Cystine peptides. Disulfide conformations in fourteen membered loops investigated by Raman spectroscopy and circular dichroism

NHCH3 (X = Gly 1, Ala 2, Aib 3, Leu 4 and D-Ala 5), have been investigated by Raman and circular dichroism (CD) spectroscopy. Solid state Raman spectra are consistent with β-turn conformations in all five peptides. These peptides exhibit similar conformations of the disulfide segment in the solid state with a characteristic disulfide stretching frequency at 519 ± 3 cm-1, indicative of a trans-gauche-gauche arrangement about the Cα—Cβ—S—S—Cβ—Cα bonds. The results correlate well with the solid state conformations determined by X-ray diffraction for peptides 3 and 4. CD studies in chloroform and dimethylsulfoxide establish solvent dependent conformational changes for peptides 1, 3 and 5. Disulfide chirality has been derived using the quadrant rule. CD results together with previously reported nuclear magnetic resonance (n.m.r.) data suggest a conformational coupling between the peptide backbone and the disulfide segment

Structural Hypotheses And Raman-Spectroscopy Investigations Of Glasses Belonging To The B2s3-Li2s-Lii System

A previous B-11 nuclear magnetic resonance investigation of glasses belonging to the B2S3-Li2S-LiI system had allowed the authors to determine the variation of the number of three and four coordinated boron atoms with composition. These results, in addition to the observation that vitreous B2S3 quite easily forms fibres during casting, have led us to propose structural hypotheses for B2S3 based glasses, which are supported by the present Raman spectroscopy study. For vitreous B2S3 the spectra were accounted for on the basis of the various types of BS3/2 triangles proposed by the model. Molecular orbital considerations allowed us to assign the most significant lines for the binary glasses by assuming that BS3/2 triangles (with or without nonbridging sulphur atoms) and BS4 tetrahedra were present. In the ternary system, lithium iodide has been found to interact slightly on the structural entities, altering their vibrational characteristics without fundamentally modifying their nature.

Synthesis of free standing carbon nanosheet using electron cyclotron resonance plasma enhanced chemical vapor deposition

Carbon nanosheets (CNSs) have been synthesized by electron cyclotron resonance (ECR) plasma enhanced chemical vapor deposition (PECVD) using a mixture of acetylene and argon gases on copper foil as the substrate. Micrometer-wide carbon sheets consisting of several atomic layers thick graphene sheets have been synthesized by controlled decomposition of carbon radicals in ECR-PECVD. Raman spectroscopy of these films revealed characteristics of a disordered graphitic sheet. Thick folded carbon-sheets and a semi transparent freestanding CNSs have been observed by scanning electron microscopy. This is a promising technique to synthesize free standing CNSs and can be used in the fabrication of nanoelecronic devices in future. (C) 2012 Elsevier B.V. All rights reserved.

Structural, EPR, optical and Raman studies of Nd2O3:Cu2+ nanophosphors

Nanocrystalline Nd2O3:Cu2+ (2 mol %) phosphors have been prepared by a low temperature solution combustion technique. Powder X-ray diffraction (PXRD) results confirm that hexagonal A-type Nd2O3 (900 degrees C, 3 h) and the lattice parameters have been evaluated by Rietveld refinement. Surface morphology of as-formed and Cu2+ doped Nd2O3 phosphors show that the particles are irregular in shape and porous in nature. TEM results also confirm the nature and size of the particles. The EPR spectrum exhibits two resonance signals with effective g values at g(parallel to) approximate to 2.12 and g(perpendicular to) approximate to 2.04. The g values indicate that the site symmetry of Cu2+ ions is octahedral symmetry with elongated tetragonal distortion. Raman studies show major peaks, which are assigned, to F-g and combination of A(g) + E-g modes. It is observed that the Raman peaks and intensity have been reduced in Cu2+ doped samples. UV-Visible absorption spectra exhibit a strong and broad absorption band at similar to 240 nm. Further, the absorption peak shifts to similar to 14 nm in Cu2+ doped samples. The optical band gap is estimated to be 5.28 eV for Cu doped Nd2O3 nanoparticles which are higher than the bulk Nd2O3 (4.7 eV). This can be attributed to the quantum confinement effect of the nanoparticles. (C) 2012 Elsevier B.V. All rights reserved.

Spontaneous assembly of iridium nanochain-like structures: surface enhanced Raman scattering activity using visible light

A facile, environmentally friendly approach to synthesize branched Ir nanochain-like structures under mild conditions, using polyfunctional capping molecules in an aqueous medium is reported; the nanostructures exhibit a surface plasmon resonance peak (SPR) in the visible region and serve as an active substrate for surface enhanced Raman scattering studies.

Synthesis of 3-dimensional porous graphene nanosheets using electron cyclotron resonance plasma enhanced chemical vapour deposition

Microwave plasma driven chemical vapour deposition was used to synthesize graphene nanosheets from a mixture of acetylene and hydrogen gas molecules. In this plasma, acetylene decomposes to carbon atoms that form nanostructures in the outlet plasma stream and get deposited on the substrate. The GNS consists of a few layers of graphene aligned vertically to the substrate. Graphene layers have been confirmed by high-resolution transmission electron microscopy, and Raman spectral studies were conducted to observe the defective nature of the sample. The growth of nanosheets in a vertical direction is assumed to be due to the effect of electric field and from the difference in the deposition rate in the axial and parallel directions. These vertical graphene sheets are attractive for various applications in energy storage and sensors.

The preparation, characterization and tribological properties of TA-C : H deposited using an electron cyclotron wave resonance plasma beam source

A compact electron cyclotron wave resonance (ECWR) source has been developed for the high rate deposition of hydrogenated tetrahedral amorphous carbon (ta-C:H). The ECWR provides growth rates of up to 900 Å/min over a 4″ diameter and an independent control of the deposition rate and ion energy. The ta-C:H was deposited using acetylene as the source gas and was characterized in terms of its sp3 content, mass density, intrinsic stress, hydrogen content, C-H bonding, Raman spectra, optical gap, surface roughness and friction coefficient. The results obtained indicated that the film properties were maximized at an ion energy of approximately 167 eV, corresponding to an energy per daughter carbon ion of 76 eV. The relationship between the incident ion energy and film densification was also explained in terms of the subsurface implantation of carbon ions into the growing film.

Hydrogen content estimation of hydrogenated amorphous carbon by visible Raman spectroscopy

In the present study, we report the hydrogen content estimation of the hydrogenated amorphous carbon (a-C:H) films using visible Raman spectroscopy in a fast and nondestructive way. Hydrogenated diamondlike carbon films were deposited by the plasma enhanced chemical vapor deposition, plasma beam source, and integrated distributed electron cyclotron resonance techniques. Methane and acetylene were used as source gases resulting in different hydrogen content and sp2/sp3 fraction. Ultraviolet-visible (UV-Vis) spectroscopic ellipsometry (1.5-5 eV) as well as UV-Vis spectroscopy were provided with the optical band gap (Tauc gap). The sp2/sp3 fraction and the hydrogen content were independently estimated by electron energy loss spectroscopy and elastic recoil detection analysis-Rutherford back scattering, respectively. The Raman spectra that were acquired in the visible region using the 488 nm line shows the superposition of Raman features on a photoluminescence (PL) background. The direct relationship of the sp2 content and the optical band gap has been confirmed. The difference in the PL background for samples of the same optical band gap (sp2 content) and different hydrogen content was demonstrated and an empirical relationship between the visible Raman spectra PL background slope and the corresponding hydrogen content was extracted. © 2004 American Institute of Physics.

Raman spectroscopy as a versatile tool for studying the properties of graphene.

Raman spectroscopy is an integral part of graphene research. It is used to determine the number and orientation of layers, the quality and types of edge, and the effects of perturbations, such as electric and magnetic fields, strain, doping, disorder and functional groups. This, in turn, provides insight into all sp(2)-bonded carbon allotropes, because graphene is their fundamental building block. Here we review the state of the art, future directions and open questions in Raman spectroscopy of graphene. We describe essential physical processes whose importance has only recently been recognized, such as the various types of resonance at play, and the role of quantum interference. We update all basic concepts and notations, and propose a terminology that is able to describe any result in literature. We finally highlight the potential of Raman spectroscopy for layered materials other than graphene.

Nonradiative recombination centers in Ga(As,N) and their annealing behavior studied by Raman spectroscopy

Nitrogen-related defects in diluted Ga(As,N) have been detected by Raman scattering in resonance with the localized E+ transition. These defects are attributed to local vibrational modes of nitrogen dimers on Ga- and As-lattice sites. Rapid thermal annealing under appropriate conditions is found to be able to remove the nitrogen dimers. The required minimum annealing temperature coincides with the threshold-like onset of strong, near-band-gap photoluminescence. This finding suggests that the nitrogen dimers are connected with nonradiative recombination centers. (C) 2004 American Institute of Physics.

Comparative Raman scattering studies of GaAs/AlxGa1-xAs and AlxGa1-xAs/AlAs superlattices

The room-temperature Raman scattering studies of longitudinal optic phonons in AlAs/AlxGa1-xAs and GaAs/AlxGa1-xAs short-period superlattices with different layer thicknesses were reported. The AlAs LO modes confined in AlAs layers and GaAs-like LO modes confined in AlxGa1-xAs layers were observed in AlAs/AlxGa1-xAs superlattices under off-resonance conditions. And the GaAs LO modes confined in GaAs layers and AlAs-like LO modes confined in AlxGa1-xAs layers were observed in GaAs/AlxGa1-xAs superlattices. In addition, the AlAs interface mode in AlAs/AlxGa1-xAs was also observed under near-resonance conditions. Based on the linear chain mode, the frequencies of confined LO modes measured by Raman scattering were unfolded according to q=m/(n+1)(2 pi/a(0)) by which the dispersion curves of AlAs-like and GaAs-like LO phonons in AlxGa1-xAs mixed crystal were obtained.

RAMAN-SCATTERING BY LO PHONONS IN (GAAS)N1/(ALAS)N2 ULTRATHIN-LAYER SUPERLATTICES

Raman spectra of (GaAs)n1/(AlAs)n2 ultrathin-layer superlattices were measured at room temperature and under off-resonance conditions. The experimental results show that there are two effects in ultrathin-layer superlattices: the confinement effect of LO phonons and the alloy effect. It is found that the relative intensity of the disorder-activated TO mode can give a measure of the alloy effect. The Raman spectra of one-monolayer superlattices measured in various scattering configurations are very similar to those of the Al0.5Ga0.5As alloy, and thus the alloy effect is prominent. However, in the case of monolayer number n greater-than-or-equal-to 4, the confined effect is prominent, while the alloy effect is only shown as an interface effect.

Observation of the resonant Raman behavior of individual single-walled carbon nanotubes

The different resonant Raman scattering process of single-walled carbon nanotubes (SWNTs) has been found between the Stokes and anti-Stokes sides of the radial breathing modes (RBMs), and this provides strong evidence that Raman spectra of some special diametric SWNTs are in resonance with their electronic transitions between the singularities in the one-dimensional electronic density of states in the valence and conduction bands, and other SWNTs axe beyond the resonant condition. Because of the coexistence of resonant and non-resonant Raman scattering processes for different diametric SWNTs, the relative intensity of each RBM does not reflect the proportion of a particular SWNT.

Facile fabrication of large area of aggregated gold nanorods film for efficient surface-enhanced Raman scattering

An effective and facile method for fabrication of large area of aggregated gold nanorods (AuNRs) film was proposed by self-assembly of AuNRs at a toluene/water interface for the first time. It was found that large area of aggregated AuNRs film could be formed at the interface of toluene and water due to the interfacial tension between the two phases. The obtained large area of aggregated AuNRs film exhibits strong surface-enhanced Raman scattering (SERS) activity with 4-aminothiophenol (4-ATP) and 2-aminothiophenol (2-ATP) as the probe molecules based on the strong electromagnetic coupling effect between the very adjacent AuNRs.

Characterization and optimization of AuNPs labeled by Raman reporters on glass based on silver enhancement

In this report, gold nanoparticles (AuNPs) labeled by Raman reporters (AuNPs-R6G) were assembled on glass and used as the seeds to in situ grow silver-coated nanostructures based on silver enhancer solution, forming the nanostructures of AuNPs-R6G@Ag, which were characterized by scanning electron microscopy (SEM) and UV-visible spectroscopy. More importantly, the obtained silver-coated nanostructures can be used as a surface enhancement Raman scattering (SERS) substrate. The different SERS activities can be controlled by the silver deposition time and assembly time of AuNPs-R6G on glass. The results indicate that the maximum SERS activity could be obtained on AuNPs-R6G when these nanostructures were assembled on glass for 2 h with silver deposition for 2 min.