Rayleigh and Raman scattering from optically active molecules

Barron, Laurence D.; Buckingham, A. D.

doi:10.1080/00268977100101091

Cited by 425 publications

(275 citation statements)

References 13 publications

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“…Since the time that measurement of Raman optical activity (ROA) was suggested 1 and applied 2 for the first time, the technique has become a reliable tool for determination of absolute configurations and conformations of chiral molecules. [3][4][5] ROA spectrum is a difference in scattering of right and left circularly polarized light, as dependent on the Raman frequency shift.…”

Section: Introductionmentioning

confidence: 99%

Interpretation of Raman and Raman Optical Activity Spectra of a Flexible Sugar Derivative, the Gluconic Acid Anion

et al. 2009

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Raman scattering and its polarized extension, Raman optical activity (ROA), are commonly used for monitoring of molecular conformational equilibria in solutions. This is complicated for saccharides due to extensive motions of the hydroxyl groups and other molecular parts. Standard interpretation procedures involving ab initio spectral simulations for a limited set of conformers are not adequate. In this study, a more general approach is proposed for the gluconic acid anion taken as a model compound, where quantum simulations of the spectra are directly coupled with molecular dynamics (MD) techniques. Such a multiscale approach reveals how the structural information is encoded in the broadened spectral lines. The spectra were simulated for solvent-solute clusters generated by MD. Conformational averaging was enabled by a limited library of conformers for which the spectral parameters could be calculated ab initio and moved on the MD geometries by Cartesian coordinate tensor transfer techniques. The B3LYP/CPCM/6-31+G** approximation was used as a default for computation of the source force fields and polarizability derivatives. The spectra thus obtained relatively faithfully reproduced most of the experimental features. The Amber and polarizable Amoeba MD force fields produced similar results; application of the latter, however, was limited by the long time necessary to achieve a converged conformational equilibrium. Both MD simulation and spectral averaging suggest that the hydroxyl groups as well as the backbone C-C bonds rotate relatively freely, with some restrictions in the vicinity of the carboxyl group. In spite of the averaging, spectral response of characteristic vibrational normal mode families, such as CH and OH bending, can clearly be identified in the spectra. The simulations thus confirm the experimental fact that flexible saccharides exhibit significant vibrational activity that reveals precious information about molecular structure and dynamics encoded in the Raman and ROA spectral shapes.

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Section: Introductionmentioning

confidence: 99%

Interpretation of Raman and Raman Optical Activity Spectra of a Flexible Sugar Derivative, the Gluconic Acid Anion

et al. 2009

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“…99,100 Although this amazing phenomenon is widely used in biological technology, such as chiral-sensitive vibrational spectroscopy, the weak ROA intensity becomes the bottleneck of applications, which is almost 10 23 -10 25 times the intensities of the parent Raman scattering. 101 SERS was reported by several groups to enhance ROA for the extremely enhanced EM field.…”

Section: Raman Optical Activitymentioning

confidence: 99%

Nanowire-supported plasmonic waveguide for remote excitation of surface-enhanced Raman scattering

et al. 2014

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Due to its amazing ability to manipulate light at the nanoscale, plasmonics has become one of the most interesting topics in the field of light-matter interaction. As a promising application of plasmonics, surface-enhanced Raman scattering (SERS) has been widely used in scientific investigations and material analysis. The large enhanced Raman signals are mainly caused by the extremely enhanced electromagnetic field that results from localized surface plasmon polaritons. Recently, a novel SERS technology called remote SERS has been reported, combining both localized surface plasmon polaritons and propagating surface plasmon polaritons (PSPPs, or called plasmonic waveguide), which may be found in prominent applications in special circumstances compared to traditional local SERS. In this article, we review the mechanism of remote SERS and its development since it was first reported in 2009. Various remote metal systems based on plasmonic waveguides, such as nanoparticle-nanowire systems, single nanowire systems, crossed nanowire systems and nanowire dimer systems, are introduced, and recent novel applications, such as sensors, plasmon-driven surface-catalyzed reactions and Raman optical activity, are also presented. Furthermore, studies of remote SERS in dielectric and organic systems based on dielectric waveguides remind us that this useful technology has additional, tremendous application prospects that have not been realized in metal systems.

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Section: Introductionmentioning

confidence: 99%

“…It is the last of these with which we are concerned. (35)(36)(37)(38)(39) have appeared, and some experimental work has been presented (25,26,29,31,32) or proposed (37, 38) for particular applications.We now report a quite general experimental approach to assay the presence of differential light scattering and to correct for its effects on measurements in a circular dichrograph.The proposed assay involves determination of whether the observed CD spectrum varies with changes in the light-collection geometry of the spectropolarimeter. The collection geometry may be described in terms of the position, size, and shape of the light-detection element relative to the incident measuring beam and the sample cell.…”

mentioning

confidence: 99%

Experimental Differential Light-Scattering Correction to the Circular Dichroism of Bacteriophage T2

Dorman

Maestre

1973

Proc. Natl. Acad. Sci. U.S.A.

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Experimental techniques are presented that can be used to assay and correct for differential light scattering effects in circular dichroism spectra of biological macrostructures. The assay is based upon use of variable detector geometries that collect light over large solid angles. Disrupted T2 virus suspensions and purified T2 phage DNA exhibit geometry-independent spectra; the spectrum of intact T2 virus is highly sensitive to detection geometry. On the basis of spectra obtained after light-scattering correction, the structure of T2 DNA in the phage particle is assigned to the C form. We conclude that: (i) The measured circular dichroism of a light-scattering specimen may be highly sensitive to light-detection geometry of the instrument. This effect is indicative of differential scattering intensity for left and right circularly polarized light. (ii) Some optically active particles, although they scatter light intensely, exhibit circular dichroism that is independent of detection geometry and, therefore, apparently uninfluenced by differential light scattering. We infer that whether differential light scattering arises may depend upon the presence or absence of ordered asymmetry in the organization of the scattering particle. (iii) The circular dichroism of any light-scattering specimen should be measured again in apparatus designed for differential light-scattering correction as a prerequisite to meaningful structural conclusions. (iv) Differential scattering effects in circular dichroism may be potentially useful as a probe for large-order organization of the scattering particle. Circular dichroism (CD) studies, although at one time devoted to simple molecules (1, 2), have recently been focused upon a variety of complex biological macrostructures. Much promising CD work has been contributed on the molecular conformation of DNA in chromosomes (3), chromatin (4-12), and related material, such as reconstituted nucleohistone (13)(14)(15)(16)(17)(18)(19) (25-27, 29, 30, 32, 33, 35), other concentration-obscuring effects (30, 32, 33), and differential light scattering (25,26,29,(31)(32)(33). It is the last of these with which we are concerned. (35)(36)(37)(38)(39) have appeared, and some experimental work has been presented (25,26,29,31,32) or proposed (37, 38) for particular applications.We now report a quite general experimental approach to assay the presence of differential light scattering and to correct for its effects on measurements in a circular dichrograph.The proposed assay involves determination of whether the observed CD spectrum varies with changes in the light-collection geometry of the spectropolarimeter. The collection geometry may be described in terms of the position, size, and shape of the light-detection element relative to the incident measuring beam and the sample cell.As a basis for later discussion, we consider first the measurement of normal, unpolarized light absorption spectra.For a photomultiplier tube (PMT) detector located on the optical axis, and with a sufficiently collim...

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Rayleigh and Raman scattering from optically active molecules

Cited by 425 publications

References 13 publications

Interpretation of Raman and Raman Optical Activity Spectra of a Flexible Sugar Derivative, the Gluconic Acid Anion

Interpretation of Raman and Raman Optical Activity Spectra of a Flexible Sugar Derivative, the Gluconic Acid Anion

Nanowire-supported plasmonic waveguide for remote excitation of surface-enhanced Raman scattering

Experimental Differential Light-Scattering Correction to the Circular Dichroism of Bacteriophage T2

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