Enhanced Raman Spectroscopy of Molecules Adsorbed on Carbon-Doped TiO2 Obtained from Titanium Carbide: A Visible-Light-Assisted Renewable Substrate

Titanium carbide (TiC) is an electrically conducting material with favorable electrochemical properties. In the present studies, carbon-doped TiO2 (C-TiO2) has been synthesized from TiC particles, as well as TiC films coated on stainless steel substrate via thermal annealing under various conditions. Several C-TiO2 substrates are synthesized by varying experimental, conditions and characterized by UV-visible spectroscopy, photoluminescence, X-ray diffraction and X-ray photoelectron spectroscopic techniques. C-TiO2 in the dry state (in powder form as well as in film form) is subsequently used as a substrate for enhancing Raman signals corresponding to 4-mercaptobenzoic acid and 4-nitrothiophenol by utilizing chemical enhancement based on charge-transfer interactions. Carbon, a nonmetal dopant in TiO2, improves the intensities of Raman signals, compared, to undoped TiO2. Significant dependence of Raman intensity on carbon doping is observed. Ameliorated performance obtained using C-TiO2 is attributed to the presence of surface defects that originate due to carbon as a dopant, which, in turn,, triggers charge transfer between TiO2 and analyte. The C-TiO2 substrates are subsequently regenerated for repetitive use by illuminating an analyte-adsorbed substrate with visible light for a period of 5 h.

High-Temperature Phase Transition Studies in a Novel Fast Ion Conductor, Na2Cd(SO4)2, Probed by Raman Spectroscopy

Temperature-dependent Raman spectroscopic studies were carried out on Na2Cd(SO4)(2) from room temperature to 600 degrees C. We observe two transitions at around 280 and 565 degrees C. These transitions are driven by the change in the SO4 ion. On the basis of these studies, one can explain the changes in the conductivity data observed around 280 and 565 degrees C. At 280 degrees C, spontaneous tilting of the SO4 ion leads to restriction of Na+ mobility. Above 565 degrees C, the SO4 ion starts to rotate freely, leading to increased mobility of Na+ ion in the channel.

Determination of beta-turn conformation by laser Raman spectroscopy

To correlate the Raman frequencies of the amide I and III bands to beta-turn structures, three peptides shown to contain beta-turn structure by x-ray diffraction and NMR were examined. The compounds examined were tertiary (formula: see text). The amide I band of these compounds is seen at 1,668, 1,665, and 1,677 cm-1, and the amide III band appears at 1,267, 1,265, and 1,286 cm-1, respectively. Thus, it is concluded that the amide I band for type III beta-turn structure appears in the range between 1,665 and 1,677 cm-1 and the amide III band between 1,265 and 1,286 cm-1.

Renormalization of the phonon spectrum in semiconducting single-walled carbon nanotubes studied by Raman spectroscopy

In situ Raman experiments together with transport measurements have been carried out in single-walled carbon nanotubes as a function of electrochemical top gate voltage (Vg). We have used the green laser (EL=2.41 eV), where the semiconducting nanotubes of diameter ~1.4 nm are in resonance condition. In semiconducting nanotubes, the G−- and G+-mode frequencies increase by ~10 cm−1 for hole doping, the frequency shift of the G− mode is larger compared to the G+ mode at the same gate voltage. However, for electron doping the shifts are much smaller: G− upshifts by only ~2 cm−1 whereas the G+ does not shift. The transport measurements are used to quantify the Fermi-energy shift (EF) as a function of the gate voltage. The electron-hole asymmetry in G− and G+ modes is quantitatively explained using nonadiabatic effects together with lattice relaxation contribution. The electron-phonon coupling matrix elements of transverse-optic (G−) and longitudinal-optic (G+) modes explain why the G− mode is more blueshifted compared to the G+ mode at the same Vg. The D and 2D bands have different doping dependence compared to the G+ and G− bands. There is a large downshift in the frequency of the 2D band (~18 cm−1) and D (~10 cm−1) band for electron doping, whereas the 2D band remains constant for the hole doping but D upshifts by ~8 cm−1. The doping dependence of the overtone of the G bands (2G bands) shows behavior similar to the dependence of the G+ and G− bands.

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

Systematic Organic UV Photoelectron Spectroscopy

Photoelectron spectroscopy (PES) provides valuable information on the ionization energies of atoms and molecules. The ionization energy (IE) is given by the relation.hv = IE + T where hv is t h e energy of the radiation and T i s the kinetic energy of the electron. The IEs are directly related to the orbital energies (Koopmans' theorem). By employing UV radiation (HeI. 21.2 eV. or HeII. 40.8 eV). extensive data on the ionization of valence electrons in organic molecules have been obtained in recent years. These studies of UV photoelectron spectroscopy. originated by Turner, have provided a direct probe into the energy levels of organic molecules. Molecular orbital calculations of various degrees of sophistication are generally employed to make assignments of the PES bands. Analysis of the vibrational structure of PES bands has not only provided structural information on the molecular ions, but has also been of value in band assignments. Dewar and co-workers [1, 2) presented summaries of available PES data on organic molecules in 1969 and 1970. Turner et al. [3] published a handbook of Hel spectra of organic molecules in 1970. Since then, a few books [4-7] discussing the principles and applications of UV photoelectron spectroscopy have appeared of which special mention should be made of the recent article by Heilbronner and Maier [7]. There has, however, been no comprehensive review of the vast amount of data on the UV-PES of organic molecules published in the literature since 1970.

Dynamic structure of charge carrier in polyaniline by near-infrared excited resonance Raman spectroscopy

New vibrational Raman features characteristic to the conductive form of polyaniline have been observed with the near-infrared excitation at 1047 nm. Based on an analogy with the resonance Raman spectrum of Michler's ketone in the lowest excited triplet (T-1) state, we consider these features as due to a dynamic structure of a diimino-1,4-phenylene unit in the polyaniline chain exchanging a positive charge very rapidly. This consideration directly leads to a conducting mechanism in which a positive charge migrates from one nitrogen to the other through the conjugated chain of polyaniline.

Probing Single and Bilayer Graphene Field Effect Transistors By Raman Spectroscopy

This article is a review of our work related to Raman studies of single layer and bilayer graphenes as a function Fermi level shift achieved by electrochemically top gating a field effect transistor. Combining the transport and in situ Raman studies of the field effect devices, a quantitative understanding is obtained of the phonon renormalization due to doping of graphene. Results are discussed in the light of time dependent perturbation theory, with electron phonon coupling parameter as an input from the density functional theory. It is seen that phonons near and Gamma and K points of the Brillouin zone are renormalized very differently by doping. Further, Gamma-phonon renormalization is different in bilayer graphene as compared to single layer, originating from their different electronic band structures near the zone boundary K-point. Thus Raman spectroscopy is not only a powerful probe to characterize the number of layers and their quality in a graphene sample, but also to quantitatively evaluate electron phonon coupling required to understand the performance of graphene devices.

Origin of visible photoluminescence from porous silicon as studied by Raman spectroscopy

In this paper we discuss the different models proposed to explain the visible luminescence in porous silicon (PS). We review our recent photoluminescence and Raman studies on PS as a function of different preparation conditions and isochronal thermal annealing. Our results can be explained by a hybrid model which incorporates both nanostructures for quantum confinement and silicon complexes (such as SiHx, and siloxene) and defects at Si/SiO2, interfaces as luminescent centres.

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.

Raman Spectroscopy of the Charge Transfer Complex (TTF)x C60 Br8

We report Raman studies on powder samples of the charge transfer complex (TTF)(x)C60Br8 at room temperature. The phonons show considerable softening with respect to the frequencies observed in the Raman spectrum of solid C60Br8. The strongest mode at 1464 cm(-1) in C60Br8 is red shifted to a doublet with peaks at 1414 and 1421 cm(-1), implying an average phonon softening Delta omega of -47 cm(-1). A comparison with the phonon softening of the corresponding A(g)(2) mode in alkali-doped C-60 (Delta omega similar to -36 cm(-1) for A(6)C(60), A = K, Rb or Cs) suggests that 8 electrons are transferred per C60Br8 molecule in the charge transfer complex. The mode at 503 cm(-1) in C60Br8 is shifted upwards, similar to that in A(6)C(60) compounds.

A determination of the structure of the intramolecular charge transfer state of 4-dimethylaminobenzonitrile (DMABN) by time-resolved resonance Raman spectroscopy

Picosecond time-resolved resonance Raman spectra of the A (intramolecular charge transfer, ICT) state of DMABN, DMABN-d(6) and DMABN-N-15 have been obtained. The isotopic shifts identify the nu (s)(ph-N) mode as a band at 1281 cm(-1). The similar to 96 cm(-1) downshift of this mode from its ground state frequency rules out the electronic coupling PICT model and unequivocally supports the electronic decoupling TICT model. However, our results suggest some pyramidal character of the A state amino conformation.