1,905 research outputs found

    Resonance polarization and phase-mismatched CARS of pheophytin b excited in the Qy band

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    Resonance polarization and phase-mismatched coherent anti-Stokes Raman scattering (CARS) measurements were performed on pheophytin b dissolved in acetone excited in the Qy absorption band, where strong broad fluorescence makes spontaneous Raman spectroscopy impossible. The phase-mismatching technique was applied to suppress solvent background and used in combination with the polarization-sensitive CARS technique to measure directly the x1111(3) and x1221(3) components to estimate depolarization ratios. The spectra were fitted by a non-linear least-squares procedure yielding vibrational band parameters. Some CARS dispersion information on the vibrational amplitudes was obtained by varying the pump wavelength. CARS excitation profiles based on transform theory were calculated and partly explain the observed amplitude dispersion. The application of the combined phase-mismatched polarization CARS technique may be useful in many other cases of highly fluorescing molecules when resonantly excited

    Modeling and Compensation of Nonlinear Distortion in Horn Loudspeakers

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    Horn loaded compression drivers are widely used in the area where high sound pressure levels together with good directivity characteristics are needed. Major disadvantage of this kind of drivers is the considerable amount of nonlinear distortion. Due to the quite high air pressures in the driver the air is driven into its nonlinear range. This paper describes a technique to reduce the distortion caused by this phenomenon. Using a Digital Signal Processor (DSP), a feedforward compensation technique, based on an equivalent lumped parameter circuit, is implemented and tested in real–time in series with the loudspeaker. Measurement and simulation results are given. The overall conclusion is that a distortion reduction is obtained in the frequency span from 600 to 1050 Hz

    Effect of axial ligands on the spectroelectrochemical properties of zinc phthalocyanine films. In situ Raman and electroreflection spectra

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    Electroreflection and Raman spectra (in situ and ex situ) of zinc phthalocyanine (ZnPc) films (80 nm thick) have been studied. Raman spectra were resonantly and preresonantly enhanced. Both electroreflection and Raman experiments reveal the homogeneous inclusion of electrolyte anions upon oxidation of the film. The anions coordinate preferentially axial positions of the ZnPc molecule. This process is accompanied by an out-of-plane deformation of the phthalocyanine macrocycle, which results in the change of both electroreflection and Raman spectra. The ZnPc molecule remains deformed when the film is saturated with anions. The detailed analysis of new bands and altered intensities in the Raman spectrum indicates that the molecular symmetry point group changes from the D4h point group to C2v. The influence of ZnPc oxidation on the Raman excitation mechanism has been also studied. Effects of axial ligands on the molecular geometry have been studied by quantum chemical calculations for the ZnPc+, ZnPc+Cl¿ and ZnPc+(Cl¿)2 species using the unrestricted Hartree¿Fock variant of the MNDO method. Calculation results show that the ZnPc molecule undergoes an out-of-plane deformation when one axial position is coordinated by the anion

    A narrow-bandwidth optical parametric oscillator

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    A narrow-bandwidth, singly resonant, picosecond optical parametric oscillator based on a non-critical phase-matched lithium triborate crystal and synchronously pumped by the second-harmonic of a Nd:YLF laser mode-locked at 76 MHz is described. An intracavity birefringent filter reduces the spectral bandwidth and allows fast scanning of the output wavelength within the phase-matched bandwidth. A signal output of 1.6 W in Fourier transform limited pulses with a duration of 22 ps and a bandwidth of 0.06 nm has been obtained. The signal and idler wavelengths were tunable from 750 to 930 nm and from 1220 to 1770 nm, respectively

    Hybrid Rayleigh, Raman and TPE fluorescence spectral confocal microscopy of living cells

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    A hybrid fluorescence–Raman confocal microscopy platform is presented, which integrates low-wavenumber-resolution Raman imaging, Rayleigh scatter imaging and two-photon fluorescence (TPE) spectral imaging, fast ‘amplitude-only’ TPE-fluorescence imaging and high-spectral-resolution Raman imaging. This multi-dimensional fluorescence–Raman microscopy platform enables rapid imaging along the fluorescence emission and/or Rayleigh scatter dimensions. It is shown that optical contrast in these images can be used to select an area of interest prior to subsequent investigation with high spatially and spectrally resolved Raman imaging. This new microscopy platform combines the strengths of Raman ‘chemical’ imaging with light scattering microscopy and fluorescence microscopy and provides new modes of correlative light microscopy. Simultaneous acquisition of TPE hyperspectral fluorescence imaging and Raman imaging illustrates spatial relationships of fluorophores, water, lipid and protein in cells. The fluorescence–Raman microscope is demonstrated in an application to living human bone marrow stromal stem cells

    Growth Rate and Morphology of a Single Calcium Carbonate Crystal on Polysulfone Film Measured with Time Lapse Raman Micro Spectroscopy

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    The growth of single, self- nucleated calcium carbonate crystals on a polysulfone (PSU) film was investigated with high resolution, time lapse Raman imaging. The Raman images were acquired on the interface of the polymer with the crystal. The growth of crystals could thus be followed in time. PSU is a polymer that is used as a membrane material in water cleaning technology. The intensity of the Raman band at the position of 1086 cm-1, which is due to the symmetric stretching of the C-O bonds in the carbonate group of calcite was used to translate the number of CO3 2- ions in a crystal to the growth in time. The growth rate of single crystals of calcium carbonate on a surface was obtained from successive Raman images. We are presenting for the first time time-lapse Raman images of single crystal growth as a direct method to determine a crystal growth rate on an industrially relevant membrane material, like polysulfone

    Subpicosecond Dynamics in Nucleotides Measured by Spontaneous Raman Spectroscopy

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    The band widths in Raman spectra are sensitive to dynamics active on a time scale from 0.1 to 10 ps. The band widths of nucleotide vibrations and their dependence on temperature, concentration, and structure are reported. From the experimental band widths and second moments, it is derived that the adenine vibrations at 725, 1336, 1480, and 1575 cm-1, and the uracil vibration at 787 cm-1, are in the fast modulation limit. The correlation times of the perturbations are faster than 0.4 ps. Thermal melting of the helical structure in polynucleotides results in larger band widths, due to an increase in vibrational dephasing and energy relaxation as a consequence of the increased interaction of the base moieties with the solvent molecules. The band width of the 725 cm-1 adenine vibration is dependent on the type and structure of the backbone. It is found to be perturbed by movements of the sugar-phosphate moiety relative to the base. The band width of the 1575 cm-1 adenine vibration is found to be sensitive to the base-pairing interaction. From a comparison of the band widths in polynucleotides with a different base sequence (homopolymer vs alternating purine-pyrimidine sequence), it is concluded that resonant vibrational energy transfer between the base molecules is not important as a relaxation process for the vibrational band widths of nucleotides. Several theoretical models for the interpretation of band widths are discussed. The theory does not take into account the strong hydrogen-bonding nature water and hence fails to describe the observations in nucleotide-water systems. The bands of the carbonyl stretching vibrations are inhomogeneously broadened. The carbonyl groups have a strong dipolar interaction with the polar water molecules and are therefore strongly perturbed by coupling to the heatbath via hydrogen bonds

    Temperature dependence of Raman vibrational bandwidths in poly(rA) and rAMP

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    Isotropic and anisotropic spontaneous Raman spectra were obtained from solutions of poly(ra) and rAMP in buffer. The temperature dependence of these spectra was measured to elucidate the influence of macromolecular dynamics and solvent dynamics on the bandwidths of base vibrations in the single stranded polynucleotide poly(rA). The temperature dependence of a bandwidth depends upon the particular vibration under study. The bands can for the larger part be described by Lorentz functions. When fitted by Voigt functions, maximally 10% of each bandprofile of the adenine base vibrations can be attributed to a Gaussian component. The second moment has been determined from the spectra for the 725 cm¿1 band. From the second moment and the bandwidth, we were able to deduce that the vibrational oscillator is in the fast modulation limit. The determined timescale (perturbation correlation time 0.13 ps) eliminate perturbations connected to long range diffusion like concentration fluctuations (timescale in the order of 10 ps). The spectra were analyzed by an extensive curve fitting procedure providing accurate bandparameters (position, width and integrated intensity). The 725 cm¿1 band of adenine has a bandwidth which is dependent upon the degree of polymerization. In RAMP it is 17.6 cm¿1, in stacked (i.e. low temperature 5°C) poly(rA) it is 11.5 cm¿1. The bandwidth of the adenine vibration at 1336 cm¿1 cm¿1 has a temperature dependence which is similar to the intensity changes of the Raman and the absorption hypochromic effect as a function of temperature. The melting transition can therefore be followed by the changes in bandwidth of suitable vibrations
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