937 resultados para resonant Raman scattering
Resumo:
We report the formation of highly scattering silver complexes of adenine, deoxyadenosine and 5'-dAMP under alkaline pH conditions in the colloidal silver solutions which are used for surface-enhanced Raman spectroscopy. These complexes, and other pH-dependent phenomena, help to explain the diversity of previously reported adenine SERS spectra. Using conditions which promote complex formation allows nucleotides to be detected at <1 ppm, even in solutions with high salt concentrations.
Resumo:
Raman spectroscopy is a noninvasive, nondestructive tool for capturing multiplexed biochemical information across diverse molecular species including proteins, lipids, DNA, and mineralizations. Based on light scattering from molecules, cells, and tissues, it is possible to detect molecular fingerprints and discriminate between subtly different members of each biochemical class. Raman spectroscopy is ideal for detecting perturbations from the expected molecular structure such as those occurring during senescence and the modification of long-lived proteins by metabolic intermediates as we age. Here, we describe the sample preparation, data acquisition, signal processing, data analysis and interpretation involved in using Raman spectroscopy for detecting age-related protein modifications in complex biological tissues.
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Thomson scattering is one of the most powerful diagnostic tools for plasma characterization, and it has been applied to a variety of plasmas. It is a nonintrusive technique, and the interpretation of the signal is relatively simple. However, this method has not been widely applied to low-temperature laser-ablated plasmas. Raman satellites have been observed in the scattering spectrum from a Mg laser-ablated plasma, giving this diagnostic the potential to be also used in density quantification of metastable states in plasmas.
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We consider the stimulated Raman transition between two long-lived states via multiple intermediate states, such as between hyperfine ground states in the alkali-metal atoms. We present a concise treatment of the general, multilevel, off-resonant case, and we show how the lightshift emerges naturally in this approach. We illustrate our results by application to alkali-metal atoms and we make specific reference to cesium. We comment on some artifacts, due solely to the geometrical overlap of states, which are relevant to existing experiments.
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We report on a temperature dependence of the frequency of all the major peaks in the Raman spectra of carbon nanotubes, using different excitation laser powers at the sample. The frequency decreases with increasing temperature for all peaks, and the shifts in Raman frequencies are linear in the temperature of the sample. In comparison, a similar dependence is found in active carbon, but no shift is observed for the highly ordered pyrolytic graphite within the same range of variation in laser power. A lowering of frequency at higher temperature implies an increase in the carbon-carbon distance at higher temperature. The relatively strong temperature dependence in carbon nanotubes and active carbon may be due to the enhanced increase in carbon-carbon distance. This enhancement may originate from the heavy defects and disorder in these materials. (C) 1998 American Institute of Physics. [S0021-8979(98)05219-0].
Resumo:
Fabricated one-dimensional (1D) materials often have abundant structural defects. Experimental observation and numerical calculation indicate that the broken translation symmetry due to structural defects may play a more important role than the quantum confinement effect in the Raman features of optical phonons in polar semiconductor quantum wires such as SiC nanorods, (C) 1999 Elsevier Science Ltd. All rights reserved.
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A simple derivatization methodology is shown to extend the application of surface-enhanced Raman spectroscopy (SERS) to the detection of trace concentration of contaminants in liquid form. Normally in SERS the target analyte species is already present in the molecular form in which it is to be detected and is extracted from solution to occupy sites of enhanced electromagnetic field on the substrate by means of chemisorption or drop-casting and subsequent evaporation of the solvent. However, these methods are very ineffective for the detection of low concentrations of contaminant in liquid form because the target (ionic) species (a) exhibits extremely low occupancy of enhancing surface sites in the bulk liquid environment and (b) coevaporates with the solvent. In this study, the target analyte species (acid) is detected via its solid derivative (salt) offering very significant enhancement of the SERS signal because of preferential deposition of the salt at the enhancing surface but without loss of chemical discrimination. The detection of nitric acid and sulfuric acid is demonstrated down to 100 ppb via reaction with ammonium hydroxide to produce the corresponding ammonium salt. This yields an improvement of ∼4 orders of magnitude in the low-concentration detection limit compared with liquid phase detection.
Resumo:
The energy transfer by stimulated Brillouin backscatter from a long pump pulse (15 ps) to a short seed pulse (1 ps)has been investigated in a proof-of-principle demonstration experiment. The two pulses were both amplified in differentbeamlines of a Nd:glass laser system, had a central wavelength of 1054 nm and a spectral bandwidth of 2 nm, and crossedeach other in an underdense plasma in a counter-propagating geometry, off-set by 10◦. It is shown that the energy transferand the wavelength of the generated Brillouin peak depend on the plasma density, the intensity of the laser pulses, and thecompetition between two-plasmon decay and stimulated Raman scatter instabilities. The highest obtained energy transferfrom pump to probe pulse is 2.5%, at a plasma density of 0.17ncr, and this energy transfer increases significantly withplasma density. Therefore, our results suggest that much higher efficiencies can be obtained when higher densities (above0.25ncr) are used.
Resumo:
Modification of citrate and hydroxylamine reduced Ag colloids with thiocholine bromide, a thiol functionalized quaternary ammonium salt, creates particles where the zeta potential is switched from the normal values of ca. -50 mV to ca. + 50 mV. These colloids are stable but can be aggregated with metal salts in much the same way as the parent colloids. They are excellent SERS substrates for detection of anionic targets since their positive zeta potentials promote adsorption of negatively charged ions. This is important because the vast majority of published SERS studies involve cationic or neutral targets. Moreover, the fact that the modifier is a quaternary ammonium ion means that the negative surface charge is maintained even at alkaline pH. The modified colloids can be used to detect compounds which cannot be detected using conventional negatively-charged citrate or hydroxylamine reduced metal nanoparticles, for example the detection limit was 5.0 x 10(-5) M for perchlorate and
Resumo:
Polymethyl methacrylate (PMMA) optical fibres are fabricated by a preform drawing process. The Raman spectra of PMMA fibres are recorded using a diode pumped solid state laser emitting at 532 nm and a CCD-spectrograph in the 400–3800 cm−1 range. The variation of the Raman intensity with the length of the optical fibre is studied. Investigations are carried out on the variation of FWHM of the Raman peak at 2957 cm−1 with the length of the optical fibre and pump power. The differential scattering cross section and gain coefficient of the Raman peak at 2957 cm−1 in PMMA are calculated in relation to that of toluene.
Resumo:
Polymethyl methacrylate (PMMA) optical fibres are fabricated by a preform drawing process. The Raman spectra of PMMA fibres are recorded using a diode pumped solid state laser emitting at 532 nm and a CCD-spectrograph in the 400–3800 cm−1 range. The variation of the Raman intensity with the length of the optical fibre is studied. Investigations are carried out on the variation of FWHM of the Raman peak at 2957 cm−1 with the length of the optical fibre and pump power. The differential scattering cross section and gain coefficient of the Raman peak at 2957 cm−1 in PMMA are calculated in relation to that of toluene
Resumo:
We derive a universal model for atom pairs interacting with non-resonant light via the polarizability anisotropy, based on the long range properties of the scattering. The corresponding dynamics can be obtained using a nodal line technique to solve the asymptotic Schrödinger equation. It consists of imposing physical boundary conditions at long range and vanishing the wavefunction at a position separating the inner zone and the asymptotic region. We show that nodal lines which depend on the intensity of the non-resonant light can satisfactorily account for the effect of the polarizability at short range. The approach allows to determine the resonance structure, energy, width, channel mixing and hybridization even for narrow resonances.
Resumo:
Non-resonant light interacting with diatomics via the polarizability anisotropy couples different rotational states and may lead to strong hybridization of the motion. The modification of shape resonances and low-energy scattering states due to this interaction can be fully captured by an asymptotic model, based on the long-range properties of the scattering (Crubellier et al 2015 New J. Phys. 17 045020). Remarkably, the properties of the field-dressed shape resonances in this asymptotic multi-channel description are found to be approximately linear in the field intensity up to fairly large intensity. This suggests a perturbative single-channel approach to be sufficient to study the control of such resonances by the non-resonant field. The multi-channel results furthermore indicate the dependence on field intensity to present, at least approximately, universal characteristics. Here we combine the nodal line technique to solve the asymptotic Schrödinger equation with perturbation theory. Comparing our single channel results to those obtained with the full interaction potential, we find nodal lines depending only on the field-free scattering length of the diatom to yield an approximate but universal description of the field-dressed molecule, confirming universal behavior.
Resumo:
The solid-state transformation of carbamazepine from form III to form I was examined by Fourier Transform Raman spectroscopy. Using a novel environmental chamber, the isothermal conversion was monitored in situ at 130◦C, 138◦C, 140◦C and 150◦C. The rate of transformation was monitored by taking the relative intensities of peaks arising from two C H bending modes; this approach minimised errors due to thermal artefacts and variations in power intensities or scattering efficiencies from the samples in which crystal habit changed from a characteristic prism morphology (form III) to whiskers (form I). The solid-state transformation at the different temperatures was fitted to various solid-state kinetic models of which four gave good fits, thus indicating the complexity of the process which is known to occur via a solid–gas–solid mechanism. Arrhenius plots from the kinetic models yielded activation energies from 344 kJ mol−1 to 368 kJ mol−1 for the transformation. The study demonstrates the value of a rapid in situ analysis of drug polymorphic type which can be of value for at-line in-process control.
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In this paper we describe a novel combination of Raman spectroscopy, isotope editing and X-ray scattering as a powerful approach to give detailed structural information on aromatic side chains in peptide fibrils. The orientation of the tyrosine residues in fibrils of the peptide YTIAALLSPYS with respect to the fibril axis has been determined from a combination of polarised Raman spectroscopy and X-ray diffraction measurements. The Raman intensity of selected tyrosine bands collected at different polarisation geometries is related to the values and orientation of the Raman tensor for those specific vibrations. Using published Raman tensor values we solved the relevant expressions for both of the two tyrosine residues present in this peptide. Ring deuteration in one of the two tyrosine side chains allowed for the calculation to be performed individually for both, by virtue of the isotopic shift that eliminates band overlapping. Sample disorder was taken into account by obtaining the distribution of orientations of the samples from X-ray diffraction experiments. The results provide previously unavailable details about the molecular conformation of this peptide, and demonstrate the value of this approach for the study of amyloid fibrils.