Laser Raman and infra-red spectra of biomolecule: 5-aminouracil

Laser Raman (200–4000 cm⁻¹) and IR (200–4000 cm⁻¹) spectra of 5-aminouracil were recorded in the region 200–4000 cm⁻¹. Assuming a planar geometry and C_s point group symmetry, it has been possible to assign all the 36 (25a′ + 11a″) normal modes of vibration for the first time. The two NH bonds of the NH₂ group appear to be equivalent as the NH₂ stretching frequencies satisfy the empirical relation proposed for the two equivalent NH bonds of the NH₂ group. The two NH₂ stretching frequencies are distinctly separated from the CH/NH ring stretching frequencies. A strong and sharp IR band at 3360 cm⁻¹ could be identified as the anti-symmetric NH₂ mode whereas the band at 3290 cm⁻¹ with smaller density could be identified as the symmetric NH₂ stretching mode. All other bands have also been assigned different fundamentals/overtones/combinations.      

A raman spectroscopic study of the interactions of 13 GHz microwave irradiation with dipalmitoylphosphatidylcholine dispersions

Summary In order to clarify the effect of 13 GHz microwave irradiation upon model membranes, vibrational Raman spectroscopy was performed for multilamellar dispersions of dipalmitoylphosphatidylcholine, before and after irradiation. Raman spectra of the phospholipid dispersions were recorded for the C−H ((2800⊢3100)cm⁻¹) and the C−C ((1050⊢1150)cm⁻¹) stretching modes, above the transition temperatureT _m of the phospholipid, before and after microwave irradiation. An intensity comparison between the irradiated and nonirradiated sample revealed an increase in the intensity ratioI ₂₉₃₀/I ₂₈₈₀ and a small perturbation in the C−C stretching region, induced by microwaves. It seems reasonable to assume that microwave irradiation brings about a change in lateral chain-chain interactions, which is possibly due to induced changes at bilayer curvature.     

Synthesis and characterization of novel nano-size polyreactive yellow 107

The reactive yellow 107 was polymerized by chemical oxidation method using potassium persulfate. The polymer was characterized by UV-VIS and Fourier transform infrared spectroscopy (FTIR) spectral studies. The peaks at 2,922 and 2,852 cm⁻¹ in the FTIR spectrum of polyreactive yellow 107 are assigned to the symmetric and asymmetric stretching vibrations of CH₂. The peak observed at 1,583 cm⁻¹ for polyreactive yellow 107 may be assigned to the stretching vibration of C=O, N=N, and C=C, 1,347 cm⁻¹ stretching vibration of C–N. The stretching vibrations of sulfone and sulfonic acid of S=O groups show a strong broad peak at 1,091 and 1,051 cm⁻¹. The conductivity of the polymer was determined to be 5.57 × 10⁻⁵ S cm⁻¹. The solubility of the chemically polymerized powder was ascertained and polyreactive yellow 107 showed good solubility in N,N-dimethyl formamide and dimethyl sulfoxide. The X-ray diffraction studies revealed the formation of nano-sized (84 nm) crystalline polymer. Using X-ray diffraction, behavior strain and dislocation density was also calculated. Scanning electron microscope analysis showed uniform crystalline nature of the polymer (200 nm). The thermogravimetric analysis, differential thermal analysis, and differential scanning calorimetry studies revealed good thermal stability of the polymer.     

Raman scattering of light and IR absorption in carbon nanotubes

Raman light scattering and IR absorption spectra of samples containing multilayer carbon nanotubes in different stages of purification by the selective oxidation technique have been investigated. It was found that the Raman spectra of carbon nanotubes exhibit softening of the mode at 1582 cm⁻¹ corresponding to E _2g vibrations of graphite hexagons and a line at 120 cm⁻¹ due to the radial vibrations of nanotubes. In IR absorption spectra measured in the region of 0.07–0.3 eV, several sets of lines with a spacing of 15 meV (120 cm⁻¹) between lines of each group have been detected. We suggest that each group corresponds to electron transitions generating electron-hole pairs in semiconducting nanotubes and contains a phononless 00-line and its phonon replicas with spacing between them equal to the “breathing” mode energy of 120 cm⁻¹. Measurements of electric conductivity at a frequency of 9300 MHz indicate that, in addition to semiconducting nanotubes, the samples contain nanotubes with properties of a highly disordered semimetal. Zh. éksp. Teor. Fiz. 113, 1883–1891 (May 1998)     

Structure-sensitive changes in the terahertz absorption spectra of merocyanine dye derivatives

The low-frequency vibrational modes of the series of merocyanines (malononitrile derivative) have been investigated by pulsed terahertz spectroscopy. The terahertz absorption spectra are shown to contain both intermolecular and intramolecular vibrational modes in the range of 0.15–3.45 THz (5–115 cm⁻¹). An unambiguous correlation is established between the purposeful modification of the molecular structure of merocyanine dyes and the change in their terahertz absorption spectra.     

Molecular mechanism of gelation upon the addition of water to a solution of poly(acrylonitrile) in dimethylsulfoxide

The solidification of a solution of poly(acrylonitrile) (PAN) in dimethylsulfoxide (DMSO) upon introduction of water into the solution is studied by Raman spectroscopy. In the absence of water, DMSO molecules are found to produce dipole-dipole bonds with PAN molecules. Upon the introduction of water, DMSO molecules produce hydrogen bonds with it and bands at 1005 and 1015 cm⁻¹ appear in the Raman spectrum, which are assigned to the valence vibrations of S=O bonds involved in the hydrogen bonds. Simultaneously, water molecules produce hydrogen bonds with PAN molecules: R-C≡N...H-O-H...N≡C-R, where R is the carbon skeleton of a PAN molecule. Accordingly, a band at 2250 cm⁻¹ arises in the Raman spectrum, which is assigned to the valence vibrations of C≡N bonds producing hydrogen bonds with a water molecule. When the water content is low and the DMSO concentration is high, the length of the hydrogen bonds varies in wide limits and the band at 2250 cm⁻¹ is wide. As the water content rises, DMSO molecules come out of PAN, the variation of the hydrogen bond length in it decreases (the band at 2250 cm⁻¹ narrows), and a high-viscosity system (gel) arises that consists of PAN molecules bonded to water molecules via “equally strong” hydrogen bonds.     

Study of optical properties and molecular structure of plasma polymerized diethylene glycol dimethyl ether

This paper deals with plasma polymerization processes of diethylene glycol dimethyl ether. Plasmas were produced at 150 mtorr in the range of 10 W to 40 W of RF power. Films were grown on silicon and quartz substrates. Molecular structure of plasma polymerized films and their optical properties were analyzed by Fourier transform infrared spectroscopy (FTIR) and ultraviolet-visible spectroscopy. The IR spectra show C–H stretching at 3000–2900 cm^-1, C=O stretching at 1730–1650 cm^-1, C–H bending at 1440–1380 cm^-1, C–O and C–O–C stretching at 1200–1000 cm^-1. The concentrations of C–H, C–O and C–O–C were investigated for different values of RF power. It can be seen that the C–H concentration increases from 0.55 to 1.0 au (arbitrary unit) with the increase of RF power from 10 to 40 W. The concentration of C–O and C–O–C decreases from 1.0 to 0.5 au in the same range of RF power. The refraction index increased from 1.47 to 1.61 with the increase of RF power. The optical gap calculated from absorption coefficient decreased from 5.15 to 3.35 eV with the increase of power. Due to its optical and hydrophilic characteristics these films can be applied, for instance, as glass lens coatings for ophthalmic applications.     

Synthesis of w-CdS quantum dots and discovery of intense sub band emission owing to longitudinal optical phonons

Cadmium sulfide (CdS) quantum dots (QDs), capped with cetyltrimethylammonium bromide (CTAB), and was synthesized as stable, aqueous, colloidal nanofluid. A series of nine intense, well-resolved emission lines between 400 and 750 nm were observed for the first time when exciting the CdS QDs nanofluid with a 355-nm high energy pulsed Nd:YAG laser radiation. The energy separation between any two successive emission lines equals to the characteristic overtone energy of 295 cm⁻¹ of the longitudinal optical phonon of CdS QDs. In addition, recording the PL spectrum by using a xenon broad band light source resulted in the observation of this characteristic overtone energy of 295 cm⁻¹. In agreement with this photoluminescence characteristic, Raman spectrum exhibited four prominent Stokes lines with Raman shift equal to and multiple of 295 cm⁻¹. Transmission electron microscopy investigation showed that the CdS QDs were spherical with hexagonal wurtzite structure and had a size in the range of 5–10 nm.     

Molecular mechanism of gelation with ethylene glycol added to a solution of polyacrylonitrile in dimethylsulfoxide

The mechanism of solidifying a solution of polyacrylonitrile (PAN) in dimethylsulfoxide (DMSO) into which ethylene glycol is added is studied by the method of Raman spectroscopy. In the absence of ethylene glycol, DMSO molecules produce dipole-dipole bonds to PAN molecules. Upon adding ethylene glycol, DMSO molecules form hydrogen bonds with it and a line at 1000 cm⁻¹ appears in the Raman spectrum, which is assigned to the valence vibrations of S=O bonds involved in the hydrogen bonds. After DMSO is removed, ethylene glycol molecules produce hydrogen bonds with two neighboring PAN molecules, giving rise to a band at 2264 cm⁻¹, which is assigned to the valence vibrations of C≡N bonds involved in these hydrogen bonds. A high-viscosity gel consisting of PAN molecules arises in which these molecules are bonded to each other through ethylene glycol molecules.     

Vibrational spectroscopy of SiC thin films deposited by excimer laser ablation

A large number of thin SiC films, prepared at different conditions by KrF excimer laser ablation of solid SiC targets and deposition onto Si substrates (some onto quartz glass (QG) and yttrium-stabilized zirconia (YSZ)) were characterized by infrared and Raman spectroscopy. The films consisted of nano- and microcrystalline SiC and contained nanocrystalline carbon in the case of QG or YSZ substrates. Raman spectra of nanocrystalline SiC (grains <30 nm) reflect the phonon density-of-state function of SiC by broad scattering effects at 220–600 and 650–950 cm⁻¹. Medium-size crystallites are represented by a relatively narrow asymmetric band at 790 cm⁻¹ and crystallites >200 nm by an additional asymmetric band at 960 cm⁻¹. Small satellite bands at 760 and 940 cm⁻¹, attributed to SiC surface layers, were resolved in some well-ordered samples. Optical modelling was needed to interpret the IR spectra. SiC films could be represented by an effective medium model containing a SiC host phase and embedded particles with free charge carriers. The crystalline order of SiC films can be estimated from the parameters of the SiC oscillators. Received: 5 October 1998 / Accepted: 8 January 1999 / Published online: 5 May 1999     

IR spectroscopic manifestations of hydration of poly(diphenyl sulfophthalide) during its storage

IR spectroscopy measurements show that films of poly(diphenyl sulfophthalide) (PDSP), a cardo polymer, interact with atmospheric moisture during storage at room conditions. A total of 15 absorption bands were isolated in spectra of PDSP hydrated during storage, which belong to sorbed water and hydrolysis products. A number of absorption bands (within 1500–1800 cm⁻¹ and 980–1100 cm⁻¹) were obtained by subtracting the spectrum of the film after heating from that of the initial hydrated film. At least six individual bands in the region of the O-H bond stretching vibration were isolated by decomposing a broad complex band (3700–2000 cm⁻¹) into Gaussian components. The isolated bands were tentatively assigned based on the available literature data and quantum-chemical calculations of the characteristics of a number of complexes of a diphenyl sulfophthalide model compound with water molecules. The IR spectra and energies of the hydrogen bonds formed were calculated at the B3LYP/6-311G(d, p) level. In particular, the absorption bands at 1010 and 1079 cm⁻¹ were assigned to the symmetric stretching vibrations of the S=O bonds in the −SO₃⁻ anion, the 1062-cm⁻¹ absorption band, to ν(C-OH), and the absorption bands at 3646, 3586, and 3475 cm⁻¹, to complexes of water with sulfophthalide cycles of the polymer. After a long storage, PDSP largely transforms into a polymeric oxonium salt, and its spectrum becomes similar to that of a polymeric salt prepared by alkaline hydrolysis. A general mechanism of the interaction of PDSP with water is proposed, according to which the hydrolysis of the sulfophthalide cycles (SPC) by sorbed water yields new hydrophilic groups, sulfoacid, and hydroxyl groups. A further sorption of water by the sulfoacid results in its ionization and the formation of various hydroxonium forms. Sorption and hydrolysis are reversible processes: water is desorbed and the SPC is recovered when the polymer is heated to 100–150°C, as can be judged from an increase in the intensity of the S=O bond vibrations of the sulfophthalide cycle at 1352 and 1192 cm⁻¹. The possibility of using strongly hydrated PDSP for manufacturing proton-conducting membranes is discussed.     

Polarized Raman spectroscopy study of NiSi film grown on Si(001) substrate

We report on the growth of NiSi film on Si(001) substrate with an orientation of NiSi[200]//Si[001]. Polarized Raman spectroscopy was used to assign the symmetry of the NiSi Raman peaks. Raman peaks at 213 cm⁻¹, 295 cm⁻¹, and 367 cm⁻¹ are assigned to be A _g symmetry and peaks at 196 cm⁻¹, and 254 cm⁻¹ are B _3g symmetry.     

High-resolution vibrational spectroscopy of the OH− ion in an Mg-related defect in LiF and NaF

Summary High-resolution (0.05 cm⁻¹) FTIR spectroscopy in the range (9÷300) K is applied to study the vibrational (stretching, bending and combination) modes of OH⁻ (and its isotopic substitution with OD⁻) perturbed by a neighbouring defect induced by Mg²⁺ in LiF and NaF. The stretching-mode spectra are analysed in the framework of the anharmonic-oscillator model: the related Morse parameters have been determined. A model is proposed for the defect, responsible for the stretching line and two bending lines, which are accounted for by an inversion doubling. In honour of Prof. Fausto Fumi on the occasion of his retirement from teaching.     

Raman spectroscopic study of the antimonate mineral bottinoite Ni[Sb2(OH)12]·6H2O and in comparison with brandholzite Mg[Sb5+2(OH)12]·6H2O

Raman spectroscopy was used to study the mineral bottinoite and a comparison with the Raman spectra of brandholzite was made. An intense sharp Raman band at 618 cm⁻¹ is attributed to the SbO symmetric stretching mode. The low intensity band at 735 cm⁻¹ is ascribed to the SbO antisymmetric stretching vibration. Low intensity Raman bands were found at 501, 516 and 578 cm⁻¹. Four Raman bands observed at 1045, 1080, 1111 and 1163 cm⁻¹ are assigned to δ SbOH deformation modes. A complex pattern resulting from the overlapping band of the water and hydroxyl units is observed. Raman bands are observed at 3223, 3228, 3368, 3291, 3458 and 3510 cm⁻¹. The first two Raman bands are assigned to water stretching vibrations. The two higher wavenumber Raman bands observed at 3466 and 3552 cm⁻¹ and two infrared bands at 3434 and 3565 cm⁻¹ are assigned to the stretching vibrations of the hydroxyl units. Observed Raman and infrared bands are connected with O H···O hydrogen bonds and their lengths 2.72, 2.79, 2.86, 2.88 and 3.0 Å (Raman) and 2.73, 2.83 and 3.07 Å (infrared). Copyright © 2010 John Wiley & Sons, Ltd.     

Narrowing of the vibrational spectrum under compression of liquid carbon dioxide

The broadening and shift of the Q bands of the 1388/1285-cm⁻¹ Fermi doublet of carbon dioxide have been measured by means of the spectroscopy of coherent anti-Stokes Raman scattering in a wide density range realized at compression in dense gaseous and liquid states. The spectrum of the low-frequency Q band exhibits an essential narrowing upon the compression of the liquid in the density range of 320–400 amagat from a maximum width of about 2.2 cm⁻¹ to about 1.7 cm⁻¹ determined by elastic dephasing. The observed dependence is connected with the progressive narrowing of the spectral contribution attributed to the collapsed rotational structure.     

Polarised raman and infrared spectra and vibrational analysis forα-naphthylamine

The Raman spectrum of polycrystalline α-naphthylamine was recorded in the region 100–4000 cm⁻¹. Polarisation measurements were made in CS₂ and CHCl₃ solutions. The infrared spectrum was recorded in nujol mull in the region 200–4000 cm⁻¹. The resolution was better than 2 cm⁻¹ and the accuracy of the measurements was within ± 2 cm⁻¹ for all the spectra. Vibrational assignments have been proposed for the observed frequencies. Out of the 54 normal modes of vibrations, 51 modes could be observed experimentally.     

Optical properties of BiFeO<Subscript>3</Subscript> ceramics in the frequency range 0.3–30.0 THz

Reflection and transmission infrared spectra of BiFeO₃ ceramic samples have been measured using submillimeter spectroscopy (on a backward-wave tube spectrometer) and Fourier-transform infrared spectroscopy in the frequency range from 5 to 1000 cm⁻¹ at temperatures in the range from 10 to 500 K. New resonant modes (probably, magnetic in nature) with the eigenfrequencies decreasing with an increase in the temperature have been recorded in the range 10–30 cm⁻¹ by IR spectroscopy for the first time. An additional absorption with a fairly large dielectric contribution has been revealed in the range 30–60 cm⁻¹. It has been demonstrated that the corresponding oscillators couple with both the lowest frequency phonon mode and the magnetic subsystem.     

Analysis of trace impurities in semiconductor gas via cavity-enhanced direct frequency comb spectroscopy

Cavity-enhanced direct frequency comb spectroscopy (CE-DFCS) has demonstrated powerful potential for trace-gas detection based on its unique combination of high bandwidth, rapid data acquisition, high sensitivity, and high resolution, which is unavailable with conventional systems. However, previous demonstrations have been limited to proof-of-principle experiments or studies of fundamental laboratory science. Here, we present the development of CE-DFCS towards an industrial application—measuring impurities in arsine, an important process gas used in III–V semiconductor compound manufacturing. A strongly absorbing background gas with an extremely complex, congested, and broadband spectrum renders trace detection exceptionally difficult, but the capabilities of CE-DFCS overcome this challenge and make it possible to identify and quantify multiple spectral lines associated with water impurities. Further, frequency combs allow easy access to new spectral regions via efficient nonlinear optical processes. Here, we demonstrate detection of multiple potential impurities across 1.75–1.95 μm (5710–5130 cm⁻¹), with a single-channel detection sensitivity (simultaneously over 2000 channels) of ∼4×10⁻⁸ cm⁻¹ Hz^−1/2 in nitrogen and, specifically, an absorption sensitivity of ∼4×10⁻⁷ cm⁻¹ Hz^−1/2 for trace water doped in arsine.     

Grafted natural rubber-based polymer electrolytes: ATR-FTIR and conductivity studies

Attenuated total reflectance–Fourier transformed infrared spectroscopy measurement is employed to study the interactions between the components of 30% methyl-grafted natural rubber (MG30), lithium trifluromethanesulfonate (LiCF₃SO₃ or LiTF), and propylene carbonate (PC). Vibrational spectra data of LiTF reveals that the ν_s(SO₃) at 1,045 cm⁻¹, δ_s(CF₃) at 777 cm⁻¹, and C=O stretching mode at 1,728 cm⁻¹ for MG30 have shifted to lower wave numbers in MG30–LiTF complexes indicating that complexation has occurred between MG30 and LiTF. The solvation of lithium ion is manifested in Li⁺ ← O=C interaction as shown by the downshifting and upshifting of C=O mode at 1,788 to 1,775 cm⁻¹ and ν_as(SO₃) at 1,250 to 1258 cm⁻¹, respectively, in LiTF–PC electrolytes. There is no experimental evidence of the interaction between MG30 and PC. Competition between MG30 and PC on associating with lithium ion is studied, and the studies show that the interaction between MG30–LiTF is stronger than that of the PC–LiTF in plasticized polymer–salt complexes. The effect of PC on the ionic conductivity of the MG30–LiTF system is explained in terms of the polymer, plasticizer, and salt interactions. The temperature dependence of conductivity of the polymer films obeys the Vogel–Tamman–Fulcher relation. Values of conductivity and activation energy of the MG30-based polymer electrolyte systems are presented and discussed.     

Raman microprobe technique diagnostic of YBCO films produced by laser ablation

Summary We have used a Raman microprobe technique for the characterisation and the diagnostic of YBCO superconducting thin films deposited by Pulsed-Laser Ablation (PLA) on MgO insulating substrates. Using polarisation analysis associated with sample rotations we developed a method for films orientation determination without any request for absolute calibration of the Raman spectra. The use of a bidimensional multichannel detector (OMA 4) allowed an overall detection time of 40 minutes. Each spectrum (shift range from 100 cm⁻¹ to 700 cm⁻¹) takes about 600 seconds. The results of this detection were used to determine the oxygen content, from the position of the Raman mode at 500 cm⁻¹ Homogeneity was checked with the spatial resolution allowed by the dimension of the focused laser beam (10 μm). Paper presented at the ?VII Congresso SATT?, Torino, 4–7 October 1994.