Energy funneling and macromolecular conformational dynamics: a 2D Raman correlation study of PEG melting

Cascading energy landscapes through funneling has been postulated as a mechanistic route for achieving the lowest energy configuration of a macromolecular system (such as proteins and polymers). In particular, understanding the molecular mechanism for the melting and crystallization of polymers is a challenging fundamental question. The structural modifications that lead to the melting of poly(ethylene glycol) (PEG) are investigated here. Specific Raman bands corresponding to different configurations of the PEG chain have been identified, and the molecular structural dynamics of PEG melting have been addressed using a combination of Raman spectroscopy, 2D Raman correlation and density functional theory (DFT) calculations. The melting dynamics of PEG have been unambiguously explained along the C-O bond rotation coordinate.

Raman Spectroscopic Study of Serum Components

Early diagnosis of disease is important, because therapeutic intervention is most successful before it spread to the subject. The best health screenings method could be the blood test because the blood contains thousands of bio-molecules coming as by-products from the diseased part of the organism and would be non-invasive approach. The major limitation of this approach is the very low concentrations of the analytes need to be detected. Raman spectroscopy has been proven as one of the cutting edge technique applied in the field of histology, cytology and clinical chemistry. The primary obstacle of Raman spectroscopy is the low signal intensities. One of the promising approaches to overcome that is surface enhanced Raman spectroscopy (SERS) which has opened novel opportunities for chemical and biomedical analytics. Albumin is one of the most abundant proteins in blood, produced by liver. The state of albumin in serum determines the health of the liver and kidney. Serum albumin helps to transport many small molecules such as fatty acids, bilirubin, calcium, drugs through the blood. In this study, SERS is being used for the quantification and to understand of binding mechanism serum albumin.

Raman Spectroscopic Studies on Screening of Myopathies

Myopathies are among the major causes of mortality in the world. There is no complete cure for this heterogeneous group of diseases, but a sensitive, specific, and fast diagnostic tool may improve therapy effectiveness. In this study, Raman spectroscopy is applied to discriminate between muscle mutants in Drosophila on the basis of associated changes at the molecular level. Raman spectra were collected from indirect flight muscles of mutants, upheld1 (up1), heldup(2) (hdp(2)), myosin heavy chain7 (Mhc7), actin88F(KM88) (Act88F(KM88)), upheld101 (up101), and Canton-S (CS) control group, for both 2 and 12 days old flies. Difference spectra (mutant minus control) of all the mutants showed an increase in nucleic acid and beta-sheet and/or random coil protein content along with a decrease in a-helix protein. Interestingly, the 12th day samples of up1 and Act88F(KM88) showed significantly higher levels of glycogen and carotenoids than CS. A principal components based linear discriminant analysis classification model was developed based on multidimensional Raman spectra, which classified the mutants according to their pathophysiology and yielded an overall accuracy of 97% and 93% for 2 and 12 days old flies, respectively. The up1 and Act88F(KM88) (nemaline-myopathy) mutants form a group that is clearly separated in a linear discriminant plane from up101 and hdp2 (cardiomyopathy) mutants. Notably, Raman spectra from a human sample with nemaline-myopathy formed a cluster with the corresponding Drosophila mutant (up1). In conclusion, this is the first demonstration in which myopathies, despite their heterogeneity, were screened on the basis of biochemical differences using Raman spectroscopy.

Experimentally validated Raman Monte Carlo simulation for a cuboid object to obtain Raman spectroscopic signatures for hidden material

In conventional Raman spectroscopic measurements of liquids or surfaces the preferred geometry for detection of the Raman signal is the backscattering (or reflection) mode. For non-transparent layered materials, sub-surface Raman signals have been retrieved using spatially offset Raman spectroscopy (SORS), usually with light collection in the same plane as the point of excitation. However, as a result of multiple scattering in a turbid medium, Raman photons will be emitted in all directions. In this study, Monte Carlo simulations for a three-dimensional layered sample with finite geometry have been performed to confirm the detectability of Raman signals at all angles and at all sides of the object. We considered a non-transparent cuboid container (high density polyethylene) with explosive material (ammonium nitrate) inside. The simulation results were validated with experimental Raman intensities. Monte Carlo simulation results reveal that the ratio of sub-surface to surface signals improves at geometries other than backscattering. In addition, we demonstrate through simulations the effects of the absorption and scattering coefficients of the layers, and that of the diameter of the excitation beam. The advantage of collecting light from all possible 4 angles, over other collection modes, is that this technique is not geometry specific and molecular identification of layers underneath non-transparent surfaces can be obtained with minimal interference from the surface layer. To what extent all sides of the object will contribute to the total signal will depend on the absorption and scattering coefficients and the physical dimensions. Copyright (c) 2015 John Wiley & Sons, Ltd.

Cell-Membrane-Mimicking Lipid-Coated Nanoparticles Confer Raman Enhancement to Membrane Proteins and Reveal Membrane-Attached Amyloid-beta Conformation

Identifying the structures of membrane bound proteins is critical to understanding their function in healthy and diseased states. We introduce a surface enhanced Raman spectroscopy technique which can determine the conformation of membrane-bound proteins, at low micromolar concentrations, and also in the presence of a substantial membrane-free fraction. Unlike conventional surface enhanced Raman spectroscopy, our approach does not require immobilization of molecules, as it uses spontaneous binding of proteins to lipid bilayer-encapsulated Ag nanoparticles. We apply this technique to probe membrane-attached oligomers of Amyloid-beta(40) (A beta(40)), whose conformation is keenly sought in the context of Alzheimer's disease. Isotope-shifts in the Raman spectra help us obtain secondary structure information at the level of individual residues. Our results show the presence of a beta-turn, flanked by two beta-sheet regions. We use solid-state NMR data to confirm the presence of the beta-sheets in these regions. In the membrane-attached oligomer, we find a strongly contrasting and near-orthogonal orientation of the backbone H-bonds compared to what is found in the mature, less-toxic A beta fibrils. Significantly, this allows a ``porin'' like beta-barrel structure, providing a structural basis for proposed mechanisms of A beta oligomer toxicity.

Resonant Raman characterisation of ultra-thin nano-protective carbon layers for magnetic storage devices

Carbon thin films are very important as protective coatings for a wide range of applications such as magnetic storage devices. The key parameter of interest is the sp3 fraction, since it controls the mechanical properties of the film. Visible Raman spectroscopy is a very popular technique to determine the carbon bonding. However, the visible Raman spectra mainly depend on the configuration and clustering of the sp2 sites. This can result in the Raman spectra of different samples looking similar albeit having a different structure. Thus, visible Raman alone cannot be used to derive the sp3 content. Here we monitor the carbon bonding by using a combined study of Raman spectra taken at two wavelengths (514 and 244 nm). We show how the G peak dispersion is a very useful parameter to investigate the carbon samples and we endorse it as a production-line characterisation tool. The dispersion is proportional to the degree of disorder, thus making it possible to distinguish between graphitic and diamond-like carbon. © 2003 Elsevier B.V. All rights reserved.

Raman spectroscopic investigation of pure and ytterbium-doped rare earth silicate crystals

Raman spectroscopy was used to study the molecular structure of a series of selected rare earth (RE) silicate crystals including Y2SiO5 (YSO), LU2SiO5 (LSO), (Lu0.5Y0.5)(2)SiO5 (LYSO) and their ytterbium-doped samples. Raman spectra show resolved bands below 500 cm(-1) region assigned to the modes of SiO4 and oxygen vibrations. Multiple bands indicate the nonequivalence of the RE-O bonds and the lifting of the degeneracy of the RE ion vibration. Low intensity bands below 500 cm(-1) are an indication of impurities. The (SiO4)(4-) tetrahedra are characterized by bands near 200 cm(-1) which show a separation of the components of nu(4) and nu(2), in the 500-700 cm(-1) region which are attributed to the distorting bending vibration and in the 880-1000 cm(-1) region which are attributed to the symmetric and antisymmetric stretching vibrational modes. The majority of the bands in the 300-610 cm(-1) region of Re2SiO5 were found to arise from vibrations involving both Si and RE ions, indicating that there is considerable mixing of Si displacements with Si-O bending modes and RE-0 stretching modes. The Raman spectra of RE silicate crystals were analyzed in terms of the molecular structure of the crystals, which enabled separation of the bands attributed to distinct vibrational units. Copyright (C) 2007 John Wiley & Sons, Ltd.

Optimized vertical carbon nanotube forests for multiplex surface-enhanced raman scattering detection

The highly sensitive and molecule-specific technique of surface-enhanced Raman spectroscopy (SERS) generates high signal enhancements via localized optical fields on nanoscale metallic materials, which can be tuned by manipulation of the surface roughness and architecture on the submicrometer level. We investigate gold-functionalized vertically aligned carbon nanotube forests (VACNTs) as low-cost straightforward SERS nanoplatforms. We find that their SERS enhancements depend on their diameter and density, which are systematically optimized for their performance. Modeling of the VACNT-based SERS substrates confirms consistent dependence on structural parameters as observed experimentally. The created nanostructures span over large substrate areas, are readily configurable, and yield uniform and reproducible SERS enhancement factors. Further fabricated micropatterned VACNTs platforms are shown to deliver multiplexed SERS detection. The unique properties of CNTs, which can be synergistically utilized in VACNT-based substrates and patterned arrays, can thus provide new generation platforms for SERS detection. © 2012 American Chemical Society.

Raman scattering of non-planar graphite: arched edges, polyhedral crystals, whiskers and cones

Planar graphite has been extensively studied by Raman scattering for years. A comparative Raman study of several different and less common non-planar graphitic materials is given here. New kinds of graphite whiskers and tubular graphite cones (synthetic and natural) have been introduced. Raman spectroscopy has been applied to the characterization of natural graphite crystal edge planes, an individual graphite whisker graphite polyhedral crystals and tubular graphite cones. Almost all of the observed Raman modes were assigned according to the selection rules and the double-resonance Raman mechanism. The polarization properties related to the structural features, the line shape of the first-order dispersive mode and its combination modes, the frequency variation of some modes in different carbon materials and other unique Raman spectral features are discussed here in detail.

Raman spectra of SiC nanorods with different excitation wavelengths

With increasing excitation wavelength from 514 to 782 mn, a significant difference in the Raman spectra of SIC nanorods was observed as compared to bulk material. The intensity ratio of the LO mode to that of the IF mode increases with the excitation wavelength increasing. This has been identified as resonant Raman scattering caused by Frohlich interaction.

A RESONANT RAMAN-STUDY ON PHONONS IN GAINAS/ALINAS MULTIPLE-QUANTUM WELLS

The LO phonon modes in the barrier layers of a GaInAs/AlInAs multiple quantum well structure are investigated by resonance Raman scattering (RRS), the excitation laser photon energy tuned to resonate with the above barrier interband transition energy. The resonance enhancement of LO phonon peaks are shown to be caused by Frohlich electron-phonon interaction. The pressure-dependent profiles for both AlAs-like (LO(2) mode) and InAs-like (LO(1) mode) Raman peak intensities are well fitted by the Gaussian lineshape. The shift between these two profiles can be explained by the outgoing RRS mechanism, providing information on the pressure-induced shift of the excitonic transition energy. The amplitude ratios of the two profiles are close to 1, showing a well defined two-mode behavior and the nearly equal polarizability for Al-As and In-As bonds in AlInAs alloy.