The spectroscopic (FTIR, FT-Raman and UV-Vis spectra), DFT and normal coordinate computations of m-nitromethylbenzoate

NASA Astrophysics Data System (ADS)

Gnanasambandan, T.; Gunasekaran, S.; Seshadri, S.

2013-08-01

A combined experimental and theoretical study on molecular structure, vibrational spectra, NBO and UV-spectral analysis of m-nitromethylbenzoate (MNMB) has been reported in the present work. The FT-IR solid phase (4000-400 cm-1) and FT-Raman spectra (3500-100 cm-1) of MNMB was recorded. The molecular geometry, harmonic vibrational frequencies and bonding features of MNMB in the ground-state have been calculated by using the density functional method B3LYP with 6-31G (d,p) and 6-31+G(d,p) basis sets. The assignments of the vibrational spectra have been carried out with the help of normal co-ordinate analysis (NCA) following the Scaled Quantum Mechanical Force Field Methodology (SQMFF). Stability of the molecule arising from hyperconjugative interactions, charge delocalization has been analyzed using natural bond orbital (NBO) analysis. The results show that charge in electron density (ED) in the σ∗ antibonding orbitals and E(2) energies confirms the occurrence of ICT (Intra-molecular Charge Transfer) within the molecule. The UV spectrum was measured in ethyl acetate solution. The energy and oscillator strength calculated by Time-Dependent Density Functional Theory (TD-DFT) result complements the experimental findings. The calculated HOMO and LUMO energies show that charge transfer occurs within the molecule. Finally the calculation results were applied to simulated infrared and Raman spectra of the title compound which show good agreement with observed spectra.

Spectral investigations and DFT studies of 3,7-dihydro-1,3,7-trimethyl-1H-purine-2,6-dione (caffeine) interaction and recognition by single amino acid derived self-assembled nanostructures

NASA Astrophysics Data System (ADS)

Govindhan, R.; Karthikeyan, B.

2018-03-01

Recognition of xanthine alkaloid caffeine with 3,5-bis(trifluoromethyl)benzylamine derived peptide nanotubes (BTTPNTs) through chemical interaction have been achieved through the host-guest like interaction. DFT simulation is carried out for caffeine interacted with BTTPNTs system and also experimentally characterized by ultraviolet-visible (UV-vis) absorbance, confocal Raman spectra (CRS) with microscopic imaging (CRM), FT-Raman, surface enhanced Raman scattering (SERS), UV-diffuse reflectance spectra (UV-DRS), high resolution transmission electron microscopy (HR-TEM) and cyclic voltammetry (CV) studies. The results are used to examine the morphologies, size of the nanostructure and study of its interaction with the caffeine molecule. The results show that BTTPNTs is having potential for sensing the caffeine molecules through the binding occurred from the NH2 of tyrosine moiety of the BTTPNTs. This intermolecular association through face-to-face stacking of BTTPNTs is explained by detailed DFT calculations.

Elaboration, structural and optical investigations of ZnO/epoxy nanocomposites

NASA Astrophysics Data System (ADS)

Moussa, S.; Namouchi, F.; Guermazi, H.

2015-07-01

Hybrid nanocomposites were elaborated by incorporating ZnO nanoparticles into a transparent epoxy polymer matrix, using the direct dispersion method. The effect of the nanoparticles on the structural and optical properties of the polymer matrix was investigated using Fourier transform infrared (FTIR), Raman and UV-Visible spectroscopies. Nanocomposites FTIR spectra showed a variation of band intensities attributed to nanoparticles agglomeration within the polymer. The UV-Visible measurements showed a redshift on the band gap energy of the nanocomposites differently from neat epoxy resin, caused by interactions between ZnO NPs and polymer chains. Raman spectra confirm these interactions and the formation of hydrogen bonds in the nanocomposites. The UV-Visible transmittance spectra revealed that addition of a very low concentration (0.2wt%) of ZnO nanoparticles to a transparent epoxy matrix would maintain high visible-light transparency. The decrease of transmittance with increasing ZnO percentage is due to light scattering which originates from the agglomeration of nanoparticles in the matrix, the mismatch between the refractive index of ZnO and that of the epoxy matrix, and the increase of the surface roughness of the nanocomposite with increasing ZnO addition. Moreover, the UV-vis absorption spectra revealed that adding more than 1wt% ZnO leads to the improvement of the UV shielding properties of the nanocomposites. These results prove that the elaborated ZnO/epoxy nanocomposites can be used as UV shielding materials.

Characterization of DNA isolated from normal and cancerous ovarian tissues by ultraviolet resonance Raman spectroscopy

NASA Astrophysics Data System (ADS)

Zhao, Xiaojie; Vinson, Michael A.; Malins, Donald C.; Spiro, Thomas G.

2000-05-01

We report significant differences in UV resonance Raman (UVRR) spectra of DNA samples from normal and cancerous tissues. The four bases of DNA, adenosine, thymine, guanosine and cytidine, can be enhanced in UVRR spectra, and their intensities are very sensitive to base stacking and DNA H-bonding. 14 DNA samples from patients at different stages of ovarian cancer, 5 from normal, 2 from primary, 3 from metastasis primary and 4 from distant metastasis tumor tissues, were characterized by 257, 238, 229, 220 and 210 nm-excited UVRR spectra. Raman spectral difference between normal and tumor DNA could be readily detected.

FT-IR, FT-Raman, UV spectra and DFT calculations on monomeric and dimeric structure of 2-amino-5-bromobenzoic acid.

PubMed

Karabacak, Mehmet; Cinar, Mehmet

2012-02-01

In this work, the molecular conformation, vibrational and electronic transition analysis of 2-amino-5-bromobenzoic acid (2A5BrBA) were presented for the ground state using experimental techniques (FT-IR, FT-Raman and UV) and density functional theory (DFT) employing B3LYP exchange correlation with the 6-311++G(d,p) basis set. FT-IR and FT-Raman spectra were recorded in the regions of 400-4000 cm(-1) and 50-4000 cm(-1), respectively. There are four conformers, C1, C2, C3 and C4 for this molecule. The geometrical parameters, energies and wavenumbers have been obtained for all four conformers. The computational results diagnose the most stable conformer of 2A5BrBA as the C1 form. The complete assignments of fundamental vibrations were performed on the basis of the total energy distribution (TED) of the vibrational modes, calculated with scaled quantum mechanics (SQM) method. Raman activities calculated by DFT method have been converted to the corresponding Raman intensities using Raman scattering theory. The UV spectra of investigated compound were recorded in the region of 200-400 nm for ethanol and water solutions. The electronic properties were evaluated with help of time-dependent DFT (TD-DFT) theoretically and results were compared with experimental observations. The thermodynamic properties of the studied compound at different temperatures were calculated, revealing the correlations between standard heat capacity, standard entropy, standard enthalpy changes and temperatures. The observed and the calculated geometric parameters, vibrational wavenumbers and electronic transitions were compared with observed data and found to be in good agreement. Copyright © 2011 Elsevier B.V. All rights reserved.

Raman spectroscopic analysis of the responds of desert cyanobacterium Nostoc sp under UV-B radiation

NASA Astrophysics Data System (ADS)

Wang, Gaohong; Hao, Zongjie; Hu, Chunxiang; Liu, Yongding

Cyanobacteria are renowned for tolerating extremes of desiccation, UV radiation, freezethaw cycles, hypersalinity and oligotrophy, which make them as candidate par excellence for terraforming in extraterrestrial planet. Recently Raman spectrum was applied to study the biochemical information changes in different field of life science. In this study, we investigated the respond of desert cyanobactreium Nostoc sp under UV-B radiation via FT-Raman spectra. It was found that the spectral biomarkers of protectant molecular of UV radiation such as β-carotene and scytonemin were induced by UV-B radiation, but Chlorophyll a content was decreased, and also the photosynthesis activity was inhibited significantly. After light adaptation without UV-B radiation, the Chlorophyll a content and photosynthesis activity returned to high level, butβ-carotene and scytonemin content remained in the cells. Those results indicated that desert Cyanobacteria have good adaptation ability for UV-B radiation and synthesis of protectant molecular may be an effective strategy for its adaptation in evolution.

The structural and spectroscopic investigation of 2-chloro-3-methylquinoline by DFT method and UV-Vis, NMR and vibrational spectral techniques combined with molecular docking analysis

NASA Astrophysics Data System (ADS)

Kose, Etem; Atac, Ahmet; Bardak, Fehmi

2018-07-01

This study comprises the structural and spectroscopic evaluation of a quinoline derivative, 2-chloro-3-methylquinoline (2Cl3MQ), via UV-Vis, 1H and 13C NMR, FT-IR and FT-Raman techniques experimentally, theoretically with DFT and TD-DFT quantum chemical calculations at B3LYP/6-311++G (d, p) level of theory, and investigation of the in silico pharmaceutical potent of 2Cl3MQ in comparison to 2ClnMQ (n = 3,4,7,8,9,10) substituted quinolines. The experimental measurements were recorded as follows; UV-vis spectra were obtained in the range of 200-400 nm in the water and ethanol solvents. 1H and 13C NMR spectra were recorded in CDCl3. Vibrational spectra were obtained in the region of 4000-400 cm-1 and 3500-10 cm-1 for FT-IR and FT-Raman spectra, respectively. Structural and spectroscopic features obtained through theoretical evaluations include: electrostatic features, atomic charges and molecular electrostatic potential surface, the frontier molecular orbital characteristics, the density of states and their overlapping nature, the electronic transition properties, thermodynamical and nonlinear optical characteristics, and predicted UV-Vis, 1H and 13C NMR, FT-IR and FT-Raman spectra. Ligand-enzyme interactions of 2ClnMQ (n = 3,4,7,8,9,10) substituted quinolines with Malate Synthase from Mycobacterium Tuberculosis (MtbMS) were investigated via molecular docking. The role of position of methyl substitution on the inhibitor character of the ligands was discussed on the basis of noncovalent interaction profiles.

A UV resonance Raman (UVRR) spectroscopic study on the extractable compounds in Scots pine (Pinus sylvestris) wood. Part II. Hydrophilic compounds.

PubMed

Nuopponen, M; Willför, S; Jääskeläinen, A-S; Vuorinen, T

2004-11-01

Hydrophilic extracts of Scots pine (Pinus sylvestris) heartwood and sapwood and a solid Scots pine knotwood sample were studied by UV resonance Raman spectroscopy (UVRRS). In addition, UVRR spectra of two hydrophilic model compounds (pinosylvin and chrysin) were analysed. UV Raman spectra were collected using 244 and 257 nm excitation wavelengths. The chemical composition of the acetone:water (95:5 v/v) extracts were also determined by gas chromatography. The aromatic and oleophilic structures of pinosylvin and chrysin showed three intense resonance enhanced bands in the spectral region of 1649-1548 cm(-1). Pinosylvin showed also a relatively intense band in the aromatic substitution region at 996 cm(-1). The spectra of the heartwood acetone:water extract showed many bands typical of pinosylvin. In addition, the extract included bands distinctive for resin and fatty acids. The sapwood acetone:water extract showed bands due to oleophilic structures at 1655-1650 cm(-1). The extract probably also contained oligomeric lignans because the UVRR spectra were in parts similar to that of guaiacyl lignin. The characteristic band of pinosylvin (996 cm(-1)) was detected in the UVRR spectrum of the resin rich knotwood. In addition, several other bands typical for wood resin were observed, which indicated that the wood resin in the knotwood was resonance enhanced even more than lignin.

A UV resonance Raman (UVRR) spectroscopic study on the extractable compounds in Scots pine ( Pinus sylvestris) wood . Part II. Hydrophilic compounds

NASA Astrophysics Data System (ADS)

Nuopponen, M.; Willför, S.; Jääskeläinen, A.-S.; Vuorinen, T.

2004-11-01

Hydrophilic extracts of Scots pine ( Pinus sylvestris) heartwood and sapwood and a solid Scots pine knotwood sample were studied by UV resonance Raman spectroscopy (UVRRS). In addition, UVRR spectra of two hydrophilic model compounds (pinosylvin and chrysin) were analysed. UV Raman spectra were collected using 244 and 257 nm excitation wavelengths. The chemical composition of the acetone:water (95:5 v/v) extracts were also determined by gas chromatography. The aromatic and oleophilic structures of pinosylvin and chrysin showed three intense resonance enhanced bands in the spectral region of 1649-1548 cm -1. Pinosylvin showed also a relatively intense band in the aromatic substitution region at 996 cm -1. The spectra of the heartwood acetone:water extract showed many bands typical of pinosylvin. In addition, the extract included bands distinctive for resin and fatty acids. The sapwood acetone:water extract showed bands due to oleophilic structures at 1655-1650 cm -1. The extract probably also contained oligomeric lignans because the UVRR spectra were in parts similar to that of guaiacyl lignin. The characteristic band of pinosylvin (996 cm -1) was detected in the UVRR spectrum of the resin rich knotwood. In addition, several other bands typical for wood resin were observed, which indicated that the wood resin in the knotwood was resonance enhanced even more than lignin.

Spectroscopic properties for identifying sapphire samples from Ban Bo Kaew, Phrae Province, Thailand

NASA Astrophysics Data System (ADS)

Mogmued, J.; Monarumit, N.; Won-in, K.; Satitkune, S.

2017-09-01

Gemstone commercial is a high revenue for Thailand especially ruby and sapphire. Moreover, Phrae is a potential gem field located in the northern part of Thailand. The studies of spectroscopic properties are mainly to identify gemstone using advanced techniques (e.g. UV-Vis-NIR spectrophotometry, FTIR spectrometry and Raman spectroscopy). Typically, UV-Vis-NIR spectrophotometry is a technique to study the cause of color in gemstones. FTIR spectrometry is a technique to study the functional groups in gem-materials. Raman pattern can be applied to identify the mineral inclusions in gemstones. In this study, the natural sapphires from Ban Bo Kaew were divided into two groups based on colors including blue and green. The samples were analyzed by UV-Vis-NIR spectrophotometer, FTIR spectrometer and Raman spectroscope for studying spectroscopic properties. According to UV-Vis-NIR spectra, the blue sapphires show higher Fe3+/Ti4+ and Fe2+/Fe3+ absorption peaks than those of green sapphires. Otherwise, green sapphires display higher Fe3+/Fe3+ absorption peaks than blue sapphires. The FTIR spectra of both blue and green sapphire samples show the absorption peaks of -OH,-CH and CO2. The mineral inclusions such as ferrocolumbite and rutile in sapphires from this area were observed by Raman spectroscope. The spectroscopic properties of sapphire samples from Ban Bo Kaew, Phrae Province, Thailand are applied to be the specific evidence for gemstone identification.

Spectral Analysis of 3-(Adamantan-1-yl)-4-Ethyl-1-[(4-Phenylpiperazin-1-yl) Methyl]-1 H-1,2,4-Triazole-5(4 H)-Thione

NASA Astrophysics Data System (ADS)

Mindarava, Y. L.; Shundalau, M. B.; Al-Wahaibi, L. H.; El-Emam, A. A.; Matsukovich, A. S.; Gaponenko, S. V.

2018-05-01

Vibrational IR (3200-650 cm-1) and Raman spectra (3200-150 cm-1) of adamantane-containing 3-(adamantan-1-yl)-4-ethyl-1-[(4-phenylpiperazin-1-yl)methyl]-1H-1,2,4-triazole-5(4H)-thione, which is promising for drug design, were examined. The UV/Vis spectrum (450-200 nm) of the compound in EtOH was measured. Full geometry optimization using density functional theory (DFT) in the B3LYP/cc-pVDZ approximation allowed the equilibrium configuration of the molecule to be determined and IR and Raman spectra to be calculated. Based on these, the experimental vibrational IR and Raman spectra were interpreted and the biological activity indices were predicted. The UV/Vis spectrum of the title compound was simulated at the time-dependent DFT/CAM-B3LYP/cc-pVDZ level with and without solvent effects and at the ab initio multi-reference perturbation theory XMCQDPT2 level. The UV/Vis spectrum that was simulated using the multi-reference XMCQDPT2 approximation agreed very successfully with the experimental data, in contrast to the single-reference DFT method. This was probably a consequence of intramolecular charge transfer.

Spectral Analysis of 3-(Adamantan-1-yl)-4-Ethyl-1-[(4-Phenylpiperazin-1-yl) Methyl]-1H-1,2,4-Triazole-5(4H)-Thione

NASA Astrophysics Data System (ADS)

Mindarava, Y. L.; Shundalau, M. B.; Al-Wahaibi, L. H.; El-Emam, A. A.; Matsukovich, A. S.; Gaponenko, S. V.

2018-05-01

Vibrational IR (3200-650 cm-1) and Raman spectra (3200-150 cm-1) of adamantane-containing 3-(adamantan-1-yl)-4-ethyl-1-[(4-phenylpiperazin-1-yl)methyl]-1H-1,2,4-triazole-5(4H)-thione, which is promising for drug design, were examined. The UV/Vis spectrum (450-200 nm) of the compound in EtOH was measured. Full geometry optimization using density functional theory (DFT) in the B3LYP/cc-pVDZ approximation allowed the equilibrium configuration of the molecule to be determined and IR and Raman spectra to be calculated. Based on these, the experimental vibrational IR and Raman spectra were interpreted and the biological activity indices were predicted. The UV/Vis spectrum of the title compound was simulated at the time-dependent DFT/CAM-B3LYP/cc-pVDZ level with and without solvent effects and at the ab initio multi-reference perturbation theory XMCQDPT2 level. The UV/Vis spectrum that was simulated using the multi-reference XMCQDPT2 approximation agreed very successfully with the experimental data, in contrast to the single-reference DFT method. This was probably a consequence of intramolecular charge transfer.

Solution and solid trinitrotoluene (TNT) photochemistry: persistence of TNT-like ultraviolet (UV) resonance Raman bands.

PubMed

Gares, Katie L; Bykov, Sergei V; Godugu, Bhaskar; Asher, Sanford A

2014-01-01

We examined the 229 nm deep-ultraviolet resonance Raman (DUVRR) spectra of solution and solid-state trinitrotoluene (TNT) and its solution and solid-state photochemistry. Although TNT photodegrades with a solution quantum yield of ϕ ∼ 0.015, the initial photoproducts show DUVRR spectra extraordinarily similar to pure TNT, due to the similar photoproduct enhancement of the -NO2 stretching vibrations. This results in TNT-like DUVRR spectra even after complete TNT photolysis. These ultraviolet resonance Raman spectral bands enable DUVRR of trace as well as DUVRR standoff TNT detection. We determined the structure of various initial TNT photoproducts by using liquid chromatography-mass spectrometry and tandem mass spectrometry. Similar TNT DUVRR spectra and photoproducts are observed in the solution and solid states.

Structural investigation of a self-assembled monolayer material 5-[(3-methylphenyl) (phenyl) amino] isophthalic acid for organic light-emitting devices.

PubMed

Saş, E Babur; Kurt, M; Can, M; Okur, S; İçli, S; Demiç, S

2014-12-10

The molecular structure and vibrations of 5-[(3-methylphenyl) (phenyl) amino] isophthalic acid (MePIFA) were investigated by infrared and Raman spectroscopies, UV-Vis, (1)H and (13)C NMR spectroscopic techniques and NBO analysis. FT-IR, FT-Raman and dispersive Raman spectra were recorded in the solid phase. (1)H and (13)C NMR spectra and UV-Vis spectrum were recorded in DMSO solution. HOMO-LUMO analysis and molecular electrostatic potential (MEP) analysis were performed. The theoretical calculations for the molecular structure and spectroscopies were performed with DFT (B3LYP) and 6-311G(d,p) basis set calculations using the Gaussian 09 program. After the geometry of the molecule was optimized, vibration wavenumbers and fundamental vibration wavenumbers were assigned on the basis of the potential energy distribution (PED) of the vibrational modes calculated with VEDA 4 program. The total (TDOS), partial (PDOS) density of state and overlap population density of state (OPDOS) diagrams analysis were made using GaussSum 2.2 program. The results of theoretical calculations for the spectra of the title compound were compared with the observed spectra. Copyright © 2014 Elsevier B.V. All rights reserved.

Structural investigation of a self-assembled monolayer material 5-[(3-methylphenyl) (phenyl) amino] isophthalic acid for organic light-emitting devices

NASA Astrophysics Data System (ADS)

Saş, E. Babur; Kurt, M.; Can, M.; Okur, S.; İçli, S.; Demiç, S.

2014-12-01

The molecular structure and vibrations of 5-[(3-methylphenyl) (phenyl) amino] isophthalic acid (MePIFA) were investigated by infrared and Raman spectroscopies, UV-Vis, 1H and 13C NMR spectroscopic techniques and NBO analysis. FT-IR, FT-Raman and dispersive Raman spectra were recorded in the solid phase. 1H and 13C NMR spectra and UV-Vis spectrum were recorded in DMSO solution. HOMO-LUMO analysis and molecular electrostatic potential (MEP) analysis were performed. The theoretical calculations for the molecular structure and spectroscopies were performed with DFT (B3LYP) and 6-311G(d,p) basis set calculations using the Gaussian 09 program. After the geometry of the molecule was optimized, vibration wavenumbers and fundamental vibration wavenumbers were assigned on the basis of the potential energy distribution (PED) of the vibrational modes calculated with VEDA 4 program. The total (TDOS), partial (PDOS) density of state and overlap population density of state (OPDOS) diagrams analysis were made using GaussSum 2.2 program. The results of theoretical calculations for the spectra of the title compound were compared with the observed spectra.

Ultraviolet Resonance Raman Enhancements in the Detection of Explosives

DTIC Science & Technology

2009-06-01

nitramines (e.g., RDX , HMX ) and aromatic compounds (e.g., DNT, TATB, TNT). 1. Types of Explosives and Chemical Composition Due to stability...resonance Raman spectra of TNT, RDX , HMX , and PETN using 40 UV wavelengths from 210 to 280 nm using a 90 collection geometry [32]. This study includes...Raman can result in a dramatic increase in the Raman scattering efficiency of select band(s) associated with the electronic transition . Other than

A Raman and UV-Vis study of catecholamines oxidized with Mn(III)

NASA Astrophysics Data System (ADS)

Barreto, W. J.; Ponzoni, S.; Sassi, P.

1998-12-01

A UV-Vis and Raman spectroscopy study of three aminochromes generated through Mn 3+ oxidation of the dopamine, L-dopa and adrenaline molecules at physiological pH was performed. The UV-Vis spectra of the catecholamines oxidized using Mn 3+ in buffer solution at pH 7.2 show a band at ca. 300 nm, formed by two transitions at 280 nm and 300 nm assigned to an La and Lb transition respectively, and other at ca. 470 nm assigned to an n- π* transition localized in the carbonyl group. This assignment is suggested by the UV-Vis and Raman spectra of ortho-aminoquinone generated by MnO 2 oxidation of a dopamine aqueous acidic solution. The resonance Raman spectra of the three chromes at buffer pH 7.2 show a very similar feature and the most intense bands are observed in the spectral range 1100-1800 cm -1. The band around 1680 cm -1 for the three compounds is assigned to a ν(CO) stretching vibration, 1630 cm -1 to the ν(CC) ring mode, two bands at 1423, 1439 cm -1; 1427, 1438 cm -1 and 1456, 1475 cm -1 are assigned to a ν(CN +) vibration, for aminochrome, dopachrome and adrenochrome, respectively. The excitation profiles for the most intense bands for aminochrome and adrenochrome were obtained. The band assigned to the ν(CN +) present a red shift with respect to the visible band peak, however the band in adrenochrome at 1475 cm -1 shows a profile similar to ν(CO) and ν(CC) modes that reflects the methyl group effect on mixing this mode more effectively with the ν(CC) ring mode.

Raman spectroscopy of white wines.

PubMed

Martin, Coralie; Bruneel, Jean-Luc; Guyon, François; Médina, Bernard; Jourdes, Michael; Teissedre, Pierre-Louis; Guillaume, François

2015-08-15

The feasibility of exploiting Raman scattering to analyze white wines has been investigated using 3 different wavelengths of the incoming laser radiation in the near-UV (325 nm), visible (532 nm) and near infrared (785 nm). To help in the interpretation of the Raman spectra, the absorption properties in the UV-visible range of two wine samples as well as their laser induced fluorescence have also been investigated. Thanks to the strong intensity enhancement of the Raman scattered light due to electronic resonance with 325 nm laser excitation, hydroxycinnamic acids may be detected and analyzed selectively. Fructose and glucose may also be easily detected below ca. 1000 cm(-1). This feasibility study demonstrates the potential of the Raman spectroscopic technique for the analysis of white wines. Copyright © 2015 Elsevier Ltd. All rights reserved.

Component Analysis and Identification of Black Tahitian Cultured Pearls From the Oyster Pinctada margaritifera Using Spectroscopic Techniques

NASA Astrophysics Data System (ADS)

Shi, L.; Wang, Y.; Liu, X.; Mao, J.

2018-03-01

Raman spectroscopy, ultraviolet, visible, and near infrared (UV-Vis-NIR) reflectance spectroscopy, and X-ray fluorescence (XRF) spectroscopy were used to characterize black Tahitian cultured pearls and imitations of these saltwater cultured pearls produced by γ-irradiation, and by coloring of cultured pearls with silver nitrate or organic dyes. Raman spectra indicated that aragonite was the major constituent of these four types of pearl. Using Raman spectroscopy at an excitation wavelength of 514 nm, black Tahitian cultured pearls exhibited characteristic 1100-1700 cm-1 bands. These bands were attributed to various organic components, including conchiolin and other black biological pigments. The peaks shown by saltwater cultured pearls colored with organic dyes varied with the type of dye used. Tahitian cultured and organic-dye-treated saltwater cultured pearls were easily identified by Raman spectroscopy. UV-Vis-NIR reflectance spectra showed bands at 408, 497, and 700 nm derived from porphyrin pigment and other black pigments. The spectra of dye-treated black saltwater pearls showed absorption peaks at 216, 261, 300, and 578 nm. The 261-nm absorption band disappeared from the spectra of γ-irradiated saltwater cultured pearls. This suggests the degradation of conchiolin in the γ-irradiated saltwater cultured pearls. XRF analysis revealed the presence of Ag on the surface of silver nitrate-dyed saltwater cultured pearls.

QM/MM methodology, docking and spectroscopic (FT-IR/FT-Raman, NMR, UV) and Fukui function analysis on adrenergic agonist

NASA Astrophysics Data System (ADS)

Uma Maheswari, J.; Muthu, S.; Sundius, Tom

2015-02-01

The Fourier transform infrared, FT-Raman, UV and NMR spectra of Ternelin have been recorded and analyzed. Harmonic vibrational frequencies have been investigated with the help of HF with 6-31G (d,p) and B3LYP with 6-31G (d,p) and LANL2DZ basis sets. The 1H and 13C nuclear magnetic resonance (NMR) chemical shifts of the molecule were calculated by GIAO method. The polarizability (α) and the first hyperpolarizability (β) values of the investigated molecule have been computed using DFT quantum mechanical calculations. Stability of the molecule arising from hyper conjugative interactions, and charge delocalization has been analyzed using natural bond orbital (NBO) analysis. The electron density-based local reactivity descriptors such as Fukui functions were calculated to explain the chemical selectivity or reactivity site in Ternelin. Finally the calculated results were compared to simulated infrared and Raman spectra of the title compound which show good agreement with observed spectra. Molecular docking studies have been carried out in the active site of Ternelin and reactivity with ONIOM was also investigated.

FT-Raman, FT-IR and UV-visible spectral investigations and ab initio computations of anti-epileptic drug: Vigabatrin

NASA Astrophysics Data System (ADS)

Edwin, Bismi; Joe, I. Hubert

2013-10-01

Vibrational analysis of anti-epileptic drug vigabatrin, a structural GABA analog was carried out using NIR FT-Raman and FTIR spectroscopic techniques. The equilibrium geometry, various bonding features and harmonic vibrational wavenumbers were studied using density functional theory method. The detailed interpretation of the vibrational spectra has been carried out with the aid of VEDA.4 program. Vibrational spectra, natural bond orbital analysis and optimized molecular structure show clear evidence for the effect of electron charge transfer on the activity of the molecule. Predicted electronic absorption spectrum from TD-DFT calculation has been compared with the UV-vis spectrum. The Mulliken population analysis on atomic charges and the HOMO-LUMO energy were also calculated. Good consistency is found between the calculated results and experimental data for the electronic absorption as well as IR and Raman spectra. The blue-shifting of the Csbnd C stretching wavenumber reveals that the vinyl group is actively involved in the conjugation path. The NBO analysis confirms the occurrence of intramolecular hyperconjugative interactions resulting in ICT causing stabilization of the system.

A potential new biosignature of life in iron-rich extreme environments: An iron (III) complex of scytonemin and proposal for its identification using Raman spectroscopy

NASA Astrophysics Data System (ADS)

Varnali, Tereza; Edwards, Howell G. M.

2013-07-01

Scytonemin is a cyanobacterial sheath pigment with potent UV absorbing (UV-A, UV-B and UV-C) properties. The importance of this biomolecule is its photoprotective function which is one of the major survival strategies adopted by extremophiles to combat high energy radiation insolation in environmentally stressed conditions. Also, iron (III) oxides offering an additional UV-protecting facility to subsurface biological colonization as well as banded iron formations with zones of iron depletion in rock matrices have attracted attention with special interest in the mobilisation and transportation of iron compounds through the rock. This study represents a novel proposal that an iron-scytonemin complex could facilitate the movement of iron through the subsurface rock as part of the this extremophilic survival strategy. The predicted Raman wavenumbers for the proposed scytonemin complex of iron(III) are derived computationally using DFT calculations. Comparison of the experimentally observed Raman spectra of scytonemin with the theoretically predicted Raman spectra of the iron-scytonemin complex show that the latter may be discriminated and the expected characteristic bands are reported in relation to structural changes that are effected upon complexation. This information will inform the future search for experimental evidence for an iron-scytonemin complex, which has not been recognised hitherto and which could provide a novel biosignature for the extremophilic colonization of terrestrial iron-rich geological matrices. Such a terrestrial scenario would be potentially of significance for the remote robotic analytical exploration of the iron-rich surface and immediate subsurface of Mars.

Characterization of cubic ceria?zirconia powders by X-ray diffraction and vibrational and electronic spectroscopy

NASA Astrophysics Data System (ADS)

Sánchez Escribano, Vicente; Fernández López, Enrique; Panizza, Marta; Resini, Carlo; Gallardo Amores, José Manuel; Busca, Guido

2003-10-01

The X-ray diffraction (XRD) patterns and the Infrared, Raman and UV-visible spectra of CeO 2ZrO 2 powders prepared by co-precipitation are presented. Raman spectra provide evidence for the largely predominant cubic structure of the powders with CeO 2 molar composition higher than 25%. Also skeletal IR spectra allow to distinguish cubic from tetragonal phases which are instead not easily distinguished on the basis of the XRD patterns. All mixed oxides including pure ceria are strong UV absorbers although also absorb in the violet visible region. By carefully selecting their composition and treatment temperature, the onset of the radiation that they cut off can be chosen in the 425-475 nm interval. Although they are likely metastable, the cubic phases are still pure even after heating at 1173 K for 4 h.

Synthesis, spectroscopic investigation and theoretical studies of 2-((E)-(2-(2-cyanoacetyl)hydrazono)methyl)-4-((E)-phenyldiazenyl)phenyl methyl carbonate

NASA Astrophysics Data System (ADS)

Arokiasamy, A.; Manikandan, G.; Thanikachalam, V.; Gokula Krishnan, K.

2017-04-01

Synthesis and computational optimization studies have been carried out by Hartree-Fock (HF) and Density Functional Theory (DFT-B3LYP) methods with 6-31+G(d, p) basis set for 2-((E)-(2-(2-cyanoacetyl)hydrazono)methyl)-4-((E)-phenyldiazenyl)phenyl methyl carbonate (CHPMC). The stable configuration of CHPMC was confirmed theoretically by potential energy surface scan analysis. The complete vibrational assignments were performed on the basis of total energy distribution (TED) analysis. The vibrational properties studied by IR and Raman spectroscopic data complemented by quantum chemical calculations support the formation of intramolecular hydrogen bond. Furthermore, the UV-Vis spectra are interpreted in terms of TD-DFT quantum chemical calculations. The shapes of the simulated absorption spectra are in good agreement with the experimental data. The comparison between the experimental and theoretical values of FT-IR, FT-Raman vibrational spectra, NMR (1H and 13C) and UV-Vis spectra have also been discussed.

Synthesis, FTIR, FT-Raman, UV-visible, ab initio and DFT studies on benzohydrazide.

PubMed

Arjunan, V; Rani, T; Mythili, C V; Mohan, S

2011-08-01

A systematic vibrational spectroscopic assignment and analysis of benzohydrazide (BH) has been carried out by using FTIR and FT-Raman spectral data. The vibrational analysis were aided by electronic structure calculations--ab initio (RHF) and hybrid density functional methods (B3LYP and B3PW91) performed with 6-31G(d,p) and 6-311++G(d,p) basis sets. Molecular equilibrium geometries, electronic energies, IR intensities, harmonic vibrational frequencies, depolarization ratios and Raman activities have been computed. Potential energy distribution (PED) and normal mode analysis have also been performed. The assignments proposed based on the experimental IR and Raman spectra have been reviewed and complete assignment of the observed spectra have been proposed. UV-visible spectrum of the compound was also recorded and the electronic properties, such as HOMO and LUMO energies and λ(max) were determined by time-dependent DFT (TD-DFT) method. The geometrical, thermodynamical parameters and absorption wavelengths were compared with the experimental data. The interactions of carbonyl and hydrazide groups on the benzene ring skeletal modes were investigated. Copyright © 2011 Elsevier B.V. All rights reserved.

Oxidative damage in DNA bases revealed by UV resonant Raman spectroscopy.

PubMed

D'Amico, Francesco; Cammisuli, Francesca; Addobbati, Riccardo; Rizzardi, Clara; Gessini, Alessandro; Masciovecchio, Claudio; Rossi, Barbara; Pascolo, Lorella

2015-03-07

We report on the use of the UV Raman technique to monitor the oxidative damage of deoxynucleotide triphosphates (dATP, dGTP, dCTP and dTTP) and DNA (plasmid vector) solutions. Nucleotide and DNA aqueous solutions were exposed to hydrogen peroxide (H2O2) and iron containing carbon nanotubes (CNTs) to produce Fenton's reaction and induce oxidative damage. UV Raman spectroscopy is shown to be maximally efficient to reveal changes in the nitrogenous bases during the oxidative mechanisms occurring on these molecules. The analysis of Raman spectra, supported by numerical computations, revealed that the Fenton's reaction causes an oxidation of the nitrogenous bases in dATP, dGTP and dCTP solutions leading to the production of 2-hydroxyadenine, 8-hydroxyguanine and 5-hydroxycytosine. No thymine change was revealed in the dTTP solution under the same conditions. Compared to single nucleotide solutions, plasmid DNA oxidation has resulted in more radical damage that causes the breaking of the adenine and guanine aromatic rings. Our study demonstrates the advantage of using UV Raman spectroscopy for rapidly monitoring the oxidation changes in DNA aqueous solutions that can be assigned to specific nitrogenous bases.

Molecular spectroscopic studies of lichen substances 1: parietin and emodin

NASA Astrophysics Data System (ADS)

Edwards, Howell G. M.; Newton, Emma M.; Wynn-Williams, David D.; Coombes, Steven R.

2003-03-01

The Raman and infrared spectra of the UV-radiation protectant parietin extracted from Xanthoria lichen species are reported and vibrational assignments made of key features which are important for the characterisation of parietin in situ in stress-tolerant living organisms. The spectra of parietin are compared with those of the chemically related emodin, which is of pharmaceutical interest. The key molecular vibrational bands of parietin will be used for the analysis of lichen specimens exposed to high UV-radiation stress growing on Leonie Island, Antarctica, under the 'ozone hole' to better understand the production of UV-protectants in controlled habitats.

Optical study of plasma sprayed hydroxyapatite coatings deposited at different spray distance

NASA Astrophysics Data System (ADS)

Belka, R.; Kowalski, S.; Żórawski, W.

2017-08-01

Series of hydroxyapatite (HA) coatings deposited on titanium substrate at different spray (plasma gun to workpiece) distance were investigated. The optical methods as dark field confocal microscopy, Raman/PL and UV-VIS spectroscopy were used for study the influence of deposition process on structural degradation of HA precursor. The hydroxyl group concentration was investigated by study the OH mode intensity in the Raman spectra. Optical absorption coefficients at near UV region were analyzed by Diffuse Reflectance Spectroscopy. PL intensity observed during Raman measurement was also considered as relation to defects concentration and degradation level. It was confirmed the different gunsubstrate distance has a great impact on structure of deposited HA ceramics.

UV Resonance Raman Elucidation of the Terminal and Internal Peptide Bond Conformations of Crystalline and Solution Oligoglycines.

PubMed

Bykov, Sergei V; Asher, Sanford A

2010-11-30

Spectroscopic investigations of macromolecules generally attempt to interpret the measured spectra in terms of the summed contributions of the different molecular fragments. This is the basis of the local mode approximation in vibrational spectroscopy. In the case of resonance Raman spectroscopy independent contributions of molecular fragments require both a local mode-like behavior and the uncoupled electronic transitions. Here we show that the deep UV resonance Raman spectra of aqueous solution phase oligoglycines show independent peptide bond molecular fragment contributions indicating that peptide bonds electronic transitions and vibrational modes are uncoupled. We utilize this result to separately determine the conformational distributions of the internal and penultimate peptide bonds of oligoglycines. Our data indicate that in aqueous solution the oligoglycine terminal residues populate conformations similar to those found in crystals (3(1)-helices and β-strands), but with a broader distribution, while the internal peptide bond conformations are centered around the 3(1)-helix Ramachandran angles.

UV resonance Raman finds peptide bond-Arg side chain electronic interactions.

PubMed

Sharma, Bhavya; Asher, Sanford A

2011-05-12

We measured the UV resonance Raman excitation profiles and Raman depolarization ratios of the arginine (Arg) vibrations of the amino acid monomer as well as Arg in the 21-residue predominantly alanine peptide AAAAA(AAARA)(3)A (AP) between 194 and 218 nm. Excitation within the π → π* peptide bond electronic transitions result in UVRR spectra dominated by amide peptide bond vibrations. The Raman cross sections and excitation profiles indicate that the Arg side chain electronic transitions mix with the AP peptide bond electronic transitions. The Arg Raman bands in AP exhibit Raman excitation profiles similar to those of the amide bands in AP which are conformation specific. These Arg excitation profiles distinctly differ from the Arg monomer. The Raman depolarization ratios of Arg in monomeric solution are quite simple with ρ = 0.33 indicating enhancement by a single electronic transition. In contrast, we see very complex depolarization ratios of Arg in AP that indicate that the Arg residues are resonance enhanced by multiple electronic transitions.

The use of UV, FT-IR and Raman spectra for the identification of the newest penem analogs: solutions based on mathematic procedure and the density functional theory.

PubMed

Cielecka-Piontek, J; Lewandowska, K; Barszcz, B; Paczkowska, M

2013-02-15

The application of ultraviolet, FT-IR and Raman spectra was proposed for identification studies of the newest penem analogs (doripenem, biapenem and faropenem). An identification of the newest penem analogs based on their separation from related substances was achieved after the application of first derivative of direct spectra in ultraviolet which permitted elimination of overlapping effects. A combination of experimental and theoretical studies was performed for analyzing the structure and vibrational spectra (FT-IR and Raman spectra) of doripenem, biapenem and faropenem. The calculations were conducted using the density functional theory with the B3LYP hybrid functional and 6-31G(d,p) basis set. The confirmation of the applicability of the DFT methodology for interpretation of vibrational IR and Raman spectra of the newest penem analogs contributed to determination of changes of vibrations in the area of the most labile bonds. By employing the theoretical approach it was possible to eliminate necessity of using reference standards which - considering the instability of penem analogs - require that correction coefficients are factored in. Copyright © 2012 Elsevier B.V. All rights reserved.

UV-resonance Raman spectroscopy of amino acids

NASA Astrophysics Data System (ADS)

Höhl, Martin; Meinhardt-Wollweber, Merve; Schmitt, Heike; Lenarz, Thomas; Morgner, Uwe

2016-03-01

Resonant enhancement of Raman signals is a useful method to increase sensitivity in samples with low concentration such as biological tissue. The investigation of resonance profiles shows the optimal excitation wavelength and yields valuable information about the molecules themselves. However careful characterization and calibration of all experimental parameters affecting quantum yield is required in order to achieve comparability of the single spectra recorded. We present an experimental technique for measuring the resonance profiles of different amino acids. The absorption lines of these molecules are located in the ultraviolet (UV) wavelength range. One limitation for broadband measurement of resonance profiles is the limited availability of Raman filters in certain regions of the UV for blocking the Rayleigh scattered light. Here, a wavelength range from 244.8 nm to 266.0 nm was chosen. The profiles reveal the optimal wavelength for recording the Raman spectra of amino acids in aqueous solutions in this range. This study provides the basis for measurements on more complex molecules such as proteins in the human perilymph. The composition of this liquid in the inner ear is essential for hearing and cannot be analyzed non-invasively so far. The long term aim is to implement this technique as a fiber based endoscope for non-invasive measurements during surgeries (e. g. cochlear implants) making it available as a diagnostic tool for physicians. This project is embedded in the interdisciplinary cluster of excellence "Hearing for all" (H4A).

FT-Raman, FT-IR and UV-visible spectral investigations and ab initio computations of anti-epileptic drug: vigabatrin.

PubMed

Edwin, Bismi; Joe, I Hubert

2013-10-01

Vibrational analysis of anti-epileptic drug vigabatrin, a structural GABA analog was carried out using NIR FT-Raman and FTIR spectroscopic techniques. The equilibrium geometry, various bonding features and harmonic vibrational wavenumbers were studied using density functional theory method. The detailed interpretation of the vibrational spectra has been carried out with the aid of VEDA.4 program. Vibrational spectra, natural bond orbital analysis and optimized molecular structure show clear evidence for the effect of electron charge transfer on the activity of the molecule. Predicted electronic absorption spectrum from TD-DFT calculation has been compared with the UV-vis spectrum. The Mulliken population analysis on atomic charges and the HOMO-LUMO energy were also calculated. Good consistency is found between the calculated results and experimental data for the electronic absorption as well as IR and Raman spectra. The blue-shifting of the C-C stretching wavenumber reveals that the vinyl group is actively involved in the conjugation path. The NBO analysis confirms the occurrence of intramolecular hyperconjugative interactions resulting in ICT causing stabilization of the system. Copyright © 2013 Elsevier B.V. All rights reserved.

Comprehensive spectroscopic studies on the interaction of biomolecules with surfactant detached multi-walled carbon nanotubes.

PubMed

Sekar, Gajalakshmi; Mukherjee, Amitava; Chandrasekaran, Natarajan

2015-04-01

This paper investigates the interaction of ten diverse biomolecules with surfactant detached Multi-Walled Carbon Nanotubes (MWCNTs) using multiple spectroscopic methods. Declining fluorescence intensity of biomolecules in combination with the hyperchromic effect in UV-Visible spectra confirmed the existence of the ground state complex formation. Quenching mechanism remains static and non-fluorescent. 3D spectral data of biomolecules suggested the possibilities of disturbances to the aromatic microenvironment of tryptophan and tyrosine residues arising out of CNTs interaction. Amide band Shifts corresponding to the secondary structure of biomolecules were observed in the of FTIR and FT-Raman spectra. In addition, there exists an increased Raman intensity of tryptophan residues of biomolecules upon interaction with CNTs. Hence, the binding of the aromatic structures of CNTs with the aromatic amino acid residues, in a particular, tryptophan was evidenced. Far UV Circular spectra have showed the loss of alpha-helical contents in biomolecules upon interaction with CNTs. Near UV CD spectra confirmed the alterations in the tryptophan positions of the peptide backbone. Hence, our results have demonstrated that the interaction of biomolecules with OH-MWCNTs would involve binding cum structural changes and alteration to their aromatic micro-environment. Copyright © 2015 Elsevier B.V. All rights reserved.

Molecular docking, spectroscopic studies and quantum calculations on nootropic drug.

PubMed

Uma Maheswari, J; Muthu, S; Sundius, Tom

2014-04-05

A systematic vibrational spectroscopic assignment and analysis of piracetam [(2-oxo-1-pyrrolidineacetamide)] have been carried out using FT-IR and FT-Raman spectral data. The vibrational analysis was aided by an electronic structure calculation based on the hybrid density functional method B3LYP using a 6-311G++(d,p) basis set. Molecular equilibrium geometries, electronic energies, IR and Raman intensities, and harmonic vibrational frequencies have been computed. The assignments are based on the experimental IR and Raman spectra, and a complete assignment of the observed spectra has been proposed. The UV-visible spectrum of the compound was recorded and the electronic properties, such as HOMO and LUMO energies and the maximum absorption wavelengths λmax were determined by the time-dependent DFT (TD-DFT) method. The geometrical parameters, vibrational frequencies and absorption wavelengths were compared with the experimental data. The complete vibrational assignments are performed on the basis of the potential energy distributions (PED) of the vibrational modes in terms of natural internal coordinates. The simulated FT-IR, FT-Raman, and UV spectra of the title compound have been constructed. Molecular docking studies have been carried out in the active site of piracetam by using Argus Lab. In addition, the potential energy surface, HOMO and LUMO energies, first-order hyperpolarizability and the molecular electrostatic potential have been computed. Copyright © 2014 Elsevier B.V. All rights reserved.

Hydrogen content estimation of hydrogenated amorphous carbon by visible Raman spectroscopy

NASA Astrophysics Data System (ADS)

Adamopoulos, G.; Robertson, J.; Morrison, N. A.; Godet, C.

2004-12-01

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 (1.5-5eV ) 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 488nm 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.

Spectroscopic and DFT studies of bis-3-hydroxypyridinium and bis-3-hydroxymethylpyridinium dibromides with tetramethylene linker

NASA Astrophysics Data System (ADS)

Komasa, Anna

2018-01-01

Experimental and theoretical IR, Raman, UV-Vis, 1H and 13C NMR spectra of 1,4-di(3-hydroxypyridinium)butane dibromide and 1,4-di(3-hydroxymethylpyridinium)butane dibromide were obtained and analyzed. Optimized geometrical structures of the studied compounds were calculated by B3LYP method using 6-311++G(d,p) basis set and employed to determine the theoretical wavenumbers and intensities of IR and Raman spectra. The frequency assignments were supported by the potential energy distribution (PED) analysis. The significant role of the intermolecular interactions and the hydrogen bond was revealed on the basis of IR spectra. The calculated GIAO/B3LYP/6-311++G(d,p) isotropic magnetic shielding constants were used to predict the 1H and 13C chemical shifts for the optimized structures. Accuracy of the prediction of 1H and 13C chemical shifts was significantly improved by a simulation of the solvent in calculations. On the basis of UV-Vis spectra the acid-base equilibrium in the water solution of 1,4-di(3-hydroxypyridinium)butane dibromide was found.

Spectroscopic and structural study of the newly synthesized heteroligand complex of copper with creatinine and urea.

PubMed

Gangopadhyay, Debraj; Singh, Sachin Kumar; Sharma, Poornima; Mishra, Hirdyesh; Unnikrishnan, V K; Singh, Bachcha; Singh, Ranjan K

2016-02-05

Study of copper complex of creatinine and urea is very important in life science and medicine. In this paper, spectroscopic and structural study of a newly synthesized heteroligand complex of copper with creatinine and urea has been discussed. Structural studies have been carried out using DFT calculations and spectroscopic analyses were carried out by FT-IR, Raman, UV-vis absorption and fluorescence techniques. The copper complex of creatinine and the heteroligand complex were found to have much increased water solubility as compared to pure creatinine. The analysis of FT-IR and Raman spectra helps to understand the coordination properties of the two ligands and to determine the probable structure of the heteroligand complex. The LIBS spectra of the heteroligand complex reveal that the complex is free from other metal impurities. UV-visible absorption spectra and the fluorescence emission spectra of the aqueous solution of Cu-Crn-urea heteroligand complex at different solute concentrations have been analyzed and the complex is found to be rigid and stable in its monomeric form at very low concentrations. Copyright © 2015 Elsevier B.V. All rights reserved.

Performance Assessment of a Plate Beam Splitter for Deep-Ultraviolet Raman Measurements with a Spatial Heterodyne Raman Spectrometer.

PubMed

Lamsal, Nirmal; Angel, S Michael

2017-06-01

In earlier works, we demonstrated a high-resolution spatial heterodyne Raman spectrometer (SHRS) for deep-ultraviolet (UV) Raman measurements, and showed its ability to measure UV light-sensitive compounds using a large laser spot size. We recently modified the SHRS by replacing the cube beam splitter (BS) with a custom plate beam splitter with higher light transmission, an optimized reflectance/transmission ratio, higher surface flatness, and better refractive index homogeneity than the cube beam splitter. Ultraviolet Raman measurements were performed using a SHRS modified to use the plate beam splitter and a matching compensator plate and compared to the previously described cube beam splitter setup. Raman spectra obtained using the modified SHRS exhibit much higher signals and signal-to-noise (S/N) ratio and show fewer spectral artifacts. In this paper, we discuss the plate beam splitter SHRS design features, the advantages over previous designs, and discuss some general SHRS issues such as spectral bandwidth, S/N ratio characteristics, and optical efficiency.

Density functional theory and Ab initio studies of vibrational spectroscopic (FT-IR, FT-Raman and UV) first order hyperpolarizabilities, NBO, HOMO-LUMO and TD-DFT analysis of the 1,2-Dihydropyrazolo (4,3-E) Pyrimidin-4-one

NASA Astrophysics Data System (ADS)

Ramachandran, G.; Muthu, S.; Uma Maheswari, J.

2013-02-01

Fourier transform Raman and Fourier transform infrared spectra of 1,2-Dihydropyrazolo (4,3-E) Pyrimidin-4-one were recorded in the regions 3500-100 cm-1 and 4000-400 cm-1 respectively in the solid phase. 1,2-Dihydropyrazolo (4, 3-E) Pyrimidin-4-one is used to treat hyperuricemia and its complication including chronic gout. The equilibrium geometry harmonic vibrational frequencies, infrared intensities and Raman intensities were calculated by Hartee Fock and density functional B3LYP methods with 6-31G (d, p) basis set, using Gaussian 03W program package on a Pentium IV/1.6 GHz personal computer. The thermodynamic functions of the title compound were also performed at the above methods and basis set. A detailed interpretation of the infrared and Raman spectra of 1,2-Dihydropyrazolo (4,3-E) Pyrimidin-4-one is reported. Stability of the molecule arising from hyper conjugative interactions, charge delocalization has been analyzed using natural bond orbital (NBO) analysis. UV-vis of the compound was recorded. The calculated HOMO and LUMO energies show that chemical activity of the molecule. The first order hyperpolarizability (β) of this novel molecular system and related properties of 1,2-Dihydropyrazolo (4,3-E) Pyrimidin-4-one are calculated using HF/6-31G (d, p) method on the finite field approach. The experimental spectra also coincide satisfactorily with those of theoretically constructed spectra.

DFT calculations and experimental FT-IR, FT-Raman, NMR, UV-Vis spectral studies of 3-fluorophenylboronic acid

NASA Astrophysics Data System (ADS)

Karabacak, M.; Kose, E.; Sas, E. B.; Kurt, M.; Asiri, A. M.; Atac, A.

2015-02-01

The spectroscopic (FT-IR, FT-Raman, 1H and 13C NMR, UV-Vis), structural, electronic and thermodynamical properties of 3-fluorophenylboronic acid (C6H4FB(OH)2), 3FPBA) were submitted by using both experimental techniques and theoretical methods (quantum chemical calculations) in this work. The experimental infrared and Raman spectra were obtained in the region 4000-400 cm-1 and 3500-10 cm-1, respectively. The equilibrium geometry and vibrational spectra were calculated by using DFT (B3LYP) with 6-311++G(d,p) basis set. The vibrational wavenumbers were also corrected with scale factor to take better results for the calculated data. The total energy distributions (TED) of the vibrational modes were performed for the assignments of the title molecule by using scaled quantum mechanics (SQM) method. The NMR chemical shifts (1H and 13C) were recorded in DMSO solution. The 1H and 13C NMR spectra were computed by using the gauge-invariant atomic orbital (GIAO) method, showing a good agreement with the experimental ones. The last one UV-Vis absorption spectra were analyzed in two solvents (ethanol and water), saved in the range of 200-400 nm. In addition these, HOMO and LUMO energies, the excitation energies, density of states (DOS) diagrams, thermodynamical properties and molecular electrostatic potential surface (MEPs) were presented. Nonlinear optical (NLO) properties and thermodynamic features were performed. The experimental results are combined with the theoretical calculations using DFT calculations to fortification of the paper. At the end of this work, the results were proved our paper had been indispensable for the literature backing.

DFT calculations and experimental FT-IR, FT-Raman, NMR, UV-Vis spectral studies of 3-fluorophenylboronic acid.

PubMed

Karabacak, M; Kose, E; Sas, E B; Kurt, M; Asiri, A M; Atac, A

2015-02-05

The spectroscopic (FT-IR, FT-Raman, (1)H and (13)C NMR, UV-Vis), structural, electronic and thermodynamical properties of 3-fluorophenylboronic acid (C6H4FB(OH)2), 3FPBA) were submitted by using both experimental techniques and theoretical methods (quantum chemical calculations) in this work. The experimental infrared and Raman spectra were obtained in the region 4000-400 cm(-1) and 3500-10 cm(-1), respectively. The equilibrium geometry and vibrational spectra were calculated by using DFT (B3LYP) with 6-311++G(d,p) basis set. The vibrational wavenumbers were also corrected with scale factor to take better results for the calculated data. The total energy distributions (TED) of the vibrational modes were performed for the assignments of the title molecule by using scaled quantum mechanics (SQM) method. The NMR chemical shifts ((1)H and (13)C) were recorded in DMSO solution. The (1)H and (13)C NMR spectra were computed by using the gauge-invariant atomic orbital (GIAO) method, showing a good agreement with the experimental ones. The last one UV-Vis absorption spectra were analyzed in two solvents (ethanol and water), saved in the range of 200-400 nm. In addition these, HOMO and LUMO energies, the excitation energies, density of states (DOS) diagrams, thermodynamical properties and molecular electrostatic potential surface (MEPs) were presented. Nonlinear optical (NLO) properties and thermodynamic features were performed. The experimental results are combined with the theoretical calculations using DFT calculations to fortification of the paper. At the end of this work, the results were proved our paper had been indispensable for the literature backing. Copyright © 2014 Elsevier B.V. All rights reserved.

A new μ3-oxo-centered tri-nuclear carboxyl bridged iron (III) complex with thio-methyl groups in the periphery: Structural, spectroscopic and electrochemical studies

NASA Astrophysics Data System (ADS)

Lu, Maofeng; Chen, Tingting; Wang, Miao; Jiang, Guomin; Lu, Tianhong; Jiang, Guoqing; Du, Jiangyan

2014-02-01

A tri-nuclear iron (III) complex [Fe3(μ3-O)(O2CC6H4SCH3)6(Py)3]FeCl4 has been synthesized and characterized by X-ray crystallography, Surface enhanced Raman Scattering (SERS), Fourier Transform Infra Red (FT-IR), Ultraviolet-Visible (UV-Vis) spectroscopy and Thermogravimetric analysis (TGA)/Differential scanning calorimetry (DSC). The functionalized thio-methyl groups around the periphery of the complex 1 may provide binding sites to the surface of some specific materials, such as noble metals. The Ag sols and complex 1-Ag sol had been characterized by SERS and UV-Vis spectroscopy. The complex 1 were also self-assembled on gold electrode by AuS bond, exhibiting an irreversible process at E1/2 = 0.967 V (ΔE = 0.525 V). Meanwhile the Raman spectra were compared with FT-IR, and the results indicated that the strong Raman lines either correspond to weak Infrared absorptions or are absent in the Infrared spectra.

Deep UV Raman spectroscopy for planetary exploration: The search for in situ organics

NASA Astrophysics Data System (ADS)

Abbey, William J.; Bhartia, Rohit; Beegle, Luther W.; DeFlores, Lauren; Paez, Veronica; Sijapati, Kripa; Sijapati, Shakher; Williford, Kenneth; Tuite, Michael; Hug, William; Reid, Ray

2017-07-01

Raman spectroscopy has emerged as a powerful, non-contact, non-destructive technique for detection and characterization of in situ organic compounds. Excitation using deep UV wavelengths (< 250 nm), in particular, offers the benefits of spectra obtained in a largely fluorescence-free region while taking advantage of signal enhancing resonance Raman effects for key classes of organic compounds, such as the aromatics. In order to demonstrate the utility of this technique for planetary exploration and astrobiological applications, we interrogated three sets of samples using a custom built Raman instrument equipped with a deep UV (248.6 nm) excitation source. The sample sets included: (1) the Mojave Mars Simulant, a well characterized basaltic sample used as an analog for Martian regolith, in which we detected ∼0.04 wt% of condensed carbon; (2) a suite of organic (aromatic hydrocarbons, carboxylic acids, and amino acids) and astrobiologically relevant inorganic (sulfates, carbonates, phosphates, nitrates and perchlorate) standards, many of which have not had deep UV Raman spectra in the solid phase previously reported in the literature; and (3) Mojave Mars Simulant spiked with a representative selection of these standards, at a concentration of 1 wt%, in order to investigate natural 'real world' matrix effects. We were able to resolve all of the standards tested at this concentration. Some compounds, such as the aromatic hydrocarbons, have especially strong signals due to resonance effects even when present in trace amounts. Phenanthrene, one of the aromatic hydrocarbons, was also examined at a concentration of 0.1 wt% and even at this level was found to have a strong signal-to-noise ratio. It should be noted that the instrument utilized in this study was designed to approximate the operation of a 'fieldable' spectrometer in order to test astrobiological applications both here on Earth as well as for current and future planetary missions. It is the foundation of SHERLOC, an arm mounted instrument recently selected by NASA to fly on the next rover mission to Mars in 2020.

Molecular structure, spectroscopic (FTIR, FT-Raman, 13C and 1H NMR, UV), polarizability and first-order hyperpolarizability, HOMO-LUMO analysis of 2,4-difluoroacetophenone

NASA Astrophysics Data System (ADS)

Jeyavijayan, S.

2015-02-01

The FTIR and FT-Raman spectra of 2,4-difluoroacetophenone (DFAP) have been recorded in the regions 4000-400 cm-1 and 3500-50 cm-1, respectively. Utilizing the observed FTIR and FT-Raman data, a complete vibrational assignment and analysis of the fundamental modes of the compound were carried out. The optimum molecular geometry, harmonic vibrational frequencies, infrared intensities and Raman scattering activities, were calculated by density functional theory (DFT/B3LYP) method with 6-31+G(d,p) and 6-311++G(d,p) basis sets. The difference between the observed and scaled wavenumber values of most of the fundamentals is very small. A detailed interpretation of the infrared and Raman spectra of DFAP is also reported based on total energy distribution (TED). Stability of the molecule arising from hyperconjugative interactions, charge delocalization have been analyzed using natural bond orbital (NBO) analysis. The MEP map shows the negative potential sites are on oxygen atom as well as the positive potential sites are around the hydrogen atoms. The UV-Vis spectral analysis of DFAP has also been done which confirms the charge transfer of DFAP. The chemical shifts of H atoms and C atoms were calculated using NMR analysis. Furthermore, the polarizability, the first hyperpolarizability and total dipole moment of the molecule have been calculated.

Specific behavior of the p-aminothiophenol--silver sol system in their Ultra-Violet-Visible (UV-Visible) and Surface Enhanced Raman (SERS) spectra.

PubMed

Firkala, Tamás; Tálas, Emília; Mihály, Judith; Imre, Tímea; Kristyán, Sándor

2013-11-15

The UV-Visible and Surface Enhanced Raman Spectroscopy (SERS) behavior of silver sol (a typical SERS agent) were studied in the presence of different bifunctional thiols such as p-aminothiophenol, p-mercaptobenzoic acid, p-nitrothiophenol, p-aminothiophenol hydrochloride, and 2-mercaptoethylamine hydrochloride in diluted aqueous solution. Our results confirm that the p-aminothiophenol induced aggregation of citrate stabilized silver colloid originates from its electrostatic nature, as well as the azo-bridge formation cannot be the reason of the observed time dependent UV-Visible spectra. Based on our parallel SERS and electrospray ionization mass spectrometry measurements, we have concluded that certain amount of oxidized form of the probe molecule has to be present for the so-called b2-mode enhancement in the SERS spectrum of p-aminothiophenol. Our findings seem to support the idea that the azo-bridge formation is responsible for the b2-mode enhancement in the SERS spectrum of p-aminothiophenol. Copyright © 2013 Elsevier Inc. All rights reserved.

FTIR, FT-Raman, FT-NMR, UV-visible and quantum chemical investigations of 2-amino-4-methylbenzothiazole.

PubMed

Arjunan, V; Sakiladevi, S; Rani, T; Mythili, C V; Mohan, S

2012-03-01

The FT-IR (4000-400 cm(-1)) and FT-Raman (4000-100 cm(-1)) spectral measurements and complete assignments of the observed spectra of 2-amino-4-methylbenzothiazole (2A4MBT) have been proposed. Ab initio and DFT calculations have been performed and the structural parameters of the compound were determined from the optimised geometry with 6-31G(d,p), 6-311++G(d,p) and cc-pVDZ basis sets and giving energies, harmonic vibrational frequencies, depolarisation ratios, IR intensities and Raman activities. (1)H and (13)C NMR spectra were recorded and (1)H and (13)C nuclear magnetic resonance chemical shifts of the molecule were calculated using the gauge independent atomic orbital (GIAO) method. UV-visible spectrum of the compound was also recorded and the electronic properties, such as HOMO, LUMO and band gap energies were measured by time-dependent DFT (TD-DFT) approach. The geometric parameters, energies, harmonic vibrational frequencies, IR intensities, Raman activities chemical shifts and absorption wavelengths were compared with the available experimental data of the molecule. The influences of methyl and amino groups on the skeletal modes and on the proton chemical shifts have been investigated. Copyright © 2011 Elsevier B.V. All rights reserved.

Vibrational spectra, UV and NMR, first order hyperpolarizability and HOMO-LUMO analysis of 2-amino-4-chloro-6-methylpyrimidine.

PubMed

Jayavarthanan, T; Sundaraganesan, N; Karabacak, M; Cinar, M; Kurt, M

2012-11-01

The solid phase FTIR and FT-Raman spectra of 2-amino-4-chloro-6-methylpyrimidine (2A4Cl6MP) have been recorded in the regions 400-4000 and 50-4,000 cm(-1), respectively. The spectra have been interpreted interms of fundamentals modes, combination and overtone bands. The structure of the molecule has been optimized and the structural characteristics have been determined by density functional theory (B3LYP) method with 6-311++G(d,p) as basis set. The vibrational frequencies were calculated and were compared with the experimental frequencies, which yield good agreement between observed and calculated frequencies. The infrared and Raman spectra have also been predicted from the calculated intensities. (1)H and (13)C NMR spectra were recorded and (1)H and (13)C nuclear magnetic resonance chemical shifts of the molecule were calculated using the gauge independent atomic orbital (GIAO) method. UV-Vis spectrum of the compound was recorded in the region 200-400 nm and the electronic properties HOMO and LUMO energies were measured by time-dependent TD-DFT approach. Nonlinear optical and thermodynamic properties were interpreted. All the calculated results were compared with the available experimental data of the title molecule. Copyright © 2012 Elsevier B.V. All rights reserved.

Electronic structure investigations of 4-aminophthal hydrazide by UV-visible, NMR spectral studies and HOMO-LUMO analysis by ab initio and DFT calculations.

PubMed

Sambathkumar, K; Jeyavijayan, S; Arivazhagan, M

2015-08-05

Combined experimental and theoretical studies were conducted on the molecular structure and vibrational spectra of 4-AminoPhthalhydrazide (APH). The FT-IR and FT-Raman spectra of APH were recorded in the solid phase. The molecular geometry and vibrational frequencies of APH in the ground state have been calculated by using the ab initio HF (Hartree-Fock) and density functional methods (B3LYP) invoking 6-311+G(d,p) basis set. The optimized geometric bond lengths and bond angles obtained by HF and B3LYP method show best agreement with the experimental values. Comparison of the observed fundamental vibrational frequencies of APH with calculated results by HF and density functional methods indicates that B3LYP is superior to the scaled Hartree-Fock approach for molecular vibrational problems. The difference between the observed and scaled wave number values of most of the fundamentals is very small. A detailed interpretation of the NMR spectra of APH was also reported. The theoretical spectrograms for infrared and Raman spectra of the title molecule have been constructed. UV-vis spectrum of the compound was recorded and the electronic properties, such as HOMO and LUMO energies, were performed by time dependent density functional theory (TD-DFT) approach. Finally the calculations results were applied to simulated infrared and Raman spectra of the title compound which show good agreement with observed spectra. And the temperature dependence of the thermodynamic properties of constant pressure (Cp), entropy (S) and enthalpy change (ΔH0→T) for APH were also determined. Copyright © 2015 Elsevier B.V. All rights reserved.

Molecular structure, vibrational spectroscopic (FT-IR, FT-Raman), UV-vis spectra, first order hyperpolarizability, NBO analysis, HOMO and LUMO analysis, thermodynamic properties of benzophenone 2,4-dicarboxylic acid by ab initio HF and density functional method

NASA Astrophysics Data System (ADS)

Chaitanya, K.

2012-02-01

The FT-IR (4000-450 cm -1) and FT-Raman spectra (3500-100 cm -1) of benzophenone 2,4-dicarboxylic acid (2,4-BDA) have been recorded in the condensed state. Density functional theory calculation with B3LYP/6-31G(d,p) basis set have been used to determine ground state molecular geometries (bond lengths and bond angles), harmonic vibrational frequencies, infrared intensities, Raman activities and bonding features of the title compounds. The assignments of the vibrational spectra have been carried out with the help of normal co-ordinate analysis (NCA) following the scaled quantum mechanical force field (SQMFF) methodology. The first order hyperpolarizability ( β0) and related properties ( β, α0 and Δ α) of 2,4-BDA is calculated using HF/6-31G(d,p) method on the finite-field approach. The stability of molecule has been analyzed by using NBO analysis. The calculated first hyperpolarizability shows that the molecule is an attractive molecule for future applications in non-linear optics. The calculated HOMO and LUMO energies show that charge transfer occurs within these molecules. Mulliken population analysis on atomic charges is also calculated. Because of vibrational analyses, the thermodynamic properties of the title compound at different temperatures have been calculated. Finally, the UV-vis spectra and electronic absorption properties were explained and illustrated from the frontier molecular orbitals.

Raman scattering measurements in flames using a tunable KrF excimer laser

NASA Technical Reports Server (NTRS)

Wehrmeyer, Joseph A.; Cheng, Tsarng-Sheng; Pitz, Robert W.

1992-01-01

A narrow-band tunable KrF excimer laser is used as a spontaneous vibrational Raman scattering source to demonstrate that single-pulse concentration and temperature measurements, with only minimal fluorescence interference, are possible for all major species (O2, N2, H2O, and H2) at all stoichiometries (fuel-lean to fuel rich) of H2-air flames. Photon-statistics-limited precisions in these instantaneous and spatially resolved single-pulse measurements are typically 5 percent, which are based on the relative standard deviations of single-pulse probability distributions. In addition to the single-pulse N2 Stokes/anti-Stokes ratio temperature measurement technique, a time-averaged temperature measurement technique is presented that matches the N2 Stokes Raman spectrum to theoretical spectra by using a single intermediate state frequency to account for near-resonance enhancement. Raman flame spectra in CH4-air flames are presented that have good signal-to-noise characteristics and show promise for single-pulse UV Raman measurements in hydrocarbon flames.

FT-IR, FT-Raman and UV-visible spectra of potassium 3-furoyltrifluoroborate salt

NASA Astrophysics Data System (ADS)

Iramain, Maximiliano A.; Davies, Lilian; Brandán, Silvia Antonia

2018-04-01

The potassium 3-furoyltrifluoroborate salt has been experimentally characterized by means of FT-IR, FT-Raman and UV-Visible spectroscopies. Here, the predicted FT-IR, FT-Raman and UV-visible spectra by using theoretical B3LYP/6-31G* and 6-311++G** calculations show very good correlations with the corresponding experimental ones. The solvation energies were predicted by using both levels of calculations. The NBO analyses reveal the high stability of the salt by using the B3LYP/6-31G* level of theory while the AIM studies evidence the ionic characteristics of the salt in both media. The strong blue colour observed on the K atom by using the molecular electrostatic potential mapped suggests that this region act as typical electrophilic site. The gap values have revealed that the salt in gas phase is more reactive than in solution, as was reported in the literature while, the F13⋯H6 interaction together with the Ksbnd O bond observed by the studies of their charges could probably modulate the reactivities of this salt in aqueous solution. The force fields were computed with the SQMFF methodology and the Molvib program to perform the complete vibrational analysis. Then, the 39 vibration normal modes classified as 26 A'+ 13 A″ were completely assigned and their force constants are also reported.

Phonon shift in chemically exfoliated WS2 nanosheet

NASA Astrophysics Data System (ADS)

Sarkar, Abdus Salam; Pal, Suman Kalyan

2018-04-01

We have synthesized few layer WS2 nanosheets in a low boiling point solvent. Few layer of WS2 sheets are characterized by various techniques such as UV-visible and Raman spectroscopy, transmission electron microscopy (TEM), atomic force microscopy (AFM) and scanning electron microscopy (SEM). UV-Vis absorption spectra confirm the well dispersed in isopropyl alcohol. SEM and TEM images indicate the sheet like morphology of WS2. Atomic force microscopy image and room temperature Raman spectroscopy confirm the exfoliation of few layer (4-5 layer) of WS2. Further, Raman spectroscopy was used as a meteorology tool to determine the temperature co-efficient. We have systematically investigated the temperature dependent Raman spectroscopic behavior of few layer WS2. Our results depict the softening of the Raman modes E12g in plane vibration and A1g out of plane vibration with increasing the temperature from 77 K to 300 K. Softening of the Raman modes could be explained in terms of the double resonance which is active in the layered materials. The observed temperature coefficients for two Raman peaks E12g and A1g, are - 0.022 cm-1 and -0.009 cm-1, respectively.

Combined micro-Raman/UV-visible/fluorescence spectrometer for high-throughput analysis of microsamples.

PubMed

Noh, Jermim; Suh, Yung Doug; Park, Yong Ki; Jin, Seung Min; Kim, Soo Ho; Woo, Seong Ihl

2007-07-01

Combined micro-Raman/UV-visible (vis)/fluorescence spectroscopy system, which can evaluate an integrated array of more than 10,000 microsamples with a minimuma size of 5 microm within a few hours, has been developed for the first time. The array of microsamples is positioned on a computer-controlled XY translation microstage with a spatial resolution of 1 mum so that the spectra can be mapped with micron precision. Micro-Raman spectrometers have a high spectral resolution of about 2 cm(-1) over the wave number range of 150-3900 cm(-1), while UV-vis and fluorescence spectrometers have high spectral resolutions of 0.4 and 0.1 nm over the wavelength range of 190-900 nm, respectively. In particular, the signal-to-noise ratio of the micro-Raman spectroscopy has been improved by using a holographic Raman grating and a liquid-nitrogen-cooled charge-coupled device detector. The performance of the combined spectroscopy system has been demonstrated by the high-throughput screening of a combinatorial ferroelectric (i.e., BaTi(x)Zr(1-x)O(3)) library. This system makes possible the structure analysis of various materials including ferroelectrics, catalysts, phosphors, polymers, alloys, and so on for the development of novel materials and the ultrasensitive detection of trace amounts of pharmaceuticals and diagnostic agents.

Monomeric and dimeric structures analysis and spectroscopic characterization of 3,5-difluorophenylboronic acid with experimental (FT-IR, FT-Raman, 1H and 13C NMR, UV) techniques and quantum chemical calculations

NASA Astrophysics Data System (ADS)

Karabacak, Mehmet; Kose, Etem; Atac, Ahmet; Asiri, Abdullah M.; Kurt, Mustafa

2014-01-01

The spectroscopic properties of 3,5-difluorophenylboronic acid (3,5-DFPBA, C6H3F2B(OH)2) were investigated by FT-IR, FT-Raman UV-Vis, 1H and 13C NMR spectroscopic techniques. FT-IR (4000-400 cm-1) and FT-Raman spectra (3500-10 cm-1) in the solid phase and 1H and 13C NMR spectra in DMSO solution were recorded. The UV spectra that dissolved in ethanol and water were recorded in the range of 200-400 nm for each solution. The structural and spectroscopic data of the molecule have been obtained for possible three conformers from DFT (B3LYP) with 6-311++G(d,p) basis set calculations. The geometry of the molecule was fully optimized, vibrational spectra were calculated and fundamental vibrations were assigned on the basis of the total energy distribution (TED) of the vibrational modes, calculated with scaled quantum mechanics (SQM) method and PQS program. Hydrogen-bonded dimer of title molecule, optimized by counterpoise correction, was also studied B3LYP at the 6-311++G(d,p) level and the effects of molecular association through O-H⋯O hydrogen bonding have been discussed. 1H and 13C NMR chemical shifts were calculated by using the gauge-invariant atomic orbital (GIAO) method. The electronic properties, such as excitation energies, oscillator strength, wavelengths, HOMO and LUMO energies, were performed by time-dependent density functional theory (TD-DFT) results complements with the experimental findings. Total and partial density of state (TDOS and PDOS) and also overlap population density of state (OPDOS) diagrams analysis were presented. The effects due to the substitutions of boric acid group and halogen were investigated. The results of the calculations were applied to simulate spectra of the title compound, which show excellent agreement with observed spectra. Besides, frontier molecular orbitals (FMO), molecular electrostatic potential (MEP), nonlinear optical properties (NLO) and thermodynamic features were performed.

Compact Solid-State 213 nm Laser Enables Standoff Deep Ultraviolet Raman Spectrometer: Measurements of Nitrate Photochemistry.

PubMed

Bykov, Sergei V; Mao, Michael; Gares, Katie L; Asher, Sanford A

2015-08-01

We describe a new compact acousto-optically Q-switched diode-pumped solid-state (DPSS) intracavity frequency-tripled neodymium-doped yttrium vanadate laser capable of producing ~100 mW of 213 nm power quasi-continuous wave as 15 ns pulses at a 30 kHz repetition rate. We use this new laser in a prototype of a deep ultraviolet (UV) Raman standoff spectrometer. We use a novel high-throughput, high-resolution Echelle Raman spectrograph. We measure the deep UV resonance Raman (UVRR) spectra of solid and solution sodium nitrate (NaNO3) and ammonium nitrate (NH4NO3) at a standoff distance of ~2.2 m. For this 2.2 m standoff distance and a 1 min spectral accumulation time, where we only monitor the symmetric stretching band, we find a solid state NaNO3 detection limit of ~100 μg/cm(2). We easily detect ~20 μM nitrate water solutions in 1 cm path length cells. As expected, the aqueous solutions UVRR spectra of NaNO3 and NH4NO3 are similar, showing selective resonance enhancement of the nitrate (NO3(-)) vibrations. The aqueous solution photochemistry is also similar, showing facile conversion of NO3(-) to nitrite (NO2(-)). In contrast, the observed UVRR spectra of NaNO3 and NH4NO3 powders significantly differ, because their solid-state photochemistries differ. Whereas solid NaNO3 photoconverts with a very low quantum yield to NaNO2, the NH4NO3 degrades with an apparent quantum yield of ~0.2 to gaseous species.

Laser wavelength selection for Raman spectroscopy of microbial pigments in situ in Antarctic desert ecosystem analogues of former habitats on Mars

NASA Astrophysics Data System (ADS)

Edwards, Howell G. M.; Newton, Emma M.; Wynn-Williams, David D.; Dickensheets, David; Schoen, Chris; Crowder, Chelle

2002-10-01

The vital ultraviolet- (UV-) protective and photosynthetic pigments of cyanobacteria and lichens (microbial symbioses) that dominate primary production in Antarctic desert ecosystems auto-fluoresce at short wavelengths. We therefore use a long-wavelength (1064 nm) infrared laser for non-intrusive in situ Raman spectrometry of their ecologically significant compounds (especially pigments). To confirm that the power loss at this longer wavelength is justified to avoid swamping by background fluorescence, we compared Raman spectra obtained with excitation at 1064, 852, 830, 785, 633 and 515 nm. These are typical of lasers used for Raman spectroscopy. We analysed communities of the cyanobacterium Nostoc commune and the highly pigmented lichens Acarospora chlorophana and Caloplaca saxicola. These require screening compounds (e.g. pigments such as scytonemin in cyanobacteria and rhizocarpic acid in the fungal symbiont of lichens). They are augmented by quenching pigments (e.g. carotenoids) to dissipate the energy of free radicals generated by penetrating UV. We also analysed organisms having avoidance strategies (e.g. endolithic communities within translucent rocks, including the common cyanobacterium Chroococcidiopsis). These require accessory pigments for photosynthesis at very low light intensities. Although some organisms gave useable Raman spectra with short-wavelength lasers, 1064 nm was the only excitation that was consistently excellent for all organisms. We conclude that a 1064 nm Raman spectrometer, miniaturized using an InGaAs detector, is the optimal instrument for in situ studies of pigmented microbial communities at the limits of life on Earth. This has practical potential for the quest for biomolecules residual from any former surface life on Mars.

Spectroscopic (FT-IR, FT-Raman, FT-NMR and UV-Vis) investigation on benzil dioxime using quantum computational methods

NASA Astrophysics Data System (ADS)

Bakkiyaraj, D.; Periandy, S.; Xavier, S.

2016-03-01

The spectral analysis of benzil dioxime is carried out using the FTIR, FT Raman, FT NMR and UV-Vis spectra of the compound with the help of quantum computations by density functional theories. The FT-IR (4000 - 400 cm-1) and FT-Raman (4000-100 cm-1) spectra are recorded in solid phase, the 1H and 13C NMR spectra in DMSO phase and the UV spectrum (200-400 nm) in ethanol phase. The different conformers of the compound and their minimum energies are studied by potential energy surface scan, using semi-empirical method PM6. The computed wavenumbers from different methods are scaled so as to agree with the experimental values and the scaling factors are reported. All the fundamental modes have been assigned based on the potential energy distribution (PED) values and the structure the molecule is analyzed interms of parameters like bond length, bond angle and dihedral angles predicted byB3LYP and CAM-B3LYP methods with cc-pVDZ basis sets. The values of dipole moment (μ), polarizability (α) and hyperpolarizability (β) of the molecule are reported, using which the non -linear optical property of the molecule is discussed. The HOMO-LUMO mappings are reported which reveals the different charge transfer possibilities within the molecule. The isotropic chemical shifts predicted for 1H and 13C atoms using gauge invariant atomic orbital (GIAO) theory show good agreement with experimental shifts and the same is discussed in comparison with atomic charges, predicted by Mullikan and APT charge analysis. NBO analysis is carried out to picture the probable electronic transitions in the molecule.

Primidone--an antiepileptic drug--characterisation by quantum chemical and spectroscopic (FTIR, FT-Raman, 1H, 13C NMR and UV-Visible) investigations.

PubMed

Arjunan, V; Santhanam, R; Subramanian, S; Mohan, S

2013-05-15

The solid phase FTIR and FT-Raman spectra of primidone were recorded in the regions 4000-400 cm(-1) and 4000-100 cm(-1), respectively. The vibrational spectra were analysed and the observed fundamentals were assigned and analysed. The experimental wavenumbers were compared with the theoretical scaled vibrational wavenumbers determined by DFT methods. The Raman intensities were also determined with B3LYP/6-31G(d,p) method. The total electron density and molecular electrostatic potential surface of the molecule were constructed by using B3LYP/6-311++G(d,p) method to display electrostatic potential (electron+nuclei) distribution. The HOMO and LUMO energies were measured. Natural bond orbital analysis of primidone has been performed to indicate the presence of intramolecular charge transfer. The (1)H and (13)C NMR spectra were recorded and the chemical shifts of the molecule were calculated. Copyright © 2013 Elsevier B.V. All rights reserved.

Influence of etching current density on microstructural, optical and electrical properties of porous silicon (PS):n-Si heterostructure

NASA Astrophysics Data System (ADS)

Das, M.; Nath, P.; Sarkar, D.

2016-02-01

In this article effect of etching current density (J) on the microstructural, optical and electrical properties of photoelectrochemically prepared heterostructure is reported. Prepared samples are characterized by FESEM, XRD, UV-Visible, Raman and photoluminescence (PL) spectra and current-voltage (I-V) characteristics. FESEM shows presence of mixture of randomly distributed meso- and micro-pores. Porous layer thickness determined by cross section view of SEM is proportional to J. XRD shows crystalline nature but gradually extent of crystallinity decreases with increasing J. Raman spectra show large red-shift and asymmetric broadening with respect to crystalline silicon (c-Si). UV-visible reflectance and PL show blue shift in peaks with increasing J. The I-V characteristics are analyzed by the conventional thermionic emission (TE) model and Cheung's model to estimate the barrier height (φb), ideality factor (n) and series resistance (Rs) for comparison between the two models. The latter model is found to fit better.

Investigation of the optical property and photocatalytic activity of mixed phase nanocrystalline titania

NASA Astrophysics Data System (ADS)

Paul, Susmita; Choudhury, Amarjyoti

2014-10-01

Mixed phase nanocrystalline titania are prepared by simple sol-gel method. The physico-chemical characteristics of the prepared nanoparticles are studied with X-ray diffraction, high-resolution transmission electron microscopy, RAMAN, BET, UV-Vis, steady state and time resolved photoluminescence. X-ray diffraction and Raman spectra clearly demarcate the anatase and rutile phase as both the phases give different diffraction patterns and Raman peaks. A comparison in the band gap indicates that pure anatase and rutile phase have band gap in the UV region, whereas a mixture of these phases has lower band gap and corresponds to the visible region. Steady state and time resolved photoluminescence are employed to understand the emissivity and carrier lifetime. The photocatalytic activity is evaluated by monitoring the degradation of phenol under visible light illumination. Due to the synergistic effect of mixed anatase and rutile phases, mixed phase nanocrystalline titania exhibit superior photocatalytic activity.

Status of miniature integrated UV resonance fluorescence and Raman sensors for detection and identification of biochemical warfare agents

NASA Astrophysics Data System (ADS)

Hug, William F.; Bhartia, Rohit; Taspin, Alexandre; Lane, Arthur; Conrad, Pamela; Sijapati, Kripa; Reid, Ray D.

2005-11-01

Laser induced native fluorescence (LINF) is the most sensitive method of detection of biological material including microorganisms, virus', and cellular residues. LINF is also a sensitive method of detection for many non-biological materials as well. The specificity with which these materials can be classified depends on the excitation wavelength and the number and location of observation wavelengths. Higher levels of specificity can be obtained using Raman spectroscopy but a much lower levels of sensitivity. Raman spectroscopy has traditionally been employed in the IR to avoid fluorescence. Fluorescence rarely occurs at wavelength below about 270nm. Therefore, when excitation occurs at a wavelength below 250nm, no fluorescence background occurs within the Raman fingerprint region for biological materials. When excitation occurs within electronic resonance bands of the biological target materials, Raman signal enhancement over one million typically occurs. Raman sensitivity within several hundred times fluorescence are possible in the deep UV where most biological materials have strong absorption. Since the Raman and fluorescence emissions occur at different wavelength, both spectra can be observed simultaneously, thereby providing a sensor with unique sensitivity and specificity capability. We will present data on our integrated, deep ultraviolet, LINF/Raman instruments that are being developed for several applications including life detection on Mars as well as biochemical warfare agents on Earth. We will demonstrate the ability to discriminate organic materials based on LINF alone. Together with UV resonance Raman, higher levels of specificity will be demonstrated. In addition, these instruments are being developed as on-line chemical sensors for industrial and municipal waste streams and product quality applications.

Quantum chemical calculations and analysis of FTIR, FT-Raman and UV-Vis spectra of temozolomide molecule

NASA Astrophysics Data System (ADS)

Bhat, Sheeraz Ahmad; Ahmad, Shabbir

2015-11-01

A combined experimental and theoretical study of the structure, vibrational and electronic spectra of temozolomide molecule, which is largely used in the treatment of brain tumours, is presented. FTIR (4000-400 cm-1) and FT-Raman spectra (4000‒50 cm-1) have been recorded and analysed using anharmonic frequency calculations using VPT2, VSCF and CC-VSCF levels of theory within B3LYP/6-311++G(d,p) framework. Anharmonic methods give accurate frequencies of fundamental modes, overtones as well as Fermi resonances and account for coupling of different modes. The anharmonic frequencies calculated using VPT2 and CC-VSCF methods show better agreement with the experimental data. Harmonic frequencies including solvent effects are also computed using IEF-PCM model. The magnitudes of coupling between pair of modes have been calculated using coupling integral based on 2MR-QFF approximation. Intermolecular interactions are discussed for three possible dimers of temozolomide. UV-Vis spectrum, examined in ethanol solvent, is compared with the calculated spectrum at TD-DFT/6-311++G(d,p) level of theory. The electronic properties, such as excitation energy, frontier molecular orbital energies and the assignments of the absorption bands are also discussed.

Comparative theoretical and experimental study on novel tri-quinoline system and its anticancer studies

NASA Astrophysics Data System (ADS)

Gayathri, Kasirajan; Radhika, Ramachandran; Shankar, Ramasamy; Malathi, Mahalingam; Savithiri, Krishnaswamy; Sparkes, Hazel A.; Howard, Judith A. K.; Mohan, Palathurai Subramaniam

2017-04-01

A novel compound 2-chloro-3,6-bis-(quinolin-8-yloxymethyl)-quinoline 3 bearing a tri-quinoline moiety has been synthesized from 2-chloro-3,6-dimethyl quinoline 1 and 8-hydroxy quinoline 2 using dry acetone and K2CO3 as a base. 3 has been characterized by using FT-IR, FT-Raman, UV-Vis, 1H NMR, 13C NMR spectra and single crystal X-ray diffraction methods. We have also made a combined experimental and theoretical study on the molecular structure, vibrational spectra, NMR, FT-IR, FT-Raman and UV-Vis spectra of 2-chloro-3,6-bis-(quinolin-8-yloxymethyl)-quinoline. The theoretical studies of the title compound have been evaluated by using density functional theory calculations using B3LYP/6-31+G(d,p) and M06-2X/6-31+G(d,p) level of theories. The calculated theoretical values were found to be in good agreement with the experimental findings. The single crystal structure 3 crystallized in the orthorhombic space group Pna21. The compound 3 exhibits higher cytotoxicity in human cervical cancer cell lines (HeLa) than human breast cancer cell lines (MCF7).

Theoretical investigations on molecular structure, vibrational spectra, HOMO, LUMO, NBO analysis and hyperpolarizability calculations of thiophene-2-carbohydrazide.

PubMed

Balachandran, V; Janaki, A; Nataraj, A

2014-01-24

The Fourier-Transform infrared and Fourier-Transform Raman spectra of thiophene-2-carbohydrazide (TCH) was recorded in the region 4000-400 cm(-1) and 3500-100 cm(-1). Quantum chemical calculations of energies, geometrical structure and vibrational wavenumbers of TCH were carried out by DFT (B3LYP) method with 6-311++G(d,p) as basis set. The difference between the observed and scaled wavenumber values of most of the fundamentals is very small. Stability of the molecule arising from hyper conjugative interaction and charge delocalization has been analyzed using natural bond orbital (NBO) analysis. UV spectrum was measured in different solvent. The energy and oscillator strength are calculated by Time Dependant Density Functional Theory (TD-DFT) results. The calculated HOMO and LUMO energies also confirm that charge transfer occurs within the molecule. The complete assignments were performed on the basis of the potential energy distribution (PED) of vibrational modes, calculated with scaled quantum mechanics (SQM) method. Finally the theoretical FT-IR, FT-Raman, and UV spectra of the title molecule have also been constructed. Copyright © 2013 Elsevier B.V. All rights reserved.

In-line UV spectroscopy for the quantification of low-dose active ingredients during the manufacturing of pharmaceutical semi-solid and liquid formulations.

PubMed

Bostijn, N; Hellings, M; Van Der Veen, M; Vervaet, C; De Beer, T

2018-07-12

UltraViolet (UV) spectroscopy was evaluated as an innovative Process Analytical Technology (PAT) - tool for the in-line and real-time quantitative determination of low-dosed active pharmaceutical ingredients (APIs) in a semi-solid (gel) and a liquid (suspension) pharmaceutical formulation during their batch production process. The performance of this new PAT-tool (i.e., UV spectroscopy) was compared with an already more established PAT-method based on Raman spectroscopy. In-line UV measurements were carried out with an immersion probe while for the Raman measurements a non-contact PhAT probe was used. For both studied formulations, an in-line API quantification model was developed and validated per spectroscopic technique. The known API concentrations (Y) were correlated with the corresponding in-line collected preprocessed spectra (X) through a Partial Least Squares (PLS) regression. Each developed quantification method was validated by calculating the accuracy profile on the basis of the validation experiments. Furthermore, the measurement uncertainty was determined based on the data generated for the determination of the accuracy profiles. From the accuracy profile of the UV- and Raman-based quantification method for the gel, it was concluded that at the target API concentration of 2% (w/w), 95 out of 100 future routine measurements given by the Raman method will not deviate more than 10% (relative error) from the true API concentration, whereas for the UV method the acceptance limits of 10% were exceeded. For the liquid formulation, the Raman method was not able to quantify the API in the low-dosed suspension (0.09% (w/w) API). In contrast, the in-line UV method was able to adequately quantify the API in the suspension. This study demonstrated that UV spectroscopy can be adopted as a novel in-line PAT-technique for low-dose quantification purposes in pharmaceutical processes. Important is that none of the two spectroscopic techniques was superior to the other for both formulations: the Raman method was more accurate in quantifying the API in the gel (2% (w/w) API), while the UV method performed better for API quantification in the suspension (0.09% (w/w) API). Copyright © 2018 Elsevier B.V. All rights reserved.

Spectroscopic (FTIR, FT-Raman), molecular electrostatic potential, NBO and HOMO-LUMO analysis of P-bromobenzene sulfonyl chloride based on DFT calculations

NASA Astrophysics Data System (ADS)

Jeyavijayan, S.

2015-02-01

The FTIR and FT-Raman spectra of P-bromobenzene sulfonyl chloride (P-BBSC) have been recorded in the regions 4000-400 cm-1 and 3500-50 cm-1, respectively. Utilizing the observed FTIR and FT-Raman data, a complete vibrational assignment and analysis of the fundamental modes of the compound were carried out. The optimum molecular geometry, harmonic vibrational frequencies, infrared intensities and Raman scattering activities, were calculated by density functional theory (DFT/B3LYP) method. A good agreement between experimental and calculated normal modes of vibrations has been observed. A detailed interpretation of the infrared and Raman spectra of P-BBSC is also reported based on total energy distribution (TED). Stability of the molecule arising from hyperconjugative interactions, charge delocalization have been analyzed using natural bond orbital (NBO) analysis. The MEP map shows the negative potential sites are on oxygen atoms as well as the positive potential sites are around the hydrogen atoms. The UV-vis spectral analysis of P-BBSC has also been done which confirms the charge transfer of the molecule.

Probing the Conformational Landscape of Polyether Building Blocks in Supersonic Jets

NASA Astrophysics Data System (ADS)

Bocklitz, Sebastian; Hewett, Daniel M.; Zwier, Timothy S.; Suhm, Martin A.

2016-06-01

Polyethylene oxides (Polyethylene glycoles) and their phenoxy-capped analogs represent a prominent class of important polymers that are highly used as precursor molecules in supramolecular reactions. After a detailed study on the simplest representative (1,2-dimethoxyethane) [1], we present results on oligoethylene oxides with increasing chain lengths obtained by spontaneous Raman scattering in a supersonic jet. Through variation of stagnation pressure, carrier gas, nozzle distance and temperature we gain information on the conformational landscape as well as the mutual interconversion of low energy conformers. The obtained results are compared to state-of-the-art quantum chemical calculations. Additionally, we present UV as well as IR-UV and UV-UV double resonance studies on 1-methoxy-2-phenoxyethane in a supersonic jet. These complementary techniques allow for conformationally selective electronic and vibrational spectra in a closely related conformational landscape. [1] S. Bocklitz, M. A. Suhm, Constraining the Conformational Landscape of a Polyether Building Block by Raman Jet Spectroscopy, Z. Phys. Chem. 2015, 229, 1625-1648.

Structural and spectroscopic (UV-Vis, IR, Raman, and NMR) characteristics of anisaldehydes that are flavoring food additives: A density functional study in comparison with experiments

NASA Astrophysics Data System (ADS)

Altun, Ahmet; Swesi, O. A. A.; Alhatab, B. S. S.

2017-01-01

The molecular structures, vibrational spectra (IR and Raman), electronic spectra (UV-Vis and DOS), and NMR spectra (13C and 1H) of p-anisaldehyde, m-anisaldehyde, and o-anisaldehyde have been studied by using the B3LYP density functional and the 6-311++G** basis set. While p-anisaldehyde has been found to contain two stable conformers at room temperature, m-anisaldehyde and o-anisaldehyde contain four stable conformers. In agreement with the calculated ground-state energetics and small transition barriers, the comparison of the experimental and calculated spectra of the anisaldehydes indicates equilibrium between all conformers at room temperature. However, the two conformers of o-anisaldehyde, in which the methoxy group lies out of the ring plane, are too rare at the equilibrium. The equilibrium conditions of the conformers of the anisaldehyde isomers have been shown readily accessible through UV-Vis and 13C NMR spectral studies but requiring very detailed vibrational analyses. The effect of the solvent has been found to red-shift the electronic absorption bands and to make the anisaldehydes more reactive and soft. Molecular electrostatic potential maps of the anisaldehydes show that their oxygen atoms are the sites for nucleophilic reactivity. Compared with the most sophisticated NBO method, ESP charges have been found mostly reliable while Mulliken charges fail badly with the present large 6-311++G** basis set. The present calculations reproduce not only the experimental spectral characteristics of the anisaldehydes but also reveal their several structural features.

A combined experimental and theoretical studies on FT-IR, FT-Raman and UV-vis spectra of 2-chloro-3-quinolinecarboxaldehyde

NASA Astrophysics Data System (ADS)

Prasad, M. V. S.; Udaya Sri, N.; Veeraiah, V.

2015-09-01

In the present study, the FT-IR and FT-Raman spectra of 2-chloro-3-quinolinecarboxaldehyde (2Cl3QC) have been recorded in the region 4000-400 and 3500-50 cm-1, respectively. The fundamental modes of vibrational frequencies of 2Cl3QC are assigned. Theoretical information on the optimized geometry, harmonic vibrational frequencies, infrared and Raman intensities were obtained by means of density functional theory (DFT) gradient calculations with complete relaxation in the potential energy surface using 6-31G(d,p) basis set. The vibrational frequencies which were determined experimentally from the spectral data are compared with those obtained theoretically from DFT calculations. A close agreement was achieved between the observed and calculated frequencies by refinement of the scale factors. The infrared and Raman spectra were also predicted from the calculated intensities. Thermodynamic properties like entropy, heat capacity, zero point energy, have been calculated for the molecule. The predicted first hyperpolarizability also shows that the molecule might have a reasonably good non-linear optical (NLO) behavior. The calculated HOMO-LUMO energy gap reveals that charge transfer occurs within the molecule. Stability of the molecule arising from hyper conjugative interactions, charge delocalization have been analyzed using natural bond orbitals (NBO) analysis. The results show that charge in electron density (ED) in the π∗ antibonding orbitals and E(2) energies confirms the occurrence of ICT (intra-molecular charge transfer) within the molecule. UV-visible spectrum of the title molecule has also been calculated using TD-DFT/CAM-B3LYP/6-31G(d,p) method. The calculated energy and oscillator strength almost exactly reproduces reported experimental data.

A combined experimental and theoretical studies on FT-IR, FT-Raman and UV-vis spectra of 2-chloro-3-quinolinecarboxaldehyde.

PubMed

Prasad, M V S; Udaya Sri, N; Veeraiah, V

2015-09-05

In the present study, the FT-IR and FT-Raman spectra of 2-chloro-3-quinolinecarboxaldehyde (2Cl3QC) have been recorded in the region 4000-400 and 3500-50 cm(-1), respectively. The fundamental modes of vibrational frequencies of 2Cl3QC are assigned. Theoretical information on the optimized geometry, harmonic vibrational frequencies, infrared and Raman intensities were obtained by means of density functional theory (DFT) gradient calculations with complete relaxation in the potential energy surface using 6-31G(d,p) basis set. The vibrational frequencies which were determined experimentally from the spectral data are compared with those obtained theoretically from DFT calculations. A close agreement was achieved between the observed and calculated frequencies by refinement of the scale factors. The infrared and Raman spectra were also predicted from the calculated intensities. Thermodynamic properties like entropy, heat capacity, zero point energy, have been calculated for the molecule. The predicted first hyperpolarizability also shows that the molecule might have a reasonably good non-linear optical (NLO) behavior. The calculated HOMO-LUMO energy gap reveals that charge transfer occurs within the molecule. Stability of the molecule arising from hyper conjugative interactions, charge delocalization have been analyzed using natural bond orbitals (NBO) analysis. The results show that charge in electron density (ED) in the π(∗) antibonding orbitals and E((2)) energies confirms the occurrence of ICT (intra-molecular charge transfer) within the molecule. UV-visible spectrum of the title molecule has also been calculated using TD-DFT/CAM-B3LYP/6-31G(d,p) method. The calculated energy and oscillator strength almost exactly reproduces reported experimental data. Copyright © 2015 Elsevier B.V. All rights reserved.

Raman Spectrum of Er-Y-codoped ZrO2 and Fluorescence Properties of Er3+

NASA Astrophysics Data System (ADS)

He, Jun; Luo, Meng-fei; Jin, Ling-yun; He, Mai; Fang, Ping; Xie, Yun-long

2007-02-01

Er-Y-codoped ZrO2 mixed oxides with monoclinic, tetragonal and cubic structures were prepared by a sol-gel method. The crystal structure of ZrO2 matrix and the effect of the ZrO2 phases on the fluorescence properties of Er3+ were studied using Raman spectroscopy. The results indicated that the fluorescence properties of Er3+ depend on its local ZrO2 crystal structures. As ZrO2 matrix transferred from monoclinic to tetragonal and cubic phase, the Raman and fluorescence bands of Er3+ decreased in intensities and tended to form a single peak. With 632.8 nm excitation, the bands between 640 and 680 nm were attributed to the fluorescence of Er3+ in the ZrO2 environment. However, only the fluorescence was observed and no Raman spectra were seen under 514.5 nm excitation, while only Raman spectra were observed under 325 nm excitation. UV Raman spectroscopy was found to be more sensitive in the surface region while the information provided by XRD mainly came from the bulk. The phase with lower symmetry forms more easily on the surface than in the bulk.

Surface enhanced Raman scattering (SERS) spectra of trinitrotoluene in silver colloids prepared by microwave heating method.

PubMed

Zhang, Chunling; Wang, Kaijun; Han, Dejun; Pang, Qing

2014-03-25

Surface enhanced Raman spectroscopy (SERS) has been demonstrated for the detection of trace levels of explosives due to its high sensitivity, speed of detection and fingerprint feature. 2,4,6-Trinitrotoluene (TNT), a leading example of nitroaromatic explosives, is causing wide concern. In this study, SERS spectra of TNT solution in silver colloids have been successfully measured and a comparison was drawn with the normal Raman spectra of bulk TNT. The silver colloids were prepared by the microwave heating method and characterized by UV-Vis spectra and the scanning electron microscopy (SEM). NaCl and pH value have a great impact on SERS intensity of TNT, the corresponding experimental research results and theoretical interpretations were further illustrated to a certain extent. Moreover, the detection limit of TNT in aqueous solution was achieved as low as 10(-10) mol L(-1) and some preliminary experiments of detecting TNT vapor (about 10 μg/L) using SERS have been carried out. Our results demonstrated the potential of SERS for probing TNT with high sensitivity, and suggest SERS as a powerful method for detection of TNT and similar species at trace levels. Copyright © 2013 Elsevier B.V. All rights reserved.

Spectroscopic studies on diamond like carbon films synthesized by pulsed laser ablation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Panda, Madhusmita; Krishnan, R., E-mail: krish@igcar.gov.in; Ravindran, T. R.

2016-05-23

Hydrogen free Diamond like Carbon (DLC) thin films enriched with C-C sp{sup 3} bonding were grown on Si (111) substrates at laser pulse energies varying from 100 to 400 mJ (DLC-100, DLC-200, DLC-300, DLC-400), by Pulsed Laser Ablation (PLA) utilizing an Nd:YAG laser operating at fundamental wavelength. Structural, optical and morphological evolutions as a function of laser pulse energy were studied by micro Raman, UV-Vis spectroscopic studies and Atomic Force Microscopy (AFM), respectively. Raman spectra analysis provided critical clues for the variation in sp{sup 3} content and optical energy gap. The sp{sup 3} content was estimated using the FWHM ofmore » the G peak and found to be in the range of 62-69%. The trend of evolution of sp{sup 3} content matches well with the evolution of I{sub D}/I{sub G} ratio with pulse energy. UV-Vis absorption study of DLC films revealed the variation of optical energy gap with laser pulse energy (1.88 – 2.23 eV), which matches well with the evolution of G-Peak position of the Raman spectra. AFM study revealed that roughness, size and density of particulate in DLC films increase with laser pulse energy.« less

A Raman scattering and FT-IR spectroscopic study on the effect of the solar radiation in Antarctica on bovine cornea

NASA Astrophysics Data System (ADS)

Yamamoto, Tatsuyuki; Murakami, Naoki; Yoshikiyo, Keisuke; Takahashi, Tetsuya; Yamamoto, Naoyuki

2010-01-01

The Raman scattering and FT-IR spectra of the corneas, transported to the Syowa station in Antarctica and exposed to the solar radiation of the mid-summer for four weeks, were studied to reveal that type IV collagen involved in corneas were fragmented. The amide I and III Raman bands were observed at 1660 and 1245 cm -1, respectively, and the amide I and II infrared bands were observed at 1655 and 1545 cm -1, respectively, for original corneas before exposure. The background of Raman signals prominently increased and the ratio of amide II infrared band versus amide I decreased by the solar radiation in Antarctica. The control experiment using an artificial UV lamp was also performed in laboratory. The decline rate of the amide II/amide I was utilized for estimating the degree of fragmentation of collagen, to reveal that the addition of vitamin C suppressed the reaction while the addition of sugars promoted it. The effect of the solar radiation in Antarctica on the corneas was estimated as the same as the artificial UV lamp of four weeks (Raman) or one week (FT-IR) exposure.

Crystal growth, electronic structure and optical properties of Sr2Mg(BO3)2

NASA Astrophysics Data System (ADS)

Lv, Xianshun; Wei, Lei; Wang, Xuping; Xu, Jianhua; Yu, Huajian; Hu, Yanyan; Zhang, Huadi; Zhang, Cong; Wang, Jiyang; Li, Qinggang

2018-02-01

Single crystals of Sr2Mg(BO3)2 (SMBO) were grown by Kyropoulos method. X-ray powder diffraction (XRD) analysis, transmission spectrum, thermal properties, band structure, density of states and charge distribution as well as Raman spectra of SMBO were described. The as-grown SMBO crystals show wide transparency range with UV cut-off below 180 nm. A direct band gap of 4.66 eV was obtained from the calculated electronic structure results. The calculated band structure and density of states results indicated the top valence band is determined by O 2p states whereas the low conduction band mainly consists of Sr 5s states. Twelve Raman peaks were observed in the experimental spectrum, fewer than the number predicted by the site group analysis. Raman peaks of SMBO were assigned combining first-principle calculation and site group analysis results. The strongest peak at 917 cm-1 in the experimental spectrum is assigned to symmetric stretching mode A1‧(ν1) of free BO3 units. SMBO is a potential Raman crystal which can be used in deep UV laser frequency conversion.

Ultraviolet micro-Raman spectrograph for the detection of small numbers of bacterial cells

NASA Astrophysics Data System (ADS)

Chadha, S.; Nelson, W. H.; Sperry, J. F.

1993-11-01

The construction of a practical UV micro-Raman spectrograph capable of selective excitation of bacterial cells and other microscopic samples has been described. A reflective objective is used to focus cw laser light on a sample and at the same time collect the scattered light at 180°. With the aid of a quartz lens the image produced is focused on the slits of a spectrograph equipped with a single 2400 grooves/mm grating optimized for 250 nm. Spectra were detected by means of a blue-intensified diode array detector. Resonance Raman spectra of Bacillus subtilis and Flavobacterium capsulatum excited by the 257.2 nm output of a cw laser were recorded in the 900-1800 cm-1 region. Bacterial cells were immobilized on a quartz plate by means of polylysine and were counted visually. Cooling was required to retard sample degradation. Sample sizes ranged from 1 to 50 cells with excitation times varying from 15 to 180 s. Excellent spectra have been obtained from 20 cells in 15 s using a spectrograph having only 3% throughput.

A computational perspective of vibrational and electronic analysis of potential photosensitizer 2-chlorothioxanthone

NASA Astrophysics Data System (ADS)

Ali, Narmeen; Mansha, Asim; Asim, Sadia; Zahoor, Ameer Fawad; Ghafoor, Sidra; Akbar, Muhammad Usman

2018-03-01

This paper deals with combined theoretical and experimental study of geometric, electronic and vibrational properties of 2-chlorothioxanthone (CTX) molecule which is potential photosensitizer. The FT-IR spectrum of CTX in solid phase was recorded in 4000-400 cm-1 region. The UV-Vis. absorption spectrum was also recorded in the laboratory as well as computed at DFT/B3LYP level in five different phases viz. gas, water, DMSO, acetone and ethanol. The quantum mechanics based theoretical IR and Raman spectra were also calculated for the title compound employing HF and DFT functional with 3-21G+, 6-31G+ and 6-311G+, 6-311G++ basis sets, respectively, and assignment of each vibrational frequency has been done on the basis of potential energy distribution (PED). A comparison has been made between theoretical and experimental vibrational spectra as well as for the UV-Vis. absorption spectra. The computed infra red & Raman spectra by DFT compared with experimental spectra along with reliable vibrational assignment based on PED. The calculated electronic properties, results of natural bonding orbital (NBO) analysis, charge distribution, dipole moment and energies have been reported in the paper. Bimolecular quenching of triplet state of CTX in the presence of triethylamine, 2-propanol triethylamine and diazobicyclooctane (DABCO) reflect the interactions between them. The bimolecular quenching rate constant is fastest for interaction of 3CTX in the presence of DABCO reflecting their stronger interactions.

FT-IR, FT-Raman, UV, NMR spectra and molecular structure investigation of (E)-2-(3-chloropyrazin-2-yl)-1-(3-ethyl-2, 6-diphenyl piperidin-4-ylidene) hydrazine: A combined experimental and theoretical study

NASA Astrophysics Data System (ADS)

Therasa Alphonsa, A.; Loganathan, C.; Athavan Alias Anand, S.; Kabilan, S.

2015-11-01

This work presents the characterization of (E)-2-(3-chloropyrazin-2-yl)-1-(3-ethyl-2, 6-diphenyl piperidin-4-ylidene) hydrazine (HDE) by quantum chemical calculations and spectral techniques. The structure was investigated by FT-IR, FT-Raman, UV-vis and NMR techniques. The geometrical parameters and energies have been obtained from Density functional theory (DFT) B3LYP (6-31G (d, p)) basis set calculations. The geometry of the molecule was fully optimized, vibrational spectra were calculated and fundamental vibrations were assigned on the basis of total energy distribution (TED) of the vibrational modes, calculated with scaled quantum mechanics (SQM) method. 1H and 13C NMR chemical shifts of the molecule were calculated using Gauge-independent atomic orbital method (GIAO). The electronic properties such as excitation energies, wavelength, HOMO, LUMO energies performed by Time dependent density functional theory (TD-DFT) results complements with the experimental findings. NBO analysis has been performed for analyzing charge delocalization throughout the molecule. The calculation results were applied to simulate spectra of the title compound, which show excellent agreement with observed spectra. To provide information about the interactions between human cytochrome protein and the novel compound theoretically, docking studies were carried out using Schrödinger software.

Preparation and characterizations of SnO2 nanopowder and spectroscopic (FT-IR, FT-Raman, UV-Visible and NMR) analysis using HF and DFT calculations.

PubMed

Ayeshamariam, A; Ramalingam, S; Bououdina, M; Jayachandran, M

2014-01-24

In this work, pure and singe phase SnO2 Nano powder is successfully prepared by simple sol-gel combustion route. The photo luminescence and XRD measurements are made and compared the geometrical parameters with calculated values. The FT-IR and FT-Raman spectra are recorded and the fundamental frequencies are assigned. The optimized parameters and the frequencies are calculated using HF and DFT (LSDA, B3LYP and B3PW91) theory in bulk phase of SnO2 and are compared with its Nano phase. The vibrational frequency pattern in nano phase gets realigned and the frequencies are shifted up to higher region of spectra when compared with bulk phase. The NMR and UV-Visible spectra are simulated and analyzed. Transmittance studies showed that the HOMO-LUMO band gap (Kubo gap) is reduced from 3.47 eV to 3.04 eV while it is heated up to 800°C. The Photoluminescence spectra of SnO2 powder showed a peak shift towards lower energy side with the change of Kubo gap from 3.73 eV to 3.229 eV for as-prepared and heated up to 800°C. Crown Copyright © 2013. Published by Elsevier B.V. All rights reserved.

Unveiling the Aggregation of Lycopene in Vitro and in Vivo: UV-Vis, Resonance Raman, and Raman Imaging Studies.

PubMed

Ishigaki, Mika; Meksiarun, Phiranuphon; Kitahama, Yasutaka; Zhang, Leilei; Hashimoto, Hideki; Genkawa, Takuma; Ozaki, Yukihiro

2017-08-31

The present study investigates the structure of lycopene aggregates both in vitro and in vivo using ultraviolet-visible (UV-vis) and Raman spectroscopies. The electronic absorption bands of the J- and H-aggregates in vitro shift to lower and higher energies, respectively, compared to that of the lycopene monomer. Along with these results, the frequencies of the ν 1 Raman bands were shifted to lower and higher frequencies, respectively. By plotting the frequencies of the ν 1 Raman band against the S 0 → S 2 transition energy, a linear relationship between the data set with different aggregation conformations can be obtained. Therefore, the band positions depending on the different conformations can be explained based on the idea that the effective conjugated C═C chain lengths within lycopene molecules are different due to the environmental effect (site-shift effect) caused by the aggregation conformation. Applying this knowledge to the in vivo measurement of a tomato fruit sample, the relationship between the aggregation conformation of lycopene and the spectral patterns observed in the UV-vis as well as Raman spectra in different parts of tomato fruits was discussed in detail. The results showed that the concentration of lycopene (particularly that of the J-aggregate) specifically increased, whereas that of chlorophyll decreased, with ripening. Furthermore, Raman imaging indicated that lycopene with different aggregate conformations was distributed inhomogeneously, even within one sample. The layer formation in tomato tissues with high concentrations of J- and H-aggregates was successfully visualized. In this manner, the presence of lycopene distributions with different aggregate conformations was unveiled in vivo.

Spectroscopic investigation on the efficient organic nonlinear crystals of pure and diethanolamine added DAST.

PubMed

Karthikeyan, C; Haja Hameed, A S; Sagaya Agnes Nisha, J; Ravi, G

2013-11-01

4-N,N'-dimethylamino-N-methyl-4-stilbazolium toyslate (DAST) and diethanolamine (DEA) added DAST crystals are grown by slow cooling method. The corresponding powder samples are examined by characterization studies such as XRD, FT-IR, FT-Raman, UV-Vis-NIR and photoluminescence studies. From the powder X-ray diffraction, their lattice parameter values are found out. Since the vibrational spectra of the molecules are considerably contributed to their linear and nonlinear optical effects, Infrared and Raman spectroscopic studies are carried out for the samples. The UV-Vis-NIR absorption spectra of the samples are used to find the nature of transitions occurred in the samples. Using the density functional theory, highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) analyses are done in order to explain the transition and density of states (DOS). The first order hyperpolarizability is calculated by HF and B3LYP/6-311 G(d,p) basis sets for the DAST molecule. From the photoluminescence (PL) spectral studies, the strong excitation emissions are observed. Copyright © 2013 Elsevier B.V. All rights reserved.

Vibrational spectral investigation, NBO, first hyperpolarizability and UV-Vis spectral analysis of 3,5-dichlorobenzonitrile and m-bromobenzonitrile by ab initio and density functional theory methods.

PubMed

Senthil kumar, J; Jeyavijayan, S; Arivazhagan, M

2015-02-05

The FT-IR and FT-Raman spectra of 3,5-dichlorobenzonitrile and m-bromobenzonitrile have been recorded in the region 4000-400 cm(-1) and 3500-50 cm(-1), respectively. The optimized geometry, wave numbers and intensity of vibrational bonds of title molecules are obtained by ab initio and DFT level of theory with complete relaxation in the potential energy surface using 6-311++G(d, p) basis set. A complete vibrational assignments aided by the theoretical harmonic frequency, analysis have been proposed. The harmonic vibrational frequencies calculated have been compared with experimental FT-IR and FT-Raman spectra. The observed and calculated frequencies are found to be in good agreement. Stability of the molecule arising from hyperconjugative interactions, charge delocalization have been analyzed using natural bond orbital (NBO) analysis. The UV-Vis spectral analysis of the molecules has also been done which confirms the charge transfer of the molecules. Furthermore, the first hyperpolarizability and total dipole moment of the molecules have been calculated. Copyright © 2014 Elsevier B.V. All rights reserved.

Silver Nanoparticle-Enhanced Resonance Raman Sensor of Chromium(III) in Seawater Samples.

PubMed

Ly, Nguyễn Hoàng; Joo, Sang-Woo

2015-04-29

Tris(hydroxymethyl)aminomethane ethylenediaminetetraacetic acid (Tris-EDTA), upon binding Cr(III) in aqueous solutions at pH 8.0 on silver nanoparticles (AgNPs), was found to provide a sensitive and selective Raman marker band at ~563 cm-1, which can be ascribed to the metal-N band. UV-Vis absorption spectra also supported the aggregation and structural change of EDTA upon binding Cr(III). Only for Cr(III) concentrations above 500 nM, the band at ~563 cm-1 become strongly intensified in the surface-enhanced Raman scattering spectra. This band, due to the metal-EDTA complex, was not observed in the case of 50 mM of K+, Cd2+, Mg2+, Ca2+, Mn2+, Co2+, Na+, Cu2+, NH4+, Hg2+, Ni2+, Fe3+, Pb2+, Fe2+, and Zn2+ ions. Seawater samples containing K, Mg, Ca, and Na ion concentrations higher than 8 mM also showed the characteristic Raman band at ~563 cm-1 above 500 nM, validating our method. Our approach may be useful in detecting real water samples by means of AgNPs and Raman spectroscopy.

Structure elucidation of organic compounds aided by the computer program system SCANNET

NASA Astrophysics Data System (ADS)

Guzowska-Swider, B.; Hippe, Z. S.

1992-12-01

Recognition of chemical structure is a very important problem currently solved by molecular spectroscopy, particularly IR, UV, NMR and Raman spectroscopy, and mass spectrometry. Nowadays, solution of the problem is frequently aided by the computer. SCANNET is a computer program system for structure elucidation of organic compounds, developed by our group. The structure recognition of an unknown substance is made by comparing its spectrum with successive reference spectra of standard compounds, i.e. chemical compounds of known chemical structure, stored in a spectral database. The computer program system SCANNET consists of six different spectral databases for following the analytical methods: IR, UV, 13C-NMR, 1H-NMR and Raman spectroscopy, and mass spectrometry. A chemist, to elucidate a structure, can use one of these spectral methods or a combination of them and search the appropriate databases. As the result of searching each spectral database, the user obtains a list of chemical substances whose spectra are identical and/or similar to the spectrum input into the computer. The final information obtained from searching the spectral databases is in the form of a list of chemical substances having all the examined spectra, for each type of spectroscopy, identical or simlar to those of the unknown compound.

Novel acid mono azo dye compound: Synthesis, characterization, vibrational, optical and theoretical investigations of 2-[(E)-(8-hydroxyquinolin-5-yl)-diazenyl]-4,5-dimethoxybenzoic acid

NASA Astrophysics Data System (ADS)

Saçmacı, Mustafa; Çavuş, Hatice Kanbur; Arı, Hatice; Şahingöz, Recep; Özpozan, Talat

2012-11-01

Novel acid mono azo dye, 2-[(E)-(8-hydroxyquinolin-5yl)-diazenyl]-4,5-dimethoxybenzoic acid (HQD), was synthesized by coupling diazonium salt solution of 2-amino-4,5-dimethoxybenzoic acid (DMA) with 8-hydroxyquinoline (HQ). This dye was characterized by UV-vis, IR & Raman, 1H and 13C NMR spectroscopic techniques and elemental analysis. The normal coordinate analysis of HQD was also performed to assign each band in vibrational spectra. DFT (B3LYP and B3PW91) calculations were employed to optimize the geometry, to interpret NMR spectra, to calculate and to determine the stable tautomeric structure of the compound. Natural Bond Orbital (NBO) analysis was performed to investigate intramolecular interactions. The vibrational spectral data obtained from solid phase IR & Raman spectra were assigned based on the results of the theoretical calculations. UV-vis spectroscopic technique was employed to obtain the optical band gap of HQD. The analysis of the optical absorption data revealed the existence of direct and indirect transitions in the optical band gaps. The optical band gaps of HQD have been found 1.95 and 1.90 eV for direct and indirect transitions, respectively.

Spectroscopic and DFT studies of flurbiprofen as dimer and its Cu(II) and Hg(II) complexes

NASA Astrophysics Data System (ADS)

Sagdinc, Seda; Pir, Hacer

2009-07-01

The vibrational study in the solid state of flurbiprofen and its Cu(II) and Hg(II) complexes was performed by IR and Raman spectroscopy. The changes observed between the IR and Raman spectra of the ligand and of the complexes allowed us to establish the coordination mode of the metal in both complexes. The comparative vibrational analysis of the free ligand and its complexes gave evidence that flurbiprofen binds metal (II) through the carboxylate oxygen. The fully optimized equilibrium structure of flurbiprofen and its metal complexes was obtained by density functional B3LYP method by using LanL2DZ and 6-31 G(d,p) basis sets. The harmonic vibrational frequencies, infrared intensities and Raman scattering activities of flurbiprofen were calculated by density functional B3LYP methods by using 6-31G(d,p) basis set. The scaled theoretical wavenumbers showed very good agreement with the experimental values. The electronic properties of the free molecule and its complexes were also performed at B3LYP/6-31G(d,p) level of theory. Detailed interpretations of the infrared and Raman spectra of flurbiprofen are reported. The UV-vis spectra of flurbiprofen and its metal complexes were also investigated in organic solvents.

DOE Office of Scientific and Technical Information (OSTI.GOV)

SEDLACEK,III, A.J.FINFROCK,C.

As a member of the science-support part of the ITT-lead LISA development program, BNL is tasked with the acquisition of UV Raman spectral fingerprints and associated scattering cross-sections for those chemicals-of-interest to the program's sponsor. In support of this role, the present report contains the first installment of UV Raman spectral fingerprint data on the initial subset of chemicals. Because of the unique nature associated with the acquisition of spectral fingerprints for use in spectral pattern matching algorithms (i.e., CLS, PLS, ANN) great care has been undertaken to maximize the signal-to-noise and to minimize unnecessary spectral subtractions, in an effortmore » to provide the highest quality spectral fingerprints. This report is divided into 4 sections. The first is an Experimental section that outlines how the Raman spectra are performed. This is then followed by a section on Sample Handling. Following this, the spectral fingerprints are presented in the Results section where the data reduction process is outlined. Finally, a Photographs section is included.« less

Quantum mechanical study of the structure and spectroscopic (FT-IR, FT-Raman, 13C, 1H and UV), first order hyperpolarizabilities, NBO and TD-DFT analysis of the 4-methyl-2-cyanobiphenyl

NASA Astrophysics Data System (ADS)

Sebastian, S.; Sundaraganesan, N.; Karthikeiyan, B.; Srinivasan, V.

2011-02-01

The Fourier transform infrared (FT-IR) and FT-Raman of 4-methyl-2-cyanobiphenyl (4M2CBP) have been recorded and analyzed. The equilibrium geometry, bonding features and harmonic vibrational frequencies have been investigated with the help of density functional theory (DFT) method. The assignments of the vibrational spectra have been carried out with the help of normal coordinate analysis (NCA) following the scaled quantum mechanical force field methodology (SQMFF). The 1H and 13C nuclear magnetic resonance (NMR) chemical shifts of the molecule were calculated by the Gauge including atomic orbital (GIAO) method. The first order hyperpolarizability ( β0) of this novel molecular system and related properties ( β, α0 and Δ α) of 4M2CBP are calculated using HF/6-311G(d,p) method on the finite-field approach. Stability of the molecule arising from hyperconjugative interactions, charge delocalization have been analyzed using natural bond orbital (NBO) analysis. The results show that charge in electron density (ED) in the σ* and π* antibonding orbitals and second order delocalization energies ( E2) confirms the occurrence of intramolecular charge transfer (ICT) within the molecule. UV-vis spectrum of the compound was recorded and the electronic properties, such as HOMO and LUMO energies, were performed by time-dependent density functional theory (TD-DFT) approach. Finally the calculations results were applied to simulated infrared and Raman spectra of the title compound which show good agreement with observed spectra.

Raman spectroscopic detection of biomolecular markers from Antarctic materials: evaluation for putative Martian habitats

NASA Astrophysics Data System (ADS)

Edwards, Howell G. M.; Newton, Emma M.; Dickensheets, David L.; Wynn-Williams, David D.

2003-08-01

The vital UV-protective and photosynthetic pigments of cyanobacteria and lichens (microbial symbioses) that dominate primary production in Antarctic desert ecosystems auto-fluoresce at short-wavelengths. A long wavelength (1064 nm) near infra-red laser has been used for non-intrusive Raman spectroscopic analysis of their ecologically significant compounds. There is now much interest in the construction of portable Raman systems for the analysis of cyanobacterial and lichen communities in the field; to this extent, Raman spectra obtained with laboratory-based systems operating at wavelengths of 852 and 1064 nm have been evaluated for potential fieldwork applications of miniaturised units. Selected test specimens of the cyanobacterial Nostoc commune, epilithic lichens Acarospora chlorophana, Xanthoria elegans and Caloplaca saxicola and the endolithic Chroococcidiopsis from Antarctic sites have been examined in the present study. Although some organisms gave useable Raman spectra with short-wavelength lasers, 1064 nm was the only excitation that was consistently excellent for all organisms. We conclude that a 1064 nm Raman spectrometer, miniaturised using an InGaAs detector, is the optimal instrument for in situ studies of pigmented communities at the limits of life on Earth. This has practical potential for the quest for biomolecules residual from any former surface or subsurface life on Mars.

Raman spectroscopic detection of biomolecular markers from Antarctic materials: evaluation for putative Martian habitats.

PubMed

Edwards, Howell G M; Newton, Emma M; Dickensheets, David L; Wynn-Williams, David D

2003-08-01

The vital UV-protective and photosynthetic pigments of cyanobacteria and lichens (microbial symbioses) that dominate primary production in Antarctic desert ecosystems auto-fluoresce at short-wavelengths. A long wavelength (1064 nm) near infra-red laser has been used for non-intrusive Raman spectroscopic analysis of their ecologically significant compounds. There is now much interest in the construction of portable Raman systems for the analysis of cyanobacterial and lichen communities in the field; to this extent, Raman spectra obtained with laboratory-based systems operating at wavelengths of 852 and 1064 nm have been evaluated for potential fieldwork applications of miniaturised units. Selected test specimens of the cyanobacterial Nostoc commune, epilithic lichens Acarospora chlorophana, Xanthoria elegans and Caloplaca saxicola and the endolithic Chroococcidiopsis from Antarctic sites have been examined in the present study. Although some organisms gave useable Raman spectra with short-wavelength lasers, 1064 nm was the only excitation that was consistently excellent for all organisms. We conclude that a 1064 nm Raman spectrometer, miniaturised using an InGaAs detector, is the optimal instrument for in situ studies of pigmented communities at the limits of life on Earth. This has practical potential for the quest for biomolecules residual from any former surface or subsurface life on Mars.

Spectroscopic (vibrational, NMR and UV-vis.) and quantum chemical investigations on 4-hexyloxy-3-methoxybenzaldehyde.

PubMed

Abbas, Ashgar; Gökce, Halil; Bahçeli, Semiha

2016-01-05

In this study, the 4-hexyloxy-3-methoxybenzaldehyde compound as one of the derivatives of vanillin which is a well known flavoring agent, C14H20O3, has been investigated by experimentally and extensively utilizing density functional theory (DFT) at the B3LYP/6-311++G(d,p) level. In this context, the optimized geometry, vibrational frequencies, (1)H and (13)C NMR chemical shifts, UV-vis. (in gas phase and in methanol solvent) spectra, HOMO-LUMO analysis, molecular electrostatic potential (MEP), thermodynamic parameters and atomic charges of 4-hexyloxy-3-methoxybenzaldehyde have been calculated. In addition, theoretically predicted IR, Raman and UV-vis. (in gas phase and in methanol solvent) spectra of the mentioned molecule have been constructed. The results calculated were compared with the experimental data. Copyright © 2015 Elsevier B.V. All rights reserved.

Raman spectroscopic study of the Chromobacterium violaceum pigment violacein using multiwavelength excitation and DFT calculations.

PubMed

Jehlička, Jan; Edwards, Howell G M; Němec, Ivan; Oren, Aharon

2015-01-01

Violacein is a bisindole pigment occurring as a biosynthetic product of Chromobacterium violaceum and Janthinobacterium lividum. It has some structural similarities to the cyanobacterial UV-protective pigment scytonemin, which has been the subject of comprehensive spectroscopic and structural studies. A detailed experimental Raman spectroscopic study with visible and near-infrared excitation of violacein produced by C. violaceum has been undertaken and supported using theoretical DFT calculations. Raman spectra with 514 and 785 nm excitation of cultivated cells as well as extracts and Gaussian (B3LYP/6-311++G(d,p)) calculations with proposed molecular vibrational assignments are reported here. Copyright © 2015 Elsevier B.V. All rights reserved.

Raman lidar for hydrogen gas concentration monitoring and future radioactive waste management.

PubMed

Liméry, Anasthase; Cézard, Nicolas; Fleury, Didier; Goular, Didier; Planchat, Christophe; Bertrand, Johan; Hauchecorne, Alain

2017-11-27

A multi-channel Raman lidar has been developed, allowing for the first time simultaneous and high-resolution profiling of hydrogen gas and water vapor. The lidar measures vibrational Raman scattering in the UV (355 nm) domain. It works in a high-bandwidth photon counting regime using fast SiPM detectors and takes into account the spectral overlap between hydrogen and water vapor Raman spectra. Measurement of concentration profiles of H 2 and H 2 O are demonstrated along a 5-meter-long open gas cell with 1-meter resolution at 85 meters. The instrument precision is investigated by numerical simulation to anticipate the potential performance at longer range. This lidar could find applications in the French project Cigéo for monitoring radioactive waste disposal cells.

Synthesis, thermogravimetric, spectroscopic and theoretical characterization of copper(II) complex with 4-chloro-2-nitrobenzenosulfonamide

NASA Astrophysics Data System (ADS)

Camí, G.; Chacón Villalba, E.; Di Santi, Y.; Colinas, P.; Estiu, G.; Soria, D. B.

2011-05-01

4-Chloro-2-nitrobenzenesulfonamide (ClNbsa) was purified and characterized. A new copper(II) complex, [Cu(ClNbsa) 2(NH 3) 2], has been prepared using the sulfonamide as ligand. The thermal behavior of both, the ligand and the Cu(II) complex, was investigated by thermogravimetric analyses (TG) and differential thermal analysis (DT), and the electronic characteristics analyzed by UV-VIS, FTIR, Raman and 1H NMR spectroscopies. The experimental IR, Raman and UV-VIS spectra have been assigned on the basis of DFT calculations at the B3LYP level of theory using the standard (6-31 + G ∗∗) basis set. The geometries have been fully optimized in vacuum and in modeled dimethylsulfoxide (DMSO) solvent, using for the latter a continuum solvation model that reproduced the experimental conditions of the UV-VIS spectroscopy. The theoretical results converged to stable conformations for the free sulfonamide and for the complex, suggesting for the latter a distorted square planar geometry in both environments.

Raman-scattered O VI λ1032 and He II λ1025 and Bipolar Outflow in the Symbiotic Star V455 Sco

NASA Astrophysics Data System (ADS)

Heo, Jeong-Eun; Angeloni, Rodolfo; Di Mille, Francesco; Palma, Tali; Chang, Seok-Jun; Hong, Chae-Lin; Lee, Hee-Won

2016-07-01

Raman-scattering by atomic hydrogen is a unique spectroscopic process that may probe the mass transfer and mass loss phenomena in symbiotic stars(SSs). In the optical high- resolution spectra of the S-type SS V455 Sco, we note the presence of two Raman-scattered features, one at around 6825 Å with a triple-peak profile formed from Raman-scattering of O VI λ1032 and the other Raman-scattered He II λ1025 at around 6545 Å. Adopting an accretion flow model with additional contribution from a collimated bipolar outflow, we propose that the blue and central peaks are contributed from the accretion flow and the bipolar flow is responsible for the remaining red peak. With the absence of [N II] λ6548, the Raman-scattered He II λ1025 at around 6545 Å is immersed in the broad Ha wings that appear to be formed by Raman-scattering of far-UV continuum near Lyman series.

Structural and optical study of tellurite-barium glasses

NASA Astrophysics Data System (ADS)

Grelowska, I.; Reben, M.; Burtan, B.; Sitarz, M.; Cisowski, J.; Yousef, El Sayed; Knapik, A.; Dudek, M.

2016-12-01

The goal of this work was to determine the effect of barium oxide on the structural, thermal and optical properties of the TeO2-BaO-Na2O (TBN) and TeO2-BaO-WO3 (TBW) glass systems. Raman spectra allow relating the glass structure and vibration properties (i.e. vibrational frequencies and Raman intensities) with the glass composition. Raman spectra show the presence of TeO4 and TeO3+1/TeO3 units that conform with the glass matrix. Differential thermal analysis DTA, XRD measurements have been considered in term of BaO addition. The spectral dependence of ellipsometric angles of the tellurite-barium glass has been studied. The optical measurements were conducted on Woollam M2000 spectroscopic ellipsometer in spectral range of 190-1700 nm. The reflectance and transmittance measurements have been done on spectrophotometer Perkin Elmer, Lambda 900 in the range of 200-2500 nm (UV-VIS-NIR). From the transmittance spectrum, the energy gap was determined.

Spectroscopic and spectrofluorimetric studies on the interaction of albendazole and trimethoprim with iodine

NASA Astrophysics Data System (ADS)

Ganesh, K.; Elango, K. P.

Raman, UV-vis, FT-IR, and fluorescence spectral techniques were employed to investigate the mechanism of interaction of albendazole (ALB) and trimethoprim (TMP) drugs with iodine. Interactions of ALB and TMP with iodine yields triiodide ion and its formation was confirmed by electronic and Raman spectra. The peaks appeared in Raman spectra of the isolated products are at around 145, 113 and 82 cm-1 are assigned to νas(I-I), νs(I-I) and δ(I3-) respectively, confirmed the presence of I3- ion. Formation constant (K), molar extinction coefficient (ɛ) and thermodynamic properties ΔH#, ΔS# and ΔG# were determined and discussed. Fluorescence quenching studies indicated that the interaction between the ALB, TMP with iodine are spontaneous and the TMP-iodine interaction is found to be stronger than that the other system. Solvent variation studies indicated that the binding constant increased with an increase in polarity of the medium.

Experimental examination of ultraviolet Raman cross sections of chemical warfare agent simulants

NASA Astrophysics Data System (ADS)

Kullander, F.; Landström, L.; Lundén, H.; Wästerby, Pär.

2015-05-01

Laser induced Raman scattering from the commonly used chemical warfare agent simulants dimethyl sulfoxide, tributyl phosphate, triethyl phosphonoacetate was measured at excitation wavelengths ranging from 210 to 410 nm using a pulsed laser based spectrometer system with a probing distance of 1.4 m and with a field of view on the target of less than 1mm. For the purpose of comparison with well explored reference liquids the Raman scattering from simulants was measured in the form of an extended liquid surface layer on top of a silicon wafer. This way of measuring enabled direct comparison to the Raman scattering strength from cyclohexane. The reference Raman spectra were used to validate the signal strength of the simulants and the calibration of the experimental set up. Measured UV absorbance functions were used to calculate Raman cross sections. Established Raman cross sections of the simulants make it possible to use them as reference samples when measuring on chemical warfare agents in droplet form.

Nondestructive identification of dye mixtures in polyester and cotton fibers using raman spectroscopy and ultraviolet-visible (UV-Vis) microspectrophotometry.

PubMed

Was-Gubala, Jolanta; Starczak, Roza

2015-01-01

Presented in this paper is an assessment of the applicability of Raman spectroscopy and microspectrophotometry (MSP) in visible and ultraviolet light (UV-Vis) in the examination of textile fibers dyed with mixtures of synthetic dyes. Fragments of single polyester fibers, stained with ternary mixtures of disperse dyes in small mass concentrations, and fragments of single cotton fibers, dyed with binary or ternary mixtures of reactive dyes, were subjected to the study. Three types of excitation sources, 514, 633, and 785 nm, were used during Raman examinations, while the MSP study was conducted in the 200 to 800 nm range. The results indicate that the capabilities for discernment of dye mixtures are similar in the spectroscopic methods that were employed. Both methods have a limited capacity to distinguish slightly dyed polyester fiber; additionally, it was found that Raman spectroscopy enables identification of primarily the major components in dye mixtures. The best results, in terms of the quality of Raman spectra, were obtained using an excitation source from the near infrared. MSP studies led to the conclusion that polyester testing should be carried out in the range above 310 nm, while for cotton fibers there is no limitation or restriction of the applied range. Also, MSP UV-Vis showed limited possibilities for discriminatory analysis of cotton fibers dyed with a mixture of reactive dyes, where the ratio of the concentration of the main dye used in the dyeing process to minor dye was higher than four. The results presented have practical applications in forensic studies, inter alia.

Raman, IR, UV-vis and EPR characterization of two copper dioxolene complexes derived from L-dopa and dopamine

NASA Astrophysics Data System (ADS)

Barreto, Wagner J.; Barreto, Sônia R. G.; Ando, Rômulo A.; Santos, Paulo S.; DiMauro, Eduardo; Jorge, Thiago

2008-12-01

The anionic complexes [Cu(L 1-) 3] 1-, L - = dopasemiquinone or L-dopasemiquinone, were prepared and characterized. The complexes are stable in aqueous solution showing intense absorption bands at ca. 605 nm for Cu(II)-L-dopasemiquinone and at ca. 595 nm for Cu(II)-dopasemiquinone in the UV-vis spectra, that can be assigned to intraligand transitions. Noradrenaline and adrenaline, under the same reaction conditions, did not yield Cu-complexes, despite the bands in the UV region showing that noradrenaline and adrenaline were oxidized during the process. The complexes display a resonance Raman effect, and the most enhanced bands involve ring modes and particularly the νCC + νCO stretching mode at ca. 1384 cm -1. The free radical nature of the ligands and the oxidation state of the Cu(II) were confirmed by the EPR spectra that display absorptions assigned to organic radicals with g = 2.0005 and g = 2.0923, and for Cu(II) with g = 2.008 and g = 2.0897 for L-dopasemiquinone and dopasemiquinone, respectively. The possibility that dopamine and L-dopa can form stable and aqueous-soluble copper complexes at neutral pH, whereas noradrenaline and adrenaline cannot, may be important in understanding how Cu(II)-dopamine crosses the cellular membrane as proposed in the literature to explain the role of copper in Wilson disease.

Polyethyleneglycol/silver functionalized reduced graphene oxide aerogel for environmental application

NASA Astrophysics Data System (ADS)

Kumari, G. Vanitha; Asha, S.; Ananth, A. Nimrodh; Rajan, M. A. Jothi; Mathavan, T.

2018-04-01

Polyethylene glycol (PEG)/Silver (Ag) functionalized reduced graphene oxide aerogel (RGOA) was synthesized. PEG/Ag decorated reduced graphene oxide aerogel was characterized using XRD, Raman spectroscopy, Fourier transform infrared spectroscopy (FT-IR). The surface morphology of PEG/Ag/RGOA was analyzed using scanning electron microscope. The non-covalent interaction between reduced graphene oxide layers and the interaction between PEG and Ag on RGOA were studied by FT-IR spectra. It was observed that the interaction between Ag and PEG could enhance the properties of RGOA. Methyl Orange (MO) dye degradation was observed from UV-Vis Spectra. The process was studied by monitoring the simultaneous decrease in the height of UV-Vis absorption peak of dye solution. The results show that PEG/RGOA and PEG/Ag/RGOA are an efficient catalyst for dye degradation.

Quantum mechanical study of the structure and spectroscopic (FT-IR, FT-Raman, 13C, 1H and UV), first order hyperpolarizabilities, NBO and TD-DFT analysis of the 4-methyl-2-cyanobiphenyl.

PubMed

Sebastian, S; Sundaraganesan, N; Karthikeiyan, B; Srinivasan, V

2011-02-01

The Fourier transform infrared (FT-IR) and FT-Raman of 4-methyl-2-cyanobiphenyl (4M2CBP) have been recorded and analyzed. The equilibrium geometry, bonding features and harmonic vibrational frequencies have been investigated with the help of density functional theory (DFT) method. The assignments of the vibrational spectra have been carried out with the help of normal coordinate analysis (NCA) following the scaled quantum mechanical force field methodology (SQMFF). The 1H and 13C nuclear magnetic resonance (NMR) chemical shifts of the molecule were calculated by the Gauge including atomic orbital (GIAO) method. The first order hyperpolarizability (β0) of this novel molecular system and related properties (β, α0 and Δα) of 4M2CBP are calculated using HF/6-311G(d,p) method on the finite-field approach. Stability of the molecule arising from hyperconjugative interactions, charge delocalization have been analyzed using natural bond orbital (NBO) analysis. The results show that charge in electron density (ED) in the σ* and π* antibonding orbitals and second order delocalization energies (E2) confirms the occurrence of intramolecular charge transfer (ICT) within the molecule. UV-vis spectrum of the compound was recorded and the electronic properties, such as HOMO and LUMO energies, were performed by time-dependent density functional theory (TD-DFT) approach. Finally the calculations results were applied to simulated infrared and Raman spectra of the title compound which show good agreement with observed spectra. Copyright © 2010 Elsevier B.V. All rights reserved.

Molecular structure, vibrational spectra, AIM, HOMO-LUMO, NBO, UV, first order hyperpolarizability, analysis of 3-thiophenecarboxylic acid monomer and dimer by Hartree-Fock and density functional theory

NASA Astrophysics Data System (ADS)

Issaoui, Noureddine; Ghalla, Houcine; Muthu, S.; Flakus, H. T.; Oujia, Brahim

2015-02-01

In this work, the molecular structure, harmonic vibrational frequencies, UV, NBO and AIM of 3-thiophenecarboxilic acid (abbreviated as 3-TCA) monomer and dimer has been investigated. The FT-IR and FT-Raman spectra were recorded. The ground-state molecular geometry and vibrational frequencies have been calculated by using the Hartree-Fock (HF) and density functional theory (DFT)/B3LYP methods and 6-311++G(d,p) as a basis set. The fundamental vibrations were assigned on the basis of the total energy distribution (TED) of the vibrational modes, calculated with VEDA program. Comparison of the observed fundamental vibrational frequencies of 3-TCA with calculated results by HF and DFT methods indicates that B3LYP is better to HF method for molecular vibrational problems. The difference between the observed and scaled wavenumber values is very small. The theoretically predicted FT-IR and FT-Raman spectra of the title compound have been constructed. A study on the Mulliken atomic charges, the electronic properties were performed by time-dependent DFT (TD-DFT) approach, frontier molecular orbitals (HOMO-LUMO), molecular electrostatic potential (MEP) and thermodynamic properties have been performed. The electric dipole moment (μ) and the first hyperpolarizability (β) values of the investigated molecule have been also computed.

Molecular structure, vibrational spectra, AIM, HOMO-LUMO, NBO, UV, first order hyperpolarizability, analysis of 3-thiophenecarboxylic acid monomer and dimer by Hartree-Fock and density functional theory.

PubMed

Issaoui, Noureddine; Ghalla, Houcine; Muthu, S; Flakus, H T; Oujia, Brahim

2015-02-05

In this work, the molecular structure, harmonic vibrational frequencies, UV, NBO and AIM of 3-thiophenecarboxilic acid (abbreviated as 3-TCA) monomer and dimer has been investigated. The FT-IR and FT-Raman spectra were recorded. The ground-state molecular geometry and vibrational frequencies have been calculated by using the Hartree-Fock (HF) and density functional theory (DFT)/B3LYP methods and 6-311++G(d,p) as a basis set. The fundamental vibrations were assigned on the basis of the total energy distribution (TED) of the vibrational modes, calculated with VEDA program. Comparison of the observed fundamental vibrational frequencies of 3-TCA with calculated results by HF and DFT methods indicates that B3LYP is better to HF method for molecular vibrational problems. The difference between the observed and scaled wavenumber values is very small. The theoretically predicted FT-IR and FT-Raman spectra of the title compound have been constructed. A study on the Mulliken atomic charges, the electronic properties were performed by time-dependent DFT (TD-DFT) approach, frontier molecular orbitals (HOMO-LUMO), molecular electrostatic potential (MEP) and thermodynamic properties have been performed. The electric dipole moment (μ) and the first hyperpolarizability (β) values of the investigated molecule have been also computed. Copyright © 2014 Elsevier B.V. All rights reserved.

Damage and annealing recovery of boron-implanted ultra-shallow junction: The correlation between beam current and surface configuration

NASA Astrophysics Data System (ADS)

Chang, Feng-Ming; Wu, Zong-Zhe; Lin, Yen-Fu; Kao, Li-Chi; Wu, Cheng-Ta; JangJian, Shiu-Ko; Chen, Yuan-Nian; Lo, Kuang Yao

2018-03-01

The condition of the beam current in the implantation process is a key issue in the damage rate and structural evolution in the sequent annealing process, especially for ultra-shallow layers. In this work, we develop a compensative optical method combined with UV Raman, X-ray photoelectron spectroscopy (XPS), and X-ray absorption near edge spectroscopy (XANES) to inspect the influence of the beam current in the implantation process. The optima condition of the beam current in the implantation process is determined by higher effective Si-B bond portion in UV Raman spectra and less the peak of B-B bond in XPS spectra which is caused by B cluster defects. Results of XANES indicate that the B oxide layer is formed on the surface of the ultra-shallow junction. The defects in the ultra-shallow junction after annealing are analyzed by novel optical analyses, which cannot be inspected by a traditional thermal wave and resistance measurement. This work exhibits the structural variation of the ultra-shallow junction via a variant beam current and provides a valuable metrology in examining the chemical states and the effective activation in the implantation technology.

Experimental and theoretical study of p-nitroacetanilide

NASA Astrophysics Data System (ADS)

Gnanasambandan, T.; Gunasekaran, S.; Seshadri, S.

2014-01-01

The spectroscopic properties of the p-nitroacetanilide (PNA) were examined by FT-IR, FT-Raman and UV-Vis techniques. FT-IR and FT-Raman spectra in solid state were observed in the region 4000-400 cm-1 and 3500-100 cm-1, respectively. The UV-Vis absorption spectrum of the compound that dissolved in ethanol was recorded in the range of 200-400 nm. The structural and spectroscopic data of the molecule in the ground state were calculated by using density functional theory (DFT) employing B3LYP methods with the 6-31G(d,p) and 6-311+G(d,p) basis sets. The geometry of the molecule was fully optimized, vibrational spectra were calculated and fundamental vibrations were assigned on the basis of the total energy distribution (TED) of the vibrational modes, calculated with scaled quantum mechanics (SQM) method. Thermodynamic properties like entropy, heat capacity and enthalpy have been calculated for the molecule. HOMO-LUMO energy gap has been calculated. The intramolecular contacts have been interpreted using natural bond orbital (NBO) and natural localized molecular orbital (NLMO) analysis. Important non-linear optical (NLO) properties such as electric dipole moment and first hyperpolarizability have been computed using B3LYP quantum chemical calculation.

Towards label-free and site-specific probing of the local pH in proteins: pH-dependent deep UV Raman spectra of histidine and tyrosine

NASA Astrophysics Data System (ADS)

Bröermann, Andreas; Steinhoff, Heinz-Jürgen; Schlücker, Sebastian

2014-09-01

The site-specific pH is an experimental probe for assessing models of structural folding and function of a protein as well as protein-protein and protein-ligand interactions. It can be determined by various techniques such as NMR, FT-IR, fluorescence and EPR spectroscopy. The latter require the use of external labels, i.e., employ pH-dependent dyes and spin labels, respectively. In this contribution, we outline an approach to a label-free and site-specific method for determining the local pH using deep ultraviolet resonance Raman (UVRR) spectroscopic fingerprints of the aromatic amino acids histidine and tyrosine in combination with a robust algorithm that determines the pH value using three UVRR reference spectra and without prior knowledge of the pKa.

Synthesis, spectroscopic (FT-IR, FT-Raman, NMR, UV-Visible), NLO, NBO, HOMO-LUMO, Fukui function and molecular docking study of (E)-1-(5-bromo-2-hydroxybenzylidene)semicarbazide

NASA Astrophysics Data System (ADS)

Raja, M.; Raj Muhamed, R.; Muthu, S.; Suresh, M.

2017-08-01

The title compound, (E)-1-(5-bromo-2-hydroxybenzylidene)semicarbazide (15BHS) was synthesized and characterized by FT-IR, FT-Raman, UV, 1HNMR and 13CNMR spectral analysis. The optimized molecular geometry, the vibrational wavenumbers, the infrared intensities and the Raman scattering activities were calculated by using density functional theory(DFT) B3LYP method with 6-311++G(d,p) basis set. The detailed interpretation of the vibrational spectra has been carried out by VEDA program. The calculated HOMO and LUMO energies show that charge transfer within the molecule. Stability of the molecule arising from hyperconjugative interactions, charge delocalization have been analyzed using natural bond orbital analysis (NBO). The first order hyperpolarizability, Molecular electrostatic potential (MEP) and Fukui functions were also performed. To study the biological activity of the investigation molecule, molecular docking was done to identify the hydrogen bond lengths and binding energy with different antifungal proteins. The thermodynamic properties (heat capacity, entropy, and enthalpy) of the 15BHS at different temperatures have been calculated.

Ion beam radiation effects on natural halite crystals

NASA Astrophysics Data System (ADS)

Arun, T.; Ram, S. S.; Karthikeyan, B.; Ranjith, P.; Ray, D. K.; Rout, B.; Krishna, J. B. M.; Sengupta, Pranesh; Parlapalli, Venkata Satyam

2017-10-01

Halites are one of the interesting material due to its color variations. Natural halites whose color ranges from transparent to dark blue were studied by UV-VIS and Raman spectroscopy. The halite crystals were irradiated with 3 MeV proton micro-beam (∼20 μm beam width with ∼80 PA beam current) for 10 and 90 min to study the radiation damage. After 10 mins of irradiation, small spot developed on the surface of transparent halite crystal whereas after 90 mins of irradiation the spot spread inside the bulk leading to a brown coloration (20 μm initial size to ∼2.0 mm final size). The irradiated portion and the un-irradiated portion of the halites was characterized by Raman spectroscopic technique. The variation in the population density was observed from the UV-Vis spectra. The change in the Raman band intensities was observed for transparent, blue colored and proton beam irradiation halites. Such variation of spectroscopic characteristics due to proton irradiation suggests that the halite can be used for the radiation monitoring.

Discrimination of Apple Liqueurs (Nalewka) Using a Voltammetric Electronic Tongue, UV-Vis and Raman Spectroscopy

PubMed Central

Śliwińska, Magdalena; Garcia-Hernandez, Celia; Kościński, Mikołaj; Dymerski, Tomasz; Wardencki, Waldemar; Namieśnik, Jacek; Śliwińska-Bartkowiak, Małgorzata; Jurga, Stefan; Garcia-Cabezon, Cristina; Rodriguez-Mendez, Maria Luz

2016-01-01

The capability of a phthalocyanine-based voltammetric electronic tongue to analyze strong alcoholic beverages has been evaluated and compared with the performance of spectroscopic techniques coupled to chemometrics. Nalewka Polish liqueurs prepared from five apple varieties have been used as a model of strong liqueurs. Principal Component Analysis has demonstrated that the best discrimination between liqueurs prepared from different apple varieties is achieved using the e-tongue and UV-Vis spectroscopy. Raman spectra coupled to chemometrics have not been efficient in discriminating liqueurs. The calculated Euclidean distances and the k-Nearest Neighbors algorithm (kNN) confirmed these results. The main advantage of the e-tongue is that, using PLS-1, good correlations have been found simultaneously with the phenolic content measured by the Folin–Ciocalteu method (R2 of 0.97 in calibration and R2 of 0.93 in validation) and also with the density, a marker of the alcoholic content method (R2 of 0.93 in calibration and R2 of 0.88 in validation). UV-Vis coupled with chemometrics has shown good correlations only with the phenolic content (R2 of 0.99 in calibration and R2 of 0.99 in validation) but correlations with the alcoholic content were low. Raman coupled with chemometrics has shown good correlations only with density (R2 of 0.96 in calibration and R2 of 0.85 in validation). In summary, from the three holistic methods evaluated to analyze strong alcoholic liqueurs, the voltammetric electronic tongue using phthalocyanines as sensing elements is superior to Raman or UV-Vis techniques because it shows an excellent discrimination capability and remarkable correlations with both antioxidant capacity and alcoholic content—the most important parameters to be measured in this type of liqueurs.  PMID:27735832

Discrimination of Apple Liqueurs (Nalewka) Using a Voltammetric Electronic Tongue, UV-Vis and Raman Spectroscopy.

PubMed

Śliwińska, Magdalena; Garcia-Hernandez, Celia; Kościński, Mikołaj; Dymerski, Tomasz; Wardencki, Waldemar; Namieśnik, Jacek; Śliwińska-Bartkowiak, Małgorzata; Jurga, Stefan; Garcia-Cabezon, Cristina; Rodriguez-Mendez, Maria Luz

2016-10-09

The capability of a phthalocyanine-based voltammetric electronic tongue to analyze strong alcoholic beverages has been evaluated and compared with the performance of spectroscopic techniques coupled to chemometrics. Nalewka Polish liqueurs prepared from five apple varieties have been used as a model of strong liqueurs. Principal Component Analysis has demonstrated that the best discrimination between liqueurs prepared from different apple varieties is achieved using the e-tongue and UV-Vis spectroscopy. Raman spectra coupled to chemometrics have not been efficient in discriminating liqueurs. The calculated Euclidean distances and the k-Nearest Neighbors algorithm (kNN) confirmed these results. The main advantage of the e-tongue is that, using PLS-1, good correlations have been found simultaneously with the phenolic content measured by the Folin-Ciocalteu method (R² of 0.97 in calibration and R² of 0.93 in validation) and also with the density, a marker of the alcoholic content method (R² of 0.93 in calibration and R² of 0.88 in validation). UV-Vis coupled with chemometrics has shown good correlations only with the phenolic content (R² of 0.99 in calibration and R² of 0.99 in validation) but correlations with the alcoholic content were low. Raman coupled with chemometrics has shown good correlations only with density (R² of 0.96 in calibration and R² of 0.85 in validation). In summary, from the three holistic methods evaluated to analyze strong alcoholic liqueurs, the voltammetric electronic tongue using phthalocyanines as sensing elements is superior to Raman or UV-Vis techniques because it shows an excellent discrimination capability and remarkable correlations with both antioxidant capacity and alcoholic content-the most important parameters to be measured in this type of liqueurs.

Synthesis and photocatalytic activity of ytterbium-doped titania/diatomite composite photocatalysts

NASA Astrophysics Data System (ADS)

Tang, Wenjian; Qiu, Kehui; Zhang, Peicong; Yuan, Xiqiang

2016-01-01

Ytterbium-doped titanium dioxide (Yb-TiO2)/diatomite composite materials with different Yb concentrations were prepared by sol-gel method. The phase structure, morphology, and chemical composition of the as-prepared composites were well characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy, Raman spectroscopy, scanning electron microscopy (SEM), and ultraviolet-visible (UV-vis) diffuse reflection spectroscopy. The XRD and Raman spectroscopy analysis indicated that the TiO2 existed in the form of pure anatase in the composites. The SEM images exhibited the well deposition and dispersion of TiO2 nanoparticles with little agglomeration on the surfaces of diatoms. The UV-vis diffuse reflection spectra showed that the band gap of TiO2 could be narrowed by the introduction of Yb species, which was further affected by doping concentration of Yb. The photocatalytic activity of synthesized samples was investigated by the degradation of methylene blue (MB) under UV light irradiation. It was observed that the photocatalytic degradation followed a pseudo-first-order kinetics according to the Langmuir-Hinshelwood model. Compared to TiO2 and TiO2/diatomite, the Yb-TiO2/diatomite composites exhibited higher photocatalytic activity toward degradation of MB using UV light irradiation.

Non-rigid molecule of copper(II) diiminate Cu[CF3C(NH)C(F)C(NH)CF3]2, its conformational polymorphism in crystal and structure in solutions (Raman, UV-vis and quantum chemistry study)

NASA Astrophysics Data System (ADS)

Bukalov, Sergey S.; Aysin, Rinat R.; Leites, Larissa A.; Kurykin, Mikhail A.; Khrustalev, Victor N.

2015-10-01

Calculation of potential energy surface (PES) of isolated molecule of copper(II) diiminate Cu[CF3С(NH)C(F)C(NH)CF3]2 (1) resulted a double-well curve with the minima corresponding to equivalent screwed conformations. The low barrier leads to molecular non-rigidity which seems to be the reason of conformational polymorphism in crystals, reported in [1]. For one of newly found polymorphs, the X-ray structure was determined. The differences in the Raman and UV-vis spectra between differently colored species and their solutions were revealed, they are determined by different geometries of Cu(II) coordination polyhedron and different systems of intermolecular interactions in crystals. Transformations of the polymorphs under thermal, mechanical and photo exposures were studied.

Conformational analysis, UV-VIS, MESP, NLO and NMR studies of 6-methoxy-1,2,3,4-tetrahydronaphthalene.

PubMed

Arivazhagan, M; Kavitha, R; Subhasini, V P

2014-07-15

The detailed HF and B3LYP/6-311++G(d,p) comparative studies on the complete FT-IR and FT-Raman spectra of 6-methoxy-1,2,3,4-tetrahydronaphthalene [MTHN] have been studied. In view of the special properties and uses, the present investigation has been undertaken to provide a satisfactorily vibrational analysis of 6-methoxy-1,2,3,4-tetrahydronaphthalene. Therefore, a thorough Raman, IR, molecular electrostatic potential (MESP), non-linear optical (NLO) properties, UV-VIS, HOMO-LUMO and NMR spectroscopic investigation are reported complemented by B3LYP theoretical predictions with basis set 6-311++G(d,p) to provide novel insight on vibrational assignments and conformational stability of MTHN. Potential energy surface scans (PES) of the CH3 group are undertaken to shed light on the rather complicated conformational interchanges in the compound under investigation. Copyright © 2014 Elsevier B.V. All rights reserved.

Laboratory and Field Spectroscopy of Moon analogue material

NASA Astrophysics Data System (ADS)

Offringa, Marloes; Foing, Bernard H.

2016-07-01

Samples derived from terrestrial analogue sites are studied to gain insight into lunar processes in their geological context (Foing, Stoker, Ehrenfreund, 2011). For this study samples from the volcanic region of the Eifel, Germany collected during our latest field campaigns in November 2015 and February 2016 (Foing et al., 2010), are analyzed with a variety of spectrometers. The aim is to obtain a database of analyzed samples that could be used as a reference for future in situ measurements. We also use a documented set of Moon-Mars relevant minerals curated at VU Amsterdam. We are using systematically for all samples UV-VIS and NIR reflectance spectrometers, and sporadically a Fourier Transform Infrared (FTIR) spectrometer, an X-Ray Fluorescence (XRF) spectrometer and a Raman laser spectrometer on control samples. Calibration of the UV-VIS and NIR reflectance spectrometers is the main focus of this research in order to obtain the clearest spectra. The calibration of the UV-VIS and NIR reflectance spectrometers requires the use of a good light source as well as suitable optical fibers to create a signal that covers the widest range in wavelengths available. To eliminate noise towards the edges of this range, multiple measurements are averaged and data is processed by dividing the signal by reference spectra. Obtained spectra can be tested for accuracy by comparing them with stationary laboratory spectrometers such as the FTIR spectrometer. The Raman, UV-VIS and NIR are also used in combination with the ExoGeoLab mock-up lander during field campaigns (Foing, Stoker, Ehrenfreund, 2011) also brought again to Eifel in February 2016, to prove the applicability of the equipment in the field. Acknowledgements: we thank Dominic Doyle for ESTEC optical lab support, Euan Monaghan (Leiden U) for FTIR measurement support, Wim van Westrenen for access to VU samples, Oscar Kamps (Utrecht U./ESTEC), Aidan Cowley (EAC) and Matthias Sperl (DLR) for support discussions

Quantum mechanical study and spectroscopic (FT-IR, FT-Raman, UV-Visible) study, potential energy surface scan, Fukui function analysis and HOMO-LUMO analysis of 3-tert-butyl-4-methoxyphenol by DFT methods.

PubMed

Saravanan, S; Balachandran, V

2014-09-15

This study represents an integral approach towards understanding the electronic and structural aspects of 3-tert-butyl-4-methoxyphenol (TBMP). Fourier-transform Infrared (FT-IR) and Fourier-transform Raman (FT-Raman) spectra of TBMP was recorded in the region 4000-400 cm(-1) and 3500-100 cm(-1), respectively. The molecular structures, vibrational wavenumbers, infrared intensities and Raman activities were calculated using DFT (B3LYP and LSDA) methods using 6-311++G (d,p) basis set. The most stable conformer of TBMP was identified from the computational results. The assignments of vibrational spectra have been carried out with the help of normal co-ordinate analysis (NCA) following the scaled quantum mechanical force field (SQMFF) methodology. The first order hyperpolarizability (β0) and related properties (β, α0 and Δα) of TBMP have been discussed. The stability and charge delocalization of the molecule was studied by Natural Bond Orbital (NBO) analysis. UV-Visible spectrum and effects of solvents have been discussed and the electronic properties such as HOMO and LUMO energies were determined by time-dependent TD-DFT approach with B3LYP/6-311++G (d,p) level of theory. The molecule orbital contributions are studied by density of energy states (DOSs). The reactivity sites are identified by mapping the electron density into electrostatic potential surface (MEP). Mulliken analysis of atomic charges is also calculated. The thermodynamic properties at different temperatures were calculated, revealing the correlations between standard heat capacities, standard entropy and standard enthalpy changes with temperatures. Global hardness, global softness, global electrophilicity and ionization potential of the title compound are determined. Copyright © 2014 Elsevier B.V. All rights reserved.

Spectral analysis of lunar analogue samples

NASA Astrophysics Data System (ADS)

Offringa, Marloes; Foing, Bernard

2016-04-01

Analyses of samples derived from terrestrial analogue sites are used to study lunar processes in their geological context (Foing, Stoker, Ehrenfreund, 2011). For this study samples from the volcanic region of the Eifel, Germany collected during field campaigns (Foing et al., 2010), are analyzed with a variety of spectrometers. The aim is to obtain a database of analyzed samples that could be used as a reference for future in situ measurements. Equipment used in the laboratory consists of a Fourier Transform Infrared (FTIR) spectrometer, an X-Ray Fluorescence (XRF) spectrometer, a Raman laser spectrometer, as well as UV-VIS and NIR reflectance spectrometers. The Raman, UV-VIS and NIR are also used in combination with the EXoGeoLab mock-up lander during field campaigns (Foing, Stoker, Ehrenfreund, 2011). Calibration of the UV-VIS and NIR reflectance spectrometers is the main focus of this research in order to obtain the clearest spectra. The calibration of the UV-VIS and NIR reflectance spectrometers requires the use of a good light source as well as suitable optical fibers to create a signal that covers the widest range in wavelengths available. To eliminate noise towards the edges of this range, multiple measurements are averaged and data is processed by dividing the signal by reference spectra. Calibration of the devices by creating a new dark and reference spectra has to take place after every sample measurement. In this way we take into account changes that occur in the signal due to the eating of the devices during the measurements. Moreover, the integration time is adjusted to obtain a clear signal without leading to oversaturation in the reflectance spectrum. The typical integration times for the UV-VIS reflectance spectrometer vary between 1 - 18 s, depending on the amount of daylight during experiments. For the NIR reflectance spectrometer the integration time resulting in the best signals is approximately 150 ms in combination with a broad spectrum light source. Together with taking an average over ±600 measurements per sample this leads to the best spectral signals that can be acquired with this set-up. Obtained spectra can be tested for accuracy by comparing them with stationary laboratory spectrometers such as the FTIR spectrometer. Future campaigns involving the employment of the spectrometers on the ExoGeoLab lander would prove the applicability of the equipment in the field.

[NIR-SERS Spectra Detection of Cytidine on Nano-Silver Films].

PubMed

Zhang, De-qing; Liu, Ren-ming; Zhang, Guo-qiang; Zhang, Yan; Xiong, Yang; Zhang, Chuan-yun; Li, Lun; Si, Min-zhen

2016-03-01

The polyvinyl alcohol (PVA) protected silver glass-like nanostructure (PVA-Ag-GNS) with high surface-enhanced Raman scattering (SERS) activity was prepared and employed to detect the near-infrared surface enhanced Raman scattering (NIR-SERS) spectra of cytidine aqueous solution (10(-2)-10(-8) mol x L(-1)). In the work, the near-infrared laser beam (785 nm) was used as the excitation light source. The experiment results show that high-quality NIR-SERS spectra were obtained in the ranges of 300 to 2 000 cm(-1) and the detection limit of cytidine aqueous solution was down to 10(-7) mol x L(-1). Meanwhile, the PVA-Ag-GNS shows a high enhancement factor (EF) of -10(8). In order to test the optical reproducibility of PVA-Ag-GNS, ten samples of cytidine aqueous solution (10(-2)-10(-5) mol x L(-1)) had been dropped onto the surface of PVA-Ag-GNS respectively. Meanwhile, these samples were measured by the portable Raman spectrometer. As a result, the PVA-Ag-GNS demonstrated good optical reproducibility in the detection of cytidine aqueous solution. In addition, to explain the reason of enhancement effect, the ultraviolet-visible (UV-Vis) extinction spectrum and scanning electron microscope (SEM) of cytidine molecules adsorbed on the surface of PVA-Ag-GNS were measured. There is plasmon resonance band at 800 nm in the UV-Vis extinction Spectrum of the compound system. Therefore, when the near-infrared laser beam (785 nm) was used as excitation light source, the compound system may produce strongly surface plasmon resonance (SPR). According to the SEM of PVA-Ag-GNS, there are much interstitial between the silver nanoparticles. So NIR-SERS is mainly attributed to electromagnetic (EM) fields associated with strong surface plasmon resonance. At last, the geometry optimization and pre-Raman spectrum of cytidine for the ground states were performed with DFT, B3LYP functional and the 6-311G basis set, and the near-infrared laser with wavelength of 785 nm was employed in the pre-Raman spectrum calculation process. The calculation results without imaginary frequency and the results match pretty well with the experimental Raman spectrum. At the same time, the assignations of Raman bands and adsorption behaviors of cytidine molecules on the surface of PVA-Ag-GNS are also discussed. According to our experiment and calculations, cytidine molecules mainly adsorbed on silver nanoparticles via the ribose moiety and amino group may get close to the local electromagnetic field.

High temperature thermochromic polydiacetylenes: Design and colorimetric properties

NASA Astrophysics Data System (ADS)

Huo, Jingpei; Hu, Zhudong; He, Guozhang; Hong, Xiaxiao; Yang, Zhihao; Luo, Shihe; Ye, Xiufang; Li, Yanli; Zhang, Yubo; Zhang, Min; Chen, Hong; Fan, Ting; Zhang, Yuyuan; Xiong, Bangyun; Wang, Zhaoyang; Zhu, Zhibo; Chen, Dongchu

2017-11-01

Three novel polydiacetylenes (PDAs) are synthesized through the self-assembly followed by the topochemical polymerization via controllable electrophoretic deposition. All the samples could undergo a multi-step thermochromic process, turning purple and red successively over a wide range from room temperature to above 250 °C. Resulting PDAs are studied by UV-vis, IR, Raman spectroscopies, and chromoisomerism by naked eye visualization; their stabilities by thermogravimetric method, and emission behavior by fluorescence spectroscopy. To study the mechanism of the thermochromic response, temperature-dependent UV-vis spectra, the results of which successfully highlighted the close relationship between chromatic transitions and the conformational changes.

Correlation between the structure modification and conductivity of 3 MeV Si ion-irradiated polyimide

NASA Astrophysics Data System (ADS)

Sun, Youmei; Zhu, Zhiyong; Li, Changlin

2002-05-01

The surface modification of the polyimide (PI/Kapton) films was carried out by 3 MeV Si + implantation to fluences ranging from 1×10 12 to 1.25×10 15 ions/cm 2. Fourier transform infrared (FTIR), Raman and ultraviolet/visible (UV/Vis) spectroscopes were employed to investigate the chemical degradation of function groups in the irradiated layer. FTIR results show that the absorbance of typical function group decreases exponentially as a function of fluence. The damage cross-section of typical bonds of PI was evaluated from the FTIR spectra. Raman analysis shows the absorbed dose for destruction of all function groups is above 218 MGy. The red shifting of the absorption edge from UV to visible reveals the band gap closing which results from increase of the cluster size. The production efficiency of the chromophores was discussed according to UV/Vis analysis. Irradiation dramatically enhances the electrical conductivity and the sheet resistivity in our experiment descends nearly 10 orders of magnitude compared with its intrinsic value.

DFT-assisted spectroscopic characterization of pyrazosulfuron-ethyl: FT-Raman, FTIR and UV-vis studies of a sulfonyl urea herbicide

NASA Astrophysics Data System (ADS)

Monicka, J. Clemy; James, C.

2014-10-01

Raman and IR spectra of pyrazosulfuron-ethyl have been reported here, and it is shown that the spectra has been fully interpreted in terms of assigning normal modes to the various spectral features by using density functional theory calculations. The Raman bands observed for PY in solid phase are characteristic for the carbonyl group, Csbnd C, Csbnd H and Nsbnd H stretching and deformation vibrations. The dimer structure of PY was optimized, including the Nsbnd H…N and Csbnd H…O intermolecular interactions. Stability of the molecule arising from hyperconjugative interactions leading to its bioactivity and charge delocalization have been analyzed using natural bond orbital analysis. Spectral analysis reveals the substantial effect of non-bonding interaction, conjugation and induction effects in the molecule which in turn influences the bioactivity of the compound. Red shifting of (∼94 cm-1) Nsbnd H stretching band substantiates the presence of strong Nsbnd H…N intramolecular hydrogen bonding in the molecule. The aromatic behavior of pyrimidine and pyrazole ring has been calculated using the HOMA method.

Spectroscopic (FT-IR, FT-Raman, NMR and UV-Visible) and quantum chemical studies of molecular geometry, Frontier molecular orbital, NLO, NBO and thermodynamic properties of salicylic acid.

PubMed

Suresh, S; Gunasekaran, S; Srinivasan, S

2014-11-11

The solid phase FT-IR and FT-Raman spectra of 2-hydroxybenzoic acid (salicylic acid) have been recorded in the region 4000-400 and 4000-100 cm(-1) respectively. The optimized molecular geometry and fundamental vibrational frequencies are interpreted with the aid of structure optimizations and normal coordinate force field calculations based on density functional theory (DFT) method and a comparative study between Hartree Fork (HF) method at 6-311++G(d,p) level basis set. The calculated harmonic vibrational frequencies are scaled and they are compared with experimentally obtained FT-IR and FT-Raman spectra. A detailed interpretation of the vibrational spectra of this compound has been made on the basis of the calculated potential energy distribution (PED). The time dependent DFT method is employed to predict its absorption energy and oscillator strength. The linear polarizability (α) and the first order hyper polarizability (β) values of the investigated molecule have been computed. The electronic properties, such as HOMO and LUMO energies, molecular electrostatic potential (MEP) are also performed. Stability of the molecule arising from hyper conjugative interaction, charge delocalization has been analyzed using natural bond orbital (NBO) analysis. Published by Elsevier B.V.

Optical characterization of composite layers prepared by plasma polymerization

NASA Astrophysics Data System (ADS)

Radeva, E.; Hikov, T.; Mitev, D.; Stroescu, H.; Nicolescu, M.; Gartner, M.; Presker, R.; Pramatarova, L.

2016-02-01

Thin composite layers from polymer/nanoparticles (Ag-nanoparticles and detonation nanodiamonds) were prepared by plasma polymerization process on the base of hexamethyldisiloxane. The variation of the layer composition was achieved by changing the type of nanoparticles. The optical measurement techniques used were UV-VIS-NIR ellipsometry (SE), Fourier-transformed infrared spectroscopy (FTIR) and Raman spectroscopy. The values of the refractive index determined are in the range 1.30 to 1.42. All samples are transparent with transmission between 85-95% and very smooth. The change in Raman and FTIR spectra of the composites verify the expected bonding between polymer and diamond nanoparticles due to the penetration of the fillers in the polymer matrix. The comparison of the spectra of the corresponding NH3 plasma treated composites revealed that the composite surface becomes more hydrophilic. The obtained results indicate that preparation of layers with desired compositions is possible at a precise control of the detonation nanodiamond materials.

Spectroscopic study of the charge-transfer complexes TiCl4/styrene and TiCl4/polystyrene

NASA Astrophysics Data System (ADS)

Gonçalves, Norberto S.; Noda, Lúcia. K.

2017-10-01

In this work, solutions of TiCl4/styrene and TiCl4/polystyrene charge-transfer complexes in CHCl3 or CDCl3 were investigated by UV-vis, resonance Raman and 1H NMR spectroscopies in order to study their molecular and electronic structures. Both show a yellow colour due to absorption in the 400 nm region, related to a charge-transfer transition. In Raman spectra, as the excitation approaches the resonance region, the primary enhancement of aromatic ring modes was mainly observed, rather than intensification of the vinylic double-bond stretch. Under the experimental conditions it was observed that formation of polystyrene takes place, as showed by 1H NMR spectra, and the most significant interaction occurs at the aromatic ring, as supported by the results from interaction of TiCl4 with polystyrene, as indicated by the charge-transfer band and resonant intensification of the aromatic ring modes.

Measuring Rocket Engine Temperatures with Hydrogen Raman Spectroscopy

NASA Technical Reports Server (NTRS)

Wehrmeyer, Joseph A.; Osborne, Robin J.; Trinh, Huu P.; Turner, James (Technical Monitor)

2001-01-01

Optically accessible, high pressure, hot fire test articles are available at NASA Marshall for use in development of advanced rocket engine propellant injectors. Single laser-pulse ultraviolet (UV) Raman spectroscopy has been used in the past in these devices for analysis of high pressure H2- and CH4-fueled combustion, but relies on an independent pressure measurement in order to provide temperature information. A variation of UV Raman (High Resolution Hydrogen Raman Spectroscopy) is under development and will allow temperature measurement without the need for an independent pressure measurement, useful for flows where local pressure may not be accurately known. The technique involves the use of a spectrometer with good spectral resolution, requiring a small entrance slit for the spectrometer. The H2 Raman spectrum, when created by a narrow linewidth laser source and obtained from a good spectral resolution spectrograph, has a spectral shape related to temperature. By best-fit matching an experimental spectrum to theoretical spectra at various temperatures, a temperature measurement is obtained. The spectral model accounts for collisional narrowing, collisional broadening, Doppler broadening, and collisional line shifting of each Raman line making up the H2 Stokes vibrational Q-branch spectrum. At pressures from atmospheric up to those associated with advanced preburner components (5500 psia), collisional broadening though present does not cause significant overlap of the Raman lines, allowing high resolution H2 Raman to be used for temperature measurements in plumes and in high pressure test articles. Experimental demonstrations of the technique are performed for rich H2-air flames at atmospheric pressure and for high pressure, 300 K H2-He mixtures. Spectrometer imaging quality is identified as being critical for successful implementation of technique.

A critical assessment of visual identification of marine microplastic using Raman spectroscopy for analysis improvement.

PubMed

Lenz, Robin; Enders, Kristina; Stedmon, Colin A; Mackenzie, David M A; Nielsen, Torkel Gissel

2015-11-15

Identification and characterisation of microplastic (MP) is a necessary step to evaluate their concentrations, chemical composition and interactions with biota. MP ≥10μm diameter filtered from below the sea surface in the European and subtropical North Atlantic were simultaneously identified by visual microscopy and Raman micro-spectroscopy. Visually identified particles below 100μm had a significantly lower percentage confirmed by Raman than larger ones indicating that visual identification alone is inappropriate for studies on small microplastics. Sixty-eight percent of visually counted MP (n=1279) were spectroscopically confirmed being plastic. The percentage varied with type, colour and size of the MP. Fibres had a higher success rate (75%) than particles (64%). We tested Raman micro-spectroscopy applicability for MP identification with respect to varying chemical composition (additives), degradation state and organic matter coating. Partially UV-degraded post-consumer plastics provided identifiable Raman spectra for polymers most common among marine MP, i.e. polyethylene and polypropylene. Copyright © 2015 Elsevier Ltd. All rights reserved.

Effect of atomic layer deposition coatings on the surface structure of anodic aluminum oxide membranes.

PubMed

Xiong, Guang; Elam, Jeffrey W; Feng, Hao; Han, Catherine Y; Wang, Hsien-Hau; Iton, Lennox E; Curtiss, Larry A; Pellin, Michael J; Kung, Mayfair; Kung, Harold; Stair, Peter C

2005-07-28

Anodic aluminum oxide (AAO) membranes were characterized by UV Raman and FT-IR spectroscopies before and after coating the entire surface (including the interior pore walls) of the AAO membranes by atomic layer deposition (ALD). UV Raman reveals the presence of aluminum oxalate in bulk AAO, both before and after ALD coating with Al2O3, because of acid anion incorporation during the anodization process used to produce AAO membranes. The aluminum oxalate in AAO exhibits remarkable thermal stability, not totally decomposing in air until exposed to a temperature >900 degrees C. ALD was used to cover the surface of AAO with either Al2O3 or TiO2. Uncoated AAO have FT-IR spectra with two separate types of OH stretches that can be assigned to isolated OH groups and hydrogen-bonded surface OH groups, respectively. In contrast, AAO surfaces coated by ALD with Al2O3 display a single, broad band of hydrogen-bonded OH groups. AAO substrates coated with TiO2 show a more complicated behavior. UV Raman results show that very thin TiO2 coatings (1 nm) are not stable upon annealing to 500 degrees C. In contrast, thicker coatings can totally cover the contaminated alumina surface and are stable at temperatures in excess of 500 degrees C.

A comparative experimental and quantum chemical study on monomeric and dimeric structures of 3,5-dibromoanthranilic acid.

PubMed

Karabacak, Mehmet; Cinar, Mehmet

2012-10-01

This study presents the structural and spectroscopic characterization of 3,5-dibromoanthranilic acid with help of experimental techniques (FT-IR, FT-Raman, UV, NMR) and quantum chemical calculations. The vibrational spectra of title compound were recorded in solid state with FT-IR and FT-Raman in the range of 4000-400 and 4000-50 cm(-1), respectively. The vibrational frequencies were also computed using B3LYP method of DFT with 6-311++G(d,p) basis set. The fundamental assignments were done on the basis of the total energy distribution (TED) of the vibrational modes, calculated with scaled quantum mechanical (SQM) method. The (1)H, (13)C and DEPT NMR spectra were recorded in DMSO solution and calculated by gauge-invariant atomic orbitals (GIAO) method. The UV absorption spectra of the compound were recorded in the range of 200-400 nm in ethanol, water and DMSO solutions. Solvent effects were calculated using time-dependent density functional theory and CIS method. The ground state geometrical structure of compound was predicted by B3LYP method and compared with the crystallographic structure of similar compounds. All calculations were made for monomeric and dimeric structure of compound. Moreover, molecular electrostatic potential (MEP) and thermodynamic properties were performed. Mulliken atomic charges of neutral and anionic form of the molecule were computed and compared with anthranilic acid. Copyright © 2012 Elsevier B.V. All rights reserved.

Spectroscopic characteristic (FT-IR, FT-Raman, UV, 1H and 13C NMR), theoretical calculations and biological activity of alkali metal homovanillates

NASA Astrophysics Data System (ADS)

Samsonowicz, M.; Kowczyk-Sadowy, M.; Piekut, J.; Regulska, E.; Lewandowski, W.

2016-04-01

The structural and vibrational properties of lithium, sodium, potassium, rubidium and cesium homovanillates were investigated in this paper. Supplementary molecular spectroscopic methods such as: FT-IR, FT-Raman in the solid phase, UV and NMR were applied. The geometrical parameters and energies were obtained from density functional theory (DFT) B3LYP method with 6-311++G** basis set calculations. The geometry of the molecule was fully optimized, vibrational spectra were calculated and fundamental vibrations were assigned. Geometric and magnetic aromaticity indices, atomic charges, dipole moments, HOMO and LUMO energies were also calculated. The microbial activity of investigated compounds was tested against Bacillus subtilis (BS), Pseudomonas aeruginosa (PA), Escherichia coli (EC), Staphylococcus aureus (SA) and Candida albicans (CA). The relationship between the molecular structure of tested compounds and their antimicrobial activity was studied. The principal component analysis (PCA) was applied in order to attempt to distinguish the biological activities of these compounds according to selected band wavenumbers. Obtained data show that the FT-IR spectra can be a rapid and reliable analytical tool and a good source of information for the quantitative analysis of the relationship between the molecular structure of the compound and its biological activity.

Experimental and theoretical study of p-nitroacetanilide.

PubMed

Gnanasambandan, T; Gunasekaran, S; Seshadri, S

2014-01-03

The spectroscopic properties of the p-nitroacetanilide (PNA) were examined by FT-IR, FT-Raman and UV-Vis techniques. FT-IR and FT-Raman spectra in solid state were observed in the region 4000-400 cm(-1) and 3500-100 cm(-1), respectively. The UV-Vis absorption spectrum of the compound that dissolved in ethanol was recorded in the range of 200-400 nm. The structural and spectroscopic data of the molecule in the ground state were calculated by using density functional theory (DFT) employing B3LYP methods with the 6-31G(d,p) and 6-311+G(d,p) basis sets. The geometry of the molecule was fully optimized, vibrational spectra were calculated and fundamental vibrations were assigned on the basis of the total energy distribution (TED) of the vibrational modes, calculated with scaled quantum mechanics (SQM) method. Thermodynamic properties like entropy, heat capacity and enthalpy have been calculated for the molecule. HOMO-LUMO energy gap has been calculated. The intramolecular contacts have been interpreted using natural bond orbital (NBO) and natural localized molecular orbital (NLMO) analysis. Important non-linear optical (NLO) properties such as electric dipole moment and first hyperpolarizability have been computed using B3LYP quantum chemical calculation. Copyright © 2013 Elsevier B.V. All rights reserved.

A combined experimental (IR, Raman and UV-Vis) and quantum chemical study of canadine

NASA Astrophysics Data System (ADS)

Joshi, Bhawani Datt; Srivastava, Anubha; Tandon, Poonam; Jain, Sudha; Ayala, A. P.

2018-02-01

Plant based natural products cover a major sector of the medicinal field, as such focus on plant research has been increased all over the world. As an attempt to aid that research, we have performed structural and spectroscopic analysis of a natural product, an alkaloid: canadine. Both ab initio Hartree-Fock (HF) and density functional theory (DFT) employing B3LYP using 6-311 ++G(d,p) basis set were used for the calculations. The calculated vibrational frequencies were scaled and compared with the experimental infrared and Raman spectra. The complete vibrational assignments were made using potential energy distribution. The structure-activity relation has also been interpreted by mapping electrostatic potential surface and evaluating the reactivity descriptors, which are valuable information for quality control of medicines and drug-receptor interactions. Natural bond orbital analysis has also been performed to understand the stability and hyperconjugative interactions of the molecule. Furthermore, UV-Vis spectra have been recorded in an ethanol solvent (EtOH) and the electronic property has been analyzed employing TD-DFT for both gaseous and solvent phase. The HOMO and LUMO calculation with their energy gap show that charge transfer occurs within the molecule. Additionally, the nonlinear optical properties of the title compound have been interpreted that predicts it's the best candidate for the NLO materials.

Interaction between Diethyldithiocarbamate and Cu(II) on Gold in Non-Cyanide Wastewater

PubMed Central

Ly, Nguyễn Hoàng; Nguyen, Thanh Danh; Zoh, Kyung-Duk; Joo, Sang-Woo

2017-01-01

A surface-enhanced Raman scattering (SERS) detection method for environmental copper ions (Cu2+) was developed according to the vibrational spectral change of diethyldithiocarbamate (DDTC) on gold nanoparticles (AuNPs). The ultraviolet-visible (UV-Vis) absorption spectra indicated that DDTC formed a complex with Cu2+, showing a prominent peak at ~450 nm. We found Raman spectral changes in DDTC from ~1490 cm−1 to ~1504 cm−1 on AuNPs at a high concentration of Cu2+ above 1 μM. The other ions of Zn2+, Pb2+, Ni2+, NH4+, Mn2+, Mg2+, K+, Hg2+, Fe2+, Fe3+, Cr3+, Co2+, Cd2+, and Ca2+ did not produce such spectral changes, even after they reacted with DDTC. The electroplating industrial wastewater samples were tested under the interference of highly concentrated ions of Fe3+, Ni2+, and Zn2+. The Raman spectroscopy-based quantification of Cu2+ ions was able to be achieved for the wastewater after treatment with alkaline chlorination, whereas the cyanide-containing water did not show any spectral changes, due to the complexation of the cyanide with the Cu2+ ions. A micromolar range detection limit of Cu2+ ions could be achieved by analyzing the Raman spectra of DDTC in the cyanide-removed water. PMID:29140287

Interaction between Diethyldithiocarbamate and Cu(II) on Gold in Non-Cyanide Wastewater.

PubMed

Ly, Nguyễn Hoàng; Nguyen, Thanh Danh; Zoh, Kyung-Duk; Joo, Sang-Woo

2017-11-15

A surface-enhanced Raman scattering (SERS) detection method for environmental copper ions (Cu 2+ ) was developed according to the vibrational spectral change of diethyldithiocarbamate (DDTC) on gold nanoparticles (AuNPs). The ultraviolet-visible (UV-Vis) absorption spectra indicated that DDTC formed a complex with Cu 2+ , showing a prominent peak at ~450 nm. We found Raman spectral changes in DDTC from ~1490 cm -1 to ~1504 cm -1 on AuNPs at a high concentration of Cu 2+ above 1 μM. The other ions of Zn 2+ , Pb 2+ , Ni 2+ , NH₄⁺, Mn 2+ , Mg 2+ , K⁺, Hg 2+ , Fe 2+ , Fe 3+ , Cr 3+ , Co 2+ , Cd 2+ , and Ca 2+ did not produce such spectral changes, even after they reacted with DDTC. The electroplating industrial wastewater samples were tested under the interference of highly concentrated ions of Fe 3+ , Ni 2+ , and Zn 2+ . The Raman spectroscopy-based quantification of Cu 2+ ions was able to be achieved for the wastewater after treatment with alkaline chlorination, whereas the cyanide-containing water did not show any spectral changes, due to the complexation of the cyanide with the Cu 2+ ions. A micromolar range detection limit of Cu 2+ ions could be achieved by analyzing the Raman spectra of DDTC in the cyanide-removed water.

Book Review: Near infrared surface-enhanced Raman spectroscopic study of antiretroviraly drugs hypericin and emodin in aqueous silver colloids

NASA Astrophysics Data System (ADS)

Sánchez-Cortés, S.; Jancura, D.; Miskovsky, P.; Bertoluzza, A.

1997-05-01

The near infrared surface-enhanced Raman spectra (NIR SERS) of antiretroviraly drugs hypericin and its analogs emodin and bianthrone were studied at different drug concentration, dimethylsulfoxide concentration, pH and time. The differences observed in the SERS spectra when varying some of these parameters are attributed to changes in the adsorbate coverage and orientation of these molecules on the silver colloids, and can be related to the monomeric drug concentration existing in the solution. Two different drug orientations on the metal surface can be deduced: perpendicular and planar, which can be characterized by two different SERS profiles. The drug reorientation on the surface is indicative of a change in the oligomer-monomer equilibrium in the solution, what implies that the SERS technique can be used as an indirect method to monitor the intermolecular interactions of these molecules in water. In addition the UV-visible absorption spectra of these drugs also reveals the existence of intermolecular interactions in water and the temperature dependence of these interactions.

The spectroscopic properties of anticancer drug Apigenin investigated by using DFT calculations, FT-IR, FT-Raman and NMR analysis

NASA Astrophysics Data System (ADS)

Mariappan, G.; Sundaraganesan, N.; Manoharan, S.

2012-09-01

The FT-Raman and FT-Infrared spectra of solid Apigenin sample were measured in order to elucidate the spectroscopic properties of title molecule in the spectral range of 3500-50 cm-1 and 4000-400 cm-1, respectively. The recorded FT-IR and FT-Raman spectral measurements favor the calculated (by B3LYP/6-31G(d,p) method) structural parameters which are further supported by spectral simulation. Additional support is given by the collected 1H and 13C NMR spectra recorded with the sample dissolved in DMSO. The predicted chemical shifts at the B3LYP/6-31G(d) level obtained using the Gauge-Invariant Atomic Orbitals (GIAO) method with and without inclusion of solvent using the Polarizable Continuum Model (PCM). By using TD-DFT method, electronic absorption spectra of the title compound have been predicted and a good agreement with the TD-DFT method and the experimental one is determined. The UV-visible absorption spectra of the compound that dissolved in Ethanol, Methanol and DMSO were recorded in the range of 800-200 nm. The formation of hydrogen bond and the most possible interaction are explained using natural bond orbital (NBO) analysis. In addition, the molecular electrostatic potential (MEP), frontier molecular orbitals (FMO) analysis and atomic charges of the title compound were investigated using theoretical calculations. The results are discussed herein and compared with similar molecules whenever appropriate.

Complex formation and vectorization of a phosphorothioate oligonucleotide with an amphipathic leucine- and lysine-rich peptide: study at molecular and cellular levels.

PubMed

Boukhalfa-Heniche, Fatima-Zohra; Hernández, Belén; Gaillard, Stéphane; Coïc, Yves-Marie; Huynh-Dinh, Tam; Lecouvey, Marc; Seksek, Olivier; Ghomi, Mahmoud

2004-04-15

Optical spectroscopic techniques such as CD, Raman scattering, and fluorescence imaging allowed us to analyze the complex formation and vectorization of a single-stranded 20-mer phosphorothioate oligodeoxynucleotide with a 15-mer amphipathic peptide at molecular and cellular levels. Different solvent mixtures (methanol and water) and molecular ratios of peptide/oligodeoxynucleotide complexes were tested in order to overcome the problems related to solubility. Optimal conditions for both spectroscopic and cellular experiments were obtained with the molecular ratio peptide/oligodeoxynucleotide equal to 21:4, corresponding to a 7:5 ratio for their respective +/- charge ratio. At the molecular level, CD and Raman spectra were consistent with a alpha-helix conformation of the peptide in water or in a methanol-water mixture. The presence of methanol increased considerably the solubility of the peptide without altering its alpha-helix conformation, as evidenced by CD and Raman spectroscopies. UV absorption melting profile of the oligodeoxynucleotide gave rise to a flat melting profile, corresponding to its random structure in solution. Raman spectra of oligodeoxynucleotide/peptide complexes could only be studied in methanol/water mixture solutions. Drastic changes observed in Raman spectra have undoubtedly shown: (a) the perturbation occurred in the peptide secondary structure, and (b) possible interaction between the lysine residues of the peptide and the oligodeoxynucleotide. At the cellular level, the complex was prepared in a mixture of 10% methanol and 90% cell medium. Cellular uptake in optimal conditions for the oligodeoxynucleotide delivery with low cytotoxicity was controlled by fluorescence imaging allowing to specifically locate the compacted oligonucleotide labeled with fluorescein at its 5'-terminus with the peptide into human glioma cells after 1 h of incubation at 37 degrees C. Copyright 2004 Wiley Periodicals, Inc.

Near infrared Raman spectra of Rhizoma dioscoreae

NASA Astrophysics Data System (ADS)

Lin, Wenshuo; Chen, Rong; Chen, Guannan; Feng, Sangyuan; Li, Yongzeng; Huang, Zufang; Li, Yongsen

2008-03-01

A novel and compact near-infrared (NIR) Raman system is developed using 785-nm diode laser, volume-phase technology holographic system, and NIR intensified charge-coupled device (CCD). Raman spectra and first derivative spectra of Rhizoma Dioscoreae are obtained. Raman spectra of Rhizoma Dioscoreae showed three strong characteristic peaks at 477.4cm -1, 863.9cm -1, and 936.0cm -1. The major ingredients are protein, amino acid, starch, polysaccharides and so on, matched with the known basic biochemical composition of Rhizoma Dioscoreae. In the first derivative spectra of Rhizoma Dioscoreae, distinguishing characteristic peaks appeared at 467.674cm -1, 484.603cm -1, 870.37cm -1, 943.368cm -1. Contrasted with Rhizoma Dioscoreae Raman spectra, in 600cm -1 to 800cm -1, 1000cm -1 to 1400cm -1 regions, changes in Rhizoma Dioscoreae Raman first derivative spectra are represented more clearly than Rhizoma Dioscoreae Raman spectra. So Rhizoma Dioscoreae raman first derivative spectra can be an accurate supplementary analysis method to Rhizoma Dioscoreae Raman spectra.

Spectroscopic study of honey from Apis mellifera from different regions in Mexico

NASA Astrophysics Data System (ADS)

Frausto-Reyes, C.; Casillas-Peñuelas, R.; Quintanar-Stephano, JL; Macías-López, E.; Bujdud-Pérez, JM; Medina-Ramírez, I.

2017-05-01

The objective of this study was to analyze by Raman and UV-Vis-NIR Spectroscopic techniques, Mexican honey from Apis Mellífera, using representative samples with different botanic origins (unifloral and multifloral) and diverse climates. Using Raman spectroscopy together with principal components analysis, the results obtained represent the possibility to use them for determination of floral origin of honey, independently of the region of sampling. For this, the effect of heat up the honey was analyzed in relation that it was possible to greatly reduce the fluorescence background in Raman spectra, which allowed the visualization of fructose and glucose peaks. Using UV-Vis-NIR, spectroscopy, a characteristic spectrum profile of transmittance was obtained for each honey type. In addition, to have an objective characterization of color, a CIE Yxy and CIE L*a*b* colorimetric register was realized for each honey type. Applying the principal component analysis and their correlation with chromaticity coordinates allowed classifying the honey samples in one plot as: cutoff wavelength, maximum transmittance, tones and lightness. The results show that it is possible to obtain a spectroscopic record of honeys with specific characteristics by reducing the effects of fluorescence.

Conformational stability, spectroscopic (FT-IR, FT-Raman and UV-Vis) analysis, NLO, NBO, FMO and Fukui function analysis of 4-hexylacetophenone by density functional theory.

PubMed

Saravanan, S; Balachandran, V

2015-03-05

The experimental and theoretical study on the structures and vibrations of 4-hexylacetophenone (abbreviated as 4HAP) are presented. The FT-IR and FT-Raman spectra of the title compound have been recorded in the region 4000-400cm(-1) and 3500-100cm(-1) respectively. The molecular structures, vibrational wavenumbers, infrared intensities and Raman activities were calculated using DFT (B3LYP and LSDA) method with 6-311++G(d,p) basis set. The most stable conformer of 4HAP is identified from the computational results. The assignments of the vibrational spectra have been carried out with the aid of normal coordinate analysis (NCA) following the scaled quantum mechanical force field methodology (SQMEF). The linear polarizability (α) and the first hyperpolarizability (βtot) values of the investigated molecule have been computed using B3LYP and LSDA with 6-311++G(d,p) basis set. Stability of the molecule arising from hyper conjugative interaction and charge transfer delocalization has been analyzed using natural bond orbital (NBO) analysis. The molecule orbital contributions are studied by density of energy states (DOSs). UV-Vis spectrum and effects of solvents have been discussed effects of solvents have been discussed and the electronic properties such as HOMO and LUMO energies were determined by time-dependent TD-DFT approach. Fukui function and Mulliken analysis on atomic charges of the title compound have been calculated. Finally, electrophilic and nucleophilic descriptors of the title molecule have been calculated. Copyright © 2014 Elsevier B.V. All rights reserved.

Vibrational and UV spectroscopic studies of 2-coumaranone by experimental and density functional theory calculations

NASA Astrophysics Data System (ADS)

Priya, Y. Sushma; Rao, K. Ramachandra; Chalapathi, P. V.; Satyavani, M.; Veeraiah, A.

2017-09-01

The vibrational and electronic properties of 2-coumaranone have been reported in the ground state using experimental techniques (FT-IR, FT-Raman, UV spectra and fluorescence microscopic imaging) and density functional theory (DFT) employing B3LYP correlation with the 6-31G(d, p) basis set. The theoretically reported optimized parameters, vibrational frequencies etc., were compared with the experimental values, which yielded good concurrence between the experimental and calculated values. The assignments of the vibrational spectra were done with the help of normal co-ordinate analysis (NCA) following the Scaled Quantum Mechanical Force Field(SQMFF) methodology. The whole assignments of fundamental modes were based on the potential energy distribution (PED) matrix. The electric dipole moment and the first order hyperpolarizability of the 2-coumaranone have been computed using quantum mechanical calculations. NBO and HOMO, LUMO analyses have been carried out. UV spectrum of 2-coumaranone was recorded in the region 100-300 nm and compared with the theoretical UV spectrum using TD-DFT and SAC-CI methods by which a good agreement is observed. Fluorescence microscopic imaging study reflects that the compound fluoresces in the green-yellow region.

Alkaline transition of pseudoazurin Met16X mutant proteins: protein stability influenced by the substitution of Met16 in the second sphere coordination.

PubMed

Abdelhamid, Rehab F; Obara, Yuji; Kohzuma, Takamitsu

2008-01-01

Several blue copper proteins are known to change the active site structure at alkaline pH (alkaline transition). Spectroscopic studies of Met16Phe, Met16Tyr, Met16Trp, and Met16Val pseudoazurin variants were performed to investigate the second sphere role through alkaline transition. The visible electronic absorption and resonance Raman spectra of Met16Phe, Met16Tyr, and Met16Trp variants showed the increasing of axial component at pH approximately 11 like wild-type PAz. The visible electronic absorption and far-UV CD spectra of Met16Val demonstrated that the destabilization of the protein structure was triggered at pH>11. Resonance Raman (RR) spectra of PAz showed that the intensity-weighted averaged Cu-S(Cys) stretching frequency was shifted to higher frequency region at pH approximately 11. The higher frequency shift of Cu-S(Cys) bond is implied the stronger Cu-S(Cys) bond at alkaline transition pH approximately 11. The visible electronic absorption and far-UV CD spectra of Met16X PAz revealed that the Met16Val variant is denatured at pH>11, but Met16Phe, Met16Tyr, and Met16Trp mutant proteins are not denatured even at pH>11. These observations suggest that Met16 is important to maintain the protein structure through the possible weak interaction between methionine -SCH3 part and coordinated histidine imidazole moiety. The introduction of pi-pi interaction in the second coordination sphere may be contributed to the enhancement of protein structure stability.

N-Sulfinylimine compounds, R-NSO: a chemistry family with strong temperament

NASA Astrophysics Data System (ADS)

Romano, R. M.; Della Védova, C. O.

2000-04-01

In this review, an update on the structural properties and theoretical studies of N-sulfinylimine compounds (R-NSO) is reported. They were deduced using several experimental techniques: gas-electron diffraction (GED), X-ray diffraction, 17O NMR, ultraviolet-visible absorption spectroscopy (UV-Vis), FTIR (including matrix studies of molecular randomisation) and Raman (including pre-resonant Raman spectra). Data are compared with those obtained by theoretical calculations. With these tools, excited state geometry using the time-dependent theory was calculated for these kinds of compounds. The existence of pre-resonant Raman effect was reported recently for R-NSO compounds. The configuration of R-NSO compounds was checked for this series confirming the existence of only one syn configuration. This finding is corroborated by theoretical calculations. The method of preparation is also summarised.

Silver Eco-Solvent Ink for Reactive Printing of Polychromatic SERS and SPR Substrates

PubMed Central

Dustov, Mavlavi; Goldt, Anastasia E.; Sukhorukova, Irina V.; Grünert, Wolfgang; Grigorieva, Anastasia V.

2018-01-01

A new reactive ink based on a silver citrate complex is proposed for a photochemical route to surface-enhanced Raman spectroscopy active substrates with controllable extinction spectra. The drop-cast test of the ink reveals homogeneous nucleation of silver and colloid particle growth originating directly from photochemical in situ reduction in droplets, while the following evaporation of the deposited ink produces small nano- and micron-size particles. The prepared nanostructures and substrates were accurately characterized by electron microscopy methods and optical extinction spectroscopy. Varying the duration of UV irradiation allows tuning the morphology of individual silver nanoparticles forming hierarchical ring structures with numerous “hot spots” for most efficient Raman enhancement. Raman measurements of probe molecules of rhodamine 6G and methylene blue reached the largest signal enhancement of 106 by the resonance effects. PMID:29425119

Silver Eco-Solvent Ink for Reactive Printing of Polychromatic SERS and SPR Substrates.

PubMed

Dustov, Mavlavi; Golovina, Diana I; Polyakov, Alexander Yu; Goldt, Anastasia E; Eliseev, Andrei A; Kolesnikov, Efim A; Sukhorukova, Irina V; Shtansky, Dmitry V; Grünert, Wolfgang; Grigorieva, Anastasia V

2018-02-09

A new reactive ink based on a silver citrate complex is proposed for a photochemical route to surface-enhanced Raman spectroscopy active substrates with controllable extinction spectra. The drop-cast test of the ink reveals homogeneous nucleation of silver and colloid particle growth originating directly from photochemical in situ reduction in droplets, while the following evaporation of the deposited ink produces small nano- and micron-size particles. The prepared nanostructures and substrates were accurately characterized by electron microscopy methods and optical extinction spectroscopy. Varying the duration of UV irradiation allows tuning the morphology of individual silver nanoparticles forming hierarchical ring structures with numerous "hot spots" for most efficient Raman enhancement. Raman measurements of probe molecules of rhodamine 6G and methylene blue reached the largest signal enhancement of 10⁶ by the resonance effects.

Thermal, optical and vibrational studies of tyrosine doped LaF3:Ce nanoparticles for bioimaging and biotagging

NASA Astrophysics Data System (ADS)

Singh, Amit T.

2018-05-01

Upconversion quantum dots of tyrosine doped LaF3:Ce nanoparticles have been synthesized by wet chemical route. The thermal studies (TGA/DTA) confirm the crystallinity and stability of different phases of synthesized nanoparticles. The UV-Visible spectra show multiple absorption edges at 215.60 nm and 243.10 nm indicating quantum dot nature of the synthesized nanoparticles. The PL spectra showed upconversion with sharp emission peak at 615 nm (red colour). The FT-RAMAN spectra of the synthesized nanoparticles show the modification of the surface of the nanoparticles in the form of functional groups and skeletal groups. Upconversion nature of the synthesized nanoparticles indicates their potential application in bioimaging and biotagging.

Thermal stability, structural features, and B-to-Z transition in DNA tetraloop hairpins as determined by optical spectroscopy in d(CG)(3)T(4)(CG)(3) and d(CG)(3)A(4)(CG)(3) oligodeoxynucleotides.

PubMed

Hernández, Belén; Baumruk, Vladimir; Gouyette, Catherine; Ghomi, Mahmoud

2005-05-01

NMR and CD data have previously shown the formation of the T(4) tetraloop hairpin in aqueous solutions, as well as the possibility of the B-to-Z transition in its stem in high salt concentration conditions. It has been shown that the stem B-to-Z transition in T(4) hairpins leads to S (south)- to N (north)-type conformational changes in the loop sugars, as well as anti to syn orientations in the loop bases. In this article, we have compared by means of UV absorption, CD, Raman, and Fourier transform infrared (FTIR), the thermodynamic and structural properties of the T(4) and A(4) tetraloop hairpins formed in 5'-d(CGCGCG-TTTT-CGCGCG)-3' and 5'-d(CGCGCG-AAAA-CGCGCG)-3', respectively. In presence of 5M NaClO(4), a complete B-to-Z transition of the stems is first proved by CD spectra. UV melting profiles are consistent with a higher thermal stability of the T(4) hairpin compared to the A(4) hairpin. Order-to-disorder transition of both hairpins has also been analyzed by means of Raman spectra recorded as a function of temperature. A clear Z-to-B transition of the stem has been confirmed in the T(4) hairpin, and not in the A(4) hairpin. With a right-handed stem, Raman and FTIR spectra have confirmed the C2'-endo/anti conformation for all the T(4) loop nucleosides. With a left-handed stem, a part of the T(4) loop sugars adopt a N-type (C3'-endo) conformation, and the C3'-endo/syn conformation seems to be the preferred one for the dA residues involved in the A(4) tetraloop.

FT-IR, FT-Raman, NMR and UV-Vis spectra and DFT calculations of 5-bromo-2-ethoxyphenylboronic acid (monomer and dimer structures)

NASA Astrophysics Data System (ADS)

Sas, E. B.; Kose, E.; Kurt, M.; Karabacak, M.

2015-02-01

In this study, the Fourier Transform Infrared (FT-IR) and Fourier Transform Raman (FT-Raman) spectra of 5-bromo-2-ethoxyphenylboronic acid (5Br2EPBA) are recorded in the solid phase in the region 4000-400 cm-1 and 3500-10 cm-1, respectively. The 1H, 13C and DEPT nuclear magnetic resonance (NMR) spectra are recorded in DMSO solution. The UV-Vis absorption spectrum of 5Br2EPBA is saved in the range of 200-400 nm in ethanol and water. The following theoretical calculations for monomeric and dimeric structures are supported by experimental results. The molecular geometry and vibrational frequencies in the ground state are calculated by using DFT methods with 6-31G(d,p) and 6-311G(d,p) basis sets. There are four conformers for the present molecule. The computational results diagnose the most stable conformer of 5Br2EPBA as Trans-Cis (TC) form. The complete assignments are performed on the basis of the total energy distribution (TED) of vibrational modes, calculated with scaled quantum mechanics (SQM) method in parallel quantum solutions (PQS) program. The 1H and 13C NMR chemical shifts of 5Br2EPBA molecule are calculated by using the Gauge Invariant Atomic Orbital (GIAO) method in DMSO and gas phase for monomer and dimer structures of the most stable conformer. Moreover, electronic properties, such as the HOMO and LUMO energies (by TD-DFT and CIS methods) and molecular electrostatic potential surface (MEPs) are investigated. Stability of the molecule arising from hyper-conjugative interactions, charge delocalization is analyzed using natural bond orbital (NBO) analysis. Nonlinear optical (NLO) properties and thermodynamic features are presented. All calculated results are compared with the experimental data of the title molecule. The correlation of theoretical and experimental results provides a detailed description of the structural and physicochemical properties of the title molecule.

FT-IR, FT-Raman, NMR and UV-Vis spectra and DFT calculations of 5-bromo-2-ethoxyphenylboronic acid (monomer and dimer structures).

PubMed

Sas, E B; Kose, E; Kurt, M; Karabacak, M

2015-02-25

In this study, the Fourier Transform Infrared (FT-IR) and Fourier Transform Raman (FT-Raman) spectra of 5-bromo-2-ethoxyphenylboronic acid (5Br2EPBA) are recorded in the solid phase in the region 4000-400 cm(-1) and 3500-10 cm(-1), respectively. The (1)H, (13)C and DEPT nuclear magnetic resonance (NMR) spectra are recorded in DMSO solution. The UV-Vis absorption spectrum of 5Br2EPBA is saved in the range of 200-400 nm in ethanol and water. The following theoretical calculations for monomeric and dimeric structures are supported by experimental results. The molecular geometry and vibrational frequencies in the ground state are calculated by using DFT methods with 6-31G(d,p) and 6-311G(d,p) basis sets. There are four conformers for the present molecule. The computational results diagnose the most stable conformer of 5Br2EPBA as Trans-Cis (TC) form. The complete assignments are performed on the basis of the total energy distribution (TED) of vibrational modes, calculated with scaled quantum mechanics (SQM) method in parallel quantum solutions (PQS) program. The (1)H and (13)C NMR chemical shifts of 5Br2EPBA molecule are calculated by using the Gauge Invariant Atomic Orbital (GIAO) method in DMSO and gas phase for monomer and dimer structures of the most stable conformer. Moreover, electronic properties, such as the HOMO and LUMO energies (by TD-DFT and CIS methods) and molecular electrostatic potential surface (MEPs) are investigated. Stability of the molecule arising from hyper-conjugative interactions, charge delocalization is analyzed using natural bond orbital (NBO) analysis. Nonlinear optical (NLO) properties and thermodynamic features are presented. All calculated results are compared with the experimental data of the title molecule. The correlation of theoretical and experimental results provides a detailed description of the structural and physicochemical properties of the title molecule. Copyright © 2014 Elsevier B.V. All rights reserved.

Detection of herbicide effects on pigment composition and PSII photochemistry in Helianthus annuus by Raman spectroscopy and chlorophyll a fluorescence

NASA Astrophysics Data System (ADS)

Vítek, Petr; Novotná, Kateřina; Hodaňová, Petra; Rapantová, Barbora; Klem, Karel

2017-01-01

The effects of herbicides from three mode-of-action groups - inhibitors of protoporphyrinogen oxidase (carfentrazone-ethyl), inhibitors of carotenoid biosynthesis (mesotrione, clomazone, and diflufenican), and inhibitors of acetolactate synthase (amidosulfuron) - were studied in sunflower plants (Helianthus annuus). Raman spectroscopy, chlorophyll fluorescence (ChlF) imaging, and UV screening of ChlF were combined to evaluate changes in pigment composition, photosystem II (PSII) photochemistry, and non-photochemical quenching in plant leaves 6 d after herbicide application. The Raman signals of phenolic compounds, carotenoids, and chlorophyll were evaluated and differences in their intensity ratios were observed. Strongly augmented relative content of phenolic compounds was observed in the case of amidosulfuron-treated plants, with a simultaneous decrease in the chlorophyll/carotenoid intensity ratio. The results were confirmed by in vivo measurement of flavonols using UV screening of ChlF. Herbicides from the group of carotenoid biosynthesis inhibitors significantly decreased both the maximum quantum efficiency of PSII and non-photochemical quenching as determined by ChlF. Resonance Raman imaging (mapping) data with high resolution (150,000-200,000 spectra) are presented, showing the distribution of carotenoids in H. annuus leaves treated by two of the herbicides acting as inhibitors of carotenoid biosynthesis (clomazone or diflufenican). Clear signs were observed that the treatment induced carotenoid depletion within sunflower leaves. The depletion spatial pattern registered differed depending on the type of herbicide applied.

Photoionization and Electron Transfer of Biphenyl within the Channels of Al-ZSM-5 Zeolites.

PubMed

Gener, Isabelle; Buntinx, Guy; Brémard, Claude

1999-06-14

Evidence of the photogenerated long-lived biphenyl radical and a trapped electron in the void space of aluminated nonacidic ZSM-5 zeolites has been obtained from the time-resolved UV/Vis absorption, Raman scattering, and EPR spectra. The restoration of the ground states implicates the existence of long-lived positive holes in the framework. © 1999 WILEY-VCH Verlag GmbH, Weinheim, Fed. Rep. of Germany.

Effects of UV light intensity on electrochemical wet etching of SiC for the fabrication of suspended graphene

NASA Astrophysics Data System (ADS)

O, Ryong-Sok; Takamura, Makoto; Furukawa, Kazuaki; Nagase, Masao; Hibino, Hiroki

2015-03-01

We report on the effects of UV light intensity on the photo assisted electrochemical wet etching of SiC(0001) underneath an epitaxially grown graphene for the fabrication of suspended structures. The maximum etching rate of SiC(0001) was 2.5 µm/h under UV light irradiation in 1 wt % KOH at a constant current of 0.5 mA/cm2. The successful formation of suspended structures depended on the etching rate of SiC. In the Raman spectra of the suspended structures, we did not observe a significant increase in the intensity of the D peak, which originates from defects in graphene sheets. This is most likely explained by the high quality of the single-crystalline graphene epitaxially grown on SiC.

Structural, optical and vibrational properties of Cr2O3 with ferromagnetic and antiferromagnetic order: A combined experimental and density functional theory study

NASA Astrophysics Data System (ADS)

Larbi, T.; Ouni, B.; Gantassi, A.; Doll, K.; Amlouk, M.; Manoubi, T.

2017-12-01

Chromium oxide (Cr2O3) thin films have been synthesized on glass substrates by the spray pyrolysis technique. The structural, morphological and optical properties of the sample have been studied by X-ray diffraction (XRD), Raman spectroscopy, FTIR spectroscopy, scanning probe microscopy and UV-vis spectroscopy respectively. X-ray diffraction results reveal that as deposited film is polycrystalline with a rhombohedral corundum structure and a preferential orientation of the crystallites along the (1 0 4) direction. IR and Raman spectra were recorded in the 100-900 cm-1 range and the observed modes were analysed and assigned to different normal modes of vibration. The direct optical band gap energy value calculated from the transmittance spectra of as-deposited thin film is about 3.38 eV. We employ first principles calculations based on density functional theory (DFT) with the B3LYP hybrid functional and a coupled perturbed Hartree-Fock/Kohn-Sham approach (CPHF/KS). We study the electronic structure, optimum geometry, and IR and Raman spectra of ferromagnetically and antiferromagnetically ordered Cr2O3. The computed results are consistent with the experimental measurements, and provide complete vibrational assignment, for the characterization of Cr2O3 thin film materials which can be used in photocatalysis and gas sensors.

Vibrational, UV spectra, NBO, first order hyperpolarizability and HOMO-LUMO analysis of carvedilol

NASA Astrophysics Data System (ADS)

Swarnalatha, N.; Gunasekaran, S.; Nagarajan, M.; Srinivasan, S.; Sankari, G.; Ramkumaar, G. R.

2015-02-01

In this work, we have investigated experimentally and theoretically on the molecular structure, vibrational spectra, UV spectral analysis and NBO studies of cardio-protective drug carvedilol. The FT-Raman and FT-IR spectra for carvedilol in the solid phase have been recorded in the region 4000-100 cm-1 and 4000-400 cm-1 respectively. Theoretical calculations were performed by using density functional theory (DFT) method at B3LYP/6-31G(d,p) and B3LYP/6-31++G(d,p) basis set levels. The harmonic vibrational frequencies, the optimized geometric parameters have been interpreted and compared with the reported experimental values. The complete vibrational assignments were performed on the basis of potential energy distribution (PED) of the vibrational modes. The thermodynamic properties and molecular electrostatic potential surfaces of the molecule were constructed. The electronic absorption spectrum was recorded in the region 400-200 nm and electronic properties such as HOMO and LUMO energies were calculated. The stability of the molecule arising from hyper conjugative interactions and charge delocalization have been analyzed from natural bond orbital (NBO) analysis. The first order hyperpolarizability of the title molecule was also calculated. The photo stability of carvedilol under different storage conditions were analyzed using UV-Vis spectral technique.

Experimental and theoretical spectroscopic studies of anticancer drug rosmarinic acid using HF and density functional theory.

PubMed

Mariappan, G; Sundaraganesan, N; Manoharan, S

2012-11-01

In this work, we reported a combined experimental and theoretical study on molecular structure, vibrational spectra and NBO analysis of anticancer drug of rosmarinic acid. The optimized molecular structure, atomic charges, vibrational frequencies, natural bond orbital analysis and ultraviolet-visible spectral interpretation of rosmarinic acid have been studied by performing HF and DFT/B3LYP/6-31G(d,p) level of theory. The FT-IR (solid and solution phase), FT-Raman (solid phase) spectra were recorded in the region 4000-400 and 3500-50 cm(-1), respectively. The UV-Visible absorption spectra of the compound that dissolved in ethanol were recorded in the range of 200-800 nm. The scaled wavenumbers are compared with the experimental values. The difference between the observed and scaled wavenumber values of most of the fundamentals is very small. The formation of hydrogen bond was investigated in terms of the charge density by the NBO calculations. Based on the UV spectra and TD-DFT calculations, the electronic structure and the assignments of the absorption bands were carried out. Besides, molecular electrostatic potential (MEP), frontier molecular orbitals (FMO) analysis were investigated using theoretical calculations. Copyright © 2012 Elsevier B.V. All rights reserved.

Optimization of advanced Wiener estimation methods for Raman reconstruction from narrow-band measurements in the presence of fluorescence background

PubMed Central

Chen, Shuo; Ong, Yi Hong; Lin, Xiaoqian; Liu, Quan

2015-01-01

Raman spectroscopy has shown great potential in biomedical applications. However, intrinsically weak Raman signals cause slow data acquisition especially in Raman imaging. This problem can be overcome by narrow-band Raman imaging followed by spectral reconstruction. Our previous study has shown that Raman spectra free of fluorescence background can be reconstructed from narrow-band Raman measurements using traditional Wiener estimation. However, fluorescence-free Raman spectra are only available from those sophisticated Raman setups capable of fluorescence suppression. The reconstruction of Raman spectra with fluorescence background from narrow-band measurements is much more challenging due to the significant variation in fluorescence background. In this study, two advanced Wiener estimation methods, i.e. modified Wiener estimation and sequential weighted Wiener estimation, were optimized to achieve this goal. Both spontaneous Raman spectra and surface enhanced Raman spectra were evaluated. Compared with traditional Wiener estimation, two advanced methods showed significant improvement in the reconstruction of spontaneous Raman spectra. However, traditional Wiener estimation can work as effectively as the advanced methods for SERS spectra but much faster. The wise selection of these methods would enable accurate Raman reconstruction in a simple Raman setup without the function of fluorescence suppression for fast Raman imaging. PMID:26203387

Wavelength Selection For Laser Raman Spectroscopy of Putative Martian Habitats and Biomolecules

NASA Astrophysics Data System (ADS)

Wynn-Williams, D. D.; Newton, E. M. G.; Edwards, H. G. M.

Pigments are key potential biomarkers for any former life on Mars because of the selective pressure of solar radiation on any biological system that could have evolved at its surface. We have found that the near -Infrared laser Raman spectrometer available to use was eminently suitable for diagnostic analysis of pigments because of their minimal autofluorescence at its 1064 nm excitation wav elength. However, we have now evaluated a diverse range of excitation wavelengths to confirm this choice, to ensure that we have the best technique to seek for pigments and their derivatives from any former surface life on Mars. The Raman is weak relative to fluorescence, which results in elevated baseline and concurrent swamping of Raman bands. We confirm the molecular information available from near-IR FT Raman spectra for two highly pigmented UV-tolerant epilithic Antarctic lichens (Acarospora chlorop hana and Caloplaca saxicola) from Victoria Land, a whole endolithic microbial community and endolithic cyanobacterium Chroococcidiopsis from within translucent sandstone of the Trans -Antarctic Mountains, and the free- living cyanobacterium Nostoc commune from Alexander Island, Antarctic Peninsula region. We also show that much of the information we require on biomolecules is not evident from lasers of shorter wavelengths. A miniature 1064 nm Raman spectrometer with an In-Ga-As detector sensitive to IR is being developed by Montana State University (now existing as a prototype) as the prime instrument for a proposed UK-led Mars rover mission (Vanguard). Preliminary spectra from this system confirm the suitability of the near-IR laser.

Damage induced in garnets by heavy ion irradiations: a study by optical spectroscopies

NASA Astrophysics Data System (ADS)

Costantini, Jean-Marc; Miro, Sandrine; Lelong, Gérald; Guillaumet, Maxime; Toulemonde, Marcel

2018-02-01

The damage induced by heavy-ion irradiation has been studied in yttrium iron garnet (Y3Fe5O12 or YIG) films, doped with Ca, Tb and Tm, grown by liquid-phase epitaxy on gadolinium gallium garnet (Gd3Ga5O12 or GGG) substrates. Irradiations of doped-YIG epitaxial films and GGG substrates with 36-MeV 183W and 12-MeV 197Au ions were applied for fluences between 1 × 1013 and 3 × 1015 cm-2 near room temperature. The radiation damage was monitored by micro-Raman spectroscopy and UV-visible optical absorption spectroscopy. Raman spectra revealed that amorphisation was achieved in YIG for both ions, whereas a high lattice disorder was induced in GGG without reaching amorphisation for the Au ion irradiation. Raman spectra also showed that a major damage of the tetrahedral sites was induced in GGG, as previously found for YIG. It is concluded that with such ions reaching the stopping power threshold of track formation in YIG and GGG the observed rate of amorphisation may result from a combination of electronic and nuclear energy losses as calculated using the unified thermal spike model.

Detecting Kerogen as a Biosignature Using Co-located UV Time-Gated Raman and Fuorescence Spectroscopy

NASA Astrophysics Data System (ADS)

Shkolyar, S.; Eshelman, E.; Farmer, J. D.; Hamilton, D.; Daly, M. G.; Youngbull, C.

2017-12-01

The Mars 2020 mission will analyze samples in situ and identify any that could have preserved biosignatures in ancient habitable environments for later return to Earth. Highest-priority targeted samples include aqueously formed sedimentary lithologies containing fossil biosignatures as aromatic carbon (kerogen). In this study, we analyze non-extracted, naturally preserved kerogen in a diverse suite of realistic Mars analogs using combined UV excitation time-gated (UV-TG) Raman and laser-induced fluorescence spectroscopy. We interrogated kerogen and its host matrix in samples to: (1) explore the capabilities of UV-TG Raman and fluorescence spectroscopy for detecting kerogen in high-priority targets in the search for a Martian fossil record; (2) assess the effectiveness of time-gating and UV laser wavelength in reducing fluorescence; and (3) identify sample-specific issues which could challenge rover-based identifications of kerogen using UV-TG Raman spectroscopy. We found that ungated UV Raman is suited to identify diagnostic kerogen Raman bands without interfering fluorescence and that fluorescence features indicating kerogen are detectable. These data highlight the value of using both co-located Raman and fluorescence data sets together to strengthen the confidence of kerogen detection as a potential biosignature and are obtainable by SHERLOC onboard Mars 2020.

Theoretical Studies on Heavy Metal Sulfides in Solution

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tossell, John A.

2007-10-31

'Calculating the stabilities, Raman and UV spectra and acidities of As sulfides in aqueous solution', J. A. Tossell, M. D. Zimmermann and G. R. Helz. Some of the Raman spectra obtained by reacting aqueous As(OH)3 with aqueous bisulfide are shown, taken from Wood, et al. (2002). To interpret these spectra we have carried out an extensive series of calculations, detailed for the case of AsS(SH){sub 2}{sup -} in Table 1 below. By employing state of the art quantum chemical techniques to determine gas-phase harmonic and anharmonic frequencies and solution phase corrections we can accurately match features in the experimental spectrummore » shown in the top figure. The AsS(SH){sub 2}{sup -}...22 H{sub 2}O nanocluster employed is shown in the lower figure. For this species we have calculated the equilibrium structure and the harmonic vibrational spectrum at the CBSB7 B3LYP level. For the free solute species AsS(SH){sub 2}{sup -} we have carried out a whole series of calculations, evaluating harmonic and anharmonic vibrational frequencies at a number of different quantum mechanical levels. In the spectra below, Fig. 3 and Fig. 5 from Wood, et al. (2002), the features around 700-800 cm{sup -1} are attributed to As-O stretches and those around 350-450 cm{sup -1} to As-S stretches. In the nanocluster an isolated vibrational feature is observed at 425 cm{sup -1}, an As=S stretch, close to the value (415 cm{sup -1}) determined by Wood, et al. (2002). Analysis of the calculated frequencies for AsS(SH){sub 2}{sup -} within a polarizable continuum model yields a similar result. Taking the highest level harmonic results, obtained from a CCSD calculation, and adding anharmonic and PCM corrections at the B3LYP level (designated (3) + (5) - (1) in Table 1) gives a frequency for the intense high frequency As=S stretch within 15 cm{sup -1} of experiment. Although there is still interesting work to be done on the stabilities and the Raman and UV spectra of As sulfides, most of the basic concepts have been worked out and we are therefore proposing to move to a new area, that of humic acids (while continuing our studies complexes formed by As oxides and sulfides, now applied to functional groups present in humic acids).« less

Contract W911NF-12-C-0102 (Advanced Diamond Technologies, Inc.)

DTIC Science & Technology

2013-06-24

resistivity, residual stress and Raman spectra measurement is finished. Raman spectra shows basically regular nanocrystalline diamond signature as expected...diamond films including thickness, resistivity, residual stress and Raman spectra measurement is finished. Raman spectra shows basically regular...15743 WF600B05 3000 0.02 0.03 0.0018 4 Fig. 2 Raman spectra (λ=532 nm) of (a) all diamond with different doping level and (b) diamond only with

Experimental and theoretical quantum chemical investigations of 8-hydroxy-5-nitroquinoline.

PubMed

Arjunan, V; Balamourougane, P S; Kalaivani, M; Raj, Arushma; Mohan, S

2012-10-01

The FT-IR and FT-Raman spectra of 8-hydroxy-5-nitroquinoline have been recorded in the regions 4000-400 and 4000-100 cm(-1), respectively. The spectra were interpreted in terms of fundamentals modes, combination and overtone bands. The normal coordinate analysis was carried out to confirm the precision of the assignments. The structure of the compound was optimised and the structural characteristics were determined by density functional theory (DFT) using B3LYP method with 6-31G(**), 6-311++G(**) and cc-pVDZ basis sets. The vibrational frequencies were calculated in all these methods and were compared with the experimental frequencies which yield good agreement between observed and calculated frequencies. The infrared and Raman spectra were also predicted from the calculated intensities. (1)H and (13)C NMR spectra were recorded and (1)H and (13)C nuclear magnetic resonance chemical shifts of the molecule were calculated using the gauge independent atomic orbital (GIAO) method. UV-Visible spectrum of the compound was recorded and the electronic properties HOMO and LUMO energies were measured by time-dependent TD-DFT approach. The influences of the nitro and hydroxy groups on the skeletal modes and on the proton chemical shifts have been investigated. Copyright © 2012 Elsevier B.V. All rights reserved.

Facile and fast synthesis of SnS2 nanoparticles by pulsed laser ablation in liquid

NASA Astrophysics Data System (ADS)

Johny, J.; Sepulveda-Guzman, S.; Krishnan, B.; Avellaneda, D.; Shaji, S.

2018-03-01

Nanoparticles (NPs) of tin disulfide (SnS2) were synthesized using pulsed laser ablation in liquid (PLAL) technique. Effects of different liquid media and ablation wavelengths on the morphology and optical properties of the nanoparticles were studied. Nd: YAG laser wavelengths of 532 nm and 1064 nm (frequency 10 Hz and pulse width 10 ns) were used to irradiate SnS2 target immersed in liquid for the synthesis of SnS2 nanoparticles. Here PLAL was a fast synthesis technique, the ablation was only for 30 s. Transmission electron microscopy (TEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), Raman spectroscopy, UV-vis absorption spectroscopy and photoluminescence spectroscopy were used to characterize the SnS2 NPs. TEM images showed that the liquid medium and laser wavelength influence the morphology of the NPs. SAED patterns and high resolution TEM (HRTEM) images confirmed the crystallinity of the particles. XRD and XPS analyses confirmed that SnS2 NPs were having exact crystalline structure and chemical states as that of the target. Raman analysis also supported the results obtained by XRD and XPS. Optical band gaps of the nanocolloids evaluated from their UV-vis absorption spectra were 2.4-3.05 eV. SnS2 NPs were having luminescence spectra in the blue-green region irrespective of the liquid media and ablation wavelength.

Defects induced in cerium dioxide single crystals by electron irradiation

DOE PAGES

Costantini, Jean-Marc; Miro, Sandrine; Touati, Nadia; ...

2018-01-12

In this work, Micro-Raman spectroscopy, X-band electron paramagnetic resonance (EPR) spectroscopy, and UV-visible optical absorption spectroscopy were used to study the damage production in cerium dioxide (CeO 2) single crystals by electron irradiation for three energies (1.0, 1.4, and 2.5 MeV). The Raman-active T 2g peak was left unchanged after 2.5-MeV electron irradiation at a high fluence. This shows that no structural modifications occurred for the cubic fluorite structure. UV-visible optical absorption spectra exhibited a characteristic sub band-gap tail for 1.4-MeV and 2.5-MeV energies, but not for 1.0 MeV. Narrow EPR lines were recorded near liquid-helium temperature after 2.5-MeV electronmore » irradiation; whereas no such signal was found for the virgin un-irradiated crystal or after 1.0-MeV irradiation for the same fluence. The angular variation of these lines in the {111} plane revealed a weak g-factor anisotropy assigned to Ce 3+ ions (with the 4f 1 configuration) in a high-symmetry local environment. Finally, it is concluded that Ce 3+ ions may be produced by a reduction resulting from the displacement damage process. However, no evidence of F + or F 0 center or hole center formation due to irradiation was found from the present EPR and optical absorption spectra.« less

Defects induced in cerium dioxide single crystals by electron irradiation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Costantini, Jean-Marc; Miro, Sandrine; Touati, Nadia

In this work, Micro-Raman spectroscopy, X-band electron paramagnetic resonance (EPR) spectroscopy, and UV-visible optical absorption spectroscopy were used to study the damage production in cerium dioxide (CeO 2) single crystals by electron irradiation for three energies (1.0, 1.4, and 2.5 MeV). The Raman-active T 2g peak was left unchanged after 2.5-MeV electron irradiation at a high fluence. This shows that no structural modifications occurred for the cubic fluorite structure. UV-visible optical absorption spectra exhibited a characteristic sub band-gap tail for 1.4-MeV and 2.5-MeV energies, but not for 1.0 MeV. Narrow EPR lines were recorded near liquid-helium temperature after 2.5-MeV electronmore » irradiation; whereas no such signal was found for the virgin un-irradiated crystal or after 1.0-MeV irradiation for the same fluence. The angular variation of these lines in the {111} plane revealed a weak g-factor anisotropy assigned to Ce 3+ ions (with the 4f 1 configuration) in a high-symmetry local environment. Finally, it is concluded that Ce 3+ ions may be produced by a reduction resulting from the displacement damage process. However, no evidence of F + or F 0 center or hole center formation due to irradiation was found from the present EPR and optical absorption spectra.« less

Heparin Assisted Photochemical Synthesis of Gold Nanoparticles and Their Performance as SERS Substrates

PubMed Central

Rodríguez-Torres, Maria del Pilar; Díaz-Torres, Luis Armando; Romero-Servin, Sergio

2014-01-01

Reactive and pharmaceutical-grade heparins were used as biologically compatible reducing and stabilizing agents to photochemically synthesize colloidal gold nanoparticles. Aggregates and anisotropic shapes were obtained photochemically under UV black-light lamp irradiation (λ = 366 nm). Heparin-functionalized gold nanoparticles were characterized by Scanning Electron Microscopy and UV-Vis spectroscopy. The negatively charged colloids were used for the Surface Enhanced Raman Spectroscopy (SERS) analysis of differently charged analytes (dyes). Measurements of pH were taken to inspect how the acidity of the medium affects the colloid-analyte interaction. SERS spectra were taken by mixing the dyes and the colloidal solutions without further functionalization or addition of any aggregating agent. PMID:25342319

Electrical and Optical Properties of Nanocrystalline A8ZnNb6O24 (A = Ba, Sr, Ca, Mg) Ceramics

NASA Astrophysics Data System (ADS)

John, Fergy; Thomas, Jijimon K.; Jacob, John; Solomon, Sam

2017-08-01

Nanoparticles of A8ZnNb6O24 (A = Ba, Sr, Ca, and Mg, abbreviated as BZN, SZN, CZN, and MZN) have been synthesized by an auto-igniting combustion technique and their structural and optical properties characterized. The phase purity, crystal structure, and particle size of the prepared nanopowders were examined by x-ray diffraction (XRD) analysis and transmission electron microscopy. The XRD results revealed that all the samples crystallized with hexagonal perovskite structure in space group P6 3 cm. The Fourier-transform infrared and Raman (FT-Raman) spectra of the samples were investigated in detail. The ultraviolet-visible (UV-Vis) absorption spectra of the samples were also recorded and their optical bandgap energy values calculated. The nanopowders synthesized by the combustion technique were sintered to 95% of theoretical density at temperature of 1250°C for 2 h. The surface morphology of the sintered pellets was studied by scanning electron microscopy. The photoluminescence spectra of the samples showed intense emission in the blue-green region. Complex impedance analysis was used to determine the grain and grain boundary effects on the dielectric behavior of the ceramics.

Evaluation of the structural, electronic, topological and vibrational properties of N-(3,4-dimethoxybenzyl)-hexadecanamide isolated from Maca (Lepidium meyenii) using different spectroscopic techniques

NASA Astrophysics Data System (ADS)

Chain, Fernando; Iramain, Maximiliano Alberto; Grau, Alfredo; Catalán, César A. N.; Brandán, Silvia Antonia

2017-01-01

N-(3,4-dimethoxybenzyl)-hexadecanamide (DMH) was characterized by using Fourier Transform infrared (FT-IR) and Raman (FT-Raman), Ultraviolet- Visible (UV-Visible) and Hydrogen and Carbon Nuclear Magnetic Resonance (1H and 13C NMR) spectroscopies. The structural, electronic, topological and vibrational properties were evaluated in gas phase and in n-hexane employing ONIOM and self-consistent force field (SCRF) calculations. The atomic charges, molecular electrostatic potentials, stabilization energies and topological properties of DMH were analyzed and compared with those calculated for N-(3,4-dimethoxybenzyl)-acetamide (DMA) in order to evaluate the effect of the side chain on the properties of DMH. The reactivity and behavior of this alkamide were predicted by using the gap energies and some descriptors. Force fields and the corresponding force constants were reported for DMA only in gas phase and n-hexane due to the high number of vibration normal modes showed by DMH, while the complete vibrational assignments are presented for DMA and both forms of DMH. The comparisons between the experimental FTIR, FT-Raman, UV-Visible and 1H and 13C NMR spectra with the corresponding theoretical ones showed a reasonable concordance.

Thermal characteristics, Raman spectra, optical and structural properties of TiO2-Bi2O3-B2O3-TeO2 glasses

NASA Astrophysics Data System (ADS)

Gupta, Nupur; Khanna, Atul; Gonzàlez, Fernando; Iordanova, Reni

2017-05-01

Tellurite and borotellurite glasses containing Bi2O3 and TiO2 were prepared and structure-property correlations were carried out by density measurements, X-ray Diffraction (XRD), Differential Scanning Calorimetry (DSC), Raman and UV-visible spectroscopy. Titanium tellurite glasses require high melt-cooling rates and were fabricated by splat quenching. On adding B2O3, the glass forming ability (GFA) enhances, and glasses could be synthesized at lower quenching rates. The density of glasses shows a direct correlation with molecular mass of the constituents. UV-visible studies were used to determine the optical band gap and refractive index. Raman studies found that the co-ordination number of tellurium ions with oxygen (NTe-O) decreases with the increase in B2O3 as well as Bi2O3 content while, TiO2 produce only a small decrease in NTe-O, which explains the lower GFA of titanium tellurite glasses that do not contain Bi2O3 and B2O3. DSC studies show that the glass transition temperature (Tg) increases with B2O3 and TiO2 concentrations and that Tg correlates well with bond enthalpy of the metal oxides.

Synthesis and Characterization of Silicon Nanowires by Electroless Etching

NASA Astrophysics Data System (ADS)

Bhujel, Rabina; Rizal, Umesh; Agarwal, Amit; Swain, Bhabani S.; Swain, Bibhu P.

2018-02-01

Silicon nanowires (SiNWs) were synthesized by two-step electroless etching of p-type Si (100) wafer and characterized by field emission scanning electron microscopy, UV-Vis spectroscopy, x-ray photoelectron spectroscopy, Fourier transform infrared spectroscopy and Raman spectroscopy. The vibrational signature at 1108 and 2087 cm-1 confirmed SiNWs were passivated by both oxygen and hydrogen atoms. Raman peak at 517 cm-1 indicated crystalline SiNWs with tailing toward redshift due to Fano effect. The Si(2p) and Si(2s) core orbital spectra of SiNWs were found at 99.8 and 150.5 eV, respectively. Moreover, the reflection of SiNWs is minimized to 1 to 5% in the 650-nm wavelength.

Investigation of Skin Cancers Using MicroRaman Spectroscopy

NASA Astrophysics Data System (ADS)

Short, M. A.; Chen, X. K.; Zeng, H.; Ajlan, A. A.; McLean, D. I.; Hui, H.

2004-03-01

We have measured the Raman spectra of skin cancers, including melanoma and basal cell carcinoma, using a confocal microRaman spectrograph. In an attempt to identify the origin of the observed Raman modes, we investigated the spectra obtained from different locations of the samples, compared the observed spectra with those measured from normal human skin and pig skin, and studied the polarization dependence of the spectra. In addition, we will discuss the effects of fluorescence in the measurement of Raman spectra of skin samples.

Raman scattering by H2 and N2 in the atmospheres of exoplanets

NASA Astrophysics Data System (ADS)

Oklopcic, Antonija; Hirata, Christopher M.; Heng, Kevin

2016-06-01

Rayleigh scattering is an important source of opacity in the atmospheres of exoplanets at short optical and near-UV wavelengths. Raman scattering is an inelastic process related to Rayleigh scattering, but with a weaker cross section. We analyze the signatures of Raman scattering imprinted in the reflected light and the geometric albedo of exoplanets. Raman scattering causes filling-in of absorption lines in the incident spectrum, thus producing sharp enhancements in the geometric albedo. It also shifts the wavelengths of spectral features in the reflected light causing the Raman ghost lines. Observing the albedo enhancements could be used to measure the column density of the scattering molecule and provide constrains on the presence of clouds and hazes in the atmosphere. Observing the Raman ghost lines could be used to spectroscopically identify the main scatterer in the atmosphere -- molecules like H2 or N2 which do not show prominent spectral signatures in the optical wavelength range. If detected, ghost lines could also provide information about the temperature of the atmosphere. Here we present how these signatures of Raman scattering in hydrogen- and nitrogen-dominated atmospheres can be used as probes of atmospheric pressure, temperature and composition. We analyze the feasibility of detecting these features in the albedo spectra of nearby exoplanets with the existing and future observational facilities.

FT-IR, FT-Raman, NMR studies and ab initio-HF, DFT-B3LYP vibrational analysis of 4-chloro-2-fluoroaniline

NASA Astrophysics Data System (ADS)

Arivazhagan, M.; Anitha Rexalin, D.

2012-10-01

The Fourier transform infrared (FT-IR) and Fourier transform Raman (FT-Raman) spectra of 4-chloro-2-fluoroaniline (CFA) have been recorded and analyzed. The equilibrium geometry, bonding features and harmonic vibrational frequencies have been investigated with the help of ab initio and density functional theory (DFT) methods. The assignments of the vibrational spectra have been carried out with the help of normal coordinate analysis (NCA) following the scaled quantum mechanical force field methodology. The 1H and 13C nuclear magnetic resonance (NMR) chemical shifts of the molecule are calculated by the Gauge including atomic orbital (GIAO) method. The first order hyperpolarizability (β0) of this novel molecular system and related properties (β, α0 and Δα) of CFA are calculated using B3LYP/6-311++G(d,p) and HF/6-311++G(d,p) methods on the finite-field approach. The calculated results also show that the CFA molecule might have microscopic nonlinear optical (NLO) behavior with non-zero values. Stability of the molecule arising from hyper conjugative interactions, charge delocalization has been analyzed using natural bond orbital (NBO) analysis. The result confirms the occurrence of intramolecular charge transfer (ICT) within the molecule. The HOMO-LUMO energies UV-vis spectral analysis and MEP are performed by B3LYP/6-311++G(d,p) approach. A detailed interpretation of the infrared and Raman spectra of CFA is also reported based on total energy distribution (TED). The difference between the observed and scaled wave number values of the most of the fundamentals is very small.

FT-IR, FT-Raman, NMR studies and ab initio-HF, DFT-B3LYP vibrational analysis of 4-chloro-2-fluoroaniline.

PubMed

Arivazhagan, M; Anitha Rexalin, D

2012-10-01

The Fourier transform infrared (FT-IR) and Fourier transform Raman (FT-Raman) spectra of 4-chloro-2-fluoroaniline (CFA) have been recorded and analyzed. The equilibrium geometry, bonding features and harmonic vibrational frequencies have been investigated with the help of ab initio and density functional theory (DFT) methods. The assignments of the vibrational spectra have been carried out with the help of normal coordinate analysis (NCA) following the scaled quantum mechanical force field methodology. The (1)H and (13)C nuclear magnetic resonance (NMR) chemical shifts of the molecule are calculated by the Gauge including atomic orbital (GIAO) method. The first order hyperpolarizability (β(0)) of this novel molecular system and related properties (β, α(0) and Δα) of CFA are calculated using B3LYP/6-311++G(d,p) and HF/6-311++G(d,p) methods on the finite-field approach. The calculated results also show that the CFA molecule might have microscopic nonlinear optical (NLO) behavior with non-zero values. Stability of the molecule arising from hyper conjugative interactions, charge delocalization has been analyzed using natural bond orbital (NBO) analysis. The result confirms the occurrence of intramolecular charge transfer (ICT) within the molecule. The HOMO-LUMO energies UV-vis spectral analysis and MEP are performed by B3LYP/6-311++G(d,p) approach. A detailed interpretation of the infrared and Raman spectra of CFA is also reported based on total energy distribution (TED). The difference between the observed and scaled wave number values of the most of the fundamentals is very small. Copyright © 2012 Elsevier B.V. All rights reserved.

Vertical growth of ZnO nanorods on ZnO seeded FTO substrate for dye sensitized solar cells

NASA Astrophysics Data System (ADS)

Marimuthu, T.; Anandhan, N.

2018-04-01

Zinc oxide (ZnO) nanorods (NRs) were electrochemically grown on fluorine doped tin oxide (FTO) and ZnO seeded FTO substrates. X-ray diffraction (XRD) patterns, Raman spectra and photoluminescence (PL) spectra reveal that the hexagonal wurtzite structured ZnO grown on a seeded FTO substrate has a high crystallinity, crystal quality and less atomic defects. Felid emission scanning electron microscope (FE-SEM) images display a high growth density of NRs grown on seeded FTO substrate compared to NRs grown on FTO substrate. The efficiency of the DSSCs based on NRs grown on FTO and seeded FTO substrates is 0.85 and 1.52 %, respectively. UV-Vis absorption spectra and electrochemical impedance spectra depict that the NRs grown on seeded FTO photoanode have higher dye absorption and charge recombination resistance than that of the NRs grown on FTO substrate.

Conformational analysis, spectroscopic study (FT-IR, FT-Raman, UV, 1H and 13C NMR), molecular orbital energy and NLO properties of 5-iodosalicylic acid

NASA Astrophysics Data System (ADS)

Karaca, Caglar; Atac, Ahmet; Karabacak, Mehmet

2015-02-01

In this study, 5-iodosalicylic acid (5-ISA, C7H5IO3) is structurally characterized by FT-IR, FT-Raman, NMR and UV spectroscopies. There are eight conformers, Cn, n = 1-8 for this molecule therefore the molecular geometry for these eight conformers in the ground state are calculated by using the ab-initio density functional theory (DFT) B3LYP method approach with the aug-cc-pVDZ-PP basis set for iodine and the aug-cc-pVDZ basis set for the other elements. The computational results identified that the most stable conformer of 5-ISA is the C1 form. The vibrational spectra are calculated DFT method invoking the same basis sets and fundamental vibrations are assigned on the basis of the total energy distribution (TED) of the vibrational modes, calculated with scaled quantum mechanics (SQM) method with PQS program. Total density of state (TDOS) and partial density of state (PDOS) and also overlap population density of state (COOP or OPDOS) diagrams analysis for C1 conformer were calculated using the same method. The energy and oscillator strength are calculated by time-dependent density functional theory (TD-DFT) results complement with the experimental findings. Besides, charge transfer occurring in the molecule between HOMO and LUMO energies, frontier energy gap, molecular electrostatic potential (MEP) are calculated and presented. The NMR chemical shifts (1H and 13C) spectra are recorded and calculated using the gauge independent atomic orbital (GIAO) method. Mulliken atomic charges of the title molecule are also calculated, interpreted and compared with salicylic acid. The optimized bond lengths, bond angles and calculated NMR and UV, vibrational wavenumbers showed the best agreement with the experimental results.

Evaluation of the structural properties of powerful pesticide dieldrin in different media and their complete vibrational assignment

NASA Astrophysics Data System (ADS)

Castillo, María V.; Iramain, Maximiliano A.; Davies, Lilian; Manzur, María E.; Brandán, Silvia Antonia

2018-02-01

Dieldrin was characterized by using Fourier Transform infrared (FT-IR) and Raman (FT-Raman), Ultraviolet-Visible (UV-Visible) spectroscopies. The structural and vibrational properties for dieldrin in gas phase and in aqueous solution were computed combining those experimental spectra with hybrids B3LYP and WB97XD calculations by using the 6-31G* and 6-311++G** basis sets. Here, the experimental available Hydrogen and Carbon Nuclear Magnetic Resonance (1H and 13C NMR) for dieldrin were also used and compared with those predicted by calculations. The B3LYP/6-311++G** method generates the most stable structures while the results have demonstrated certain dependence of the volume and dipole moment values with the method, size of the basis set and, with the studied media. The lower solvation energy for dieldrin (-32.94 kJ/mol) is observed for the higher contraction volume (-2.4 Å3) by using the B3LYP/6-31G* method. The NBO studies suggest a high stability of dieldrin in gas phase by using the WB97XD/6-31G* method due to the n→π* and n*→π* interactions while the AIM analyses support this high stability by the C18⋯H26 and C14⋯O7 contacts. The different topological properties observed in the R5 ring suggest that probably this ring plays a very important role in the toxics properties of dieldrin. The frontier orbitals show that when dieldrin is compared with other toxics substances the reactivity increases in the following order: CO < STX < dieldrin < C6Cl6

Effects of different levels of vitamin C on UV radiation-induced DNA damage

NASA Astrophysics Data System (ADS)

Zhou, Dianfeng; Heng, Hang; Ji, Kang; Ke, Weizhong

2005-05-01

The Raman spectra of DNA in different levels of vitamin C with 10- and 30-min ultraviolet (UV) radiations were reported. The intensity of UV radiation was 18.68 W/m2. The experimental results proved that vitamin C could alone prevent UV radiation from damaging DNA, but the effects depended on the concentration of vitamin C. When the concentration of vitamin C was about 0.08-0.4 mmol/L, vitamin C decreased UV radiation-induced DNA's damage. When the concentration of vitamin C exceeded 0.4 mmol/L, vitamin C accelerated DNA's damage instead. Maybe the reason is that when DNA in aqueous solution is radiated by UV, free radicals come into being, and vitamin C can scavenge free radicals, so vitamin C in lower concentration can protect DNA. The quantity of free radicals is finite, when vitamin C is superfluous, free radicals have been scavenged absolutely and vitamin C is residual. Vitamin C is a strong reductant. When the mixture of DNA and residual vitamin C is radiated by UV, vitamin C reacts with DNA. The more residual vitamin C and the longer time of UV radiation, the more DNA is damaged.

Photocatalytic oxidation of propylene on La and N codoped TiO2 nanoparticles

NASA Astrophysics Data System (ADS)

Liu, Jinfeng; Li, Haiyan; Zong, Lanlan; Li, Qiuye; Wang, Xiaodong; Zhang, Min; Yang, Jianjun

2015-02-01

Lanthanum- and nitrogen-codoped TiO2 photocatalysts was synthesized using orthorhombic nanotubes titanic acid as the precursor by a simple impregnation and subsequent calcination method. The morphology, phase structure, and properties of La- and N-codoped TiO2 were well characterized by transmission electron microscopy, X-ray diffraction, Raman spectra, X-ray photoelectron spectroscopy, and UV-Vis diffuse reflectance spectra. The La-/N-codoped TiO2 showed excellent photoactivity of propylene oxidation compared with the single-doped TiO2 and La-/N-codoped P25 TiO2 nanoparticles under visible light irradiation. The origin of the enhancement of the visible light-responsive photocatalytic activity was discussed in detail.

Optical, Fluorescence with quantum analysis of hydrazine (1, 3- Dinitro Phenyl) by DFT and Ab initio approach

NASA Astrophysics Data System (ADS)

Cecily Mary Glory, D.; Sambathkumar, K.; Madivanane, R.; Velmurugan, G.; Gayathri, R.; Nithiyanantham, S.; Venkatachalapathy, M.; Rajkamal, N.

2018-07-01

Experimental and computational study of molecular structure, vibrational and UV-spectral analysis of Hydrazine (1, 3- Dinitrophenyl) (HDP) derivatives. The crystal was grown by slow cooling method and the crystalline perfection of single crystals was evaluated by high resolution X-ray diffractometry (HRXRD) using a multicrystal X-ray diffractometer. Fluorescence, FT-IR and FT-Raman spectra of HDP crystal were recorded. The assignments of the vibrational spectra have been carried out with the help of normal co-ordinate analysis (NCA) followed by scaled quantum force field methodology (SQMFF). NMR studies have confirmed respectively the crystal structure and functional groups of the grown crystal. The energy and oscillator strength calculated by Time-Dependent Density Functional Theory (TD-DFT) result complements the experimental findings. The calculated MESP, UV, HOMO-LUMO energies show that charge transfer done within the molecule. And various thermodynamic parameters are studied. Fukui determines the local reactive site of electrophilic, nucleophilic, descriptor.

Incoherent and Laser Photodeposition on Thin Films.

DTIC Science & Technology

1980-09-01

wavelength, an incoherent Oriel Mercury arc lamp (model HR-l) with a 1000 watt u-v out- a put centered at 2537A was used. This source emitted o down...Royal Society of London Series A, 156: 108-129 (1936). 18. Gutowsky, H.S.. "The Infra-Red and Raman Spectra of Dimethyl Mercury and Dimethyl Zinc," The...II), - Cadmium (II) and - Mercury (II)," Spectrochimica Acta, 33A: 669-680 (1977). 20. Bakke, A.M.W.. "A Molecular Structure Study of Dimethylmercury

Spectroscopic studies of interactions between dyes and model molecules of Alzheimer's disease

NASA Astrophysics Data System (ADS)

Elhaddaoui, A.; Delacourte, A.; Turrell, S.

1993-06-01

Raman, FTIR, fluorescence, and UV-visible spectra are used to study interactions between amuloid-labelling dyes and poly-L-lysine and bovine insulin, two proteins which play the role of models of (beta) amyloid of Alzheimers disease. It is found that though the (beta) conformation of the peptide is not essential, it helps to encourage binding which appears to be stable and specific in nature, involving SO3- groups of the dyes and NH2 groups of the proteins.

Structural and photocatalytic studies of hydrothermally synthesized Mn2+-TiO2 nanoparticles under UV and visible light irradiation

NASA Astrophysics Data System (ADS)

Kamble, Ravi; Sabale, Sandip; Chikode, Prashant; Puri, Vijaya; Mahajan, Smita

2016-11-01

Pure TiO2 and Mn2+-TiO2 nanoparticles have been prepared by simple hydrothermal method with different Mn2+ concentrations. Obtained samples were analysed to determine it’s structural, optical, morphological and compositional properties using x-ray diffraction, UV-DRS, Raman, photoluminescence, XPS, TEM and EDS analysis. The EDS micrograph confirms the existence of Mn2+ atoms in TiO2 matrix with 0.86, 1.60 and 1.90 wt%. The crystallite size as well as band gap decreases with increase in Mn2+ concentration. The average particle size obtained from TEM was found 8-11 nm which is in good agreement with XRD results. Raman bands at 640, 518 and 398 cm-1 further confirmed pure phase anatase in all samples. XPS shows the proper substitutions of few sites of Ti4+ ions by Mn2+ ions in the TiO2 host lattice. The intensity of PL spectra for Mn2+-TiO2 shows a gradual decrease in the peak intensity with increasing Mn2+ concentration in TiO2, it implies lower electron-hole recombination rate as Mn2+ ions increases. The obtained samples were further studied for its photocatalytic activities using malachite green dye under UV light and visible light.

Processing and optical characterization of lead calcium titanate borosilicate glass doped with germanium

NASA Astrophysics Data System (ADS)

Gautam, C. R.; Das, Sangeeta; Gautam, S. S.; Madheshiya, Abhishek; Singh, Anod Kumar

2018-04-01

In this study, various compositions of lead calcium titanate borosilicate glass doped with a fixed amount of germanium were synthesized using the rapid melt quench technique. The amorphous nature of the synthesized glass was confirmed by X-ray diffraction and scanning electron microscopy analyses. The structural and optical properties were deduced using Raman, Fourier transform infrared (FTIR), and ultraviolet-visible (UV-Vis) spectroscopy. FTIR spectroscopy confirmed the presence of borate groups in triangular and tetrahedral coordination. Infrared and Raman analyses detected the vibrational bonds of Gesbnd Osbnd Ge, Bsbnd Osbnd Ge, Sisbnd Osbnd Ge, Sisbnd Osbnd Si, and Pbsbnd Osbnd Ge. The energy band gaps were evaluated for the prepared glass samples based on Tauc plots of the UV-Vis spectra. The calculated values of the optical band gap decreased from 2.91 to 2.85 eV as the PbO content increased from x = 0.0 to x = 0.7. Furthermore, the Urbach energy was studied based on the UV-Vis results to confirm the disordered structure of the glass. The calculated densities of the glass samples (1.5835 g/cm3 to 3.9184 g/cm3) increased as the concentration of PbO increased, whereas they decreased with the molar volume.

Spectral analysis, vibrational assignments, NBO analysis, NMR, UV-Vis, hyperpolarizability analysis of 2-aminofluorene by density functional theory.

PubMed

Jone Pradeepa, S; Sundaraganesan, N

2014-05-05

In this present investigation, the collective experimental and theoretical study on molecular structure, vibrational analysis and NBO analysis has been reported for 2-aminofluorene. FT-IR spectrum was recorded in the range 4000-400 cm(-1). FT-Raman spectrum was recorded in the range 4000-50 cm(-1). The molecular geometry, vibrational spectra, and natural bond orbital analysis (NBO) were calculated for 2-aminofluorene using Density Functional Theory (DFT) based on B3LYP/6-31G(d,p) model chemistry. (13)C and (1)H NMR chemical shifts of 2-aminofluorene were calculated using GIAO method. The computed vibrational and NMR spectra were compared with the experimental results. The total energy distribution (TED) was derived to deepen the understanding of different modes of vibrations contributed by respective wavenumber. The experimental UV-Vis spectra was recorded in the region of 400-200 nm and correlated with simulated spectra by suitably solvated B3LYP/6-31G(d,p) model. The HOMO-LUMO energies were measured with time dependent DFT approach. The nonlinearity of the title compound was confirmed by hyperpolarizabilty examination. Using theoretical calculation Molecular Electrostatic Potential (MEP) was investigated. Copyright © 2014 Elsevier B.V. All rights reserved.

Ultraviolet Raman Wide-Field Hyperspectral Imaging Spectrometer for Standoff Trace Explosive Detection.

PubMed

Hufziger, Kyle T; Bykov, Sergei V; Asher, Sanford A

2017-02-01

We constructed the first deep ultraviolet (UV) Raman standoff wide-field imaging spectrometer. Our novel deep UV imaging spectrometer utilizes a photonic crystal to select Raman spectral regions for detection. The photonic crystal is composed of highly charged, monodisperse 35.5 ± 2.9 nm silica nanoparticles that self-assemble in solution to produce a face centered cubic crystalline colloidal array that Bragg diffracts a narrow ∼1.0 nm full width at half-maximum (FWHM) UV spectral region. We utilize this photonic crystal to select and image two different spectral regions containing resonance Raman bands of pentaerythritol tetranitrate (PETN) and NH 4 NO 3 (AN). These two deep UV Raman spectral regions diffracted were selected by angle tuning the photonic crystal. We utilized this imaging spectrometer to measure 229 nm excited UV Raman images containing ∼10-1000 µg/cm 2 samples of solid PETN and AN on aluminum surfaces at 2.3 m standoff distances. We estimate detection limits of ∼1 µg/cm 2 for PETN and AN films under these experimental conditions.

Confocal Raman spectroscopy: In vivo biochemical changes in the human skin by topical formulations under UV radiation.

PubMed

Tosato, M G; Orallo, D E; Ali, S M; Churio, M S; Martin, A A; Dicelio, L

2015-12-01

A new approach to the study of the effects on human skin of mycosporine-like amino acids (MAAs) and gadusol (Gad) incorporated in polymer gel is proposed in this work. The depth profile and photoprotector effects of Pluronic F127® gels containing each of the natural actives were evaluated by in vivo confocal Raman spectroscopy aiming at the analysis of the biochemical changes on human skin. Hierarchical cluster analysis (HCA) showed that the data corresponding to different depths of the skin, from surface to 4 μm, and from 6 to 16 μm, remained in the same cluster. In vivo Raman spectra, classified into five different layers of epidermis according to their similarities, indicated that the amount of Gad gel increased by about 26% in the outermost layer of the stratum corneum (SC) and that MAAs gel at 2 μm depth was 103.4% higher than in the outermost layer of the SC. Variations in the SC of urocanic acid at 1490-1515 cm(-1) and 1652 cm(-1) and histidine at 1318 cm(-1) were calculated, before and after UV exposure with or without gels. With the application of gels the vibrational modes that correspond to lipids in trans conformation (1063 and 1128 cm(-1)) increased with respect to normal skin, whereas gauche conformation (1085 cm(-1)) disappeared. Our studies suggest that gels protected the skin against the stress of the natural defense mechanism caused by high levels of UV exposure. Copyright © 2015 Elsevier B.V. All rights reserved.

[Ultrastructure and Raman Spectral Characteristics of Two Kinds of Acute Myeloid Leukemia Cells].

PubMed

Liang, Hao-Yue; Cheng, Xue-Lian; Dong, Shu-Xu; Zhao, Shi-Xuan; Wang, Ying; Ru, Yong-Xin

2018-02-01

To investigate the Raman spectral characteristics of leukemia cells from 4 patients with acute promyelocytic leukemia (M 3 ) and 3 patients with acute monoblastic leukemia (M 5 ), establish a novel Raman label-free method to distinguish 2 kinds of acute myeloid leukemia cells so as to provide basis for clinical research. Leukemia cells were collected from bone marrow of above-mentioned patients. Raman spectra were acquired by Horiba Xplora Raman spectrometer and Raman spectra of 30-50 cells from each patient were recorded. The diagnostic model was established according to principle component analysis (PCA), discriminant function analysis (DFA) and cluster analysis, and the spectra of leukemia cells from 7 patients were analyzed and classified. Characteristics of Raman spectra were analyzed combining with ultrastructure of leukemia cells. There were significant differences between Raman spectra of 2 kinds of leukemia cells. Compared with acute monoblastic leukemia cells, the spectra of acute promyelocytic leukemia cells showed stronger peaks in 622, 643, 757, 852, 1003, 1033, 1117, 1157, 1173, 1208, 1340, 1551, 1581 cm -1 . The diagnostic models established by PCA-DFA and cluster analysis could successfully classify these Raman spectra of different samples with a high accuracy of 100% (233/233). The model was evaluated by "Leave-one-out" cross-validation and reached a high accuracy of 97% (226/233). The level of macromolecules of M 3 cells is higher than that of M 5 . The diagnostic models established by PCA-DFA can classify these Raman spectra of different cells with a high accuracy. Raman spectra shows consistent result with ultrastructure by TEM.

Synthesis, crystal structure, vibrational spectroscopy, optical properties and theoretical studies of a new organic-inorganic hybrid material: [((CH3)2NH2)(+)]6·[(BiBr6)(3-)]2.

PubMed

Ben Ahmed, A; Feki, H; Abid, Y

2014-12-10

A new organic-inorganic hybrid material, [((CH3)2NH2)(+)]6·[(BiBr6)(3-)]2, has been synthesized and characterized by X-ray diffraction, FT-IR, Raman spectroscopy and UV-Visible absorption. The studied compound crystallizes in the triclinic system, space group P1¯ with the following parameters: a=8.4749(6)(Å), b=17.1392(12)(Å), c=17.1392(12)(Å), α=117.339(0)°, β=99.487(0)°, γ=99.487(0)° and Z=2. The crystal lattice is composed of a two discrete (BiBr6)(3-) anions surrounded by six ((CH3)2NH2)(+) cations. Complex hydrogen bonding interactions between (BiBr6)(3-) and organic cations from a three-dimensional network. Theoretical calculations were performed using density functional theory (DFT) for studying the molecular structure, vibrational spectra and optical properties of the investigated molecule in the ground state. The full geometry optimization of designed system is performed using DFT method at B3LYP/LanL2DZ level of theory using the Gaussian03. The optimized geometrical parameters obtained by DFT calculations are in good agreement with single crystal XRD data. The vibrational spectral data obtained from FT-IR and Raman spectra are assigned based on the results of the theoretical calculations. The energy and oscillator strength calculated by Time-Dependent Density Functional Theory (TD-DFT) results complements with the experimental findings. The simulated spectra satisfactorily coincide with the experimental UV-Visible spectrum. The results show good consistent with the experiment and confirm the contribution of metal orbital to the HOMO-LUMO boundary. Copyright © 2014 Elsevier B.V. All rights reserved.

Experimental spectroscopic (FTIR, FT-Raman, FT-NMR, UV-Visible) and DFT studies of 1-ethyl-1,4-dihydro-7-methyl-4oxo-1,8 napthyridine-3-carboxylic acids.

PubMed

Muthu, S; Elamurugu Porchelvi, E

2013-12-01

The solid phase FTIR and FT-Raman spectra of 1-ethyl-1,4-dihydro-7-methyl-4oxo-1,8 napthyridine-3-carboxylic acid (EDMONCA) have been recorded in the regions 4000-500 and 4000-400 cm(-1) respectively. The equilibrium geometry, harmonic vibrational frequencies have been investigated by DFT/B3LYP and B3PW91 methods with 6-311G (d,p) basis set. The different between the observed and scaled wave number values of most of the fundamental is very small. The assignments of the vibrational spectra have been carried out with the aid of normal coordinate analysis (NCA) following the scaled quantum mechanical force field methodology (SQMFFM). Stability of the molecule arising from hyper conjugative interactions, charge delocalization has been analyzed using natural bond orbital (NBO) analysis. UV-Visible spectrum of the compound was recorded and the electronic properties HOMO and LOMO energies were measured. The electric dipole moment (μD) and first hyperpolarizability (βtot) values of the investigated molecule were computed using ab initio quantum mechanical calculations. The calculated results also show that the EDMONCA molecule may have microscopic nonlinear optics (NLO) behavior with non-zero values. (1)H and (13)C NMR spectra were recorded and (1)H and (13)C nuclear magnetic resonance chemical shift of the molecule were calculated using the gauge independent atomic orbital (GIAO) method. Thermal stability of EDMONCA was studied by thermogravimetric analysis (TGA). Next Fukui function was calculated to explain the chemical selectivity or reactivity site in EDMONCA. Finally molecular electrostatic potential (MEP) and other molecular properties were performed. Copyright © 2013 Elsevier B.V. All rights reserved.

Efficient photocatalytic degradation of rhodamine-B by Fe doped CuS diluted magnetic semiconductor nanoparticles under the simulated sunlight irradiation

NASA Astrophysics Data System (ADS)

Sreelekha, N.; Subramanyam, K.; Amaranatha Reddy, D.; Murali, G.; Rahul Varma, K.; Vijayalakshmi, R. P.

2016-12-01

The present work is planned for a simple, inexpensive and efficient approach for the synthesis of Cu1-xFexS (x = 0.00, 0.01, 0.03, 0.05 and 0.07) nanoparticles via simplistic chemical co-precipitation route by using ethylene diamine tetra acetic acid (EDTA) as a capping molecules. As synthesized nanoparticles were used as competent catalysts for degradation of rhodamine-B organic dye pollutant. The properties of prepared samples were analyzed with energy dispersive analysis of X-rays (EDAX), X-ray diffraction (XRD), transmission electron microscopy (TEM), UV-visible optical absorption spectroscopy, Fourier transform infrared (FTIR) spectra, Raman spectra and vibrating sample magnetometer (VSM). EDAX spectra corroborated the existence of Fe in prepared nanoparticles within close proximity to stoichiometric ratio. XRD, FTIR and Raman patterns affirmed that configuration of single phase hexagonal crystal structure as that of (P63/mmc) CuS, without impurity crystals. The average particle size estimated by TEM scrutiny is in the assortment of 5-10 nm. UV-visible optical absorption measurements showed that band gap narrowing with increasing the Fe doping concentration. VSM measurements revealed that 3% Fe doped CuS nanoparticles exhibited strong ferromagnetism at room temperature and changeover of magnetic signs from ferromagnetic to the paramagnetic nature with increasing the Fe doping concentration in CuS host lattice. Among all Fe doped CuS nanoparticles, 3% Fe inclusion CuS sample shows better photocatalytic performance in decomposition of RhB compared with the pristine CuS. Thus as synthesized Cu0·97Fe0·03S nanocatalysts are tremendously realistic compounds for photocatalytic fictionalization in the direction of organic dye degradation under visible light.

UV-Enhanced IR Raman System for Identifying Biohazards

NASA Technical Reports Server (NTRS)

Stirbl, Robert; Moynihan, Philip; Lane, Arthur

2003-01-01

An instrumentation system that would include an ultraviolet (UV) laser or light-emitting diode, an infrared (IR) laser, and the equivalent of an IR Raman spectrometer has been proposed to enable noncontact identification of hazardous biological agents and chemicals. In prior research, IR Raman scattering had shown promise as a means of such identification, except that the Raman-scattered light was often found to be too weak to be detected or to enable unambiguous identification in practical applications. The proposed system would utilize UV illumination as part of a two-level optical-pumping scheme to intensify the Raman signal sufficiently to enable positive identification.

Effect on the partial least-squares prediction of yarn properties combining raman and infrared measurements and applying wavelength selection.

PubMed

de Groot, P J; Swierenga, H; Postma, G J; Melssen, W J; Buydens, L M C

2003-06-01

The combination of Raman and infrared spectroscopy on the one hand and wavelength selection on the other hand is used to improve the partial least-squares (PLS) prediction of seven selected yarn properties. These properties are important for on-line quality control during production. From 71 yarn samples, the Raman and infrared spectra are measured and reference methods are used to determine the selected properties. Making separate PLS models for all yarn properties using the Raman and infrared spectra, prior to wavelength selection, reveals that Raman spectroscopy outperforms infrared spectroscopy. If wavelength selection is applied, the PLS prediction error decreases and the correlation coefficient increases for all properties. However, a substantial wavelength selection effect is present for the infrared spectra compared to the Raman spectra. For the infrared spectra, wavelength selection results in PLS prediction errors comparable with the prediction performance of the Raman spectra prior to wavelength selection. Concatenating the Raman and infrared spectra does not enhance the PLS prediction performance, not even after wavelength selection. It is concluded that an infrared spectrometer, combined with a wavelength selection procedure, can be used if no (suitable) Raman instrument is available.

Quantitative fiber-optic Raman spectroscopy for tissue Raman measurements

NASA Astrophysics Data System (ADS)

Duraipandian, Shiyamala; Bergholt, Mads; Zheng, Wei; Huang, Zhiwei

2014-03-01

Molecular profiling of tissue using near-infrared (NIR) Raman spectroscopy has shown great promise for in vivo detection and prognostication of cancer. The Raman spectra measured from the tissue generally contain fundamental information about the absolute biomolecular concentrations in tissue and its changes associated with disease transformation. However, producing analogues tissue Raman spectra present a great technical challenge. In this preliminary study, we propose a method to ensure the reproducible tissue Raman measurements and validated with the in vivo Raman spectra (n=150) of inner lip acquired using different laser powers (i.e., 30 and 60 mW). A rapid Raman spectroscopy system coupled with a ball-lens fiber-optic Raman probe was utilized for tissue Raman measurements. The investigational results showed that the variations between the spectra measured with different laser powers are almost negligible, facilitating the quantitative analysis of tissue Raman measurements in vivo.

Using Deep UV Raman Spectroscopy to Identify In Situ Microbial Activity

NASA Astrophysics Data System (ADS)

Sapers, H. M.; Wanger, G.; Amend, J.; Orphan, V. J.; Bhartia, R.

2017-12-01

Microbial communities living in close association with lithic substrates play a critical role in biogeochemical cycles. Understanding the interactions between microorganisms and their abiotic substrates requires knowledge of microbial activity. Identifying active cells adhered to complex environmental substrates, especially in low biomass systems, remains a challenge. Stable isotope probing (SIP) provides a means to trace microbial activity in environmental systems. Active members of the community take up labeled substrates and incorporate the labels into biomolecules that can be detected through downstream analyses. Here we show for the first time that Deep UV (248 nm) Raman spectroscopy can differentiate microbial cells labeled with stable isotopes. Previous studies have used Raman spectroscopy with a 532 nm source to identify active bacterial cells by measuring a Raman shift between peaks corresponding to amino acids incorporating 13C compared to controls. However, excitation at 532 nm precludes detection on complex substrates due to high autofluorescence of native minerals. Excitation in the DUV range offers non-destructive imaging on mineral surfaces - retaining critical contextual information. We prepared cultures of E. coli grown in 50 atom% 13C glucose spotted onto Al wafers to test the ability of DUV Raman spectroscopy to differentiate labeled and unlabeled cells. For the first time, we are able to demonstrate a distinct and repeatable shift between cells grown in labeled media and unlabeled media when imaged on Al wafers with DUV Raman spectroscopy. The Raman spectra are dominated by the characteristic Raman bands of guanine. The dominant marker peak for guanine attributed to N7-C8 and C8-N9 ring stretching and C8-H in-plane bending, is visible at 1480 cm-1 in the unlabeled cells and is blue-shifted by 20 wavenumbers to 1461 cm-1 in the labeled cells. The ability of DUV Raman to effectively identify regions containing cells that have incorporated isotopic labels will allow in situ detection of metabolically-targeted active community members on complex natural substrates providing a crucial link between microbial activity and environmental context.

Molecular structure, vibrational spectra, NBO, UV and first order hyperpolarizability, analysis of 4-Chloro-dl-phenylalanine by density functional theory.

PubMed

Govindarasu, K; Kavitha, E

2014-12-10

The Fourier transform infrared (4000-400cm(-1)) and Fourier transform Raman (3500-50cm(-1)) spectra of 4-Chloro-dl-phenylalanine (4CLPA) were recorded and analyzed. The equilibrium geometry, bonding features and harmonic vibrational wavenumbers were investigated with the help of density functional theory (DFT) method using B3LYP/6-31G(d,p) as basis set. The observed vibrational wavenumbers were compared with the calculated results. Natural bond orbital analysis confirms the presence of intramolecular charge transfer and the hydrogen bonding interaction. Predicted electronic absorption spectra from TD-DFT calculation have been analyzed comparing with the UV-Vis (200-800nm) spectrum. The effects of chlorine and ethylene group substituent in benzene ring in the vibrational wavenumbers have been analyzed. The HOMO-LUMO energy gap explains the charge interaction taking place within the molecule. The first order hyperpolarizability (β0) and related properties (β, α0 and Δα) of 4CLPA were calculated. The Chemical reactivity and chemical potential of 4CLPA is calculated. In addition, molecular electrostatic potential (MEP), frontier molecular orbital (FMO) analysis were investigated using theoretical calculations. Published by Elsevier B.V.

Single Molecule Raman Spectroscopy Under High Pressure

NASA Astrophysics Data System (ADS)

Fu, Yuanxi; Dlott, Dana

2014-06-01

Pressure effects on surface-enhanced Raman scattering spectra of Rhdoamine 6G adsorbed on silver nanoparticle surfaces was studied using a confocal Raman microscope. Colloidal silver nanoparticles were treated with Rhodamine 6G (R6G) and its isotopically substituted partner, R6G-d4. Mixed isotopomers let us identify single-molecule spectra, since multiple-molecule spectra would show vibrational transitions from both species. The nanoparticles were embedded into a poly vinyl alcohol film, and loaded into a diamond anvil cell for the high-pressure Raman scattering measurement. Argon was the pressure medium. Ambient pressure Raman scattering spectra showed few single-molecule spectra. At moderately high pressure ( 1GPa), a surprising effect was observed. The number of sites with observable spectra decreased dramatically, and most of the spectra that could be observed were due to single molecules. The effects of high pressure suppressed the multiple-molecule Raman sites, leaving only the single-molecule sites to be observed.

Structural modification of poly(methyl methacrylate) by proton irradiation

NASA Astrophysics Data System (ADS)

Choi, H. W.; Woo, H. J.; Hong, W.; Kim, J. K.; Lee, S. K.; Eum, C. H.

2001-01-01

A general survey is presented on the structural modification of poly(methyl methacrylate) (PMMA) by proton implantation. The implanted PMMA films were characterized by FT-IR attenuated total reflection (FT-IR ATR), Raman, Rutherford backscattering spectroscopy (RBS), gel permeation chromatography (GPC) and surface profiling. The ion fluence of 350 keV protons ranged from 2×10 14 to 1×10 15 ions/cm 2. The IR and Raman spectra showed the reduction of peaks from the pendant group of PMMA. The change of absorption and composition was observed by UV-VIS and RBS, respectively. These results showed that the pendant group is readily decomposed and eliminated by proton irradiation. The change of molecular weight distribution was also measured by GPC and G-value of scission was estimated to be 0.67.

The spectroscopic (FT-IR, FT-Raman, UV) and first order hyperpolarizability, HOMO and LUMO analysis of 3-aminobenzophenone by density functional method

NASA Astrophysics Data System (ADS)

Karabacak, M.; Kurt, M.; Cinar, M.; Ayyappan, S.; Sudha, S.; Sundaraganesan, N.

In this work, experimental and theoretical study on the molecular structure and the vibrational spectra of 3-aminobenzophenone (3-ABP) is presented. The vibrational frequencies of the title compound were obtained theoretically by DFT/B3LYP calculations employing the standard 6-311++G(d,p) basis set for optimized geometry and were compared with Fourier transform infrared spectrum (FTIR) in the region of 400-4000 cm-1 and with Fourier Transform Raman spectrum in the region of 50-4000 cm-1. Complete vibrational assignments, analysis and correlation of the fundamental modes for the title compound were carried out. The vibrational harmonic frequencies were scaled using scale factor, yielding a good agreement between the experimentally recorded and the theoretically calculated values.

Rapid acquisition of mean Raman spectra of eukaryotic cells for a robust single cell classification.

PubMed

Schie, Iwan W; Kiselev, Roman; Krafft, Christoph; Popp, Jürgen

2016-11-14

Raman spectroscopy has previously been used to identify eukaryotic and prokaryotic cells. While prokaryotic cells are small in size and can be assessed by a single Raman spectrum, the larger size of eukaryotic cells and their complex organization requires the acquisition of multiple Raman spectra to properly characterize them. A Raman spectrum from a diffraction-limited spot at an arbitrary location within a cell results in spectral variations that affect classification approaches. To probe whole cells with Raman imaging at high spatial resolution is time consuming, because a large number of Raman spectra need to be collected, resulting in low cell throughput and impairing statistical analysis due to low cell numbers. Here we propose a method to overcome the effects of cellular heterogeneity by acquiring integrated Raman spectra covering a large portion of a cell. The acquired spectrum represents the mean macromolecular composition of a cell with an exposure time that is comparable to acquisition of a single Raman spectrum. Data sets were collected from T lymphocyte Jurkat cells, and pancreatic cell lines Capan1 and MiaPaca2. Cell classification by support vector machines was compared for single spectra, spectra of images and integrated Raman spectra of cells. The integrated approach provides better and more stable prediction for individual cells, and in the current implementation, the mean macromolecular information of a cell can be acquired faster than with the acquisition of individual spectra from a comparable region. It is expected that this approach will have a major impact on the implementation of Raman based cell classification.

Photocatalytic Activity of Vanadium-Substituted ETS-10

DOE Office of Scientific and Technical Information (OSTI.GOV)

Nash,M.; Rykov, S.; Lobo, R.

2007-01-01

Various amounts of vanadium have been isomorphously substituted for titanium in ETS-10, creating samples with V/(V+Ti) ratios of 0.13, 0.33, 0.43, and 1.00 and characterized experimentally using Raman, near-edge X-ray absorption fine structure (NEXAFS), X-ray powder diffraction, N{sub 2} adsorption, scanning electron microscopy (SEM), UV/vis spectroscopy, and diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS). Raman spectra reveal a disordered chain structure that contains different V-O bonds along with the presence of a V-O-Ti peak. The UV/vis spectra of the vanadium samples have three new absorption features in the visible region at 450, 594, and 850 nm, suggesting both V{sup 4+}more » and V{sup 5+} are present in the samples. NEXAFS results confirm the presence of both V{sup 5+} and V{sup 4+} in the vanadium samples, with a fraction of V{sup 4+} within the range of 0.2-0.4. The addition of vanadium lowers the band gap energy of ETS-10 from 4.32 eV to a minimum of 3.58 eV for the 0.43ETVS-10 sample. Studies of the photocatalytic polymerization of ethylene show that the 594 nm transition has no photocatalytic activity. The visible transition around 450 nm in the vanadium-incorporated samples is photocatalytically active, and the lower-concentration vanadium samples have higher photocatalytic activity than that of ETS-10 and AM-6, the all-vanadium analogue of ETS-10.« less

Excitation wavelength selection for quantitative analysis of carotenoids in tomatoes using Raman spectroscopy.

PubMed

Hara, Risa; Ishigaki, Mika; Kitahama, Yasutaka; Ozaki, Yukihiro; Genkawa, Takuma

2018-08-30

The difference in Raman spectra for different excitation wavelengths (532 nm, 785 nm, and 1064 nm) was investigated to identify an appropriate wavelength for the quantitative analysis of carotenoids in tomatoes. For the 532 nm-excited Raman spectra, the intensity of the peak assigned to the carotenoid has no correlation with carotenoid concentration, and the peak shift reflects carotenoid composition changing from lycopene to β-carotene and lutein. Thus, 532 nm-excited Raman spectra are useful for the qualitative analysis of carotenoids. For the 785 nm- and 1064 nm-excited Raman spectra, the peak intensity of the carotenoid showed good correlation with carotenoid concentration; thus, regression models for carotenoid concentration were developed using these Raman spectra and partial least squares regression. A regression model designed using the 785 nm-excited Raman spectra showed a better result than the 532 nm- and 1064 nm-excited Raman spectra. Therefore, it can be concluded that 785 nm is the most suitable excitation wavelength for the quantitative analysis of carotenoid concentration in tomatoes. Copyright © 2018 Elsevier Ltd. All rights reserved.

Nonplanar property study of antifungal agent tolnaftate-spectroscopic approach

NASA Astrophysics Data System (ADS)

Arul Dhas, D.; Hubert Joe, I.; Roy, S. D. D.; Balachandran, S.

2011-09-01

Vibrational analysis of the thionocarbamate fungicide tolnaftate which is antidermatophytic, antitrichophytic and antimycotic agent, primarily inhibits the ergosterol biosynthesis in the fungus, was carried out using NIR FT-Raman and FTIR spectroscopic techniques. The equilibrium geometry, various bonding features, harmonic vibrational wavenumbers and torsional potential energy surface (PES) scan studies have been computed using density functional theory method. The detailed interpretation of the vibrational spectra has been carried out with the aid of VEDA.4 program. Vibrational spectra, natural bonding orbital (NBO) analysis and optimized molecular structure show the clear evidence for electronic interaction of thionocarbamate group with aromatic ring. Predicted electronic absorption spectrum from TD-DFT calculation has been compared with the UV-vis spectrum. The Mulliken population analysis on atomic charges and the HOMO-LUMO energy were also calculated. Vibrational analysis reveals that the simultaneous IR and Raman activation of the C-C stretching mode in the phenyl and naphthalene ring provide evidence for the charge transfer interaction between the donor and acceptor groups and is responsible for its bioactivity as a fungicide.

Spectroscopic analysis of cinnamic acid using quantum chemical calculations

NASA Astrophysics Data System (ADS)

Vinod, K. S.; Periandy, S.; Govindarajan, M.

2015-02-01

In this present study, FT-IR, FT-Raman, 13C NMR and 1H NMR spectra for cinnamic acid have been recorded for the vibrational and spectroscopic analysis. The observed fundamental frequencies (IR and Raman) were assigned according to their distinctiveness region. The computed frequencies and optimized parameters have been calculated by using HF and DFT (B3LYP) methods and the corresponding results are tabulated. On the basis of the comparison between computed and experimental results assignments of the fundamental vibrational modes are examined. A study on the electronic and optical properties; absorption wavelengths, excitation energy, dipole moment and frontier molecular orbital energies, were performed by HF and DFT methods. The alternation of the vibration pattern of the pedestal molecule related to the substitutions was analyzed. The 13C and 1H NMR spectra have been recorded and the chemical shifts have been calculated using the gauge independent atomic orbital (GIAO) method. The Mulliken charges, UV spectral analysis and HOMO-LUMO analysis of have been calculated and reported. The molecular electrostatic potential (MEP) was constructed.

Linear Regression Links Transcriptomic Data and Cellular Raman Spectra.

PubMed

Kobayashi-Kirschvink, Koseki J; Nakaoka, Hidenori; Oda, Arisa; Kamei, Ken-Ichiro F; Nosho, Kazuki; Fukushima, Hiroko; Kanesaki, Yu; Yajima, Shunsuke; Masaki, Haruhiko; Ohta, Kunihiro; Wakamoto, Yuichi

2018-06-08

Raman microscopy is an imaging technique that has been applied to assess molecular compositions of living cells to characterize cell types and states. However, owing to the diverse molecular species in cells and challenges of assigning peaks to specific molecules, it has not been clear how to interpret cellular Raman spectra. Here, we provide firm evidence that cellular Raman spectra and transcriptomic profiles of Schizosaccharomyces pombe and Escherichia coli can be computationally connected and thus interpreted. We find that the dimensions of high-dimensional Raman spectra and transcriptomes measured by RNA sequencing can be reduced and connected linearly through a shared low-dimensional subspace. Accordingly, we were able to predict global gene expression profiles by applying the calculated transformation matrix to Raman spectra, and vice versa. Highly expressed non-coding RNAs contributed to the Raman-transcriptome linear correspondence more significantly than mRNAs in S. pombe. This demonstration of correspondence between cellular Raman spectra and transcriptomes is a promising step toward establishing spectroscopic live-cell omics studies. Copyright © 2018 Elsevier Inc. All rights reserved.

UV Raman scattering measurements in a Mach 2 H2-air flame for assessment of CFD models

NASA Technical Reports Server (NTRS)

Cheng, T. S.; Wehrmeyer, J. A.; Pitz, R. W.; Jarrett, O., Jr.; Northam, G. B.

1991-01-01

An UV narrowband tunable excimer laser is used for spontaneous Raman scattering measurements in hydrogen diffusion flames. The UV Raman system is characterized by a repetition rate of about 100 Hz, a temporal resolution of about 20 ns, and a spatial resolution of about 0.4 mm. It is concluded that a single KrF excimer laser based on spontaneous Raman scattering in conjunction with laser-induced predissociative fluorescence is capable of measuring instantaneously and simultaneously major species (H2, O2, N2, H2O), minor species (OH), and temperature.

The role of habitat structure for biomolecule integrity and microbial survival under extreme environmental stress in Antarctica (and Mars?): ecology and technology

NASA Astrophysics Data System (ADS)

Wynn-Williams, D. A.; Newton, E. M.; Edwards, H. G. M.

2001-08-01

The integrity of cells and biomolecules in stressed environments is enhanced within microhabitats. Despite desiccation and low temperatures in Antarctic deserts, the greatest near-surface factor is solar radiation. Photosynthetic microbial communities that pioneer polar deserts harness photosynthetically active radiation (PAR) whilst concurrently adopting protective strategies against UVB with screening pigments or avoidance in stratified habitats. To analyse whole communities in situ, we use laser Raman spectroscopy as a non-intrusive technique for organic compounds and mineral substrata. We use the distinctive spectra of cyanobacterial and lichen UV-screening pigments, and energy-quenching carotenoids to define their functional locations. Their occurrence in extreme habitats and in the fossil record permits extrapolation to conditions on early Earth and analogous habitats on early Mars. We describe our Raman spectral database accumulated with a laboratory FT Raman spectrometer and expansion to Antarctic fieldwork and astrobiology with a novel miniature 1064 nm laser system with an Indium-Gallium-Arsenide detector.

On the constituents of aqueous polyselenide electrolytes: A combined theoretical and Raman spectroscopic study

DOE Office of Scientific and Technical Information (OSTI.GOV)

Goldbach, A.; Johnson, J.; Meisel, D.

1999-05-12

The speciation of aqueous polyselenide solutions at high pH values has been investigated by Raman and Uv/vis absorption spectroscopy. Complementary, ab initio molecular orbital calculations at the HF/6-31+G{sup *} level of theory have been carried out on the vibrational frequencies of polyselenide dianions Se{sub x}{sup 2{minus}} (x = 2--4), polyselenide radical anions Se{sub x}{sup {minus}} (x = 2, 3), and protonated polyselenides HSe{sub x}{sup {minus}} (x = 1--3) in order to substantiate the assignment of the experimental Raman spectra. Although the optical spectra suggest the successive formation of Se{sub 2}{sup 2{minus}}, Se{sub 3}{sup 2{minus}}, and Se{sub 4}{sup 2{minus}} with progressivemore » oxidation of the solutions, only two characteristic Raman bands are observed at 269 and 324 cm{sup {minus}1}. A sequence of overtones of the 269 cm{sup {minus}1} band is observed after excitation with blue light. Likewise strong overtones of the 324 cm{sup {minus}1} band appear after excitation with green light. The 269 cm{sup {minus}1} features is assigned to Se{sub 4}{sup 2{minus}} while the 324 cm{sup {minus}1} band is attributed to the radical anion Se{sub 2}{sup {minus}}. The occurrence of polyselenide radicals in aqueous solution is without precedent, and the formation of Se{sub 2}{sup {minus}} is ascribed to a photolytic process in the electrolyte. The only protonated species observed in this study is HSe{sup {minus}}, which is characterized by a Raman band at 2,303 cm{sup {minus}1}.« less

Fluorescence background removal method for biological Raman spectroscopy based on empirical mode decomposition.

PubMed

Leon-Bejarano, Maritza; Dorantes-Mendez, Guadalupe; Ramirez-Elias, Miguel; Mendez, Martin O; Alba, Alfonso; Rodriguez-Leyva, Ildefonso; Jimenez, M

2016-08-01

Raman spectroscopy of biological tissue presents fluorescence background, an undesirable effect that generates false Raman intensities. This paper proposes the application of the Empirical Mode Decomposition (EMD) method to baseline correction. EMD is a suitable approach since it is an adaptive signal processing method for nonlinear and non-stationary signal analysis that does not require parameters selection such as polynomial methods. EMD performance was assessed through synthetic Raman spectra with different signal to noise ratio (SNR). The correlation coefficient between synthetic Raman spectra and the recovered one after EMD denoising was higher than 0.92. Additionally, twenty Raman spectra from skin were used to evaluate EMD performance and the results were compared with Vancouver Raman algorithm (VRA). The comparison resulted in a mean square error (MSE) of 0.001554. High correlation coefficient using synthetic spectra and low MSE in the comparison between EMD and VRA suggest that EMD could be an effective method to remove fluorescence background in biological Raman spectra.

Towards eye-safe standoff Raman imaging systems

NASA Astrophysics Data System (ADS)

Glimtoft, Martin; Bââth, Petra; Saari, Heikki; Mäkynen, Jussi; Näsilä, Antti; Östmark, Henric

2014-05-01

Standoff Raman imaging systems have shown the ability to detect single explosives particles. However, in many cases, the laser intensities needed restrict the applications where they can be safely used. A new generation imaging Raman system has been developed based on a 355 nm UV laser that, in addition to eye safety, allows discrete and invisible measurements. Non-dangerous exposure levels for the eye are several orders of magnitude higher in UVA than in the visible range that previously has been used. The UV Raman system has been built based on an UV Fabry-Perot Interferometer (UV-FPI) developed by VTT. The design allows for precise selection of Raman shifts in combination with high out-of-band blocking. The stable operation of the UV-FPI module under varying environmental conditions is arranged by controlling the temperature of the module and using a closed loop control of the FPI air gap based on capacitive measurement. The system presented consists of a 3rd harmonics Nd:YAG laser with 1.5 W average output at 1000 Hz, a 200 mm Schmidt-Cassegrain telescope, UV-FPI filter and an ICCD camera for signal gating and detection. The design principal leads to a Raman spectrum in each image pixel. The system is designed for field use and easy manoeuvring. Preliminary results show that in measurements of <60 s on 10 m distance, single AN particles of <300 μm diameter can be identified.

Detection and aggregation of the antitumoral drug parietin in ethanol/water mixture and on plasmonic metal nanoparticles studied by surface-enhanced optical spectroscopy: Effect of pH and ethanol concentration.

PubMed

Lopez-Tobar, Eduardo; Verebova, Valeria; Blascakova, Ludmila; Jancura, Daniel; Fabriciova, Gabriela; Sanchez-Cortes, Santiago

2016-04-15

In the present paper, we have investigated the effect of ethanol in aqueous media, the pH and the presence of Ag nanoparticles (NPs) on the aggregation processes of the antitumoral anthraquinone parietin in aqueous media and on the metal surface. UV-visible absorption, fluorescence and Raman spectra of parietin were used for such purpose. The present study provides information about the deprotonation and molecular aggregation processes occurring in parietin under different environments: ethanol/water mixture and when adsorbed onto Ag nanoparticles. The effect of ethanol on the optical properties of parietin in alcohol-water mixtures was also investigated at different ethanol concentrations with the time. For the case of the adsorption and organization of parietin molecules on the surface of Ag NPs, special attention was paid to the use of surface-enhanced optical techniques, SEF (surface-enhanced fluorescence) and SERS (surface-enhanced Raman scattering), for the characterization of the parietin aggregates and the ionization of the molecule on the surface. In particular, we have studied the variation of the SEF signal with the pH, which depends on the molecular organization of the molecule on the surface. Furthermore, a detailed analysis of the SERS spectra at different pH was accomplished and the main Raman bands of the protonated, mono-deprotonated and di-deprotonated parietin were identified. Finally, the second ionization pK of parietin on metal NPs was deduced from the SERS spectra. Copyright © 2016 Elsevier B.V. All rights reserved.

Detection and aggregation of the antitumoral drug parietin in ethanol/water mixture and on plasmonic metal nanoparticles studied by surface-enhanced optical spectroscopy: Effect of pH and ethanol concentration

NASA Astrophysics Data System (ADS)

Lopez-Tobar, Eduardo; Verebova, Valeria; Blascakova, Ludmila; Jancura, Daniel; Fabriciova, Gabriela; Sanchez-Cortes, Santiago

2016-04-01

In the present paper, we have investigated the effect of ethanol in aqueous media, the pH and the presence of Ag nanoparticles (NPs) on the aggregation processes of the antitumoral anthraquinone parietin in aqueous media and on the metal surface. UV-visible absorption, fluorescence and Raman spectra of parietin were used for such purpose. The present study provides information about the deprotonation and molecular aggregation processes occurring in parietin under different environments: ethanol/water mixture and when adsorbed onto Ag nanoparticles. The effect of ethanol on the optical properties of parietin in alcohol-water mixtures was also investigated at different ethanol concentrations with the time. For the case of the adsorption and organization of parietin molecules on the surface of Ag NPs, special attention was paid to the use of surface-enhanced optical techniques, SEF (surface-enhanced fluorescence) and SERS (surface-enhanced Raman scattering), for the characterization of the parietin aggregates and the ionization of the molecule on the surface. In particular, we have studied the variation of the SEF signal with the pH, which depends on the molecular organization of the molecule on the surface. Furthermore, a detailed analysis of the SERS spectra at different pH was accomplished and the main Raman bands of the protonated, mono-deprotonated and di-deprotonated parietin were identified. Finally, the second ionization pK of parietin on metal NPs was deduced from the SERS spectra.

Raman Scattering by Molecular Hydrogen and Nitrogen in Exoplanetary Atmospheres

NASA Astrophysics Data System (ADS)

Oklopčić, Antonija; Hirata, Christopher M.; Heng, Kevin

2016-11-01

An important source of opacity in exoplanet atmospheres at short visible and near-UV wavelengths is Rayleigh scattering of light on molecules. It is accompanied by a related, albeit weaker process—Raman scattering. We analyze the signatures of Raman scattering imprinted in the reflected light and the geometric albedo of exoplanets, which could provide information about atmospheric properties. Raman scattering affects the geometric albedo spectra of planets in the following ways. First, it causes filling-in of strong absorption lines in the incident radiation, thus producing sharp peaks in the albedo. Second, it shifts the wavelengths of spectral features in the reflected light causing the so-called Raman ghost lines. Raman scattering can also cause a broadband reduction of the albedo due to wavelength shifting of a stellar spectrum with red spectral index. Observing the Raman peaks in the albedo could be used to measure the column density of gas, thus providing constraints on the presence of clouds in the atmosphere. Observing the Raman ghost lines could be used to spectroscopically identify the main scatterer in the atmosphere, even molecules like H2 or N2, which do not have prominent spectral signatures in the optical wavelength range. If detected, ghost lines could also provide information about the temperature of the atmosphere. In this paper, we investigate the effects of Raman scattering in hydrogen- and nitrogen-dominated atmospheres. We analyze the feasibility of detecting the signatures of Raman scattering with the existing and future observational facilities, and of using these signatures as probes of exoplanetary atmospheres.

VizieR Online Data Catalog: Raman scattering cross sections for H2 (Oklopcic+,

NASA Astrophysics Data System (ADS)

Oklopcic, A.; Hirata, C. M.; Heng, K.

2017-02-01

An important source of opacity in exoplanet atmospheres at short visible and near-UV wavelengths is Rayleigh scattering of light on molecules. It is accompanied by a related, albeit weaker process-Raman scattering. We analyze the signatures of Raman scattering imprinted in the reflected light and the geometric albedo of exoplanets, which could provide information about atmospheric properties. Raman scattering affects the geometric albedo spectra of planets in the following ways. First, it causes filling-in of strong absorption lines in the incident radiation, thus producing sharp peaks in the albedo. Second, it shifts the wavelengths of spectral features in the reflected light causing the so-called Raman ghost lines. Raman scattering can also cause a broadband reduction of the albedo due to wavelength shifting of a stellar spectrum with red spectral index. Observing the Raman peaks in the albedo could be used to measure the column density of gas, thus providing constraints on the presence of clouds in the atmosphere. Observing the Raman ghost lines could be used to spectroscopically identify the main scatterer in the atmosphere, even molecules like H2 or N2, which do not have prominent spectral signatures in the optical wavelength range. If detected, ghost lines could also provide information about the temperature of the atmosphere. In this paper, we investigate the effects of Raman scattering in hydrogen- and nitrogen-dominated atmospheres. We analyze the feasibility of detecting the signatures of Raman scattering with the existing and future observational facilities, and of using these signatures as probes of exoplanetary atmospheres. (1 data file).

RAMAN SCATTERING BY MOLECULAR HYDROGEN AND NITROGEN IN EXOPLANETARY ATMOSPHERES

DOE Office of Scientific and Technical Information (OSTI.GOV)

Oklopčić, Antonija; Hirata, Christopher M.; Heng, Kevin, E-mail: oklopcic@astro.caltech.edu

2016-11-20

An important source of opacity in exoplanet atmospheres at short visible and near-UV wavelengths is Rayleigh scattering of light on molecules. It is accompanied by a related, albeit weaker process—Raman scattering. We analyze the signatures of Raman scattering imprinted in the reflected light and the geometric albedo of exoplanets, which could provide information about atmospheric properties. Raman scattering affects the geometric albedo spectra of planets in the following ways. First, it causes filling-in of strong absorption lines in the incident radiation, thus producing sharp peaks in the albedo. Second, it shifts the wavelengths of spectral features in the reflected lightmore » causing the so-called Raman ghost lines. Raman scattering can also cause a broadband reduction of the albedo due to wavelength shifting of a stellar spectrum with red spectral index. Observing the Raman peaks in the albedo could be used to measure the column density of gas, thus providing constraints on the presence of clouds in the atmosphere. Observing the Raman ghost lines could be used to spectroscopically identify the main scatterer in the atmosphere, even molecules like H{sub 2} or N{sub 2}, which do not have prominent spectral signatures in the optical wavelength range. If detected, ghost lines could also provide information about the temperature of the atmosphere. In this paper, we investigate the effects of Raman scattering in hydrogen- and nitrogen-dominated atmospheres. We analyze the feasibility of detecting the signatures of Raman scattering with the existing and future observational facilities, and of using these signatures as probes of exoplanetary atmospheres.« less

Approximate chemical analysis of volcanic glasses using Raman spectroscopy

PubMed Central

Morgavi, Daniele; Hess, Kai‐Uwe; Neuville, Daniel R.; Borovkov, Nikita; Perugini, Diego; Dingwell, Donald B.

2015-01-01

The effect of chemical composition on the Raman spectra of a series of natural calcalkaline silicate glasses has been quantified by performing electron microprobe analyses and obtaining Raman spectra on glassy filaments (~450 µm) derived from a magma mingling experiment. The results provide a robust compositionally‐dependent database for the Raman spectra of natural silicate glasses along the calcalkaline series. An empirical model based on both the acquired Raman spectra and an ideal mixing equation between calcalkaline basaltic and rhyolitic end‐members is constructed enabling the estimation of the chemical composition and degree of polymerization of silicate glasses using Raman spectra. The model is relatively insensitive to acquisition conditions and has been validated using the MPI‐DING geochemical standard glasses1 as well as further samples. The methods and model developed here offer several advantages compared with other analytical and spectroscopic methods such as infrared spectroscopy, X‐ray fluorescence spectroscopy, electron and ion microprobe analyses, inasmuch as Raman spectroscopy can be performed with a high spatial resolution (1 µm2) without the need for any sample preparation as a nondestructive technique. This study represents an advance in efforts to provide the first database of Raman spectra for natural silicate glasses and yields a new approach for the treatment of Raman spectra, which allows us to extract approximate information about the chemical composition of natural silicate glasses using Raman spectroscopy. We anticipate its application in handheld in situ terrestrial field studies of silicate glasses under extreme conditions (e.g. extraterrestrial and submarine environments). © 2015 The Authors Journal of Raman Spectroscopy Published by John Wiley & Sons Ltd PMID:27656038

Laser induced fluorescence of biochemical for UV LIDAR application.

PubMed

Gupta, L; Sharma, R C; Razdan, A K; Maini, A K

2014-05-01

Laser induced fluorescence spectroscopy in the ultraviolet regime has been used for the detection of biochemical through a fiber coupled CCD detector from a distance of 2 m. The effect of concentration and laser excitation energy on the fluorescence spectra of nicotinamide adenine dinucleotide (NADH) has been investigated. The signature fluorescence peak of NADH was centred about 460 nm. At lower concentration Raman peak centred at 405 nm was also observed. The origin of this peak has been discussed. Detection limit with the proposed set up is found to be 1 ppm.

Theoretical studies of surface enhanced hyper-Raman spectroscopy: The chemical enhancement mechanism

NASA Astrophysics Data System (ADS)

Valley, Nicholas; Jensen, Lasse; Autschbach, Jochen; Schatz, George C.

2010-08-01

Hyper-Raman spectra for pyridine and pyridine on the surface of a tetrahedral 20 silver atom cluster are calculated using static hyperpolarizability derivatives obtained from time dependent density functional theory. The stability of the results with respect to choice of exchange-correlation functional and basis set is verified by comparison with experiment and with Raman spectra calculated for the same systems using the same methods. Calculated Raman spectra were found to match well with experiment and previous theoretical calculations. The calculated normal and surface enhanced hyper-Raman spectra closely match experimental results. The chemical enhancement factors for hyper-Raman are generally larger than for Raman (102-104 versus 101-102). Integrated hyper-Raman chemical enhancement factors are presented for a set of substituted pyridines. A two-state model is developed to predict these chemical enhancement factors and this was found to work well for the majority of the molecules considered, providing a rationalization for the difference between hyper-Raman and Raman enhancement factors.

Measurements of Raman scattering in the middle ultraviolet band from persistent chemical warfare agents

NASA Astrophysics Data System (ADS)

Kullander, Fredrik; Landström, Lars; Lundén, Hampus; Mohammed, Abdesalam; Olofsson, Göran; Wästerby, Pär.

2014-05-01

The very low Raman scattering cross section and the fluorescence background limit the measuring range of Raman based instruments operating in the visible or infrared band. We are exploring if laser excitation in the middle ultraviolet (UV) band between 200 and 300 nm is useful and advantageous for detection of persistent chemical warfare agents (CWA) on various kinds of surfaces. The UV Raman scattering from tabun, mustard gas, VX and relevant simulants in the form of liquid surface contaminations has been measured using a laboratory experimental setup with a short standoff distance around 1 meter. Droplets having a volume of 1 μl were irradiated with a tunable pulsed laser swept within the middle UV band. A general trend is that the signal strength moves through an optimum when the laser excitation wavelength is swept between 240 and 300 nm. The signal from tabun reaches a maximum around 265 nm, the signal from mustard gas around 275 nm. The Raman signal from VX is comparably weak. Raman imaging by the use of a narrow bandpass UV filter is also demonstrated.

Synthesis of a ternary Ag/RGO/ZnO nanocomposite via microwave irradiation and its application for the degradation of Rhodamine B under visible light.

PubMed

Surendran, Divya Kollikkara; Xavier, Marilyn Mary; Viswanathan, Vandana Parakkal; Mathew, Suresh

2017-06-01

Reduced graphene oxide supporting plasmonic photocatalyst (Ag) on ZnO has been synthesized via a facile two-step microwave synthesis using RGO/ZnO and AgNO 3 . First step involves fabrication of RGO/ZnO via microwave irradiation. The nanocomposites were characterized by X-ray diffraction analysis, transmission electron microscopy, Fourier transform infrared spectroscopy, and Raman spectroscopy. Ag/RGO/ZnO shows enhanced photoactivity under visible light for the degradation of Rhodamine B. Enhanced charge separation and migration have been assigned using UV-vis diffuse reflectance spectra, photoluminescence spectra, electrochemical impedance spectra, and TCSPC analysis. The improved photoactivity of Ag/RGO/ZnO can be ascribed to the prolonged lifetime of photogenerated electron-hole pairs and effective interfacial hybridization between RGO and Ag with ZnO nanoparticles. Ag nanoparticles can absorb visible light via surface plasmon resonance to enhance photocatalytic activity.

A combined Surface Enhanced Raman Spectroscopy (SERS)/UV-vis approach for the investigation of dye content in commercial felt tip pens inks.

PubMed

Saviello, Daniela; Trabace, Maddalena; Alyami, Abeer; Mirabile, Antonio; Giorgi, Rodorico; Baglioni, Piero; Iacopino, Daniela

2018-05-01

The development of protocols for the protection of the large patrimony of works of art created by felt tip pen media since the 1950's requires detailed knowledge of the main dyes constituting commercial ink mixtures. In this work Surface Enhanced Raman Scattering (SERS) and UV-vis spectroscopy were used for the first time for the systematic identification of dye composition in commercial felt tip pens. A large selection of pens comprising six colors of five different brands was analyzed. Intense SERS spectra were obtained for all colors, allowing identification of main dye constituents. Poinceau 4R and Eosin dyes were found to be the main constituents of red and pink colors; Rhodamine and Tartrazine were found in orange and yellow colors; Erioglaucine was found in green and blue colors. UV-vis analysis of the same inks was used to support SERS findings but also to unequivocally assign some uncertain dye identifications, especially for yellow and orange colors. The spectral data of all felt tip pens collected through this work were assembled in a database format. The data obtained through this systematic investigation constitute the basis for the assembly of larger reference databases that ultimately will support the development of conservation protocols for the long term preservation of modern art collections. Copyright © 2018 Elsevier B.V. All rights reserved.

Combined experimental and theoretical study on the Raman and Raman optical activity signatures of pentamethylundecane diastereoisomers.

PubMed

Drooghaag, Xavier; Marchand-Brynaert, Jacqueline; Champagne, Benoît; Liégeois, Vincent

2010-09-16

The synthesis and the separation of the four stereoisomers of 2,4,6,8,10-pentamethylundecane (PMU) are described together with their characterization by Raman spectroscopy. In parallel, theoretical calculations of the Raman and vibrational Raman optical activity (VROA) spectra are reported and analyzed in relation with the recorded spectra. A very good agreement is found between the experimental and theoretical spectra. The Raman spectra are also shown to be less affected by the change of configuration than the VROA spectra. Nevertheless, by studying the overlap between the theoretical Raman spectra, we show clear relationships between the spectral fingerprints and the structures displaying a mixture of the TGTGTGTG conformation of the (4R,6s,8S)-PMU (isotactic compound) with the TTTTTTTT conformation of the (4R,6r,8S)-PMU (syndiotactic compound). Then, the fingerprints of the VROA spectra of the five conformers of the (4R,8R)-PMU have been related to the fingerprints of the regular (TG)(N) isotactic compound as a function of the torsion angles. Since the (TT)(N) syndiotactic compound has no VROA signatures, the VROA spectroscopy is very sensitive to the helical structures, as demonstrated here.

Spectroscopic and quantum chemical studies on bromopyrazone.

PubMed

Gökce, Halil; Bahçeli, Semiha

2014-12-10

In this study, the FT-IR, micro-Raman and UV-vis. spectra of bromopyrazone molecule, C10H8BrN3O, (with synonym,1-phenyl-4-amino-5-bromopyridazon-(6) or 5-amino-4-bromo-2-phenyl-3(2H)-pyridazinone) were recorded experimentally. The molecular structure, vibrational wavenumbers, electronic transition absorption wavelengths in ethanol solvent, HOMOs and LUMOs analyses, molecular electrostatic potential (MEP), natural bond orbitals (NBO), nonlinear optical (NLO) properties and atomic charges of bromopyrazone molecule have been calculated by using DFT/B3LYP method with 6-311++G(d,p) basis set in ground state. The obtained results show that the calculated vibrational frequencies and UV-vis. values are in a good agreement with experimental data. Copyright © 2014 Elsevier B.V. All rights reserved.

A combined remote Raman and LIBS instrument for characterizing minerals with 532 nm laser excitation.

PubMed

Sharma, Shiv K; Misra, Anupam K; Lucey, Paul G; Lentz, Rachel C F

2009-08-01

The authors have developed an integrated remote Raman and laser-induced breakdown spectroscopy (LIBS) system for measuring both the Raman and LIBS spectra of minerals with a single 532 nm laser line of 35 mJ/pulse and 20 Hz. The instrument has been used for analyzing both Raman and LIBS spectra of carbonates, sulfates, hydrous and anhydrous silicates, and iron oxide minerals in air. These experiments demonstrate that by focusing a frequency-doubled 532 nm Nd:YAG pulsed laser beam with a 10x beam expander to a 529-microm diameter spot on a mineral surface located at 9 m, it is possible to measure simultaneously both the remote Raman and LIBS spectra of calcite, gypsum and olivine by adjusting the laser power electronically. The spectra of calcite, gypsum, and olivine contain fingerprint Raman lines; however, it was not possible to measure the remote Raman spectra of magnetite and hematite at 9 m because of strong absorption of 532 nm laser radiation and low intensities of Raman lines from these minerals. The remote LIBS spectra of both magnetite and hematite contain common iron emission lines but show difference in the minor amount of Li present in these two minerals. Remote Raman and LIBS spectra of a number of carbonates, sulfates, feldspars and phyllosilicates at a distance of 9 m were measured with a 532-nm laser operating at 35 mJ/pulse and by changing photon flux density at the sample by varying the spot diameter from 10 mm for Raman to 530 microm for LIBS measurements. The complementary nature of these spectra is highlighted and discussed. The combined Raman and LIBS system can also be re-configured to perform micro-Raman and micro-LIBS analyses, which have applications in trace/residue analysis and analysis of very small samples in the nano-gram range.

Experimental and theoretical investigation on the molecular structure, spectroscopic and electric properties of 2,4-dinitrodiphenylamine, 2-nitro-4-(trifluoromethyl)aniline and 4-bromo-2-nitroaniline

NASA Astrophysics Data System (ADS)

Hernández-Paredes, Javier; Hernández-Negrete, Ofelia; Carrillo-Torres, Roberto C.; Sánchez-Zeferino, Raúl; Duarte-Moller, Alberto; Alvarez-Ramos, Mario E.

2015-10-01

2,4-Dinitrodiphenylamine (I), 2-nitro-4-(trifluoromethyl)aniline (II) and 4-bromo-2-nitroaniline (III) have been investigated by DFT and experimental FTIR, Raman and UV-Vis spectroscopies. The gas-phase molecular geometries were consistent with similar compounds already reported in the literature. From the vibrational analysis, the main functional groups were identified and their absorption bands were assigned. Some differences were found between the calculated and the experimental UV-Vis spectra. These differences were analyzed and explained in terms of the TD-DFT/B3LYP limitations, which were mainly attributed to charge-transfer (CT) effects. These findings were in agreement with previous works, which reported that TD-DFT/B3LYP calculations diverge from experimental results when the electronic transitions involve CT. Despite this, TD-DFT/B3LYP calculations provided satisfactory results and a detailed description of the electronic transitions involved in the absorption bands of the UV-Vis spectra. In terms of the NLO properties, it was found that compound (I) is a good candidate for NLO applications and deserves further study due to its good β values. However, the β values for compounds (II) and (III) were negatively affected compared to those found on o-nitroaniline.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Atanasov, Petar A., E-mail: paatanas@ie.bas.bg; Nedyalkov, Nikolay N.; Valova, Eugenia I.

We present an experimental analysis on surface structuring of polydimethylsiloxane films with UV (263 nm) femtosecond laser pulses, in air. Laser processed areas are analyzed by optical microscopy, SEM, and μ-Raman spectroscopy. The laser-treated sample shows the formation of a randomly nanostructured surface morphology. μ-Raman spectra, carried out at both 514 and 785 nm excitation wavelengths, prior and after laser treatment allow evidencing the changes in the sample structure. The influence of the laser fluence on the surface morphology is studied. Finally, successful electro-less metallization of the laser-processed sample is achieved, even after several months from the laser-treatment contrary to previous observationmore » with nanosecond pulses. Our findings address the effectiveness of fs-laser treatment and chemical metallization of polydimethylsiloxane films with perspective technological interest in micro-fabrication devices for MEMS and nano-electromechanical systems.« less

Development of porous metal oxide thin films by co-evaporation

NASA Astrophysics Data System (ADS)

Tesfamichael, T.; Motta, Nunzio; Bostrom, Thor; Bell, J. M.

2007-03-01

This paper focuses on the development of mixed metal oxide thin films and physical characterization of the films. The films were produced by co-evaporation of titanium oxide and tungsten oxide powders. This allowed the development of titanium oxide-tungsten oxide films as analyzed using XPS. Examination in the SEM and AFM showed that the films were nanoporous with the pore size and pore orientation varying as a function of the deposition angle. UV-vis spectra of the films show an increase of transmittance with increasing deposition angle which is attributed to the structure and porosity of the films. Raman analysis indicated that the as-deposited films have broad and weak Raman characteristics, attributed to the nanocrystal nature of the films and the presence of defects, and the peak broadening deceases after annealing the film, as expected.

SHERLOC on Mars 2020

NASA Astrophysics Data System (ADS)

Beegle, L. W.; Bhartia, R.; DeFlores, L. P.; Abbey, W.; Asher, S. A.; Burton, A. S.; Fries, M.; Conrad, P. G.; Clegg, S. M.; Wiens, R. C.; Edgett, K. S.; Ehlmann, B. L.; Nealson, K. H.; Minitti, M. E.; Popp, J.; Langenhorst, F.; Sobron, P.; Steele, A.; Williford, K. H.; Yingst, R. A.

2017-12-01

The Scanning Habitable Environments with Raman & Luminescence for Organics & Chemicals (SHERLOC) investigation is part of the Mars 2020 integrated payload. SHERLOC enables non-contact, spatially resolved, and highly sensitivity detection and characterization of organics and minerals in the Martian surface and near subsurface. SHERLOC is an arm-mounted, Deep UV (DUV) resonance Raman and fluorescence spectrometer utilizing a 248.6-nm DUV laser. Deep UV induced native fluorescence is very sensitive to condensed carbon and aromatic organics, enabling detection at or below 10-6 w/w (1 ppm) at <100 µm spatial scales. SHERLOC's deep UV resonance Raman enables detection and classification of aromatic and aliphatic organics with sensitivities of 10-2 to below 10-4 w/w. In addition to organics, the deep UV Raman enables detection and classification of minerals relevant to aqueous chemistry with grain sizes below 20 µm. SHERLOC will be able to map the distribution of organic material with respect to visible features and minerals that are identifiable with the Raman spectrometer. These maps will enable analysis of the distribution of organics with minerals.

Mildly reduced graphene oxide-Ag nanoparticle hybrid films for surface-enhanced Raman scattering

PubMed Central

2012-01-01

Large-area mildly reduced graphene oxide (MR-GO) monolayer films were self-assembled on SiO2/Si surfaces via an amidation reaction strategy. With the MR-GO as templates, MR-GO-Ag nanoparticle (MR-GO-Ag NP) hybrid films were synthesized by immersing the MR-GO monolayer into a silver salt solution with sodium citrate as a reducing agent under UV illumination. SEM image indicated that Ag NPs with small interparticle gap are uniformly distributed on the MR-GO monolayer. Raman spectra demonstrated that the MR-GO monolayer beneath the Ag NPs can effectively quench the fluorescence signal emitted from the Ag films and dye molecules under laser excitation, resulting in a chemical enhancement (CM). The Ag NPs with narrow gap provided numerous hot spots, which are closely related with electromagnetic mechanism (EM), and were believed to remarkably enhance the Raman signal of the molecules. Due to the co-contribution of the CM and EM effects as well as the coordination mechanism between the MR-GO and Ag NPs, the MR-GO-Ag NP hybrid films showed more excellent Raman signal enhancement performance than that of either Ag films or MR-GO monolayer alone. This will further enrich the application of surface-enhanced Raman scattering in molecule detection. PMID:22471923

Combined fluorescence-Raman spectroscopy measurements with an optical fiber probe for the diagnosis of melanocytic lesions

NASA Astrophysics Data System (ADS)

Cosci, Alessandro; Cicchi, Riccardo; Rossari, Susanna; De Giorgi, Vincenzo; Massi, Daniela; Pavone, Francesco S.

2012-02-01

We have designed and developed an optical fiber-probe for spectroscopic measurements on human tissues. The experimental setup combines fluorescence spectroscopy and Raman spectroscopy in a multidimensional approach. Concerning fluorescence spectroscopy, the excitation is provided by two laser diodes, one emitting in the UV (378 nm) and the other emitting in the visible (445 nm). These two lasers are used to selectively excite fluorescence from NADH and FAD, which are among the brightest endogenous fluorophores in human tissues. For Raman and NIR spectroscopy, the excitation is provided by a third laser diode with 785 nm excitation wavelength. Laser light is delivered to the tissue through the central optical fiber of a fiber bundle. The surrounding 48 fibers of the bundle are used for collecting fluorescence and Raman and for delivering light to the spectrograph. Fluorescence and Raman spectra are acquired on a cooled CCD camera. The instrument has been tested on fresh human skin biopsies clinically diagnosed as malignant melanoma, melanocytic nevus, or healthy skin, finding an optimal correlation with the subsequent histological exam. In some cases our examination was not in agreement with the clinical observation, but it was with the histological exam, demonstrating that the system can potentially contribute to improve clinical diagnostic capabilities and hence reduce the number of unnecessary biopsies.

Quick detection of traditional Chinese medicine ‘Atractylodis Macrocephalae Rhizoma’ pieces by surface-enhanced Raman spectroscopy

NASA Astrophysics Data System (ADS)

Huang, Hao; Shi, Hong; Feng, Shangyuan; Lin, Juqiang; Chen, Weiwei; Yu, Yun; Lin, Duo; Xu, Qian; Chen, Rong

2013-01-01

A surface-enhanced Raman spectroscopy (SERS) method was developed for the analysis of traditional Chinese medicine ‘Atractylodis Macrocephalae Rhizoma’ pieces (AMRP) for the first time with the aim to develop a quick method for traditional Chinese medicine detection. Both Raman spectra and SERS spectra were obtained from AMRP, and tentative assignments of the Raman bands in the measured spectra suggested that only a few weak Raman peaks could be observed in the regular Raman spectra, while primary Raman peaks at around 536, 555, 619, 648, 691, 733, 790, 958, 1004, 1031, 1112, 1244, 1324, 1395, 1469, 1574 and 1632 cm-1 could be observed in the SERS spectra, with the strongest signals at 619, 733, 958, 1324, 1395 and 1469 cm-1. This was due to a strong interaction between the silver colloids and the AMRP, which led to an extraordinary enhancement in the intensity of the Raman scattering in AMRP. This exploratory study suggests the SERS technique has great potential for providing a novel non-destructive method for effectively and accurately detecting traditional Chinese medicine without complicated separation and extraction.

Gem and mineral identification using GL Gem Raman and comparison with other portable instruments

NASA Astrophysics Data System (ADS)

Culka, Adam; Hyršl, Jaroslav; Jehlička, Jan

2016-11-01

Several mainly silicate minerals in their gemstone varieties have been analysed by the Gem Raman portable system by Gemlab R&T, Vancouver, Canada, in order to ascertain the general performance of this relatively non-expensive tool developed exactly for the purpose of gemstone identification. The Raman spectra of gemstones acquired by this system have been subsequently critically compared with the data obtained by several other portable or handheld Raman instruments. The Raman spectra acquired with the Gem Raman instrument were typically of lesser quality when compared with the spectra taken by other instruments. Characteristic features such as steep baseline probably due to the fluorescence of the minerals, Raman bands much broader and therefore less resolved closely located Raman bands, and generally greater shifts of the band positions from the reference values were encountered. Some gemstone groups such as rubies did not provide useful Raman spectra at all. Nevertheless, general identification of gemstones was possible for a selection of gemstones.

The temporal evolution process from fluorescence bleaching to clean Raman spectra of single solid particles optically trapped in air

NASA Astrophysics Data System (ADS)

Gong, Zhiyong; Pan, Yong-Le; Videen, Gorden; Wang, Chuji

2017-12-01

We observe the entire temporal evolution process of fluorescence and Raman spectra of single solid particles optically trapped in air. The spectra initially contain strong fluorescence with weak Raman peaks, then the fluorescence was bleached within seconds, and finally only the clean Raman peaks remain. We construct an optical trap using two counter-propagating hollow beams, which is able to stably trap both absorbing and non-absorbing particles in air, for observing such temporal processes. This technique offers a new method to study dynamic changes in the fluorescence and Raman spectra from a single optically trapped particle in air.

Absorption and resonance Raman spectra of Pb2, Pb3, and Pb4 in xenon matrices

NASA Technical Reports Server (NTRS)

Stranz, D. D.; Khanna, R. K.

1981-01-01

Matrix isolation techniques are used to investigate the spectra of lead molecules and, in particular, to obtain resonance Raman spectra of lead vapors isolated in solid xenon matrices. The presence of Pb2 is confirmed by the visible adsorption, and Raman spectra yield a vibrational frequency for the ground state of 108 per cm and a dissociation energy of 8200 per cm. A second resonance Raman progression indicates a Pb3 species of D3h symmetry. Finally, two additional Raman features at approximately 111 per cm spacing are evidence for a third species, tentatively identified as Pb4.

Characterization of sp3 bond content of carbon films deposited by high power gas injection magnetron sputtering method by UV and VIS Raman spectroscopy.

PubMed

Zdunek, Krzysztof; Chodun, Rafał; Wicher, Bartosz; Nowakowska-Langier, Katarzyna; Okrasa, Sebastian

2018-04-05

This paper presents the results of investigations of carbon films deposited by a modified version of the magnetron sputtering method - HiPGIMS (High Power Gas Injection Magnetron Sputtering). In this experiment, the magnetron system with inversely polarized electrodes (sputtered cathode at ground potential and positively biased, spatially separated anode) was used. This arrangement allowed us to conduct the experiment using voltages ranging from 1 to 2kV and a power supply system equipped with 25/50μF capacitor battery. Carbon films were investigated by VIS/UV Raman spectroscopy. Sp 3 /sp 2 bonding ratio was evaluated basing the elementary components of registered spectra. Our investigation showed that sp 3 bond content increases with discharge power but up to specific value only. In extreme conditions of generating plasma impulses, we detected a reversed relation of the sp 3 /sp 2 ratio. In our opinion, a energy of plasma pulse favors nucleation of a sp 3 phase because of a relatively higher ionization state but in extreme cases the influence of energy is reversed. Copyright © 2018 Elsevier B.V. All rights reserved.

Quaternary ammonium oxidative demethylation: X-ray crystallographic, resonance Raman, and UV-visible spectroscopic analysis of a Rieske-type demethylase.

PubMed

Daughtry, Kelly D; Xiao, Youli; Stoner-Ma, Deborah; Cho, Eunsun; Orville, Allen M; Liu, Pinghua; Allen, Karen N

2012-02-08

Herein, the structure resulting from in situ turnover in a chemically challenging quaternary ammonium oxidative demethylation reaction was captured via crystallographic analysis and analyzed via single-crystal spectroscopy. Crystal structures were determined for the Rieske-type monooxygenase, stachydrine demethylase, in the unliganded state (at 1.6 Å resolution) and in the product complex (at 2.2 Å resolution). The ligand complex was obtained from enzyme aerobically cocrystallized with the substrate stachydrine (N,N-dimethylproline). The ligand electron density in the complex was interpreted as proline, generated within the active site at 100 K by the absorption of X-ray photon energy and two consecutive demethylation cycles. The oxidation state of the Rieske iron-sulfur cluster was characterized by UV-visible spectroscopy throughout X-ray data collection in conjunction with resonance Raman spectra collected before and after diffraction data. Shifts in the absorption band wavelength and intensity as a function of absorbed X-ray dose demonstrated that the Rieske center was reduced by solvated electrons generated by X-ray photons; the kinetics of the reduction process differed dramatically for the liganded complex compared to unliganded demethylase, which may correspond to the observed turnover in the crystal.

Spectroscopic properties of halite from Kłodawa salt mine, central Poland

NASA Astrophysics Data System (ADS)

Zelek, Sylwia M.; Wesełucha-Birczyńska, Aleksandra; Szklarzewicz, Janusz; Stadnicka, Katarzyna M.

2015-02-01

The dynamics of colour centre transformation was investigated in blue halite single crystals from Kłodawa Salt Mine, Central Poland, using UV-vis spectroscopy. The following colour centres were considered: F, R1, R2, as well as plasmons and M centres. The R2 centres predominated in navy blue (A) and pale blue (B) halites. Other relatively large populations were plasmons found in all examined samples. In purple (C) halite samples the plasmon population is the highest one among others and R1 centres appeared to be equally significant, whereas M centres were almost absent. For A and C samples unidentified bands were observed at 26,500 to 26,200 cm-1, respectively. The bleaching process of the blue halites was investigated using temperature dependent UV-vis and micro-Raman spectroscopies. In micro-Raman 300-100 cm-1 region three very intense sharp bands were attributed to the colour centres and colloidal Na precipitation in A and B halites. The one broad band in the range 3,500 to 500 cm-1, which was characteristic even for the colourless sample D but absent in the spectra of colourless NaCl obtained after recrystallization of sample A, requires further study.

Aromatic hydrazones derived from nicotinic acid hydrazide as fluorimetric pH sensing molecules: Structural analysis by computational and spectroscopic methods in solid phase and in solution

NASA Astrophysics Data System (ADS)

Benković, T.; Kenđel, A.; Parlov-Vuković, J.; Kontrec, D.; Chiş, V.; Miljanić, S.; Galić, N.

2018-02-01

Structural analyses of aroylhydrazones were performed by computational and spectroscopic methods (solid state NMR, 1 and 2D NMR spectroscopy, FT-IR (ATR) spectroscopy, Raman spectroscopy, UV-Vis spectrometry and spectrofluorimetry) in solid state and in solution. The studied compounds were N‧-(2,3-dihydroxyphenylmethylidene)-3-pyridinecarbohydrazide (1), N‧-(2,5-dihydroxyphenylmethylidene)-3-pyridinecarbohydrazide (2), N‧-(3-chloro-2-hydroxy-phenylmethylidene)-3-pyridinecarbohydrazide (3), and N‧-(2-hydroxy-4-methoxyphenyl-methylidene)-3-pyridinecarbohydrazide (4). Both in solid state and in solution, all compounds were in ketoamine form (form I, sbnd COsbnd NHsbnd Ndbnd Csbnd), stabilized by intramolecular H-bond between hydroxyl proton and nitrogen atom of the Cdbnd N group. In solid state, the Cdbnd O group of 1-4 were involved in additional intermolecular H-bond between closely packed molecules. Among hydrazones studied, the chloro- and methoxy-derivatives have shown pH dependent and reversible fluorescence emission connected to deprotonation/protonation of salicylidene part of the molecules. All findings acquired by experimental methods (NMR, IR, Raman, and UV-Vis spectra) were in excellent agreement with those obtained by computational methods.

The green hydrothermal synthesis of nanostructured Cu2ZnSnSe4 as solar cell material and study of their structural, optical and morphological properties

NASA Astrophysics Data System (ADS)

Vanalakar, S. A.; Agawane, G. L.; Kamble, A. S.; Patil, P. S.; Kim, J. H.

2017-12-01

Cu2ZnSnSe4 (CZTSe) has attracted intensive attention as an absorber material for the thin-film solar cells due to its high absorption coefficient, direct band gap, low toxicity, and abundance of its constituent elements. In this study nanostructured CZTSe nanoparticles are prepared via green hydrothermal synthesis without using toxic solvents, organic amines, catalysts or noxious chemicals. The structural, optical, and morphological properties of CZTSe nanostructured powder were studied using X-ray diffraction (XRD), Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), UV-vis absorption spectroscopy, and transmission electron microscope (TEM) techniques. Raman peaks at 170, 195, and 232 cm-1 confirm the formation of pure phase CZTSe nanostructured particles. In addition, the EDS and XPS results confirm the appropriate chemical purity of the annealed CZTSe nanoparticles. Meanwhile, the TEM analysis showed the presence of phase pure oval like CZTSe particle with size of about 80-140 nm. The UV-Vis-NIR absorption spectra analysis showed that the optical band gap of CZTSe nanostructured particles is about 1.14 eV. This band gap energy is close to the optimum value of a photovoltaic solar cell absorber material.

Quantitative methods for structural characterization of proteins based on deep UV resonance Raman spectroscopy.

PubMed

Shashilov, Victor A; Sikirzhytski, Vitali; Popova, Ludmila A; Lednev, Igor K

2010-09-01

Here we report on novel quantitative approaches for protein structural characterization using deep UV resonance Raman (DUVRR) spectroscopy. Specifically, we propose a new method combining hydrogen-deuterium (HD) exchange and Bayesian source separation for extracting the DUVRR signatures of various structural elements of aggregated proteins including the cross-beta core and unordered parts of amyloid fibrils. The proposed method is demonstrated using the set of DUVRR spectra of hen egg white lysozyme acquired at various stages of HD exchange. Prior information about the concentration matrix and the spectral features of the individual components was incorporated into the Bayesian equation to eliminate the ill-conditioning of the problem caused by 100% correlation of the concentration profiles of protonated and deuterated species. Secondary structure fractions obtained by partial least squares (PLS) and least squares support vector machines (LS-SVMs) were used as the initial guess for the Bayessian source separation. Advantages of the PLS and LS-SVMs methods over the classical least squares calibration (CLSC) are discussed and illustrated using the DUVRR data of the prion protein in its native and aggregated forms. Copyright (c) 2010 Elsevier Inc. All rights reserved.

Surface-enhanced Raman scattering (SERS) spectra of sodium benzoate and 4-picoline in Ag colloids prepared by γ-irradiation

NASA Astrophysics Data System (ADS)

Choi, Seong-Ho; Park, Hyun Gyu

2005-04-01

PVP-protected silver colloids were prepared by γ-irradiation and chemical reduction method. Surface-enhanced Raman scattering (SERS) spectra of sodium benzoate and 4-picoline in Ag colloids prepared by γ-irradiation were recorded. The SERS spectra of sodium benzoate were successfully recorded in Ag colloids, whereas the Raman spectra did not appear without Ag colloids. The Raman spectra of 4-picoline were not detected without Ag colloids, while the SERS spectra of 4-picoline were increased by adding Ag colloids. The carboxylate group of sodium benzoate and N donor of 4-picoline were adsorbed on the surface of Ag nanoparticles.

Chemical composition of matrix-embedded ternary II-VI nanocrystals derived from first- and second-order Raman spectra

NASA Astrophysics Data System (ADS)

Azhniuk, Yu. M.; Hutych, Yu. I.; Lopushansky, V. V.; Prymak, M. V.; Gomonnai, A. V.; Zahn, D. R. T.

2016-12-01

A one- and multiphonon Raman scattering study is performed for an extensive set of CdS1-xSex, Cd1-yZnyS, Cd1-yZnySe, and CdSe1-xTex nanocrystals to investigate the applicability of first- and second-order Raman spectra for the determination of the matrix-embedded ternary nanocrystal composition. For one-mode ternary systems both the LO and 2LO phonon frequencies in the Raman spectra are shown to be a good measure of the nanocrystal composition. For two-mode systems, the approaches based on the difference of the LO phonon frequencies (first-order Raman spectra) or double LO overtone and combination tone frequencies (second-order Raman spectra) as well as on the LO phonon band intensity ratios are analysed. The weak electron-phonon coupling in the II-VI nanocrystals and the polaron constant values for the nanocrystal sublattices are discussed.

Multifunctional silver nanoparticle-doped silica for solid-phase extraction and surface-enhanced Raman scattering detection

NASA Astrophysics Data System (ADS)

Markina, Natalia E.; Markin, Alexey V.; Zakharevich, Andrey M.; Gorin, Dmitry A.; Rusanova, Tatiana Yu.; Goryacheva, Irina Yu.

2016-12-01

Multifunctional silica gel with embedded silver nanoparticles (SiO2-AgNP) is proposed for application as sorbent for solid-phase extraction (SPE) and simultaneously as substrate for surface-enhanced Raman spectroscopy (SERS) due to their high sorption properties and ability to enhance Raman signal (SERS-active sorbents). SiO2-AgNP was synthesized via alkaline hydrolysis of tetraethyl orthosilicate with simultaneous reduction of silver ions to silver nanoparticles (AgNP) within the SiO2 bulk. Synthesis of AgNP directly to the SiO2 matrix enables to exclude any additional stabilizers for the nanoparticles that educes signal-to-noise ratio during SERS measurement. Apart from Raman spectroscopy, obtained sorbents were also characterized by scanning electron microscopy and UV-visible diffuse reflectance spectroscopy. The influence of AgNO3 concentration used during the SiO2-AgNP synthesis on its gelling time, color, diffuse reflectance spectra, and enhancement of Raman signal was investigated. A Raman enhancement factor of SiO2-AgNP with optimal composition was around 105. Finally, the sorbents were applied for SPE and subsequent SERS detection of model compounds (rhodamine 6G and folic acid). It was found that SPE enables to decrease detectable concentrations by two orders. Therefore, SPE combined with SERS has high potential for further analytical investigations.

Enhanced broadband near-infrared luminescence from Pr3+-doped tellurite glass with silver nanoparticles

NASA Astrophysics Data System (ADS)

Cheng, Pan; Zhou, Yaxun; Zhou, Minghan; Su, Xiue; Zhou, Zizhong; Yang, Gaobo

2017-11-01

Pr3+-doped tellurite glasses containing metallic silver NPs were synthesized by the conventional melt-quenching technique. Structural, thermal and optical properties of the synthesized glass samples were characterized by X-Ray diffraction (XRD) curves, Raman spectra, differential scanning calorimeter (DSC) curves, transmission electron microscopy (TEM) images, UV/Vis/NIR absorption and near-infrared fluorescence emission spectra. The XRD curves confirmed the amorphous structural nature of the synthesized glasses, the Raman spectra identified the presence of different vibrational groups, the DSC curves verified the good thermal stability, and the TEM images revealed the nucleated silver NPs with average diameter about 10 nm dispersed in the glass matrix and its surface Plasmon resonance (SPR) absorption band was located at around 510 nm. Besides, Judd-Ofelt intensity parameters Ωt (t = 2, 4, 6) and other important spectroscopic parameters like transition probability, radiative lifetime, branching ratio were calculated to evaluate the radiative properties of Pr3+ levels from the measured optical absorption spectra. It was found that Pr3+-doped tellurite glasses could emit an ultra-broadband fluorescence extending from 1250 to 1650 nm under the 488 nm excitation, and this fluorescence emission increased further with the introduction of silver NPs. The enhanced fluorescence was mainly attributed to the increased local electric field around Pr3+ induced by silver NPs. The present results demonstrate that Pr3+-Ag codoped tellurite glass is a promising candidate for the near-infrared band ultra-broadband fiber amplifiers covering the expanded low-loss communication window.

Structure, spectra and thermal, mechanical, Faraday rotation properties of novel diamagnetic SeO2-PbO-Bi2O3-B2O3 glasses

NASA Astrophysics Data System (ADS)

Chen, Qiuling; Su, Kai; Li, Yantao; Zhao, Zhiwei

2018-06-01

Faraday rotation diamagnetic glass has attracted research attentions in photonics, sensing and magneto optical devices due to their high refractive index, wide transmittance in UV and Fourier transform infrared (FT-IR) range and temperature independent Faraday rotation. Selenite modified heavy metal oxides glasses with composition of xSeO2-(10-x) B2O3-45PbO-45Bi2O3 (x = 0, 1, 5 and 10mol%) and 15%SeO2-40%PbO-45%Bi2O3 have been fabricated by melt-quenching method in present study. The influence of SeO2 on glass forming ability, thermal, mechanical properties and Faraday rotation were evaluated through X-ray Diffraction (XRD), Fourier transforms infrared spectra (FT-IR), Raman, X-ray photoelectron spectroscopy (XPS), differential scanning calorimetry (DSC), Vicker's hardness and Verdet constant measurements. XRD spectra reveal that the good vitrification was achieved for glass with SeO2 amounts ≤10% even without B2O3. FT-IR, Raman and XPS spectra ascertain the existence of characteristic vibration of SeO4, SeO3, PbO4, BiO3 and BO3 units. The incorporation of SeO2 increases the connectivity of glassy network by increasing the Tg, thermal stability and mechanical hardness. The small band gap, high polarizable Se4+ ions and isolated SeO3 units contribute to Faraday rotation improvement.

Detection of munitions grade g-series nerve agents using Raman excitation at 1064 nm

NASA Astrophysics Data System (ADS)

Roy, Eric; Wilcox, Phillip G.; Hoffland, Soren; Pardoe, Ian

2015-05-01

Raman spectroscopy is a powerful tool for obtaining molecular structure information of a sample. While Raman spectroscopy is a common laboratory based analytical tool, miniaturization of opto-electronic components has allowed handheld Raman analyzers to become commercially available. These handheld systems are utilized by Military and First Responder operators tasked with rapidly identifying potentially hazardous chemicals in the field. However, one limitation of many handheld Raman detection systems is strong interference caused by fluorescence of the sample or underlying surface which obscures the characteristic Raman signature of the target analyte. Munitions grade chemical warfare agents (CWAs) are produced and stored in large batches and typically have more impurities from the storage container, degradation, or unreacted precursors. In this work, Raman spectra of munitions grade CWAs were collected using a handheld Raman spectrometer with a 1064 nm excitation laser. While Raman scattering generated by a 1064 nm laser is inherently less efficient than excitation at shorter wavelengths, high quality spectra were easily obtained due to significantly reduced fluorescence of the munitions grade CWAs. The spectra of these less pure, but more operationally relevant, munitions grade CWAs were then compared to spectra of CASARM grade CWAs, as well as Raman spectra collected using the more common 785 nm excitation laser.

Graphene Dendrimer-stabilized silver nanoparticles for detection of methimazole using Surface-enhanced Raman scattering with computational assignment

NASA Astrophysics Data System (ADS)

Saleh, Tawfik A.; Al-Shalalfeh, Mutasem M.; Al-Saadi, Abdulaziz A.

2016-08-01

Graphene functionalized with polyamidoamine dendrimer, decorated with silver nanoparticles (G-D-Ag), was synthesized and evaluated as a substrate with surface-enhanced Raman scattering (SERS) for methimazole (MTZ) detection. Sodium borohydride was used as a reducing agent to cultivate silver nanoparticles on the dendrimer. The obtained G-D-Ag was characterized by using UV-vis spectroscopy, scanning electron microscope (SEM), high-resolution transmission electron microscope (TEM), Fourier-transformed infrared (FT-IR) and Raman spectroscopy. The SEM image indicated the successful formation of the G-D-Ag. The behavior of MTZ on the G-D-Ag as a reliable and robust substrate was investigated by SERS, which indicated mostly a chemical interaction between G-D-Ag and MTZ. The bands of the MTZ normal spectra at 1538, 1463, 1342, 1278, 1156, 1092, 1016, 600, 525 and 410 cm-1 were enhanced due to the SERS effect. Correlations between the logarithmical scale of MTZ concentrations and SERS signal intensities were established, and a low detection limit of 1.43 × 10-12 M was successfully obtained. The density functional theory (DFT) approach was utilized to provide reliable assignment of the key Raman bands.

Graphene Dendrimer-stabilized silver nanoparticles for detection of methimazole using Surface-enhanced Raman scattering with computational assignment

PubMed Central

Saleh, Tawfik A.; Al-Shalalfeh, Mutasem M.; Al-Saadi, Abdulaziz A.

2016-01-01

Graphene functionalized with polyamidoamine dendrimer, decorated with silver nanoparticles (G-D-Ag), was synthesized and evaluated as a substrate with surface-enhanced Raman scattering (SERS) for methimazole (MTZ) detection. Sodium borohydride was used as a reducing agent to cultivate silver nanoparticles on the dendrimer. The obtained G-D-Ag was characterized by using UV-vis spectroscopy, scanning electron microscope (SEM), high-resolution transmission electron microscope (TEM), Fourier-transformed infrared (FT-IR) and Raman spectroscopy. The SEM image indicated the successful formation of the G-D-Ag. The behavior of MTZ on the G-D-Ag as a reliable and robust substrate was investigated by SERS, which indicated mostly a chemical interaction between G-D-Ag and MTZ. The bands of the MTZ normal spectra at 1538, 1463, 1342, 1278, 1156, 1092, 1016, 600, 525 and 410 cm−1 were enhanced due to the SERS effect. Correlations between the logarithmical scale of MTZ concentrations and SERS signal intensities were established, and a low detection limit of 1.43 × 10−12 M was successfully obtained. The density functional theory (DFT) approach was utilized to provide reliable assignment of the key Raman bands. PMID:27572919

Discriminating model for diagnosis of basal cell carcinoma and melanoma in vitro based on the Raman spectra of selected biochemicals

NASA Astrophysics Data System (ADS)

Silveira, Landulfo; Silveira, Fabrício Luiz; Bodanese, Benito; Zângaro, Renato Amaro; Pacheco, Marcos Tadeu T.

2012-07-01

Raman spectroscopy has been employed to identify differences in the biochemical constitution of malignant [basal cell carcinoma (BCC) and melanoma (MEL)] cells compared to normal skin tissues, with the goal of skin cancer diagnosis. We collected Raman spectra from compounds such as proteins, lipids, and nucleic acids, which are expected to be represented in human skin spectra, and developed a linear least-squares fitting model to estimate the contributions of these compounds to the tissue spectra. We used a set of 145 spectra from biopsy fragments of normal (30 spectra), BCC (96 spectra), and MEL (19 spectra) skin tissues, collected using a near-infrared Raman spectrometer (830 nm, 50 to 200 mW, and 20 s exposure time) coupled to a Raman probe. We applied the best-fitting model to the spectra of biochemicals and tissues, hypothesizing that the relative spectral contribution of each compound to the tissue Raman spectrum changes according to the disease. We verified that actin, collagen, elastin, and triolein were the most important biochemicals representing the spectral features of skin tissues. A classification model applied to the relative contribution of collagen III, elastin, and melanin using Euclidean distance as a discriminator could differentiate normal from BCC and MEL.

Time Resolved Raman and Fluorescence Spectrometer for Planetary Mineralogy

NASA Astrophysics Data System (ADS)

Blacksberg, Jordana; Rossman, George

2010-05-01

Raman spectroscopy is a prime candidate for the next generation of planetary instruments, as it addresses the primary goal of mineralogical analysis which is structure and composition. It does not require sample preparation and provides unique mineral fingerprints, even for mixed phase samples. However, large fluorescence return from many mineral samples under visible light excitation can seriously compromise the quality of the spectra or even render Raman spectra unattainable. Fluorescence interference is likely to be a problem on Mars and is evident in Raman spectra of Martian Meteorites[1]. Our approach uses time resolution for elimination of fluorescence from Raman spectra, allowing for traditional visible laser excitation (532 nm). Since Raman occurs instantaneously with the laser pulse and fluorescence lifetimes vary from nsec to msec depending on the mineral, it is possible to separate them out in time. Complementary information can also be obtained simultaneously using the time resolved fluorescence data. The Simultaneous Spectral Temporal Adaptive Raman Spectrometer (SSTARS) is a planetary instrument under development at the Jet Propulsion Laboratory, capable of time-resolved in situ Raman and fluorescence spectroscopy. A streak camera and pulsed miniature microchip laser provide psec scale time resolution. Our ability to observe the complete time evolution of Raman and fluorescence in minerals provides a foundation for design of pulsed Raman and fluorescence spectrometers in diverse planetary environments. We will discuss the SSTARS instrument design and performance capability. We will also present time-resolved pulsed Raman spectra collected from a relevant set of minerals selected using available data on Mars mineralogy[2]. Of particular interest are minerals resulting from aqueous alteration on Mars. For comparison, we will present Raman spectra obtained using a commercial continuous wave (CW) green (514 nm) Raman system. In many cases using a CW laser the strong mineral fluorescence saturates the detector and Raman spectra are unattainable. This problem is overcome by using time resolved Raman where fluorescence is eliminated. [1]Frosch et al., Anal. Chem. 2007, 79, 1101-1108 [2]Bell, J.,ed, The Martian Surface: Composition, Mineralogy, and physical Properties, Cambridge University Press, 2008

Excited-state Raman spectroscopy with and without actinic excitation: S{sub 1} Raman spectra of trans-azobenzene

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dobryakov, A. L.; Quick, M.; Ioffe, I. N.

We show that femtosecond stimulated Raman spectroscopy can record excited-state spectra in the absence of actinic excitation, if the Raman pump is in resonance with an electronic transition. The approach is illustrated by recording S{sub 1} and S{sub 0} spectra of trans-azobenzene in n-hexane. The S{sub 1} spectra were also measured conventionally, upon nπ* (S{sub 0} → S{sub 1}) actinic excitation. The results are discussed and compared to earlier reports.

Optical, structural, and chemical properties of CR-39 implanted with 5.2 MeV doubly charged carbon ions

NASA Astrophysics Data System (ADS)

Ali, Dilawar; Butt, M. Z.; Ishtiaq, Mohsin; Waqas Khaliq, M.; Bashir, Farooq

2016-11-01

Poly-allyl-diglycol-carbonate (CR-39) specimens were irradiated with 5.2 MeV doubly charged carbon ions using Pelletron accelerator. Ion dose was varied from 5 × 1013 to 5 × 1015 ions cm-2. Optical, structural, and chemical properties were investigated by UV-vis spectroscopy, x-ray diffractometer, and FTIR/Raman spectroscopy, respectively. It was found that optical absorption increases with increasing ion dose. Absorption edge shifts from UV region to visible region. The measured opacity values of pristine and ion implanted CR-39 range from 0.0519 to 4.7959 mm-1 following an exponential growth (9141%) with the increase in ion dose. The values of direct and indirect band gap energy decrease exponentially with an increase in ion dose by 59% and 71%, respectively. However, average refractive index in the visible region increases from 1.443 to 2.864 with an increase in ion dose, by 98%. A linear relation between band gap energy and crystallite size was observed. Both the number of carbon atoms in conjugation length and the number of carbon atoms per cluster increase linearly with the increase in ion dose. FTIR spectra showed that on C+2 ions irradiation, the intensity of all bands decreases gradually without appearance of any new band, indicating degradation of polymer after irradiation. Raman spectra revealed that the density of -CH2- group decreases on C+2 ions irradiation. However, the structure of CR-39 is completely destroyed on irradiation with ion dose 1 × 1015 and 5 × 1015 ions cm-2.

Molecular structure investigation of neutral, dimer and anion forms of 3,4-pyridinedicarboxylic acid: A combined experimental and theoretical study

NASA Astrophysics Data System (ADS)

Karabacak, Mehmet; Bilgili, Sibel; Atac, Ahmet

2015-01-01

In this study, the structural and vibrational analysis of 3,4-pyridinedicarboxylic acid (3,4-PDCA) are presented using experimental techniques as FT-IR, FT-Raman, NMR, UV and quantum chemical calculations. FT-IR and FT-Raman spectra of 3,4-pyridinedicarboxylic acid in the solid phase are recorded in the region 4000-400 cm-1 and 4000-50 cm-1, respectively. The geometrical parameters and energies of all different and possible monomer, dimer, anion-1 and anion-2 conformers of 3,4-PDCA are obtained from Density Functional Theory (DFT) with B3LYP/6-311++G(d,p) basis set. There are sixteen conformers (C1sbnd C16) for this molecule (neutral form). The most stable conformer of 3,4-PDCA is the C1 conformer. The complete assignments are performed on the basis of the total energy distribution (TED) of the vibrational modes calculated with scaled quantum mechanics (SQM) method. 1H and 13C NMR spectra are recorded and the chemical shifts are calculated by using DFT/B3LYP methods with 6-311++G(d,p) basis set. The UV absorption spectrum of the studied compound is recorded in the range of 200-400 nm by dissolved in ethanol. The optimized geometric parameters were compared with experimental data via the X-ray results derived from complexes of this molecule. In addition these, molecular electrostatic potential (MEP), thermodynamic and electronic properties, HOMO-LUMO energies and Mulliken atomic charges, are performed.

Molecular structure investigation of neutral, dimer and anion forms of 3,4-pyridinedicarboxylic acid: a combined experimental and theoretical study.

PubMed

Karabacak, Mehmet; Bilgili, Sibel; Atac, Ahmet

2015-01-25

In this study, the structural and vibrational analysis of 3,4-pyridinedicarboxylic acid (3,4-PDCA) are presented using experimental techniques as FT-IR, FT-Raman, NMR, UV and quantum chemical calculations. FT-IR and FT-Raman spectra of 3,4-pyridinedicarboxylic acid in the solid phase are recorded in the region 4000-400 cm(-1) and 4000-50 cm(-1), respectively. The geometrical parameters and energies of all different and possible monomer, dimer, anion(-1) and anion(-2) conformers of 3,4-PDCA are obtained from Density Functional Theory (DFT) with B3LYP/6-311++G(d,p) basis set. There are sixteen conformers (C1C16) for this molecule (neutral form). The most stable conformer of 3,4-PDCA is the C1 conformer. The complete assignments are performed on the basis of the total energy distribution (TED) of the vibrational modes calculated with scaled quantum mechanics (SQM) method. (1)H and (13)C NMR spectra are recorded and the chemical shifts are calculated by using DFT/B3LYP methods with 6-311++G(d,p) basis set. The UV absorption spectrum of the studied compound is recorded in the range of 200-400 nm by dissolved in ethanol. The optimized geometric parameters were compared with experimental data via the X-ray results derived from complexes of this molecule. In addition these, molecular electrostatic potential (MEP), thermodynamic and electronic properties, HOMO-LUMO energies and Mulliken atomic charges, are performed. Copyright © 2014 Elsevier B.V. All rights reserved.

Characteristics Of Bridging Oxo And Sulfido Groups In Multinuclear Iron Proteins

NASA Astrophysics Data System (ADS)

Loehr, Thomas M.

1989-07-01

The presence of oxo-bridged dinuclear iron clusters has been established in the respiratory protein, hemerythrin (Hr), and in the DNA-biosynthesis regulatory enzyme, ribonucleotide reductase (Rr). For the iron proteins uteroferrin and purple acid phosphatase (PAP) evidence for μ-oxo-bridged centers is less clear. Resonance Raman (RR) spectra obtained by excitation into an 0(2-) --> Fe(III) CT band may show strong symmetric and weak antisymmetric Fe-0-Fe vibrational modes. We have investigated the spectra of a variety of μ-oxo-bridged Fe(III) complexes to establish the dependence of Raman scattering intensities upon structural parameters. Intensities were found to relate to the nature of the ligand trans to the oxo group: nitrogen ligands with unsaturation (e.g., pyrazole and imidazole) lead to strong scattering, whereas saturated ligands provide only poor scattering. The Fe-0 bonds in Hr and Rr are strong scatterers; the former is known from x-ray crystallography to have a histidyl ligand trans to the μ-oxo group. On this basis, a similar ligand structure is likely in the reductase. In contrast, PAP shows no oxo-bridge with UV and near-UV excitation. We propose that a different structural framework is necessary to account for this result. Hydrogen bonding of protein side chains to oxo and sulfido ligands is proposed to explain changes in frequencies for samples dissolved in water vs. D20. Differences in hydrogen-bond strengths between 0...(D) and S...(D) systems are transferred to the observed Fe-0 and Fe-S bond vibrations.

Study of conformational stability, structural, electronic and charge transfer properties of cladrin using vibrational spectroscopy and DFT calculations.

PubMed

Singh, Swapnil; Singh, Harshita; Srivastava, Anubha; Tandon, Poonam; Sinha, Kirti; Bharti, Purnima; Kumar, Sudhir; Kumar, Padam; Maurya, Rakesh

2014-11-11

In the present work, a detailed conformational study of cladrin (3-(3,4-dimethoxy phenyl)-7-hydroxychromen-4-one) has been done by using spectroscopic techniques (FT-IR/FT-Raman/UV-Vis/NMR) and quantum chemical calculations. The optimized geometry, wavenumber and intensity of the vibrational bands of the cladrin in ground state were calculated by density functional theory (DFT) employing 6-311++G(d,p) basis sets. The study has been focused on the two most stable conformers that are selected after the full geometry optimization of the molecule. A detailed assignment of the FT-IR and FT-Raman spectra has been done for both the conformers along with potential energy distribution for each vibrational mode. The observed and scaled wavenumber of most of the bands has been found to be in good agreement. The UV-Vis spectrum has been recorded and compared with calculated spectrum. In addition, 1H and 13C nuclear magnetic resonance spectra have been also recorded and compared with the calculated data that shows the inter or intramolecular hydrogen bonding. The electronic properties such as HOMO-LUMO energies were calculated by using time-dependent density functional theory. Molecular electrostatic potential has been plotted to elucidate the reactive part of the molecule. Natural bond orbital analysis was performed to investigate the molecular stability. Non linear optical property of the molecule have been studied by calculating the electric dipole moment (μ) and the first hyperpolarizability (β) that results in the nonlinearity of the molecule. Copyright © 2014 Elsevier B.V. All rights reserved.

Electronic structure and normal vibrations of the 1-ethyl-3-methylimidazolium ethyl sulfate ion pair.

PubMed

Dhumal, Nilesh R; Kim, Hyung J; Kiefer, Johannes

2011-04-21

Electronic and structural properties of the ion pair 1-ethyl-3-methylimidazolium ethyl sulfate are studied using density functional methods. Three locally stable conformers of the ion pair complex are considered to analyze molecular interactions between its cation and anion. Manifestations of these interactions in the vibrational spectra are discussed and compared with experimental IR and Raman spectroscopy data. NBO analysis and difference electron density coupled with molecular electron density topography are used to interpret the frequency shifts of the normal vibrations of the ion pair, compared to the free anion and cation. Excitation energies of low-lying singlet excited states of the conformers are also studied. The density functional theory results are found to be in a reasonable agreement with experimental UV/vis absorption spectra.

Preliminary observations on differences in the Raman spectra of cancerous and noncancerous cells and connective tissue of human skin

NASA Astrophysics Data System (ADS)

Short, Michael A.; Lui, Harvey; McLean, David I.; Zeng, Haishan; Alajlan, Abdulmajeed; Chen, Michael X.

2005-04-01

A less invasive method of reliably detecting skin cancers is required. Raman spectroscopy is just one of several spectroscopic methods that look promising, but are not yet sufficiently reliable. More information is needed on how and why the Raman spectra of cancerous skin tissue is different from its normal counterpart. We have used confocal micro-Raman spectroscopy with a spatial resolution of about a micron to obtain spectra of unstained thin sections of human skin. We found that there were clear differences in the Raman spectra between cancerous and non-cancerous tissue both in cells and in the connective tissue. The DNA contribution to the spectra was generally stronger in malignant cells than normal ones. In regions of the dermis far away from the tumor one obtains the usual collagen spectra of normal skin, but adjacent to the tumor the spectra no longer appeared to be those of native collagen.

Sensitivity of Raman spectroscopy to normal patient variability

NASA Astrophysics Data System (ADS)

Vargis, Elizabeth; Byrd, Teresa; Logan, Quinisha; Khabele, Dineo; Mahadevan-Jansen, Anita

2011-11-01

Many groups have used Raman spectroscopy for diagnosing cervical dysplasia; however, there have been few studies looking at the effect of normal physiological variations on Raman spectra. We assess four patient variables that may affect normal Raman spectra: Race/ethnicity, body mass index (BMI), parity, and socioeconomic status. Raman spectra were acquired from a diverse population of 75 patients undergoing routine screening for cervical dysplasia. Classification of Raman spectra from patients with a normal cervix is performed using sparse multinomial logistic regression (SMLR) to determine if any of these variables has a significant effect. Results suggest that BMI and parity have the greatest impact, whereas race/ethnicity and socioeconomic status have a limited effect. Incorporating BMI and obstetric history into classification algorithms may increase sensitivity and specificity rates of disease classification using Raman spectroscopy. Studies are underway to assess the effect of these variables on disease.

Structure of poly(ethylene glycol)-modified horseradish peroxidase in organic solvents: infrared amide I spectral changes upon protein dehydration are largely caused by protein structural changes and not by water removal per se.

PubMed Central

Al-Azzam, Wasfi; Pastrana, Emil A; Ferrer, Yancy; Huang, Qing; Schweitzer-Stenner, Reinhard; Griebenow, Kai

2002-01-01

Fourier transform infrared (FTIR) spectroscopy has emerged as a powerful tool to guide the development of stable lyophilized protein formulations by providing information on the structure of proteins in amorphous solids. The underlying assumption is that IR spectral changes in the amide I and III region upon protein dehydration are caused by protein structural changes. However, it has been claimed that amide I IR spectral changes could be the result of water removal per se. Here, we investigated whether such claims hold true. The structure of horseradish peroxidase (HRP) and poly(ethylene glycol)-modified HRP (HRP-PEG) has been investigated under various conditions (in aqueous solution, the amorphous dehydrated state, and dissolved/suspended in toluene and benzene) by UV-visible (UV-Vis), FTIR, and resonance Raman spectroscopy. The resonance Raman and UV-Vis spectra of dehydrated HRP-PEG dissolved in neat toluene or benzene were very similar to that of HRP in aqueous buffer, and thus the heme environment (heme iron spin, coordination, and redox state) was essentially the same under both conditions. Therefore, the three-dimensional structure of HRP-PEG dissolved in benzene and toluene was similar to that in aqueous solution. The amide I IR spectra of HRP-PEG in aqueous buffer and of dehydrated HRP-PEG dissolved in neat benzene and toluene were also very similar, and the secondary structure compositions (percentages of alpha-helices and beta-sheets) were within the standard error the same. These results are irreconcilable with recent claims that water removal per se could cause substantial amide I IR spectral changes (M. van de Weert, P.I. Haris, W.E. Hennink, and D.J. Crommelin. 2001. Anal. Biochem. 297:160-169). On the contrary, amide I IR spectral changes upon protein dehydration are caused by perturbations in the secondary structure. PMID:12496131

Spectroscopic diagnosis of laryngeal carcinoma using near-infrared Raman spectroscopy and random recursive partitioning ensemble techniques.

PubMed

Teh, Seng Khoon; Zheng, Wei; Lau, David P; Huang, Zhiwei

2009-06-01

In this work, we evaluated the diagnostic ability of near-infrared (NIR) Raman spectroscopy associated with the ensemble recursive partitioning algorithm based on random forests for identifying cancer from normal tissue in the larynx. A rapid-acquisition NIR Raman system was utilized for tissue Raman measurements at 785 nm excitation, and 50 human laryngeal tissue specimens (20 normal; 30 malignant tumors) were used for NIR Raman studies. The random forests method was introduced to develop effective diagnostic algorithms for classification of Raman spectra of different laryngeal tissues. High-quality Raman spectra in the range of 800-1800 cm(-1) can be acquired from laryngeal tissue within 5 seconds. Raman spectra differed significantly between normal and malignant laryngeal tissues. Classification results obtained from the random forests algorithm on tissue Raman spectra yielded a diagnostic sensitivity of 88.0% and specificity of 91.4% for laryngeal malignancy identification. The random forests technique also provided variables importance that facilitates correlation of significant Raman spectral features with cancer transformation. This study shows that NIR Raman spectroscopy in conjunction with random forests algorithm has a great potential for the rapid diagnosis and detection of malignant tumors in the larynx.

Effect of pH on the chemical modification of quercetin and structurally related flavonoids characterized by optical (UV-visible and Raman) spectroscopy.

PubMed

Jurasekova, Z; Domingo, C; Garcia-Ramos, J V; Sanchez-Cortes, S

2014-07-07

In this work we report the study of the chemical modifications undergone by flavonoids, especially by quercetin (QUC), under alkaline conditions by UV-visible absorption, Raman and surface-enhanced Raman scattering (SERS) spectroscopy, the study was performed in aqueous solution and also on Ag nanoparticles (AgNPs). Several processes are involved in the effect of alkaline pH both in solution and on AgNPs: autoxidation affecting mainly the C-ring of the molecule and giving rise to the molecular fragmentation leading to simpler molecular products, and/or the dimerization and further polymerization leading to species with a higher molecular weight. In addition, there exists a clear structure-instability correlation concerning mainly particular groups in the molecule: the C3-OH group in the C-ring, the catechol moiety in the B-ring and the C2=C3 bond also existing in the C-ring. QUC possesses all these groups and exhibits high instability in alkaline solution. The SERS spectra registered at different pH revealed a change in the dimerization protocol of QUC going from the A- and C-rings-like-condensation to B-ring-like-condensation. Increasing the knowledge of the chemical properties of these compounds and determining the structure-activity relationship under specific environmental factors allow us to improve their beneficial properties for health as well as the preservation of Cultural Heritage objects, for example, by preventing their degradation.

Raman Scattered He II 4332 and Photoionization Model in the Symbiotic Star V1016 Cygni

NASA Astrophysics Data System (ADS)

Lee, H.-W.; Heo, J.-E.; Lee, B.-C.

2014-08-01

Symbiotic stars are wide binary systems of a white dwarf and a mass losing giant. They exhibit unique Raman scattered features as a result of inelastic scattering of far UV line photons by atomic hydrogen. Co-existence of a far UV He II emission region and a thick H I region in symbiotic stars is necessary for the formation of Raman-scattered features blueward of hydrogen Balmer emission lines. Being a single electron atom, He II has the same atomic structure as the hydrogen atom and hence emits far UV emission lines that are slightly blueward of hydrogen Lyman lines. These far UV He II emission lines can be Raman scattered to appear blueward of hydrogen Balmer lines. In particular, the symbiotic star V1016 Cyg is found to exhibit Raman scattered He II 4332 feature in the BOES high resolution spectrum. Our profile fitting of Raman scattered He II 4332 is consistent with the mass loss geometry proposed by Jung & Lee (2004). We use the photoionization code ‘ CLOUDY' to estimate the far UV He II emission lines and make comparisons with the observed Raman scattered He II 4332 blueward of Hγ in the high resolution echelle V1016 Cyg. The emission nebula is assumed to be of uniform density of 108 cm-3 that is illuminated by a black body characterized by its temperature and total luminosity. With our comparisons we conclude that the Raman scattered He II features are consistent with the existence of a photoionized nebula by a hot black body source with temperature 7-8× 104 K with a luminosity 1038erg s-1.

Raman Imaging of Plant Cell Walls in Sections of Cucumis sativus

PubMed Central

Zeise, Ingrid; Heiner, Zsuzsanna; Holz, Sabine; Joester, Maike; Büttner, Carmen

2018-01-01

Raman microspectra combine information on chemical composition of plant tissues with spatial information. The contributions from the building blocks of the cell walls in the Raman spectra of plant tissues can vary in the microscopic sub-structures of the tissue. Here, we discuss the analysis of 55 Raman maps of root, stem, and leaf tissues of Cucumis sativus, using different spectral contributions from cellulose and lignin in both univariate and multivariate imaging methods. Imaging based on hierarchical cluster analysis (HCA) and principal component analysis (PCA) indicates different substructures in the xylem cell walls of the different tissues. Using specific signals from the cell wall spectra, analysis of the whole set of different tissue sections based on the Raman images reveals differences in xylem tissue morphology. Due to the specifics of excitation of the Raman spectra in the visible wavelength range (532 nm), which is, e.g., in resonance with carotenoid species, effects of photobleaching and the possibility of exploiting depletion difference spectra for molecular characterization in Raman imaging of plants are discussed. The reported results provide both, specific information on the molecular composition of cucumber tissue Raman spectra, and general directions for future imaging studies in plant tissues. PMID:29370089

Raman Imaging of Plant Cell Walls in Sections of Cucumis sativus.

PubMed

Zeise, Ingrid; Heiner, Zsuzsanna; Holz, Sabine; Joester, Maike; Büttner, Carmen; Kneipp, Janina

2018-01-25

Raman microspectra combine information on chemical composition of plant tissues with spatial information. The contributions from the building blocks of the cell walls in the Raman spectra of plant tissues can vary in the microscopic sub-structures of the tissue. Here, we discuss the analysis of 55 Raman maps of root, stem, and leaf tissues of Cucumis sativus , using different spectral contributions from cellulose and lignin in both univariate and multivariate imaging methods. Imaging based on hierarchical cluster analysis (HCA) and principal component analysis (PCA) indicates different substructures in the xylem cell walls of the different tissues. Using specific signals from the cell wall spectra, analysis of the whole set of different tissue sections based on the Raman images reveals differences in xylem tissue morphology. Due to the specifics of excitation of the Raman spectra in the visible wavelength range (532 nm), which is, e.g., in resonance with carotenoid species, effects of photobleaching and the possibility of exploiting depletion difference spectra for molecular characterization in Raman imaging of plants are discussed. The reported results provide both, specific information on the molecular composition of cucumber tissue Raman spectra, and general directions for future imaging studies in plant tissues.

Electronic [UV-Visible] and vibrational [FT-IR, FT-Raman] investigation and NMR-mass spectroscopic analysis of terephthalic acid using quantum Gaussian calculations.

PubMed

Karthikeyan, N; Prince, J Joseph; Ramalingam, S; Periandy, S

2015-03-15

In this research work, the vibrational IR, polarization Raman, NMR and mass spectra of terephthalic acid (TA) were recorded. The observed fundamental peaks (IR, Raman) were assigned according to their distinctiveness region. The hybrid computational calculations were carried out for calculating geometrical and vibrational parameters by DFT (B3LYP and B3PW91) methods with 6-31++G(d,p) and 6-311++G(d,p) basis sets and the corresponding results were tabulated. The molecular mass spectral data related to base molecule and substitutional group of the compound was analyzed. The modification of the chemical property by the reaction mechanism of the injection of dicarboxylic group in the base molecule was investigated. The (13)C and (1)H NMR spectra were simulated by using the gauge independent atomic orbital (GIAO) method and the absolute chemical shifts related to TMS were compared with experimental spectra. The study on the electronic and optical properties; absorption wavelengths, excitation energy, dipole moment and frontier molecular orbital energies, were performed by hybrid Gaussian calculation methods. The orbital energies of different levels of HOMO and LUMO were calculated and the molecular orbital lobe overlapping showed the inter charge transformation between the base molecule and ligand group. From the frontier molecular orbitals (FMO), the possibility of electrophilic and nucleophilic hit also analyzed. The NLO activity of the title compound related to Polarizability and hyperpolarizability were also discussed. The present molecule was fragmented with respect to atomic mass and the mass variation depends on the substitutions have also been studied. Crown Copyright © 2014. Published by Elsevier B.V. All rights reserved.

Spectroscopic (FT-IR, FT-Raman, UV and NMR) investigation and NLO, HOMO-LUMO, NBO analysis of organic 2,4,5-trichloroaniline.

PubMed

Govindarajan, M; Karabacak, M; Periandy, S; Tanuja, D

2012-11-01

In this work, the experimental and theoretical study on the molecular structure and vibrational spectra of 2,4,5-trichloroaniline (C(6)H(4)NCl(3), abbreviated as 2,4,5-TClA) were studied. The FT-IR and FT-Raman spectra were recorded. The molecular geometry and vibrational frequencies in the ground state were calculated by using the Hartree-Fock (HF) and density functional theory (DFT) methods (B3LYP) with 6-311++G(d,p) basis set. Comparison of the observed fundamental vibrational frequencies of 2,4,5-TClA with calculated results by HF and DFT indicates that B3LYP is superior to HF method for molecular vibrational problems. The difference between the observed and scaled wavenumber values of most of the fundamentals is very small. The theoretically predicted FT-IR and FT-Raman spectra of the title molecule have been constructed. A study on the electronic properties, such as HOMO and LUMO energies, were performed by time-dependent DFT (TD-DFT) approach. Besides, molecular electrostatic potential (MEP) and thermodynamic properties were performed. The electric dipole moment (μ) and the first hyperpolarizability (β) values of the investigated molecule were computed using ab initio quantum mechanical calculations. The calculated results also show that the 2,4,5-TClA molecule may have microscopic nonlinear optical (NLO) behavior with non-zero values. Mulliken atomic charges of 2,4,5-TClA was calculated and compared with aniline and chlorobenzene molecules. The (13)C nuclear magnetic resonance (NMR) chemical shifts of the molecule were calculated by the gauge independent atomic orbital (GIAO) method and compared with experimental results. Copyright © 2012 Elsevier B.V. All rights reserved.

Diagnosing basal cell carcinoma in vivo by near-infrared Raman spectroscopy: a Principal Components Analysis discrimination algorithm

NASA Astrophysics Data System (ADS)

Silveira, Landulfo, Jr.; Silveira, Fabrício L.; Bodanese, Benito; Pacheco, Marcos Tadeu T.; Zângaro, Renato A.

2012-02-01

This work demonstrated the discrimination among basal cell carcinoma (BCC) and normal human skin in vivo using near-infrared Raman spectroscopy. Spectra were obtained in the suspected lesion prior resectional surgery. After tissue withdrawn, biopsy fragments were submitted to histopathology. Spectra were also obtained in the adjacent, clinically normal skin. Raman spectra were measured using a Raman spectrometer (830 nm) with a fiber Raman probe. By comparing the mean spectra of BCC with the normal skin, it has been found important differences in the 800-1000 cm-1 and 1250-1350 cm-1 (vibrations of C-C and amide III, respectively, from lipids and proteins). A discrimination algorithm based on Principal Components Analysis and Mahalanobis distance (PCA/MD) could discriminate the spectra of both tissues with high sensitivity and specificity.

Molecular structure, vibrational, electronic and thermal properties of 4-vinylcyclohexene by quantum chemical calculations

NASA Astrophysics Data System (ADS)

Nagabalasubramanian, P. B.; Periandy, S.; Karabacak, Mehmet; Govindarajan, M.

2015-06-01

The solid phase FT-IR and FT-Raman spectra of 4-vinylcyclohexene (abbreviated as 4-VCH) have been recorded in the region 4000-100 cm-1. The optimized molecular geometry and vibrational frequencies of the fundamental modes of 4-VCH have been precisely assigned and analyzed with the aid of structure optimizations and normal coordinate force field calculations based on density functional theory (DFT) method at 6-311++G(d,p) level basis set. The theoretical frequencies were properly scaled and compared with experimentally obtained FT-IR and FT-Raman spectra. Also, the effect due the substitution of vinyl group on the ring vibrational frequencies was analyzed and a detailed interpretation of the vibrational spectra of this compound has been made on the basis of the calculated total energy distribution (TED). The time dependent DFT (TD-DFT) method was employed to predict its electronic properties, such as electronic transitions by UV-Visible analysis, HOMO and LUMO energies, molecular electrostatic potential (MEP) and various global reactivity and selectivity descriptors (chemical hardness, chemical potential, softness, electrophilicity index). Stability of the molecule arising from hyper conjugative interaction, charge delocalization has been analyzed using natural bond orbital (NBO) analysis. Atomic charges obtained by Mulliken population analysis and NBO analysis are compared. Thermodynamic properties (heat capacity, entropy and enthalpy) of the title compound at different temperatures are also calculated.

Ocean Raman Scattering in Satellite Backscatter UV Measurements

NASA Technical Reports Server (NTRS)

Vasilkov, Alexander P.; Joiner, Joanna; Gleason, James; Bhartia, Pawan; Bhartia, P. K. (Technical Monitor)

2002-01-01

Ocean Raman scattering significantly contributes to the filling-in of solar Fraunhofer lines measured by satellite backscatter ultraviolet (buy) instruments in the cloudless atmosphere over clear ocean waters. A model accounting for this effect in buy measurements is developed and compared with observations from the Global Ozone Monitoring Experiment (GONE). The model extends existing models for ocean Raman scattering to the UV spectral range. Ocean Raman scattering radiance is propagated through the atmosphere using a concept of the Lambert equivalent reflectively and an accurate radiative transfer model for Rayleigh scattering. The model and observations can be used to evaluate laboratory measurements of pure water absorption in the UV. The good agreement between model and observations suggests that buy instruments may be useful for estimating chlorophyll content.

Whispering gallery modes in photoluminescence and Raman spectra of a spherical microcavity with CdTe quantum dots: anti-Stokes emission and interference effects

PubMed Central

Gaponik, Nikolai; Gerlach, Matthias; Donegan, John F; Savateeva, Diana; Rogach, Andrey L

2006-01-01

We have studied the photoluminescence and Raman spectra of a system consisting of a polystyrene latex microsphere coated by CdTe colloidal quantum dots. The cavity-induced enhancement of the Raman scattering allows the observation of Raman spectra from only a monolayer of CdTe quantum dots. Periodic structure with very narrow peaks in the photoluminescence spectra of a single microsphere was detected both in the Stokes and anti-Stokes spectral regions, arising from the coupling between the emission of quantum dots and spherical cavity modes.

Use of Raman spectroscopy in the analysis of nickel allergy

NASA Astrophysics Data System (ADS)

Alda, Javier; Castillo-Martinez, Claudio; Valdes-Rodriguez, Rodrigo; Hernández-Blanco, Diana; Moncada, Benjamin; González, Francisco J.

2013-06-01

Raman spectra of the skin of subjects with nickel allergy are analyzed and compared to the spectra of healthy subjects to detect possible biochemical differences in the structure of the skin that could help diagnose metal allergies in a noninvasive manner. Results show differences between the two groups of Raman spectra. These spectral differences can be classified using principal component analysis. Based on these findings, a novel computational technique to make a fast evaluation and classification of the Raman spectra of the skin is presented and proposed as a noninvasive technique for the detection of nickel allergy.

Polarized Raman spectra in β-Ga2O3 single crystals

NASA Astrophysics Data System (ADS)

Onuma, T.; Fujioka, S.; Yamaguchi, T.; Itoh, Y.; Higashiwaki, M.; Sasaki, K.; Masui, T.; Honda, T.

2014-09-01

Polarized Raman spectra were measured from (010) Mg-doped, (100) Si-doped, and (001) unintentionally-doped β-Ga2O3 substrates prepared by either the floating zone growth or edge-defined film-fed growth methods. The Ag and Bg Raman active modes were perfectly separated in the spectra according to the polarization selection rules. To the best of our knowledge, this is the first experimental observation of a complete set of polarized Raman spectra of β-Ga2O3. The results are ensured by the high uniformity of crystalline orientation and surface flatness of the present substrates.

NIR Raman spectroscopy in medicine and biology: results and aspects

NASA Astrophysics Data System (ADS)

Schrader, B.; Dippel, B.; Erb, I.; Keller, S.; Löchte, T.; Schulz, H.; Tatsch, E.; Wessel, S.

1999-05-01

Analyses of biomaterial by 'classical' Raman spectroscopy with excitation in the visible range has not been possible since the fluorescence of many essential constituents of all animal and plant cells and tissues overlays the Raman spectra completely. Fluorescence, however, is virtually avoided, when Raman spectra are excited with the Nd : YAG laser line at 1064 nm. Within seven dissertations we explored different fields of potential applications to medical diagnostics. Identification and qualification of tissues and cells is possible. Tumors show small but significant differences to normal tissues; in order to develop a reliable tool for tumor diagnostics more research is necessary, especially a collection of reference spectra in a data bank is needed. Raman spectra of biomineralization structures in teeth and bones show pathological tissues as well as the development of new mineralized structures. NIR Raman spectra of flowers, leaves, and fruit show, without special preparation, their constituents: alkaloids, the essential oils, natural dyes, flavors, spices and drugs. They allow application to taxonomy, optimizing plant breeding and control of food.

FTIR, FT-RAMAN, NMR, spectra, normal co-ordinate analysis, NBO, NLO and DFT calculation of N,N-diethyl-4-methylpiperazine-1-carboxamide molecule

NASA Astrophysics Data System (ADS)

Muthu, S.; Elamurugu Porchelvi, E.

2013-11-01

The Fourier Transform Infrared (FT-IR) and FT-Raman of N,N-diethyl-4-methylpiperazine-1-carboxamide (NND4MC) have been recorded and analyzed. The structure of the compound was optimized and the structural characteristics were determined by density functional theory (DFT) using B3LYP method with 6-31G(d,p) and 6-311G(d,p) basis sets. The difference between the observed and scaled wavenumber values of most of the fundamentals is very small. The theoretically predicted FT-IR and FT-Raman spectra of the title molecule have been constructed. The detailed interpretation of the vibrational spectra has been carried out with aid of normal coordinate analysis (NCA) following the scaled quantum mechanical force field methodology. Stability of the molecule arising from hyperconjugative interactions and charge delocalization has been analyzed using natural bond orbital (NBO) analysis. The results show that electron density (ED) in the σ* and π* antibonding orbitals and second order delocalization energies (E2) confirm the occurrence of intramolecular charge transfer (ICT) within the molecule. The electronic dipole moment (μD) and the first hyperpolarizability (βtot) values of the investigated molecule were computed using Density Functional Theory (DFT/B3LYP) with 6-31G(d,p) and 6-311G(d,p) basis sets. The calculated results also show that the NND4MC molecule may have microscopy nonlinear optical (NLO) behavior with non zero values. Mulliken atomic charges of NND4MC were calculated. The 13C nuclear magnetic resonance (NMR) chemical shifts of the molecule were calculated by the gauge independent atomic orbital (GIAO) method and compared with experimental results. The UV-Vis spectrum of the compound was recorded. The theoretical electronic absorption spectra have been calculated by using CIS, TD-DFT methods. A study on the electronic properties, such as HOMO and LUMO energies, molecular electrostatic potential (MEP) were also performed.

Effect of substrates on structural and optical properties of tin oxide (SnO2) nanostructures.

PubMed

Johari, Anima; Bhatnagar, M C; Rana, Vikas

2012-10-01

We report on controlling the morphology of tin oxide (SnO2) nanostructures and the study of the effect of surface morphology on structural and optical properties of SnO2 nanostuctures. In present work, Tin oxide (SnO2) nanostructures such as nanowires and nanorods have been grown by thermal evaporation of SnO2 powder. To demonstrate the effect of different substrates on the morphology of grown SnO2 nanostructures, the thermal evaporation of SnO2 powder was carried out on Si and gold catalyzed Si (Au/Si) substrates. The scanning-electron-microscopic analysis shows the growth of SnO2 nanowires on Au/Si substrate and growth of SnO2 nanorods on Si substrate. The scanning-and transmission-electron-microscopic analysis shows that the diameter of SnO2 nanowires and nanorods are about 70 nm and 95 nm respectively and their length is about 80 microm and 30 microm respectively. The vapor-liquid-solid (VLS) growth of SnO2 nanowires and vapor-solid (VS) growth of SnO2 nanorods is also confirmed with the help of TEM and EDX spectra. The synthesized SnO2 nanowires show tetragonal rutile structure of SnO2, whereas SnO2 nanorods show tetragonal rutile as well as cassiterite structure of SnO2. UV-Vis absorption spectra showed the optical band gaps of 4.1 eV and 3.8 eV for the SnO2 nanowires and the nanorods, respectively. The SnO2 nanowires and nanorods show photoluminescence with broad emission peaks centred at around 600 nm and 580 nm respectively. Raman spectra of SnO2 nanowires shows three Raman shifts (478, 632, 773 cm(-1)) corresponding to Eg, A1g and B2g vibration modes, whereas in Raman spectra of SnO2 nanorods, A1g peak is dramatically reduced and the B2g mode is totally quenched.

[Raman spectroscopy fluorescence background correction and its application in clustering analysis of medicines].

PubMed

Chen, Shan; Li, Xiao-ning; Liang, Yi-zeng; Zhang, Zhi-min; Liu, Zhao-xia; Zhang, Qi-ming; Ding, Li-xia; Ye, Fei

2010-08-01

During Raman spectroscopy analysis, the organic molecules and contaminations will obscure or swamp Raman signals. The present study starts from Raman spectra of prednisone acetate tablets and glibenclamide tables, which are acquired from the BWTek i-Raman spectrometer. The background is corrected by R package baselineWavelet. Then principle component analysis and random forests are used to perform clustering analysis. Through analyzing the Raman spectra of two medicines, the accurate and validity of this background-correction algorithm is checked and the influences of fluorescence background on Raman spectra clustering analysis is discussed. Thus, it is concluded that it is important to correct fluorescence background for further analysis, and an effective background correction solution is provided for clustering or other analysis.

Temperature dependent Raman spectroscopy of melamine and structural analogs in milk powder

USDA-ARS?s Scientific Manuscript database

Hyperspectral Raman imaging has the potential for rapid screening of solid-phase samples for potential adulterants. We found that the Raman spectra of melamine analogs changed dramatically and uniquely as a function of elevated temperature. Raman spectra were acquired for urea, biuret, cyanuric acid...

Methylation stabilizes the imino tautomer of dAMP and amino tautomer of dCMP in solution.

PubMed

Jayanth, Namrata; Puranik, Mrinalini

2011-05-19

Alkylating agents cause methylation of adenosine and cytidine in DNA to generate 1-methyladenosine and 3-methylcytidine. These modified nucleosides can serve as regulators of cells or can act as agents of mutagenesis depending on the context and the partner enzymes. Solution structures and the chemical interactions with enzymes that lead to their recognition are of inherent interest. At physiological pH, 1-methyladenosine and 3-methylcytidine are presumed to be in the protonated amino forms in the literature. We report the structures, ionization states, and UV resonance Raman spectra of both substrates over a range of pH (2.5-11.0). The Raman excitation wavelength was tuned to selectively enhance Raman scattering from the nucleobase (260 nm) and further specifically from the imino form (210 nm) of 1-me-dAMP. We find that contrary to the general assumption, 1-me-dAMP is present in its neutral imino form at physiological pH and 3-me-dCMP is in the amino form. © 2011 American Chemical Society

Spectroscopic studies (FTIR, FT-Raman and UV-Visible), normal coordinate analysis, NBO analysis, first order hyper polarizability, HOMO and LUMO analysis of (1R)-N-(Prop-2-yn-1-yl)-2,3-dihydro-1H-inden-1-amine molecule by ab initio HF and density functional methods.

PubMed

Muthu, S; Ramachandran, G

2014-01-01

The Fourier transform infrared (FT-IR) and FT-Raman of (1R)-N-(Prop-2-yn-1-yl)-2,3-dihydro-1H-inden-1-amine (1RNPDA) were recorded in the regions 4000-400 cm(-1) and 4000-100 cm(-1) respectively. A complete assignment and analysis of the fundamental vibrational modes of the molecule were carried out. The observed fundamental modes have been compared with the harmonic vibrational frequencies computed using HF method by employing 6-31G(d,p) basis set and DFT(B3LYP) method by employing 6-31G(d,p) basis set. The vibrational studies were interpreted in terms of Potential Energy Distribution (PED). The complete vibrational frequency assignments were made by Normal Co-ordinate Analysis (NCA) following the scaled quantum mechanical force field methodology (SQMFF). The first order hyper polarizability (β0) of this molecular system and related properties (α, μ, and Δα) are calculated using B3LYP/6-31G(d,p) method based on the finite-field approach. The thermodynamic functions of the title compound were also performed at the above methods and basis set. A detailed interpretation of the infrared and Raman spectra of 1RNPDA is reported. The (1)H and (13)C nuclear magnetic resonance (NMR) chemical shifts of the molecule were calculated using the GIAO method confirms with the experimental values. Stability of the molecule arising from hyper-conjugative interactions and charge delocalization has been analyzed using Natural Bond Orbital (NBO) analysis. UV-vis spectrum of the compound was recorded and electronic properties such as excitation energies, oscillator strength and wavelength were performed by TD-DFT/B3LYP using 6-31G(d,p) basis set. The HOMO and LUMO energy gap reveals that the energy gap reflects the chemical activity of the molecule. The observed and calculated wave numbers are formed to be in good agreement. The experimental spectra also coincide satisfactorily with those of theoretically constructed spectra. Copyright © 2013 Elsevier B.V. All rights reserved.

Raman microscopy of freeze-dried mouse eyeball-slice in conjunction with the "in vivo cryotechnique".

PubMed

Terada, Nobuo; Ohno, Nobuhiko; Saitoh, Sei; Fujii, Yasuhisa; Ohguro, Hiroshi; Ohno, Shinichi

2007-07-01

The wavelength of Raman-scattered light depends on the molecular composition of the substance. This is the first attempt to acquire Raman spectra of a mouse eyeball removed from a living mouse, in which the eyeball was preserved using the "in vivo cryotechnique" followed by freeze-drying. Eyeballs were cryofixed using a rapid freezing cryotechnique, and then sliced in the cryostat machine. The slices were sandwiched between glass slides, freeze-dried, and analyzed with confocal Raman microscopy. Important areas including various eyeball tissue layers were selected using bright-field microscopy, and then the Raman spectra were obtained at 240 locations. Four typical patterns of Raman spectra were electronically mapped on the specimen images obtained by the bright-field microscopy. Tissue organization was confirmed by embedding the same eyeball slice used for Raman spectra into epoxy resin and the thick sections were prepared with the inverted capsule method. Each Raman spectral pattern represents a different histological layer in the eyeball which was mapped by comparing the images of toluidine blue staining and Raman mapping with different colors. In the choroid and pigment cell layer, the Raman spectrum had two peaks, corresponding to melanin. Some of the peaks of the Raman spectra obtained from the blood vessels in sclera and the photoreceptor layer were similar to those obtained from the purified hemoglobin and rhodopsin proteins, respectively. Our experimental protocol can distinguish different tissue components with Raman microscopy; therefore, this method can be very useful for examining the distribution of a biological structures and/or chemical components in rapidly frozen freeze-dried tissue.

The Raman and SERS spectra of indigo and indigo-Ag2 complex: DFT calculation and comparison with experiment.

PubMed

Ricci, Marilena; Lofrumento, Cristiana; Becucci, Maurizio; Castellucci, Emilio M

2018-01-05

Using time-dependent density functional theory in conjunction with B3LYP functional and LANL2DZ/6-31+g(d,p) basis sets, static and pre-resonance Raman spectra of the indigo-Ag 2 complex have been calculated. Structure optimization, excitation energies and pre-resonance Raman spectra of the indigo molecule have been obtained at the same level of theory. The available experimental Raman spectra at 1064, 785 and 514nm and the SERS spectra at 785 and 514nm have been well reproduced by the calculation. Experimental SERS spectra are confronted with the calculated pre-resonance Raman spectra obtained for the indigo-Ag 2 complex. The Raman activities calculated under the infinite lifetime approximation show a strong dependence upon the proximity to the energy and the oscillator strength of the excitation electronic transition. The comparison of the integrated EFs for indigo and indigo-Ag 2 calculated Raman spectra, gave some hints as to the enhancement mechanisms acting for the different excitation wavelengths. Whereas for excitation at a wavelength corresponding to 785nm, the enhancement mechanism for the Raman spectrum of the metal complex seems the chemical one, the strong increment (ten times) of the integrated EF of the Raman spectra of the complex in the case of 514nm excitation, suggests the onset of other enhancement mechanisms. Assuming that intra-cluster transitions with high oscillator strength can be thought of as to mimic surface plasmons excitations, we suggest the onset of the electromagnetic mechanisms (EM) as the origin of the Raman spectrum enhancement. Nevertheless, other enhancement effects cannot be ruled out, as a new molecular transition gains strength in the proximity of the excitation wavelength, as a consequence of the symmetry lowering of the molecule in the complex. A large variation across vibrational modes, by a factor of at least 10 4 , was found for the EFs. This large variation in the EFs can indicate that B-term Herzberg-Teller scattering, due to metal and/or charge transfer states, can feed intensity to the inactive (in the molecule) and/or non totally symmetric modes. Copyright © 2017 Elsevier B.V. All rights reserved.

The Raman and SERS spectra of indigo and indigo-Ag2 complex: DFT calculation and comparison with experiment

NASA Astrophysics Data System (ADS)

Ricci, Marilena; Lofrumento, Cristiana; Becucci, Maurizio; Castellucci, Emilio M.

2018-01-01

Using time-dependent density functional theory in conjunction with B3LYP functional and LANL2DZ/6-31+g(d,p) basis sets, static and pre-resonance Raman spectra of the indigo-Ag2 complex have been calculated. Structure optimization, excitation energies and pre-resonance Raman spectra of the indigo molecule have been obtained at the same level of theory. The available experimental Raman spectra at 1064, 785 and 514 nm and the SERS spectra at 785 and 514 nm have been well reproduced by the calculation. Experimental SERS spectra are confronted with the calculated pre-resonance Raman spectra obtained for the indigo-Ag2 complex. The Raman activities calculated under the infinite lifetime approximation show a strong dependence upon the proximity to the energy and the oscillator strength of the excitation electronic transition. The comparison of the integrated EFs for indigo and indigo-Ag2 calculated Raman spectra, gave some hints as to the enhancement mechanisms acting for the different excitation wavelengths. Whereas for excitation at a wavelength corresponding to 785 nm, the enhancement mechanism for the Raman spectrum of the metal complex seems the chemical one, the strong increment (ten times) of the integrated EF of the Raman spectra of the complex in the case of 514 nm excitation, suggests the onset of other enhancement mechanisms. Assuming that intra-cluster transitions with high oscillator strength can be thought of as to mimic surface plasmons excitations, we suggest the onset of the electromagnetic mechanisms (EM) as the origin of the Raman spectrum enhancement. Nevertheless, other enhancement effects cannot be ruled out, as a new molecular transition gains strength in the proximity of the excitation wavelength, as a consequence of the symmetry lowering of the molecule in the complex. A large variation across vibrational modes, by a factor of at least 104, was found for the EFs. This large variation in the EFs can indicate that B-term Herzberg-Teller scattering, due to metal and/or charge transfer states, can feed intensity to the inactive (in the molecule) and/or non totally symmetric modes.

Surface-Enhanced Raman and Surface-Enhanced Hyper-Raman Scattering of Thiol-Functionalized Carotene

PubMed Central

2016-01-01

A thiol-modified carotene, 7′-apo-7′-(4-mercaptomethylphenyl)-β-carotene, was used to obtain nonresonant surface-enhanced Raman scattering (SERS) spectra of carotene at an excitation wavelength of 1064 nm, which were compared with resonant SERS spectra at an excitation wavelength of 532 nm. These spectra and surface-enhanced hyper-Raman scattering (SEHRS) spectra of the functionalized carotene were compared with the spectra of nonmodified β-carotene. Using SERS, normal Raman, and SEHRS spectra, all obtained for the resonant case, the interaction of the carotene molecules with silver nanoparticles, as well as the influence of the resonance enhancement and the SERS enhancement on the spectra, were investigated. The interaction with the silver surface occurs for both functionalized and nonfunctionalized β-carotene, but only the stronger functionalization-induced interaction enables the acquisition of nonresonant SERS spectra of β-carotene at low concentrations. The resonant SEHRS and SERS spectra are very similar. Nevertheless, the SEHRS spectra contain additional bands of infrared-active modes of carotene. Increased contributions from bands that experience low resonance enhancement point to a strong interaction between silver nanoparticles and electronic levels of the molecules, thereby giving rise to a decrease in the resonance enhancement in SERS and SEHRS. PMID:28077983

Blood analysis by Raman spectroscopy.

PubMed

Enejder, Annika M K; Koo, Tae-Woong; Oh, Jeankun; Hunter, Martin; Sasic, Slobodan; Feld, Michael S; Horowitz, Gary L

2002-11-15

Concentrations of multiple analytes were simultaneously measured in whole blood with clinical accuracy, without sample processing, using near-infrared Raman spectroscopy. Spectra were acquired with an instrument employing nonimaging optics, designed using Monte Carlo simulations of the influence of light-scattering-absorbing blood cells on the excitation and emission of Raman light in turbid medium. Raman spectra were collected from whole blood drawn from 31 individuals. Quantitative predictions of glucose, urea, total protein, albumin, triglycerides, hematocrit, and hemoglobin were made by means of partial least-squares (PLS) analysis with clinically relevant precision (r(2) values >0.93). The similarity of the features of the PLS calibration spectra to those of the respective analyte spectra illustrates that the predictions are based on molecular information carried by the Raman light. This demonstrates the feasibility of using Raman spectroscopy for quantitative measurements of biomolecular contents in highly light-scattering and absorbing media.

Raman spectra of lignin model compounds

Treesearch

Umesh P. Agarwal; Richard S. Reiner; Ashok K. Pandey; Sally A. Ralph; Kolby C. Hirth; Rajai H. Atalla

2005-01-01

To fully exploit the value of Raman spectroscopy for analyzing lignins and lignin containing materials, a detailed understanding of lignins’ Raman spectra needs to be achieved. Although advances made thus far have led to significant growth in application of Raman techniques, further developments are needed to improve upon the existing knowledge. Considering that lignin...

Computer-generated predictions of the structure and of the IR and Raman spectra of VX. Final report, May-August 1992

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hameka, H.F.; Jensen, J.O.

1993-05-01

This report presents the computed optimized geometry and vibrational IR and Raman frequencies of the V-agent VX. The computations are performed with the Gaussian 90 Program Package using 6-31G* basis sets. We assign the vibrational frequencies and correct each frequency by multiplying it with a previously derived 6-31G* correction factor. The result is a computer-generated prediction of the IR and Raman spectra of VX. This study was intended as a blind test of the utility of IR spectral prediction. Therefore, we intentionally did not look at experimental data on the IR and Raman spectra of VX.... IR Spectra, VX, Ramanmore » spectra, Computer predictions.« less

Cancer detection based on Raman spectra super-paramagnetic clustering

NASA Astrophysics Data System (ADS)

González-Solís, José Luis; Guizar-Ruiz, Juan Ignacio; Martínez-Espinosa, Juan Carlos; Martínez-Zerega, Brenda Esmeralda; Juárez-López, Héctor Alfonso; Vargas-Rodríguez, Héctor; Gallegos-Infante, Luis Armando; González-Silva, Ricardo Armando; Espinoza-Padilla, Pedro Basilio; Palomares-Anda, Pascual

2016-08-01

The clustering of Raman spectra of serum sample is analyzed using the super-paramagnetic clustering technique based in the Potts spin model. We investigated the clustering of biochemical networks by using Raman data that define edge lengths in the network, and where the interactions are functions of the Raman spectra's individual band intensities. For this study, we used two groups of 58 and 102 control Raman spectra and the intensities of 160, 150 and 42 Raman spectra of serum samples from breast and cervical cancer and leukemia patients, respectively. The spectra were collected from patients from different hospitals from Mexico. By using super-paramagnetic clustering technique, we identified the most natural and compact clusters allowing us to discriminate the control and cancer patients. A special interest was the leukemia case where its nearly hierarchical observed structure allowed the identification of the patients's leukemia type. The goal of this study is to apply a model of statistical physics, as the super-paramagnetic, to find these natural clusters that allow us to design a cancer detection method. To the best of our knowledge, this is the first report of preliminary results evaluating the usefulness of super-paramagnetic clustering in the discipline of spectroscopy where it is used for classification of spectra.

Solvatochromism of 9,10-phenanthrenequinone: An electronic and resonance Raman spectroscopic study

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ravi Kumar, Venkatraman; Rajkumar, Nagappan; Umapathy, Siva, E-mail: umapathy@ipc.iisc.ernet.in

2015-01-14

Solvent effects play a vital role in various chemical, physical, and biological processes. To gain a fundamental understanding of the solute-solvent interactions and their implications on the energy level re-ordering and structure, UV-VIS absorption, resonance Raman spectroscopic, and density functional theory calculation studies on 9,10-phenanthrenequinone (PQ) in different solvents of diverse solvent polarity has been carried out. The solvatochromic analysis of the absorption spectra of PQ in protic dipolar solvents suggests that the longest (1n-π{sup 1}*; S{sub 1} state) and the shorter (1π-π{sup 1}*; S{sub 2} state) wavelength band undergoes a hypsochromic and bathochromic shift due to intermolecular hydrogen bondmore » weakening and strengthening, respectively. It also indicates that hydrogen bonding plays a major role in the differential solvation of the S{sub 2} state relative to the ground state. Raman excitation profiles of PQ (400–1800 cm{sup −1}) in various solvents followed their corresponding absorption spectra therefore the enhancements on resonant excitation are from single-state rather than mixed states. The hyperchromism of the longer wavelength band is attributed to intensity borrowing from the nearby allowed electronic transition through vibronic coupling. Computational calculation with C{sub 2ν} symmetry constraint on the S{sub 2} state resulted in an imaginary frequency along the low-frequency out-of-plane torsional modes involving the C=O site and therefore, we hypothesize that this mode could be involved in the vibronic coupling.« less

Analytic calculations of anharmonic infrared and Raman vibrational spectra

PubMed Central

Louant, Orian; Ruud, Kenneth

2016-01-01

Using a recently developed recursive scheme for the calculation of high-order geometric derivatives of frequency-dependent molecular properties [Ringholm et al., J. Comp. Chem., 2014, 35, 622], we present the first analytic calculations of anharmonic infrared (IR) and Raman spectra including anharmonicity both in the vibrational frequencies and in the IR and Raman intensities. In the case of anharmonic corrections to the Raman intensities, this involves the calculation of fifth-order energy derivatives—that is, the third-order geometric derivatives of the frequency-dependent polarizability. The approach is applicable to both Hartree–Fock and Kohn–Sham density functional theory. Using generalized vibrational perturbation theory to second order, we have calculated the anharmonic infrared and Raman spectra of the non- and partially deuterated isotopomers of nitromethane, where the inclusion of anharmonic effects introduces combination and overtone bands that are observed in the experimental spectra. For the major features of the spectra, the inclusion of anharmonicities in the calculation of the vibrational frequencies is more important than anharmonic effects in the calculated infrared and Raman intensities. Using methanimine as a trial system, we demonstrate that the analytic approach avoids errors in the calculated spectra that may arise if numerical differentiation schemes are used. PMID:26784673

In-vitro micro-Raman study of tissue samples for detecting cervical and ovarian cancer with 785-nm laser excitation

NASA Astrophysics Data System (ADS)

Sharma, S. K.; Kamemoto, L. E.; Misra, A. K.; Goodman, M. T.; Luk, H. W.; Killeen, J. L.

2010-04-01

We present results of in vitro micro-Raman spectroscopy of normal and cancerous cervical and ovarian tissues excited with 785 nm near-infrared (NIR) laser. Micro- Raman spectra of squamous cervical cells of both cervix and ovarian tissues show significant differences in the spectra of normal and cancerous cells. In particular, several well-defined Raman peaks in the 775-975 cm-1 region are observed in the spectra of normal cervix squamous cells but are completely missing in the spectra of invasive cervical cancer cells. In the high-frequency 2800-3100 cm-1 region it is shown that the peak area under CH stretching band is much lower than the corresponding area in the spectra of normal cells. In the case of ovarian tissues, the micro-Raman spectra show noticeable spectral differences between normal cells and ovarian serous cancer cells. In particular, we observed the accumulation of β-carotene in ovarian serous cancer cells compared to normal ovarian cells from women with no ovarian cancer. The NIR micro-Raman spectroscopy offers a potential molecular technique for detecting cervical and ovarian cancer from the respective tissues.

Improved sensing using simultaneous deep-UV Raman and fluorescence detection-II

NASA Astrophysics Data System (ADS)

Hug, W. F.; Bhartia, R.; Sijapati, K.; Beegle, L. W.; Reid, R. D.

2014-05-01

Photon Systems in collaboration with JPL is continuing development of a new technology robot-mounted or hand-held sensor for reagentless, short-range, standoff detection and identification of trace levels chemical, biological, and explosive (CBE) materials on surfaces. This deep ultraviolet CBE sensor is the result of Army STTR and DTRA programs. The evolving 10 to 15 lb, 20 W, sensor can discriminate CBE from background clutter materials using a fusion of deep UV excited resonance Raman (RR) and laser induced native fluorescence (LINF) emissions collected is less than 1 ms. RR is a method that provides information about molecular bonds, while LINF spectroscopy is a much more sensitive method that provides information regarding the electronic configuration of target molecules. Standoff excitation of suspicious packages, vehicles, persons, and other objects that may contain hazardous materials is accomplished using excitation in the deep UV where there are four main advantages compared to near-UV, visible or near-IR counterparts. 1) Excited between 220 and 250 nm, Raman emission occur within a fluorescence-free region of the spectrum, eliminating obscuration of weak Raman signals by fluorescence from target or surrounding materials. 2) Because Raman and fluorescence occupy separate spectral regions, detection can be done simultaneously, providing an orthogonal set of information to improve both sensitivity and lower false alarm rates. 3) Rayleigh law and resonance effects increase Raman signal strength and sensitivity of detection. 4) Penetration depth into target in the deep UV is short, providing spatial/spectral separation of a target material from its background or substrate. 5) Detection in the deep UV eliminates ambient light background and enable daylight detection.

Experimental and theoretical investigation on the molecular structure, spectroscopic and electric properties of 2,4-dinitrodiphenylamine, 2-nitro-4-(trifluoromethyl)aniline and 4-bromo-2-nitroaniline.

PubMed

Hernández-Paredes, Javier; Hernández-Negrete, Ofelia; Carrillo-Torres, Roberto C; Sánchez-Zeferino, Raúl; Duarte-Moller, Alberto; Alvarez-Ramos, Mario E

2015-10-05

2,4-Dinitrodiphenylamine (I), 2-nitro-4-(trifluoromethyl)aniline (II) and 4-bromo-2-nitroaniline (III) have been investigated by DFT and experimental FTIR, Raman and UV-Vis spectroscopies. The gas-phase molecular geometries were consistent with similar compounds already reported in the literature. From the vibrational analysis, the main functional groups were identified and their absorption bands were assigned. Some differences were found between the calculated and the experimental UV-Vis spectra. These differences were analyzed and explained in terms of the TD-DFT/B3LYP limitations, which were mainly attributed to charge-transfer (CT) effects. These findings were in agreement with previous works, which reported that TD-DFT/B3LYP calculations diverge from experimental results when the electronic transitions involve CT. Despite this, TD-DFT/B3LYP calculations provided satisfactory results and a detailed description of the electronic transitions involved in the absorption bands of the UV-Vis spectra. In terms of the NLO properties, it was found that compound (I) is a good candidate for NLO applications and deserves further study due to its good β values. However, the β values for compounds (II) and (III) were negatively affected compared to those found on o-nitroaniline. Copyright © 2015 Elsevier B.V. All rights reserved.

Remote Raman Spectroscopy of Minerals at Elevated Temperature Relevant to Venus Exploration

NASA Technical Reports Server (NTRS)

Sharma, Shiv K.; Misra, Anupam K.; Singh, Upendra N.

2008-01-01

We have used a remote time-resolved telescopic Raman system equipped with 532 nm pulsed laser excitation and a gated intensified CCD (ICCD) detector for measuring Raman spectra of a number of minerals at high temperature to 970 K. Remote Raman measurements were made with samples at 9-meter in side a high-temperature furnace by gating the ICCD detector with 2 micro-sec gate to minimize interference from blackbody emission from mineral surfaces at high temperature as well as interference from ambient light. A comparison of Raman spectra of gypsum (CaSO4.2H2O), dolomite (CaMg(CO3)2), and olivine (Mg2Fe2-xSiO4), as a function of temperature shows that the Raman lines remains sharp and well defined even in the high-temperature spectra. In the case of gypsum, Raman spectral fingerprints of CaSO4.H2O at 518 K were observed due to dehydration of gypsum. In the case of dolomite, partial mineral dissociation was observed at 973 K at ambient pressure indicating that some of the dolomite might survive on Venus surface that is at approximately 750 K and 92 atmospheric pressure. Time-resolved Raman spectra of low clino-enstatite (MgSiO3) measured at 75 mm from the sample in side the high-temperature furnace also show that the Raman lines remains sharp and well defined in the high temperature spectra. These high-temperature remote Raman spectra of minerals show that time-resolved Raman spectroscopy can be used as a potential tool for exploring Venus surface mineralogy at shorter (75 mm) and long (9 m) distances from the samples both during daytime and nighttime. The remote Raman system could also be used for measuring profiles of molecular species in the dense Venus atmosphere during descent as well as on the surface.

Raman Spectra of High-κ Dielectric Layers Investigated with Micro-Raman Spectroscopy Comparison with Silicon Dioxide

PubMed Central

Borowicz, P.; Taube, A.; Rzodkiewicz, W.; Latek, M.; Gierałtowska, S.

2013-01-01

Three samples with dielectric layers from high-κ dielectrics, hafnium oxide, gadolinium-silicon oxide, and lanthanum-lutetium oxide on silicon substrate were studied by Raman spectroscopy. The results obtained for high-κ dielectrics were compared with spectra recorded for silicon dioxide. Raman spectra suggest the similarity of gadolinium-silicon oxide and lanthanum-lutetium oxide to the bulk nondensified silicon dioxide. The temperature treatment of hafnium oxide shows the evolution of the structure of this material. Raman spectra recorded for as-deposited hafnium oxide are similar to the results obtained for silicon dioxide layer. After thermal treatment especially at higher temperatures (600°C and above), the structure of hafnium oxide becomes similar to the bulk non-densified silicon dioxide. PMID:24072982

Chemical instability of graphene oxide following exposure to highly reactive radicals in advanced oxidation processes.

PubMed

Wang, Zhaohui; Sun, Linyan; Lou, Xiaoyi; Yang, Fei; Feng, Min; Liu, Jianshe

2017-12-01

The rapidly increasing and widespread use of graphene oxide (GO) as catalyst supports, requires further understanding of its chemical stability in advanced oxidation processes (AOPs). In this study, UV/H 2 O 2 and UV/persulfate (UV/PS) processes were selected to test the chemical instability of GO in terms of their performance in producing highly reactive hydroxyl radicals (OH) and sulfate radicals (SO 4 - ), respectively. The degradation intermediates were characterized using UV-visible absorption spectra (UV-vis), X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), Raman spectroscopy, and matrix-assisted laser desorption and ionization time-of-flight mass spectrometry (MALDI-TOF-MS). Experimental data indicate that UV/PS process was more effective in enhancing GO degradation than the UV/H 2 O 2 system. The overall oxygen-containing functionalities (e.g. CO, CO and OCO groups) dramatically declined. After radical attack, sheet-like GO was destructed into lots of flakes and some low-molecular-weight molecules were detected. The results suggest GO is most vulnerable against SO 4 - radical attack, which deserves special attention while GO acts as a catalyst support or even as a catalyst itself. Therefore, stability of GO and its derivatives should be carefully assessed before they are applied to SO 4 - -based AOPs. Copyright © 2017 Elsevier Inc. All rights reserved.

Infrared, Raman and NMR spectra, conformational stability, normal coordinate analysis and B3LYP calculations of 5-Amino-3-methyl-1-phenyl-1H-pyrazole-4-carbaldehyde

NASA Astrophysics Data System (ADS)

Bahgat, Khaled; EL-Emary, Talaat

2013-02-01

FT Raman and IR spectra of the crystallized biologically active molecule, 5-Amino-3-methyl-1-phenyl-1H-pyrazole-4-carbaldehyde (5-APHC, C11H11N3O) have been recorded and analyzed. The equilibrium geometry, bonding features and harmonic vibrational frequencies of 5-APHC have been investigated with the help of B3LYP density functional theory (DFT) method with 6-31G(d) and 6-311+G(d,p) as basis set. The calculated molecular geometry has been compared with the experimental data. The assignments of the vibrational spectra have been carried out with the help of normal coordinate analysis (NCA) following the scaled quantum mechanical force field (SQM) technique. The optimized geometry shows the co-planarity of the aldehyde group with pyrazole ring. Potential energy surface (PES) scan studies has also been carried out by ab initio calculations with B3LYP/6-311+G(d,p) basis set. The red shifting of NH2 stretching wavenumber indicates the formation of N-H⋯O hydrogen bonding. 1H and 13C NMR spectra were recorded and 1H and 13C nuclear magnetic resonance chemical shifts of the molecule were calculated using the gauge independent atomic orbital (GIAO) method. UV-Vis spectrum of the compound was recorded in the region 200-400 nm and the electronic properties HOMO and LUMO energies were calculated by time-dependent TD-DFT approach. Mulliken charges of the 5-APHC molecule was also calculated and interpreted.

FTIR, FT-Raman, UV-Visible spectra and quantum chemical calculations of allantoin molecule and its hydrogen bonded dimers.

PubMed

Alam, Mohammad Jane; Ahmad, Shabbir

2015-02-05

FTIR, FT-Raman and electronic spectra of allantoin molecule are recorded and investigated using DFT and MP2 methods with 6-311++G(d,p) basis set. The molecular structure, anharmonic vibrational spectra, natural atomic charges, non-linear optical properties, etc. have been computed for the ground state of allantoin. The anharmonic vibrational frequencies are calculated using PT2 algorithm (Barone method) as well as VSCF and CC-VSCF methods. These methods yield results that are in remarkable agreement with the experiment. The coupling strengths between pairs of modes are also calculated using coupling integral based on 2MR-QFF approximation. The simulations on allantoin dimers have been also performed at B3LYP/6-311++G(d,p) level of theory to investigate the effect of the intermolecular interactions on the molecular structure and vibrational frequencies of the monomer. Vibrational assignments are made with the great accuracy using PED calculations and animated modes. The combination and overtone bands have been also identified in the FTIR spectrum with the help of anharmonic computations. The electronic spectra are simulated in gas and solution at TD-B3LYP/6-311++G(d,p) level of theory. The important global quantities such as electro-negativity, electronic chemical potential, electrophilicity index, chemical hardness and softness based on HOMO, LUMO energy eigenvalues are also computed. NBO analysis has been performed for monomer and dimers of allantoin at B3LYP/6-311++G(d,p) level of theory. Copyright © 2014 Elsevier B.V. All rights reserved.

Structural, optical and dielectric properties of transition metal (MFe2O4; M = Co, Ni and Zn) nanoferrites

NASA Astrophysics Data System (ADS)

Chand, Prakash; Vaish, Swapnil; Kumar, Praveen

2017-11-01

In the present work, transition metal spinel ferrite (MFe2O4; M = Co, Ni, Zn) nanostructures synthesized by chemical co-precipitation method. XRD analysis confirms the formation of cubic spinel-type structure with space group Fd3m and the average crystallite size calculated by Scherrer's formula found to be in 9-14 nm range. Scanning electron microscopy was used to study surface morphology of the samples. Moreover, Raman and PL spectra also confirm the formation of the cubic structure. The Raman spectra measured on cobalt, nickel and zinc ferrite revealed a larger number of phonon bands than expected for the cubic spinel structure. The calculated optical energy band gaps, obtained by Tauc's relation from UV-Vis absorption spectra are found to be as 2.44, 3.54 and 3.25 eV for CoFe2O4, NiFe2O4&ZnFe2O, respectively. The analysis of the complex impedance spectra of all ferrites samples shows the presence of one semicircular arc at all selected temperatures, signifying a key role of the grain boundary contribution. The dielectric constants (ε ‧) were measured in the frequency range from 10 Hz to 5 MHz at different temperatures and is found to be decreased suddenly with an increase in frequency and maintain a steady state or constant at higher frequencies for all the three samples. The AC conductivity is found to be increased with frequency and temperature of all the three samples which is explained on the basis of Koop's phenomenological theory.

DFT simulation, quantum chemical electronic structure, spectroscopic and structure-activity investigations of 4-acetylpyridine

NASA Astrophysics Data System (ADS)

Atilgan, A.; Yurdakul, Ş.; Erdogdu, Y.; Güllüoğlu, M. T.

2018-06-01

The spectroscopic (UV-Vis and infrared), structural and some electronic property observations of the 4-acetylpyridine (4-AP) were reported, which are investigated by using some spectral methods and DFT calculations. FT-IR spectra were obtained for 4-AP at room temperature in the region 4000 cm-1- 400 cm-1. In the DFT calculations, the B3LYP functional with 6-311G++G(d,p) basis set was applied to carry out the quantum mechanical calculations. The Fourier Transform Infrared (FT-IR) and FT-Raman spectra were interpreted by using of normal coordinate analysis based on scaled quantum mechanical force field. The present work expands our understanding of the both the vibrational and structural properties as well as some electronic properties of the 4-AP by means of the theoretical and experimental methods.

Eye-safe UV Raman spectroscopy for remote detection of explosives and their precursors in fingerprint concentration

NASA Astrophysics Data System (ADS)

Almaviva, S.; Angelini, F.; Chirico, R.; Palucci, A.; Nuvoli, M.; Schnuerer, F.; Schweikert, W.; Romolo, F. S.

2014-10-01

We report the results of Raman investigation performed at stand-off distance between 6-10 m with a new apparatus, capable to detect traces of explosives with surface concentrations similar to those of a single fingerprint. The device was developed as part of the RADEX prototype (RAman Detection of EXplosives) and is capable of detecting the Raman signal with a single laser shot of few ns (10-9 s) in the UV range (wavelength 266 nm), in conditions of safety for the human eye. This is because the maximum permissible exposure (MPE) for the human eye is established to be 3 mJ/cm2 in this wavelength region and pulse duration. Samples of explosives (PETN, TNT, Urea Nitrate, Ammonium Nitrate) were prepared starting from solutions deposited on samples of common fabrics or clothing materials such as blue jeans, leather, polyester or polyamide. The deposition process takes place via a piezoelectric-controlled plotter device, capable of producing drops of welldefined volume, down to nanoliters, on a surface of several cm2, in order to carefully control the amount of explosive released to the tissue and thus simulate a slight stain on a garment of a potential terrorist. Depending on the type of explosive sampled, the detected density ranges from 0.1 to 1 mg/cm2 and is comparable to the density measured in a spot on a dress or a bag due to the contact with hands contaminated with explosives, as it could happen in the preparation of an improvised explosive device (IED) by a terrorist. To our knowledge the developed device is at the highest detection limits nowadays achievable in the field of eyesafe, stand-off Raman instruments. The signals obtained show some vibrational bands of the Raman spectra of our samples with high signal-to-noise ratio (SNR), allowing us to identify with high sensitivity (high number of True Positives) and selectivity (low number of False Positives) the explosives, so that the instrument could represent the basis for an automated and remote monitoring device.

Raman scattering spectra of superconducting Bi2Sr2CaCu2O8 single crystals

NASA Astrophysics Data System (ADS)

Kirillov, D.; Bozovic, I.; Geballe, T. H.; Kapitulnik, A.; Mitzi, D. B.

1988-12-01

Raman spectra of Bi2Sr2CaCu2O8 single crystals with superconducting phase-transition temperature of 90 K have been studied. The spectra contained phonon lines and electronic continuum. Phonon energies and polarization selection rules were measured. A gap in the electronic continuum spectrum was observed in a superconducting state. Noticeable similarity between Raman spectra of Bi2Sr2CaCu2O8 and YBa2Cu3O7 was found.

Conformational, electronic, and spectroscopic characterization of isophthalic acid (monomer and dimer structures) experimentally and by DFT

NASA Astrophysics Data System (ADS)

Bardak, F.; Karaca, C.; Bilgili, S.; Atac, A.; Mavis, T.; Asiri, A. M.; Karabacak, M.; Kose, E.

2016-08-01

Isophthalic acid (C6H4(CO2H)2) is a noteworthy organic compound widely used in coating and synthesis of resins and the production of commercially important polymers such as drink plastic bottles. The effects of isophthalic acid (IPA) on human health, toxicology, and biodegradability are the main focus of many researchers. Because structural and spectroscopic investigation of molecules provides a deep understanding of interactional behaviors of compounds, this study stands for exploring those features. Therefore, the spectroscopic, structural, electronic, and thermodynamical properties of IPA were thoroughly studied in this work experimentally using UV-Vis, 1H and 13C NMR, FT-IR, FT-Raman and theoretically via DFT and TD-DFT calculations. The UV-Vis absorption spectrum in water was taken in the region 200-400 nm. The NMR chemical shifts (1H and 13C) were recorded in DMSO solution. The infrared and Raman spectra of the solid IPA were recorded in the range of 4000-400 cm- 1 and 3500-50 cm- 1, respectively. DFT and TD-DFT calculations were performed at the level of B3LYP/6-311++G(d,p) in determination of geometrical structure, electronic structure analysis and normal mode. The 13C and 1H nuclear magnetic resonance (NMR) spectra were estimated by using the gauge-invariant atomic orbital (GIAO) method. The scaled quantum mechanics (SQM) method was used to determine the total energy distribution (TED) to assign the vibrational modes accurately. Weak interactions such as hydrogen bonding and Van der Walls were analyzed via reduced density gradient (RDG) analysis in monomeric and dimeric forms. Furthermore, the excitation energies, density of state (DOS) diagram, thermodynamical properties, molecular electro-static potential (MEP), and nonlinear optical (NLO) properties were obtained.

Highly textured and transparent RF sputtered Eu2O3 doped ZnO films

PubMed Central

Sreedharan, Remadevi Sreeja; Ganesan, Vedachalaiyer; Sudarsanakumar, Chellappan Pillai; Bhavsar, Kaushalkumar; Prabhu, Radhakrishna; Mahadevan Pillai, Vellara Pappukutty Pillai

2015-01-01

Background Zinc oxide (ZnO) is a wide, direct band gap II-VI oxide semiconductor. ZnO has large exciton binding energy at room temperature, and it is a good host material for obtaining visible and infrared emission of various rare-earth ions. Methods Europium oxide (Eu2O3) doped ZnO films are prepared on quartz substrate using radio frequency (RF) magnetron sputtering with doping concentrations 0, 0.5, 1, 3 and 5 wt%. The films are annealed in air at a temperature of 773 K for 2 hours. The annealed films are characterized using X-ray diffraction (XRD), micro-Raman spectroscopy, atomic force microscopy, ultraviolet (UV)-visible spectroscopy and photoluminescence (PL) spectroscopy. Results XRD patterns show that the films are highly c-axis oriented exhibiting hexagonalwurtzite structure of ZnO. Particle size calculations using Debye-Scherrer formula show that average crystalline size is in the range 15–22 nm showing the nanostructured nature of the films. The observation of low- and high-frequency E2 modes in the Raman spectra supports the hexagonal wurtzite structure of ZnO in the films. The surface morphology of the Eu2O3 doped films presents dense distribution of grains. The films show good transparency in the visible region. The band gaps of the films are evaluated using Tauc plot model. Optical constants such as refractive index, dielectric constant, loss factor, and so on are calculated using the transmittance data. The PL spectra show both UV and visible emissions. Conclusion Highly textured, transparent, luminescent Eu2O3 doped ZnO films have been synthesized using RF magnetron sputtering. The good optical and structural properties and intense luminescence in the ultraviolet and visible regions from the films suggest their suitability for optoelectronic applications. PMID:25765728

Molecular structure, spectroscopic studies, and coppersbnd oxygen bond strength of α-methyl and α-ethyl derivatives of copper (II) acetylacetonate; Experimental and theoretical approach

NASA Astrophysics Data System (ADS)

Seyedkatouli, Seyedabdollah; Vakili, Mohammad; Tayyari, Sayyed Faramarz; Afzali, Raheleh

2018-05-01

This paper presents a combined experimental and theoretical study on the Cusbnd O bond strength of copper (II) α-methylacetylacetonate, Cu(3-Meacac)2, and copper (II) α-ethylacetylacetonate, Cu(3-Etacac)2, complexes in comparison to that in copper (II) acetylacetonate, Cu(acac)2. For this purpose, the molecular structure, UV spectra, and complete vibrational assignment of target molecules were investigated by DFT, Natural Bond Orbital (NBO) theory, and Atoms-in-Molecules (AIM) analysis at the B3LYP/6-311G* level of theory. The mentioned results are compared with those in Cu(acac)2. Fourier transform-Raman, IR, and UV spectra of these complexes have been also recorded. A complete assignment of the observed band frequencies has been done. All theoretical and experimental spectroscopic results are consisting with a stronger metal-oxygen bond in Cu(3-Meacac)2 and Cu(3-Etacac)2 complexes compared with Cu(acac)2. In addition, these results confirm that there is no significant difference between the Cusbnd O bond strength of the Cu(3-Meacac)2 and Cu(3-Etacac)2 complexes.

Mesoporous titanosilicates with high loading of titanium synthesized in mild acidic buffer solution.

PubMed

Tang, Jianting; Liu, Jian; Yang, Jie; Feng, Zhaochi; Fan, Fengtao; Yang, Qihua

2009-07-15

Mesoporous titanosilicates with high titanium content were synthesized under mild acidic conditions (pH=4.4, HAc-NaAc buffer solution) by co-condensation of acetylacetone-modified titanium isopropoxide (Ti(OBu(n))(3) (acac)) and mixture of sodium silicate with tetramethoxysilane (TMOS) or tetraethoxysilane (TEOS) or tetrakis(2-hydroxyethyl)orthosilicate (EGMS), using block copolymer Pluronic P123 as template. The combined results of XRD, N(2) sorption and TEM show that the highly regular structure of the mesoporous titanosilicates can still be obtained when Ti/Si molar ratio in the final product is as high as 0.059. The results of UV-vis diffuse reflectance spectra and UV resonance Raman spectra show that the framework titanium species are predominant in the mesoporous titanosilicates when Ti/Si molar ratio in the final product is less than 0.042. The mixture of sodium silicate and EGMS was proved to be the best silicon source for the synthesis of titanosilicates with ordered mesostructure and high titanium content. The efficiency of this synthetic method may be attributed to the mild acidic medium as well as the modified hydrolysis-condensation rate and hydrophility of the precursors.

Elaboration of nano titania-magnetic reduced graphene oxide for degradation of tartrazine dye in aqueous solution

NASA Astrophysics Data System (ADS)

Nada, Amr A.; Tantawy, Hesham R.; Elsayed, Mohamed A.; Bechelany, Mikhael; Elmowafy, Mohamed E.

2018-04-01

In this paper, magnetic nanocomposites are synthesized by loading reduced graphene oxide (RG) with two components of nanoparticles consisting of titanium dioxide (TiO2) and magnetite (Fe3O4) with varying amounts. The structural and magnetic features of the prepared composite photocatalysts were investigated by powder X-ray diffraction (XRD), Fourier transform infrared spectra (FT-IR), transmission electron microscopy (TEM), UV-vis diffuse reflectance spectra (UV-vis/DRS), Raman and vibrating sample magnetometer (VSM). The resulting TiO2/magnetite reduced graphene oxide (MRGT) composite demonstrated intrinsic visible light photocatalytic activity, on degradation of tartrazine (TZ) dye from a synthetic aqueous solution. Specifically, it exhibits higher photocatalytic activity than magnetite reduced graphene oxide (MRG) and TiO2 nanoparticles. The photocatalytic degradation of TZ dye when using MRG and TiO2 for 3 h under visible light was 35% and 10% respectively, whereas for MRGT it was more than 95%. The higher photocatalytic efficiency of MRGT is due to the existence of reduced graphene oxide and magnetite which enhances the photocatalytic efficiency of the composite in visible light towards the degradation of harmful soluble azo dye (tartrazine).

Optical and structural properties of Mo-doped NiTiO3 materials synthesized via modified Pechini methods

NASA Astrophysics Data System (ADS)

Pham, Thanh-Truc; Kang, Sung Gu; Shin, Eun Woo

2017-07-01

In this study, molybdenum (Mo)-doped nickel titanate (NiTiO3) materials were successfully synthesized as a function of Mo content through a modified Pechini method followed by a solvothermal treatment process. Various characterization methods were employed to investigate the optical and structural properties of the materials. XRD patterns clearly showed that the NiTiO3 structure maintained a single phase with no observed crystalline structure transformations, even after the addition of 10 wt.% Mo. In the Raman spectra and XRD patterns, peak positions shifted with a change in Mo content, confirming that the NiTiO3 lattice was doped with Mo. On the other hand, Mo doping of NiTiO3 materials changed their optical properties. DRS-UV demonstrated that the addition of Mo increased photon absorption within the UV region. Relaxation processes were inhibited by Mo doping, which was evident in the PL spectra. Structural properties of the prepared materials were studied via FE-SEM and HR-TEM. The measured surface area increased proportionally with Mo content due to a reduction in grain size of the materials.

Vibrational, NMR and UV-visible spectroscopic investigation and NLO studies on benzaldehyde thiosemicarbazone using computational calculations

NASA Astrophysics Data System (ADS)

Moorthy, N.; Prabakar, P. C. Jobe; Ramalingam, S.; Pandian, G. V.; Anbusrinivasan, P.

2016-04-01

In order to investigate the vibrational, electronic and NLO characteristics of the compound; benzaldehyde thiosemicarbazone (BTSC), the XRD, FT-IR, FT-Raman, NMR and UV-visible spectra were recorded and were analysed with the calculated spectra by using HF and B3LYP methods with 6-311++G(d,p) basis set. The XRD results revealed that the stabilized molecular systems were confined in orthorhombic unit cell system. The cause for the change of chemical and physical properties behind the compound has been discussed makes use of Mulliken charge levels and NBO in detail. The shift of molecular vibrational pattern by the fusing of ligand; thiosemicarbazone group with benzaldehyde has been keenly observed. The occurrence of in phase and out of phase molecular interaction over the frontier molecular orbitals was determined to evaluate the degeneracy of the electronic energy levels. The thermodynamical studies of the temperature region 100-1000 K to detect the thermal stabilization of the crystal phase of the compound were investigated. The NLO properties were evaluated by the determination of the polarizability and hyperpolarizability of the compound in crystal phase. The physical stabilization of the geometry of the compound has been explained by geometry deformation analysis.

Quantum chemical calculation (electronic and topologic) and experimental (FT-IR, FT-Raman and UV) analysis of isonicotinic acid N-oxide

NASA Astrophysics Data System (ADS)

Karaca, Caglar; Atac, Ahmet; Karabacak, Mehmet

2015-04-01

In this work, the molecular conformation, vibrational and electronic analysis of isonicotinic acid N-oxide (iso-NANO) were presented in the ground state using experimental techniques (FT-IR, FT-Raman and UV) and density functional theory (DFT) employing B3LYP exchange correlation with the 6-311++G(d,p) basis set. The geometry optimization and energies associated possible two conformers (Rot-I and Rot-II) were computed. The vibrational spectra were calculated and fundamental vibrations were assigned on the basis of the total energy distribution (TED) of the vibrational modes, calculated with scaled quantum mechanics (SQM) method and PQS program. The obtained structures were analyzed with the Atoms in Molecules (AIMs) methodology. The computational results diagnose the most stable conformer of iso-NANO as the Rot-I form. Total density of state (TDOS) and partial density of state (PDOS) and also overlap population density of state (OPDOS) diagrams analysis for the most stable conformer (Rot-I) were calculated using the same method. Thermodynamic properties (heat capacity, entropy and enthalpy) of the title compound at different temperatures were calculated. As a result, the optimized geometry and calculated spectroscopic data show a good agreement with the experimental results.

Identification of geometrical isomers and comparison of different isomeric samples of astaxanthin.

PubMed

Qiu, Dan; Wu, Yue-Chan; Zhu, Wen-Li; Yin, Hong; Yi, Long-Tao

2012-09-01

A high-performance liquid chromatographic (HPLC) analysis system for isomeric astaxanthin was developed. The separation system consisted of a C(30) column and an elution system of methanol/MTBE/water/dichloromethane (77:13:8:2, v/v/v/v). Using the combination of HPLC diode array detector and HPLC atmospheric pressure chemical ionization mass spectrometry, 11 geometrical isomers and 4 epoxides of astaxanthin were successfully identified. Referred to crystal, only isomerization with different degrees was found for solvent dissolving and iodine catalysis, while melting of astaxanthin caused isomerization, slight oxidation, and more noticeable polymerization confirmed by gel permeation chromatography. Chemical changes in isomeric samples all caused a decrease in UV content. The vibrational spectra (infrared and Raman) showed that epoxide was the only new functional group generated for melting. Changes of several key bands and formations of new bands were found in iodine catalysis and melting samples because of isomerization. Practical Application:  Eleven geometrical isomers and 4 epoxides, which were normally generated for solvent dissolving, iodine catalysis, and melting of astaxanthin, have been identified by C(30) -HPLC-MS technology. Furthermore, different samples were measured by gel permeation chromatography, UV, infrared, and Raman, based on the analysis of messages, the effect of each processing was well understood. © 2012 Institute of Food Technologists®

Spectroscopic (FT-IR, FT-Raman, and UV-visible) and quantum chemical studies on molecular geometry, Frontier molecular orbitals, NBO, NLO and thermodynamic properties of 1-acetylindole.

PubMed

Shukla, Vikas K; Al-Abdullah, Ebtehal S; El-Emam, Ali A; Sachan, Alok K; Pathak, Shilendra K; Kumar, Amarendra; Prasad, Onkar; Bishnoi, Abha; Sinha, Leena

2014-12-10

Quantum chemical calculations of ground state energy, geometrical structure and vibrational wavenumbers of 1-acetylindole were carried out using density functional (DFT/B3LYP) method with 6-311++G(d,p) basis set. The FT-IR and FT-Raman spectra were recorded in the condensed state. The fundamental vibrational wavenumbers were calculated and a good correlation between experimental and scaled calculated wavenumbers has been accomplished. Electric dipole moment, polarizability and first static hyperpolarizability values of 1-acetylindole have been calculated at the same level of theory and basis set. The results show that the 1-acetylindole molecule possesses nonlinear optical (NLO) behavior with non-zero values. Stability of the molecule arising from hyper-conjugative interactions and charge delocalization has been analyzed using natural bond orbital (NBO) analysis. UV-Visible spectrum of the molecule was recorded in the region 200-500nm and the electronic properties like HOMO and LUMO energies and composition were obtained using TD-DFT method. The calculated energies and oscillator strengths are in good correspondence with the experimental data. The thermodynamic properties of the compound under investigation were calculated at different temperatures. Copyright © 2014 Elsevier B.V. All rights reserved.

Acquisition of pro-oxidant activity of fALS-linked SOD1 mutants as revealed using circular dichroism and UV-resonance Raman spectroscopy

NASA Astrophysics Data System (ADS)

Fujimaki, Nobuhiro; Nishiya, Ken; Miura, Takashi; Nakabayashi, Takakazu

2016-11-01

The acquisition of pro-oxidant activity of the mutated form of human Cu, Zn-superoxide dismutase (SOD1) has been investigated to clarify the relationship between mutations in SOD1 and the pathogenesis of amyotrophic lateral sclerosis (ALS). Ala4 → Val (A4V) and Gly93 → Ala (G93A) mutants, which are representative ALS-linked SOD1 mutants, have been found to exhibit both the denaturation and the gain of pro-oxidant activity after incubation in the apo-form at a physiological condition of 37 °C and pH 7.4 and the rebinding of Cu2+. These characteristics are similar to those previously reported for the His43 → Arg (H43R) mutant. UV-resonance Raman spectra indicated that the coordination structure of the Cu-binding site catalyzing the oxidation reaction is the same among the denatured A4V, G93A, and H43R. Since wild-type SOD1 does not exhibit the denaturation in its apo-form at 37 °C and pH 7.4, the instability of the protein structure due to mutation can be considered as a significant factor that induces the denaturation and the subsequent pro-oxidant activity.

Au nanoparticle arrays produced by Pulsed Laser Deposition for Surface Enhanced Raman Spectroscopy

NASA Astrophysics Data System (ADS)

Agarwal, N. R.; Neri, F.; Trusso, S.; Lucotti, A.; Ossi, P. M.

2012-09-01

Using UV pulses from KrF excimer laser, Au targets were ablated in varying pressures of argon to deposit Au nanoparticle (NP) arrays. The morphology of these films from island structures to isolated NPs, observed by SEM and TEM, depends on the gas pressure (10-100 Pa) and pulse number keeping other deposition parameters constant. By fast imaging of the plasma with an iCCD camera at different time delays with respect to the arrival of the laser pulse, we study the plasma propagation regime and we measured its initial velocity. These data and the measured average ablated mass per pulse were introduced to the mixed propagation model to calculate the average asymptotic size of clusters grown in the plume which were compared with NP sizes from TEM measurements. UV-visible Spectroscopy revealed changes of surface plasmon resonance with respect to NP size and spatial density and distribution on the surface. Suitable wavelength to excite the localized surface plasmon was chosen to detect ultra-low concentrations of Rhodamine and Apomorphine as an application to biomedical sensors, using Surface Enhanced Raman Spectroscopy (SERS). A comparison of SERS spectra taken under identical conditions from commercial substrates and from PLD substrates show that the latter have superior performances.

Identification of copper phthalocyanine blue polymorphs in unaged and aged paint systems by means of micro-Raman spectroscopy and Random Forest.

PubMed

Anghelone, Marta; Jembrih-Simbürger, Dubravka; Schreiner, Manfred

2015-10-05

Copper phthalocyanine (CuPc) blues (PB15) are largely used in art and industry as pigments. In these fields mainly three different polymorphic modifications of PB15 are employed: alpha, beta and epsilon. Differentiating among these CuPc forms can give important information for developing conservation strategy and can help in relative dating, since each form was introduced in the market in different time periods. This study focuses on the classification of Raman spectra measured using 532 nm excitation wavelength on: (i) dry pigment powders, (ii) unaged mock-ups of self-made paints, (iii) unaged commercial paints, and (iv) paints subjected to accelerated UV ageing. The ratios among integrated Raman bands are taken in consideration as features to perform Random Forest (RF). Features selection based on Gini Contrast score was carried out on the measured dataset to determine the Raman bands ratios with higher predictive power. These were used as polymorphic markers, in order to establish an easy and accessible method for the identification. Three different ratios and the presence of a characteristic vibrational band allowed the identification of the crystal modification in pigments powder as well as in unaged and aged paint films. Copyright © 2015 Elsevier B.V. All rights reserved.

Double optical fibre-probe device for the diagnosis of melanocytic lesions

NASA Astrophysics Data System (ADS)

Cicchi, Riccardo; Cosci, Alessandro; Rossari, Susanna; De Giorgi, Vincenzo; Kapsokalyvas, Dimitrios; Massi, Daniela; Pavone, Francesco S.

2012-06-01

We have designed and developed an optical fiber-probe for spectroscopic measurements on human tissues. The experimental setup combines fluorescence spectroscopy and Raman spectroscopy in a multidimensional approach. Concerning fluorescence spectroscopy, the excitation is provided by two laser diodes, one emitting in the UV (378 nm) and the other emitting in the visible (445 nm). These two lasers are used to selectively excite fluorescence from NADH and FAD, which are among the brightest endogenous fluorophores in human tissues. For Raman and NIR spectroscopy, the excitation is provided by a third laser diode with 785 nm excitation wavelength. Laser light is delivered to the tissue through the central optical fiber of a fiber bundle. The surrounding 48 fibers of the bundle are used for collecting fluorescence and Raman and for delivering light to the spectrograph. Fluorescence and Raman spectra are acquired on a cooled CCD camera. The instrument has been tested on fresh human skin biopsies clinically diagnosed as malignant melanoma, melanocytic nevus, or healthy skin, finding an optimal correlation with the subsequent histological exam. In some cases our examination was not in agreement with the clinical observation, but it was with the histological exam, demonstrating that the system can potentially contribute to improve clinical diagnostic capabilities and hence reduce the number of unnecessary biopsies.

Observation of the degradation of three types of plastic pellets exposed to UV irradiation in three different environments.

PubMed

Cai, Liqi; Wang, Jundong; Peng, Jinping; Wu, Ziqing; Tan, Xiangling

2018-07-01

Plastic debris represents one of the most prevalent and persistent pollution problems in the marine environment. In particular, microplastics that are mainly degraded from larger plastic debris have become a growing environmental concern. However, studies on the degradation of plastics in the aquatic environment that hydrobios reside in have been limited, while several studies regarding the degradation of plastics have been conducted under outdoor or accelerated weathering conditions. Thus, observation of the degradation of three types of virgin plastic pellets exposed to UV irradiation in three different environments (i.e., simulated seawater, ultrapure water, and a waterless (air) condition) was carried out. Data on the changes in physical and chemical properties were collected. The FTIR spectra showed that hydroxyl groups and carbonyl groups developed in three types of weathered plastic pellets under the air and ultrapure water environmental conditions after 3months of UV irradiation, while only carbonyl groups were found in plastic pellets in the simulated seawater environment. In contrast, the Raman spectra showed no significant changes in the weathered plastic pellets, but there were different intensities of characteristic peaks after exposure to UV irradiation. In addition, SEM images illustrated that granular oxidation, cracks and flakes were common patterns during degradation, and the plastic pellets in the three different environments experienced different levels of chemical weathering. We suggest that further studies on the degradation processes of plastic debris are needed to predict the fate of plastic debris in the environment. Copyright © 2018 Elsevier B.V. All rights reserved.

Dual-resolution Raman spectroscopy for measurements of temperature and twelve species in hydrocarbon–air flames

DOE Office of Scientific and Technical Information (OSTI.GOV)

Magnotti, Gaetano; Barlow, Robert S.

2016-07-12

This study introduces dual-resolution Raman spectroscopy as a novel diagnostics approach for measurements of temperature and species in flames where multiple hydrocarbons are present. Simultaneous measurement of multiple hydrocarbons is challenging because their vibrational Raman spectra in the C–H stretch region are closely overlapped and are not well known over the range of temperature encountered in flames. Overlap between the hydrocarbon spectra is mitigated by adding a second spectrometer, with a higher dispersion grating, to collect the Raman spectra in the C–H stretch region. A dual-resolution Raman spectroscopy instrument has been developed and optimized for measurements of major species (Nmore » 2, O 2, H 2O, CO 2, CO, H 2, DME) and major combustion intermediates (CH 4, CH 2O, C 2H 2, C 2H 4 and C 2H 6) in DME–air flames. The temperature dependences of the hydrocarbon Raman spectra over fixed spectral regions have been determined through a series of measurements in laminar Bunsen-burner flames, and have been used to extend a library of previously acquired Raman spectra up to flame temperature. The paper presents the first Raman measurements of up to twelve species in hydrocarbon flames, and the first quantitative Raman measurements of formaldehyde in flames. Lastly, the accuracy and precision of the instrument are determined from measurements in laminar flames and the applicability of the instrument to turbulent DME–air flames is discussed.« less

Fabrication of hierarchical ZnO nanostructures on cotton fabric for wearable device applications

NASA Astrophysics Data System (ADS)

Pandiyarasan, V.; Suhasini, S.; Archana, J.; Navaneethan, M.; Majumdar, Abhijit; Hayakawa, Y.; Ikeda, H.

2017-10-01

We have investigated ZnO nanostructures on cotton fabric (CF) s a flexible material for an application of wearable thermoelectric (TE) power generator which requires super-hydrophobicity, UV protection, and high TE efficiency. Field emission scanning electron microscopy images revealed that the formed ZnO nanostructures have a mixture of nanorods and nanosheets and are uniformly coated on the CF. XRD pattern and Raman spectra revealed that the ZnO nanostructure has a wurtzite structure. Contact angle measurements showed that the ZnO-nanostructures-coated CF possessed a high super hydrophobic nature with an angle of 132.5°. ZnO nanocomposite/CF sample exhibited an excellent UV protection factor 183.84. Seebeck coefficient, electrical resistivity and thermoelectric power factor of the ZnO nanostructures on cotton fabric were evaluated to be 28 μV/K, 0.04 Ω-cm, and 22 μW/m K2, respectively.

Remote-Raman spectroscopic study of minerals under supercritical CO2 relevant to Venus exploration.

PubMed

Sharma, Shiv K; Misra, Anupam K; Clegg, Samuel M; Barefield, James E; Wiens, Roger C; Acosta, Tayro E; Bates, David E

2011-10-01

The authors have utilized a recently developed compact Raman spectrometer equipped with an 85 mm focal length (f/1.8) Nikon camera lens and a custom mini-ICCD detector at the University of Hawaii for measuring remote Raman spectra of minerals under supercritical CO(2) (Venus chamber, ∼102 atm pressure and 423 K) excited with a pulsed 532 nm laser beam of 6 mJ/pulse and 10 Hz. These experiments demonstrate that by focusing a frequency-doubled 532 nm Nd:YAG pulsed laser beam with a 10× beam expander to a 1mm spot on minerals located at 2m inside a Venus chamber, it is possible to measure the remote Raman spectra of anhydrous sulfates, carbonates, and silicate minerals relevant to Venus exploration during daytime or nighttime with 10s integration time. The remote Raman spectra of gypsum, anhydrite, barite, dolomite and siderite contain fingerprint Raman lines along with the Fermi resonance doublet of CO(2). Raman spectra of gypsum revealed dehydration of the mineral with time under supercritical CO(2) at 423 K. Fingerprint Raman lines of olivine, diopside, wollastonite and α-quartz can easily be identified in the spectra of these respective minerals under supercritical CO(2). The results of the present study show that time-resolved remote Raman spectroscopy with a compact Raman spectrometer of moderate resolution equipped with a gated intensified CCD detector and low power laser source could be a potential tool for exploring Venus surface mineralogy both during daytime and nighttime from a lander. Copyright © 2011 Elsevier B.V. All rights reserved.

Vibrational fingerprinting of bacterial pathogens by surface enhanced Raman scattering (SERS)

NASA Astrophysics Data System (ADS)

Premasiri, W. Ranjith; Moir, D. T.; Ziegler, Lawrence D.

2005-05-01

The surface enhanced Raman scattering (SERS) spectra of vegetative whole-cell bacteria were obtained using in-situ grown gold nanoparticle cluster-covered silicon dioxide substrates excited at 785 nm. SERS spectra of Gram-negative bacteria; E. coli and S. typhimurium, and Gram-positive bacteria; B. subtilis, B. cereus, B. thuringeinsis and B. anthracis Sterne, have been observed. Raman enhancement factors of ~104-105 per cell are found for both Gram positive and Gram negative bacteria on this novel SERS substrate. The bacterial SERS spectra are species specific and exhibit greater species differentiation and reduced spectral congestion than their corresponding non-SERS (bulk) Raman spectra. Fluorescence observed in the 785 nm excited bulk Raman emission of Bacillus species is not apparent in the corresponding SERS spectra. The surface enhancement effect allows the observation of Raman spectra at the single cell level excited by low incident laser powers (< 3 mW) and short data acquisition times (~20 sec.). Comparison with previous SERS studies suggests that these SERS vibrational signatures are sensitively dependent on the specific morphology and nature of the SERS active substrate. Exposure to biological environments, such as human blood serum, has an observable effect on the bacterial SERS spectra. However, reproducible, species specific SERS vibrational fingerprints are still obtained. The potential of SERS for detection and identification of bacteria with species specificity on these gold nanoparticle coated substrates is demonstrated by these results.

Osteoarthritis screening using Raman spectroscopy of dried human synovial fluid drops

NASA Astrophysics Data System (ADS)

Esmonde-White, Karen A.; Mandair, Gurjit S.; Esmonde-White, Francis W. L.; Raaii, Farhang; Roessler, Blake J.; Morris, Michael D.

2009-02-01

We describe the use of Raman spectroscopy to investigate synovial fluid drops deposited onto fused silica microscope slides. This spectral information can be used to identify chemical changes in synovial fluid associated with osteoarthritis (OA) damage to knee joints. The chemical composition of synovial fluid is predominately proteins (enzymes, cytokines, or collagen fragments), glycosaminoglycans, and a mixture of minor components such as inorganic phosphate crystals. During osteoarthritis, the chemical, viscoelastic and biological properties of synovial fluid are altered. A pilot study was conducted to determine if Raman spectra of synovial fluid correlated with radiological scoring of knee joint damage. After informed consent, synovial fluid was drawn and x-rays were collected from the knee joints of 40 patients. Raman spectra and microscope images were obtained from the dried synovial fluid drops using a Raman microprobe and indicate a coarse separation of synovial fluid components. Individual protein signatures could not be identified; Raman spectra were useful as a general marker of overall protein content and secondary structure. Band intensity ratios used to describe protein and glycosaminoglycan structure were used in synovial fluid spectra. Band intensity ratios of Raman spectra indicate that there is less ordered protein secondary structure in synovial fluid from the damage group. Combination of drop deposition with Raman spectroscopy is a powerful approach to examining synovial fluid for the purposes of assessing osteoarthritis damage.

Condensing Raman spectrum for single-cell phenotype analysis.

PubMed

Sun, Shiwei; Wang, Xuetao; Gao, Xin; Ren, Lihui; Su, Xiaoquan; Bu, Dongbo; Ning, Kang

2015-01-01

In recent years, high throughput and non-invasive Raman spectrometry technique has matured as an effective approach to identification of individual cells by species, even in complex, mixed populations. Raman profiling is an appealing optical microscopic method to achieve this. To fully utilize Raman proling for single-cell analysis, an extensive understanding of Raman spectra is necessary to answer questions such as which filtering methodologies are effective for pre-processing of Raman spectra, what strains can be distinguished by Raman spectra, and what features serve best as Raman-based biomarkers for single-cells, etc. In this work, we have proposed an approach called rDisc to discretize the original Raman spectrum into only a few (usually less than 20) representative peaks (Raman shifts). The approach has advantages in removing noises, and condensing the original spectrum. In particular, effective signal processing procedures were designed to eliminate noise, utilising wavelet transform denoising, baseline correction, and signal normalization. In the discretizing process, representative peaks were selected to signicantly decrease the Raman data size. More importantly, the selected peaks are chosen as suitable to serve as key biological markers to differentiate species and other cellular features. Additionally, the classication performance of discretized spectra was found to be comparable to full spectrum having more than 1000 Raman shifts. Overall, the discretized spectrum needs about 5storage space of a full spectrum and the processing speed is considerably faster. This makes rDisc clearly superior to other methods for single-cell classication.

Time-Resolved Remote-Raman Spectroscopic study of Minerals at High Temperature and under Supercritical CO2 Relevant to Venus Exploration

NASA Astrophysics Data System (ADS)

Sharma, S. K.; Misra, A. K.; Clegg, S. M.; Barefield, J. E.; Wiens, R. C.; Acosta, T.

2009-12-01

We have used a remote time-resolved (TR) telescopic Raman system equipped with 532 nm pulsed laser excitation and a gated intensified CCD (ICCD) detector for measuring Raman spectra of a number of minerals under two sets of conditions. The first set of experiments involved probing samples as a function of temperature ranging from 300 to 973 K at 1 atm. These experiments involve a 5x beam expander to focus the 532 nm (30 mJ/pulse 20 Hz) laser beams onto the sample at 9 m from the remote Raman system. The second set of experiments involved placing the samples in a high pressure vessel with a sapphire window containing supercritical CO2 at pressures up to 93 atm and 423 K. At high temperatures and ambient pressure, the remote Raman measurements were made with samples at 9 meter distance inside a high temperature furnace by gating the ICCD detector with 2 micro-s gate to minimize interference from blackbody emission from mineral surfaces at high temperature as well as interference from ambient light. A comparison of Raman spectra of gypsum (CaSO4.2H2O), dolomite (CaMg(CO3)2), and olivine (Mg2Fe2-xSiO4), as a function of temperature shows that the Raman lines remains sharp and well defined even in the high temperature spectra. In the pressure vessel, Cr3+ fluorescence from sapphire window interfere with the Raman spectra of hydrous minerals in the high-frequency region (2500-4500 cm-1). With time-resolved Raman measurements the interference of the fluorescence in the Raman spectra on minerals was minimized by gating ICCD to <100 ns. The Fermi resonance doublet of CO2 molecules consisting of Raman lines at 1285 (2ν2) and 1388 (ν1) cm-1 does not interfere with the major Raman fingerprints of silicates, carbonate, sulfates minerals. With suitable time delay of the ICCD detector, the Raman bands from supercritical CO2 atmosphere can be minimized providing pure Raman spectra of the mineral targets. We will present remote Raman data on silicates (olivine, pyroxene, quartz, feldspars and talc), dolomite, gypsum, hydrous iron sulfate and barite under supercritical CO2 environment. With TR remote Raman system using 532 nm (15 mJ/pulse, 20Hz) laser excitation, a large varieties of minerals could be easily identified from their respective Raman fingerprints typically in 1s. Minerals with low Raman cross section (e.g., feldspars, pyroxene, olivine, talc, etc) can be detected and quantified from their respective Raman spectra in 10 to 30 s. These results show that time-resolve remote Raman system is capable of making spectral measurements at several hundred to thousand target points on Venus surface within limited (a few hours) expected lifetime of a lander because of extreme temperature and pressure conditions.

Roto-translational Raman spectra of pairs of hydrogen molecules from first principles.

PubMed

Gustafsson, Magnus; Frommhold, Lothar; Li, Xiaoping; Hunt, K L C

2009-04-28

We calculate the collision-induced, roto-translational, polarized, and depolarized Raman spectra of pairs of H(2) molecules. The Schrodinger equation of H(2)-H(2) scattering in the presence of a weak radiation field is integrated in the close-coupled scheme. This permits the accounting for the anisotropy of the intermolecular potential energy surface and thereby it includes mixing of polarizability components. The static polarizability invariants, trace and anisotropy, of two interacting H(2) molecules were obtained elsewhere [Li et al., J. Chem. Phys. 126, 214302 (2007)] from first principles. Here we report the associated spherical tensor components which, along with the potential surface, are input in the calculation of the supramolecular Raman spectra. Special attention is paid to the interferences in the wings of the rotational S(0)(0) and S(0)(1) lines of the H(2) molecule. The calculated Raman pair spectra show reasonable consistency with existing measurements of the polarized and depolarized Raman spectra of pairs of H(2) molecules.

Principal component analysis and analysis of variance on the effects of Entellan New on the Raman spectra of fibers.

PubMed

Yu, Marcia M L; Sandercock, P Mark L

2012-01-01

During the forensic examination of textile fibers, fibers are usually mounted on glass slides for visual inspection and identification under the microscope. One method that has the capability to accurately identify single textile fibers without subsequent demounting is Raman microspectroscopy. The effect of the mountant Entellan New on the Raman spectra of fibers was investigated to determine if it is suitable for fiber analysis. Raman spectra of synthetic fibers mounted in three different ways were collected and subjected to multivariate analysis. Principal component analysis score plots revealed that while spectra from different fiber classes formed distinct groups, fibers of the same class formed a single group regardless of the mounting method. The spectra of bare fibers and those mounted in Entellan New were found to be statistically indistinguishable by analysis of variance calculations. These results demonstrate that fibers mounted in Entellan New may be identified directly by Raman microspectroscopy without further sample preparation. © 2011 American Academy of Forensic Sciences.

An Investigation on Micro-Raman Spectra and Wavelet Data Analysis for Pemphigus Vulgaris Follow-up Monitoring.

PubMed

Camerlingo, Carlo; Zenone, Flora; Perna, Giuseppe; Capozzi, Vito; Cirillo, Nicola; Gaeta, Giovanni Maria; Lepore, Maria

2008-06-01

A wavelet multi-component decomposition algorithm has been used for data analysis of micro-Raman spectra of blood serum samples from patients affected by pemphigus vulgaris at different stages. Pemphigus is a chronic, autoimmune, blistering disease of the skin and mucous membranes with a potentially fatal outcome. Spectra were measured by means of a Raman confocal microspectrometer apparatus using the 632.8 nm line of a He-Ne laser source. A discrete wavelet transform decomposition method has been applied to the recorded Raman spectra in order to overcome problems related to low-level signals and the presence of noise and background components due to light scattering and fluorescence. This numerical data treatment can automatically extract quantitative information from the Raman spectra and makes more reliable the data comparison. Even if an exhaustive investigation has not been done in this work, the feasibility of the follow-up monitoring of pemphigus vulgaris pathology has been clearly proved with useful implications for the clinical applications.

An Investigation on Micro-Raman Spectra and Wavelet Data Analysis for Pemphigus Vulgaris Follow-up Monitoring

PubMed Central

Camerlingo, Carlo; Zenone, Flora; Perna, Giuseppe; Capozzi, Vito; Cirillo, Nicola; Gaeta, Giovanni Maria; Lepore, Maria

2008-01-01

A wavelet multi-component decomposition algorithm has been used for data analysis of micro-Raman spectra of blood serum samples from patients affected by pemphigus vulgaris at different stages. Pemphigus is a chronic, autoimmune, blistering disease of the skin and mucous membranes with a potentially fatal outcome. Spectra were measured by means of a Raman confocal microspectrometer apparatus using the 632.8 nm line of a He-Ne laser source. A discrete wavelet transform decomposition method has been applied to the recorded Raman spectra in order to overcome problems related to low-level signals and the presence of noise and background components due to light scattering and fluorescence. This numerical data treatment can automatically extract quantitative information from the Raman spectra and makes more reliable the data comparison. Even if an exhaustive investigation has not been done in this work, the feasibility of the follow-up monitoring of pemphigus vulgaris pathology has been clearly proved with useful implications for the clinical applications. PMID:27879899

Modulated FT- Raman Fiber-Optic Spectroscopy: A technique for Remotely Monitoring High-Temperature Reactions in Real-Time

NASA Technical Reports Server (NTRS)

Cooper, John B.; Wise, Kent L.; Jensen, Brian J.

1997-01-01

A modification to a commercial FT-Raman spectrometer is presented for the elimination of thermal backgrounds in FT-Raman spectra. The modification involves the use of a mechanical chopper to modulate the CW laser, remote collection of the signal via fiber optics, and connection of a dual-phase digital signal processor lock-in amplifier between the detector and the spectrometer's collection electronics to demodulate and filter the optical signals. The resulting modulated FT-Raman fiber-optic spectrometer is capable of completely eliminating thermal backgrounds at temperatures exceeding 370 C. In addition, the signal/noise of generated Raman spectra is greater than for spectra collected with the conventional FT-Raman under identical conditions and incident laser power. This is true for both room-temperature and hot samples. The method allows collection of data using preexisting spectrometer software. The total cost of the modification (excluding fiber optics) is approximately $3000 and requires less than 2 h to implement. This is the first report of Fr-Raman spectra collected at temperatures in excess of 300 C in the absence of thermal backgrounds.

Vibrational spectra and ab initio analysis of tert-butyl, trimethylsilyl, and trimethylgermyl derivatives of 3,3-dimethylcyclopropene II. 3,3-Dimethyl-1,2-bis(trimethylsilyl)cyclopropene

NASA Astrophysics Data System (ADS)

Panchenko, Yu. N.; De Maré, G. R.; Abramenkov, A. V.; Baird, M. S.; Tverezovsky, V. V.; Nizovtsev, A. V.; Bolesov, I. G.

2003-07-01

The IR and Raman spectra of 3,3-dimethyl-1,2-bis(trimethylsilyl)cyclopropene (I) (synthesised using standard procedures) were measured in the liquid phase. Total geometry optimisation was performed at the HF/6-31G* level. The HF/6-31G*//HF/6-31G* quantum mechanical force field (QMFF) was calculated and used to determine the theoretical fundamental vibrational frequencies, their predicted IR intensities, Raman activities, and Raman depolarisation ratios. Using Pulay's scaling method and the theoretical molecular geometry, the QMFF of I was scaled by a set of scaling factors used previously for 3,3-dimethyl-1,2-bis(tert-butyl)cyclopropene (17 scale factors for a 105-dimensional problem). The scaled QMFF obtained was used to solve the vibrational problem. The quantum mechanical values of the Raman activities were converted to differential Raman cross sections. The figures for the experimental and theoretical Raman and IR spectra are presented. Assignments of the experimental vibrational spectra of I are given. They take into account the calculated potential energy distribution and the correlation between the estimations of the experimental IR and Raman intensities and Raman depolarisation ratios and the corresponding theoretical values (including Raman cross sections) calculated using the unscaled QMFF.

Raman spectroscopic analysis of Mexican natural artists' materials

NASA Astrophysics Data System (ADS)

Vandenabeele, Peter; Ortega-Avilès, Mayahuel; Castilleros, Dolores Tenorio; Moens, Luc

2007-12-01

This work represents the Raman spectra of 15 natural artists' materials that were obtained from local market in Mexico. Some of these products are not endemic to the region, but are often used in local conservation practice. Other materials are of local origin and have been used for centuries by local craftsmen. The Raman spectra that are reported here are: Chia oil, linseed oil, Campeche wax, beeswax, white copal, dammar, colophony, mastic, pixoy, chapopote, chucum, aje gum, gutta gum, peach gum and gum Arabic. The sample of pixoy was mixed with TiO 2, although it was not clear whether this was done intentionally or not. The Raman spectrum of chapopote, the local name for bitumen, contained features of carbonaceous and terpenoid matter. The Raman spectra of chapopote and chucum suffered severely from fluorescence, resulting in noisy Raman spectra. Aje gum and gutta gum are not gums, since they are resinous (terpenoid) in nature. Aje is a rare animal resin originating from Coccus axin.

Raman spectra of thiolated arsenicals with biological importance.

PubMed

Yang, Mingwei; Sun, Yuzhen; Zhang, Xiaobin; McCord, Bruce; McGoron, Anthony J; Mebel, Alexander; Cai, Yong

2018-03-01

Surface enhanced Raman scattering (SERS) has great potential as an alternative tool for arsenic speciation in biological matrices. SERS measurements have advantages over other techniques due to its ability to maintain the integrity of arsenic species and its minimal requirements for sample preparation. Up to now, very few Raman spectra of arsenic compounds have been reported. This is particularly true for thiolated arsenicals, which have recently been found to be widely present in humans. The lack of data for Raman spectra in arsenic speciation hampers the development of new tools using SERS. Herein, we report the results of a study combining the analysis of experimental Raman spectra with that obtained from density functional calculations for some important arsenic metabolites. The results were obtained with a hybrid functional B3LYP approach using different basis sets to calculate Raman spectra of the selected arsenicals. By comparing experimental and calculated spectra of dimethylarsinic acid (DMA V ), the basis set 6-311++G** was found to provide computational efficiency and precision in vibrational frequency prediction. The Raman frequencies for the rest of organoarsenicals were studied using this basis set, including monomethylarsonous acid (MMA III ), dimethylarsinous acid (DMA III ), dimethylmonothioarinic acid (DMMTA V ), dimethyldithioarsinic acid (DMDTA V ), S-(Dimethylarsenic) cysteine (DMA III (Cys)) and dimethylarsinous glutathione (DMA III GS). The results were compared with fingerprint Raman frequencies from As─O, As─C, and As─S obtained under different chemical environments. These fingerprint vibrational frequencies should prove useful in future measurements of different species of arsenic using SERS. Copyright © 2017 Elsevier B.V. All rights reserved.

Development of nanostructured biocompatible materials for chemical and biological sensors

NASA Astrophysics Data System (ADS)

Curley, Michael; Chilvery, Ashwith K.; Kukhatreva, Tatiana; Sharma, Anup; Corda, John; Farley, Carlton

2012-10-01

This research is focused on the fabrication of thin films followed by Surface Enhanced Raman Spectroscopy (SERS) testing of these films for various applications. One technique involves the mixture of nanoparticles with twophoton material to be used as an indicator dye. Another method involved embedding silver nanoparticles in a ceramic nano-membrane. The substrates were characterized by both Atom Force Microscopy (AFM) and Scanning Electron Microscopy (SEM). We applied the nanostructured substrate to measure the SERS spectra of 10-6 Mol/L Rhodomine 6G(Rh6G), e-coli bacteria and RDX explosive. Our results showed that silver coated ceramic membranes can serve as appropriate substrates to enhance Raman signals. In addition, we demonstrated that the in-house-made colloidal silver can work for enhancement of the Raman spectra for bacteria. We measured the Raman spectra of Rh6G molecules on a substrate absorbed by a nanofluid of silver. We observed several strong Raman bands - 613cm-1,768 cm-1,1308cm-1 1356 cm-1,1510cm-1, which correspond to Rh6G vibrational modes υ53,υ65,υ115,υ117,υ146 respectively, using a ceramic membrane coated by silver. The Raman spectra of Rh6G absorbed by silver nanofluid showed strong enhancement of Raman bands 1175cm-1 and 1529cm-1, 1590 cm-1. Those correspond to vibrational frequency modes - υ103,υ151,152. We also measured the Raman spectra of e-coli bacteria, both absorbed by silver nanofluid, and on nanostructured substrate. In addition, the Fourier Transfer Infrared Spectra (FTIR) of the bacteria was measured.

Near-field Raman spectroscopy

NASA Astrophysics Data System (ADS)

Ayars, Eric James

2000-10-01

The purpose of this research is to investigate differences observed between Raman spectra when seen through a Near-field Scanning Optical Microscope (NSOM) and spectra of the same materials in conventional Raman or micro-Raman configurations. One source of differences in the observed spectra is a strong z polarized component in the near-field radiation; observations of the magnitude of this effect are compared with theoretical predictions for the field intensity near an NSOM tip. Large electric field gradients near the sharp NSOM probe may be another source of differences. This Gradient-Field Raman (GFR) effect was observed, and there is good evidence that it plays a significant role in Surface-Enhanced Raman Spectroscopy (SERS). The NSOM data seen, however, are not sufficient to prove conclusively that the spectral variations seen are due to the field gradients.

[Micro-Raman and fluorescence spectra of several agrochemicals].

PubMed

Xiao, Yi-lin; Zhang, Peng-xiang; Qian, Xiao-fan

2004-05-01

Raman and fluorescence spectra from several agrochemicals were measured, which are sold for the use in vegetables, fruits and grains. Characteristic vibration Raman peaks from some of the agrochemicals were recorded, hence the spectra can be used for their identification. Other marketed agrochemicals demonstrated strong fluorescence under 514.5 nm excitation. It was found that the fluorescence spectra of the agrochemicals are very different. According to these results one can detect the trace amount of agrochemicals left on the surface of fruits, vegetables and grains in situ and conveniently.

[In Vivo Study of Chitin in Fungal Hyphae Based on Confocal Raman Microscopy].

PubMed

Li, Xiao-li; Luo, Liu-bin; Zhou, Bin-xiong; Hu, Xiao-qian; Sun, Chan-jun; He, Yong

2016-01-01

Chitin is an important structural polysaccharide of fungal cell wall. In this paper, aerial hyphae of Colletotrichum camelliae Massee was first studied by confocal Raman microscopy in vivo. Firstly, the optimal experimental parameters of hyphae for collecting the Raman spectra were determined, and the typical Raman spectra of hyphae, chitin standard and background were acquired. By comparing analysis, characteristic peaks of chitin were found in hyphae. Then, a region of interesting on hyphae was selected for Raman scanning. Through principal component analysis, the Raman signal of hyphae and background in the scanning area can be separated clearly. Combined with loading weight plot, two main characteristic peaks of hyphae were obtained, 1 622 cm(-1) was belong to chitin and 1 368 cm(-1) was assigned to pectic polysaccharide. Finally, two and three dimension chemical images of fungal hyphae were realized based on Raman fingerprint spectra of chitin in a nondestructive way.

Differentiating Pseudomonas sp. strain ADP cells in suspensions and biofilms using Raman spectroscopy and scanning electron microscopy.

PubMed

Henry, Victoria A; Jessop, Julie L P; Peeples, Tonya L

2017-02-01

High quality spectra of Pseudomonas sp. strain ADP in the planktonic and biofilm state were obtained using Raman microspectroscopy. These spectra enabled the identification of key differences between free and biofilm cells in the fingerprint region of Raman spectra in the nucleic acid, carbohydrate, and protein regions. Scanning electron microscopy (SEM) enabled detailed visualization of ADP biofilm with confirmation of associated extracellular matrix structure. Following extraction and Raman analysis of extracellular polymeric substances, Raman spectral differences between free and biofilm cells were largely attributed to the contribution of extracellular matrix components produced in mature biofilms. Raman spectroscopy complemented with SEM proves to be useful in distinguishing physiological properties among cells of the same species. Graphical Abstract Raman spectroscopy complemented with SEM proves to be useful in distinguishing physiological properties among cells of the same species.

Analysis of Individual Cells and Endospores by Micro-Raman Spectroscopy

NASA Astrophysics Data System (ADS)

Esposito, Anthony; Huser, Thomas; Talley, Chad; Hollars, Christopher; Balhorn, Rod; Lane, Stephen

2003-03-01

We have collected Raman spectra of individual sperm cells by confocal micro-Raman spectroscopy. The high spatial resolution of this technique allows for compositional analysis of different sections of the sperm cells. The relative intensities of protein and DNA Raman transitions allow one to define a protein-DNA ratio. We have also collected the Raman spectra of individual bacterial endospores from four species in the genus Bacillus. The spectra were generally dominated by scattering from calcium dipicolinate, although scattering assignable to protein bands was also observed. A small fraction of the spores did not exhibit Raman scattering from CaDPA, possibly due to incomplete sporulation. These examples demonstrate the applicability of micro-Raman spectroscopy as a non-invasive method for addressing variability in the composition of cells.* *This work was performed under the auspices of the U.S. Department of Energy by the University of California, Lawrence Livermore National Laboratory under contract number W-7405-Eng-48.

Dental caries detection by optical spectroscopy: a polarized Raman approach with fibre-optic coupling

NASA Astrophysics Data System (ADS)

Ko, A. C.-T.; Choo-Smith, L.-P.; Werner, J.; Hewko, M.; Sowa, M. G.; Dong, C.; Cleghorn, B.

2006-09-01

Incipient dental caries lesions appear as white spots on the tooth surface; however, accurate detection of early approximal lesions is difficult due to limited sensitivity of dental radiography and other traditional diagnostic tools. A new fibre-optic coupled spectroscopic method based on polarized Raman spectroscopy (P-RS) with near-IR laser excitation is introduced which provides contrast for detecting and characterizing incipient caries. Changes in polarized Raman spectra are observed in PO 4 3- vibrations arising from hydroxyapatite of mineralized tooth tissue. Demineralization-induced morphological/orientational alteration of enamel crystallites is believed to be responsible for the reduction of Raman polarization anisotropy observed in the polarized Raman spectra of caries lesions. Supporting evidence obtained by polarized Raman spectral imaging is presented. A specially designed fibre-optic coupled setup for simultaneous measurement of parallel- and cross-polarized tooth Raman spectra is demonstrated in this study.

Infrared and Raman spectra of N-acetyl- L-amino acid methylamides with aromatic side groups

NASA Astrophysics Data System (ADS)

Matsuura, Hiroatsu; Hasegawa, Kodo; Miyazawa, Tatsuo

Infrared and Raman spectra of N-acetyl- L-phenylalanine methylamide, N-acetyl- L-tyrosine methylamide and N-acetyl- L-tryptophan methylamide, as model compounds of aromatic amino acid residues in proteins, were measured in the solid state and in methanol solutions. Vibrational assignments of the spectra were made by utilizing the deuteration effect and by comparison with the spectra of related compounds which include toluene, p-cresol and 3-methylindole. The amide I, III and IV bands were strong in Raman scattering, but other characteristic amide bands were ill-defined. In the Raman spectra of methanol solutions, only the bands due to the aromatic side group vibrations were markedly observed, but those due to the peptide backbone vibrations were very weak, suggesting the coexistence of various molecular conformations in solution.

Raman and FTIR spectroscopic studies on two hydroxylated tung oils (HTO) bearing conjugated double bonds

NASA Astrophysics Data System (ADS)

Zhuang, Yuwei; Ren, Zhiyong; Jiang, Lei; Zhang, Jiaxiang; Wang, Huafen; Zhang, Guobao

2018-06-01

Tung oil (TO) was used as a model compound to study two hydroxylated tung oils (HTO), prepared from TO by either aminolysis (HTO-am) or alcoholysis (HTO-al). Main bands in Raman and FTIR spectra were initially assigned based on the detailed analysis of the compound spectra before and after exposure to elevated temperature (200 °C). The effect of heat treatment in air on spectral bands, and especially on the changes associated with double bonds, were then investigated. In the present work, changes in spectral bands due to heat treatment were compared with those revealed in the previous work of others. The results show that the conjugated triene structure of TO has been retained during alcoholysis and aminolysis, to yield the HTOs studied; yet the change of the triene structure caused by heating is different among the three samples; the H-bonding strength between OH and Cdbnd O in HTO-am is higher than that in HTO-al; the changes in HTO vOH and vCdbnd O bands in FTIR caused by the present heat treatment were significant; for TO, there is a big difference between changes in spectra as caused by thermal exposure, compared to those caused by ageing under UV light or exposure to a catalyst. The present work has laid additional groundwork for further study of the reactions of such triply conjugated double bond structures under different ageing conditions.

Isotope effects in liquid water probed by transmission mode x-ray absorption spectroscopy at the oxygen K-edge.

PubMed

Schreck, Simon; Wernet, Philippe

2016-09-14

The effects of isotope substitution in liquid water are probed by x-ray absorption spectroscopy at the O K-edge as measured in transmission mode. Confirming earlier x-ray Raman scattering experiments, the D2O spectrum is found to be blue shifted with respect to H2O, and the D2O spectrum to be less broadened. Following the earlier interpretations of UV and x-ray Raman spectra, the shift is related to the difference in ground-state zero-point energies between D2O and H2O, while the difference in broadening is related to the difference in ground-state vibrational zero-point distributions. We demonstrate that the transmission-mode measurements allow for determining the spectral shapes with unprecedented accuracy. Owing in addition to the increased spectral resolution and signal to noise ratio compared to the earlier measurements, the new data enable the stringent determination of blue shift and broadening in the O K-edge x-ray absorption spectrum of liquid water upon isotope substitution. The results are compared to UV absorption data, and it is discussed to which extent they reflect the differences in zero-point energies and vibrational zero-point distributions in the ground-states of the liquids. The influence of the shape of the final-state potential, inclusion of the Franck-Condon structure, and differences between liquid H2O and D2O resulting from different hydrogen-bond environments in the liquids are addressed. The differences between the O K-edge absorption spectra of water from our transmission-mode measurements and from the state-of-the-art x-ray Raman scattering experiments are discussed in addition. The experimentally extracted values of blue shift and broadening are proposed to serve as a test for calculations of ground-state zero-point energies and vibrational zero-point distributions in liquid H2O and D2O. This clearly motivates the need for new calculations of the O K-edge x-ray absorption spectrum of liquid water.

In-situ detection of drugs-of-abuse on clothing using confocal Raman microscopy.

PubMed

Ali, Esam M A; Edwards, Howell G M; Hargreaves, Michael D; Scowen, Ian J

2008-05-12

This study describes the application of confocal Raman microscopy to the detection and identification of drugs-of-abuse in situ on undyed natural synthetic fibres, and coloured textile specimens. Raman spectra were obtained from drug particles trapped between the fibres of the specimens. Pure samples of cocaine hydrochloride and N-methyl-3,4-methylenedioxy-amphetamine HCl (MDMA-HCl) were used in this study. Raman spectra were collected from drug particles of an average size in the range 5-15 microm. Despite the presence of spectral bands arising from the natural and synthetic polymer and dyed textiles, the drugs could be identified by their characteristic Raman bands. If necessary, interfering bands could be successfully removed by spectral subtraction. Furthermore, Raman spectra were recorded from drug particles trapped between the fibres of highly fluorescent specimens. Interference from the fibres, including background fluorescence, was overcome by careful focusing of the confocal beam and the resulting spectra allow ready differentiation from interference from the fibres substrate bands. Spectra of several drugs-of-abuse on dyed and undyed clothing substrates were readily obtained within 3 min with little or no sample preparation and with no alteration of the evidential material.

Analytic calculations of hyper-Raman spectra from density functional theory hyperpolarizability gradients

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ringholm, Magnus; Ruud, Kenneth; Bast, Radovan

We present the first analytic calculations of the geometrical gradients of the first hyperpolarizability tensors at the density-functional theory (DFT) level. We use the analytically calculated hyperpolarizability gradients to explore the importance of electron correlation effects, as described by DFT, on hyper-Raman spectra. In particular, we calculate the hyper-Raman spectra of the all-trans and 11-cis isomers of retinal at the Hartree-Fock (HF) and density-functional levels of theory, also allowing us to explore the sensitivity of the hyper-Raman spectra on the geometrical characteristics of these structurally related molecules. We show that the HF results, using B3LYP-calculated vibrational frequencies and force fields,more » reproduce the experimental data for all-trans-retinal well, and that electron correlation effects are of minor importance for the hyper-Raman intensities.« less

UV photostability of insect repellents evaluated through Raman spectroscopy

NASA Astrophysics Data System (ADS)

Bório, Viviane G.; Fernandes, Adjaci U.; Silveira, Landulfo

2016-02-01

The use of insect repellents either indoors or at places with incidence of solar radiation has been common due to dengue epidemics in Brazil. The lack of studies on the photostability of these substances has motivated this study, where the main goal was to verify the photostability and photodegradation of some of the commercially insect repellents available under the simulated ultraviolet (UV) radiation, by evaluating the molecular changes using dispersive Raman spectroscopy (830 nm excitation). A laboratory-made chamber was used for irradiating the repellents, where UV-A + UV-B radiations (UV-A: 5.5 mW/cm2 and UV-B 1.5 mW/cm2) can be obtained. The chamber internal temperature did not exceed 31 °C during experiments. The compounds n,n-diethyl-m-toluamide (DEET), IR-3535, andiroba and citronella oils, used as active ingredients in insect repellents, and commercial formula containing DEET (14.5% in ethanol and isopropyl myristate) and IR-3535 (16% in carbopol) were continuously irradiated for 8 h. The Raman spectrum of each sample was obtained before and after UV exposure. The compounds and the commercial formula containing IR-3535 showed photo-stability when irradiated, since no changes in the peaks were found. The commercial formula containing DEET showed spectral decrease at 524, 690, 1003 and 1606 cm-1, assigned to the DEET, and increase at 884 cm-1, assigned to the ethanol. These results indicate that the excipient could influence the photostability of the active ingredient. The Raman spectroscopy can be suitable to monitor the photodegradation under UV irradiation rapidly and reliably.

Analysis of disulphide bonds found in human hair by Raman spectroscopy

NASA Astrophysics Data System (ADS)

Pina-Ruiz, A. L.; Cordova-Fraga, T.; Plascencia-Castro, A. S.; Hernandez-Rayas, A.; Ruvalcaba, J. M.

2017-04-01

Raman spectroscopy offers information-rich spectra, making it a technique easy to use in areas such as biology, chemistry, and in the field. Human hair spectra has been recorded obtaining interesting information about its composition. Correlating information obtained from these spectra to bone health and determining if Raman spectroscopy could be used as a diagnostic tool of bone health is proposed. Spectra from healthy women were compared to the spectra of women who have suffered a bone fracture, all which were aged 39-60. This technique has potential to become a regular diagnostic tool and further investigation to improve and validate this method are needed.

Efficient "on-the-fly" calculation of Raman spectra from ab-initio molecular dynamics: Application to hydrophobic/hydrophilic solutes in bulk water.

PubMed

Partovi-Azar, Pouya; Kühne, Thomas D

2015-11-05

We present a novel computational method to accurately calculate Raman spectra from first principles. Together with an extension of the second-generation Car-Parrinello method of Kühne et al. (Phys. Rev. Lett. 2007, 98, 066401) to propagate maximally localized Wannier functions together with the nuclei, a speed-up of one order of magnitude can be observed. This scheme thus allows to routinely calculate finite-temperature Raman spectra "on-the-fly" by means of ab-initio molecular dynamics simulations. To demonstrate the predictive power of this approach we investigate the effect of hydrophobic and hydrophilic solutes in water solution on the infrared and Raman spectra. © 2015 Wiley Periodicals, Inc.

Raman microspectroscopy of optically trapped micro- and nanoobjects

NASA Astrophysics Data System (ADS)

Jonáš, Alexandr; Ježek, Jan; Šerý, Mojmír; Zemánek, Pavel

2008-12-01

We describe and characterize an experimental system for Raman microspectroscopy of micro- and nanoobjects optically trapped in aqueous suspensions with the use of a single-beam gradient optical trap (Raman tweezers). This system features two separate lasers providing light for the optical trapping and excitation of the Raman scattering spectra from the trapped specimen, respectively. Using independent laser beams for trapping and spectroscopy enables optimizing the parameters of both beams for their respective purposes. Moreover, it is possible to modulate the position of the trapped object relative to the Raman beam focus for maximizing the detected Raman signal and obtaining spatially resolved images of the trapped specimen. Using this experimental system, we have obtained Raman scattering spectra of individual optically confined micron and sub-micron sized polystyrene beads and baker's yeast cells. Sufficiently high signal-to-noise ratio of the spectra could be achieved using a few tens of milliwatts of the Raman beam power and detector integration times on the order of seconds.

ZnO nanofiber (NFs) growth from ZnO nanowires (NWs) by controlling growth temperature on flexible Teflon substrate by CBD technique for UV photodetector

NASA Astrophysics Data System (ADS)

Farhat, O. F.; Halim, M. M.; Ahmed, Naser M.; Qaeed, M. A.

2016-12-01

In this study, ZnO nanofibers (ZnO NFs) were successfully grown for the first time on Teflon substrates using CBD technique. The well-aligned ZnO nanorods (ZnO NRs) were transformed to ZnO nanofibers (NFs) by varying growth temperature and growth time. The high intensity and distinct growth orientation of peaks observed in the XRD spectra of the NFs indicate high crystal quality. The field emission scanning electron microscopy (FESEM) revealed high density of small diameter sized and long ZnO nanofibers (NFs) that are distributed in random directions. Raman analyses revealed a high E2 (high) peak at 436 nm, which indicates the wurtzite structure of ZnO. A flexible ZnO nanofiber (NFs)-based metal-semiconductor-metal UV detector was fabricated and analyzed for photo response and sensitivity under low power illumination (375 nm, 1.5 mW/cm2). The results showed a sensitivity of 4045% which can be considered a relatively high response and baseline recovery for UV detection.

Effect of annealing temperature on the structural and optical properties of CeO{sub 2}:Ni thin films

DOE Office of Scientific and Technical Information (OSTI.GOV)

Murugan, R.; Vijayaprasath, G.; Sakthivel, P.

2016-05-06

High quality Ni-doped CeO{sub 2} (CeO{sub 2}:Ni) thin films were deposited on glass substrates at room temperature by using radio frequency magnetron sputtering. The effect of annealing temperature on structural and optical properties of the CeO{sub 2}:Ni films was investigated. The structural, optical and vibrational properties of the films were determined using X-ray diffraction (XRD), photoluminescence spectrometer (PL) and Raman spectrometer. It was found that the as-deposited film has a fluorite cubic structure. By increasing annealing temperature from 100°C to 300°C, the crystalline quality of the thin films could be improved. The UV and visible band emissions were observed inmore » the photoluminescence spectra, due to exciton, defect related emissions respectively. The micro-Raman results show the characteristic peak of CeO{sub 2} F{sub 2g} at 465 cm{sup −1} and 2L0 at 1142 cm{sup −1}. Defect peaks like D and 0 bands were observed at 641 cm{sup −1} and 548 cm{sup −1} respectively. It is found from the spectra that the peak intensity of the films increased with increase of annealing temperature.« less

Vibrational spectroscopic studies of Isoleucine by quantum chemical calculations.

PubMed

Moorthi, P P; Gunasekaran, S; Ramkumaar, G R

2014-04-24

In this work, we reported a combined experimental and theoretical study on molecular structure, vibrational spectra and NBO analysis of Isoleucine (2-Amino-3-methylpentanoic acid). The optimized molecular structure, vibrational frequencies, corresponding vibrational assignments, thermodynamics properties, NBO analyses, NMR chemical shifts and ultraviolet-visible spectral interpretation of Isoleucine have been studied by performing MP2 and DFT/cc-pVDZ level of theory. The FTIR, FT-Raman spectra were recorded in the region 4000-400 cm(-1) and 3500-50 cm(-1) respectively. The UV-visible absorption spectra of the compound were recorded in the range of 200-800 nm. Computational calculations at MP2 and B3LYP level with basis set of cc-pVDZ is employed in complete assignments of Isoleucine molecule on the basis of the potential energy distribution (PED) of the vibrational modes, calculated using VEDA-4 program. The calculated wavenumbers are compared with the experimental values. The difference between the observed and calculated wavenumber values of most of the fundamentals is very small. (13)C and (1)H nuclear magnetic resonance chemical shifts of the molecule were calculated using the gauge independent atomic orbital (GIAO) method and compared with experimental results. The formation of hydrogen bond was investigated in terms of the charge density by the NBO calculations. Based on the UV spectra and TD-DFT calculations, the electronic structure and the assignments of the absorption bands were carried out. Besides, molecular electrostatic potential (MEP) were investigated using theoretical calculations. Copyright © 2014 Elsevier B.V. All rights reserved.

Analysis of root surface properties by fluorescence/Raman intensity ratio.

PubMed

Nakamura, Shino; Ando, Masahiro; Hamaguchi, Hiro-O; Yamamoto, Matsuo

2017-11-01

The aim of this study is to evaluate the existence of residual calculus on root surfaces by determining the fluorescence/Raman intensity ratio. Thirty-two extracted human teeth, partially covered with calculus on the root surface, were evaluated by using a portable Raman spectrophotometer, and a 785-nm, 100-mW laser was applied for fluorescence/Raman excitation. The collected spectra were normalized to the hydroxyapatite Raman band intensity at 960 cm -1 . Raman spectra were recorded from the same point after changing the focal distance of the laser and the target radiating angle. In seven teeth, the condition of calculus, cementum, and dentin were evaluated. In 25 teeth, we determined the fluorescence/Raman intensity ratio following three strokes of debridement. Raman spectra collected from the dentin, cementum, and calculus were different. After normalization, spectra values were constant. The fluorescence/Raman intensity ratio of calculus region showed significant differences compared to the cementum and dentin (p < 0.05). The fluorescence/Raman intensity ratio decreased with calculus debridement. For this analysis, the delta value was defined as the difference between the values before and after three strokes, with the final 2 delta values close to zero, indicating a gradual asymptotic curve and the change in intensity ratio approximating that of individual constants. Fluorescence/Raman intensity ratio was effectively used to cancel the angle- and distance-dependent fluctuations of fluorescence collection efficiency during measurement. Changes in the fluorescence/Raman intensity ratio near zero suggested that cementum or dentin was exposed, and calculus removed.

Detection of molecular changes induced by antibiotics in Escherichia coli using vibrational spectroscopy

NASA Astrophysics Data System (ADS)

Xuan Nguyen, N. T.; Sarter, Samira; Hai Nguyen, N.; Daniel, Philippe

2017-08-01

This study aimed to test Raman (400-1800 cm- 1) and Infra-red (1900-500 cm- 1) spectroscopies followed by statistical analysis (principal component analysis) to detect molecular changes induced by antibiotics (ampicillin, cefotaxime - cell wall synthesis inhibitors, tetracycline - protein synthesis inhibitor, ciprofloxacin - DNA synthesis inhibitor) against Escherichia coli TOP10. In case of ampicillin and cefotaxime, a decrease in protein bands in both Raman (1240, 1660 cm- 1), and IR spectra (1230, 1530, 1630 cm- 1), and an increase in carbohydrate bands (1150, 1020 cm- 1) in IR spectra were observed. Tetracycline addition caused an increase in nucleic acid bands (775, 1478, 1578 cm- 1), a sharp decrease in phenylalanine (995 cm- 1) in Raman spectra and the amide I and amide II bands (1630, 1530 cm- 1) in IR spectra, an increase in DNA in both Raman (1083 cm- 1) and IR spectra (1080 cm- 1). Regarding ciprofloxacin, an increase in nucleic acids (775, 1478, 1578 cm- 1) in Raman spectra and in protein bands (1230, 1520, 1630 cm- 1), in DNA (1080 cm- 1) in IR spectra were detected. Clear discrimination of antibiotic-treated samples compared to the control was recorded, showing that Raman and IR spectroscopies, coupled to principal component analysis for data, could be used to detect molecular modifications in bacteria exposed to different classes of antibiotics. These findings contribute to the understanding of the mechanisms of action of antibiotics in bacteria.

Gigantol from Dendrobium chrysotoxum Lindl. binds and inhibits aldose reductase gene to exert its anti-cataract activity: An in vitro mechanistic study.

PubMed

Wu, Jie; Li, Xue; Wan, Wencheng; Yang, Qiaohong; Ma, Weifeng; Chen, Dan; Hu, Jiangmiao; Chen, C-Y Oliver; Wei, Xiaoyong

2017-02-23

Dendrobium. chrysotoxum Lindl is a commonly used species of medicinal Dendrobium which belongs to the family of Orchidaceae, locally known as "Shihu" or "Huangcao". D. chrysotoxum Lindl is widely known for medicinal values in traditional Chinese medicine as it possesses anti-inflammatory, anti-hyperglycemic induction, antitumor and antioxidant properties. To characterize the interaction between gigantol extracted from D. chrysotoxum Lindl and the AR gene, and determine gigantol's efficacy against cataractogenesis. Human lens epithelial cells (HLECs) were induced by glucose as the model group. Reverse transcription polymerase chain reaction (RT-PCR) was used to assess AR gene expression. Then, the mode of interaction of gigantol with the AR gene was evaluated by UV-visible spectroscopy, atomic force microscope (AFM) and surface-enhanced Raman spectroscopy (SERS). The binding constant was determined by UV-visible. Gigantol depressed AR gene expression in HLECs. UV-visible spectra preliminarily indicated that interaction between the AR gene and gigantol may follow the groove mode, with a binding constant of 1.85×10 3 L/mol. Atomic force microscope (AFM) data indicated that gigantol possibly bound to insert AR gene base pairs of the double helix. Surface-enhanced Raman spectroscopy (SERS) studies further supported these observations. Gigantol extracted from D. chrysotoxum Lindl not only has inhibitory effects on aldose reductase, but also inhibits AR gene expression. These findings provide a more comprehensive theoretical basis for the use of Dendrobium for the treatment of diabetic cataract. Copyright © 2017 Elsevier Ireland Ltd. All rights reserved.

Surface-enhanced Raman scattering studies of the reduction of p-nitroaniline catalyzed by a nanonized Ag porous-glass hybrid composite.

PubMed

Huang, Genin Gary; Sou, Nga-Lai; Hung, Mei-Jou

2016-09-05

Nanonized noble metal composites have been known for their excellent catalytic properties. However, the mechanism and intermediates formed on the surfaces of nanocatalysts during catalysis are speculated with mostly insufficient evidence. In this study, to obtain further understanding of the roles of noble metal nanocatalysts in a catalytic reaction, surface-enhanced Raman scattering (SERS) was used to monitor the surfaces of silver (Ag) nanocatalysts. Furthermore, UV-Vis spectrometry was used to trace the concentration variations of reactants and products in bulk solutions, thereby correlating the variations of the Ag nanocatalyst surfaces with those in the bulk solutions. Nanonized Ag porous-glass hybrid composites were prepared by reducing naked Ag nanoparticles on porous-glass filter plates and were used as catalysts for nitroanilines reduction. The complete process was monitored using SERS and UV-Vis spectrometry simultaneously. The results indicated that the reactant and product molecules adsorbed on the Ag nanocatalysts can reach equilibrium, and the equilibrium is affected by the reaction conditions, including reducing agent concentration, pH of the reaction system, and temperature. In addition, the reduction of reactants in the bulk solutions is also related to the behavior of Ag nanocatalyst surfaces. Furthermore, Ag nanocatalysts can act as electron relays even if their surfaces are occupied by reactants and products. Analyzing the collected SERS and UV-Vis spectra can provide a new insight into Ag nanoparticle catalysis, and the role of Ag nanocatalysts can be further comprehended. Copyright © 2016 Elsevier B.V. All rights reserved.

Assessment of Cell Line Models of Primary Human Cells by Raman Spectral Phenotyping

PubMed Central

Swain, Robin J.; Kemp, Sarah J.; Goldstraw, Peter; Tetley, Teresa D.; Stevens, Molly M.

2010-01-01

Abstract Researchers have previously questioned the suitability of cell lines as models for primary cells. In this study, we used Raman microspectroscopy to characterize live A549 cells from a unique molecular biochemical perspective to shed light on their suitability as a model for primary human pulmonary alveolar type II (ATII) cells. We also investigated a recently developed transduced type I (TT1) cell line as a model for alveolar type I (ATI) cells. Single-cell Raman spectra provide unique biomolecular fingerprints that can be used to characterize cellular phenotypes. A multivariate statistical analysis of Raman spectra indicated that the spectra of A549 and TT1 cells are characterized by significantly lower phospholipid content compared to ATII and ATI spectra because their cytoplasm contains fewer surfactant lamellar bodies. Furthermore, we found that A549 spectra are statistically more similar to ATI spectra than to ATII spectra. The spectral variation permitted phenotypic classification of cells based on Raman spectral signatures with >99% accuracy. These results suggest that A549 cells are not a good model for ATII cells, but TT1 cells do provide a reasonable model for ATI cells. The findings have far-reaching implications for the assessment of cell lines as suitable primary cellular models in live cultures. PMID:20409492

Classification model based on Raman spectra of selected morphological and biochemical tissue constituents for identification of atherosclerosis in human coronary arteries.

PubMed

Peres, Marines Bertolo; Silveira, Landulfo; Zângaro, Renato Amaro; Pacheco, Marcos Tadeu Tavares; Pasqualucci, Carlos Augusto

2011-09-01

This study presents the results of Raman spectroscopy applied to the classification of arterial tissue based on a simplified model using basal morphological and biochemical information extracted from the Raman spectra of arteries. The Raman spectrograph uses an 830-nm diode laser, imaging spectrograph, and a CCD camera. A total of 111 Raman spectra from arterial fragments were used to develop the model, and those spectra were compared to the spectra of collagen, fat cells, smooth muscle cells, calcification, and cholesterol in a linear fit model. Non-atherosclerotic (NA), fatty and fibrous-fatty atherosclerotic plaques (A) and calcified (C) arteries exhibited different spectral signatures related to different morphological structures presented in each tissue type. Discriminant analysis based on Mahalanobis distance was employed to classify the tissue type with respect to the relative intensity of each compound. This model was subsequently tested prospectively in a set of 55 spectra. The simplified diagnostic model showed that cholesterol, collagen, and adipocytes were the tissue constituents that gave the best classification capability and that those changes were correlated to histopathology. The simplified model, using spectra obtained from a few tissue morphological and biochemical constituents, showed feasibility by using a small amount of variables, easily extracted from gross samples.

Real-time Raman spectroscopy of optically trapped living cells and organelles

NASA Astrophysics Data System (ADS)

Xie, Changan; Goodman, Charles; Dinno, Mumtaz A.; Li, Yong-Qing

2004-12-01

We report on real-time Raman spectroscopic studies of optically trapped living cells and organelles using an inverted confocal laser-tweezers-Raman-spectroscopy (LTRS) system. The LTRS system was used to hold a single living cell in a physiological solution or to hold a functional organelle within a living cell and consequently measured its Raman spectra. We have measured the changes in Raman spectra of a trapped yeast cell as the function of the temperature of the bathing solution and studied the irreversible cell degeneration during the heat denaturation. In addition, we measured the in-vitro Raman spectra of the nuclei within living pine cells and B. sporeformer, Strep. salivarius, and E. coli bacteria suspended in solution and showed the possibility of using LTRS system as a sensor for rapid identification of microbes in a fluid.

Identification of Foreign Particles in Human Tissues using Raman Microscopy.

PubMed

Campion, Alan; Smith, Kenneth J; Fedulov, Alexey V; Gregory, David; Fan, Yuwei; Godleski, John J

2018-06-12

The precise identification of foreign particles in tissue for patient care and research has been studied using polarized light microscopy, electron microscopy with X-ray analysis, and electron diffraction. The goal of this study was to unambiguously identify particles in tissues using a combina-tion of polarized light microscopy and Raman microscopy, which provides chemical composition and microstructural characterization of complex materials with submicron spatial resolution. We designed a model system of stained and unstained cells that contained birefringent talc particles, and systematically investigated the influence of slide and coverslip materials, laser wavelengths, and mounting media on the Raman spectra ob-tained. Hematoxylin and eosin stained slides did not produce useful results because of fluorescence interference from the stains. Unstained cell samples prepared with standard slides and coverslips produce high quality Raman spectra when excited at 532 nm; the spectra are uniquely as-signed to talc. We also obtain high quality Raman spectra specific for talc in unstained tissue samples (pleural tissue following talc pleurodesis and ovarian tissue following long-term perineal talc exposure). Raman microscopy is sufficiently sensitive and compositionally selective to identify particles as small as one micron in diameter. Among commonly used coverslip mounting media, Cytoseal 60 is recommended; Permount was unacceptable due to intense background interference. Raman spectra have been catalogued for thousands of substances, which suggests that this approach is likely to be successful in identifying other particles of interest in tissues, potentially making Raman microscopy a powerful new tool in pathology.

Molecular structure, chemical reactivity, nonlinear optical activity and vibrational spectroscopic studies on 6-(4-n-heptyloxybenzyoloxy)-2-hydroxybenzylidene)amino)-2H-chromen-2-one: A combined density functional theory and experimental approach

NASA Astrophysics Data System (ADS)

Pegu, David; Deb, Jyotirmoy; Saha, Sandip Kumar; Paul, Manoj Kumar; Sarkar, Utpal

2018-05-01

In this work, we have synthesized new coumarin Schiff base molecule, viz., 6-(4-n-heptyloxybenzyoloxy)-2-hydroxybenzylidene)amino)-2H-chromen-2-one and characterized its structural, electronic and spectroscopic properties experimentally and theoretically. The theoretical analysis of UV-visible absorption spectra reflects a red shift in the absorption maximum in comparison to the experimental results. Most of the vibrational assignments of infrared and Raman spectra predicted using density functional theory approach match well with the experimental findings. Further, the chemical reactivity analysis confirms that solvent highly affects the reactivity of the studied compound. The large hyperpolarizability value of the compound concludes that the system exhibits significant nonlinear optical features and thus, points out their possibility in designing material with high nonlinear activity.

In-line near-infrared (NIR) and Raman spectroscopy coupled with principal component analysis (PCA) for in situ evaluation of the transesterification reaction.

PubMed

Fontalvo-Gómez, Miriam; Colucci, José A; Velez, Natasha; Romañach, Rodolfo J

2013-10-01

Biodiesel was synthesized from different commercially available oils while in-line Raman and near-infrared (NIR) spectra were obtained simultaneously, and the spectral changes that occurred during the reaction were evaluated with principal component analysis (PCA). Raman and NIR spectra were acquired every 30 s with fiber optic probes inserted into the reaction vessel. The reaction was performed at 60-70 °C using magnetic stirring. The time of reaction was 90 min, and during this time, 180 Raman and NIR spectra were collected. NIR spectra were collected using a transflectance probe and an optical path length of 1 mm at 8 cm(-1) spectral resolution and averaging 32 scans; for Raman spectra a 3 s exposure time and three accumulations were adequate for the analysis. Raman spectroscopy showed the ester conversion as evidenced by the displacement of the C=O band from 1747 to 1744 cm(-1) and the decrease in the intensity of the 1000-1050 cm(-1) band and the 1405 cm(-1) band as methanol was consumed in the reaction. NIR spectra also showed the decrease in methanol concentration with the band in the 4750-5000 cm(-1) region; this signal is present in the spectra of the transesterification reaction but not in the neat oils. The variations in the intensity of the methanol band were a main factor in the in-line monitoring of the transesterification reaction using Raman and NIR spectroscopy. The score plot of the first principal component showed the progress of the reaction. The final product was analyzed using (1)H nuclear magnetic resonance ((1)H NMR) spectroscopy and using mid-infrared spectroscopy, confirming the conversion of the oils to biodiesel.

Evaluation of Raman spectra of human brain tumor tissue using the learning vector quantization neural network

NASA Astrophysics Data System (ADS)

Liu, Tuo; Chen, Changshui; Shi, Xingzhe; Liu, Chengyong

2016-05-01

The Raman spectra of tissue of 20 brain tumor patients was recorded using a confocal microlaser Raman spectroscope with 785 nm excitation in vitro. A total of 133 spectra were investigated. Spectra peaks from normal white matter tissue and tumor tissue were analyzed. Algorithms, such as principal component analysis, linear discriminant analysis, and the support vector machine, are commonly used to analyze spectral data. However, in this study, we employed the learning vector quantization (LVQ) neural network, which is typically used for pattern recognition. By applying the proposed method, a normal diagnosis accuracy of 85.7% and a glioma diagnosis accuracy of 89.5% were achieved. The LVQ neural network is a recent approach to excavating Raman spectra information. Moreover, it is fast and convenient, does not require the spectra peak counterpart, and achieves a relatively high accuracy. It can be used in brain tumor prognostics and in helping to optimize the cutting margins of gliomas.

Study of dynamical process of heat denaturation in optically trapped single microorganisms by near-infrared Raman spectroscopy

NASA Astrophysics Data System (ADS)

Xie, Changan; Li, Yong-qing; Tang, Wei; Newton, Ronald J.

2003-11-01

The development of laser traps has made it possible to investigate single cells and record real-time Raman spectra during a heat-denaturation process when the temperature of the surrounding medium is increased. Large changes in the phenylalanine band (1004 cm-1) of near-infrared spectra between living and heat-treated cells were observed in yeast and Escerichia coli and Enterobacter aerogenes bacteria. This change appears to reflect the change in environment of phenylalanine as proteins within the cells unfold as a result of increasing temperatures. As a comparison, we measured Raman spectra of native and heat-denatured solutions of bovine serum albumin proteins, and a similar change in the phenylalanine band of spectra was observed. In addition, we measured Raman spectra of native and heat-treated solutions of pure phenylalanine molecules; no observable difference in vibrational spectra was observed. These findings may make it possible to study conformational changes in proteins within single cells.

Raman investigation with group theoretical method on structural polymorphism of the nonlinear optical hexamine: p-nitrophenol cocrystals

NASA Astrophysics Data System (ADS)

Vijayalakshmi, S.; Kalyanaraman, S.; Ravindran, T. R.

2014-09-01

We have synthesized organic non-centrosymmetric cocrystals of 1:1 and 1:2 mole ratios of non-proton-transferred hexamine and p-nitrophenol complexes by using a slow evaporation method. The cocrystal with different stoichiometric variation gets crystallized into different crystallographic structures. The non-proton-transfer process of the complexes and the charge transfer (CT) interaction are established through Fourier transform infrared (FTIR) spectroscopy. The contribution of the water molecule in the 1:2 adduct is explained through FTIR analysis. The result has an important bearing in our present study. Existence of two different crystallographic structures (polymorphism) is confirmed by the lower frequency modes that appeared in Raman spectra. The variation in the Raman active modes at lower frequencies that arise on account of polymorphism is addressed through factor group analysis. From the UV-vis analysis, the interesting result of hyperchromic and hypochromic shifts being observed in the 1:1 and 1:2 adducts, respectively, supports the polymorphic behavior. On seeing the variation in properties, particularly nonlinear optical properties, the higher second harmonic generation (SHG) efficiency compared with KDP is observed by using the Kurtz-Perry method for both complexes.

Raman microspectroscopy of nucleus and cytoplasm for human colon cancer diagnosis.

PubMed

Liu, Wenjing; Wang, Hongbo; Du, Jingjing; Jing, Chuanyong

2017-11-15

Subcellular Raman analysis is a promising clinic tool for cancer diagnosis, but constrained by the difficulty of deciphering subcellular spectra in actual human tissues. We report a label-free subcellular Raman analysis for use in cancer diagnosis that integrates subcellular signature spectra by subtracting cytoplasm from nucleus spectra (Nuc.-Cyt.) with a partial least squares-discriminant analysis (PLS-DA) model. Raman mapping with the classical least-squares (CLS) model allowed direct visualization of the distribution of the cytoplasm and nucleus. The PLS-DA model was employed to evaluate the diagnostic performance of five types of spectral datasets, including non-selective, nucleus, cytoplasm, ratio of nucleus to cytoplasm (Nuc./Cyt.), and nucleus minus cytoplasm (Nuc.-Cyt.), resulting in diagnostic sensitivity of 88.3%, 84.0%, 98.4%, 84.5%, and 98.9%, respectively. Discriminating between normal and cancerous cells of actual human tissues through subcellular Raman markers is feasible, especially when using the nucleus-cytoplasm difference spectra. The subcellular Raman approach had good stability, and had excellent diagnostic performance for rectal as well as colon tissues. The insights gained from this study shed new light on the general applicability of subcellular Raman analysis in clinical trials. Copyright © 2017 Elsevier B.V. All rights reserved.

Raman Spectroscopy of DNA Packaging in Individual Human Sperm Cells distinguishes Normal from Abnormal Cells

DOE Office of Scientific and Technical Information (OSTI.GOV)

Huser, T; Orme, C; Hollars, C

Healthy human males produce sperm cells of which about 25-40% have abnormal head shapes. Increases in the percentage of sperm exhibiting aberrant sperm head morphologies have been correlated with male infertility, and biochemical studies of pooled sperm have suggested that sperm with abnormal shape may contain DNA that has not been properly repackaged by protamine during spermatid development. We have used micro-Raman spectroscopy to obtain Raman spectra from individual human sperm cells and examined how differences in the Raman spectra of sperm chromatin correlate with cell shape. We show that Raman spectra of individual sperm cells contain vibrational marker modesmore » that can be used to assess the efficiency of DNA-packaging for each cell. Raman spectra obtained from sperm cells with normal shape provide evidence that DNA in these sperm is very efficiently packaged. We find, however, that the relative protein content per cell and DNA packaging efficiencies are distributed over a relatively wide range for sperm cells with both normal and abnormal shape. These findings indicate that single cell Raman spectroscopy should be a valuable tool in assessing the quality of sperm cells for in-vitro fertilization.« less

Resonance raman spectroscopy of an ultraviolet-sensitive insect rhodopsin

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pande, C.; Deng, H.; Rath, P.

1987-11-17

The authors present the first visual pigment resonance Raman spectra from the UV-sensitive eyes of an insect, Ascalaphus macaronius (owlfly). This pigment contains 11-cis-retinal as the chromophore. Raman data have been obtained for the acid metarhodopsin at 10/sup 0/C in both H/sub 2/O and D/sub 2/O. The C=N stretching mode at 1660 cm/sup -1/ in H/sub 2/O shifts to 1631 cm/sup -1/ upon deuteriation of the sample, clearly showing a protonated Schiff base linkage between the chromophore and the protein. The structure-sensitive fingerprint region shows similarities to the all-trans-protonated Schiff base of model retinal chromophores, as well as to themore » octopus acid metarhodopsin and bovine metarhodopsin I. Although spectra measured at -100/sup 0/C with 406.7-nm excitation, to enhance scattering from rhodopsin (lambda/sub max/ 345 nm), contain a significant contribution from a small amount of contaminants (cytochrome(s) and/or accessory pigment) in the sample, the C=N stretch at 1664 cm/sup -1/ suggests a protonated Schiff base linkage between the chromophore and the protein in rhodopsin as well. For comparison, this mode also appears at approx. 1660 cm/sup -1/ in both the vertebrate (bovine) and the invertebrate (octopus) rhodopsins. These data are particularly interesting since the absorption maximum of 345 nm for rhodopsin might be expected to originate from an unprotonated Schiff base linkage. That the Schiff base linkage in the owlfly rhodopsin, like in bovine and in octopus, is protonated suggests that a charged chromophore is essential to visual transduction.« less

Study the chemical composition and biological outcomes resulting from the interaction of the hormone adrenaline with heavy elements: Infrared, Raman, electronic, 1H NMR, XRD and SEM studies

NASA Astrophysics Data System (ADS)

Ibrahim, Omar B.; Mohamed, Mahmoud A.; Refat, Moamen S.

2014-01-01

Heavy metal adrenaline complexes formed from the reaction of adrenaline with Al3+, Zn2+, Sn2+, Sb3+, Pb2+and Bi3+ ions in methanolic solvent at 60 °C. The final reaction products have been isolated and characterization using elemental analyses (% of carbon, hydrogen and nitrogen), conductivity measurements, mid infrared, Raman laser, UV-Vis, 1H NMR spectra, X-ray powder diffraction, scanning electron microscopy and energy-dispersive X-ray spectroscopy (EDX). Upon the spectroscopic, conductivity and elemental analyses, the stoichiometric reactions indicated that the data obtained refer to 1:2 (M:L) for Zn2+, Sn2+, Pb2+and Bi3+ complexes [Zn(Adr)2(Cl)2], [Sn(Adr)2]Cl2, [Pb(Adr)2](NO3)2 and [Bi(Adr)2(Cl)2]Cl, while the molar ratio 1:3 (M:L) for Al3+ and Sb3+ with formulas [Al(Adr)3](NO3)3 and [Sb(Adr)3]Cl3. The infrared and Raman laser spectra interpreted the mode of interactions which associated through the two phenolic groups of catechol moiety. The adrenaline chelates have been screened for their in vitro antibacterial activity against four bacteria, Gram-positive (Bacillus subtilis and Staphylococcus aureus) and Gram-negative (Escherichia coli and Pseudomonas aeruginosa) and two strains of fungus (Aspergillus flavus and Candida albicans). The metal chelates were shown to possess more antibacterial and antifungal activities than the free adrenaline chelate.

Investigation on tip enhanced Raman spectra of graphene

NASA Astrophysics Data System (ADS)

Li, Xinjuan; Liu, Yanqi; Zeng, Zhuo; Wang, Peijie; Fang, Yan; Zhang, Lisheng

2018-02-01

Tip-enhanced Raman scattering (TERS) is a promising analytical approach for some two-dimensional materials and offers the possibility to correlate imaging and chemical data. Tip-enhanced Raman spectra of graphene are discussed in some details, including substrate, gap between tip-apex and sample surface as well as Ag-nanowire. The TERS spectra give special emphasis to the possibility of TERS tip to induce a large number of defects only while got the tip attached to sample surface. Then the dependence of the TERS spectra of graphene and gap between the probe tip and sample surface was studied, and distribution features of electromagnetic (EM) field around tip were also simulated by finite-difference time-domain (FDTD). The Raman signal enhancement of graphene was further discussed with respect to experimental data. Furthermore, the Ag-nanowire as a nano-antenna could significantly enhance the weak Raman signal of D-band of monolayer graphene is shown, and the TERS spectra of graphene with regard to different regions of Ag-nanowires (endpoints, body) were obtained toward investigating into the distribution of electromagnetic field.

Rapid in situ detection of street samples of drugs of abuse on textile substrates using microRaman spectroscopy.

PubMed

Ali, Esam M A; Edwards, Howell G M; Scowen, Ian J

2011-10-01

Trace amounts of street samples of cocaine hydrochloride and N-methyl-3,4-methylenedioxy-amphetamine (MDMA) on natural and synthetic textiles were successfully detected in situ using confocal Raman microscopy. The presence of some excipient bands in the spectra of the drugs did not prevent the unambiguous identification of the drugs. Raman spectra of the drugs were readily obtained without significant interference from the fibre substrates. Interfering bands arising from the fibre natural or synthetic polymer structure and/or dye molecules did not overlap with the characteristic Raman bands of the drugs. If needed, interfering bands could be successfully removed by spectral subtraction. Also, Raman spectra could be acquired from drug particles trapped between the fibres of highly fluorescent textile specimens. The total acquisition time of the spectra of the drug particles was 90 s accomplished non-destructively and without detachment from their substrates. Sample preparation was not required and spectra of the drugs could be obtained non-invasively preserving the integrity of the evidential material for further analysis. Copyright © 2010 Elsevier B.V. All rights reserved.

Rapid in situ detection of street samples of drugs of abuse on textile substrates using microRaman spectroscopy

NASA Astrophysics Data System (ADS)

Ali, Esam M. A.; Edwards, Howell G. M.; Scowen, Ian J.

2011-10-01

Trace amounts of street samples of cocaine hydrochloride and N-methyl-3,4-methylenedioxy-amphetamine (MDMA) on natural and synthetic textiles were successfully detected in situ using confocal Raman microscopy. The presence of some excipient bands in the spectra of the drugs did not prevent the unambiguous identification of the drugs. Raman spectra of the drugs were readily obtained without significant interference from the fibre substrates. Interfering bands arising from the fibre natural or synthetic polymer structure and/or dye molecules did not overlap with the characteristic Raman bands of the drugs. If needed, interfering bands could be successfully removed by spectral subtraction. Also, Raman spectra could be acquired from drug particles trapped between the fibres of highly fluorescent textile specimens. The total acquisition time of the spectra of the drug particles was 90 s accomplished non-destructively and without detachment from their substrates. Sample preparation was not required and spectra of the drugs could be obtained non-invasively preserving the integrity of the evidential material for further analysis.

Raman spectra of amino acids and their aqueous solutions

NASA Astrophysics Data System (ADS)

Zhu, Guangyong; Zhu, Xian; Fan, Qi; Wan, Xueliang

2011-03-01

Amino acids are the basic "building blocks" that combine to form proteins and play an important physiological role in all life-forms. Amino acids can be used as models for the examination of the importance of intermolecular bonding in life processes. Raman spectra serve to obtain information regarding molecular conformation, giving valuable insights into the topology of more complex molecules (peptides and proteins). In this paper, amino acids and their aqueous solution have been studied by Raman spectroscopy. Comparisons of certain values for these frequencies in amino acids and their aqueous solutions are given. Spectra of solids when compared to those of the solute in solution are invariably much more complex and almost always sharper. We present a collection of Raman spectra of 18 kinds of amino acids ( L-alanine, L-arginine, L-aspartic acid, cystine, L-glutamic acid, L-glycine, L-histidine, L-isoluecine, L-leucine, L-lysine, L-phenylalanine, L-methionone, L-proline, L-serine, L-threonine, L-tryptophan, L-tyrosine, L-valine) and their aqueous solutions that can serve as references for the interpretation of Raman spectra of proteins and biological materials.

Optical Characterization of Lead Monoxide Films Grown by Laser-Assisted Deposition

NASA Astrophysics Data System (ADS)

Baleva, M.; Tuncheva, V.

1994-05-01

The Raman spectra of PbO films, grown by laser-assisted deposition (LAD) at different substrate temperatures are investigated. The spectra of the films, deposited on amorphous, single crystal quartz and polycrystal PbTe substrates, are compared with the Raman spectra of tetragonal and orthorhombic powder samples. The phonon frequencies determined in our experiment with powder samples coincide fairly well with those obtained by Adams and Stevens, J. Chem. Soc., Dalton Trans., 1096 (1977). Thus the Raman spectra of the powder samples presented in this paper can be considered as unambiguous characteristics of the two different PbO crystal phases. It was concluded that the Raman scattering may serve as a tool for identification of PbO films and their crystal modifications. On the basis of this investigation it was concluded that the film structure changes from orthorhombic to tetragonal with increased substrate temperature, and that the nature of the substrate influences the crystal structure of the films. On the basis of the Raman spectra of the β-PbO films with prevailing (001) orientation of crystallization, an assignment of the modes is proposed.

Raman spectroscopic study of reaction dynamics

NASA Astrophysics Data System (ADS)

MacPhail, R. A.

1990-12-01

The Raman spectra of reacting molecules in liquids can yield information about various aspects of the reaction dynamics. The author discusses the analysis of Raman spectra for three prototypical unimolecular reactions, the rotational isomerization of n-butane and 1,2-difluoroethane, and the barrierless exchange of axial and equatorial hydrogens in cyclopentane via pseudorotation. In the first two cases the spectra are sensitive to torsional oscillations of the gauche conformer, and yield estimates of the torsional solvent friction. In the case of cyclopentane, the spectra can be used to discriminate between different stochastic models of the pseudorotation dynamics, and to determine the relevant friction coefficients.

In-line ATR-UV and Raman Spectroscopy for Monitoring API Dissolution Process During Liquid-Filled Soft-Gelatin Capsule Manufacturing.

PubMed

Wan, Boyong; Zordan, Christopher A; Lu, Xujin; McGeorge, Gary

2016-10-01

Complete dissolution of the active pharmaceutical ingredient (API) is critical in the manufacturing of liquid-filled soft-gelatin capsules (SGC). Attenuated total reflectance UV spectroscopy (ATR-UV) and Raman spectroscopy have been investigated for in-line monitoring of API dissolution during manufacturing of an SGC product. Calibration models have been developed with both techniques for in-line determination of API potency. Performance of both techniques was evaluated and compared. The ATR-UV methodology was found to be able to monitor the dissolution process and determine the endpoint, but was sensitive to temperature variations. The Raman technique was also capable of effectively monitoring the process and was more robust to the temperature variation and process perturbations by using an excipient peak for internal correction. Different data preprocessing methodologies were explored in an attempt to improve method performance.

Spectroscopic properties of Eu3+/Nd3+ co-doped phosphate glasses and opaque glass-ceramics

NASA Astrophysics Data System (ADS)

Narro-García, R.; Desirena, H.; López-Luke, T.; Guerrero-Contreras, J.; Jayasankar, C. K.; Quintero-Torres, R.; De la Rosa, E.

2015-08-01

This paper reports the fabrication and characterization of Eu3+/Nd3+ co-doped phosphate (PNE) glasses and glass-ceramics as a function of Eu3+ concentration. The precursor glasses were prepared by the conventional melt quenching technique and the opaque glass-ceramics were obtained by heating the precursor glasses at 450 °C for 30 h. The structural and optical properties of the glass and glass-ceramics were analyzed by means of X-ray diffraction, Raman spectroscopy, UV-VIS-IR absorption spectroscopy, photoluminescence spectra and lifetimes. The amorphous and crystalline structures of the precursor glass and opaque glass-ceramic were confirmed by X-ray diffraction respectively. The Raman spectra showed that the maximum phonon energy decreased from 1317 cm-1 to 1277 cm-1 with the thermal treatment. The luminescence spectra of the glass and glass-ceramic samples were studied under 396 nm and 806 nm excitation. The emission intensity of the bands observed in opaque glass-ceramic is stronger than that of the precursor glass. The luminescence spectra show strong dependence on the Eu3+ ion concentration in the Nd3+ ion photoluminescence (PL) intensity, which suggest the presence of energy transfer (ET) and cross-relaxation (CR) processes. The lifetimes of the 4F3/2 state of Nd3+ ion in Eu3+/Nd3+ co-doped phosphate glasses and glass-ceramics under 806 nm excitation were measured. It was observed that the lifetimes of the 4F3/2 level of Nd3+ of both glasses and glass-ceramics decrease with the increasing Eu3+ concentration. However in the case of opaque glass-ceramics the lifetimes decrease only 16%.

FT-Raman and FT-IR spectra of some heterobimetallic complexes with phenylcyclopentadienyl ligands

NASA Astrophysics Data System (ADS)

Nie, Chong-Shi; Guo, Jianhua; Qian, Changtao; Tan, Ying

1996-11-01

The FT-Raman and selected IR spectra of 14 heterobimetallic complexes of (CO) 3CrC 6H 5-C 5H 4M(CO) n(NO) mX (M = transition metal, X = other ligands) are reported. FT-Raman exhibits distinct strong characteristic bands of coordinated C 6H 5-C 5H 4 ligand ring deformation near 1540, 1490 and 1280 cm -1 and the coordinated phenyl ring deformation mode near 1000 cm -1, which are negligible in IR spectra. It is also easy to find the M-CO stretching and M-C-O bending as well as phenyl-M stretching bands in the FT-Raman spectra. The v(CO) IR absorptions in THF solution were reasonably assigned according to the local symmetry of the complexes.

Raman spectroscopic study of plasma-treated salmon DNA

NASA Astrophysics Data System (ADS)

Joon Lee, Geon; Kwon, Young-Wan; Hee Kim, Yong; Ha Choi, Eun

2013-01-01

In this research, we studied the effect of plasma treatment on the optical/structural properties of the deoxyribonucleic acid (DNA) extracted from salmon sperm. DNA-cetyltrimethylammonium (CTMA) films were obtained by complexation of DNA with CTMA. Circular dichroism (CD) and Raman spectra indicated that DNA retained its double helical structure in the solid film. The Raman spectra exhibited several vibration modes corresponding to the nuclear bases and the deoxyribose-phosphate backbones of the DNA, as well as the alkylchains of CTMA. Dielectric-barrier-discharge (DBD) plasma treatment induced structural modification and damage to the DNA, as observed by changes in the ultraviolet-visible absorption, CD, and Raman spectra. The optical emission spectra of the DBD plasma confirmed that DNA modification was induced by plasma ions such as reactive oxygen species and reactive nitrogen species.

Comparative studies by IR, Raman, and surface-enhanced Raman spectroscopy of azodicarbonamide, biurea and semicarbazide hydrochloride

NASA Astrophysics Data System (ADS)

Xie, Yunfei; Li, Pei; Zhang, Jin; Wang, Heya; Qian, He; Yao, Weirong

2013-10-01

Azodicarbonamide is widely applied in the food industry as a new flour gluten fortifier in China, Canada, the United States, and some other countries, whose metabolites of biurea and semicarbazide hydrochloride are reaction products during baking. In this study, IR, Raman and surface-enhanced Raman scattering (SERS) spectra of azodicarbonamide, biurea, and semicarbazide hydrochloride have been studied, and vibrational bands have been assigned on the basis of density functional theory (DFT) calculations. The calculated Raman spectra were in good agreement with experimental Raman spectra. The SERS method coupled with active gold substrates has also been applied for detection of the three chemicals with pure water as solvent, with the limit of detection of this method being as low as 10 μg/mL (less than 45 μg/mL). These results showed that azodicarbonamide and its metabolites could be detected by the vibrational spectra technique, which might be applied as a powerful tool for the rapid detection on these species derived from agents added to flour.

Hydrocarbon-Fueled Rocket Plume Measurement Using Polarized UV Raman Spectroscopy

NASA Technical Reports Server (NTRS)

Wehrmeyer, Joseph A.

2002-01-01

The influence of pressure upon the signal strength and polarization properties of UV Raman signals has been investigated experimentally up to pressures of 165 psia (11 atm). No significant influence of pressure upon the Raman scattering cross section or depolarization ratio of the N2 Raman signal was found. The Raman scattering signal varied linearly with pressure for the 300 K N2 samples examined, thus showing no enhancement of cross section with increasing pressure. However at the highest pressures associated with rocket engine combustion, there could be an increase in the Raman scattering cross section, based upon others' previous work at higher pressures than those examined in this work. The influence of pressure upon thick fused silica windows, used in the NASA Modular Combustion Test Article, was also investigated. No change in the transmission characteristics of the windows occurred as the pressure difference across the windows increased from 0 psig up to 150 psig. A calibration was performed on the UV Raman system at Vanderbilt University, which is similar to the one at the NASA-Marshall Test Stand 115. The results of this calibration are described in the form of temperature-dependent functions, f(T)'s, that account for the increase in Raman scattering cross section with an increase in temperature and also account for the reduction in collected Raman signal if wavelength integration does not occur across the entire wavelength range of the Raman signal. These functions generally vary only by approximately 10% across their respective temperature ranges, except for the case Of CO2, where there is a factor of three difference in its f(T) from 300 K to 2500 K. However this trend for CO2 is consistent with the experimental work of others, and is expected based on the low characteristic vibrational temperature Of CO2. A time-averaged temperature measurement technique has been developed, using the same equipment as for the work mentioned above, that is based upon high-spectral resolution UV Raman scattering. This technique can provide temperature measurements for flows where pressure cannot be measured.

Swift UVOT Grism Observations of Nearby Type Ia Supernovae - I. Observations and Data Reduction

NASA Astrophysics Data System (ADS)

Pan, Y.-C.; Foley, R. J.; Filippenko, A. V.; Kuin, N. P. M.

2018-05-01

Ultraviolet (UV) observations of Type Ia supernovae (SNe Ia) are useful tools for understanding progenitor systems and explosion physics. In particular, UV spectra of SNe Ia, which probe the outermost layers, are strongly affected by the progenitor metallicity. In this work, we present 120 Neil Gehrels Swift Observatory UV spectra of 39 nearby SNe Ia. This sample is the largest UV (λ < 2900 Å) spectroscopic sample of SNe Ia to date, doubling the number of UV spectra and tripling the number of SNe with UV spectra. The sample spans nearly the full range of SN Ia light-curve shapes (Δm15(B) ≈ 0.6-1.8 mag). The fast turnaround of Swift allows us to obtain UV spectra at very early times, with 13 out of 39 SNe having their first spectra observed ≳ 1 week before peak brightness and the earliest epoch being 16.5 days before peak brightness. The slitless design of the Swift UV grism complicates the data reduction, which requires separating SN light from underlying host-galaxy light and occasional overlapping stellar light. We present a new data-reduction procedure to mitigate these issues, producing spectra that are significantly improved over those of standard methods. For a subset of the spectra we have nearly simultaneous Hubble Space Telescope UV spectra; the Swift spectra are consistent with these comparison data.

Effect of hormonal variation on in vivo high wavenumber Raman spectra improves cervical precancer detection

NASA Astrophysics Data System (ADS)

Duraipandian, Shiyamala; Zheng, Wei; Ng, Joseph; Low, Jeffrey J. H.; Ilancheran, A.; Huang, Zhiwei

2012-03-01

Raman spectroscopy is a unique analytical probe for molecular vibration and is capable of providing specific spectroscopic fingerprints of molecular compositions and structures of biological tissues. The aim of this study is to improve the classification accuracy of cervical precancer by characterizing the variations in the normal high wavenumber (HW - 2800-3700cm-1) Raman spectra arising from the menopausal status of the cervix. A rapidacquisition near-infrared (NIR) Raman spectroscopic system was used for in vivo tissue Raman measurements at 785 nm excitation. Individual HW Raman spectrum was measured with a 5s exposure time from both normal and precancer tissue sites of 15 patients recruited. The acquired Raman spectra were stratified based on the menopausal status of the cervix before the data analysis. Significant differences were noticed in Raman intensities of prominent band at 2924 cm-1 (CH3 stretching of proteins) and the broad water Raman band (in the 3100-3700 cm-1 range) with a peak at 3390 cm-1 in normal and dysplasia cervical tissue sites. Multivariate diagnostic decision algorithm based on principal component analysis (PCA) and linear discriminant analysis (LDA) was utilized to successfully differentiate the normal and precancer cervical tissue sites. By considering the variations in the Raman spectra of normal cervix due to the hormonal or menopausal status of women, the diagnostic accuracy was improved from 71 to 91%. By incorporating these variations prior to tissue classification, we can significantly improve the accuracy of cervical precancer detection using HW Raman spectroscopy.

[AgBr colloids prepared by electrolysis and their SERS activity research].

PubMed

Si, Min-Zhen; Fang, Yan; Dong, Gang; Zhang, Peng-Xiang

2008-01-01

Ivory-white AgBr colloids were prepared by means of electrolysis. Two silver rods 1.0 cm in diameter and 10.0 cm long were respectively used as the negative and positive electrodes, the aqueous solution of hexadecyl trimethyl ammonium bromide was used as the electrolyte, and a 7 V direct current was applied on the silver rods for three hours. The obtained AgBr colloids were characterized by UV-Vis spectroscopy, transmission electron microscopy, and SERS using a 514. 5 nm laser line on Renishaw 2000 Raman spectrometer. These particles are about nanometer size and their shapes are as spherical or elliptic, with a slight degree of particle aggregation. The UV-Vis spectra exhibit a large plasmon resonance band at about 292.5 nm, similar to that reported in the literature. The AgBr colloids were very stable at room temperature for months. In order to test if these AgBr colloids can be used for SERS research, methyl orange, Sudan red and pyridine were used. It was found that AgBr colloids have SERS activity to these three molicules. For methyl orange, the intense Raman peaks are at 1 123, 1 146, 1 392, 1 448 and 1 594 cm(-1); for Sudan red, the intense Raman peaks are at 1 141, 1 179, 1 433 and 1 590 cm(-1); and for pyridine, the intense Raman peaks are at 1 003, 1 034 and 1 121 cm(-1). It is noticeable that SERS of methyl orange was observed on AgBr colloids, but not on the gray and yellow silver colloids prepared by traditional means. The possible reason was explained. One major advantage of this means is the absence of the spectral interference such as citrate, BH4- arising from reaction products of the colloids formation process. On AgBr colloids, one can get some molecular SERS impossible to get on the gray and yellow silver colloids.

Surface-Enhanced Hyper-Raman Spectra of Adenine, Guanine, Cytosine, Thymine, and Uracil

PubMed Central

2016-01-01

Using picosecond excitation at 1064 nm, surface-enhanced hyper-Raman scattering (SEHRS) spectra of the nucleobases adenine, guanine, cytosine, thymine, and uracil with two different types of silver nanoparticles were obtained. Comparing the SEHRS spectra with SERS data from the identical samples excited at 532 nm and with known infrared spectra, the major bands in the spectra are assigned. Due to the different selection rules for the one- and two-photon excited Raman scattering, we observe strong variation in relative signal strengths of many molecular vibrations obtained in SEHRS and SERS spectra. The two-photon excited spectra of the nucleobases are found to be very sensitive with respect to molecule–nanoparticle interactions. Using both the SEHRS and SERS data, a comprehensive vibrational characterization of the interaction of nucleobases with silver nanostructures can be achieved. PMID:28077982

Density functional theoretical modeling, electrostatic surface potential and surface enhanced Raman spectroscopic studies on biosynthesized silver nanoparticles: observation of 400 PM sensitivity to explosives.

PubMed

Sil, Sanchita; Chaturvedi, Deepika; Krishnappa, Keerthi B; Kumar, Srividya; Asthana, S N; Umapathy, Siva

2014-04-24

Interaction of adsorbate on charged surfaces, orientation of the analyte on the surface, and surface enhancement aspects have been studied. These aspects have been explored in details to explain the surface-enhanced Raman spectroscopic (SERS) spectra of 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane (HNIW or CL-20), a well-known explosive, and 2,4,6-trinitrotoluene (TNT) using one-pot synthesis of silver nanoparticles via biosynthetic route using natural precursor extracts of clove and pepper. The biosynthesized silver nanoparticles (bio Ag Nps) have been characterized using UV-vis spectroscopy, scanning electron microscopy and atomic force microscopy. SERS studies conducted using bio Ag Nps on different water insoluble analytes, such as CL-20 and TNT, lead to SERS signals at concentration levels of 400 pM. The experimental findings have been corroborated with density functional computational results, electrostatic surface potential calculations, Fukui functions and ζ potential measurements.

Electrochromic Properties of Tungsten Oxide Films Prepared by Reactive Sputtering

NASA Astrophysics Data System (ADS)

Kim, Min Hong; Kang, Tai Young; Jung, Yu Sup; Kim, Kyung Hwan

2013-05-01

WO3-x thin films were deposited on induim tin oxide (ITO) glass substrates with various oxygen flow ratios from 0.55 to 0.7 by the reactive facing-target sputtering method, at a power density of 4 W/cm2 and room temperature. The structural properties of the WO3-x thin films were measured by X-ray diffractometry and Raman spectral analysis. As-deposited WO3-x thin films had an amorphous structure. In the Raman spectra, WO3-x thin films exhibited two strong peaks at 770 and 950 cm-1 attributed to the vibrations of W6+-O and W6+=O bonds, respectively. The electrochemical and optical properties of WO3-x thin films were measured by cyclic voltammetry and UV/vis spectrometry. The results showed the highest charge density at an oxygen flow ratio of 0.7 and the highest transmittance in the visible range. The maximum coloration efficiency was 30.82 cm2/C at an oxygen flow ratio of 0.7.

Influence of surface plasmon resonance of Sn nanoparticles and nanosheets on the photoluminescence and Raman spectra of SnS quantum dots

NASA Astrophysics Data System (ADS)

Warrier, Anita R.; Gandhimathi, R.

2018-04-01

We report on enhancement of photoluminescence of SnS quantum dots by embedding them in a mesh of Sn nanostructures. SnS quantum dots with band gap ˜2.7 eV are embedded in a mesh of Sn nanostructures, that are synthesized from tin chloride solution using sodium borohydride as reducing agent. The synthesized Sn nanostructures have a morphology dependent, tunable surface plasmon resonance ranging from UV region (295 nm) to visible region (400 nm) of the electromagnetic spectrum. In the SnS-Sn nanohybrids, the excitons are strongly coupled with plasmons leading to a shift in the excitonic binding energy (˜ 400 meV). Due to the influence of Sn nanoparticles on the SnS quantum dots, the photoluminescence and Raman line intensity is enhanced by an order of ˜103 The enhancement is more pronounced for Sn nanosheets due to the large surface area and visible light surface plasmon resonance.

Discrimination of selected species of pathogenic bacteria using near-infrared Raman spectroscopy and principal components analysis

NASA Astrophysics Data System (ADS)

de Siqueira e Oliveira, Fernanda S.; Giana, Hector E.; Silveira, Landulfo, Jr.

2012-03-01

It has been proposed a method based on Raman spectroscopy for identification of different microorganisms involved in bacterial urinary tract infections. Spectra were collected from different bacterial colonies (Gram negative: E. coli, K. pneumoniae, P. mirabilis, P. aeruginosa, E. cloacae and Gram positive: S. aureus and Enterococcus sp.), grown in culture medium (Agar), using a Raman spectrometer with a fiber Raman probe (830 nm). Colonies were scraped from Agar surface placed in an aluminum foil for Raman measurements. After pre-processing, spectra were submitted to a Principal Component Analysis and Mahalanobis distance (PCA/MD) discrimination algorithm. It has been found that the mean Raman spectra of different bacterial species show similar bands, being the S. aureus well characterized by strong bands related to carotenoids. PCA/MD could discriminate Gram positive bacteria with sensitivity and specificity of 100% and Gram negative bacteria with good sensitivity and high specificity.

Application of NIR Raman spectroscopy for detecting and characterizing early dental caries

NASA Astrophysics Data System (ADS)

Ko, A. C.; Choo-Smith, L.-P.; Zhu, R.; Hewko, M.; Dong, C.; Cleghorn, B.; Sowa, M. G.

2006-02-01

Early dental caries detection facilitates implementation of non-surgical methods for arresting caries progression and promoting tooth remineralization. We present a method based on Raman spectroscopy with near-IR laser excitation to provide biochemical contrast for detecting and characterizing incipient carious lesions found in extracted human teeth. Changes in Raman spectra are observed in PO 4 3- vibrations arising from hydroxyapatite of mineralized tooth tissue. Examination of various intensities of the PO 4 3- ν2, ν3, ν4 vibrations showed consistent increased intensities in spectra of carious lesions compared to sound enamel. The spectral changes are attributed to demineralization-induced alterations of enamel crystallite morphology and/or orientation. This hypothesis is supported by reduced Raman polarization anisotropy derived from polarized Raman spectra of carious lesions. Polarized Raman spectral imaging of carious lesions found on whole (i.e. un-sectioned) tooth samples will also be presented.

Raman spectra and optical trapping of highly refractive and nontransparent particles

NASA Astrophysics Data System (ADS)

Xie, Changan; Li, Yong-qing

2002-08-01

We measured the Raman spectra of single optically trapped highly refractive and nontransparent microscopic particles suspended in a liquid using an inverted confocal laser-tweezers-Raman-spectroscopy system. A low-power diode-laser beam of TEM00 mode was used both for optical trapping and Raman excitation of refractive, absorptive, and reflective metal particles. To form a stable trap for a nontransparent particle, the beam focus was located near the top of the particle and the particle was pushed against a glass plate by the axial repulsive force. Raman spectra from single micron-sized crystals with high index of refraction including silicon, germanium, and KNbO3, and from absorptive particles of black and color paints were recorded. Surface-enhanced Raman scattering of R6G and phenylalanine molecules absorbed on the surface of a trapped cluster of silver particles was also demonstrated.

The detection of drugs of abuse in fingerprints using Raman spectroscopy I: latent fingerprints

NASA Astrophysics Data System (ADS)

Day, Joanna S.; Edwards, Howell G. M.; Dobrowski, Steven A.; Voice, Alison M.

2004-02-01

This paper describes the application of Raman spectroscopy to the detection of exogenous substances in latent fingerprints. The scenario considered was that of an individual handling a substance and subsequently depositing a contaminated fingerprint. Five drugs of abuse (codeine phosphate, cocaine hydrochloride, amphetamine sulphate, barbital and nitrazepam) and five non-controlled substances of similar appearance, which may be used in the adulteration of drugs of abuse (caffeine, aspirin, paracetamol, starch and talc), were studied in both sweat-rich and sebum-rich latent fingerprints. The substances studied could be clearly distinguished using their Raman spectra and were all successfully detected in latent fingerprints. Photobleaching was necessary to reduce the fluorescence background in the spectra of some substances. Raman spectra obtained from the substances in sweat-rich latent fingerprints were of a similar quality to spectra that obtained from the substances under normal sampling conditions. Interfering Raman bands arising from latent fingerprint material were present in the spectra obtained from the substances in sebum-rich fingerprints. These bands did not prevent identification of the substances and could be successfully removed by spectral subtraction. The most difficult aspect of the detection of these substances in latent fingerprints was visually locating the substance in the fingerprint in order to obtain a Raman spectrum.

An infrared and Raman spectroscopic study of natural zinc phosphates.

PubMed

Frost, Ray L

2004-06-01

Zinc phosphates are important in the study of the phosphatisation of metals. Raman spectroscopy in combination with infrared spectroscopy has been used to characterise the zinc phosphate minerals. The minerals may be characterised by the patterns of the hydroxyl stretching vibrations in both the Raman and infrared spectra. Spencerite is characterised by a sharp Raman band at 3516 cm(-1) and tarbuttite by a single band at 3446 cm(-1). The patterns of the Raman spectra of the hydroxyl stretching region of hopeite and parahopeite are different in line with their differing crystal structures. The Raman spectrum of the PO4 stretching region shows better band separated peaks than the infrared spectra which consist of a complex set of overlapping bands. The position of the PO4 symmetric stretching mode can be used to identify the zinc phosphate mineral. It is apparent that Raman spectroscopy lends itself to the fundamental study of the evolution of zinc phosphate films.

FTIR, FT-RAMAN, NMR, spectra, normal co-ordinate analysis, NBO, NLO and DFT calculation of N,N-diethyl-4-methylpiperazine-1-carboxamide molecule.

PubMed

Muthu, S; Elamurugu Porchelvi, E

2013-11-01

The Fourier Transform Infrared (FT-IR) and FT-Raman of N,N-diethyl-4-methylpiperazine-1-carboxamide (NND4MC) have been recorded and analyzed. The structure of the compound was optimized and the structural characteristics were determined by density functional theory (DFT) using B3LYP method with 6-31G(d,p) and 6-311G(d,p) basis sets. The difference between the observed and scaled wavenumber values of most of the fundamentals is very small. The theoretically predicted FT-IR and FT-Raman spectra of the title molecule have been constructed. The detailed interpretation of the vibrational spectra has been carried out with aid of normal coordinate analysis (NCA) following the scaled quantum mechanical force field methodology. Stability of the molecule arising from hyperconjugative interactions and charge delocalization has been analyzed using natural bond orbital (NBO) analysis. The results show that electron density (ED) in the σ(*) and π(*) antibonding orbitals and second order delocalization energies (E2) confirm the occurrence of intramolecular charge transfer (ICT) within the molecule. The electronic dipole moment (μD) and the first hyperpolarizability (βtot) values of the investigated molecule were computed using Density Functional Theory (DFT/B3LYP) with 6-31G(d,p) and 6-311G(d,p) basis sets. The calculated results also show that the NND4MC molecule may have microscopy nonlinear optical (NLO) behavior with non zero values. Mulliken atomic charges of NND4MC were calculated. The (13)C nuclear magnetic resonance (NMR) chemical shifts of the molecule were calculated by the gauge independent atomic orbital (GIAO) method and compared with experimental results. The UV-Vis spectrum of the compound was recorded. The theoretical electronic absorption spectra have been calculated by using CIS, TD-DFT methods. A study on the electronic properties, such as HOMO and LUMO energies, molecular electrostatic potential (MEP) were also performed. Copyright © 2013 Elsevier B.V. All rights reserved.

A new eye-safe UV Raman spectrometer for the remote detection of energetic materials in fingerprint concentrations: Characterization by PCA and ROC analyzes.

PubMed

Almaviva, Salvatore; Chirico, Roberto; Nuvoli, Marcello; Palucci, Antonio; Schnürer, Frank; Schweikert, Wenka

2015-11-01

We report the results of proximal Raman investigations at a distance of 7 m, to detect traces of explosives (from 0.1 to 0.8 mg/cm(2)) on common clothes with a new eye-safe apparatus. The instrument excites the target with a single laser shot of few ns (10(-9)s) in the UV range (laser wavelength 266 nm) detecting energetic materials like Pentaerythritol tetranitrate (PETN), Trinitrotoluene (TNT), Urea Nitrate (UN) and Ammonium Nitrate (AN). Samples were prepared using a piezoelectric-controlled plotter device to realize well-calibrated amounts of explosives on several cm(2). Common fabrics and tissues such as polyester, polyamide and leather were used as substrates, representative of base-materials used in the production of jackets or coats. Other samples were prepared by touching the substrate with a silicon finger contaminated with explosives, to simulate a spot left by contaminated hands on a jacket or bag during the preparation of an improvised explosive device (IED) by a terrorist. The observed Raman signals showed some peculiar molecular bands of the analyzed compounds, allowing us to identify and discriminate them with high sensitivity and selectivity, also in presence of the interfering signal from the underlying fabric. A dedicated algorithm was developed to remove noise and fluorescence background from the single laser shot spectra and an automatic spectral recognition procedure was also implemented, evaluating the intensity of the characteristic Raman bands of each explosive and allowing their automatic classification. Principal component analysis (PCA) was used to show the discrimination potentialities of the apparatus on different sets of explosives and to highlight possible criticalities in the detection. Receiver operating characteristic (ROC) curves were used to discuss and quantify the sensitivity and the selectivity of the proposed recognition procedure. To our knowledge the developed device is at the highest sensitivity nowadays achievable in the field of eye-safe, Raman devices for proximal detection. Copyright © 2015 Elsevier B.V. All rights reserved.

Raman background photobleaching as a possible method of cancer diagnostics

NASA Astrophysics Data System (ADS)

Brandt, Nikolai N.; Brandt, Nikolai B.; Chikishev, Andrey Y.; Gangardt, Mihail G.; Karyakina, Nina F.

2001-06-01

Kinetics of photobleaching of background in Raman spectra of aqueous solutions of plant toxins ricin and ricin agglutinin, ricin binding subunit, and normal and malignant human blood serum were measured. For the excitation of the spectra cw and pulsed laser radiation were used. The spectra of Raman background change upon laser irradiation. Background intensity is lower for the samples with small molecular weight. The cyclization of amino acid residues in the toxin molecules as well as in human blood serum can be a reason of the Raman background. The model of the background photobleaching is proposed. The differences in photobleaching kinetics in the cases of cw and pulsed laser radiation are discussed. It is shown that Raman background photobleaching can be very informative for cancer diagnostics.

Interplay of valley selection and helicity exchange of light in Raman scattering for graphene and MoS2

NASA Astrophysics Data System (ADS)

Tatsumi, Yuki; Saito, Riichiro

2018-03-01

Raman spectra of graphene and MoS2 are calculated for incident and scattered circularly polarized light. In the case of graphene, the well known G -band Raman spectra have a not well known property that the helicity of the incident circularly polarized light changes to another helicity in the scattered light. Using the electron-photon and electron-phonon matrix elements by first-principles calculation, we calculate resonant Raman spectra of graphene and MoS2 for circularly polarized light which are compared with recent experiments. The Raman intensity for circularly polarized light is relevant to optical valley polarization in the case of MoS2. We also discuss how the helicity-selection rule can be modified by applying stress to graphene.

Kerr-gated picosecond Raman spectroscopy and Raman photon migration of equine bone tissue with 400-nm excitation

NASA Astrophysics Data System (ADS)

Morris, Michael D.; Goodship, Allen E.; Draper, Edward R. C.; Matousek, Pavel; Towrie, Michael; Parker, Anthony W.

2004-07-01

We show that Raman spectroscopy with visible lasers, even in the deep blue is possible with time-gated Raman spectroscopy. A 4 picosec time gate allows efficient fluorescence rejection, up to 1000X, and provides almost background-free Raman spectra with low incident laser power. The technology enables spectroscopy with better than 10X higher scattering efficiency than is possible with the NIR (785 nm and 830 nm) lasers that are conventionally used. Raman photon migration is shown to allow depth penetration. We show for the first time that Kerr-gated Raman spectra of bone tissue with blue laser excitation enables both fluorescence rejection and depth penetration.

Surface Enhanced Raman Spectroscopy (SERS) and multivariate analysis as a screening tool for detecting Sudan I dye in culinary spices

NASA Astrophysics Data System (ADS)

Di Anibal, Carolina V.; Marsal, Lluís F.; Callao, M. Pilar; Ruisánchez, Itziar

2012-02-01

Raman spectroscopy combined with multivariate analysis was evaluated as a tool for detecting Sudan I dye in culinary spices. Three Raman modalities were studied: normal Raman, FT-Raman and SERS. The results show that SERS is the most appropriate modality capable of providing a proper Raman signal when a complex matrix is analyzed. To get rid of the spectral noise and background, Savitzky-Golay smoothing with polynomial baseline correction and wavelet transform were applied. Finally, to check whether unadulterated samples can be differentiated from samples adulterated with Sudan I dye, an exploratory analysis such as principal component analysis (PCA) was applied to raw data and data processed with the two mentioned strategies. The results obtained by PCA show that Raman spectra need to be properly treated if useful information is to be obtained and both spectra treatments are appropriate for processing the Raman signal. The proposed methodology shows that SERS combined with appropriate spectra treatment can be used as a practical screening tool to distinguish samples suspicious to be adulterated with Sudan I dye.

Development and biological applications of optical tweezers and Raman spectroscopy

NASA Astrophysics Data System (ADS)

Xie, Chang'an

Optical tweezers is a three-dimensional manipulation tool that employs a gradient force that originates from the single highly focused laser beam. Raman spectroscopy is a molecular analytical tool that can give a highly unique "fingerprint" for each substance by measuring the unique vibrations of its molecules. The combination of these two optical techniques offers a new tool for the manipulation and identification of single biological cells and microscopic particles. In this thesis, we designed and implemented a Laser-Tweezers-Raman-Spectroscopy (LTRS) system, also called the Raman-tweezers, for the simultaneous capture and analysis of both biological particles and non-biological particles. We show that microparticles can be conveniently captured at the focus of a laser beam and the Raman spectra of trapped particles can be acquired with high quality. The LTRS system overcomes the intrinsic Brownian motion and cell motility of microparticles in solution and provides a promising tool for in situ identifying suspicious agents. In order to increase the signal to noise ratio, several schemes were employed in LTRS system to reduce the blank noise and the fluorescence signal coming from analytes and the surrounding background. These techniques include near-infrared excitation, optical levitation, confocal microscopy, and frequency-shifted Raman difference. The LTRS system has been applied for the study in cell biology at the single cell level. With the built Raman-tweezers system, we studied the dynamic physiological processes of single living cells, including cell cycle, the transcription and translation of recombinant protein in transgenic yeast cells and the T cell activation. We also studied cell damage and associated biochemical processes in optical traps, UV radiations, and evaluated heating by near-infrared Raman spectroscopy. These studies show that the Raman-tweezers system is feasible to provide rapid and reliable diagnosis of cellular disorders and can be used as a valuable tool to study cellular processes within single living cells or intracellular organelles and may aid research in molecular and cellular biology.

Background photobleaching in raman spectra of aqueous solutions of plant toxins

NASA Astrophysics Data System (ADS)

Brandt, Nikolai N.; Chikishev, Andrey Y.; Tonevitsky, Alexander G.

2002-05-01

Kinetics of background photobleaching in Raman spectra of aqueous solutions of ricin, ricin agglutinin and ricin binding subunit were measured. It was found that the spectrum of Raman background changes upon laser irradiation. Background intensity is lower for the samples with lower molecular weight. Photobleaching is characterized by oscillations in the multi exponentially decaying intensity.

Characterization of Materials by Raman Scattering

NASA Astrophysics Data System (ADS)

Kozielski, M.

2007-03-01

The paper reports on the use of phonon spectra obtained with the Raman spectroscopy for characterization of different materials. The Raman scattering spectra obtained for zinc selenide crystals, mixed crystals zinc selenide admixtured with magnesium or beryllium, oxide crystals including strontium lanthanum gallate, molecular crystals of triammonium hydrogen diseleniate and a homologous series of polyoxyethylene glycols are analysed.

Optical properties of InN thin films

NASA Astrophysics Data System (ADS)

Malakhov, Vladislav Y.

2000-04-01

The basic optical properties of low temperature plasma enhanced chemical reactionary sputtered (PECRS) InN thin films are presented. Optical absorption and reflectance spectra of InN polycrystalline films at room temperature in visible and near infrared (NIR) regions were taken to determine direct band gap energy (2.03 eV), electron plasma resonances energy (0.6 eV), damping constant (0.18 eV), and optical effective mass of electrons (0.11). In addition the UV and visible reflectance spectra have been used to reproduce accurately dielectric function of wurtzite InN for assignments of the peak structures to interband transitions (1.5 - 12.0 eV) as well as to determine dielectric constant (9.3) and refractive index (>3.0). The revealed reflectance peaks at 485 and 590 cm-1 respectively in IR spectra are connected with TO and LO optical vibration modes of InN films. Some TO (485 cm-1) and LO (585 cm-1) phonon features of indium nitride polycrystalline films on ceramics were observed in Raman spectra and also discussed. The excellent possibilities of InN polycrystalline layers for potential application in optoelectronic devices such as LEDs based InGaAlN and high efficiency solar cells are confirmed.

The interaction of 2-mercaptobenzimidazole with human serum albumin as determined by spectroscopy, atomic force microscopy and molecular modeling.

PubMed

Li, Yuqin; Jia, Baoxiu; Wang, Hao; Li, Nana; Chen, Gaopan; Lin, Yuejuan; Gao, Wenhua

2013-04-01

The interaction of 2-mercaptobenzimidazole (MBI) with human serum albumin (HSA) was studied in vitro by equilibrium dialysis under normal physiological conditions. This study used fluorescence, ultraviolet-visible spectroscopy (UV-vis), Fourier transform infrared (FT-IR), circular dichroism (CD) and Raman spectroscopy, atomic force microscopy (AFM) and molecular modeling techniques. Association constants, the number of binding sites and basic thermodynamic parameters were used to investigate the quenching mechanism. Based on the fluorescence resonance energy transfer, the distance between the HSA and MBI was 2.495 nm. The ΔG(0), ΔH(0), and ΔS(0) values across temperature indicated that the hydrophobic interaction was the predominant binding Force. The UV, FT-IR, CD and Raman spectra confirmed that the HSA secondary structure was altered in the presence of MBI. In addition, the molecular modeling showed that the MBI-HSA complex was stabilized by hydrophobic forces, which resulted from amino acid residues. The AFM results revealed that the individual HSA molecule dimensions were larger after interaction with MBI. Overall, this study suggested a method for characterizing the weak intermolecular interaction. In addition, this method is potentially useful for elucidating the toxigenicity of MBI when it is combined with the biomolecular function effect, transmembrane transport, toxicological testing and other experiments. Copyright © 2012 Elsevier B.V. All rights reserved.

Studies on the Fe3+ Doping Effect on Structural, Optical and Catalytic Properties of Hydrothermally Synthesized TiO2 Photocatalyst

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kamble, Ravi; Sabale, Sandip; Chikode, Prashant

2017-08-01

Pure TiO2 and Fe3+-TiO2 nanoparticles have been prepared by simple hydrothermal method with different Fe3+ concentrations. The synthesized nanoparticles are analysed to determine its structural, optical, morphological and compositional properties using X-ray diffraction, Raman, UV-DRS, photoluminescence, Mossbauer, XPS, TEM and SEM/EDS. The EDS micrograph confirms the existence of Fe3+ atoms in the TiO2 matrix with 0.85, 1.52 and 1.87 weight percent. The crystallite size and band gap decrease with increase in Fe3+concentration. The average particle size obtained from TEM is 7-11 nm which is in good agreement with XRD results. Raman bands at 640 cm-1, 517 cm-1 and 398 cm-1more » further confirm pure phase anatase in all samples. XPS shows the proper substitutions of few sites of Ti4+ ions by Fe3+ ions in the TiO2 host lattice. The intensity of PL spectra for Fe3+-TiO2 shows a gradual decrease in the peak intensity with increasing Fe3+ concentration in TiO2, and it indicates lower recombination rate as Fe3+ ions increases. These nanoparticles are further studied for its photocatalytic activities using malachite green dye under UV light, visible light and sunlight.« less

Characterization of the Interactions between Titanium Dioxide Nanoparticles and Polymethoxyflavones Using Surface-Enhanced Raman Spectroscopy.

PubMed

Cao, Xiaoqiong; Ma, Changchu; Gao, Zili; Zheng, Jinkai; He, Lili; McClements, David Julian; Xiao, Hang

2016-12-14

Nanosized titanium dioxide (TiO 2 ) particles are commonly present in TiO 2 food additives (E171) and have been associated with potential adverse effects on health. However, little knowledge is available regarding the interactions between TiO 2 nanoparticles (NPs) and other food components, such as flavonoids. In this study, we aim to study the molecular interactions between TiO 2 anatase NPs and three structurally closely related polymethoxyflavones (PMFs, flavonoids found in citrus fruits), namely, 3',4'-didemethylnobiletin (DDN), 5-demethylnobiletin (5DN), and 5,3',4'-tridemethylnobiletin (TDN), using ultraviolet-visible (UV-vis) spectrometry and surface-enhanced Raman spectroscopy (SERS). In the UV-vis absorption spectra, bathochromic effects were observed after DDN and TDN conjugated with TiO 2 NPs. The results from SERS analysis clearly demonstrated that DDN and TDN could bind TiO 2 NPs with the functional groups 3'-OH and 4'-OH on ring B and formed charge-transfer complexes. However, 5DN with functional groups C═O on ring C and 5-OH on ring A could not bind TiO 2 NPs. Knowledge on the molecular interactions between TiO 2 NPs and food components, such as flavonoids, will facilitate the understanding of the fate of TiO 2 NPs during food processing and in the gastrointestinal tract after oral consumption.

Theoretical study of novel complexed structures for methoxy derivatives of scytonemin: potential biomarkers in iron-rich stressed environments.

PubMed

Varnali, Tereza; Edwards, Howell G M

2013-09-01

Scytonemin is a cyanobacterial sheath pigment with potent UV (UVA, UVB, and UVC) absorbing properties. Di- and tetramethoxy derivatives of scytonemin have also been found and described in the literature. The importance of these biomolecules is their photoprotective function, which is one of the major survival strategies adopted by extremophiles in environmentally stressed conditions. Also, iron compounds [particularly iron(III) oxides] offer an additional UV-protecting facility to subsurface endolithic biological colonization; hence, banded iron formations (accompanied by zones of depletion of iron) in rock matrices have attracted attention with special interest in the method of transportation of iron compounds through the rock. Di- and tetramethoxyscytonemin and their iron(III) complexes have been modeled and studied computationally by using density functional theory calculations at the level of B3LYP/6-31G** methodology. We propose new structures that could feature in survival strategy and facilitate the movement of iron through the rock especially for iron-rich stressed terrestrial environments exemplified by the Río Tinto system with the added potential of subsurface Mars exploration. This study represents a continuation of our previous work on scytonemin. The calculated Raman spectra of the proposed iron complexes are compared with those of their parent compounds and discussed in relation to structural changes effected in the parent ligand upon complexation. This information leads to new insights to be gained by experimental Raman spectroscopists and the characterization of spectroscopic biosignatures for the database being compiled for the remote Raman analytical interrogation of the martian surface and subsurface being proposed for the ESA ExoMars mission planned for launch in 2018.

Transmission Raman Measurements Using a Spatial Heterodyne Raman Spectrometer (SHRS).

PubMed

Strange, K Alicia; Paul, Kelly C; Angel, S Michael

2017-02-01

A spatial heterodyne Raman spectrometer (SHRS) was used to measure transmission Raman spectra of highly scattering compounds. Transmission Raman spectral intensities of ibuprofen were only 2.4 times lower in intensity than backscatter Raman spectra. The throughput was about eight times higher than an f/1.8 dispersive spectrometer, and the width of the area viewed was found to be seven to nine times higher, using 50.8 mm and 250 mm focal length collection lenses. However, the signal-to-noise (S/N) ratio was two times lower for the SHRS than the f/1.8 dispersive spectrometer, apparently due to high levels of stray light.

[Study of alkaline lignin from Arundo donax linn based on FT Raman spectroscopy].

PubMed

You, Ting-ting; Ma, Jian-feng; Guo, Si-qin; Xu, Feng

2014-08-01

Arundo donax linn, as a perennial energy crop, has promising application prospect. In the present study, Fourier transform Raman (FT Raman) spectroscopy was applied to determine the structural information of materials, milled wood lignin (MWL), and alkaline lignins (AL, under different treated time) from A. donax stem nondestructively. The results indicated that, extractable compounds in A. donax had negative contribution to the Raman spectra without rising new Raman peaks. FT Raman spectrum of MWL indicated that MWL from A. donax was HGS type lignins. Compared with the spectra of MWL from wood materials, the peak at 1173 cm(-1) was much higher in intensity for the MWL from A. donax stem, which may be assigned to hydroxycinnamic acid by analyzing the standard. With respect to FT Raman spectra of ALs, the relatively highest intensity of 1173 cm(-1) was found in alkaline lignin (AL2), which was treated for 40 min by alkaline. Moreover, the peak of coniferaldehyde/sinapaldehyde (1630 cm(-1)) was lowest in intensity while the band attributed to coniferyl alcohol/sinapyl alcohol (1660 cm(-1)) was almost disappeared in AL2. It could be inferred that AL2 demonstrated a highest content of phenolic acid, which may improve its potential application, such as for antioxidant activity. Furthermore, the results obtained by FT Raman spectra were verified by two dimensional heteronuclear singlequantum coherence nuclear magnetic resonance analyses. Above all, FT Raman spectroscopy provided alternative safe, rapid, accurate, and nondestructive technology for lignin structure determination.

Raman active components of skin cancer.

PubMed

Feng, Xu; Moy, Austin J; Nguyen, Hieu T M; Zhang, Jason; Fox, Matthew C; Sebastian, Katherine R; Reichenberg, Jason S; Markey, Mia K; Tunnell, James W

2017-06-01

Raman spectroscopy (RS) has shown great potential in noninvasive cancer screening. Statistically based algorithms, such as principal component analysis, are commonly employed to provide tissue classification; however, they are difficult to relate to the chemical and morphological basis of the spectroscopic features and underlying disease. As a result, we propose the first Raman biophysical model applied to in vivo skin cancer screening data. We expand upon previous models by utilizing in situ skin constituents as the building blocks, and validate the model using previous clinical screening data collected from a Raman optical fiber probe. We built an 830nm confocal Raman microscope integrated with a confocal laser-scanning microscope. Raman imaging was performed on skin sections spanning various disease states, and multivariate curve resolution (MCR) analysis was used to resolve the Raman spectra of individual in situ skin constituents. The basis spectra of the most relevant skin constituents were combined linearly to fit in vivo human skin spectra. Our results suggest collagen, elastin, keratin, cell nucleus, triolein, ceramide, melanin and water are the most important model components. We make available for download (see supplemental information) a database of Raman spectra for these eight components for others to use as a reference. Our model reveals the biochemical and structural makeup of normal, nonmelanoma and melanoma skin cancers, and precancers and paves the way for future development of this approach to noninvasive skin cancer diagnosis.

Raman active components of skin cancer

PubMed Central

Feng, Xu; Moy, Austin J; Nguyen, Hieu T. M.; Zhang, Jason; Fox, Matthew C.; Sebastian, Katherine R.; Reichenberg, Jason S.; Markey, Mia K.; Tunnell, James W.

2017-01-01

Raman spectroscopy (RS) has shown great potential in noninvasive cancer screening. Statistically based algorithms, such as principal component analysis, are commonly employed to provide tissue classification; however, they are difficult to relate to the chemical and morphological basis of the spectroscopic features and underlying disease. As a result, we propose the first Raman biophysical model applied to in vivo skin cancer screening data. We expand upon previous models by utilizing in situ skin constituents as the building blocks, and validate the model using previous clinical screening data collected from a Raman optical fiber probe. We built an 830nm confocal Raman microscope integrated with a confocal laser-scanning microscope. Raman imaging was performed on skin sections spanning various disease states, and multivariate curve resolution (MCR) analysis was used to resolve the Raman spectra of individual in situ skin constituents. The basis spectra of the most relevant skin constituents were combined linearly to fit in vivo human skin spectra. Our results suggest collagen, elastin, keratin, cell nucleus, triolein, ceramide, melanin and water are the most important model components. We make available for download (see supplemental information) a database of Raman spectra for these eight components for others to use as a reference. Our model reveals the biochemical and structural makeup of normal, nonmelanoma and melanoma skin cancers, and precancers and paves the way for future development of this approach to noninvasive skin cancer diagnosis. PMID:28663910

Application of Raman spectroscopy, surface-enhanced Raman scattering (SERS), and density functional theory for the identification of phenethylamines.

PubMed

Taplin, Francis; O'Donnell, Deanna; Kubic, Thomas; Leona, Marco; Lombardi, John

2013-10-01

We evaluated the normal Raman (NR) and the surface-enhanced Raman scattering (SERS) of three sympathomimetic amines: phenethylamine, ephedrine, and 3,4-methylenedioxymethamphetamine (MDMA). In addition, quantum mechanical calculations-geometry optimization and calculations of the harmonic vibrational frequencies-were performed using the density functional theory (DFT) approach. Vibrational assignments were made by comparing the experimental and calculated spectra. The study found that both NR and SERS provided excellent spectra for the drugs tested. Certain conditions, such as response to various laser wavelengths and background fluorescence of the analyte, could be easily managed using SERS techniques. The DFT-calculated spectra could be correlated with the experimental spectra without the aid of a scaling factor. We also present a set of discriminant bands, useful for distinguishing the three compounds, despite their structural similarities.

Raman spectroscopy of different types of Mexican copal resins

NASA Astrophysics Data System (ADS)

Vandenabeele, Peter; Grimaldi, Dulce Maria; Edwards, Howell G. M.; Moens, Luc

2003-08-01

Dispersive Raman spectra of six copal resins, that were purchased in local markets in Mexico, are presented. The spectra were interpreted and compared with each other. For all these spectra, the relative intensity of the Raman band at approximately 1645 cm -1, attributed to the exomethylene ν(CC) stretching vibration, was rather low, especially as fresh samples are involved. In one resin, viz. Incienso, CaCO 3 was detected. Probably this inorganic pigment was added as a whitener. In the spectrum of Lágrima a starch fraction was present. Raman spectra of a sample from an Aztec figurine were recorded. It was shown that its composition was inhomogeneous at the micrometer level. Here, too, CaCO 3 was observed. It was not possible to identify the resin applied in the antique figurine due to material degradation by age and environmental exposure.

Medium-range structural properties of vitreous germania obtained through first-principles analysis of vibrational spectra.

PubMed

Giacomazzi, Luigi; Umari, P; Pasquarello, Alfredo

2005-08-12

We analyze the principal vibrational spectra of vitreous GeO(2) and derive therefrom structural properties referring to length scales beyond the basic tetrahedral unit. We generate a model structure that yields a neutron structure factor in accord with experiment. The inelastic-neutron, the infrared, and the Raman spectra, calculated within a density-functional approach, also agree with respective experimental spectra. The accord for the Raman spectrum supports a Ge-O-Ge angle distribution centered at 135 degrees. The Raman feature X(2) is found to result from vibrations in three-membered rings, and therefore constitutes a distinctive characteristic of the medium-range structure.

Discrimination of Medicine Radix Astragali from Different Geographic Origins Using Multiple Spectroscopies Combined with Data Fusion Methods

NASA Astrophysics Data System (ADS)

Wang, Hai-Yan; Song, Chao; Sha, Min; Liu, Jun; Li, Li-Ping; Zhang, Zheng-Yong

2018-05-01

Raman spectra and ultraviolet-visible absorption spectra of four different geographic origins of Radix Astragali were collected. These data were analyzed using kernel principal component analysis combined with sparse representation classification. The results showed that the recognition rate reached 70.44% using Raman spectra for data input and 90.34% using ultraviolet-visible absorption spectra for data input. A new fusion method based on Raman combined with ultraviolet-visible data was investigated and the recognition rate was increased to 96.43%. The experimental results suggested that the proposed data fusion method effectively improved the utilization rate of the original data.

Time-resolved remote Raman study of minerals under supercritical CO2 and high temperatures relevant to Venus exploration.

PubMed

Sharma, Shiv K; Misra, Anupam K; Clegg, Samuel M; Barefield, James E; Wiens, Roger C; Acosta, Tayro

2010-07-13

We report time-resolved (TR) remote Raman spectra of minerals under supercritical CO(2) (approx. 95 atm pressure and 423 K) and under atmospheric pressure and high temperature up to 1003 K at distances of 1.5 and 9 m, respectively. The TR Raman spectra of hydrous and anhydrous sulphates, carbonate and silicate minerals (e.g. talc, olivine, pyroxenes and feldspars) under supercritical CO(2) (approx. 95 atm pressure and 423 K) clearly show the well-defined Raman fingerprints of each mineral along with the Fermi resonance doublet of CO(2). Besides the CO(2) doublet and the effect of the viewing window, the main differences in the Raman spectra under Venus conditions are the phase transitions, the dehydration and decarbonation of various minerals, along with a slight shift in the peak positions and an increase in line-widths. The dehydration of melanterite (FeSO(4).7H(2)O) at 423 K under approximately 95 atm CO(2) is detected by the presence of the Raman fingerprints of rozenite (FeSO(4).4H(2)O) in the spectrum. Similarly, the high-temperature Raman spectra under ambient pressure of gypsum (CaSO(4).2H(2)O) and talc (Mg(3)Si(4)O(10)(OH)(2)) indicate that gypsum dehydrates at 518 K, but talc remains stable up to 1003 K. Partial dissociation of dolomite (CaMg(CO(3))(2)) is observed at 973 K. The TR remote Raman spectra of olivine, alpha-spodumene (LiAlSi(2)O(6)) and clino-enstatite (MgSiO(3)) pyroxenes and of albite (NaAlSi(3)O(8)) and microcline (KAlSi(3)O(8)) feldspars at high temperatures also show that the Raman lines remain sharp and well defined in the high-temperature spectra. The results of this study show that TR remote Raman spectroscopy could be a potential tool for exploring the surface mineralogy of Venus during both daytime and nighttime at short and long distances.

Raman scattering or fluorescence emission? Raman spectroscopy study on lime-based building and conservation materials.

PubMed

Kaszowska, Zofia; Malek, Kamilla; Staniszewska-Slezak, Emilia; Niedzielska, Karina

2016-12-05

This work presents an in-depth study on Raman spectra excited with 1064 and 532nm lasers of lime binders employed in the past as building materials and revealed today as valuable conservation materials. We focus our interest on the bands of strong intensity, which are present in the spectra of all binders acquired with laser excitation at 1064nm, but absent in the corresponding spectra acquired with laser excitation at 532nm. We suggest, that the first group of spectra represents fluorescence phenomena of unknown origin and the second true Raman scattering. In our studies, we also include two other phases of lime cycle, i.e. calcium carbonate (a few samples of calcite of various origins) and calcium oxide (quicklime) to assess how structural and chemical transformations of lime phases affect the NIR-Raman spectral profile. Furthermore, we analyse a set of carbonated limewashes and lime binders derived from old plasters to give an insight into their spectral characteristics after excitation with the 1064nm laser line. NIR-Raman micro-mapping results are also presented to reveal the spatial distribution of building materials and fluorescent species in the cross-section of plaster samples taken from a 15th century chapel. Our study shows that the Raman analysis can help identify lime-based building and conservation materials, however, a caution is advised in the interpretation of the spectra acquired using 1064nm excitation. Copyright © 2016. Published by Elsevier B.V.

Fraction of boroxol rings in vitreous boron oxide from a first-principles analysis of Raman and NMR spectra.

PubMed

Umari, P; Pasquarello, Alfredo

2005-09-23

We determine the fraction f of B atoms belonging to boroxol rings in vitreous boron oxide through a first-principles analysis. After generating a model structure of vitreous B2O3 by first-principles molecular dynamics, we address a large set of properties, including the neutron structure factor, the neutron density of vibrational states, the infrared spectra, the Raman spectra, and the 11B NMR spectra, and find overall good agreement with corresponding experimental data. From the analysis of Raman and 11B NMR spectra, we yield consistently for both probes a fraction f of approximately 0.75. This result indicates that the structure of vitreous boron oxide is largely dominated by boroxol rings.

Combining Raman and laser induced breakdown spectroscopy by double pulse lasing.

PubMed

Lednev, Vasily N; Pershin, Sergey M; Sdvizhenskii, Pavel A; Grishin, Mikhail Ya; Fedorov, Alexander N; Bukin, Vladimir V; Oshurko, Vadim B; Shchegolikhin, Alexander N

2018-01-01

A new approach combining Raman spectrometry and laser induced breakdown spectrometry (LIBS) within a single laser event was suggested. A pulsed solid state Nd:YAG laser running in double pulse mode (two frequency-doubled sequential nanosecond laser pulses with dozens microseconds delay) was used to combine two spectrometry methods within a single instrument (Raman/LIBS spectrometer). First, a low-energy laser pulse (power density far below ablation threshold) was used for Raman measurements while a second powerful laser pulse created the plasma suitable for LIBS analysis. A short time delay between two successive pulses allows measuring LIBS and Raman spectra at different moments but within a single laser flash-lamp pumping. Principal advantages of the developed instrument include high quality Raman/LIBS spectra acquisition (due to optimal gating for Raman/LIBS independently) and absence of target thermal alteration during Raman measurements. A series of high quality Raman and LIBS spectra were acquired for inorganic salts (gypsum, anhydrite) as well as for pharmaceutical samples (acetylsalicylic acid). To the best of our knowledge, the quantitative analysis feasibility by combined Raman/LIBS instrument was demonstrated for the first time by calibration curves construction for acetylsalicylic acid (Raman) and copper (LIBS) in gypsum matrix. Combining ablation pulses and Raman measurements (LIBS/Raman measurements) within a single instrument makes it an efficient tool for identification of samples hidden by non-transparent covering or performing depth profiling analysis including remote sensing. Graphical abstract Combining Raman and laser induced breakdown spectroscopy by double pulse lasing.

Experimental and theoretical elucidation of structural and antioxidant properties of vanillylmandelic acid and its carboxylate anion

NASA Astrophysics Data System (ADS)

Dimić, Dušan; Milenković, Dejan; Ilić, Jelica; Šmit, Biljana; Amić, Ana; Marković, Zoran; Dimitrić Marković, Jasmina

2018-06-01

Vanillylmandelic acid (VMA), an important metabolite of catecholamines that is routinely screened as tumor marker, was investigated by the various spectroscopic techniques (IR, Raman, UV-Vis, antioxidant decolorization assay and NMR). Structures optimized by the employment of five common functionals (M05-2X, M06-2X, B3LYP, CAM-B3LYP, B3LYP-D3) were compared with the crystallographic data. The M05-2X functional reproduced the most reliable experimental bond lengths and angles (correlation coefficient >0.999). The importance of intramolecular hydrogen bonds for structural stability was discussed and quantified by the NBO analysis. The most prominent bands in vibrational spectrum were analyzed and compared to the experimental data. The positions of the carbon and hydrogen atoms in NMR spectra were well reproduced. The differences in UV-Vis spectrum were investigated by adding the explicit solvent and by performing NBO and QTAIM analyses. The discrepancy in the two spectra of about 50 nm could be explained by the solvent effect on carboxyl group. The most probable antioxidant activity mechanism was discussed for VMA and its carboxylate anion. The Molecular Docking study with the C - reactive protein additionally proved that variety of functional groups present in VMA and its anion allowed strong hydrogen and hydrophobic interactions.

Micro-Raman spectroscopy study of ALVAC virus infected chicken embryo cells

NASA Astrophysics Data System (ADS)

Misra, Anupam K.; Kamemoto, Lori E.; Hu, Ningjie; Dykes, Ava C.; Yu, Qigui; Zinin, Pavel V.; Sharma, Shiv K.

2011-05-01

Micro- Raman spectroscopic investigation of ALVAC virus and of normal chicken embryo fibroblast cells and the cells infected with ALVAC virus labeled with green fluorescence protein (GFP) were performed with a 785 nm laser. Good quality Micro-Raman spectra of the Alvac II virus were obtained. These spectra show that the ALVAC II virus contains buried tyrosine residues and the coat protein of the virus has α-helical structure. A comparison of Raman spectra of normal and virus infected chicken embryo fibroblast cells revealed that the virus infected cells show additional bands at 535, 928, and 1091 cm-1, respectively, corresponding to δ(C-O-C) glycosidic ring, protein α-helix, and DNA (O-P-O) modes. In addition, the tyrosine resonance double (833 and 855 cm-1) shows reversal in the intensity of the higher-frequency band as compared to the normal cells that can be used to identify the infected cells. In the C-H stretching region, the infected cells show bands with higher intensity as compared to that of the corresponding bands in the normal cells. We also found that the presence of GFP does not affect the Raman spectra of samples when using a 785 nm micro-Raman system because the green fluorescence wavelength of GFP is well below the Stokes-Raman shifted spectral region.

A comparison of the far-infrared and low-frequency Raman spectra of glass-forming liquids

NASA Astrophysics Data System (ADS)

Perova, T. S.; Vij, J. K.; Christensen, D. H.; Nielsen, O. F.

1999-04-01

Far-infrared and low-frequency Raman spectra in the wavenumber range from 15 to 500 cm -1 were recorded for glycerol, triacetin (glycerol triacetate) and o-terphenyl at temperatures from 253 to 355 K. The far-infrared spectra of glycerol appear complex compared with the spectra of triacetin owing to the presence of hydrogen bonding in glycerol. The experimental results obtained for o-terphenyl are in good agreement with normal mode analyses carried out for crystalline o-terphenyl (A. Criado, F.J. Bermejo, A. de Andres, Mol. Phys. 82 (1994) 787). The far-infrared results are compared with the low-frequency Raman spectra of these three glass-forming liquids. The difference in temperature dependences found from these spectra is explained on the basis of different temperature contributions of the relaxational and vibrational processes to the low-frequency vibrational spectra.

Comparison of experimental and calculated chiroptical spectra for chiral molecular structure determination.

PubMed

Polavarapu, Prasad L; Covington, Cody L

2014-09-01

For three different chiroptical spectroscopic methods, namely, vibrational circular dichroism (VCD), electronic circular dichroism (ECD), and Raman optical activity (ROA), the measures of similarity of the experimental spectra to the corresponding spectra predicted using quantum chemical theories are summarized. In determining the absolute configuration and/or predominant conformations of chiral molecules, these similarity measures provide numerical estimates of agreement between experimental observations and theoretical predictions. Selected applications illustrating the similarity measures for absorption, circular dichroism, and corresponding dissymmetry factor (DF) spectra, in the case of VCD and ECD, and for Raman, ROA, and circular intensity differential (CID) spectra in the case of ROA, are presented. The analysis of similarity in DF or CID spectra is considered to be much more discerning and accurate than that in absorption (or Raman) and circular dichroism (or ROA) spectra, undertaken individually. © 2014 Wiley Periodicals, Inc.

Airborne pipeline leak detection: UV or IR?

NASA Astrophysics Data System (ADS)

Babin, François; Gravel, Jean-François; Allard, Martin

2016-05-01

This paper presents a study of different approaches to the measurement of the above ground vapor plume created by the spill caused by a small 0.1 l/min (or less) leak in an underground liquid petroleum pipeline. The scenarios are those for the measurement from an airborne platform. The usual approach is that of IR absorption, but in the case of liquid petroleum products, there are drawbacks that will be discussed, especially when using alkanes to detect a leak. The optical measurements studied include UV enhanced Raman lidar, UV fluorescence lidar and IR absorption path integrated lidars. The breadboards used for testing the different approaches will be described along with the set-ups for leak simulation. Although IR absorption would intuitively be the most sensitive, it is shown that UV-Raman could be an alternative. When using the very broad alkane signature in the IR, the varying ground spectral reflectance are a problem. It is also determined that integrated path measurements are preferred, the UV enhanced Raman measurements showing that the vapor plume stays very close to the ground.

Photoluminescence and reflectivity of polymethylmethacrylate implanted by low-energy carbon ions at high fluences

NASA Astrophysics Data System (ADS)

Wang, Jun; Zhu, Fei; Zhang, Bei; Liu, Huixian; Jia, Guangyi; Liu, Changlong

2012-11-01

Polymethylmethacrylate (PMMA) specimens were implanted with 30 keV carbon ions in a fluence range of 1 × 1016 to 2 × 1017 cm-2, and photoluminescence (PL) and reflectivity of the implanted samples were examined. A luminescent band with one peak was found in PL spectra excited by 480 nm line, but its intensity did not vary in parallel with ion fluence. The strongest PL occurred at the fluence of 5 × 1016 cm-2. Results from visible-light-excited micro-Raman spectra indicated that the formation of hydrogenated amorphous carbon structures in subsurface layer and their evolutions with ion fluence could be responsible for the observed PL responses. Measurements of the small-angle reflectance spectra from both the implanted and rear surfaces of samples in the ultraviolet-visible (UV-vis) range demonstrated a kind of both fluence-dependent and wavelength-related reflectivity variations, which were attributed to the structural changes induced by ion implantation. A noticeable reflectivity modification, which may be practically used, could be found at the fluence of 1 × 1016 cm-2.

Enhanced photocatalytic performance of RGO/Ag nanocomposites produced via a facile microwave irradiation for the degradation of Rhodamine B in aqueous solution

NASA Astrophysics Data System (ADS)

Divya, K. S.; Chandran, Akash; Reethu, V. N.; Mathew, Suresh

2018-06-01

A series of RGO/Ag nanocomposites with different weight addition ratios of graphene oxide (GO) have been successfully prepared in situ through the simultaneous reduction of GO and AgNO3 via a facile microwave irradiation. X-ray diffraction analysis, Fourier Transform Infrared Spectroscopy, UV-vis diffuse reflectance spectra, Scanning electron microscopy, Photoluminescence spectra, Raman spectra, Atomic Force Microscopy, X-ray photoelectron spectroscopy (XPS) and Transmission electron microscopy are employed to determine the properties of the samples. It is found that RGO/Ag nanocomposites with a proper weight addition ratios of GO exhibit higher photocatalytic activity toward liquid phase photodegradation of Rhodamine B under visible light irradiation. The improved photoactivity of RGO/Ag nanocomposites can be ascribed to the integrative synergestic effect of enhanced adsorption capacity, the prolonged lifetime of photogenerated electron-hole pairs and effective interfacial hybridization between RGO and Ag nanoparticles. This study also shows that graphene sheets act as electronic conductive channels to efficiently separate charge carriers from Ag nanoparticles.

Density functional theory study on Herzberg-Teller contribution in Raman scattering from 4-aminothiophenol-metal complex and metal-4-aminothiophenol-metal junction

NASA Astrophysics Data System (ADS)

Liu, Shasha; Zhao, Xiuming; Li, Yuanzuo; Zhao, Xiaohong; Chen, Maodu

2009-06-01

Density functional theory (DFT) and time-dependent DFT calculations have been performed to investigate the Raman scattering spectra of metal-molecule complex and metal-molecule-metal junction architectures interconnected with 4-aminothiophenol (PATP) molecule. The simulated profiles of normal Raman scattering (NRS) spectra for the two complexes (Ag2-PATP and PATP-Au2) and the two junctions (Ag2-PATP-Au2 and Au2-PATP-Ag2) are similar to each other, but exhibit obviously different Raman intensities. Due to the lager static polarizabilities of the two junctions, which directly influence the ground state chemical enhancement in NRS spectra, the calculated normal Raman intensities of them are stronger than those of two complexes by the factor of 102. We calculate preresonance Raman scattering (RRS) spectra with incident light at 1064 nm, which is much lower than the S1 electronic transition energy of complexes and junctions. Ag2-PATP-Au2 and Au2-PATP-Ag2 junctions yield higher Raman intensities than those of Ag2-PATP and PATP-Au2 complexes, especially for b2 modes. This effect is mainly attributed to charge transfer (CT) between the metal gap and the PAPT molecule which results in the occurrence of CT resonance enhancement. The calculated pre-RRS spectra strongly depend on the electronic transition state produced by new structures. With excitation at 514.5 nm, the calculated pre-RRS spectra of two complexes and two junctions are stronger than those of with excitation at 1064 nm. A charge difference densities methodology has been used to visually describe chemical enhancement mechanism of RRS spectrum. This methodology aims at visualizing intermolecular CT which provides direct evidence of the Herzberg-Teller mechanism.

Micro-Raman spectroscopy of tissue samples for oral pathology follow-up monitoring

NASA Astrophysics Data System (ADS)

Delfino, I.; Camerlingo, C.; Zenone, F.; Perna, G.; Capozzi, V.; Cirillo, N.; Gaeta, G. M.; Lepore, M.

2010-04-01

An "in vitro" study of Raman spectra from oral human tissues is reported in order to the develop a diagnostic method suitable for "in vivo" oral pathology follow-up. The investigated pathology is Pemphigus Vulgaris (PV) for which new techniques for guiding and monitoring therapy would be particularly useful. Raman spectra were obtained in the wavenumber regions from 1000 to 1800 cm-1 and 2700 to 3200 cm-1 from tissues from patients at different stages of pathology (active PV, under therapy and in PV remission stage) as confirmed by histopathological and immunofluorescence analysis. Differences in the spectra depending on tissue illness stage arise in 1150-1250 cm-1 (amide III) and 1420-1450 cm-1 (CH3 deformation) regions and around 1650 cm-1 (amide I) and 2930 cm-1 (CH3 symmetric stretch). A wavelet deconvolution procedure was applied to the spectra for better discriminating among the three different stages of illness and a linear regression analysis was used to fully exploit the content of information of Raman spectra.

Spectral reconstruction for shifted-excitation Raman difference spectroscopy (SERDS).

PubMed

Guo, Shuxia; Chernavskaia, Olga; Popp, Jürgen; Bocklitz, Thomas

2018-08-15

Fluorescence emission is one of the major obstacles to apply Raman spectroscopy in biological investigations. It is usually several orders more intense than Raman scattering and hampers further analysis. In cases where the fluorescence emission is too intense to be efficiently removed via routine mathematical baseline correction algorithms, an alternative approach is needed. One alternative approach is shifted-excitation Raman difference spectroscopy (SERDS), where two Raman spectra are recorded with two slightly different excitation wavelengths. Ideally, the fluorescence emission at the two excitations does not change while the Raman spectrum shifts according to the excitation wavelength. Hence the fluorescence is removed in the difference of the two recorded Raman spectra. For better interpretability a spectral reconstruction procedure is necessary to recover the fluorescence-free Raman spectrum. This is challenging due to the intensity variations between the two recorded Raman spectra caused by unavoidable experimental changes as well as the presence of noise. Existent approaches suffer from drawbacks like spectral resolution loss, fluorescence residual, and artefacts. In this contribution, we proposed a reconstruction method based on non-negative least squares (NNLS), where the intensity variations between the two measurements are utilized in the reconstruction model. The method achieved fluorescence-free reconstruction on three real-world SERDS datasets without significant information loss. Thereafter, we quantified the performance of the reconstruction based on artificial datasets from four aspects: reconstructed spectral resolution, precision of reconstruction, signal-to-noise-ratio (SNR), and fluorescence residual. The artificial datasets were constructed with varied Raman to fluorescence intensity ratio (RFIR), SNR, full-width at half-maximum (FWHM), excitation wavelength shift, and fluorescence variation between the two spectra. It was demonstrated that the NNLS approach provides a faithful reconstruction without significantly changing the spectral resolution. Meanwhile, the reconstruction is almost robust to fluorescence variations between the two spectra. Last but not the least the SNR was improved after reconstruction for extremely noisy SERDS datasets. Copyright © 2018 Elsevier B.V. All rights reserved.

Compact and portable multiline UV and visible Raman lasers in hydrogen-filled HC-PCF.

PubMed

Wang, Y Y; Couny, F; Light, P S; Mangan, B J; Benabid, F

2010-04-15

We report on the realization of compact UV visible multiline Raman lasers based on two types of hydrogen-filled hollow-core photonic crystal fiber. The first, with a large pitch Kagome lattice structure, offers a broad spectral coverage from near IR through to the much sought after yellow, deep-blue and UV, whereas the other, based on photonic bandgap guidance, presents a pump conversion concentrated in the visible region. The high Raman efficiency achieved through these fibers allows for compact, portable diode-pumped solid-state lasers to be used as pumps. Each discrete component of this laser system exhibits a spectral density several orders of magnitude larger than what is achieved with supercontinuum sources and a narrow linewidth, making it an ideal candidate for forensics and biomedical applications.

A new on-axis micro-spectrophotometer for combining Raman, fluorescence and UV/Vis absorption spectroscopy with macromolecular crystallography at the Swiss Light Source

PubMed Central

Pompidor, Guillaume; Dworkowski, Florian S. N.; Thominet, Vincent; Schulze-Briese, Clemens; Fuchs, Martin R.

2013-01-01

The combination of X-ray diffraction experiments with optical methods such as Raman, UV/Vis absorption and fluorescence spectroscopy greatly enhances and complements the specificity of the obtained information. The upgraded version of the in situ on-axis micro-spectrophotometer, MS2, at the macromolecular crystallography beamline X10SA of the Swiss Light Source is presented. The instrument newly supports Raman and resonance Raman spectroscopy, in addition to the previously available UV/Vis absorption and fluorescence modes. With the recent upgrades of the spectral bandwidth, instrument stability, detection efficiency and control software, the application range of the instrument and its ease of operation were greatly improved. Its on-axis geometry with collinear X-ray and optical axes to ensure optimal control of the overlap of sample volumes probed by each technique is still unique amongst comparable facilities worldwide and the instrument has now been in general user operation for over two years. PMID:23955041

The analysis of colored acrylic, cotton, and wool textile fibers using micro-Raman spectroscopy. Part 2: comparison with the traditional methods of fiber examination.

PubMed

Buzzini, Patrick; Massonnet, Genevieve

2015-05-01

In the second part of this survey, the ability of micro-Raman spectroscopy to discriminate 180 fiber samples of blue, black, and red cottons, wools, and acrylics was compared to that gathered with the traditional methods for the examination of textile fibers in a forensic context (including light microscopy methods, UV-vis microspectrophotometry and thin-layer chromatography). This study shows that the Raman technique plays a complementary and useful role to obtain further discriminations after the application of light microscopy methods and UV-vis microspectrophotometry and assure the nondestructive nature of the analytical sequence. These additional discriminations were observed despite the lower discriminating powers of Raman data considered individually, compared to those of light microscopy and UV-vis MSP. This study also confirms that an instrument equipped with several laser lines is necessary for an efficient use as applied to the examination of textile fibers in a forensic setting. © 2015 American Academy of Forensic Sciences.

A new on-axis micro-spectrophotometer for combining Raman, fluorescence and UV/Vis absorption spectroscopy with macromolecular crystallography at the Swiss Light Source.

PubMed

Pompidor, Guillaume; Dworkowski, Florian S N; Thominet, Vincent; Schulze-Briese, Clemens; Fuchs, Martin R

2013-09-01

The combination of X-ray diffraction experiments with optical methods such as Raman, UV/Vis absorption and fluorescence spectroscopy greatly enhances and complements the specificity of the obtained information. The upgraded version of the in situ on-axis micro-spectrophotometer, MS2, at the macromolecular crystallography beamline X10SA of the Swiss Light Source is presented. The instrument newly supports Raman and resonance Raman spectroscopy, in addition to the previously available UV/Vis absorption and fluorescence modes. With the recent upgrades of the spectral bandwidth, instrument stability, detection efficiency and control software, the application range of the instrument and its ease of operation were greatly improved. Its on-axis geometry with collinear X-ray and optical axes to ensure optimal control of the overlap of sample volumes probed by each technique is still unique amongst comparable facilities worldwide and the instrument has now been in general user operation for over two years.

Ultraviolet Spectra of Two Magnetic White Dwarfs and Ultraviolet Spectra of Subluminous Objects Found in the Kiso Schmidt Survey and Ultraviolet Absorptions in the Spectra of DA White Dwarfds

NASA Technical Reports Server (NTRS)

Wegner, Gary A.

1988-01-01

Research under NASA Grant NAG5-287 has carried out a number of projects in conjunction with the International Ultraviolet Explorer (IUE) satellite. These include: (1) studies of the UV spectra of DA white dwarfs which show quasi-molecular bands of H2 and H2(+); (2) the peculiar star HR6560; (3) the UV spectra of two magnetic white dwarfs that also show the quasi-molecular features; (4) investigations of the UV spectra of subluminous stars, primarily identified from visual wavelength spectroscopy in the Kiso survey of UV excess stars, some of which show interesting metal lines in their UV spectra; and (5) completion of studies of UV spectra of DB stars. The main result of this research has been to further knowledge of the structure and compositions of subluminous stars which helps cast light on their formation and evolution.

Temperature-dependent μ-Raman investigation of struvite crystals.

PubMed

Prywer, Jolanta; Kasprowicz, D; Runka, T

2016-04-05

The effect of temperature on the vibrational properties of struvite crystals grown from silica gels was systematically studied by μ-Raman spectroscopy. The time-dependent Raman spectra recorded in the process of long time annealing of struvite crystal at 353 K do not indicate structural changes in the struvite crystal with the time of annealing. The temperature-dependent Raman spectra recorded in the range 298-423 K reveal a phase transition in struvite at about 368 K. Above this characteristic temperature, some of bands assigned to vibrations of the PO4 and NH4 tetrahedra and water molecules observed in the Raman spectra in low temperatures (orthorhombic phase) change their spectral parameters or disappear, which indicates a transition to a higher symmetry structure of struvite in the range of high temperatures. Copyright © 2016 Elsevier B.V. All rights reserved.

Resonant Raman spectra of diindenoperylene thin films

NASA Astrophysics Data System (ADS)

Scholz, R.; Gisslén, L.; Schuster, B.-E.; Casu, M. B.; Chassé, T.; Heinemeyer, U.; Schreiber, F.

2011-01-01

Resonant and preresonant Raman spectra obtained on diindenoperylene (DIP) thin films are interpreted with calculations of the deformation of a relaxed excited molecule with density functional theory (DFT). The comparison of excited state geometries based on time-dependent DFT or on a constrained DFT scheme with observed absorption spectra of dissolved DIP reveals that the deformation pattern deduced from constrained DFT is more reliable. Most observed Raman peaks can be assigned to calculated A_g-symmetric breathing modes of DIP or their combinations. As the position of one of the laser lines used falls into a highly structured absorption band, we have carefully analyzed the Raman excitation profile arising from the frequency dependence of the dielectric tensor. This procedure gives Raman cross sections in good agreement with the observed relative intensities, both in the fully resonant and in the preresonant case.

Application of Raman spectroscopy and surface-enhanced Raman scattering to the analysis of synthetic dyes found in ballpoint pen inks.

PubMed

Geiman, Irina; Leona, Marco; Lombardi, John R

2009-07-01

The applicability of Raman spectroscopy and surface-enhanced Raman scattering (SERS) to the analysis of synthetic dyes commonly found in ballpoint inks was investigated in a comparative study. Spectra of 10 dyes were obtained using a dispersive system (633 nm, 785 nm lasers) and a Fourier transform system (1064 nm laser) under different analytical conditions (e.g., powdered pigments, solutions, thin layer chromatography [TLC] spots). While high fluorescence background and poor spectral quality often characterized the normal Raman spectra of the dyes studied, SERS was found to be generally helpful. Additionally, dye standards and a single ballpoint ink were developed on a TLC plate following a typical ink analysis procedure. SERS spectra were successfully collected directly from the TLC plate, thus demonstrating a possible forensic application for the technique.

Resonant Raman spectra of diindenoperylene thin films.

PubMed

Scholz, R; Gisslén, L; Schuster, B-E; Casu, M B; Chassé, T; Heinemeyer, U; Schreiber, F

2011-01-07

Resonant and preresonant Raman spectra obtained on diindenoperylene (DIP) thin films are interpreted with calculations of the deformation of a relaxed excited molecule with density functional theory (DFT). The comparison of excited state geometries based on time-dependent DFT or on a constrained DFT scheme with observed absorption spectra of dissolved DIP reveals that the deformation pattern deduced from constrained DFT is more reliable. Most observed Raman peaks can be assigned to calculated A(g)-symmetric breathing modes of DIP or their combinations. As the position of one of the laser lines used falls into a highly structured absorption band, we have carefully analyzed the Raman excitation profile arising from the frequency dependence of the dielectric tensor. This procedure gives Raman cross sections in good agreement with the observed relative intensities, both in the fully resonant and in the preresonant case.

Synthesis of nanocrystalline NiO/ZnO heterostructured composite powders by sol-gel auto combustion method and their characterizations

NASA Astrophysics Data System (ADS)

Tangcharoen, Thanit; Klysubun, Wantana; Kongmark, Chanapa

2018-03-01

Nanocrystalline NiO/ZnO heterostructured composite powders were prepared by the sol-gel auto combustion method, based on nickel and zinc nitrate precursors and using diethanolamine (DEA) as novel fuel. The composition of different NiO and ZnO ratios, ranging from 100/0, 95/5, 90/10, 80/20, 60/40, 50/50, 40/60, 20/80, 10/90, 5/95 to 0/100, were studied. The structural, chemical bonding, morphological, optical, and fluorescence properties including the local atomic structure of each calcined sample were systematically investigated by means of X-ray diffraction (XRD), Raman spectroscopy, scanning electron microscopy (SEM), UV-visible diffuse reflectance spectroscopy (UV-DRS), photoluminescence (PL) spectroscopy, and synchrotron X-ray absorption spectroscopy (XAS), respectively. For the ZnO concentration below 20%, both XRD and Raman spectroscopy results revealed only the NiO phase. This conformed to the observation of Zn K-edge and Ni K-edge X-ray absorption near edge structure (XANES). The Zn ions found in the samples of low ZnO concentration exhibited six-fold coordination with oxygen atoms rather than the four-fold coordination found in the wurtzite (WZ) structure of ZnO. In contrast, the Ni ions which are found in the samples of low NiO concentration (≤10%) are coordinated both tetrahedrally and octahedrally by four or six oxygen atoms, respectively, rather than the six-fold coordination which is usually observed for Ni ions in the rock salt (RS) form of NiO. All analytical results obtained from experimental XANES spectra were verified by the theoretical calculation of absorption spectra using the FEFF9.7 code. The UV-DRS results showed that there was an increase in the reflectance efficiency for both infrared and visible light conditions as the content of ZnO increases; meanwhile, the values for the energy gap (Eg) of all composite samples were higher than that of pure NiO and ZnO. In addition, the PL spectra revealed major blue emission bands observed at 490 nm when the excitation wavelength was 300 nm. As the ZnO phase developed, a variety of violet emission bands occurred within the range of 400 nm-450 nm, which was obviously related to the change in Eg. The intrinsic defects occurred in the NiO/ZnO composite powders were probably responsible for this phenomenon.

Vibrational and electronic investigations, NLO, FMO analysis on a hetarylazoindole disperse dye by density functional theory

NASA Astrophysics Data System (ADS)

Çatıkkaş, Berna; Aktan, Ebru; Yalçın, Ergin

2016-08-01

This work deals with the optimized molecular structure, vibrational spectra, nonlinear optic (NLO) and frontier molecule orbital (FMO) properties of 1-Methyl-2-phenyl-3-(1,3,4-thiadiazol-2-yldiazenyl)-1H-indole (MPI) by quantum chemical calculations. The Fourier transform infrared (FT-MIR and FT-FIR) and Raman spectra of 1-Methyl-2-phenyl-3-(1,3,4-thiadiazol-2-yldiazenyl)-1H-indole (MPI) were recorded in the region (4000-400 cm-1 and 400-30 cm-1) and (3200-92 cm-1), respectively. The analysis and complete vibrational assignments of the fundamental modes of the MPI molecule were carried out by using the observed FT-IR and FT-Raman data and calculated Total Energy Distribution (TED) according to Scaled Quantum Mechanics procedure. The calculated geometrical parameters of the MPI molecule are in agreement with the obtained values from XRD studies. On the other hand, the difference between the scaled and observed wavenumber values of the most of the fundamentals are very small. 1H NMR and 13C NMR chemical shift values, and energy gap between LUMO-HOMO and molecular electrostatic potential (MEP) were investigated by using density functional theory (B3LYP) methods. UV/Visible spectra and λ maximum absorption values, the oscillator strengths in the chloroform, methanol and DMSO solvation in combination with different basis sets were calculated by using the time-dependent density functional theory (TD-DFT). Additionally, the predicted nonlinear optical (NLO) properties of the MPI are quite greater than that of urea at the B3LYP/6-31++G(d,p) level.

Raman Spectra and Cross Sections of Ammonia, Chlorine, Hydrogen Sulfide, Phosgene, and Sulfur Dioxide Toxic Gases in the Fingerprint Region 400-1400 cm-1

DTIC Science & Technology

2016-02-11

AIP ADVANCES 6, 025310 (2016) Raman spectra and cross sections of ammonia , chlorine, hydrogen sulfide, phosgene, and sulfur dioxide toxic gases in...Received 10 December 2015; accepted 3 February 2016; published online 11 February 2016) Raman spectra of ammonia (NH3), chlorine (Cl2), hydrogen...and cross sections of ammonia (NH3), chlorine (Cl2), hydrogen sulfide (H2S), phosgene (CCl2O), and sulfur dioxide (SO2) toxic gases in the fingerprint

Raman band intensities of tellurite glasses.

PubMed

Plotnichenko, V G; Sokolov, V O; Koltashev, V V; Dianov, E M; Grishin, I A; Churbanov, M F

2005-05-15

Raman spectra of TeO2-based glasses doped with WO3, ZnO, GeO2, TiO2, MoO3, and Sb2O3 are measured. The intensity of bands in the Raman spectra of MoO3-TeO2 and MoO3-WO3-TeO2 glasses is shown to be 80-95 times higher than that for silica glass. It is shown that these glasses can be considered as one of the most promising materials for Raman fiber amplifiers.

Structure and optical properties of TiO2 thin films deposited by ALD method

NASA Astrophysics Data System (ADS)

Szindler, Marek; Szindler, Magdalena M.; Boryło, Paulina; Jung, Tymoteusz

2017-12-01

This paper presents the results of study on titanium dioxide thin films prepared by atomic layer deposition method on a silicon substrate. The changes of surface morphology have been observed in topographic images performed with the atomic force microscope (AFM) and scanning electron microscope (SEM). Obtained roughness parameters have been calculated with XEI Park Systems software. Qualitative studies of chemical composition were also performed using the energy dispersive spectrometer (EDS). The structure of titanium dioxide was investigated by X-ray crystallography. A variety of crystalline TiO2 was also confirmed by using the Raman spectrometer. The optical reflection spectra have been measured with UV-Vis spectrophotometry.

A novel, eco-friendly technique for covalent functionalization of graphene nanoplatelets and the potential of their nanofluids for heat transfer applications

NASA Astrophysics Data System (ADS)

Sadri, Rad; Hosseini, Maryam; Kazi, S. N.; Bagheri, Samira; Zubir, Nashrul; Ahmadi, Goodarz; Dahari, Mahidzal; Zaharinie, Tuan

2017-05-01

In this study, a facile and eco-friendly covalent functionalization technique is developed to synthesize highly stable graphene nanoplatelets (GNPs) in aqueous media. This technique involves free radical grafting of gallic acid onto the surface of GNPs rather than corrosive inorganic acids. Raman spectroscopy, X-ray photoelectron spectroscopy and transmission electron microscopy are used to confirm the covalent functionalization of GNPs with gallic acid (GAGNPs). The solubility of the GAGNPs in aqueous media is verified using zeta potential and UV-vis spectra measurements. The nanofluid shows significant improvement in thermo-physical properties, indicating its superb potential for various thermal applications.

Synthesis and spectral studies of platinum metal complexes of benzoin thiosemicarbazone

NASA Astrophysics Data System (ADS)

Offiong, Offiong E.

1994-11-01

The platinum metal chelates of benzoin thiosemicarbazone obtained with Ru(III), Rh(III), Ir(III), Pd(II) and Pt(II) were prepared from their corresponding halide salts. The complexes were characterized by elemental analysis, conductance measurement, IR, Raman, 1H-NMR, 13C-NMR and UV-visible spectra studies. Various ligand field parameters and nephelauxetic parameters were also calculated. The mode of bonding and the geometry of the ligand environment around the metal ion have been discussed in the light of the available data obtained. Complexes of Ru(III), Rh(III) and Ir(III) are six-coordinate octahedral, while Pd(II) and Pt(II) halide complexes are four-coordinated with halides bridging.

Enhanced charge transport and photovoltaic performance of PBDTTT-C-T/PC70BM solar cells via UV-ozone treatment.

PubMed

Adhikary, Prajwal; Venkatesan, Swaminathan; Adhikari, Nirmal; Maharjan, Purna P; Adebanjo, Olusegun; Chen, Jihua; Qiao, Qiquan

2013-10-21

In this work, the electron transport layer of PBDTTT-C-T/PC70BM polymer solar cells were subjected to UV-ozone treatment, leading to improved cell performances from 6.46% to 8.34%. The solar cell efficiency reached a maximum of 8.34% after an optimal 5 minute UV-ozone treatment, and then decreased if treated for a longer time. To the best of our knowledge, the mechanism behind the effects of UV-ozone treatment on the improvement of charge transport and cell performance is not fully understood. We have developed a fundamental understanding of the UV-ozone treatment mechanism, which explains both the enhancements in charge transport and photovoltaic performance at an optimal treatment time, and also the phenomenon whereby further treatment time leads to a drop in cell efficiency. Transient photocurrent measurements indicated that the cell charge transport times were 1370 ns, 770 ns, 832 ns, 867 ns, and 1150 ns for the 0 min, 5 min, 10 min, 15 min, and 20 min UV-ozone treatment times, respectively. Therefore the 5 min UV-ozone treatment time led to the shortest transport time and the most efficient charge transport in the cells. The 5 min UV-ozone treated sample exhibited the highest peak intensity (E2) in the Raman spectra of the treated films, at about 437 cm(-1), indicating that it possessed the best wurtzite phase crystallinity of the ZnO films. Further increasing the UV-ozone treatment time from 5 to 20 min induced the formation of p-type defects (e.g. interstitial oxygen atoms), pushing the ZnO Fermi-level further away from the vacuum level, and decreasing the wurtzite crystallinity.

A novel method for detection of phosphorylation in single cells by surface enhanced Raman scattering (SERS) using composite organic-inorganic nanoparticles (COINs).

PubMed

Shachaf, Catherine M; Elchuri, Sailaja V; Koh, Ai Leen; Zhu, Jing; Nguyen, Lienchi N; Mitchell, Dennis J; Zhang, Jingwu; Swartz, Kenneth B; Sun, Lei; Chan, Selena; Sinclair, Robert; Nolan, Garry P

2009-01-01

Detection of single cell epitopes has been a mainstay of immunophenotyping for over three decades, primarily using fluorescence techniques for quantitation. Fluorescence has broad overlapping spectra, limiting multiplexing abilities. To expand upon current detection systems, we developed a novel method for multi-color immuno-detection in single cells using "Composite Organic-Inorganic Nanoparticles" (COINs) Raman nanoparticles. COINs are Surface-Enhanced Raman Scattering (SERS) nanoparticles, with unique Raman spectra. To measure Raman spectra in single cells, we constructed an automated, compact, low noise and sensitive Raman microscopy device (Integrated Raman BioAnalyzer). Using this technology, we detected proteins expressed on the surface in single cells that distinguish T-cells among human blood cells. Finally, we measured intracellular phosphorylation of Stat1 (Y701) and Stat6 (Y641), with results comparable to flow cytometry. Thus, we have demonstrated the practicality of applying COIN nanoparticles for measuring intracellular phosphorylation, offering new possibilities to expand on the current fluorescent technology used for immunoassays in single cells.

A Novel Method for Detection of Phosphorylation in Single Cells by Surface Enhanced Raman Scattering (SERS) using Composite Organic-Inorganic Nanoparticles (COINs)

PubMed Central

Shachaf, Catherine M.; Elchuri, Sailaja V.; Koh, Ai Leen; Zhu, Jing; Nguyen, Lienchi N.; Mitchell, Dennis J.; Zhang, Jingwu; Swartz, Kenneth B.; Sun, Lei; Chan, Selena; Sinclair, Robert; Nolan, Garry P.

2009-01-01

Background Detection of single cell epitopes has been a mainstay of immunophenotyping for over three decades, primarily using fluorescence techniques for quantitation. Fluorescence has broad overlapping spectra, limiting multiplexing abilities. Methodology/Principal Findings To expand upon current detection systems, we developed a novel method for multi-color immuno-detection in single cells using “Composite Organic-Inorganic Nanoparticles” (COINs) Raman nanoparticles. COINs are Surface-Enhanced Raman Scattering (SERS) nanoparticles, with unique Raman spectra. To measure Raman spectra in single cells, we constructed an automated, compact, low noise and sensitive Raman microscopy device (Integrated Raman BioAnalyzer). Using this technology, we detected proteins expressed on the surface in single cells that distinguish T-cells among human blood cells. Finally, we measured intracellular phosphorylation of Stat1 (Y701) and Stat6 (Y641), with results comparable to flow cytometry. Conclusions/Significance Thus, we have demonstrated the practicality of applying COIN nanoparticles for measuring intracellular phosphorylation, offering new possibilities to expand on the current fluorescent technology used for immunoassays in single cells. PMID:19367337

Detection of nasopharyngeal cancer using confocal Raman spectroscopy and genetic algorithm technique

NASA Astrophysics Data System (ADS)

Li, Shao-Xin; Chen, Qiu-Yan; Zhang, Yan-Jiao; Liu, Zhi-Ming; Xiong, Hong-Lian; Guo, Zhou-Yi; Mai, Hai-Qiang; Liu, Song-Hao

2012-12-01

Raman spectroscopy (RS) and a genetic algorithm (GA) were applied to distinguish nasopharyngeal cancer (NPC) from normal nasopharyngeal tissue. A total of 225 Raman spectra are acquired from 120 tissue sites of 63 nasopharyngeal patients, 56 Raman spectra from normal tissue and 169 Raman spectra from NPC tissue. The GA integrated with linear discriminant analysis (LDA) is developed to differentiate NPC and normal tissue according to spectral variables in the selected regions of 792-805, 867-880, 996-1009, 1086-1099, 1288-1304, 1663-1670, and 1742-1752 cm-1 related to proteins, nucleic acids and lipids of tissue. The GA-LDA algorithms with the leave-one-out cross-validation method provide a sensitivity of 69.2% and specificity of 100%. The results are better than that of principal component analysis which is applied to the same Raman dataset of nasopharyngeal tissue with a sensitivity of 63.3% and specificity of 94.6%. This demonstrates that Raman spectroscopy associated with GA-LDA diagnostic algorithm has enormous potential to detect and diagnose nasopharyngeal cancer.

Spontaneous Raman Scattering Diagnostics for High-pressure Gaseous Flames

NASA Technical Reports Server (NTRS)

Kojima, Jun; Nguyen, Quang-Viet; Reddy, D. R. (Technical Monitor)

2002-01-01

A high-pressure (up to 60 atm) gaseous burner facility with optical access that provides steady, reproducible flames with high precision, and the ability to use multiple fuel/oxidizer combinations has been developed. In addition, a high-performance spontaneous Raman scattering system for use in the above facility has also been developed. Together, the two systems will be used to acquire and establish a comprehensive Raman scattering spectral database for use as a quantitative high-pressure calibration of single-shot Raman scattering measurements in high-pressure combustion systems. Using these facilities, the Raman spectra of H2-Air flames were successfully measured at pressures up to 20 atm. The spectra demonstrated clear rotational and ro-vibrational Raman features of H2, N2, and H2O. theoretical Raman spectra of pure rotational H2, vibrational H2, and vibrational N2 were calculated using a classical harmonic-oscillator model with pressure broadening effects and fitted to the data. At a gas temperature of 1889 K for a phi = 1.34 H2-Air flame, the model and the data showed good agreement, confirming a ro-vibrational equilibrium temperature.

Raman scattering of Cisplatin near silver nanoparticles

NASA Astrophysics Data System (ADS)

Mirsaleh-Kohan, Nasrin; Duplanty, Michael; Torres, Marjorie; Moazzezi, Mojtaba; Rostovtsev, Yuri V.

2018-03-01

The Raman scattering of Cisplatin (the first generation of anticancer drugs) has been studied. In the presence of silver nanoparticles, strong modifications of Raman spectra have been observed. The Raman frequencies have been shifted and the line profiles are broadened. We develop a theoretical model to explain the observed features of the Raman scattering. The model takes into account self-consistently the interaction of molecules with surface plasmonic waves excited in the silver nanoparticles, and it provides a qualitative agreement with the observed Raman spectra. We have demonstrated that the using silver nanoparticles can increase sensitivity of the technique, and potentially it has a broader range of applications to both spectroscopy and microscopy.

FT-IR, FT-Raman, UV-visible, and NMR spectroscopy and vibrational properties of the labdane-type diterpene 13-epi-sclareol.

PubMed

Chain, Fernando E; Leyton, Patricio; Paipa, Carolina; Fortuna, Mario; Brandán, Silvia A

2015-03-05

In this work, FT-IR, FT-Raman, UV-Visible and NMR spectroscopies and density functional theory (DFT) calculations were employed to study the structural and vibrational properties of the labdane-type diterpene 13-epi-sclareol using the hybrid B3LYP method together with the 6-31G(∗) basis set. Three stable structures with minimum energy found on the potential energy curves (PES) were optimized, and the corresponding molecular electrostatic potentials, atomic charges, bond orders, stabilization energies and topological properties were computed at the same approximation level. The complete assignment of the bands observed in the vibrational spectrum of 13-epi-sclareol was performed taking into account the internal symmetry coordinates for the three structures using the scaled quantum mechanical force field (SQMFF) methodology at the same level of theory. In addition, the force constants were calculated and compared with those reported in the literature for similar compounds. The predicted vibrational spectrum and the calculated (1)H NMR and (13)C NMR chemical shifts are in good agreement with the corresponding experimental results. The theoretical UV-Vis spectra for the most stable structure of 13-epi-sclareol demonstrate a better correlation with the corresponding experimental spectrum. The study of the three conformers by means of the theory of atoms in molecules (AIM) revealed different H bond interactions and a strong dependence of the interactions on the distance between the involved atoms. Furthermore, the natural bond orbital (NBO) calculations showed the characteristics of the electronic delocalization for the two six-membered rings with chair conformations. Copyright © 2014 Elsevier B.V. All rights reserved.

Discrimination of selected species of pathogenic bacteria using near-infrared Raman spectroscopy and principal components analysis

NASA Astrophysics Data System (ADS)

de Siqueira e Oliveira, Fernanda SantAna; Giana, Hector Enrique; Silveira, Landulfo

2012-10-01

A method, based on Raman spectroscopy, for identification of different microorganisms involved in bacterial urinary tract infections has been proposed. Spectra were collected from different bacterial colonies (Gram-negative: Escherichia coli, Klebsiella pneumoniae, Proteus mirabilis, Pseudomonas aeruginosa and Enterobacter cloacae, and Gram-positive: Staphylococcus aureus and Enterococcus spp.), grown on culture medium (agar), using a Raman spectrometer with a fiber Raman probe (830 nm). Colonies were scraped from the agar surface and placed on an aluminum foil for Raman measurements. After preprocessing, spectra were submitted to a principal component analysis and Mahalanobis distance (PCA/MD) discrimination algorithm. We found that the mean Raman spectra of different bacterial species show similar bands, and S. aureus was well characterized by strong bands related to carotenoids. PCA/MD could discriminate Gram-positive bacteria with sensitivity and specificity of 100% and Gram-negative bacteria with sensitivity ranging from 58 to 88% and specificity ranging from 87% to 99%.

Analysis of Heme Iron Coordination in DGCR8: The Heme-Binding Component of the Microprocessor Complex.

PubMed

Girvan, Hazel M; Bradley, Justin M; Cheesman, Myles R; Kincaid, James R; Liu, Yilin; Czarnecki, Kazimierz; Fisher, Karl; Leys, David; Rigby, Stephen E J; Munro, Andrew W

2016-09-13

DGCR8 is the RNA-binding partner of the nuclease Drosha. Their complex (the "Microprocessor") is essential for processing of long, primary microRNAs (pri-miRNAs) in the nucleus. Binding of heme to DGCR8 is essential for pri-miRNA processing. On the basis of the split Soret ultraviolet-visible (UV-vis) spectrum of ferric DGCR8, bis-thiolate sulfur (cysteinate, Cys(-)) heme iron coordination of DGCR8 heme iron was proposed. We have characterized DGCR8 heme ligation using the Δ276 DGCR8 variant and combined electron paramagnetic resonance (EPR), magnetic circular dichroism (MCD), electron nuclear double resonance, resonance Raman, and electronic absorption spectroscopy. These studies indicate DGCR8 bis-Cys heme iron ligation, with conversion from bis-thiolate (Cys(-)/Cys(-)) axial coordination in ferric DGCR8 to bis-thiol (CysH/CysH) coordination in ferrous DGCR8. Pri-miRNA binding does not perturb ferric DGCR8's optical spectrum, consistent with the axial ligand environment being separated from the substrate-binding site. UV-vis absorption spectra of the Fe(II) and Fe(II)-CO forms indicate discrete species exhibiting peaks with absorption coefficients substantially larger than those for ferric DGCR8 and that previously reported for a ferrous form of DGCR8. Electron-nuclear double resonance spectroscopy data exclude histidine or water as axial ligands for ferric DGCR8 and favor bis-thiolate coordination in this form. UV-vis MCD and near-infrared MCD provide data consistent with this conclusion. UV-vis MCD data for ferrous DGCR8 reveal features consistent with bis-thiol heme iron coordination, and resonance Raman data for the ferrous-CO form are consistent with a thiol ligand trans to the CO. These studies support retention of DGCR8 cysteine coordination upon reduction, a conclusion distinct from those of previous studies of a different ferrous DGCR8 isoform.

Synthesis, characterization and photocatalysis enhancement of Eu2O3-ZnO mixed oxide nanoparticles

NASA Astrophysics Data System (ADS)

Mohamed, W. S.; Abu-Dief, Ahmed M.

2018-05-01

Pure ZnO nanoparticles (NPs) and mixed Eu2O3 and ZnO NPs with different Eu2O3 ratios (5%, 10%, and 15%) were synthesized by a precipitation method under optimum conditions. The synthesized samples were characterized by means of X-ray diffraction, scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy, transmission electron microscopy (TEM), Fourier transform infrared (FTIR) spectroscopy, Raman spectroscopy, and UV-vis diffuse reflectance spectroscopy. The as-synthesized ZnO NPs exhibit high phase purity and a highly crystalline wurtzite ZnO structure. The mixed Eu2O3 and ZnO NPs exhibit a Eu2O3 zinc blend phase in addition to the wurtzite phase of pure ZnO, confirming the high purity and good crystallinity of the as-synthesized samples. The high-purity formation of ZnO and Eu2O3 phases was confirmed by FTIR and Raman spectra. Microstructural analysis by SEM and TEM confirmed the sphere-like morphology with different particle sizes (29-40 nm) of the as-synthesized samples. The photocatalytic activities of pure ZnO NPs and mixed Eu2O3 and ZnO NPs for the degradation of methylene blue were evaluated under ultraviolet (UV) irradiation. The results show that Eu2O3 plays an important role in the enhancement of the photocatalytic properties of ZnO NPs. We found that mixed 5% Eu2O3 and ZnO NPs exhibit the highest photocatalytic activity (degradation efficiency of 96.5% after 180 min of UV irradiation) as compared with pure ZnO NPs (degradation efficiency of 80.3% after 180 min of UV irradiation). The increased photocatalytic activity of the optimum mixed Eu2O3 and ZnO NPs is due to the high crystallinity, high surface area with small particle size, and narrow energy gap.

Amide I vibrational mode suppression in surface (SERS) and tip (TERS) enhanced Raman spectra of protein specimens

PubMed Central

Kurouski, Dmitry; Postiglione, Thomas; Deckert-Gaudig, Tanja; Deckert, Volker; Lednev, Igor K.

2013-01-01

Surface- and tip-enhanced Raman spectroscopy (SERS and TERS) are modern spectroscopic techniques, which are becoming widely used and show a great potential for the structural characterisation of biological systems. Strong enhancement of the Raman signal through localised surface plasmon resonance enables chemical detection at the single-molecule scale. Enhanced Raman spectra collected from biological specimens, such as peptides, proteins or microorganisms, were often observed to lack the amide I band, which is commonly used as a marker for the interpretation of secondary protein structure. The cause of this phenomenon was unclear for many decades. In this work, we investigated this phenomenon for native insulin and insulin fibrils using both TERS and SERS and compared these spectra to the spectra of well-defined homo peptides. The results indicate that the appearance of the amide I Raman band does not correlate with the protein aggregation state, but is instead determined by the size of the amino acid side chain. For short model peptides, the absence of the amide I band in TERS and SERS spectra correlates with the presence of a bulky side chain. Homo-glycine and -alanine, which are peptides with small side chain groups (H and CH3, respectively), exhibited an intense amide I band in almost 100% of the acquired spectra. Peptides with bulky side chains, such as tyrosine and tryptophan, exhibited the amide I band in 70% and 31% of the acquired spectra, respectively. PMID:23330149

Potentiometric and Conductometric Study of Aqueous Solutions of Lithium and Sodium Salts of Poly(thiophen-3-ylacetic acid).

PubMed

Hostnik, Gregor; Vlachy, Vojko; Bondarev, Dmitrij; Jiří, Vohlídal; Cerar, Janez

2012-09-01

The title polymer, PTAA, practically free of ester groups was obtained by oxidative polymerization of methyl thiophen-3-ylacetate and subsequent basic hydrolysis of primary polymer. Poly(thiophen-3-ylacetic acid) has been thoroughly characterized by NMR, IR, Raman, and UV/Vis spectroscopy. The polyacid behavior during neutralization titrations with lithium and sodium hydroxides, carried out under nitrogen atmosphere, has been studied by conductometry and potentiometry. Henderson-Hasselbach plots of potentiometric titration curves show a break point at pH around 6, where the curve slope drops from 1.8 (at lower pH) to a value from 1.05 to 1.3 (at higher pH values). The UV/Vis spectra monitored during back titration show: (i) monotonous decrease of both λmax and εmax as pH decreases, (ii) the presence of the isosbestic point at 401 nm that can be ascribed to conformational transition of PTAA chains, and (iii) absence of the isosbestic point at 392 nm reported previously by other authors.

Studies on structural, optical, thermal and vibrational properties of thienyl chalcone derivative: 1-(4-Nitrophenyl)-3-(2-thienyl)prop-2-en-1-one

NASA Astrophysics Data System (ADS)

de Toledo, T. A.; da Costa, R. C.; Bento, R. R. F.; Al-Maqtari, H. M.; Jamalis, J.; Pizani, P. S.

2018-03-01

The structural, optical, thermal and vibrational properties of thienyl chalcone derivative 1-(4-Nitrophenyl)-3-(2-thienyl)prop-2-en-1-one, C13H9NO3S were investigated combining nuclear magnetic resonance (1H and 13C NMR), X-ray diffraction (XRD), Fourier transform infrared (FTIR), UV-vis spectroscopy at room temperature assisted by density functional theory (DFT) calculations and Raman scattering at the temperature range 303-463 K. The electronic properties, including excitation energies, oscillator strengths, HOMO and LUMO energies were calculated by time-dependent DFT (TD-DFT) to complement the experimental findings. The B3LYP/6-311G (d,p) (B3LYP/cc-pVTZ) calculations led to the identification of 'two minima on the molecules' potential energy surfaces. From these calculations, it was predicted that the most stable conformer for C13H9NO3S in the gas phase is founded at 0 K relationship to dihedral angle C8sbnd C9sbnd C10sbnd S1, in agreement with XRD results. The molecular plot showed that the electrical charge mobility in the molecule occurs from thiophene to benzene ring. The optical band gap energy calculated from the difference between HOMO and LUMO orbitals was founded to be ∼3.87 (3.82) eV, in close agreement with the experimental value of 2.94 eV. The comparison between experimental and theoretical vibrational spectra gives a precise knowledge of the fundamental vibrational modes and leads to a better interpretation of the experimental Raman and infrared spectra. As temperature increases from room temperature to 443 K, it was observed the current phonon anharmonicity effects associated to changes in the Raman line intensities, line-widths and red-shift, in special in the external modes region, whereas the internal modes region remains almost unchanged due its strong chemical bonds. Furthermore, C13H9NO3S goes to phase transition in the temperature range 453-463 K. This thermal phenomenon was attributed to the disappearance of the lattice (∼10-200 cm-1) and molecular (∼300-4000 cm-1) modes in the Raman spectra. Finally, the vibrational mode assignment given in terms of potential energy distribution (PED) analysis leads to a more comprehensive interpretation of the vibrational spectra and origin of instability the investigated material.

Complementary analysis of tissue homogenates composition obtained by Vis and NIR laser excitations and Raman spectroscopy.

PubMed

Staniszewska-Slezak, Emilia; Malek, Kamilla; Baranska, Malgorzata

2015-08-05

Raman spectroscopy and four excitation lines in the visible (Vis: 488, 532, 633 nm) and near infrared (NIR: 785 nm) were used for biochemical analysis of rat tissue homogenates, i.e. myocardium, brain, liver, lung, intestine, and kidney. The Vis Raman spectra are very similar for some organs (brain/intestines and kidney/liver) and dominated by heme signals when tissues of lung and myocardium were investigated (especially with 532 nm excitation). On the other hand, the NIR Raman spectra are specific for each tissue and more informative than the corresponding ones collected with the Vis excitations. The spectra analyzed without any special pre-processing clearly illustrate different chemical composition of each tissue and give information about main components e.g. lipids or proteins, but also about the content of some specific compounds such as amino acid residues, nucleotides and nucleobases. However, in order to obtain the whole spectral information about tissues complex composition the spectra of Vis and NIR excitations should be collected and analyzed together. A good agreement of data gathered from Raman spectra of the homogenates and those obtained previously from Raman imaging of the tissue cross-sections indicates that the presented here approach can be a method of choice for an investigation of biochemical variation in animal tissues. Moreover, the Raman spectral profile of tissue homogenates is specific enough to be used for an investigation of potential pathological changes the organism undergoes, in particular when supported by the complementary FTIR spectroscopy. Copyright © 2015 Elsevier B.V. All rights reserved.

The Use of Raman Tweezers and Chemometric Analysis to Discriminate the Urological Cell Lines, PC-3, LNCaP, BPH and MGH-U1

NASA Astrophysics Data System (ADS)

Harvey, T. J.; Hughes, C.; Ward, A. D.; Gazi, E.; Faria, E. Correia; Clarke, N. W.; Brown, M.; Snook, R.; Gardner, P.

2008-11-01

Here we report on investigations into using Raman optical tweezers to analyse both live and chemically fixed prostate and bladder cells. Spectra were subjected to chemometric analysis to discriminate and classify the cell types based on their spectra. Subsequent results revealed the potential of Raman tweezers as a potential clinical diagnostic tool.

Quantitative Analysis of Spectral Interference of Spontaneous Raman Scattering in High-Pressure Fuel-Rich H2-Air Combustion

NASA Technical Reports Server (NTRS)

Kojima, Jun; Nguyen, Quang-Viet

2004-01-01

We present a theoretical study of the spectral interferences in the spontaneous Raman scattering spectra of major combustion products in 30-atm fuel-rich hydrogen-air flames. An effective methodology is introduced to choose an appropriate line-shape model for simulating Raman spectra in high-pressure combustion environments. The Voigt profile with the additive approximation assumption was found to provide a reasonable model of the spectral line shape for the present analysis. The rotational/vibrational Raman spectra of H2, N2, and H2O were calculated using an anharmonic-oscillator model using the latest collisional broadening coefficients. The calculated spectra were validated with data obtained in a 10-atm fuel-rich H2-air flame and showed excellent agreement. Our quantitative spectral analysis for equivalence ratios ranging from 1.5 to 5.0 revealed substantial amounts of spectral cross-talk between the rotational H2 lines and the N2 O-/Q-branch; and between the vibrational H2O(0,3) line and the vibrational H2O spectrum. We also address the temperature dependence of the spectral cross-talk and extend our analysis to include a cross-talk compensation technique that removes the nterference arising from the H2 Raman spectra onto the N2, or H2O spectra.

Influence of Fe substitution on structure and Raman spectra of La0.67Sr0.33MnO3: Experimental and density functional studies

NASA Astrophysics Data System (ADS)

Astik, Nidhi M.; Soni, Himadri; Jha, Prafulla K.; Sathe, Vasant

2018-07-01

We present experimental and theoretical studies on the effect of Fe doping at Mn site, on the structural, morphological, electronic and vibrational properties of La0.67Sr0.3MnO3 nanoparticle. The samples of La0.67Sr0.3MnO3 and La0.67Sr0.33Mn1-xFexO3 (x = 0.15, 0.25 and 0.35) have been prepared by ball milling route. The phase purity of these samples has been confirmed using X-ray diffraction, while compositional analysis is done using EDAX. The morphological analysis done using scanning microscope indicates the agglomeration. The vibrational analysis which is done using Raman scattering and density functional theory (DFT) calculations show a substantial shift in A1g and Eg modes with Fe doping. The Eg modes become broader with Fe doping. The UV-visible spectra were measured in the energy range of 1-5 eV and compared with DFT results. The spin polarized density functional calculations show an increase in density of states at Fermi level due to MnO6octahedra modification and significant magnetism on Fe doping. The total magnetic moment is found from 16 to 17 μB for considered concentration. The effective mass of carriers is also calculated and found increasing with increasing concentration.

Raman spectra of single cells with autofluorescence suppression by modulated wavelength excitation

NASA Astrophysics Data System (ADS)

Krafft, Christoph; Dochow, Sebastian; Bergner, Norbert; Clement, Joachim H.; Praveen, Bavishna B.; Mazilu, Michael; Marchington, Rob; Dholakia, Kishan; Popp, Jürgen

2012-01-01

Raman spectroscopy is a non-invasive technique offering great potential in the biomedical field for label-free discrimination between normal and tumor cells based on their biochemical composition. First, this contribution describes Raman spectra of lymphocytes after drying, in laser tweezers, and trapped in a microfluidic environment. Second, spectral differences between lymphocytes and acute myeloid leukemia cells (OCI-AML3) are compared for these three experimental conditions. Significant similarities of difference spectra are consistent with the biological relevance of the spectral features. Third, modulated wavelength Raman spectroscopy has been applied to this model system to demonstrate background suppression. Here, the laser excitation wavelength of 785 nm was modulated with a frequency of 40 mHz by 0.6 nm. 40 spectra were accumulated with an exposure time of 5 seconds each. These data were subjected to principal component analysis to calculate modulated Raman signatures. The loading of the principal component shows characteristics of first derivatives with derivative like band shapes. The derivative of this loading corresponds to a pseudo-second derivative spectrum and enables to determine band positions.

Raman and Brillouin scattering studies of bulk 2H-WSe2

NASA Astrophysics Data System (ADS)

Akintola, K.; Andrews, G. T.; Curnoe, S. H.; Koehler, M. R.; Keppens, V.

2015-10-01

Raman and Brillouin spectroscopy were used to probe optic and acoustic phonons in bulk 2H-WSe2. Raman spectra collected under different polarization conditions allowed assignment of spectral peaks to various first- and second-order processes. In contrast to some previous studies, a Raman peak at  ˜259 cm-1was found not to be due to the A1g mode but to a second-order process involving phonons at either the M or K point of the Brillouin zone. Resonance effects due to excitons were also observed in the Raman spectra. Brillouin spectra of 2H-WSe2 contain a single peak doublet arising from a Rayleigh surface mode propagating with a velocity of 1340+/- 20 m s-1. This value is comparable to that estimated from Density Functional Theory calculations and also to those for the transition metal diselenides 2H-TaSe2 and 2H-NbSe2. Unlike these two materials, however, peaks arising from scattering via the elasto-optic mechanism were not observed in Brillouin spectra of WSe2 despite its lower opacity.

Wavelet data analysis of micro-Raman spectra for follow-up monitoring in oral pathologies

NASA Astrophysics Data System (ADS)

Camerlingo, C.; Zenone, F.; Perna, G.; Capozzi, V.; Cirillo, N.; Gaeta, G. M.; Lepore, M.

2008-02-01

A wavelet multi-component decomposition algorithm has been used for data analysis of micro-Raman spectra from human biological samples. In particular, measurements have been performed on some samples of oral tissue and blood serum from patients affected by pemphigus vulgaris at different stages. Pemphigus is a chronic, autoimmune, blistering disease of the skin and mucous membranes with a potentially fatal outcome. The disease is characterized histologically by intradermal blisters and immunopathologically by the finding of tissue bound and circulating immunoglobulin G (IgG) antibody directed against the cell surface of keratinocytes. More than 150 spectra were measured by means of a Raman confocal microspectrometer apparatus using the 632.8 nm line of a He-Ne laser source. A discrete wavelet transform decomposition method has been applied to the recorded Raman spectra in order to overcome related to low-level signals and the presence of noise and background components due to light scattering and fluorescence. The results indicate that appropriate data processing can contribute to enlarge the medical applications of micro-Raman spectroscopy.

Raman Spectroscopy for Analysis of Thorium Compounds

DOE Office of Scientific and Technical Information (OSTI.GOV)

Su, Yin-Fong; Johnson, Timothy J.; Olsen, Khris B.

2016-05-12

The thorium fuel cycle is an alternative to the uranium fuel cycle in that when 232Th is irradiated with neutrons it is converted to 233U, another fissile isotope. There are several chemical forms of thorium which are used in the Th fuel cycle. Recently, Raman spectroscopy has become a very portable and facile analytical technique useful for many applications, including e.g. determining the chemical composition of different materials such as for thorium compounds. The technique continues to improve with the development of ever-more sensitive instrumentation and better software. Using a laboratory Fourier-transform (FT)-Raman spectrometer with a 785 nm wavelength laser,more » we were able to obtain Raman spectra from a series of thorium-bearing compounds of unknown origin. These spectra were compared to the spectra of in-stock-laboratory thorium compounds including ThO2, ThF4, Th(CO3)2 and Th(C2O4)2. The unknown spectra showed very good agreement to the known standards, demonstrating the applicability of Raman spectroscopy for detection and identification of these nuclear materials.« less

Optical properties of MgF2 nano-composite films dispersed with noble metal nanoparticles synthesized by sol-gel method

NASA Astrophysics Data System (ADS)

Wakaki, Moriaki; Soujima, Nobuaki; Shibuya, Takehisa

2015-03-01

Porous MgF2 films synthesized by a sol-gel method exhibit the lowest refractive index among the dielectric optical materials and are the most useful materials for the anti-reflection coatings. On the other hand, surface plasmon resonance (SPR) absorptions of noble metal nanoparticles in various solid matrices have been extensively studied. New functional materials like a SERS (Surface Enhanced Raman Spectroscopy) tips are expected by synthesizing composite materials between porous MgF2 films featured by the network of MgF2 nanoparticles and noble metal nanoparticles introduced within the network. In this study, fundamental physical properties including morphology and optical properties are characterized for these materials to make clear the potential of the composite system. Composite materials of MgF2 films dispersed with noble metal (Ag, Au) nanoparticles were prepared using the sol-gel technique with various annealing temperatures and densities of noble metal nanoparticles. The structural morphology was analyzed by an X-ray diffractometer (XRD) and a scanning electron microscope (SEM). The size and shape distributions of the metal nanoparticles were observed using a transmission electron microscope (TEM). The optical properties of fabricated composite films were characterized by UV-Vis-NIR and FT-IR spectrophotometers. The absorption spectra due to the surface plasmon resonance (SPR) of the metal nanoparticles were analyzed using the dielectric function considering the effective medium approximation, typically Maxwell-Garnett model. The Raman scattering spectra were also studied to check the enhancement effect of specimen dropped on the MgF2: Ag nano-composite films deposited on Si substrate. Enhancement of the Raman intensity of pyridine solution specimen was observed.

Raman spectroscopy in biomedicine – non-invasive in vitro analysis of cells and extracellular matrix components in tissues

PubMed Central

Brauchle, Eva; Schenke-Layland, Katja

2013-01-01

Raman spectroscopy is an established laser-based technology for the quality assurance of pharmaceutical products. Over the past few years, Raman spectroscopy has become a powerful diagnostic tool in the life sciences. Raman spectra allow assessment of the overall molecular constitution of biological samples, based on specific signals from proteins, nucleic acids, lipids, carbohydrates, and inorganic crystals. Measurements are non-invasive and do not require sample processing, making Raman spectroscopy a reliable and robust method with numerous applications in biomedicine. Moreover, Raman spectroscopy allows the highly sensitive discrimination of bacteria. Rama spectra retain information on continuous metabolic processes and kinetics such as lipid storage and recombinant protein production. Raman spectra are specific for each cell type and provide additional information on cell viability, differentiation status, and tumorigenicity. In tissues, Raman spectroscopy can detect major extracellular matrix components and their secondary structures. Furthermore, the non-invasive characterization of healthy and pathological tissues as well as quality control and process monitoring of in vitro-engineered matrix is possible. This review provides comprehensive insight to the current progress in expanding the applicability of Raman spectroscopy for the characterization of living cells and tissues, and serves as a good reference point for those starting in the field. PMID:23161832

REMOTE RAMAN SPECTROSCOPY OF VARIOUS MIXED AND COMPOSITE MINERAL PHASES AT 7.2 m DISTANCE

NASA Technical Reports Server (NTRS)

Sharma, S. K.; Misra, A. K.; Ismail, Syed; Singh, U. N.

2006-01-01

Remote Raman [e.g.,1-5] and micro-Raman spectroscopy [e.g., 6-10] are being evaluated on geological samples for their potential applications on Mars rover or lander. The Raman lines of minerals are sharp and distinct. The Raman finger-prints of minerals do not shift appreciably but remain distinct even in sub-micron grains and, therefore, can be used for mineral identification in fine-grained rocks [e.g., 4,7]. In this work we have evaluated the capability of a directly coupled remote Raman system (co-axial configuration) for distinguishing the mineralogy of multiple crystals in the exciting laser beam. We have measured the Raman spectra of minerals in the near vicinity of each other and excited with a laser beam (e.g. -quartz (Qz) and K-feldspar (Feld) plates, each 5 mm thick). The spectra of composite transparent mineral plates of 5 mm thickness of -quartz and gypsum over calcite crystal were measured with the composite samples perpendicular to the exciting laser beam. The measurements of remote Raman spectra of various bulk minerals, and mixed and composite minerals with our portable UH remote Raman system were carried out at the Langley Research Center in a fully illuminated laboratory.

Principles and applications of Raman spectroscopy in pharmaceutical drug discovery and development.

PubMed

Gala, Urvi; Chauhan, Harsh

2015-02-01

In recent years, Raman spectroscopy has become increasingly important as an analytical technique in various scientific areas of research and development. This is partly due to the technological advancements in Raman instrumentation and partly due to detailed fingerprinting that can be derived from Raman spectra. Its versatility of applications, rapidness of collection and easy analysis have made Raman spectroscopy an attractive analytical tool. The following review describes Raman spectroscopy and its application within the pharmaceutical industry. The authors explain the theory of Raman scattering and its variations in Raman spectroscopy. The authors also highlight how Raman spectra are interpreted, providing examples. Raman spectroscopy has a number of potential applications within drug discovery and development. It can be used to estimate the molecular activity of drugs and to establish a drug's physicochemical properties such as its partition coefficient. It can also be used in compatibility studies during the drug formulation process. Raman spectroscopy's immense potential should be further investigated in future.

Raman spectroscopic study on the excystation process in a single unicellular organism amoeba (Acanthamoeba polyphaga)

NASA Astrophysics Data System (ADS)

Lin, Yu-Chung; Perevedentseva, Elena; Cheng, Chia-Liang

2015-05-01

An in vivo Raman spectroscopic study of amoeba (Acanthamoeba polyphaga) is presented. The changes of the spectra during the amoeba cyst activation and excystation are analyzed. The spectra show the changes of the relative intensities of bands corresponding to protein, lipid, and carotenoid components during cyst activation. The presence of carotenoids in the amoeba is observed via characteristic Raman bands. These signals in the Raman spectra are intense in cysts but decrease in intensity with cyst activation and exhibit a correlation with the life cycle of amoeba. This work demonstrates the feasibility of using Raman spectroscopy for the detection of single amoeba microorganisms in vivo and for the analysis of the amoeba life activity. The information obtained may have implications for the estimation of epidemiological situations and for the diagnostics and prognosis of the development of amoebic inflammations.

Raman spectroscopic study on the excystation process in a single unicellular organism amoeba (Acanthamoeba polyphaga).

PubMed

Lin, Yu-Chung; Perevedentseva, Elena; Cheng, Chia-Liang

2015-05-01

An in vivo Raman spectroscopic study of amoeba (Acanthamoeba polyphaga) is presented. The changes of the spectra during the amoeba cyst activation and excystation are analyzed. The spectra show the changes of the relative intensities of bands corresponding to protein, lipid, and carotenoid components during cyst activation. The presence of carotenoids in the amoeba is observed via characteristic Raman bands. These signals in the Raman spectra are intense in cysts but decrease in intensity with cyst activation and exhibit a correlation with the life cycle of amoeba. This work demonstrates the feasibility of using Raman spectroscopy for the detection of single amoeba microorganisms in vivo and for the analysis of the amoeba life activity. The information obtained may have implications for the estimation of epidemiological situations and for the diagnostics and prognosis of the development of amoebic inflammations.

Comparative study of mobile Raman instrumentation for art analysis.

PubMed

Vandenabeele, P; Castro, K; Hargreaves, M; Moens, L; Madariaga, J M; Edwards, H G M

2007-04-04

In archaeometry, one of the main concerns is to extract information from an art object, without damaging it. Raman spectroscopy is being applied in this research field with recent developments in mobile instrumentation facilitating more routine analysis. This research paper evaluates the performances of five mobile Raman instruments (Renishaw RA100, Renishaw Portable Raman Analyser RX210, Ocean Optics RSL-1, Delta Nu Inspector Raman, Mobile Art Analyser--MArtA) in three different laboratories. A set of samples were collected, in order to obtain information on the spectral performances of the instruments including: spectral resolution, calibration, laser cut-off, the ability to record spectra of organic and inorganic pigments through varnish layers and on the possibilities to identify biomaterials. Spectra were recorded from predefined regions on a canvas painting to simulate the investigation of artworks and the capabilities to record spectra from hardly accessible areas was evaluated.

Evaluation of linear discriminant analysis for automated Raman histological mapping of esophageal high-grade dysplasia

NASA Astrophysics Data System (ADS)

Hutchings, Joanne; Kendall, Catherine; Shepherd, Neil; Barr, Hugh; Stone, Nicholas

2010-11-01

Rapid Raman mapping has the potential to be used for automated histopathology diagnosis, providing an adjunct technique to histology diagnosis. The aim of this work is to evaluate the feasibility of automated and objective pathology classification of Raman maps using linear discriminant analysis. Raman maps of esophageal tissue sections are acquired. Principal component (PC)-fed linear discriminant analysis (LDA) is carried out using subsets of the Raman map data (6483 spectra). An overall (validated) training classification model performance of 97.7% (sensitivity 95.0 to 100% and specificity 98.6 to 100%) is obtained. The remainder of the map spectra (131,672 spectra) are projected onto the classification model resulting in Raman images, demonstrating good correlation with contiguous hematoxylin and eosin (HE) sections. Initial results suggest that LDA has the potential to automate pathology diagnosis of esophageal Raman images, but since the classification of test spectra is forced into existing training groups, further work is required to optimize the training model. A small pixel size is advantageous for developing the training datasets using mapping data, despite lengthy mapping times, due to additional morphological information gained, and could facilitate differentiation of further tissue groups, such as the basal cells/lamina propria, in the future, but larger pixels sizes (and faster mapping) may be more feasible for clinical application.

Matrix Effects in Quantitative Assessment of Pharmaceutical Tablets Using Transmission Raman and Near-Infrared (NIR) Spectroscopy.

PubMed

Sparén, Anders; Hartman, Madeleine; Fransson, Magnus; Johansson, Jonas; Svensson, Olof

2015-05-01

Raman spectroscopy can be an alternative to near-infrared spectroscopy (NIR) for nondestructive quantitative analysis of solid pharmaceutical formulations. Compared with NIR spectra, Raman spectra have much better selectivity, but subsampling was always an issue for quantitative assessment. Raman spectroscopy in transmission mode has reduced this issue, since a large volume of the sample is measured in transmission mode. The sample matrix, such as particle size of the drug substance in a tablet, may affect the Raman signal. In this work, matrix effects in transmission NIR and Raman spectroscopy were systematically investigated for a solid pharmaceutical formulation. Tablets were manufactured according to an experimental design, varying the factors particle size of the drug substance (DS), particle size of the filler, compression force, and content of drug substance. All factors were varied at two levels plus a center point, except the drug substance content, which was varied at five levels. Six tablets from each experimental point were measured with transmission NIR and Raman spectroscopy, and their concentration of DS was determined for a third of those tablets. Principal component analysis of NIR and Raman spectra showed that the drug substance content and particle size, the particle size of the filler, and the compression force affected both NIR and Raman spectra. For quantitative assessment, orthogonal partial least squares regression was applied. All factors varied in the experimental design influenced the prediction of the DS content to some extent, both for NIR and Raman spectroscopy, the particle size of the filler having the largest effect. When all matrix variations were included in the multivariate calibrations, however, good predictions of all types of tablets were obtained, both for NIR and Raman spectroscopy. The prediction error using transmission Raman spectroscopy was about 30% lower than that obtained with transmission NIR spectroscopy.

Optical properties of β-Ga2O3 nanorods synthesized by a simple and cost-effective method using egg white solution

NASA Astrophysics Data System (ADS)

Phumying, Santi; Labauyai, Sarawut; Chareonboon, Wirat; Phokha, Sumalin; Maensiri, Santi

2015-06-01

In this paper, we report on the optical properties of gallium oxide (β-Ga2O3) nanorods synthesized by a simple, cost-effective and environment-friendly method using gallium(III) nitrate hydrate and freshly extracted egg white (ovalbumin) in an aqueous medium. The extracted egg white acted as a matrix for the entrapment of gallium ions to generate a gelled precursor. The structure of the prepared samples was studied by X-ray diffraction and Raman spectroscopy to confirm the formation of β-Ga2O3 with a monoclinic structure after calcination of the precursor in air at 750, 850, and 950 °C for 3 h. Scanning electron microscopy images revealed the morphology and formation of nanorods with different sizes and shapes in the samples, resulting from the effect of the calcination temperature. All the samples showed a strong UV absorption with the band gap in the range of 3.87-3.97 eV. Room-temperature photoluminescence spectra of all the samples also showed a strong UV emission. The UV emission results were discussed based on the basis of charge recombination.

Spectral analysis of the structure of ultradispersed diamonds

NASA Astrophysics Data System (ADS)

Uglov, V. V.; Shimanski, V. I.; Rusalsky, D. P.; Samtsov, M. P.

2008-07-01

The structure of ultradispersed diamonds (UDD) is studied by spectral methods. The presence of diamond crystal phase in the UDD is found based on x-ray analysis and Raman spectra. The Raman spectra also show sp2-and sp3-hybridized carbon. Analysis of IR absorption spectra suggests that the composition of functional groups present in the particles changes during the treatment.

Spectral discrimination of serum from liver cancer and liver cirrhosis using Raman spectroscopy

NASA Astrophysics Data System (ADS)

Yang, Tianyue; Li, Xiaozhou; Yu, Ting; Sun, Ruomin; Li, Siqi

2011-07-01

In this paper, Raman spectra of human serum were measured using Raman spectroscopy, then the spectra was analyzed by multivariate statistical methods of principal component analysis (PCA). Then linear discriminant analysis (LDA) was utilized to differentiate the loading score of different diseases as the diagnosing algorithm. Artificial neural network (ANN) was used for cross-validation. The diagnosis sensitivity and specificity by PCA-LDA are 88% and 79%, while that of the PCA-ANN are 89% and 95%. It can be seen that modern analyzing method is a useful tool for the analysis of serum spectra for diagnosing diseases.

Stand-off detection of explosives vapors by resonance-enhanced Raman spectroscopy

NASA Astrophysics Data System (ADS)

Johansson, Ida; Ceco, Ema; Ehlerding, Anneli; Östmark, Henric

2013-06-01

This paper describes a system for stand-off vapor detection based on Resonant Raman spectroscopy, RRS. The system is a step towards a RRS LIDAR (Light Detection And Ranging) system, capable of detecting vapors from explosives and explosives precursors at long distances. The current system was used to detect the vapor of nitromethane and mononitrotoluene outdoors in the open air, at a stand-off distance of 11-13 meters. Also, the signal dependence upon irradiation wavelength and sample concentration was studied in controlled laboratory conditions. A tunable Optical Parametric Oscillator pumped by an Nd:YAG laser, with a pulse length of 6 ns, was operated in the UV range of interest, 210-400 nm, illuminating the sample vapor. The backscattered Raman signal was collected by a telescope and a roundto- slit optical fiber was used to transmit collected light to the spectrometer with minimum losses. A gated intensified charge-coupled device (ICCD) registered the spectra. The nitromethane cross section was resonance enhanced more than a factor 30 700, when measured at 220 nm, compared to the 532 nm value. The results show that a decrease in concentration can have a positive effect on the sensitivity of the system, due to a decrease in absorption and selfabsorption in the sample.

Spectroscopic characterization of mononitrosyl complexes in heme-nonheme diiron centers within the myoglobin scaffold (FeBMbs): relevance to denitrifying NO reductase†

PubMed Central

Hayashi, Takahiro; Miner, Kyle D.; Yeung, Natasha; Lin, Ying-Wu; Lu, Yi; Moënne-Loccoz, Pierre

2011-01-01

Denitrifying NO reductases are evolutionarily related to the superfamily of heme-copper terminal oxidases. These transmembrane protein complexes utilize a heme-nonheme diiron center to reduce two NO molecules to N2O. To understand this reaction, the diiron site has been modeled using sperm whale myoglobin as a scaffold and mutating distal residues Leu-29 and Phe-43 to histidines, and Val-68 to a glutamic acid to create a nonheme FeB site. The impact of incorporation of metal ions at this engineered site on the reaction of the ferrous heme with one NO was examined by UV-vis absorption, EPR, resonance Raman, and FTIR spectroscopies. UV-vis absorption and resonance Raman spectra demonstrate that the first NO molecule binds to the ferrous heme, but while the apoproteins and CuI- or ZnII-loaded proteins show characteristic EPR signatures of S = 1/2 six-coordinate heme {FeNO}7 species observable at liquid nitrogen temperature, the FeII-loaded proteins are EPR silent at ≥ 30 K. Vibrational modes from the heme [Fe-N-O] unit are identified in the RR and FTIR spectra using 15NO and 15N18O. The apo- and CuI-bound proteins exhibit ν(FeNO) and ν(NO) that are only marginally distinct from those reported for native myoglobin. However, binding of FeII at the FeB site shifts the heme ν(FeNO) by +17 cm-1 and the ν(NO) by -50 cm-1 to 1549 cm-1. This low ν(NO) is without precedent for a six-coordinate heme {FeNO}7 species and suggests that the NO group adopts a strong nitroxyl character stabilized by electrostatic interaction with the nearby nonheme FeII. Detection of a similarly low ν(NO) in the ZnII-loaded protein supports this interpretation. PMID:21634416

Raman Spectrograph for Ocean Worlds: Integrating Cavity Enhanced Spectroscopy

NASA Astrophysics Data System (ADS)

Retherford, Kurt D.; Moore, Thomas Z.; Davis, Michael W.; Howett, Carly; Soto, Alejandro; Raut, Ujjwal; Molyneux, Philippa M.; Nowicki, Keith; Mandt, Kathleen; E Schmidt, Britney; Mason, John; Yakovlev, Vladislav V.; Fry, Edward S.; RSO Team

2017-10-01

We present a new concept for a Raman spectrograph instrument designed to conduct high sensitivity measurements of biomarkers within Ocean Worlds environments. Our Raman Spectrograph for Ocean worlds (RSO) instrument is a UV+IR multi-laser enhanced Raman system capable of detecting complex, biologically-relevant molecular species mixed within icy surfaces in the outer Solar System. Incorporating two or more lasers with different excitation-emission pathways is crucial for thorough and definitive interpretation of the spectral fingerprints that identify unknown constituents within a sample. Our approach strives to remove fluorescence-driven ambiguities from degenerate, non-unique signatures expected for the most interesting trace constituents, i.e., those best revealed by UV excitation. Our design for deep-UV measurements is based on a novel high-reflectivity integrating cavity invented at Texas A&M University and further developed at SwRI. We report nanomole-range sensitivities of several complex organic molecules measured with our laboratory prototype cavities. Weak optical signals from Raman or fluorescence based instruments require sensitive low-noise detectors and long integration times, which by comparison are undesirable for the high radiation environment and limited battery power conditions anticipated for the Europa Lander mission. The two-to-five orders of magnitude enhanced sensitivity over standard Raman spectroscopy enabled by the integrating cavity enhanced spectroscopy technique makes it well suited for the Europa Lander payload and other future Ocean Worlds missions.