has been analyzed via XRD, BET surface area analysis, UV-DRS, HR-SEM, EDAX, TEM, Raman and photoluminescence spectra. The structural study showed that all the CeO2–TiO2 nanocomposites crystallized in tetragonal structure with anatase phase. Morphological study revealed that the nanocomposites are in spherical shape with size between 13–15 nm. Raman and PL spectra confirmed the presence and influence of oxygen vacancy defects. The adsorption ability of the CeO2–TiO2 nanocomposites was investigated for congo red dye under dark condition. CeO2–TiO2 nanocomposites have enhanced adsorptive performance in comparison with bare TiO2 nanoparticles. The enhanced adsorptive activity of CeO2–TiO2 nanocomposites is due to the higher surface area of the nanocomposites and oxygen vacancies present in the surface of the nanocomposites. The pseudo second order kinetic equation fits well with higher correlation coefficient compared to the pseudo first order in explaining the reaction kinetics.

  10. Raman Spectroscopy and Electrochemical Investigations of Pt Electrocatalyst Supported on Carbon Prepared through Plasma Pyrolysis of Natural Gas

    Directory of Open Access Journals (Sweden)

    Tereza Cristina Santos Evangelista

    2015-01-01

    Full Text Available Physicochemical and electrochemical characterisations of Pt-based electrocatalysts supported on carbon (Vulcan carbon, C1, and carbon produced by plasma pyrolysis of natural gas, C2 toward ethanol electrooxidation were investigated. The Pt20/C180 and Pt20/C280 electrocatalysts were prepared by thermal decomposition of polymeric precursors at 350°C. The electrochemical and physicochemical characterisations of the electrocatalysts were performed by means of X-ray diffraction (XRD, transmission electron microscope (TEM, Raman scattering, cyclic voltammetry, and chronoamperometry tests. The XRD results show that the Pt-based electrocatalysts present platinum metallic which is face-centered cubic structure. The results indicate that the Pt20/C180 electrocatalyst has a smaller particle size (10.1–6.9 nm compared with the Pt20/C280 electrocatalyst; however, the Pt20/C280 particle sizes are similar (12.8–10.4 nm and almost independent of the reflection planes, which suggests that the Pt crystallites grow with a radial shape. Raman results reveal that both Vulcan carbon and plasma carbon are graphite-like materials consisting mostly of sp2 carbon. Cyclic voltammetry and chronoamperometry data obtained in this study indicate that the deposition of Pt on plasma carbon increases its electrocatalytic activity toward ethanol oxidation reaction.

  11. Computational Chemistry Meets Experiments for Explaining the Behavior of Bibenzyl: A Thermochemical and Spectroscopic (Infrared, Raman, and NMR) Investigation.

    Science.gov (United States)

    Latouche, Camille; Barone, Vincenzo

    2014-12-09

    The structure, conformational behavior, and spectroscopic parameters of bibenzyl have been investigated by a computational protocol including proper treatment of anharmonic and hindered rotor contributions. Conventional hybrid functionals overstabilize the anti conformer while low-order post-Hartree-Fock (MP2) approaches strongly favor the gauche conformer. However, inclusion of semiempirical dispersion effects in density functionals or coupled cluster post-Hartree-Fock models agree in forecasting the simultaneous presence of both conformers in the gas phase with a slightly larger stability (0.7 kcal·mol(-1)) of the gauche conformer. Addition of thermal and entropic effects finally leads to very close Gibbs free energies for both conformers and, thus, to a slight preference for the gauche form due to statistical factors (2 vs 1). The situation remains essentially the same in solution. On these grounds, perturbative vibrational computations including both electrical and mechanical anharmonicities lead to IR and Raman spectra in remarkable agreement with experiment. Full assignment of the IR spectra explains the presence of peaks from gauche or anti conformers. Comparison between computed and experimental Raman spectra confirms that both conformers are present in liquid phase, whereas the anti conformer seems to be preponderant in the solid state. Also computed NMR parameters are in good agreement with experiment.

  12. Quantitative analysis of the redox states of cytochromes in a living L929 (NCTC) cell by resonance Raman microspectroscopy.

    Science.gov (United States)

    Kakita, Minoru; Okuno, Masanari; Hamaguchi, Hiro-o

    2013-03-01

    Raman spectra and images of a living L929 (NCTC) cell have been measured with 532 nm excitation. Both reduced and oxidized forms of cytochromes b and c (cyt b and cyt c) have been observed in situ without any pretreatment. The redox states of cyts b and c have been assessed quantitatively with a spectral analysis. It has been found that reduced cyt c is more abundant than oxidized cyt c, while oxidized cyt b is slightly more abundant than reduced cyt b in a living cell. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. Polarized multiplex coherent anti-Stokes Raman scattering using a picosecond laser and a fiber supercontinuum.

    Science.gov (United States)

    Michel, Sébastien; Courjaud, Antoine; Mottay, Eric; Finot, Christophe; Dudley, John; Rigneault, Hervé

    2011-02-01

    We perform multiplex coherent anti-Stokes Raman scattering (CARS) micro-spectroscopy with a picosecond pulsed laser and a broadband supercontinuum (SC) generated in photonic crystal fiber. CARS signal stability is achieved using an active fiber coupler that avoids thermal and mechanical drifts. We obtain multiplex CARS spectra for test liquids in the 600-2000 cm(-1) spectral range. In addition we investigate the polarization dependence of the CARS spectra when rotating the pump beam linear polarization state relative to the linearly polarized broad stokes SC. From these polarization measurements we deduce the Raman depolarization ratio, the resonant versus nonresonant contribution, the Raman resonance frequency, and the linewidth.

  14. Appropriate observables for investigating narrow resonances in kaon photoproduction off a proton

    CERN Document Server

    Mart, T

    2011-01-01

    The existence of non-strange partner of pentaquark, the J^p = 1/2^+ narrow resonance, has been investigated by utilizing kaon photoproduction off a proton. It is found that the corresponding mass is 1650 MeV and the appropriate observables for investigating this resonance are the recoiled hyperon polarization, the beam-recoil double polarization C_x, and differential cross section at backward angles. Future kaon photoproduction experiments at low energies should focus on these observables.

  15. Control of surface plasmon resonance in out-diffused silver nanoislands for surface-enhanced Raman scattering

    Science.gov (United States)

    Piliugina, E. S.; Heisler, F.; Chervinskii, S. D.; Samusev, A. K.; Lipovskii, A. A.

    2015-12-01

    We present the studies of self-assembled silver nanoislands on the surface of silver ion-exchanged glasses. The nanoislands were formed by out-diffusion of reduced silver atoms from the bulk of the glass to its surface. Control of silver ions distribution in the glass by thermal poling after the ion exchange allowed formation of relatively big, up to 250 nm, isolated silver nanoislands while without the poling an ensemble of silver nanoislands with average size from several to tens of nanometers with random size distribution was formed. The nanoislands were characterized using atomic force microscopy and spectral measurements. We used optical absorption spectroscopy for “random” nanoislands and dark field scattering spectroscopy for isolated ones, corresponding spectra showed peaks in the vicinity of 450 nm and 600 nm, respectively. The “random” nanoislands significantly enhanced Raman scattering from Rhodamine 6G, also the modification of Raman signal from deposited on the surface of the samples bacteriorhodopsin in purple membranes was registered.

  16. High-pressure Fourier transform micro-Raman spectroscopic investigation of diiodine-heterocyclic thioamide adducts.

    Science.gov (United States)

    dos Santos, João Henrique Z; Butler, Ian S; Daga, Vasiliki; Hadjikakou, Sotiris; Hadjiliadis, Nick

    2002-10-01

    The pressure dependences of the Fourier transform micro-Raman spectra of four heterocyclic thioamides [[(bztzdtH)I2] x I2] (1) (bztzdtH = benzothiazole-2-thione), [(bztzdtH)I2] (2), [[(tzdtH)2I+] x I3- x 2I2] (3) (tzdtH = thiazoline-2-thione), and [[(bzimtH)I2]2 x I2 x 2H2O] (4) (bzimtH = benzimidazole-2-thione) have been studied between ambient pressure and 50 kbar. For 1, generation of I3- ions through disproportionation reactions is evident as the pressure is increased. There are empirical linear correlations between the frequency and (I-I) bond length and the applied pressure. The iodine adduct of thioamide 2 is more sensitive to pressure when compared to the 1 or 4 iodine adducts. This difference in behavior may be attributed to differences in crystal structures or to a lower I-I bond order. Monitoring of other vibrational transitions of the thiomide structure reveals several less important pressure dependences.

  17. Investigation of dodecane in three-dimensional porous graphene sponge by Raman mapping

    Science.gov (United States)

    Guo, Xitao; Bi, Hengchang; Zafar, Amina; Liang, Zheng; Shi, Zhixiang; Sun, Litao; Ni, Zhenhua

    2016-02-01

    Three-dimensional (3D) carbon nano-materials, e.g. a graphene sponge (GS) are promising candidates for the removal of pollutants and the separation of oil and water. A systematic study on how oils or organic solvents disperse in the porous structures of 3D carbon nano-materials, and the factors affecting their sorption process, would be beneficial for designing a superior sorbent with desirable porous structures. Here, confocal Raman spectroscopic imaging was utilized to explore the absorption and desorption processes of dodecane (a constituent in petroleum products) in 3D porous GS with different pore size. It was found that dodecane predominately locates within the interior pores composed of reduced graphene oxide (rGO) sheets, which provide storage spaces for the absorbed molecules. The larger pore GS has a higher absorption capacity and faster desorption rate compared to the smaller one, which is due to the higher pore volume and weaker interaction with the absorbed molecules. A possible mechanism was also proposed to explain the role of porous macrostructures on the absorption and desorption properties of GSs.

  18. Investigation of lipid homeostasis in living Drosophila by coherent anti-Stokes Raman scattering microscopy

    Science.gov (United States)

    Chien, Cheng-Hao; Chen, Wei-Wen; Wu, June-Tai; Chang, Ta-Chau

    2012-12-01

    To improve our understanding of lipid metabolism, Drosophila is used as a model animal, and its lipid homeostasis is monitored by coherent anti-Stokes Raman scattering microscopy. We are able to achieve in vivo imaging of larval fat body (analogous to adipose tissue in mammals) and oenocytes (analogous to hepatocytes) in Drosophila larvae at subcellular level without any labeling. By overexpressing two lipid regulatory proteins-Brummer lipase (Bmm) and lipid storage droplet-2 (Lsd-2)-we found different phenotypes and responses under fed and starved conditions. Comparing with the control larva, we observed more lipid droplet accumulation by ˜twofold in oenocytes of fat-body-Bmm-overexpressing (FB-Bmm-overexpressing) mutant under fed condition, and less lipid by ˜fourfold in oenocytes of fat-body-Lsd-2-overexpressing (FB-Lsd-2-overexpressing) mutant under starved condition. Moreover, together with reduced size of lipid droplets, the lipid content in the fat body of FB-Bmm-overexpressing mutant decreases much faster than that of the control and FB-Lsd-2-overexpressing mutant during starvation. From long-term starvation assay, we found FB-Bmm-overexpressing mutant has a shorter lifespan, which can be attributed to faster consumption of lipid in its fat body. Our results demonstrate in vivo observations of direct influences of Bmm and Lsd-2 on lipid homeostasis in Drosophila larvae.

  19. Investigation of an Ultrafast Harmonic Resonant RF Kicker

    Energy Technology Data Exchange (ETDEWEB)

    Huang, Yulu [Univ. of Chinese Academy of Sciences (CAS), Beijing (China)

    2016-10-01

    An Energy Recovery Linac (ERL) based multi-turn electron Circulator Cooler Ring (CCR) is envisaged in the proposed Jefferson Lab Electron Ion Collider (JLEIC) to cool the ion bunches with high energy (55 MeV), high current (1.5 A), high repetition frequency (476.3 MHz), high quality magnetized electron bunches. A critical component in this scheme is a pair of ultrafast kickers for the exchange of electron bunches between the ERL and the CCR. The ultrafast kicker should operate with the rise and fall time in less than 2.1 ns, at the repetition rate of ~10s MHz, and should be able to run continuously during the whole period of cooling. These -and-fall time being combined together, are well beyond the state-of-art of traditional pulsed power supplies and magnet kickers. To solve this technical challenge, an alternative method is to generate this high repetition rate, fast rise-and-fall time short pulse continuous waveform by summing several finite number of (co)sine waves at harmonic frequencies of the kicking repetition frequency, and these harmonic modes can be generated by the Quarter Wave Resonater (QWR) based multifrequency cavities. Assuming the recirculator factor is 10, 10 harmonic modes (from 47.63 MHz to 476.3 MHz) with proper amplitudes and phases, plus a DC offset are combined together, a continuous short pulse waveform with the rise-and-fall time in less than 2.1 ns, repetition rate of 47.63 MHz waveform can be generated. With the compact and matured technology of QWR cavities, the total cost of both hardware development and operation can be reduced to a modest level. Focuse on the technical scheme, three main topics will be discussed in this thesis: the synthetization of the kicking pulse, the design and optimization of the deflecting QWR multi-integer harmonic frequency resonator and the fabrication and bench measurements of a half scale copper prototype. In the kicking pulse synthetization part, we begin with the Fourier Series expansion of an ideal

  20. Redox induced protonation of heme propionates in cytochrome c oxidase: Insights from surface enhanced resonance Raman spectroscopy and QM/MM calculations.

    Science.gov (United States)

    Sezer, Murat; Woelke, Anna-Lena; Knapp, Ernst Walter; Schlesinger, Ramona; Mroginski, Maria Andrea; Weidinger, Inez M

    2017-02-01

    Understanding the coupling between heme reduction and proton translocation in cytochrome c oxidase (CcO) is still an open problem. The propionic acids of heme a3 have been proposed to act as a proton loading site (PLS) in the proton pumping pathway, yet this proposal could not be verified by experimental data so far. We have set up an experiment where the redox states of the two hemes in CcO can be controlled via external electrical potential. Surface enhanced resonance Raman (SERR) spectroscopy was applied to simultaneously monitor the redox state of the hemes and the protonation state of the heme propionates. Simulated spectra based on QM/MM calculations were used to assign the resonant enhanced CH2 twisting modes of the propionates to the protonation state of the individual heme a and heme a3 propionates respectively. The comparison between calculated and measured H2OD2O difference spectra allowed a sound band assignment. In the fully reduced enzyme at least three of the four heme propionates were found to be protonated whereas in the presence of a reduced heme a and an oxidized heme a3 only protonation of one heme a3 propionates was observed. Our data supports the postulated scenario where the heme a3 propionates are involved in the proton pathway.

  1. Reduction of the thermal conductivity in free-standing silicon nano-membranes investigated by non-invasive Raman thermometry

    Directory of Open Access Journals (Sweden)

    E. Chávez-Ángel

    2014-01-01

    Full Text Available We report on the reduction of the thermal conductivity in ultra-thin suspended Si membranes with high crystalline quality. A series of membranes with thicknesses ranging from 9 nm to 1.5 μm was investigated using Raman thermometry, a novel contactless technique for thermal conductivity determination. A systematic decrease in the thermal conductivity was observed as reducing the thickness, which is explained using the Fuchs-Sondheimer model through the influence of phonon boundary scattering at the surfaces. The thermal conductivity of the thinnest membrane with d = 9 nm resulted in (9 ± 2 W/mK, thus approaching the amorphous limit but still maintaining a high crystalline quality.

  2. Investigation of Perchlorate and Water at the Surface of Mars with Raman Scattering

    Science.gov (United States)

    Nikolakakos, G.; Whiteway, J. A.

    2015-12-01

    A major accomplishment of the NASA Phoenix Mars mission was the identification of perchlorate (ClO4-) in the regolith by the Wet Chemistry Laboratory instrument. More recently, the Sample Analysis at Mars instrument on the NASA Curiosity Rover detected the presence of perchlorate in Gale Crater, suggesting that it is globally distributed. Perchlorates are of great interest on Mars due to their high affinity for water vapor (deliquescence) 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 the hydrological cycle on Mars. A sample of magnesium perchlorate was subjected to the water vapor pressure and temperatures found at the landing site of the Phoenix Mars mission. Laser Raman scattering was applied to detect the onset of deliquescence and provide a relative estimate of the quantity of water taken up and subsequently released by the sample. As the temperature of the sample decreased at the same rate as measured on Mars during the evening, significant uptake of water from the atmosphere was observed to occur prior to the frost point temperature being reached. As the temperature was lowered, water uptake continued as saturation was reached and frost formed on the surface surrounding the perchlorate sample. Freezing of the brine film was observed at the eutectic temperature of -67°C and thawing occurred at a temperature of -62°C.

  3. Molecular near-field antenna effect in resonance hyper-Raman scattering: Intermolecular vibronic intensity borrowing of solvent from solute through dipole-dipole and dipole-quadrupole interactions

    Energy Technology Data Exchange (ETDEWEB)

    Shimada, Rintaro; Hamaguchi, Hiro-o, E-mail: hhama@nctu.edu.tw [Department of Applied Chemistry and Institute of Molecular Science, National Chiao Tung University, 1001 University Road, Hsinchu 30010, Taiwan (China)

    2014-05-28

    We quantitatively interpret the recently discovered intriguing phenomenon related to resonance Hyper-Raman (HR) scattering. In resonance HR spectra of all-trans-β-carotene (β-carotene) in solution, vibrations of proximate solvent molecules are observed concomitantly with the solute β-carotene HR bands. It has been shown that these solvent bands are subject to marked intensity enhancements by more than 5 orders of magnitude under the presence of β-carotene. We have called this phenomenon the molecular-near field effect. Resonance HR spectra of β-carotene in benzene, deuterated benzene, cyclohexane, and deuterated cyclohexane have been measured precisely for a quantitative analysis of this effect. The assignments of the observed peaks are made by referring to the infrared, Raman, and HR spectra of neat solvents. It has been revealed that infrared active and some Raman active vibrations are active in the HR molecular near-field effect. The observed spectra in the form of difference spectra (between benzene/deuterated benzene and cyclohexane/deuterated cyclohexane) are quantitatively analyzed on the basis of the extended vibronic theory of resonance HR scattering. The theory incorporates the coupling of excited electronic states of β-carotene with the vibrations of a proximate solvent molecule through solute–solvent dipole–dipole and dipole–quadrupole interactions. It is shown that the infrared active modes arise from the dipole–dipole interaction, whereas Raman active modes from the dipole–quadrupole interaction. It is also shown that vibrations that give strongly polarized Raman bands are weak in the HR molecular near-field effect. The observed solvent HR spectra are simulated with the help of quantum chemical calculations for various orientations and distances of a solvent molecule with respect to the solute. The observed spectra are best simulated with random orientations of the solvent molecule at an intermolecular distance of 10 Å.

  4. FT-Raman and FT-Infrared investigations of archaeological artefacts from Foeni Neolithic site (Banat, Romania

    Directory of Open Access Journals (Sweden)

    Simona Cîntă Pînzaru

    2008-08-01

    Full Text Available An impressive collection of chert artefacts from the Foeni Neolithic archaeological site (Timiş County, Banat region, Romania is hosted by the Banat Museum in Timişoara. A representative set of seven specimens was non-destructively investigated using FT-Raman and ATR-FT-IR spectroscopy. The research was carried out for checking if these readily-available, non-destructive, fast, and cheap methods, which do not require preliminary sample preparation could provide significant information for characterizing the mineral composition of chert artefacts. Based on vibrational data, it was confirmed that the raw material was represented by microcrystalline quartz and moganite, with local concentrations of accessory minerals (calcite, dolomite, and clay minerals. In spite of their wide macroscopic heterogeneity (colour, transparency, based on single point FT-Raman measurements the chert artefacts could not be assigned to distinctive groups of raw silica materials, in order to provide specific arguments for provenance studies. However, the presence of specific accessory minerals (dolomite, illite pointed to distinctive genetic conditions in the case of one lithic material. Sets of measurements (mapping are required for statistically characterizing each artefact specimen. IR data were less significant, due to the rough surface texture of the specimens in contact with the ZnSe crystal of the ATR-FT-IR module. However, illite was identified based solely on its contribution to the IR spectrum. This pioneering study on chert artefacts from Romania based on optical spectroscopic methods shows that there are good premises for a systematic investigation of highly-valuable museum collections, in particular in terms of chert geology.

  5. In Vitro Polarized Resonance Raman Study of N719 and N719-TBP in Dye Sensitized Solar Cells

    DEFF Research Database (Denmark)

    Hassing, Søren; Jernshøj, Kit Drescher; Nguyen, Phuong Tuyet;

    2016-01-01

    the adsorption of the dye on TiO2 can be obtained. Furthermore it is found that the polarization fluorescence anisotropy is very different for adsorbed and non-adsorbed dye molecules. This information is automatically obtained when processing the Raman data. The conclusion is that if the polarization properties......Abstract: The working efficiency of dye-sensitized solar cells (DSCs) depends on the long-term stability of the dye itself and on the microscopic structure of the dye-semiconductor interface. Previous experimental studies of DSCs based on ruthenium dye with bipyridine ligands (N719) adsorbed...... on N719/TiO2 – DSCs that by combining an analysis of the wave number dependent polarization of these modes with the small shifts observed in the visible absorption spectra of adsorbed, non-adsorbed molecules and degradation products new and more reliable information about dye stability and about...

  6. Resonance Enhanced Multi-Photon Ionization (rempi) and Double Resonance Uv-Uv and Ir-Uv Spectroscopic Investigation Isocytosine

    Science.gov (United States)

    Lee, Seung Jun; Min, Ahreum; Ahn, Ahreum; Moon, Cheol Joo; Choi, Myong Yong; Ishiuchi, Shun-Ichi; Miyazaki, Mitsuhiko; Fujii, Masaaki

    2013-06-01

    Isocytosine(iC), 2-aminouracil, is a non-natural nucleobase and its functional group's positions resemble those of guanine; therefore, its spectroscopic investigation is worthy of attention especially for the natural/unnatural base pairs with guanine and isoguanine. In this study, resonance enhanced multi-photon ionization (REMPI) and UV/IR-UV double resonance spectra of iC in the gas phase are presented. The collaboration work between Tokyo Institute of Technology, Japan and Gyeongsang National University, Korea using laser ablation and thermal evaporation, respectively, for producing jet-cooled iC is presented and discussed. The REMPI spectrum of iC monomers is recorded in the spectral range of 35000 to 36400cm-1, showing very congested π-π* vibronic bands. UV-UV hole burning spectroscopy is further conducted to investigate the conformational landscapes of iC monomers. Moreover, the presence of free OH band from IR-UV double resonance spectroscopy in combination with quantum chemical calculations convinces that the iC monomer in free-jet expansion experiment is an enol tautomer. However, a possible presence of a keto tautomer of iC may be provided by employing a pico-second experiment on iC.

  7. Investigation of Corrosion Inhibitors by Nuclear Quadrupole Resonance Relaxometry Method

    Directory of Open Access Journals (Sweden)

    Nikolay Sinyavsky

    2015-12-01

    Full Text Available The changes taking place with the corrosion-resistant coating, but not the state of the surface subjected to corrosion are investigated in this paper in contrast to traditional approaches. We used the method of nitrogen relaxometry NQR and multi-exponential inversion of decay of longitudinal and transverse components of the nuclear magnetization is applied for the first time for this purpose. The results of experimental studies of changes in the distributions of spin-spin and spin-lattice relaxation of crystallite powder of sodium nitrite and urotropin, the mixture of which is used as a corrosion inhibitor of ferrous metals are considered.

  8. Theoretical Investigation of C-H Vibrational Spectroscopy. 2. Unified Assignment Method of IR, Raman, and Sum Frequency Generation Spectra of Ethanol.

    Science.gov (United States)

    Wang, Lin; Ishiyama, Tatsuya; Morita, Akihiro

    2017-09-14

    Using the flexible and polarizable model in the preceding paper, we performed comprehensive analysis of C-H stretching vibrations of ethanol and partially deuterated ones by molecular dynamics (MD) simulation. The overlapping band structures of the C-H stretching region including (i) methyl and methylene, (ii) the number of modes with Fermi resonances, and (iii) different trans/gauche conformers are disentangled by various analysis methods, such as isotope exchange, empirical potential parameter shift analysis, and separate calculations of conformers. The present analysis with MD simulation revealed unified assignment of infrared, Raman, and sum frequency generation (SFG) spectra. The analysis confirmed that the different conformers have significant influence on the assignment of CH2 vibrations. Band components and their signs in the imaginary χ((2)) spectra of SFG under various polarizations are also understood from the common assignment with the infrared and Raman spectra.

  9. Magnetic resonance investigations of lipid motion in isotropic bicelles.

    Science.gov (United States)

    Andersson, August; Mäler, Lena

    2005-08-16

    The dynamics of DMPC in different isotropic bicelles have been investigated by NMR and EPR methods. The local dynamics were obtained by interpretation of 13C NMR relaxation measurements of DMPC in the bicelles, and these results were compared to EPR spectra of spin-labeled lipids. The overall size of the bicelles was investigated by PFG NMR translational diffusion measurements. The dynamics and relative sizes were compared among three different bicelles: [DMPC]/[DHPC] = 0.25, [DMPC]/[DHPC] = 0.5, and [DMPC]/[CHAPS] = 0.5. The local motion is found to depend much more strongly on the choice of the detergent, rather than the overall size of the bicelle. The results provide an explanation for differences in apparent dynamics for different peptides, which are bound to bicelles. This in turn determines under what conditions reasonable NMR spectra can be observed. A model is presented in which extensive local motion, in conjunction with the overall size, affects the spectral properties. An analytical expression for the size dependence of the bicelles, relating the radius of the bilayer region with physical properties of the detergent and the lipid, is also presented.

  10. Passively mode locked Raman laser

    CERN Document Server

    Liang, W; Savchenkov, A A; Matsko, A B; Seidel, D; Maleki, L

    2010-01-01

    We report on the observation of a novel mode locked optical comb generated at the Raman offset (Raman comb) in an optically pumped crystalline whispering gallery mode resonator. Mode locking is confirmed via measurement of the radio-frequency beat note produced by the optical comb on a fast photodiode. Neither the conventional Kerr comb nor hyper-parametric oscillation is observed when the Raman comb is present.

  11. Raman scattering investigations of the interaction of a COV with pure and acid doped ice particles

    Science.gov (United States)

    Facq, S.; Oancea, A.; Focsa, C.; Chazallon, B.

    2009-04-01

    Ice present in polar stratosphere is as well a common component of the troposphere, particularly in cirrus clouds widespread in tropopause and upper troposphere region. With water droplets, ice constitutes the condensed matter that can interact with atmospheric trace gases via many different trapping processes (co-deposition i.e; incorporation during growing ice conditions, adsorption, freezing etc). The incorporation of trace gases in ice surface/volume can both affect the atmospheric chemistry and the ice structure and reactivity. This can therefore modify the nature and composition of the incorporated species in ice, or in the gas phase. Recently, field measurements have demonstrated the presence of nitric acid in ice particles from cirrus clouds(1,2) (concentration between 0.63 wt% and 2.5 wt %). Moreover, laboratory experiments have shown that the uptake of atmospheric trace gases can be enhanced up to 1 or 2 orders of magnitude in these doped ice particles. Among trace gases capable to interact with atmospheric condensed matter figure volatile organic compounds such as aldehydes, ketones and alcohols (ex: ethanol and methanol). They play an important role in the upper troposphere (3,4) and snowpack chemistry (5) as they can be easily photolysed, producing free radicals and so influence the oxidizing capacity and the ozone-budget of the atmosphere (3,4). The temperature range at which these physico-chemical processes occur extents between ~ 190 K and 273K. Interaction between ice and trace gases are therefore largely dependent on the ice surface properties as well as on the phase formation dynamic (crystalline or not). This study aims to examine and characterize the incorporation of a COV (ex: ethanol), at the surface or in the volume of ice formed by different growth mechanisms (vapour deposition or droplets freezing). Vibrational spectra of water OH and ethanol CH-spectral regions are analysed using confocal micro-Raman spectroscopy at different temperatures

  12. Continuous-wave Raman Lasing in Aluminum Nitride Microresonators

    CERN Document Server

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

    2016-01-01

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

  13. Investigation of the cutaneous penetration behavior of dexamethasone loaded to nano-sized lipid particles by EPR spectroscopy, and confocal Raman and laser scanning microscopy.

    Science.gov (United States)

    Lohan, Silke B; Saeidpour, Siavash; Solik, Agnieszka; Schanzer, Sabine; Richter, Heike; Dong, Pin; Darvin, Maxim E; Bodmeier, Roland; Patzelt, Alexa; Zoubari, Gaith; Unbehauen, Michael; Haag, Rainer; Lademann, Jürgen; Teutloff, Christian; Bittl, Robert; Meinke, Martina C

    2017-07-01

    An improvement of the penetration efficiency combined with the controlled release of actives in the skin can facilitate the medical treatment of skin diseases immensely. Dexamethasone (Dx), a synthetic glucocorticoid, is frequently used for the treatment of inflammatory skin diseases. To investigate the penetration of nano-sized lipid particles (NLP) loaded with Dx in comparison to a commercially available base cream, different techniques were applied. Electron paramagnetic resonance (EPR) spectroscopy was used to monitor the penetration of Dx, which was covalently labeled with the spin probe 3-(Carboxy)-2,2,5,5-tetramethyl-1-pyrrolidinyloxy (PCA). The penetration into hair follicles was studied using confocal laser scanning microscopy (CLSM) with curcumin-loaded NLP. The penetration of the vehicle was followed by confocal Raman microscopy (CRM). Penetration studies using excised porcine skin revealed a more than twofold higher penetration efficiency for DxPCA into the stratum corneum (SC) after 24h incubation compared to 4h incubation when loaded to the NLP, whereas when applied in the base cream, almost no further penetration was observed beyond 4h. The distribution of DxPCA within the SC was investigated by consecutive tape stripping. The release of DxPCA from the base cream after 24h in deeper SC layers and the viable epidermis was shown by EPR. For NLP, no release from the carrier was observed, although DxPCA was detectable in the skin after the complete SC was removed. This phenomenon can be explained by the penetration of the NLP into the hair follicles. However, penetration profiles measured by CRM indicate that NLP did not penetrate as deeply into the SC as the base cream formulation. In conclusion, NLP can improve the accumulation of Dx in the skin and provide a reservoir within the SC and in the follicular infundibula. Copyright © 2017 Elsevier B.V. All rights reserved.

  14. Using 13C-labeled benzene and Raman gas spectroscopy to investigate respiration and biodegradation kinetics following soil contamination

    Science.gov (United States)

    Jochum, Tobias; Popp, Juergen; Frosch, Torsten

    2016-04-01

    Soil and groundwater contamination with benzene can cause serious environmental damages. However, many soil microorganisms are capable to adapt and known to strongly control the fate of organic contamination. Cavity enhanced Raman gas spectroscopy (CERS) was applied to investigate the short-term response of indigenous soil bacteria to a sudden surface contamination with benzene regarding the temporal variations of gas products and their exchange rates with the adjacent atmosphere. 13C-labeled benzene was spiked on a silty-loamy soil column (sampled from Hainich National Park, Germany) in order to track and separate the changes in heterotrophic soil respiration - involving 12CO2 and O2 - from the microbial process of benzene degradation, which ultimately forms 13CO2.1 The respiratory quotient (RQ) of 0.98 decreased significantly after the spiking and increased again within 33 hours to a value of 0.72. This coincided with maximum 13CO2 concentration rates (0.63 μ mol m-2 s-1), indicating highest benzene degradation at 33 hours after the spiking event. The diffusion of benzene in the headspace and the biodegradation into 13CO2 were simultaneously monitored and 12 days after the benzene spiking no measurable degradation was detected anymore.1 The RQ finally returned to a value of 0.96 demonstrating the reestablished aerobic respiration. In summary, this study shows the potential of combining Raman gas spectroscopy and stable isotopes to follow soil microbial biodegradation dynamics while simultaneously monitoring the underlying respiration behavior. Support by the Collaborative Research Center 1076 Aqua Diva is kindly acknowledged. We thank Beate Michalzik for soil analysis and discussion. 1. T. Jochum, B. Michalzik, A. Bachmann, J. Popp and T. Frosch, Analyst, 2015, 140, 3143-3149.

  15. FT-Raman investigation of milled-wood lignins : softwood, hardwood, and chemically modified black spruce lignins

    Science.gov (United States)

    Umesh P. Agarwal; James D. McSweeny; Sally A. Ralph

    2011-01-01

    Raman spectroscopy is being increasingly applied to study wood and other lignin-containing biomass/biomaterials. Lignin’s contribution to the Raman spectra of such materials needs to be understood in the context of various lignin structures, substructures, and functional groups so that lignin-specific features could be identified and the spectral information could be...

  16. Reversible Charge Trapping in Bis-Carbazole-Diimide Redox Polymers with Complete Luminescence Quenching Enabling Nondestructive Read-Out by Resonance Raman Spectroscopy

    Science.gov (United States)

    2017-01-01

    The coupling of substituted carbazole compounds through carbon–carbon bond formation upon one-electron oxidation is shown to be a highly versatile approach to the formation of redox polymer films. Although the polymerization of single carbazole units has been proposed earlier, we show that by tethering pairs of carbazoles double sequential dimerization allows for facile formation of redox polymer films with fine control over film thickness. We show that the design of the monomers and in particular the bridging units is key to polymer formation, with the diaminobenzene motif proving advantageous, in terms of the matching to the redox potentials of the monomer and polymer film and thereby avoiding limitations in film thickness (autoinsulation), but introduces unacceptable instability due to the intrinsic redox activity of this moiety. The use of a diimide protecting group both avoids complications due to p-diamino-benzene redox chemistry and provides for a redox polymer in which the photoluminescence of the bis-carbazole moiety can be switched reversibly (on/off) with redox control. The monomer design approach is versatile enabling facile incorporation of additional functional units, such as naphthalene. Here we show that a multicomponent carbazole/naphthalene containing monomer (APCNDI) can form redox polymer films showing both p- and n- conductivity under ambient conditions and allows access to five distinct redox states, and a complex electrochromic response covering the whole of the UV/vis–NIR spectral region. The highly effective quenching of the photoluminescence of both components in poly-APCNDI enables detailed characterization of the redox polymer films. The poly-APCNDI films show extensive charge trapping, which can be read out spectroscopically in the case of films and is characterized as kinetic rather than chemical in origin on the basis of UV/vis–NIR absorption and resonance Raman spectroscopic analyses. The strong resonantly enhanced Raman

  17. Raman Spectroscopy of Ocular Tissue

    Science.gov (United States)

    Ermakov, Igor V.; Sharifzadeh, Mohsen; Gellermann, Warner

    excised tissue samples and synthetic preparations and thus to identify potential biomarkers for the onset of this disease. Using resonance Raman detection techniques, the concentration and spatial distribution of macular pigment, a protective compound, can be detected in the living human retina Useable in clinical settings for patient screening, the technology is suitable to investigate correlations between pigment concentration levels and risk for macular degeneration and to monitor increases in pigment levels occurring as a result of dietary intervention strategies.

  18. Equatorial ionosphere semiannual oscillation investigated from Schumann resonance measurements on board the C/NOFS satellite

    Science.gov (United States)

    Simões, Fernando; Pfaff, Robert; Freudenreich, Henry; Klenzing, Jeffrey; Rowland, Douglas; Bromund, Kenneth; Kepko, Larry; Le, Guan; Liebrecht, Maria Carmen; Martin, Steven; Uribe, Paulo

    2013-11-01

    of Schumann resonance signatures in the equatorial ionosphere offers remote sensing capabilities for the investigation of tropospheric and space weather effects in the ionosphere. Schumann resonances are electromagnetic oscillations in the earth-ionosphere cavity produced by lightning activity. Analysis of AC electric field measurements gathered by the Communications/Navigation Outage Forecasting System satellite reveals a semiannual pattern in Schumann resonance data recorded during nighttime in the equatorial ionosphere. This pattern observed in the Schumann resonance amplitude is expected to help validate—or at least constrain—potential mechanisms proposed to explain the semiannual oscillation observed in different geophysical records, such as those reported in a variety of tropospheric, ionospheric/thermospheric, and magnetospheric observations.

  19. Shining light on neurosurgery diagnostics using Raman spectroscopy.

    Science.gov (United States)

    Broadbent, Brandy; Tseng, James; Kast, Rachel; Noh, Thomas; Brusatori, Michelle; Kalkanis, Steven N; Auner, Gregory W

    2016-10-01

    Surgical excision of brain tumors provides a means of cytoreduction and diagnosis while minimizing neurologic deficit and improving overall survival. Despite advances in functional and three-dimensional stereotactic navigation and intraoperative magnetic resonance imaging, delineating tissue in real time with physiological confirmation is challenging. Raman spectroscopy is a promising investigative and diagnostic tool for neurosurgery, which provides rapid, non-destructive molecular characterization in vivo or in vitro for biopsy, margin assessment, or laboratory uses. The Raman Effect occurs when light temporarily changes a bond's polarizability, causing change in the vibrational frequency, with a corresponding change in energy/wavelength of the scattered photon. The recorded inelastic scattering results in a "fingerprint" or Raman spectrum of the constituent under investigation. The amount, location, and intensity of peaks in the fingerprint vary based on the amount of vibrational bonds in a molecule and their ensemble interactions with each other. Distinct differences between various pathologic conditions are shown as different intensities of the same peak, or shifting of a peak based on the binding conformation. Raman spectroscopy has potential for integration into clinical practice, particularly in distinguishing normal and diseased tissue as an adjunct to standard pathologic diagnosis. Further, development of fiber-optic Raman probes that fit through the instrument port of a standard endoscope now allows researchers and clinicians to utilize spectroscopic information for evaluation of in vivo tissue. This review highlights the need for such an instrument, summarizes neurosurgical Raman work performed to date, and discusses the future applications of neurosurgical Raman spectroscopy.

  20. Anti-Stokes Resonance Raman of Ir Illuminated Dendrimer Iron (III)-Porphyrins%红外辐照下树枝状铁(iii)卟啉的反斯托克斯共振拉曼

    Institute of Scientific and Technical Information of China (English)

    MO Yu-jun; D.L.Jiang; M.Uymura; T.Aida; T.Kitagawa

    2005-01-01

    The benzene dendrimers of Fe(Ⅲ) tetraphenyl porphyrin chloride[LnFe(Ⅲ)TPPCl] with n = 3, 4, and 5 (n: number of layers) have been synthesized and the IR illumination effects at benzene bands were examined with anti- Stokes resonance Raman speetroseopy for their dioxane solutions.Boltzman temperatures were determined from the Stokes to anti - Stokes intensity ratio for the speetra excited at 413.1 nm in the presence and absence of IR illumination.

  1. Resonances

    DEFF Research Database (Denmark)

    an impetus or drive to that account: change, innovation, rupture, or discontinuity. Resonances: Historical Essays on Continuity and Change explores the historiographical question of the modes of interrelation between these motifs in historical narratives. The essays in the collection attempt to realize...... theoretical consciousness through historical narrative ‘in practice’, by discussing selected historical topics from Western cultural history, within the disciplines of history, literature, visual arts, musicology, archaeology, philosophy, and theology. The title Resonances indicates the overall perspective...

  2. Investigation of Real-Time Photorepair Activity on DNA via Surface Plasmon Resonance

    OpenAIRE

    2012-01-01

    4/24/2014 PLOS ONE: Investigation of Real-Time Photorepair Activity on DNA via Surface Plasmon Resonance http://www.plosone.org/article/info%3Adoi%2F10.1371%2Fjournal.pone.0044392 1/9 Published: August 29, 2012 DOI: 10.1371/journal.pone.0044392 Investigation of Real-Time Photorepair Activity on DNA via Surface Plasmon Resonance Rıza Kizilel , Enis Demir, Selimcan Azizoglu, Hande Asımgi, Ibrahim Halil Kavakli , Seda Kizilel Corrections 25 Oct 2012: Kizilel R, Demir E, Aziz...

  3. A Micro Raman Investigation of Viscoelasticity in Short Fibre Reinforced Polymer Matrix Composites

    DEFF Research Database (Denmark)

    Schjødt-Thomsen, Jan

    The purpose of the present Ph.D. project is to investigate the load transfer mechanisms between the fibre and matrix and the stress/strain fields in and around single fibres in short fibre reinforced viscoelastic polymer matrix composites subjected to various loading histories. The materials...

  4. Observation of second-order hyper-Raman generation in LiNbO3 whispering-gallery mode disk resonators

    CERN Document Server

    Simons, Matt T

    2011-01-01

    In this manuscript we report experimental demonstration of nonlinear frequency conversion at several optical frequencies in a whispering-gallery mode resonator (WGMR). Due to the enhancement of nonlinear interactions inside a WGMR, interaction of a 1064 nm pump field with a LiNbO3 disk produced a weak, but measurable non-phase matched 532 nm second harmonic field at room temperature (>100C below the phase-matching temperature), for pump powers of a few tens of mW. For higher pump powers, we observed the generation of four additional fields at 545 nm, 559 nm, 573 nm, and 587 nm. The relative spectral shift between two consecutive fields corresponds to a 455 cm^-1 vibrational mode in LiNbO3 crystal. Our preliminary analysis indicates that these fields are the result of a multi-phonon hyper-Raman scattering, in which two photons of the pump field are converted into one photon of a higher-frequency field and one or several optical phonons.

  5. Observation of second-order hyper-Raman generation in LiNbO3 whispering-gallery mode disk resonators.

    Science.gov (United States)

    Simons, Matt T; Novikova, Irina

    2011-08-15

    In this Letter we report experimental demonstration of nonlinear frequency conversion at several optical frequencies in a whispering-gallery mode resonator (WGMR). Because of the enhancement of nonlinear interactions inside a WGMR, interaction of a 1064 nm pump field with a LiNbO(3) disk produced a weak but measurable non-phase-matched 532 nm second-harmonic field at room temperature (>100 °C below the phase-matching temperature) for pump powers of a few tens of milliwatts. For higher pump powers, we observed the generation of four additional fields at 545, 559, 573, and 587 nm. The relative spectral shift between two consecutive fields corresponds to a 455 cm(-1) vibrational mode in LiNbO(3) crystal. Our preliminary analysis indicates that these fields are the result of a multiphonon hyper-Raman scattering in which two photons of the pump field are converted into one photon of a higher-frequency field and one or several optical phonons.

  6. Comparison of simplified sum-over-state expressions to calculate resonance Raman intensities including Franck-Condon and Herzberg-Teller effects

    Science.gov (United States)

    Guthmuller, Julien

    2016-02-01

    Sum-over-state (SOS) expressions to simulate absorption spectroscopy and resonance Raman (RR) scattering including Franck-Condon (FC) and Herzberg-Teller (HT) effects are described. Starting from the general SOS method, several simplified SOS formulae are derived. In particular, within the so-called independent mode displaced harmonic oscillator model, it is shown that including the vibronic structure in the absorption and RR spectra only requires the calculation of FC overlap integrals of the type , where g, e, and v stand for the electronic ground state, excited state, and vibrational quantum number, respectively. Additionally, an approximation of the latter approach is introduced, referred as the simplified Φe method, in which the FC factors are neglected. This method is advantageous from the computational point of view and it is demonstrated that it reproduces the main characteristics of the more involved approaches. The merits and drawbacks of the different methods are discussed by applying them to the prototypical compound of Rhodamine 6G. Overall, this work intends to unravel and clarify some differences in the SOS theories of RR scattering.

  7. Quaternary ammonium oxidative demethylation: X-ray crystallographic, resonance Raman, and UV-visible spectroscopic analysis of a Rieske-type demethylase.

    Science.gov (United States)

    Daughtry, Kelly D; Xiao, Youli; Stoner-Ma, Deborah; Cho, Eunsun; Orville, Allen M; Liu, Pinghua; Allen, Karen N

    2012-02-08

    Herein, the structure resulting from in situ turnover in a chemically challenging quaternary ammonium oxidative demethylation reaction was captured via crystallographic analysis and analyzed via single-crystal spectroscopy. Crystal structures were determined for the Rieske-type monooxygenase, stachydrine demethylase, in the unliganded state (at 1.6 Å resolution) and in the product complex (at 2.2 Å resolution). The ligand complex was obtained from enzyme aerobically cocrystallized with the substrate stachydrine (N,N-dimethylproline). The ligand electron density in the complex was interpreted as proline, generated within the active site at 100 K by the absorption of X-ray photon energy and two consecutive demethylation cycles. The oxidation state of the Rieske iron-sulfur cluster was characterized by UV-visible spectroscopy throughout X-ray data collection in conjunction with resonance Raman spectra collected before and after diffraction data. Shifts in the absorption band wavelength and intensity as a function of absorbed X-ray dose demonstrated that the Rieske center was reduced by solvated electrons generated by X-ray photons; the kinetics of the reduction process differed dramatically for the liganded complex compared to unliganded demethylase, which may correspond to the observed turnover in the crystal.

  8. Au-Ag-Au double shell nanoparticles-based localized surface plasmon resonance and surface-enhanced Raman scattering biosensor for sensitive detection of 2-mercapto-1-methylimidazole.

    Science.gov (United States)

    Liao, Xue; Chen, Yanhua; Qin, Meihong; Chen, Yang; Yang, Lei; Zhang, Hanqi; Tian, Yuan

    2013-12-15

    In this paper, Au-Ag-Au double shell nanoparticles were prepared based on the reduction of the metal salts HAuCl4 and AgNO3 at the surface of seed particles. Due to the synergistic effect between Au and Ag, the hybrid nanoparticles are particularly stable and show excellent performances on the detection of 2-mercapto-1-methylimidazole (methimazole). The binding of target molecule at the surface of Au-Ag-Au double shell nanoparticles was demonstrated based on both localized surface plasmon resonance (LSPR) and surface-enhanced Raman scattering (SERS) spectra. The LSPR intensity is directly proportional to the methimazole concentration in the range of 0.10-3.00×10(-7) mol L(-1). The SERS spectrum can be applied in identification of methimazole molecule. The LSPR coupled with SERS based on the Au-Ag-Au double shell nanoparticles would be very attractive for the quantitative determination and qualitative analysis of the analytes in medicines.

  9. Resonance Raman spectroscopy of chemically modified and isotopically labelled purple membranes: I. A critical examination of the carbon-nitrogen vibrational modes

    Energy Technology Data Exchange (ETDEWEB)

    Ehrenberg, B. (Cornell Univ., Ithaca, NY); Lemley, A.T.; Lewis, A.; Zastrow, M.V.; Crespi, H.L.

    1980-01-01

    Resonance Raman spectra of bacteriorhodopsin are compared to the spectra of this protein modified in the following ways: (1) selective deuteration at the C-15 carbon atom of retinal, (2) full deuteration of the retinal, (3) the addition of a conjugated double bond in the ..beta..-ionone ring (3-dehydroretinal), (4) full deuteration of the protein and lipid components, (5) /sup 15/N enrichment of the entire membrane and (6) deuteration of the entire membrane. A detailed comparison of the /sup 15/N-enriched membrane and naturally occurring purple membrane from 800 cm/sup -1/ to 1700 cm/sup -1/ reveals that /sup 15/N enrichment affects the frequency of only two vibrational modes. These occur at 1642 cm/sup -1/ and 1620 cm/sup -1/ in naturally occurring purple membrane and at 1628 cm/sup -1/ and 1615 cm/sup -1/ in the /sup 15/N-enriched samples. Therefore, this pair of bands reflects the states of protonation of the Schiff base.

  10. Structure-dependent localized surface plasmon resonance characteristics and surface enhanced Raman scattering performances of quasi-periodic nanoarrays: Measurements and analysis

    Energy Technology Data Exchange (ETDEWEB)

    Chen, Dong; Zhou, Jun, E-mail: zhoujun@nbu.edu.cn [Institute of Photonics, Faculty of Science, Ningbo University, Ningbo 315211 (China); Rippa, Massimo; Petti, Lucia [Institute of Applied Sciences and Intelligent Systems “E. Caianiello” of CNR, Via Campi Flegrei 34, 80072 Pozzuoli (Italy)

    2015-10-28

    A set of periodic and quasi-periodic Au nanoarrays with different morphologies have been fabricated by using electron beam lithography technique, and their optical properties have been examined experimentally and analyzed theoretically by scanning near-field optical microscope and finite element method, respectively. Results present that the localized surface plasmon resonance of the as-prepared Au nanoarrays exhibit the structure-depended characteristics. Comparing with the periodic nanoarrays, the quasi-periodic ones demonstrate stronger electric field enhancement, especially for Thue-Morse nanoarray. Meanwhile, the surface enhanced Raman scattering (SERS) spectra of 4-mercaptobenzoic acid molecular labeled nanoarrays show that the quasi-periodic nanoarrays exhibit distinct SERS enhancement, for example, a higher enhancement factor of ∼10{sup 7} is obtained for the Thue-Morse nanoarray consisted of square pillars of 100 nm size. Therefore, it is significant to optimally design and fabricate the chip-scale quasi-periodic nanoarrays with high localized electric field enhancement for SERS applications in biosensing field.

  11. Microscopic solvation environments in a prototype room-temperature ionic liquid as elucidated by resonance Raman spectroscopy of iodine and bromine

    Science.gov (United States)

    Saha, Satyen; Okajima, Hajime; Homma, Osamu; Hamaguchi, Hiro-o.

    2017-04-01

    Microscopic solvation environments in a prototype ionic liquid, bmimTf2N; 1-butyl-3-methyl-imidazolium-bis(trifluoromethanesulfonyl)imide, have been studied with the use of halides, X2 and Xn- (X = I, Br; n = 3,5), as molecular probes. Resonance Raman spectroscopy has been used to detect these halogen species existing in bmimTf2N as well as in reference solvents including heptane, cyclohexane, KX/H2O and benzene. In heptane and cyclohexane, only free X2 species are detected. In KX/H2O, only Xn- and, in benzene, only benzene-X2 complexes are detected. On the contrary, free X2 and Xn- are concomitantly detected in bmimTf2N, indicating that there are two distinct solvation environments in bmimTf2N, non-polar environments that solvate free X2 and polar environments that stabilize Xn-. These two distinct solvation environments are most likely to arise from microscopic structural heterogeneity of ionic liquids.

  12. N-hydroxyguanidines as new heme ligands: UV-visible, EPR, and resonance Raman studies of the interaction of various compounds bearing a C=NOH function with microperoxidase-8.

    Science.gov (United States)

    Lefevre-Groboillot, D; Dijols, S; Boucher, J L; Mahy, J P; Ricoux, R; Desbois, A; Zimmermann, J L; Mansuy, D

    2001-08-21

    Interaction between microperoxidase-8 (MP8), a water-soluble hemeprotein model, and a wide range of N-aryl and N-alkyl N'-hydroxyguanidines and related compounds has been investigated using UV-visible, EPR, and resonance Raman spectroscopies. All the N-hydroxyguanidines studied bind to the ferric form of MP8 with formation of stable low-spin iron(III) complexes characterized by absorption maxima at 405, 535, and 560 nm. The complex obtained with N-(4-methoxyphenyl) N'-hydroxyguanidine exhibits EPR g-values at 2.55, 2.26, and 1.86. The resonance Raman (RR) spectrum of this complex is also in agreement with an hexacoordinated low-spin iron(III) structure. The dissociation constants (K(s)) of the MP8 complexes with mono- and disubstituted N-hydroxyguanidines vary between 15 and 160 microM at pH 7.4. Amidoximes also form low-spin iron(III) complexes of MP8, although with much larger dissociation constants. Under the same conditions, ketoximes, aldoximes, methoxyguanidines, and guanidines completely fail to form such complexes with MP8. The K(s) values of the MP8-N-hydroxyguanidine complexes decrease as the pH of the solution is increased, and the affinity of the N-hydroxyguanidines toward MP8 increases with the pK(a) of these ligands. Altogether these results show that compounds involving a -C(NHR)=NOH moiety act as good ligands of MP8-Fe(III) with an affinity that depends on the electron-richness of this moiety. The analysis of the EPR spectrum of the MP8-N-hydroxyguanidine complexes according to Taylor's equations shows a strong axial distortion of the iron, typical of those observed for hexacoordinated heme-Fe(III) complexes with at least one pi donor axial ligand (HO(-), RO(-), or RS(-)). These data strongly suggest that N-hydroxyguanidines bind to MP8 iron via their oxygen atom after deprotonation or weakening of their O-H bond. It thus seems that N-hydroxyguanidines could constitute a new class of strong ligands for hemeproteins and iron(III)-porphyrins.

  13. A Study of the Dynamics of the Heme Pocket and C-helix in CooA upon CO Dissociation Using Time-Resolved Visible and UV Resonance Raman Spectroscopy.

    Science.gov (United States)

    Otomo, Akihiro; Ishikawa, Haruto; Mizuno, Misao; Kimura, Tetsunari; Kubo, Minoru; Shiro, Yoshitsugu; Aono, Shigetoshi; Mizutani, Yasuhisa

    2016-08-18

    CooA is a CO-sensing transcriptional activator from the photosynthetic bacterium Rhodospirillum rubrum that binds CO at the heme iron. The heme iron in ferrous CooA has two axial ligands: His77 and Pro2. CO displaces Pro2 and induces a conformational change in CooA. The dissociation of CO and/or ligation of the Pro2 residue are believed to trigger structural changes in the protein. Visible time-resolved resonance Raman spectra obtained in this study indicated that the ν(Fe-His) mode, arising from the proximal His77-iron stretch, does not shift until 50 μs after the photodissociation of CO. Ligation of the Pro2 residue to the heme iron was observed around 50 μs after the photodissociation of CO, suggesting that the ν(Fe-His) band exhibits no shift until the ligation of Pro2. UV resonance Raman spectra suggested structural changes in the vicinity of Trp110 in the C-helix upon CO binding, but no or very small spectral changes in the time-resolved UV resonance Raman spectra were observed from 100 ns to 100 μs after the photodissociation of CO. These results strongly suggest that the conformational change of CooA is induced by the ligation of Pro2 to the heme iron.

  14. Semiconductors Investigated by Time Resolved Raman Absorption and Photoluminescence Spectroscopy Using Femtosecond and Picosecond Laser Techniques.

    Science.gov (United States)

    1983-05-05

    This report summarizes the research progress achieved in the period 1979-1982 in the research effort supported by AFOSR 80-0079. Two main areas of research are: picosecond and subpicosecond laser development and application and time-resolved studies of semiconductors. In the subpicosecond laser development program we investigated a variety of cavities of different physical parameters. A stable and reliable oscillator, which produces 200 fsec pulses, has been developed using

  15. Raman Scattering Proof-of-Concept Investigation to Detect Particle Phase in the Propulsion System Lab (PSL) Icing Duct Project

    Data.gov (United States)

    National Aeronautics and Space Administration — To determine a percent freeze-out between liquid water and solid ice will add an important dimension to the cloud characterization. This Raman technique might also...

  16. An Investigation on the He−(1s2s2 2S Resonance in Debye Plasmas

    Directory of Open Access Journals (Sweden)

    Arijit Ghoshal

    2017-01-01

    Full Text Available The effect of Debye plasma on the 1 s 2 s 2 2 S resonance states in the scattering of electron from helium atom has been investigated within the framework of the stabilization method. The interactions among the charged particles in Debye plasma have been modelled by Debye–Huckel potential. The 1 s 2 s excited state of the helium atom has been treated as consisting of a H e + ionic core plus an electron moving around. The interaction between the core and the electron has then been modelled by a model potential. It has been found that the background plasma environment significantly affects the resonance states. To the best of our knowledge, such an investigation of 1 s 2 s 2 2 S resonance states of the electron–helium system embedded in Debye plasma environment is the first reported in the literature.

  17. Ferromagnetic resonance investigation in permalloy magnetic antidot arrays on alumina nanoporous membranes

    Energy Technology Data Exchange (ETDEWEB)

    Rodríguez-Suárez, R.L., E-mail: rrodriguez@fis.puc.cl [Facultad de Física, Pontificia Universidad Católica de Chile, Av. Vicuña Mackenna 4860 Casilla 306, Santiago (Chile); Palma, J.L.; Burgos, E.O. [Departamento de Física, Universidad de Santiago de Chile (USACH), Avda. Ecuador 3493, 917-0124 Santiago (Chile); Michea, S. [Facultad de Física, Pontificia Universidad Católica de Chile, Av. Vicuña Mackenna 4860 Casilla 306, Santiago (Chile); Departamento de Física, Universidad de Santiago de Chile (USACH), Avda. Ecuador 3493, 917-0124 Santiago (Chile); Escrig, J.; Denardin, J.C. [Departamento de Física, Universidad de Santiago de Chile (USACH), Avda. Ecuador 3493, 917-0124 Santiago (Chile); Center for the Development of Nanoscience and Nanotechnology (CEDENNA), Avda. Ecuador 3493, 917-0124 Santiago (Chile); Aliaga, C. [Center for the Development of Nanoscience and Nanotechnology (CEDENNA), Avda. Ecuador 3493, 917-0124 Santiago (Chile); Facultad de Química y Biología, Universidad de Santiago de Chile, Casilla 40, Correo 33, Santiago (Chile)

    2014-01-15

    The magnetic properties of Ni{sub 80}Fe{sub 20} antidot arrays with hole diameters of 18 and 70 nm fabricated by a template-assisted method were investigated using the ferromagnetic resonance technique. Tuning the antidot arrays by changing the hole diameter enables control on the angular dependence of the ferromagnetic resonance field. The scanning electron microscope images reveal a quite regular hexagonal arrangement of the pores, however the angular dependence of the resonance field do not exhibit the six-fold symmetry expected for this symmetry. Micromagnetic simulations performed on a perfect hexagonal lattice, when compared with those made on our real system taken from the scanning microscope images, reveal that the presence of defects in the antidot lattice affects the ferromagnetic resonance field symmetry. - Highlights: • We use the FMR technique to investigate the magnetic properties of Py antidots. • We studied the effect of pore diameter on FMR angular measurement. • FMR field does not exhibit the six-fold symmetry. • For all angular positions there are two resonance modes always present. • Micromagnetic simulations agree with the experimental results with defects.

  18. Investigation of the Pygmy Dipole Resonance in (alpha, alpha 'gamma) coincidence experiments

    NARCIS (Netherlands)

    Savran, D.; Babilon, M.; van den Berg, A. M.; Harakeh, M. N.; Hasper, J.; Wortche, H. J.; Zilges, A.

    2007-01-01

    We report on first results from experiments using the (alpha, alpha'gamma) reaction at E alpha = 136 MeV to investigate bound electric dipole (El) excitations building the so-called Pygmy Dipole Resonance (PDR) in the semi-magic nucleus Ce-140. The method of (alpha, alpha'gamma) allows the separatio

  19. Experimental investigations with a TEA-CO/sub 2/ laser with unstable resonators

    Energy Technology Data Exchange (ETDEWEB)

    Lavigne, P.; Lachambre, J.L.; Gilbert, J.; Otis, G.

    1975-10-01

    An extensive parametric investigation of a TEA-CO/sub 2/ laser operated in an unstable confocal resonator is discussed. The coupling mirror diameter and the cavity magnification giving the optimum use of the laser medium for different applications are experimentally determined.

  20. Raman spectroscopy

    Science.gov (United States)

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

  1. Experimental and numerical investigation of parametric resonance of flexible hose conveying non-harmonic fluid flow

    Science.gov (United States)

    Łuczko, Jan; Czerwiński, Andrzej

    2016-07-01

    The article presents an analysis of a model describing transverse vibrations of an elastic hose induced by non-harmonic fluid flow pulsation. The equation of motion is given as a nonlinear partial differential equation with periodically variable coefficients. The Galerkin method is employed, utilising orthogonal polynomials as shape functions. The effect of selected parameters on increased vibration intensity range and the character and form of vibrations is investigated. It is demonstrated that sub-harmonic and quasi-periodic vibrations can be induced in the simple and combination parametric resonance range. The occurrence of the parametric resonance phenomenon is evidenced by experimental data.

  2. Numerical Investigation of Terahertz Emission Properties of Microring Difference-Frequency Resonators

    DEFF Research Database (Denmark)

    Iwaszczuk, Krzysztof; Bisgaard, Christer Zoffmann; Andronico, Alessio;

    2013-01-01

    We investigate the electromagnetic design of whispering gallery mode (WGM) terahertz (THz) resonators. Terahertz radiation is generated by difference-frequency mixing of two electrically pumped high-order near-infrared laser WGM's at room temperature in the active cavity. Due to the leaky nature...... this symmetry by modification of the dielectric environment of the resonator, and demonstrate a fabrication-optimized structure based on a concentric grating design which efficiently couples the emitted radiation into a narrow, near-gaussian forward-propagating cone of well-defined linear or circular...

  3. Investigation of electron-atom/molecule scattering resonances: Two complex multiconfigurational self-consistent field approaches

    Energy Technology Data Exchange (ETDEWEB)

    Samanta, Kousik [Department of Chemistry, Rice University, Houston, TX 77005 (United States); Yeager, Danny L. [Department of Chemistry, Texas A and M University, College Station, TX 77843 (United States)

    2015-01-22

    Resonances are temporarily bound states which lie in the continuum part of the Hamiltonian. If the electronic coordinates of the Hamiltonian are scaled (“dilated”) by a complex parameter, η = αe{sup iθ} (α, θ real), then its complex eigenvalues represent the scattering states (resonant and non-resonant) while the eigenvalues corresponding to the bound states and the ionization and the excitation thresholds remain real and unmodified. These make the study of these transient species amenable to the bound state methods. We developed a quadratically convergent multiconfigurational self-consistent field method (MCSCF), a well-established bound-state technique, combined with a dilated Hamiltonian to investigate resonances. This is made possible by the adoption of a second quantization algebra suitable for a set of “complex conjugate biorthonormal” spin orbitals and a modified step-length constraining algorithm to control the walk on the complex energy hypersurface while searching for the stationary point using a multidimensional Newton-Raphson scheme. We present our computational results for the {sup 2}PBe{sup −} shape resonances using two different computationally efficient methods that utilize complex scaled MCSCF (i.e., CMCSCF). These two methods are to straightforwardly use CMCSCF energy differences and to obtain energy differences using an approximation to the complex multiconfigurational electron propagator. It is found that, differing from previous computational studies by others, there are actually two {sup 2}PBe{sup −} shape resonances very close in energy. In addition, N{sub 2} resonances are examined using one of these methods.

  4. Change in Tongue Morphology in Response to Expiratory Resistance Loading Investigated by Magnetic Resonance Imaging

    OpenAIRE

    2013-01-01

    [Purpose] The purpose of this study was to investigate the effect of expiratory resistance load on the tongue area encompassing the suprahyoid and genioglossus muscles. [Subjects] The subjects were 30 healthy individuals (15 males, 15 females, mean age: 28.9 years). [Methods] Magnetic resonance imaging was used to investigate morphological changes in response to resistive expiratory pressure loading in the area encompassing the suprahyoid and genioglossus muscles. Images were taken when water...

  5. Spectroscopic (far or terahertz, mid-infrared and Raman) investigation, thermal analysis and biological activity of piplartine

    Science.gov (United States)

    Srivastava, Anubha; Karthick, T.; Joshi, B. D.; Mishra, Rashmi; Tandon, Poonam; Ayala, A. P.; Ellena, Javier

    2017-09-01

    Research in the field of medicinal plants including Piper species like long pepper (Piper longum L.- Piperaceae) is increasing all over the world due to its use in traditional and Ayurvedic medicine. Piplartine (piperlongumine, 5,6-dihydro-1-[(2E)-1-oxo-3-(3,4,5-trimethoxyphenyl)-2-propenyl]-2(1H)-pyridinone), a biologically active alkaloid/amide was isolated from the phytochemical investigations of Piper species, as long pepper. This alkaloid has cytotoxic, anti-fungal, anti-diabetic, anti-platelet aggregation, anti-tumoral, anxiolytic, anti-depressant, anti-leishmanial, and genotoxic activities, but, its anticancer property is the most promising and has been widely explored. The main purpose of the work is to present a solid state characterization of PPTN using thermal analysis and vibrational spectroscopy. Quantum mechanical calculations based on the density functional theory was also applied to investigate the molecular conformation and vibrational spectrum, which was compared with experimental results obtained by Raman scattering, far (terahertz) and mid-infrared adsorption spectroscopy. NBO analysis has been performed which predict that most intensive interactions in PPTN are the hyperconjugative interactions between n(1) N6 and π*(O1sbnd C7) having delocalization energy of 50.53 kcal/mol, Topological parameters have been analyzed using 'AIM' analysis which governs the three bond critical points (BCPs), one di-hydrogen, and four ring critical points (RCPs). MEP surface has been plotted which forecast that the most negative region is associated with the electronegative oxygen atoms (sites for nucleophilic activity). Theoretically, to confirm that the title compound has anti-cancer, anti-diabetic and anti-platelet aggregation activities, it was analyzed by molecular docking interactions with the corresponding target receptors. The obtained values of H-bonding parameters and binding affinity prove that its anti-cancer activity is the more prominent than the

  6. Coupled electron-nuclear dynamics in resonant 1 σ →2 π x-ray Raman scattering of CO molecules

    Science.gov (United States)

    Couto, Rafael C.; Guarise, Marco; Nicolaou, Alessandro; Jaouen, Nicolas; Chiuzbǎian, Gheorghe S.; Lüning, Jan; Ekholm, Victor; Rubensson, Jan-Erik; Sâthe, Conny; Hennies, Franz; Guimarães, Freddy F.; Ågren, Hans; Gel'mukhanov, Faris; Journel, Loïc; Simon, Marc; Kimberg, Victor

    2016-03-01

    We present a detailed experimental-theoretical analysis of O K -edge resonant 1 σ -2 π inelastic x-ray scattering (RIXS) from carbon monoxide with unprecedented energy resolution. We employ high-level ab initio calculations to compute the potential energy curves of the states involved in the RIXS process and simulate the measured RIXS spectra using the wave-packet-propagation formalism, including Coulomb coupling in the final-state manifold. The theoretical analysis allows us to explain all the key features of the experimental spectra, including some that were not seen before. First, we clearly show the interference effect between different RIXS channels corresponding to the transition via orthogonal Π1x and Π1y core-excited states of CO. Second, the RIXS region of 13 eV energy loss presents a triple structure, revealed only by the high-resolution measurement. In previous studies, this region was attributed solely to a valence state. Here we show a strong Coulomb mixing of the Rydberg and valence final states, which opens the forbidden RIXS channels to the "dark" final Rydberg states and drastically changes the RIXS profile. Third, using a combination of high-resolution experiment and high-level theory, we improve the |4 σ-12 π1> final-state potential-energy curve by fitting its bottom part with the experiment. Also, the coupling constants between Rydberg and valence states were refined via comparison with the experiment. Our results illustrate the large potential of the RIXS technique for advanced studies of highly excited states of neutral molecules.

  7. The Experimental Investigation Of The Screen Operation In The Parametric Resonance Conditions

    Directory of Open Access Journals (Sweden)

    Bąk Łukasz

    2015-12-01

    Full Text Available In this paper the experimental studies of the screen working in the parametric resonance condition are discussed. The investigations are conducted for laboratory parametric resonance screen. The measuring test is performed for four cases of tension force values. The full sheet metal instead of the sieve is used. For each considered case the natural frequency of the plate and the parameter modulation frequency are determined. The achieved results are presented and discussed. It is shown that the highest sieve plate amplitude is obtained when the parameter modulation frequency is two times larger than natural frequency of the sieve plate. This parametric resonance vibration was observed only for tension force equal to 4000 N because of the rotational speed limits of electrical vibratos.

  8. Raman Spectroscopy for Homeland Security Applications

    Directory of Open Access Journals (Sweden)

    Gregory Mogilevsky

    2012-01-01

    Full Text Available Raman spectroscopy is an analytical technique with vast applications in the homeland security and defense arenas. The Raman effect is defined by the inelastic interaction of the incident laser with the analyte molecule’s vibrational modes, which can be exploited to detect and identify chemicals in various environments and for the detection of hazards in the field, at checkpoints, or in a forensic laboratory with no contact with the substance. A major source of error that overwhelms the Raman signal is fluorescence caused by the background and the sample matrix. Novel methods are being developed to enhance the Raman signal’s sensitivity and to reduce the effects of fluorescence by altering how the hazard material interacts with its environment and the incident laser. Basic Raman techniques applicable to homeland security applications include conventional (off-resonance Raman spectroscopy, surface-enhanced Raman spectroscopy (SERS, resonance Raman spectroscopy, and spatially or temporally offset Raman spectroscopy (SORS and TORS. Additional emerging Raman techniques, including remote Raman detection, Raman imaging, and Heterodyne imaging, are being developed to further enhance the Raman signal, mitigate fluorescence effects, and monitor hazards at a distance for use in homeland security and defense applications.

  9. Experimental investigation on a thermoacoustic engine having a looped tube and resonator

    Science.gov (United States)

    Yu, Z. B.; Li, Q.; Chen, X.; Guo, F. Z.; Xie, X. J.

    2005-08-01

    The purpose of this paper is to study the impact of regenerator hydraulic radius, resonator length, and mean pressure on the characteristics of the tested thermoacoustic engine, which has a looped tube and resonator. Two different acoustic oscillations are observed in the tested engine [Yu ZB, Li Q, Chen X, Guo FZ, Xie XJ, Wu JH. Investigation on the oscillation modes in a thermoacoustic stirling prime mover: mode stability and mode transition. Cryogenics 2003;43(12):687-91]. In this paper, they are called two acoustic modes, high frequency mode (with a frequency independent of the resonator length) and low frequency mode (with a frequency depending on the resonator length). Experimental results indicate that the relative penetration depth (the ratio of penetration depth over hydraulic radius) plays an important role in the excitation and pressure amplitude of the two acoustic modes. For each tested regenerator hydraulic radius, there is a measured optimal relative penetration depth, which leads to the lowest onset temperature difference. Note that, in the tested engine, the measured optimal relative viscous penetration depths are in the range 3-5 (for low frequency mode). Furthermore, experimental results also show that the resonator length affects the presence of high frequency mode in this engine.

  10. Experimental investigations on the splitting of coherent population trapping resonances by the nuclear magnetic moment

    Energy Technology Data Exchange (ETDEWEB)

    Lammegger, Roland; Vasari, Ivan; Neureiter, Christian; Windholz, Laurentius [Inst. f. Experimentalphysik, Techn. Univ. Graz (Austria)

    2007-07-01

    Coherent population trapping (CPT) is a resonance phenomenon due to a quantum mechanical interference effect within an atomic system. The resonantly driven atomic level population is being trapped into a superpositional dark state, yielding the atomic medium transparent for the exciting electromagnetic fields. The observation of this effect requires a special electronic structure ({lambda}-system) and suitable lifetimes which can be found e.g. in alkali atoms. We present experimental investigations on the behavior of the CPT resonances split by the nuclear magnetic moment under different external magnetic fields, laser polarizations and laser intensities. We focus our considerations on a special type of the {lambda}-System formation. In this case the center of gravity of the pair of split CPT resonances (called pseudoresonance) is sensitive to external magnetic fields only to second order in the magnetic field strength. The short term frequency stability of this pseudoresonance approaches the level of 10{sup -14}/{radical}({tau}). Thus such resonances seems to be a good candidate for applications in compact atomic clocks used e.g. in GPS receivers and Satellites.

  11. Graphitic carbon nanospheres: A Raman spectroscopic investigation of thermal conductivity and morphological evolution by pulsed laser irradiation

    Energy Technology Data Exchange (ETDEWEB)

    Agarwal, Radhe; Sahoo, Satyaprakash, E-mail: satya504@gmail.com, E-mail: rkatiyar@hpcf.upr.edu; Chitturi, Venkateswara Rao; Katiyar, Ram S., E-mail: satya504@gmail.com, E-mail: rkatiyar@hpcf.upr.edu [Department of Physics, University of Puerto Rico, San Juan, Puerto Rico 00936-8377 (United States)

    2015-12-07

    Graphitic carbon nanospheres (GCNSs) were prepared by a unique acidic treatment of multi-walled nanotubes. Spherical morphology with a narrow size distribution was confirmed by transmission electron microscopy studies. The room temperature Raman spectra showed a clear signature of D- and G-peaks at around 1350 and 1591 cm{sup −1}, respectively. Temperature dependent Raman scattering measurements were performed to understand the phonon dynamics and first order temperature coefficients related to the D- and G-peaks. The temperature dependent Raman spectra in a range of 83–473 K were analysed, where the D-peak was observed to show a red-shift with increasing temperature. The relative intensity ratio of D- to G-peaks also showed a significant rise with increasing temperature. Such a temperature dependent behaviour can be attributed to lengthening of the C-C bond due to thermal expansion in material. The estimated value of the thermal conductivity of GCNSs ∼0.97 W m{sup −1} K{sup −1} was calculated using Raman spectroscopy. In addition, the effect of pulsed laser treatment on the GCNSs was demonstrated by analyzing the Raman spectra of post irradiated samples.

  12. In Vitro Polarized Resonance Raman Study of N719 and N719-TBP in Dye Sensitized Solar Cells

    DEFF Research Database (Denmark)

    Hassing, Søren; Jernshøj, Kit Drescher; Nguyen, Phuong Tuyet

    2016-01-01

    changes of overlapping Raman modes, whereas conclusions about the dye-stability was based on the observation that fresh and aged DSCs had almost identical RRS spectra. In the present paper we address the problems mentioned above, by utilizing the unique property of Raman scattering that the polarization...

  13. Subpicosecond oxygen trapping in the heme pocket of the oxygen sensor FixL observed by time-resolved resonance Raman spectroscopy.

    Science.gov (United States)

    Kruglik, Sergei G; Jasaitis, Audrius; Hola, Klara; Yamashita, Taku; Liebl, Ursula; Martin, Jean-Louis; Vos, Marten H

    2007-05-01

    Dissociation of oxygen from the heme domain of the bacterial oxygen sensor protein FixL constitutes the first step in hypoxia-induced signaling. In the present study, the photodissociation of the heme-O2 bond was used to synchronize this event, and time-resolved resonance Raman (TR(3)) spectroscopy with subpicosecond time resolution was implemented to characterize the heme configuration of the primary photoproduct. TR(3) measurements on heme-oxycomplexes are highly challenging and have not yet been reported. Whereas in all other known six-coordinated heme protein complexes with diatomic ligands, including the oxymyoglobin reported here, heme iron out-of-plane motion (doming) occurs faster than 1 ps after iron-ligand bond breaking; surprisingly, no sizeable doming is observed in the oxycomplex of the Bradyrhizobium japonicum FixL sensor domain (FixLH). This assessment is deduced from the absence of the iron-histidine band around 217 cm(-1) as early as 0.5 ps. We suggest that efficient ultrafast oxygen rebinding to the heme occurs on the femtosecond time scale, thus hindering heme doming. Comparing WT oxy-FixLH, mutant proteins FixLH-R220H and FixLH-R220Q, the respective carbonmonoxy-complexes, and oxymyoglobin, we show that a hydrogen bond of the terminal oxygen atom with the residue in position 220 is responsible for the observed behavior; in WT FixL this residue is arginine, crucially implicated in signal transmission. We propose that the rigid O2 configuration imposed by this residue, in combination with the hydrophobic and constrained properties of the distal cavity, keep dissociated oxygen in place. These results uncover the origin of the "oxygen cage" properties of this oxygen sensor protein.

  14. Assessment of mode-mixing and Herzberg-Teller effects on two-photon absorption and resonance hyper-Raman spectra from a time-dependent approach.

    Science.gov (United States)

    Ma, HuiLi; Zhao, Yi; Liang, WanZhen

    2014-03-07

    A time-dependent approach is presented to simulate the two-photon absorption (TPA) and resonance hyper-Raman scattering (RHRS) spectra including Duschinsky rotation (mode-mixing) and Herzberg-Teller (HT) vibronic coupling effects. The computational obstacles for the excited-state geometries, vibrational frequencies, and nuclear derivatives of transition dipole moments, which enter the expressions of TPA and RHRS cross sections, are further overcome by the recently developed analytical excited-state energy derivative approaches in the framework of time-dependent density functional theory. The excited-state potential curvatures are evaluated at different levels of approximation to inspect the effects of frequency differences, mode-mixing and HT on TPA and RHRS spectra. Two types of molecules, one with high symmetry (formaldehyde, p-difluorobenzene, and benzotrifluoride) and the other with non-centrosymmetry (cis-hydroxybenzylidene-2,3-dimethylimidazolinone in the deprotonated anion state (HDBI(-))), are used as test systems. The calculated results reveal that it is crucial to adopt the exact excited-state potential curvatures in the calculations of TPA and RHRS spectra even for the high-symmetric molecules, and that the vertical gradient approximation leads to a large deviation. Furthermore, it is found that the HT contribution is evident in the TPA and RHRS spectra of HDBI(-) although its one- and two-photon transitions are strongly allowed, and its effect results in an obvious blueshift of the TPA maximum with respect to the one-photon absorption maximum. With the HT and solvent effects getting involved, the simulated blueshift of 1291 cm(-1) agrees well with the experimental measurement.

  15. Assessment of mode-mixing and Herzberg-Teller effects on two-photon absorption and resonance hyper-Raman spectra from a time-dependent approach

    Energy Technology Data Exchange (ETDEWEB)

    Ma, HuiLi [State Key Laboratory of Physical Chemistry of Solid Surfaces, Collaborative Innovation Center of Chemistry for Energy Materials, and Institute of Fujian Provincial Theoretical and Computational Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005 (China); Department of Chemical Physics, University of Science and Technology of China, Hefei 230026 (China); Zhao, Yi; Liang, WanZhen, E-mail: liangwz@xmu.edu.cn [State Key Laboratory of Physical Chemistry of Solid Surfaces, Collaborative Innovation Center of Chemistry for Energy Materials, and Institute of Fujian Provincial Theoretical and Computational Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005 (China)

    2014-03-07

    A time-dependent approach is presented to simulate the two-photon absorption (TPA) and resonance hyper-Raman scattering (RHRS) spectra including Duschinsky rotation (mode-mixing) and Herzberg-Teller (HT) vibronic coupling effects. The computational obstacles for the excited-state geometries, vibrational frequencies, and nuclear derivatives of transition dipole moments, which enter the expressions of TPA and RHRS cross sections, are further overcome by the recently developed analytical excited-state energy derivative approaches in the framework of time-dependent density functional theory. The excited-state potential curvatures are evaluated at different levels of approximation to inspect the effects of frequency differences, mode-mixing and HT on TPA and RHRS spectra. Two types of molecules, one with high symmetry (formaldehyde, p-difluorobenzene, and benzotrifluoride) and the other with non-centrosymmetry (cis-hydroxybenzylidene-2,3-dimethylimidazolinone in the deprotonated anion state (HDBI{sup −})), are used as test systems. The calculated results reveal that it is crucial to adopt the exact excited-state potential curvatures in the calculations of TPA and RHRS spectra even for the high-symmetric molecules, and that the vertical gradient approximation leads to a large deviation. Furthermore, it is found that the HT contribution is evident in the TPA and RHRS spectra of HDBI{sup −} although its one- and two-photon transitions are strongly allowed, and its effect results in an obvious blueshift of the TPA maximum with respect to the one-photon absorption maximum. With the HT and solvent effects getting involved, the simulated blueshift of 1291 cm{sup −1} agrees well with the experimental measurement.

  16. Structure of enzyme-bound substrates: resonance Raman and kinetic evidence for differential enzyme-substrate contacts in N-(Pentafluoro-benzoyl)glycine dithioacyl and thioacyl papain

    Science.gov (United States)

    Lee, H.; Angus, R. H.; Storer, A. C.; Carey, P. R.

    1989-12-01

    Resonance Raman (RR) spectroscopy is used to probe the structure of the substrate in the substrate-enzyme complex N-pentafluorobenzoyl) glycine (dithioacyl) papain (C 6F 5C(=O) NHCH 2C(=S)S-papain). This system was chosen since the high electron withdrawing capacity of the C 6F 5 group markedly affects electron density of the -NH- moiety which, in turn, is known to change catalytic activity. The RR spectrum of the enzyme-substrate complex is interpreted by reference to the model compound N-(pentafluorobenzoyl) glycine ethyl dithioester (C 6F 5(CO))NHCH 2C(=S)SC 2H 5. The RR spectra of this compound in aqueous or organic solvents can be understood in terms of the known conformational states of N-acylglycine dithioesters. Comparison of model with enzyme-substrate RR spectra shows that the substrate is binding in the active site in a conformer known as conformer B characterized by a small-NHCH 2CS(thiol) torsional angle and close N-to-S (thiol) contact. Kinetic rate-structure correlations are developed involving k3, the rate constant for deacylation, and the strength of the N-to-S (thiol) interaction. N-(Pentafluorobenzoyl) glycine dithioacyl papain fits the rate-structure correlation whereas the corresponding pentafluorobenzoyl glycine thiol intermediate does not. It is proposed that the difference in the size of the CS compared to the CO group brings about a small change in the dithioacyl papain compared to the thiolacyl papain conformation such that enzyme-substrate contacts involving ortho and meta F atoms in the thiol acyl enzyme case are weakened or removed in the case of the dithioacyl papain.

  17. Spectroscopic studies of thiatri-, penta- and heptamethine cyanine dyes II. Infrared and resonance Raman spectra of thiatri-, penta- and heptamethine cyanine dyes

    Science.gov (United States)

    Fujimoto, Yasuhiko; Katayama, Norihisa; Ozaki, Yukihiro; Yasui, Shigeo; Iriyama, Keiji

    1992-11-01

    Infrared (IR) and resonance Raman (RR) spectra of thiatri-, penta- and heptamethine cyanine dyes in the solid state and in solution have been measured. Most of the intense bands observed in the 1600-1100 cm -1 region of the RR spectra may be assigned to totally symmetric stretching modes of the central conjugated system of the cyanines, while most of the strong IR bands in the 1600-1300 cm -1 region are probably due to antisymmetric stretching modes. The intense RR bands do not have their counterparts in the IR spectra and vice versa. A pseudo-mutual exclusion rule seems to be operative for the cyanine vibrational spectra in the 1600-1300 cm -1 region, indicating that the central conjugated systems of the cyanines have nearly symmetrical structure, i.e. the extended all-trans forms of the methine chains and the bond orders of 1.5 of the CC and CN bonds in both the solution and solid states. The IR spectra of 3-ethyl-2-[3-(3-ethyl-2-benzothiazolinylidene)-1-propenyl]benzothiazolium iodide (NK-76) and 3-ethyl-2-[7-(3-ethyl-2-benzothiazolinylidene)-1,3,5-heptatrienyl]benzothiazolium iodide (NK-126) change little between the solid and solution states while those of 3-octadecyl-2-[3-(3-octadecyl-2-benzothiazolinylidene)-1-propenyl]benzothiazolium iodide (NK-2560) and 3-octadecyl-2-[7-(3-octadecyl-2-benzothiazolinylidene)-1,3,5-heptatrienyl]benzothiazolium perchlorate (NK-2861) alter significantly between the two states in the frequencies of bands due to the stretching modes of their central conjugated systems. The results suggest that the electronic states of the central conjugated systems of NK-2560 and NK-2861 undergo appreciable changes on going from the solid to the solution states.

  18. Resonance Raman spectroscopy reveals pH-dependent active site structural changes of lactoperoxidase compound 0 and its ferryl heme O-O bond cleavage products.

    Science.gov (United States)

    Mak, Piotr J; Thammawichai, Warut; Wiedenhoeft, Dennis; Kincaid, James R

    2015-01-14

    The first step in the enzymatic cycle of mammalian peroxidases, including lactoperoxidase (LPO), is binding of hydrogen peroxide to the ferric resting state to form a ferric-hydroperoxo intermediate designated as Compound 0, the residual proton temporarily associating with the distal pocket His109 residue. Upon delivery of this "stored" proton to the hydroperoxo fragment, it rapidly undergoes O-O bond cleavage, thereby thwarting efforts to trap it using rapid mixing methods. Fortunately, as shown herein, both the peroxo and the hydroperoxo (Compound 0) forms of LPO can be trapped by cryoradiolysis, with acquisition of their resonance Raman (rR) spectra now permitting structural characterization of their key Fe-O-O fragments. Studies were conducted under both acidic and alkaline conditions, revealing pH-dependent differences in relative populations of these intermediates. Furthermore, upon annealing, the low pH samples convert to two forms of a ferryl heme O-O bond-cleavage product, whose ν(Fe═O) frequencies reflect substantially different Fe═O bond strengths. In the process of conducting these studies, rR structural characterization of the dioxygen adduct of LPO, commonly called Compound III, has also been completed, demonstrating a substantial difference in the strengths of the Fe-O linkage of the Fe-O-O fragment under acidic and alkaline conditions, an effect most reasonably attributed to a corresponding weakening of the trans-axial histidyl imidazole linkage at lower pH. Collectively, these new results provide important insight into the impact of pH on the disposition of the key Fe-O-O and Fe═O fragments of intermediates that arise in the enzymatic cycles of LPO, other mammalian peroxidases, and related proteins.

  19. Wall-to-wall stress induced in (6,5) semiconducting nanotubes by encapsulation in metallic outer tubes of different diameters: a resonance Raman study of individual C60-derived double-wall carbon nanotubes.

    Science.gov (United States)

    Villalpando-Paez, Federico; Muramatsu, Hiroyuki; Kim, Yoong Ahm; Farhat, Hootan; Endo, Morinobu; Terrones, Mauricio; Dresselhaus, Mildred S

    2010-03-01

    We measure resonant Raman scattering from 11 individual C(60)-derived double-wall carbon nanotubes all having inner semiconducting (6,5) tubes and various outer metallic tubes. The Raman spectra show the radial breathing modes (RBM) of the inner and the outer tubes to be simultaneously in resonance with the same laser energy. We observe that an increase in the RBM frequency of the inner tubes is related to an increase in the RBM frequency of the outer tubes. The Raman spectra also contain a sharp G(-) feature that increases in frequency as the nominal diameter of the outer metallic tubes decreases. Finally, the one-phonon second-order D-band mode shows a two-way frequency splitting that decreases with decreasing nominal wall-to-wall distance. We suggest that the stress which increases with decreasing nominal wall-to-wall distance is responsible for the hardening that is observed in the frequencies of the RBM, D and G(-) modes of the inner (6,5) semiconducting tubes.

  20. Spectroscopic (infrared, Raman, UV and NMR) analysis, Gaussian hybrid computational investigation (MEP maps/HOMO and LUMO) on cyclohexanone oxime

    Science.gov (United States)

    Ramalingam, S.; Karabacak, M.; Periandy, S.; Puviarasan, N.; Tanuja, D.

    2012-10-01

    In the present analysis, FT-IR/FT-Raman spectra of the cyclohexanone oxime (CHO, C6H11NO) are recorded. The observed vibrational frequencies are assigned and the computational calculations are carried out by HF and DFT (B3LYP and B3PW91) methods with 6-311++G(d,p) basis set and the corresponding results are tabulated. In order to yield good coherence with observed values, the calculated frequencies are scaled by appropriate scale factors. The complete assignments are performed on the basis of the total energy distribution (TED) of the vibrational modes, calculated with scaled quantum mechanics (SQM) method. The alternation of structure of cyclohexanone due to the substitution of NOH is investigated. The vibrational sequence pattern of the molecule related to the substitutions is analyzed. Comparison of the observed fundamental vibrational frequencies of CHO and calculated results by density functional (B3LYP and B3PW91) and HF methods indicates that B3LYP is superior to the scaled HF and B3PW91 approach for molecular vibrational problems. Moreover, 13C NMR and 1H NMR chemical shifts are calculated by using the gauge independent atomic orbital (GIAO) method with HF/B3LYP/B3PW91 methods and the same basis set. A study on the electronic properties; absorption wavelengths, excitation energy, dipole moment and frontier molecular orbital energies, are performed by HF and DFT methods. The calculated HOMO and LUMO energies show that charge transfer occurs within the molecule. Besides frontier molecular orbitals (FMO), molecular electrostatic potential (MEP) was performed. NLO properties and Mulliken charges of the CHO was also calculated and interpreted. The thermodynamic properties (heat capacity, entropy, and enthalpy) of the title compound at different temperatures are calculated in gas phase.