Sample records for absorption spectroscopic characterization

  1. Absorption spectroscopic study of EDA complexes of.

    PubMed

    Bhattacharya, S; Nayak, S K; Chattopadhyay, S K; Banerjee, M; Mukherjee, A K

    2001-02-01

    [70]Fullerene has been shown to form 1:1 molecular complexes with toluene, p-xylene, m-xylene, 1,2,4,5-tetramethyl benzene (durene) and pentamethyl benzene (PMB) in CCl4 medium by absorption spectroscopic method. Isosbestic points have been detected in case of complexes with PMB and durene. Charge transfer absorption band could not be detected but the intensity of the broad absorption band of C70 in CCl4 decreases systematically with increase in the concentration of the added methylbenzenes. From this trend the formation constants (Kc) of the complexes have been determined at three different wavelengths. The constancy of Kc with respect to change in the wavelength of measurement supports the view that complex of a single stoichiometry (1:1) is formed in each case. PMID:11206565

  2. Integrated approaches of x-ray absorption spectroscopic and electron microscopic techniques on zinc speciation and characterization in a final sewage sludge product.

    PubMed

    Kim, Bojeong; Levard, Clément; Murayama, Mitsuhiro; Brown, Gordon E; Hochella, Michael F

    2014-05-01

    Integration of complementary techniques can be powerful for the investigation of metal speciation and characterization in complex and heterogeneous environmental samples, such as sewage sludge products. In the present study, we combined analytical transmission electron microscopy (TEM)-based techniques with X-ray absorption spectroscopy (XAS) to identify and characterize nanocrystalline zinc sulfide (ZnS), considered to be the dominant Zn-containing phase in the final stage of sewage sludge material of a full-scale municipal wastewater treatment plant. We also developed sample preparation procedures to preserve the organic and sulfur-rich nature of sewage sludge matrices for microscopic and spectroscopic analyses. Analytical TEM results indicate individual ZnS nanocrystals to be in the size range of 2.5 to 7.5 nm in diameter, forming aggregates of a few hundred nanometers. Observed lattice spacings match sphalerite. The ratio of S to Zn for the ZnS nanocrystals is estimated to be 1.4, suggesting that S is present in excess. The XAS results on the Zn speciation in the bulk sludge material also support the TEM observation that approximately 80% of the total Zn has the local structure of a 3-nm ZnS nanoparticle reference material. Because sewage sludge is frequently used as a soil amendment on agricultural lands, future studies that investigate the oxidative dissolution rate of ZnS nanoparticles as a function of size and aggregation state and the change of Zn speciation during post sludge-processing and soil residency are warranted to help determine the bioavailability of sludge-born Zn in the soil environment. PMID:25602819

  3. Spectroscopic characterization of polymers: report

    SciTech Connect

    Koenig, J.L.

    1987-10-01

    Polymer characterization has presented major difficulties to the analytical chemist, who has had to develop techniques to cope with the challenge. Even the elementary problem of measuring molecular weight is not easy. Yet such measurements are essential, because the physical, mechanical, and flow properties depend on the length of the polymer chain. Because of the limited solubility and high viscosity of polymers, many classical techniques have been of little use or have had to be extensively modified to measure the molecular weight of polymers. Size-exclusion chromatographic techniques such as gel permeation have been developed to measure these molecular weight distributions. Special chromatographic instruments with a range of spectroscopic detectors (including infrared and laser-light scattering) have emerged commercially to aid the analytical chemist in the fundamental endeavor to measure the length of the polymer chain and its distribution. The author describes the advantages and disadvantages and disadvantages of various spectroscopic techniques.

  4. Synthesis, Spectroscopic and Thermal Characterization of Copper(II) and Iron(III) Complexes of Folic Acid and Their Absorption Efficiency in the Blood

    PubMed Central

    Hamed, E.; Attia, M. S.; Bassiouny, K.

    2009-01-01

    The absorption efficiency of any drug in blood is of prime importance. Compounds having the general formula: Kn[M(FO)2(H2O)2] · xH2O, where (M = Cu(II) or Fe(III), n = 2 or 1, FO = folate anion, x = 2 or 3 with respect), were prepared, and their absorption efficiency in rodent's blood was determined. The obtained compounds were characterized by elemental analysis, infrared as well as thermogravimetric analysis and polarization of light. The results suggest that the two folate complexes were formed in 1 : 2 molar ratio (metal : folic acid) which acted as a bidentate ligand through both carboxylic groups. Polarization of light proved that the folate complexes have symmetric geometry. Biological application proved that Cu(II) and Fe(III) complexes were absorbed more efficiently in rodent blood than folic acid itself. PMID:19746175

  5. Ultraviolet-Absorption Spectroscopic Biofilm Monitor

    NASA Technical Reports Server (NTRS)

    Micheels, Ronald H.

    2004-01-01

    An ultraviolet-absorption spectrometer system has been developed as a prototype instrument to be used in continuous, real-time monitoring to detect the growth of biofilms. Such monitoring is desirable because biofilms are often harmful. For example, biofilms in potable-water and hydroponic systems act as both sources of pathogenic bacteria that resist biocides and as a mechanism for deterioration (including corrosion) of pipes. Biofilms formed from several types of hazardous bacteria can thrive in both plant-growth solutions and low-nutrient media like distilled water. Biofilms can also form in condensate tanks in air-conditioning systems and in industrial heat exchangers. At present, bacteria in potable-water and plant-growth systems aboard the space shuttle (and previously on the Mir space station) are monitored by culture-plate counting, which entails an incubation period of 24 to 48 hours for each sample. At present, there are no commercially available instruments for continuous monitoring of biofilms in terrestrial or spaceborne settings.

  6. PRECISION RADIAL VELOCITIES OF DOUBLE-LINED SPECTROSCOPIC BINARIES WITH AN IODINE ABSORPTION CELL

    E-print Network

    PRECISION RADIAL VELOCITIES OF DOUBLE-LINED SPECTROSCOPIC BINARIES WITH AN IODINE ABSORPTION CELL October 15; accepted 2005 February 25 ABSTRACT A spectroscopic technique employing an iodine absorption the absorption cell technique to a new level by introducing an iodine (I2) absorption cell with the modeling

  7. Characterization of the physico-chemical properties of polymeric materials for aerospace flight. [differential thermal and atomic absorption spectroscopic analysis of nickel cadmium batteries

    NASA Technical Reports Server (NTRS)

    Rock, M.

    1981-01-01

    Electrodes and electrolytes of nickel cadmium sealed batteries were analyzed. Different thermal analysis of negative and positive battery electrodes was conducted and the temperature ranges of occurrence of endotherms indicating decomposition of cadmium hydroxide and nickel hydroxide are identified. Atomic absorption spectroscopy was used to analyze electrodes and electrolytes for traces of nickel, cadmium, cobalt, and potassium. Calibration curves and data are given for each sample analyzed. Instrumentation and analytical procedures used for each method are described.

  8. Vibrational spectroscopic characterization of fluoroquinolones

    NASA Astrophysics Data System (ADS)

    Neugebauer, U.; Szeghalmi, A.; Schmitt, M.; Kiefer, W.; Popp, J.; Holzgrabe, U.

    2005-05-01

    Quinolones are important gyrase inhibitors. Even though they are used as active agents in many antibiotics, the detailed mechanism of action on a molecular level is so far not known. It is of greatest interest to shed light on this drug-target interaction to provide useful information in the fight against growing resistances and obtain new insights for the development of new powerful drugs. To reach this goal, on a first step it is essential to understand the structural characteristics of the drugs and the effects that are caused by the environment in detail. In this work we report on Raman spectroscopical investigations of a variety of gyrase inhibitors (nalidixic acid, oxolinic acid, cinoxacin, flumequine, norfloxacin, ciprofloxacin, lomefloxacin, ofloxacin, enoxacin, sarafloxacin and moxifloxacin) by means of micro-Raman spectroscopy excited with various excitation wavelengths, both in the off-resonance region (532, 633, 830 and 1064 nm) and in the resonance region (resonance Raman spectroscopy at 244, 257 and 275 nm). Furthermore DFT calculations were performed to assign the vibrational modes, as well as for an identification of intramolecular hydrogen bonding motifs. The effect of small changes in the drug environment was studied by adding successively small amounts of water until physiological low concentrations of the drugs in aqueous solution were obtained. At these low concentrations resonance Raman spectroscopy proved to be a useful and sensitive technique. Supplementary information was obtained from IR and UV/vis spectroscopy.

  9. Vibrational spectroscopic characterization of fluoroquinolones.

    PubMed

    Neugebauer, U; Szeghalmi, A; Schmitt, M; Kiefer, W; Popp, J; Holzgrabe, U

    2005-05-01

    Quinolones are important gyrase inhibitors. Even though they are used as active agents in many antibiotics, the detailed mechanism of action on a molecular level is so far not known. It is of greatest interest to shed light on this drug-target interaction to provide useful information in the fight against growing resistances and obtain new insights for the development of new powerful drugs. To reach this goal, on a first step it is essential to understand the structural characteristics of the drugs and the effects that are caused by the environment in detail. In this work we report on Raman spectroscopical investigations of a variety of gyrase inhibitors (nalidixic acid, oxolinic acid, cinoxacin, flumequine, norfloxacin, ciprofloxacin, lomefloxacin, ofloxacin, enoxacin, sarafloxacin and moxifloxacin) by means of micro-Raman spectroscopy excited with various excitation wavelengths, both in the off-resonance region (532, 633, 830 and 1064 nm) and in the resonance region (resonance Raman spectroscopy at 244, 257 and 275 nm). Furthermore DFT calculations were performed to assign the vibrational modes, as well as for an identification of intramolecular hydrogen bonding motifs. The effect of small changes in the drug environment was studied by adding successively small amounts of water until physiological low concentrations of the drugs in aqueous solution were obtained. At these low concentrations resonance Raman spectroscopy proved to be a useful and sensitive technique. Supplementary information was obtained from IR and UV/vis spectroscopy. PMID:15820884

  10. Intrinsic Absorption Properties in Active Galaxies Observed with the Far Ultraviolet Spectroscopic Explorer

    E-print Network

    Jay P. Dunn; D. Michael Crenshaw; S. B. Kraemer; M. L. Trippe

    2008-07-01

    In a continuing survey of active galactic nuclei observed by the Far Ultraviolet Spectroscopic Explorer, we provide a deeper analysis of intrinsic absorption features found in 35 objects. Our survey is for low-redshift and moderate-luminosity objects, mostly Seyfert galaxies. We find a strong correlation between maximum radial velocity and luminosity. We also examine the relationships between equivalent width (EW), full width at half maximum, velocity: and continuum flux. The correlation between velocity and luminosity has been explored previously by Laor & Brandt, but at a significantly higher redshift and heavily weighted by broad absorption line quasars. We also have examined each object with multiple observations for variability in each of the aforementioned quantities, and have characterized the variation of EW with the continuum flux. In our survey, we find that variability of O VI lambda1032, lambda1038 is less common than of the UV doublets of CIV and N V seen at longer wavelengths, because the O VI absorption is usually saturated. Lyman beta absorption variability is more frequent. In a target-by-target examination we find that broad absorption line absorption and narrow absorption line absorbers are related in terms of maximum outflow velocity and luminosity, and both can be exhibited in similar luminosity objects. We also find one object that shows radial velocity change, seven objects that show equivalent width variability, and two objects that show either transverse velocity changes or a change in ionization.

  11. Spectroscopic Characterization of Streptavidin Functionalized Quantum dots1

    PubMed Central

    Wu, Yang; Lopez, Gabriel P.; Sklar, Larry A.; Buranda, Tione

    2007-01-01

    The spectroscopic properties of quantum dots can be strongly influenced by the conditions of their synthesis. In this work we have characterized several spectroscopic properties of commercial, streptavidin functionalized quantum dots (QD525, lot#1005-0045 and QD585, Lot#0905-0031 from Invitrogen). This is the first step in the development of calibration beads, to be used in a generalizable quantification scheme of multiple fluorescent tags in flow cytometry or microscopy applications. We used light absorption, photoexcitation, and emission spectra, together with excited-state lifetime measurements to characterize their spectroscopic behavior, concentrating on the 400-500nm wavelength ranges that are important in biological applications. Our data show an anomalous dependence of emission spectrum, lifetimes, and quantum yield (QY) on excitation wavelength that is particularly pronounced in the QD525. For QD525, QY values ranged from 0.2 at 480nm excitation up to 0.4 at 450nm and down again to 0.15 at 350nm. For QD585, QY values were constant at 0.2 between 500nm and 400nm, but dropped to 0.1 at 350nm. We attribute the wavelength dependences to heterogeneity in size and surface defects in the QD525, consistent with characteristics previously described in the chemistry literature. The results are discussed in the context of bridging the gap between what is currently known in the physical chemistry literature of quantum dots, and the quantitative needs of assay development in biological applications. PMID:17368555

  12. Spectroscopic Methods of Remote Sensing for Vegetation Characterization

    NASA Astrophysics Data System (ADS)

    Kokaly, R. F.

    2013-12-01

    Imaging spectroscopy (IS), often referred to as hyperspectral remote sensing, is one of the latest innovations in a very long history of spectroscopy. Spectroscopic methods have been used for understanding the composition of the world around us, as well as, the solar system and distant parts of the universe. Continuous sampling of the electromagnetic spectrum in narrow bands is what separates IS from previous forms of remote sensing. Terrestrial imaging spectrometers often have hundreds of channels that cover the wavelength range of reflected solar radiation, including the visible, near-infrared (NIR), and shortwave infrared (SWIR) regions. In part due to the large number of channels, a wide variety of methods have been applied to extract information from IS data sets. These can be grouped into several broad classes, including: multi-channel indices, statistical procedures, full spectrum mixing models, and spectroscopic methods. Spectroscopic methods carry on the more than 150 year history of laboratory-based spectroscopy applied to material identification and characterization. Spectroscopic methods of IS relate the positions and shapes of spectral features resolved by airborne and spaceborne sensors to the biochemical and physical composition of vegetation in a pixel. The chlorophyll 680nm, water 980nm, water 1200nm, SWIR 1700nm, SWIR 2100nm, and SWIR 2300nm features have been the subject of study. Spectral feature analysis (SFA) involves isolating such an absorption feature using continuum removal (CR) and calculating descriptors of the feature, such as center position, depth, width, area, and asymmetry. SFA has been applied to quantify pigment and non-pigment biochemical concentrations in leaves, plants, and canopies. Spectral feature comparison (SFC) utilizes CR of features in each pixel's spectrum and linear regression with continuum-removed features in reference spectra in a library of known vegetation types to map vegetation species and communities. SFC has been applied to map the distributions of minerals in soils and rocks; however, its application to characterize vegetation cover has been less widespread than SFA. Using IS data and the USGS Processing Routines in IDL for Spectroscopic Measurements (PRISM; http://pubs.usgs.gov/of/2011/1155/), this talk will examine requirements for and limitations in applying SFA and SFC to characterize vegetation. A time series of Airborne Visible/InfraRed Imaging Spectrometer (AVIRIS) data collected in the marshes of Louisiana following the Deepwater Horizon oil spill will be used to examine the impact of varying leaf water content on the shapes of the SWIR 1700, 2100, and 2300 nm features and the implications of these changes on vegetation identification and biochemical estimation. The USGS collection of HyMap data over Afghanistan, the largest terrestrial coverage of IS data to date, will be used to demonstrate the characterization of vegetation in arid and semi-arid regions, in which chlorophyll absorption is often weak and soil and rock mineral absorption features overlap vegetation features. Hyperion data, overlapping the HyMap data, will be presented to illustrate the complications that arise when signal-to-noise is low. The benefits of and challenges to applying a spectroscopic remote sensing approach to imaging spectrometer data will be discussed.

  13. Spectroscopic characterizations of organic/inorganic nanocomposites

    NASA Astrophysics Data System (ADS)

    Govani, Jayesh R.

    2009-12-01

    In the present study, pure and 0.3 wt%, 0.4 wt%, as well as 0.5 wt% L-arginine doped potassium dihydrogen phosphate (KDP) crystals were grown using solution growth techniques and further subjected to infrared (IR) absorption and Raman studies for confirmation of chemical group functionalization for investigating the incorporation mechanism of the L-arginine organic material into the KDP crystal structure. Infrared spectroscopic analysis suggests that structural changes are occurring for the L-arginine molecule as a result of its interaction with the KPD crystal. Infrared spectroscopic technique confirms the disturbance of the N-H, C-H and C-N bonds of the amino acid, suggesting successful incorporation of L-arginine into the KDP crystals. Raman analysis also reveals modification of the N-H, C-H and C-N bonds of the amino acid, implying successful inclusion of L-arginine into the KDP crystals. With the help of Gaussian software, a prediction of possible incorporation mechanisms of the organic material was obtained from comparison of the simulated infrared and Raman vibrational spectra with the experimental results. Furthermore, we also studied the effect of L-arginine doping on the thermal stability of the grown KDP crystal by employing Thermo gravimetric analysis (TGA). TGA suggests that increasing the level of L-arginine doping speeds the decomposition process and it weakens the KDP crystal, which indicates successful doping of the KDP crystals with L-arginine amino acid. Urinary stones are one of the oldest and most widely spread diseases in humans, animals and birds. Many remedies have been employed through the ages for the treatment of urinary stones. Recent medicinal measures reflect the modern advances, which are based on surgical removal, percutaneous techniques and extracorporeal shock wave lithotripsy (ESWL). Although these procedures are valuable, they are quite expensive for most people. Furthermore, recurrence of these diseases is awfully frequent with these procedures and the patients have to be subjected to careful follow up for several years. In contrast, in traditional therapeutic systems, most of the remedies were taken from plants and they proved to be helpful. However, the rationale behind their use is not thoroughly established through systematic pharmacological and clinical studies. In this regard, in the present investigation, with a view towards acquiring more insights, we have performed a detailed study of kidney stone formation and growth inhibition based on a traditional medicine approach with herbal extracts. The intricacy of calculi formation (i.e. nucleation, transformation, and aggregation) in a natural system such as urine is replicated to a certain extent in the present study by using a simplified single diffusion gel growth technique. Crystals were synthesized in a static gel environment without and with the presence of 1% and 2% concentration of Rotula Aquatica Lour (RAL) herbal extracts and further subjected to Raman, infrared absorption, X-ray photoelectron spectroscopy (XPS), and photoluminescence to analyze the effects of RAL on the growth of manganese-based calculi. Raman spectroscopy clearly provided an indication of the newberyite type of crystal as well as information on the chemical interaction between crystal and inhibitor. It also indicates the presence of organic components due to the RAL plant material. Infrared absorption spectroscopy indicates the presence of a strong reflecting component in the inhibitor as well as the newberyite type of crystal. XPS results indicated the presence of metallic zinc in the crystal with inhibitor. Furthermore, a considerable increase in the intensity of the magnesium and oxygen lines are noticed with the addition of the herbal extract, which suggest that the inhibitor chemical composition includes a substantial quantity of Mg and O. XPS analysis also demonstrates the presence of modified phosphorus oxidation states and suggest that they might make a contribution, too. The photoluminescence spectra of the crystal with inhibitor indicate the p

  14. Electrical Conductivity, Near-Infrared Absorption, and Thermal Lens Spectroscopic Studies of Percolation of Microemulsions

    E-print Network

    Reid, Scott A.

    Electrical Conductivity, Near-Infrared Absorption, and Thermal Lens Spectroscopic Studies studied below and above the percolation thresholds by electrical conductivity, near-infrared absorption quenching, neutron and light scattering, and electrical conductivity.1,2 However, in spite of these numerous

  15. Spectroscopic and Microscopic Characterization of Uranium Biomineralization in Myxococcus xanthus

    Microsoft Academic Search

    Fadwa Jroundi; Mohamed Larbi Merroun; José Maria Arias; André Rossberg; Sonja Selenska-Pobell; María Teresa González-Muñoz

    2007-01-01

    In this work, synchrotron-based X-ray absorption spectroscopy (XAS) and transmission electron microscopy (TEM) studies were carried out to elucidate at molecular scale the interaction mechanisms of Myxococcus xanthus with uranium at different pH values. Extended X-ray absorption fine structure (EXAFS) spectroscopic measurements showed that there are significant differences in the structural parameters of the U complexes formed by this bacterium

  16. Spectroscopic characterization and laser performance of diode-laser-pumped Nd: GdVO 4

    Microsoft Academic Search

    T. Jensen; V. G. Ostroumov; J.-P. Meyn; G. Huber; A. I. Zagumennyi; I. A. Shcherbakov

    1994-01-01

    We have carried out a detailed spectroscopic characterization of Nd: GdVO4, a new laser crystal with high effective absorption and emission cross sections. The accidental degeneracy of the upper4F3\\/2 laser level decreases the number of emission lines and creates -together with the anisotropic crystal field - high emission cross sections (7.6 × 10-19 cm2 at 1.06 µm and 300 K).

  17. Spectroscopic characterization of matrix isolated transient species

    NASA Astrophysics Data System (ADS)

    Lue, Christopher J.

    Part I describes the electronic spectra of various actinide containing compounds isolated in solid Ar using laser induced fluorescence (LIF) spectroscopy. The IR spectra for many of the same molecules were also recorded to aid in the identification of the fluorescing species in the LIF spectra. LIF spectra of UO2 isolated in solid Ar were recorded to investigate the interactions between actinide compounds and the rare gas matrix host. At the time of the experiments, it had been proposed that for UO2 and CUO, the interactions between the actinide containing molecule and Ar were strong enough to reorder the low-lying electronic states of the molecule. The experiments presented here showed no evidence of a reordering of low-lying electronic states based on comparison of the matrix spectra with theoretical predictions and gas phase spectra. An attempt to observe fluorescence from higher order uranium oxides was undertaken. A matrix was made by ablating U metal in a 1.0% O2/Ar mixture. UO3 was a probable molecule formed in the experiment. And, while absorptions belonging to UO3 were observed in IR spectra, LIF from the same matrix provided evidence that another molecule was fluorescing. Two different vibrational frequencies observed in the U-O symmetric stretching region were indicative of at least two low-lying electronic states in fluorescing molecule. UO3 is a closed shell molecule, and it is unlikely that it has any low-lying electronic states. Instead, the fluorescence was attributed to the open shell species (UO2)+(O2) -. LIF and IR spectra of thermally vaporized UCl4 isolated in solid Ar were recorded. UCl4 contains U(IV), which is the most stable oxidation state other than U(VI). Before these experiments, no fluorescence had been recorded that could be attributed to UCl4. Based on the observed vibrational frequencies in the fluorescence bands and the lifetime of the fluorescence, it was determine that there was at least two different fluorescing species. The short lived fluorescence was assigned to UCl 4, and the long-lived fluorescence was assigned to UOCl x. A low resolution map for the electronic levels in UOCl x was created. One of the first LIF studies of actinide containing molecules was performed by Grzybowski and Andrews[1] for UF6. While, the same group later recorded IR spectra for the UFx fragements[2], no fluorescence spectra were recorded. Spectra were recorded here of UF x fragments trapped in solid formed by either passing UF 6 through a microwave discharge or ablating U atoms into an F2 /Ar mixture. At the time of these experiments, the IR spectrometer was not available, and the molecules producing the fluorescence could not be deduced solely from the LIF spectra. A comparison with previous IR spectra[2] gave some indication of possible candidates. In all the experiments that investigated uranium containing matrices with IR spectroscopy, UN2 was observed. A search was undertaken to observe fluorescence from UN2. To insure a good yield of UN 2, 1% N2 was added to the carrier gas. The fluorescence spectra observed in these experiments was very intriguing, but was determined not to be coming from UN2, rather it appears to be coming from U atom clusters. However further experiments are necessary to confirm how many atoms are in the clusters. The final part of this thesis focuses on the electronic spectra of Xe-OH isolated solid Ar. Rare gas radical systems (Rg-X) such as Rg-OH are a good model system for studying weak, long range intermolecular interactions. It is known that when Rg=Xe, the strength of the interaction is much larger. For most Rg-OH complexes, the spectroscopic constants have been determined previously[3]. However, the constants for Xe-OH ares currently undetermined. Gas-phase studies were undertaken to determined these constants.[4] However, these experiments were in conflict with previous LIF spectra recorded in a matrix in which Goodman and Brus[5] observed that the A ? X emission band for Xe-OH is redshifted approximately 5,000 cm-1, which is unusually large. Additionally, they found

  18. A compact, cost-effective diffuse reflectance spectroscopic imaging system for quantitative tissue absorption and scattering

    NASA Astrophysics Data System (ADS)

    Lo, Justin Y.; Yu, Bing; Kuech, Thomas F.; Ramanujam, Nirmala

    2011-03-01

    There is clinical utility for a wide-field, spectroscopic imaging device for quantitative tissue absorption and scattering in a number of applications. We present the design of a compact, cost-effective spectroscopic imaging system, which consists of a broadband source with bandpass filters and a light guide for illumination and an inexpensive array of silicon photodiodes for detection. A single-pixel version of the system was tested in liquid phantoms simulating a wide range of human breast tissue and optical properties can be extracted with absorption and reduced scattering errors of 12.6% and 4.7%, respectively. We show proof-of-concept for performing fast, wide-field spectroscopic imaging with a simple design. The design also allows for scaling and expansion into higher pixel number and density in future iterations of custom device design, which includes in-house photodiode array fabrication processes and integration of on-board current amplifier circuits.

  19. Spectroscopic study of low-temperature hydrogen absorption in palladium

    NASA Astrophysics Data System (ADS)

    Ienaga, K.; Takata, H.; Onishi, Y.; Inagaki, Y.; Tsujii, H.; Kimura, T.; Kawae, T.

    2015-01-01

    We report real-time detection of hydrogen (H) absorption in metallic palladium (Pd) nano-contacts immersed in liquid H2 using inelastic electron spectroscopy (IES). After introduction of liquid H2, the spectra exhibit the time evolution from the pure Pd to the Pd hydride, indicating that H atoms are absorbed in Pd nano-contacts even at the temperature where the thermal process is not expected. The IES time and bias voltage dependences show that H absorption develops by applying bias voltage 30 ˜ 50 mV, which can be explained by quantum tunneling. The results represent that IES is a powerful method to study the kinetics of high density H on solid surface.

  20. Spectroscopic characterizations of organic\\/inorganic nanocomposites

    Microsoft Academic Search

    Jayesh R. Govani

    2009-01-01

    In the present study, pure and 0.3 wt%, 0.4 wt%, as well as 0.5 wt% L-arginine doped potassium dihydrogen phosphate (KDP) crystals were grown using solution growth techniques and further subjected to infrared (IR) absorption and Raman studies for confirmation of chemical group functionalization for investigating the incorporation mechanism of the L-arginine organic material into the KDP crystal structure. Infrared

  1. Fracture Characterization with NMR Spectroscopic Techniques

    Microsoft Academic Search

    C. T. Philip Chang; Jinli Qiao; Songhua Chen; A. Ted Watson

    1997-01-01

    Determination of suitable techniques and analyses that can be implemented by NMR well logging can greatly improve the characterization of underground petroleum reservoirs and aquifers. In this paper, the feasibility for using various NMR methods for detection and characterization of fractures is explored. Analyses of experimental data obtained with a variety of samples are presented. It is shown that relaxation

  2. Extraction, Purification, and Spectroscopic Characterization of a Mixture of Capsaicinoids

    ERIC Educational Resources Information Center

    Wagner, Carl E.; Cahill, Thomas M.; Marshall, Pamela A.

    2011-01-01

    This laboratory experiment provides a safe and effective way to instruct undergraduate organic chemistry students about natural-product extraction, purification, and NMR spectroscopic characterization. On the first day, students extract dried habanero peppers with toluene, perform a pipet silica gel column to separate carotenoids from…

  3. Vibrational Spectroscopic Characterization of Hematite, Maghemite, and Magnetite Thin

    E-print Network

    Vibrational Spectroscopic Characterization of Hematite, Maghemite, and Magnetite Thin Films University, 100 West 18th Avenue, Columbus, Ohio 43210 ABSTRACT Thin films of three iron oxide polymorphs, hematite, maghemite, and magnetite, were produced on KBr substrates using a conventional electron beam

  4. Electrodeposited C 60 n? films: Spectroscopic characterization

    Microsoft Academic Search

    M. T. Jones; P. Boulas; Q. Yan; B. Soucaze-Guillous; W. Koh; W. Kutner; R. Czemuszewicz; K. M. Kadish

    1995-01-01

    Raman and ESR spectroscopy were used to characterize electrodeposited films of C60 and Cs3C60. The observation of the diagnostic 1442 cm?1 band in the Raman spectrum of electrodeposited Cs3C60 confirms the ?3 oxidation state of C60.

  5. Impedance spectroscopic characterization of solar cell

    NASA Astrophysics Data System (ADS)

    Gautham, S.; Ramanathan, S.

    2014-10-01

    Impedance spectroscopy is used to characterize a commercial solar cell, at various dc bias potentials, under illumination and dark conditions. Interesting features are observed in medium and low frequency range, at large bias potentials. All the models reported in literature utilize combinations of resistances and capacitances, but the results indicate that inductances are necessary to model the actual solar cell, since an inductive loop is observed in the medium frequency range, especially at large bias potential, both under illumination and dark conditions. A new circuit which captures all the trends semi quantitatively is proposed to model the data.

  6. Metalorganic ion pairs with dithiooxalate d 8 metal donors and viologens. Spectroscopic, structural and electronic characterization

    Microsoft Academic Search

    Roland Benedix; Matthias Hofbauer; Mario Möbius; Falk Knoch

    1997-01-01

    Ion-pair charge-transfer complexes of the type {A2+[M(dto)2]2?}, where A2+ represents bipyridinium and phenanthrolinium compounds of different redox potential, M=Ni, Pd, Pt, and dto=1,2-dithiooxalate, were synthesized and characterized with respect to their spectroscopic, structural and electronic properties. A weak absorption band at the red-tail of the low-energy two-band system of the complex donor component can be attributed to the ion-pair charge-transfer

  7. Absorption spectroscopic study of EDA complexes of [70] fullerene with a series of methyl benzenes

    NASA Astrophysics Data System (ADS)

    Bhattacharya, Sumanta; Nayak, Sandip K.; Chattopadhyay, Subrata K.; Banerjee, Manas; Mukherjee, Asok K.

    2001-02-01

    [70]Fullerene has been shown to form 1:1 molecular complexes with toluene, p-xylene, m-xylene, 1,2,4,5-tetramethyl benzene (durene) and pentamethyl benzene (PMB) in CCl 4 medium by absorption spectroscopic method. Isosbestic points have been detected in case of complexes with PMB and durene. Charge transfer absorption band could not be detected but the intensity of the broad absorption band of C 70 in CCl 4 decreases systematically with increase in the concentration of the added methylbenzenes. From this trend the formation constants ( Kc) of the complexes have been determined at three different wavelengths. The constancy of Kc with respect to change in the wavelength of measurement supports the view that complex of a single stoichiometry (1:1) is formed in each case.

  8. Interaction between indium tin oxide nanoparticles and cytochrome c: A surface-enhanced Raman scattering and absorption spectroscopic study

    NASA Astrophysics Data System (ADS)

    Yang, Yimin; Du, Deyang; Kong, Fan; Fan, Jiyang; Qiu, Teng

    2015-06-01

    Indium-tin-oxide (ITO) nanoparticles were annealed in vacuum or reducing atmosphere to obtain different surface structures and investigate their influence on the adsorptive character and conformation of cytochrome c (Cyt c) molecule. Annealing-induced morphometric or structural changes of ITO nanoparticles were characterized by instruments of transmission electron microscopy, x-ray diffraction, and Raman scattering. Semiconductor ITO nanoparticle-enhanced Raman scattering of Cyt c was observed and the enhanced efficiency was found to closely depend on the surface structures which control the adsorbance of buffer anions needed for Cyt c loading. Direct electron transfer between Cyt c and ITO surface at the moment of molecular elastic collision was found and a reverse electron transfer process for O-terminated surface and metal-terminated surface was observed, according to absorption spectroscopic measurement on the residual solution.

  9. Spectroscopic characterization of femtosecond laser filament in argon gas

    SciTech Connect

    Liu, W.; Bernhardt, J.; Theberge, F.; Chin, S. L.; Chateauneuf, M.; Dubois, J. [Institute of Modern Optics, Nankai University, Key Laboratory of Opto-electronic Information Science and Technology, Education Ministry of China, Tianjin 300071 (China); Centre d'Optique, Photonique et Laser (COPL) and Departement de physique, de genie physique et d'optique, Universite Laval, Quebec, Quebec G1K 7P4 (Canada); Defence Research and Development Canada--Valcartier, 2459 Pie-XI Blvd. North, Quebec, Quebec, G3J 1X5 Canada (Canada)

    2007-08-01

    We report a spectroscopic approach to measure the plasma density and electron temperature inside a filament created by an intense femtosecond laser pulse in atmospheric pressure argon gas. The technique relies on the proportionality between the Stark broadened argon fluorescence line width due to electron impact and the plasma density, while the electron temperature is determined from the well known Boltzmann plot. The obtained maximum plasma density is about 5.5x10{sup 16} cm{sup -3}, and the electron temperature is about 5800 K. Our method provides a promising and convenient way to characterize the filament for further understanding the fundamental physics and potential applications of filamentation.

  10. Spectroscope

    NSDL National Science Digital Library

    McDonald Observatory

    2008-01-01

    In this activity, learners construct their own spectroscope as they explore and observe spectra from familiar light sources. Learners can be challenged to make technological improvements to their spectroscopes and/or participate in extension activities that expand their understanding of different kinds of spectra and sharpen their observing skills.

  11. Characterization of the UV absorption feature in asteroid 1 Ceres

    Microsoft Academic Search

    Jian-Yang Li

    2007-01-01

    We propose to obtain the UV spectrum of asteroid 1 Ceres from 120 nm to 200 nm with ACS\\/SBC objective prism to characterize the broad and deep absorption feature within this wavelength range as reported by ACS observations of Ceres in 2003\\/04 Li et al. 2006. Our scientific goals include, 1 to characterize the absorption band, 2 to determine the

  12. Spectroscope

    NSDL National Science Digital Library

    Oakland Discovery Center

    2011-01-01

    In this activity (posted on March 12, 2011), learners follow the steps to construct a spectroscope, a tool used to analyze light and color. First, learners use relatively simple materials to construct the device. Then, learners look through their spectroscopes at a variety of different light sources including incandescents, LEDs, compact fluorescents, sun light, etc. and compare what they observe. This resource includes a few examples of how certain chemicals form different colors of light.

  13. Characterization by spectroscopic Ellipsometry, the physical properties of silver nanoparticles.

    NASA Astrophysics Data System (ADS)

    Coanga, Jean-Maurice

    2013-04-01

    Physicists are able to change their minds through their experiments. I think it is time to go kick the curse and go further in research if we want a human future. I work in the Nano-Optics and Plasmonics research. I defined with ellipsomètrie the structure of new type of Nano particles of silver. It's same be act quickly to replace the old dirty leaded electronic-connexion chip and by the other hand to find a new way for the heath care of cancer disease by nanoparticles the next killers of bad cells. Silver nanoparticle layers are obtained by Spark Plasma Sintering are investigated as an alternative to lead alloy based material for solder joint in power mechatronics modules. These layers are characterized by mean of conventional techniques that is the dilatometry technique, the resistivity measurement through the van der Pauw method, and the flash laser technique. Furthermore, the nanoparticles of silver layer are deeply studied by UV-Visible spectroscopic ellipsometry. Spectroscopic angles parameters are determined in function of temperature and dielectric constants are deduced and analyzed through an optical model which takes into account a Drude and a Lorentz component within the Bruggeman effective medium approximation (EMA). The relaxation times and the electrical conductivity are plot in function of temperature. The obtained electrical conductivity give significant result in good agreement to those reported by four points electrical measurement method.

  14. HPLC AND Mass Spectroscopic Characterization of Mango (Mangifera Indica L.) Gallotannins Following Enzymatic Hydrolysis 

    E-print Network

    Krenek, Kimberly A.

    2009-06-09

    A Senior Scholars Thesis by KIMBERLY ANN KRENEK HPLC AND MASS SPECTROSCOPIC CHARACTERIZATION OF MANGO (Mangifera Indica L.) GALLOTANNINS FOLLOWING ENZYMATIC HYDROLYSIS Submitted to the Office of Undergraduate... Research Texas A&M University in partial fulfillment of the requirements for the designation as UNDERGRADUATE RESEARCH SCHOLAR April 2009 Major: Food Science HPLC AND MASS SPECTROSCOPIC CHARACTERIZATION OF MANGO (Mangifera...

  15. Thermal and Spectroscopic Characterization of a Proton Pumping Rhodopsin from an Extreme Thermophile*

    PubMed Central

    Tsukamoto, Takashi; Inoue, Keiichi; Kandori, Hideki; Sudo, Yuki

    2013-01-01

    So far retinylidene proteins (?rhodopsin) have not been discovered in thermophilic organisms. In this study we investigated and characterized a microbial rhodopsin derived from the extreme thermophilic bacterium Thermus thermophilus, which lives in a hot spring at around 75 °C. The gene for the retinylidene protein, named thermophilic rhodopsin (TR), was chemically synthesized with codon optimization. The codon optimized TR protein was functionally expressed in the cell membranes of Escherichia coli cells and showed active proton transport upon photoillumination. Spectroscopic measurements revealed that the purified TR bound only all-trans-retinal as a chromophore and showed an absorption maximum at 530 nm. In addition, TR exhibited both photocycle kinetics and pH-dependent absorption changes, which are characteristic of rhodopsins. Of note, time-dependent thermal denaturation experiments revealed that TR maintained its absorption even at 75 °C, and the denaturation rate constant of TR was much lower than those of other proton pumping rhodopsins such as archaerhodopsin-3 (200 ×), Haloquadratum walsbyi bacteriorhodopsin (by 10-times), and Gloeobacter rhodopsin (100 ×). Thus, these results suggest that microbial rhodopsins are also distributed among thermophilic organisms and have high stability. TR should allow the investigation of the molecular mechanisms of ion transport and protein folding. PMID:23740255

  16. Near-infrared diode laser based spectroscopic detection of ammonia: a comparative study of photoacoustic and direct optical absorption methods

    NASA Technical Reports Server (NTRS)

    Bozoki, Zoltan; Mohacsi, Arpad; Szabo, Gabor; Bor, Zsolt; Erdelyi, Miklos; Chen, Weidong; Tittel, Frank K.

    2002-01-01

    A photoacoustic spectroscopic (PAS) and a direct optical absorption spectroscopic (OAS) gas sensor, both using continuous-wave room-temperature diode lasers operating at 1531.8 nm, were compared on the basis of ammonia detection. Excellent linear correlation between the detector signals of the two systems was found. Although the physical properties and the mode of operation of both sensors were significantly different, their performances were found to be remarkably similar, with a sub-ppm level minimum detectable concentration of ammonia and a fast response time in the range of a few minutes.

  17. Cloning, expression, and spectroscopic characterization of Cucumis sativus stellacyanin in its nonglycosylated form.

    PubMed Central

    Nersissian, A. M.; Mehrabian, Z. B.; Nalbandyan, R. M.; Hart, P. J.; Fraczkiewicz, G.; Czernuszewicz, R. S.; Bender, C. J.; Peisach, J.; Herrmann, R. G.; Valentine, J. S.

    1996-01-01

    The cDNA encoding the 182 amino acid long precursor stellacyanin from Cucumis sativus was isolated and characterized. The protein precursor consists of four sequence domains: I, a 23 amino acid hydrophobic N-terminal signal peptide with features characteristic of secretory proteins; II, a 109 amino acid copper-binding domain; III, a 26 amino acid hydroxyproline- and serine-rich peptide characteristic of motifs found in the extension family, extracellular structural glycoproteins found in plant cell walls; and IV, a 22 amino acid hydrophobic extension. Maturation of the protein involves posttranslational processing of domains I and IV. The copper-binding domain (domain II), which shares high sequence identity with other stellacyanins, has been expressed without its carbohydrate attachment sites, refolded from the Escherichia coli inclusion bodies, purified, and characterized by electronic absorption, EPR, ESEEM, and RR spectroscopy. Its spectroscopic properties are nearly identical to those of stellacyanin from the Japanese lacquer tree Rhus vernicifera, the most extensively studied and best characterized stellacyanin, indicating that this domain folds correctly, even in the absence of its carbohydrate moiety. The presence of a hydroxyproline- and serine-rich domain III suggests that stellacyanin may have a function other than that of a diffusible electron transfer protein, conceivably participating in redox reactions localized at the plant cell wall, which are known to occur in response to wounding or infection of the plant. PMID:8931137

  18. Spectroscopic characterization of collagen cross-links in bone

    NASA Technical Reports Server (NTRS)

    Paschalis, E. P.; Verdelis, K.; Doty, S. B.; Boskey, A. L.; Mendelsohn, R.; Yamauchi, M.

    2001-01-01

    Collagen is the most abundant protein of the organic matrix in mineralizing tissues. One of its most critical properties is its cross-linking pattern. The intermolecular cross-linking provides the fibrillar matrices with mechanical properties such as tensile strength and viscoelasticity. In this study, Fourier transform infrared (FTIR) spectroscopy and FTIR imaging (FTIRI) analyses were performed in a series of biochemically characterized samples including purified collagen cross-linked peptides, demineralized bovine bone collagen from animals of different ages, collagen from vitamin B6-deficient chick homogenized bone and their age- and sex-matched controls, and histologically stained thin sections from normal human iliac crest biopsy specimens. One region of the FTIR spectrum of particular interest (the amide I spectral region) was resolved into its underlying components. Of these components, the relative percent area ratio of two subbands at approximately 1660 cm(-1) and approximately 1690 cm(-1) was related to collagen cross-links that are abundant in mineralized tissues (i.e., pyridinoline [Pyr] and dehydrodihydroxylysinonorleucine [deH-DHLNL]). This study shows that it is feasible to monitor Pyr and DHLNL collagen cross-links spatial distribution in mineralized tissues. The spectroscopic parameter established in this study may be used in FTIRI analyses, thus enabling the calculation of relative Pyr/DHLNL amounts in thin (approximately 5 microm) calcified tissue sections with a spatial resolution of approximately 7 microm.

  19. Surface spectroscopic characterization of cobalt-molybdenum-alumina catalysts

    SciTech Connect

    Chin, R.L.; Hercules, D.M.

    1982-08-05

    The structural characteristics of Co/Mo/Al/sub 2/O/sub 3/ hydrodesulfurization catalysts have been investigated with a variety of surface spectroscopic techniques: ESCA, ISS, and photoacoustic spectroscopy (PAS). All catalysts were prepared by sequential impregnation of Mo and Co into ..gamma..-Al/sub 2/O/sub 3/ with the Mo concentration held constant at 15% MoO/sub 3/ by weight as the cobalt concentration was varied from 1 to 9% CoO. In all catalysts interaction between Co and the support was observed which rendered a portion of the Co inert toward H/sub 2/ reduction and H/sub 2/S sulfidation. This interaction species (Co-t) is dominant for catalysts of low cobalt loading (i.e., 1% CoO). As the cobalt concentration is increased a new phase is formed characterized by interactions between Co and Mo. This species (Co-M) is produced up to a concentration of 7% CoO. Above this level, Co/sub 3/O/sub 4/ is formed. From ISS it was determined that the Co ions were situated beneath the Mo ions as Co-t and the Co-Mo interaction species. The presence of cobalt was found to have no effect on the reduction or sulfidation of Mo. 10 figures, 5 tables.

  20. Analyzing cell structure and dynamics with confocal light scattering and absorption spectroscopic microscopy

    NASA Astrophysics Data System (ADS)

    Qiu, Le; Vitkin, Edward; Fang, Hui; Zaman, Munir M.; Andersson, Charlotte; Salahuddin, Saira; Modell, Mark D.; Freedman, Steven D.; Hanlon, Eugene B.; Itzkan, Irving; Perelman, Lev T.

    2007-02-01

    We recently developed a new microscopic optical technique capable of noninvasive analysis of cell structure and cell dynamics on the submicron scale [1]. It combines confocal microscopy, a well-established high-resolution microscopic technique, with light scattering spectroscopy (LSS) and is called confocal light absorption and scattering spectroscopic (CLASS) microscopy. CLASS microscopy requires no exogenous labels and is capable of imaging and continuously monitoring individual viable cells, enabling the observation of cell and organelle functioning at scales on the order of 100 nm. To test the ability of CLASS microscopy to monitor cellular dynamics in vivo we performed experiments with human bronchial epithelial cells treated with DHA and undergoing apoptosis. The treated and untreated cells show not only clear differences in organelle spatial distribution but time sequencing experiments on a single cell show disappearance of certain types of organelles and change of the nuclear shape and density with the progression of apoptosis. In summary, CLASS microscopy provides an insight into metabolic processes within the cell and opens doors for the noninvasive real-time assessment of cellular dynamics. Noninvasive monitoring of cellular dynamics with CLASS microscopy can be used for a real-time dosimetry in a wide variety of medical and environmental applications that have no immediate observable outcome, such as photodynamic therapy, drug screening, and monitoring of toxins.

  1. Theory for the Spectroscopic Mode Frequencies and THz Absorption of Multiferroic BiFeO3

    NASA Astrophysics Data System (ADS)

    Fishman, Randy; Lee, Jun Hee

    2015-03-01

    A microscopic model for BiFeO3 that includes two Dzyaloshinskii-Moriya interactions and easy-axis anisotropy along the ferroelectric polarization predicts both the zero-field spectroscopic modes as well as their splitting and evolution in a magnetic field. Due to simultaneously broken time-reversal and spatial-inversion symmetries, the absorption of light changes slightly as the magnetic field or the direction of light propagation is reversed. We discuss three sets of physical mechanisms that contribute to the THz abosorption and directional dichroism (DD) of BiFeO3: spin current, magnetostriction, and anisotropy. First-principles calculations are used to obtain relationships among some of the polarization matrix elements induced by broken inversion symmetries in R3c structure. While our model nicely describes the DD along the magnetic field direction [1,-1,0], it fails to predict the weak DD observed for field along [1,1,0]. Research sponsored by the U.S. Department of Energy, Office of Basic Energy Sciences, Division of Materials Sciences and Engineering.

  2. PROCESSING OF HIGH LEVEL WASTE: SPECTROSCOPIC CHARACTERIZATION OF REDOX REACTIONS IN SUPERCRITICAL WATER

    EPA Science Inventory

    Current efforts are focused on the oxidative dissolution of chromium compounds found in Hanford tank waste sludge. Samples of chromium oxides and hydroxides with varying degrees of hydration are being characterized using Raman, FTIR, and XPS spectroscopic techniques. Kinetics of ...

  3. Spectroscopic method for determination of the absorption coefficient in brain tissue

    NASA Astrophysics Data System (ADS)

    Johansson, Johannes D.

    2010-09-01

    I use Monte Carlo simulations and phantom measurements to characterize a probe with adjacent optical fibres for diffuse reflectance spectroscopy during stereotactic surgery in the brain. Simulations and measurements have been fitted to a modified Beer-Lambert model for light transport in order to be able to quantify chromophore content based on clinically measured spectra in brain tissue. It was found that it is important to take the impact of the light absorption into account when calculating the apparent optical path length, lp, for the photons in order to get good estimates of the absorption coefficient, ?a. The optical path length was found to be well fitted to the equation lp=a+b ln(Is)+c ln(?a)+d ln(Is)ln(?a), where Is is the reflected light intensity for scattering alone (i.e., zero absorption). Although coefficients a-d calculated in this study are specific to the probe used here, the general form of the equation should be applicable to similar probes.

  4. Spectroscopic method for determination of the absorption coefficient in brain tissue.

    PubMed

    Johansson, Johannes D

    2010-01-01

    I use Monte Carlo simulations and phantom measurements to characterize a probe with adjacent optical fibres for diffuse reflectance spectroscopy during stereotactic surgery in the brain. Simulations and measurements have been fitted to a modified Beer-Lambert model for light transport in order to be able to quantify chromophore content based on clinically measured spectra in brain tissue. It was found that it is important to take the impact of the light absorption into account when calculating the apparent optical path length, lp, for the photons in order to get good estimates of the absorption coefficient, ?a. The optical path length was found to be well fitted to the equation lp=a+b ln(Is)+c ln(?a)+d ln(Is)ln(?a), where Is is the reflected light intensity for scattering alone (i.e., zero absorption). Although coefficients a-d calculated in this study are specific to the probe used here, the general form of the equation should be applicable to similar probes. PMID:21054121

  5. Absorption line shape recovery beyond the detection bandwidth limit: application to the precision spectroscopic measurement of the Boltzmann constant

    E-print Network

    François Rohart; Sinda Mejri; Papa Lat Tabara Sow; Sean K. Tokunaga; Christian Chardonnet; Benoît Darquié; H. Dinesan; E. Fasci; A. Castrillo; L. Gianfrani; Christophe Daussy

    2014-07-09

    A theoretical model of the influence of detection bandwidth properties on observed line shapes in laser absorption spectroscopy is described. The model predicts artificial frequency shifts, extra broadenings and line asymmetries which must be taken into account in order to obtain accurate central frequencies and other spectroscopic parameters. This reveals sources of systematic effects most probably underestimated so far potentially affecting spectroscopic measurements. This may impact many fields of research, from atmospheric and interstellar physics to precision spectroscopic measurements devoted to metrological applications, tests of quantum electrodynamics or other fundamental laws of nature. Our theoretical model is validated by linear absorption experiments performed on H2O and NH3 molecular lines recorded by precision laser spectroscopy in two distinct spectral regions, near- and mid-infrared. Possible means of recovering original line shape parameters or experimental conditions under which the detection bandwidth has a negligible impact, given a targeted accuracy, are proposed. Particular emphasis is put on the detection bandwidth adjustments required to use such high-quality molecular spectra for a spectroscopic determination of the Boltzmann constant at the 1 ppm level of accuracy.

  6. Structural and spectroscopic characterization of mixed planetary ices.

    PubMed

    Plattner, Nuria; Lee, Myung Won; Meuwly, Markus

    2010-01-01

    Mixed ices play a central role in characterizing the origin, evolution, stability and chemistry of planetary ice surfaces. Examples include the polar areas of Mars, the crust of the Jupiter moon Europa, or atmospheres of planets and their satellites, particularly in the outer solar system. Atomistic simulations using accurate representations of the interaction potentials have recently shown to be suitable to quantitatively describe both, the mid- and the far-infrared spectrum of mixed H2O/CO amorphous ices. In this work, molecular dynamics simulations are used to investigate structural and spectroscopic properties of mixed and crystalline ices containing H2O, CO and CO2. Particular findings include: (a) the sensitivity of the water bending mode to the local environment of the water molecules which, together with structural insights from MD simulations, provides a detailed picture for the relationship between spectroscopy and structure; and (b) the sensitivity of the low-frequency spectrum to the structure of the mixed CO2/H2O ice. Specifically, for mixed H2O/CO2 ices with low water contents isolated water molecules are found which give rise to a band shifted by only 12 cm(-1) from the gas-phase value whereas for increasing water concentration (for a 1 : 1 mixture) the band progressively shifts to higher frequency because water clusters can form. More generally it is found that changes in the ice structure due to the presence of CO2 are larger compared to changes induced by the presence of CO and that this difference is reflected in the shape of the water bending vibration. Thus, the water bending vibration appears to be a suitable diagnostic for structural and chemical aspects of mixed ices. PMID:21302549

  7. Functional and Spectroscopic Characterization of Chlamydomonas reinhardtii Truncated Hemoglobins

    PubMed Central

    Droghetti, Enrica; Tundo, Grazia R.; Sanz-Luque, Emanuel; Polticelli, Fabio; Visca, Paolo; Smulevich, Giulietta; Ascenzi, Paolo; Coletta, Massimo

    2015-01-01

    The single-cell green alga Chlamydomonas reinhardtii harbors twelve truncated hemoglobins (Cr-TrHbs). Cr-TrHb1-1 and Cr-TrHb1-8 have been postulated to be parts of the nitrogen assimilation pathway, and of a NO-dependent signaling pathway, respectively. Here, spectroscopic and reactivity properties of Cr-TrHb1-1, Cr-TrHb1-2, and Cr-TrHb1-4, all belonging to clsss 1 (previously known as group N or group I), are reported. The ferric form of Cr-TrHb1-1, Cr-TrHb1-2, and Cr-TrHb1-4 displays a stable 6cLS heme-Fe atom, whereas the hexa-coordination of the ferrous derivative appears less strongly stabilized. Accordingly, kinetics of azide binding to ferric Cr-TrHb1-1, Cr-TrHb1-2, and Cr-TrHb1-4 are independent of the ligand concentration. Conversely, kinetics of CO or NO2? binding to ferrous Cr-TrHb1-1, Cr-TrHb1-2, and Cr-TrHb1-4 are ligand-dependent at low CO or NO2? concentrations, tending to level off at high ligand concentrations, suggesting the presence of a rate-limiting step. In agreement with the different heme-Fe environments, the pH-dependent kinetics for CO and NO2?binding to ferrous Cr-TrHb1-1, Cr-TrHb1-2, and Cr-TrHb1-4 are characterized by different ligand-linked protonation events. This raises the question of whether the simultaneous presence in C. reinhardtii of multiple TrHb1s may be related to different regulatory roles. PMID:25993270

  8. Confocal Light Absorption and Scattering Spectroscopic (CLASS) imaging: From cancer detection to sub-cellular function

    NASA Astrophysics Data System (ADS)

    Qiu, Le

    Light scattering spectroscopy (LSS), an optical technique that relates the spectroscopic properties of light elastically scattered by small particles to their size, refractive index and shape, has been recently successfully employed for sensing morphological and biochemical properties of epithelial tissues and cells in vivo. LSS does not require exogenous markers, is non-invasive, and, due to its multispectral nature, can sense biological structures well beyond the diffraction limit. All that makes LSS be a very good candidate to be used both in clinical medicine for in vivo detection of disease and in cell biology to monitor cell function on the organelle scale. Recently we developed two LSS-based imaging modalities: clinical Polarized LSS (PLSS) Endoscopic Technique for locating early pre-cancerous changes in GI tract and Confocal Light Absorption and Scattering Spectroscopic (CLASS) Microscopy for studying cells in vivo without exogenous markers. One important application of the clinical PLSS endoscopic instrument, a noncontact scanning imaging device compatible with the standard clinical endoscopes and capable of detecting dysplastic changes, is to serve as a guide for biopsy in Barrett's esophagus (BE). The instrument detects parallel and perpendicular components of the polarized light, backscattered from epithelial tissues, and determines characteristics of epithelial nuclei from the residual spectra. It also can find tissue oxygenation, hemoglobin content and other properties from the diffuse light component. By rapidly scanning esophagus the PLSS endoscopic instrument makes sure the entire BE portion is scanned and examined for the presence of dysplasia. CLASS microscopy, on the other hand, combines principles of light scattering spectroscopy (LSS) with confocal microscopy. Its main purpose is to image cells on organelle scale in vivo without the use of exogenous labels which may affect the cell function. The confocal geometry selects specific region and images are obtained by scanning the confocal volume across the sample. The new beam scanning CLASS microscope is a significant improvement over the previous proof-of-principle device. With this new device we have already performed experiments to monitor morphological changes in cells during apoptosis, differentiated fetal from maternal nucleated red blood cells, and detected plasmon scattering spectra of single gold nanorod.

  9. Low-temperature and time-resolved spectroscopic characterization of the LOV2 domain of Avena sativa phototropin 1

    E-print Network

    van Stokkum, Ivo

    Low-temperature and time-resolved spectroscopic characterization of the LOV2 domain of Avena sativa) domains. The spectroscopic properties of the LOV2 domain of phototropin 1 of Avena sativa (oat) have been

  10. Characterizing Atmospheric Absorption for Precision Photometry

    Microsoft Academic Search

    R. Chris Smith; David Burke; Christopher Stubbs; Tim Axelrod; Chuck Claver; William High; Stephan Blondin; Abi Saha; Patrick Kelly

    2008-01-01

    For the next generation of ground-based imaging surveys, many of which will be attempting to achieve better than 1% photometry, precise calibration of all aspects of the observations will be a necessity. This focus on calibration together with the detailed characterization and understanding of possible systematic effects crucial in order to reach the scientific goals of LSST, as well as

  11. Silicon Heterojunction Solar Cell Characterization and Optimization Using In Situ and Ex Situ Spectroscopic Ellipsometry: Preprint

    SciTech Connect

    Levi, D.; Iwaniczko, E.; Page, M.; Branz, H.; Wang, T.

    2006-05-01

    We use in-situ and ex-situ spectroscopic ellipsometry to characterize the optical, electronic, and structural properties of individual layers and completed silicon heterojunction devices. The combination of in-situ measurements during thin film deposition with ex-situ measurements of completed devices allows us to understand both the growth dynamics of the materials and the effects of each processing step on material properties. In-situ ellipsometry measurements enable us to map out how the optical properties change with deposition conditions, pointing the way towards reducing the absorption loss and increasing device efficiency. We use the measured optical properties and thickness of the i-, n-, and p-layers in optical device modeling to determine how the material properties affect device performance. Our best solar energy conversion efficiencies are 16.9% for a non-textured, single-sided device with an aluminum back surface field contact on a p-type float zone silicon wafer, and 17.8% for a textured double-sided device on a p-type float zone silicon wafer.

  12. Photochemistry of Furyl- and Thienyldiazomethanes: Spectroscopic Characterization of Triplet 3-Thienylcarbene

    PubMed Central

    Pharr, Caroline R.; Kopff, Laura A.; Bennett, Brian; Reid, Scott A.; McMahon, Robert J.

    2014-01-01

    Photolysis (? > 543 nm) of 3-thienyldiazomethane (1), matrix isolated in Ar or N2 at 10 K, yields triplet 3-thienylcarbene (13) and ?-thial-methylenecyclopropene (9). Carbene 13 was characterized by IR, UV/vis, and EPR spectroscopy. The conformational isomers of 3-thienylcarbene (s-E and s-Z) exhibit an unusually large difference in zero-field splitting parameters in the triplet EPR spectrum (|D/hc| = 0.508 cm?1, |E/hc| = 0.0554 cm?1; |D/hc| = 0.579 cm?1, |E/hc| = 0.0315 cm?1). Natural Bond Orbital (NBO) calculations reveal substantially differing spin densities in the 3-thienyl ring at the positions adjacent to the carbene center, which is one factor contributing to the large difference in D values. NBO calculations also reveal a stabilizing interaction between the sp orbital of the carbene carbon in the s-Z rotamer of 13 and the antibonding ? orbital between sulfur and the neighboring carbon—an interaction that is not observed in the s-E rotamer of 13. In contrast to the EPR spectra, the electronic absorption spectra of the rotamers of triplet 3-thienylcarbene (13) are indistinguishable under our experimental conditions. The carbene exhibits a weak electronic absorption in the visible spectrum (?max = 467 nm) that is characteristic of triplet arylcarbenes. Although studies of 2-thienyldiazomethane (2), 3-furyldiazomethane (3), or 2-furyldiazomethane (4) provided further insight into the photochemical interconversions among C5H4S or C5H4O isomers, these studies did not lead to the spectroscopic detection of the corresponding triplet carbenes (2-thienylcarbene (11), 3-furylcarbene (23), or 2-furylcarbene (22), respectively). PMID:22463599

  13. Combined Mössbauer spectroscopic, multi-edge X-ray absorption spectroscopic, and density functional theoretical study of the radical SAM enzyme spore photoproduct lyase.

    PubMed

    Silver, Sunshine C; Gardenghi, David J; Naik, Sunil G; Shepard, Eric M; Huynh, Boi Hanh; Szilagyi, Robert K; Broderick, Joan B

    2014-03-01

    Spore photoproduct lyase (SPL), a member of the radical S-adenosyl-L-methionine (SAM) superfamily, catalyzes the direct reversal of the spore photoproduct, a thymine dimer specific to bacterial spores, to two thymines. SPL requires SAM and a redox-active [4Fe-4S] cluster for catalysis. Mössbauer analysis of anaerobically purified SPL indicates the presence of a mixture of cluster states with the majority (40 %) as [2Fe-2S](2+) clusters and a smaller amount (15 %) as [4Fe-4S](2+) clusters. On reduction, the cluster content changes to primarily (60 %) [4Fe-4S](+). The speciation information from Mössbauer data allowed us to deconvolute iron and sulfur K-edge X-ray absorption spectra to uncover electronic (X-ray absorption near-edge structure, XANES) and geometric (extended X-ray absorption fine structure, EXAFS) structural features of the Fe-S clusters, and their interactions with SAM. The iron K-edge EXAFS data provide evidence for elongation of a [2Fe-2S] rhomb of the [4Fe-4S] cluster on binding SAM on the basis of an Fe···Fe scatterer at 3.0 Å. The XANES spectra of reduced SPL in the absence and presence of SAM overlay one another, indicating that SAM is not undergoing reductive cleavage. The X-ray absorption spectroscopy data for SPL samples and data for model complexes from the literature allowed the deconvolution of contributions from [2Fe-2S] and [4Fe-4S] clusters to the sulfur K-edge XANES spectra. The analysis of pre-edge features revealed electronic changes in the Fe-S clusters as a function of the presence of SAM. The spectroscopic findings were further corroborated by density functional theory calculations that provided insights into structural and electronic perturbations that can be correlated by considering the role of SAM as a catalyst or substrate. PMID:24532333

  14. Surface spectroscopic characterization of cobalt-molybdenum-alumina catalysts

    Microsoft Academic Search

    Roland L. Chin; David M. Hercules

    1982-01-01

    The structural characteristics of Co\\/Mo\\/AlâOâ hydrodesulfurization catalysts have been investigated with a variety of surface spectroscopic techniques: ESCA, ISS, and photoacoustic spectroscopy (PAS). All catalysts were prepared by sequential impregnation of Mo and Co into ..gamma..-AlâOâ with the Mo concentration held constant at 15% MoOâ by weight as the cobalt concentration was varied from 1 to 9% CoO. In all

  15. Raman spectroscopic characterization on cervical neoplasm in biopsy direction

    NASA Astrophysics Data System (ADS)

    Shin, Hsiao Hsin; Tsai, Yan Sheng; Wang, Tao Yuan; Chu, Shou Chia; Chiang, Huihua Kenny

    2007-02-01

    Raman spectroscopy was applied to distinguish the spectroscopic information between normal cervical tissues (14) and cervical neoplasia (17), including low grade squamous intraepithelial lesions (6) and high grade squamous intraepithelial lesions (11). Standard pathological sections of these cervical tissues were measured from superficial to stroma layers. We have normalized significant Raman peaks, 1250 and 1579-1656 cm -1 by taking a ratio over a stationary Raman at 1004 cm -1, and successfully discriminated between normal and neoplasm cervical tissues.

  16. White-light continuum probed femtosecond time-resolved absorption spectroscopic measurement of ?-carotene under high pressure

    NASA Astrophysics Data System (ADS)

    Liu, Wei-Long; Zheng, Zhi-Ren; Zhang, Jian-Ping; Wu, Wen-Zhi; Li, Ai-Hua; Zhang, Wei; Huo, Ming-Ming; Liu, Zhi-Guo; Zhu, Rui-Bin; Zhao, Lian-Cheng; Su, Wen-Hui

    2012-04-01

    We have performed a femtosecond time-resolved absorption spectroscopic experiment of ?-carotene in n-hexane solution under high pressure up to ˜1.0 GPa. Using white-light continuum in the visible spectral region as probe light, we found that the energy level of S1 state descends, whereas its lifetime becomes longer with the rising pressure. We ascribe this tendency deviating from the energy gap law to the viscosity effects on the Cdbnd C stretching vibrations, which is fully consistent with the microviscosity theory. This Letter may provide some insights on the light harvesting and photoprotection functions of carotenoids in photosynthetic organisms.

  17. Characterization of potassium glycinate for carbon dioxide absorption purposes

    Microsoft Academic Search

    A. F. Portugal; P. W. J. Derks; G. F. Versteeg; F. D. Magalhães; A. Mendes

    2007-01-01

    Aqueous solutions of potassium glycinate were characterized for carbon dioxide absorption purposes. Density and viscosity of these solutions, with concentrations ranging from 0.1 to 3M, were determined at temperatures from 293 to 313K. Diffusivity of CO2 in solution was estimated applying the modified Stokes–Einstein relation. Solubilities of N2O at the same temperatures and concentrations were measured and the ion specific

  18. Spectroscopic characterization of true enzyme-substrate intermediates of aspartate aminotransferase trapped at subzero temperatures.

    PubMed

    Sterk, M; Gehring, H

    1991-11-01

    Absorption and circular dichroism spectra of stable enzyme-substrate intermediates of aspartate aminotransferase were recorded at subzero temperatures (down to -65 degrees C) in the cryosolvent water/methanol. The intermediates were formed either between the pyridoxal form of the enzyme and its amino acid substrates, or between the pyridoxamine form and its oxo acid substrates. Kd values determined by spectroscopic titration were very close to the Km values reported for the different substrates. The adsorption complex of the pyridoxal form was probably obtained on addition of cysteine sulfinate. This complex is characterized by an increased absorption at 430 nm together with a positive Cotton effect, as also observed in the case of the complex with the competitive inhibitor maleate indicating protonation of the internal aldimine. Addition of the substrates aspartate or glutamate to the pyridoxal form seemed to result in the direct accumulation of the external aldimine which showed a slight decrease in both the absorbance and the Cotton effect at 360 nm. Additionally, a bathochromic shift of 5 nm was observed in the case of glutamate. At 430 nm, only a minor increase in absorbance, but not in circular dichroism, was observed with aspartate, and no changes were found with glutamate and the substrate analog 2-methylaspartate, indicating a deprotonated external aldimine. Presumably, the ketimine intermediate was obtained on addition of the oxo acids 2-oxoglutarate or oxalacetate to the pyridoxamine form. The intermediate showed a slight bathochromic shift (2 nm) of the absorption band and decreased circular dichroism. On formation of the ketimine, a tyrosine residue, probably active-site Tyr225, becomes partly ionized. The finding that the external aldimine can probably be accumulated in the conversion of the pyridoxal to the pyridoxamine form with the natural substrates would confirm the proton abstraction at C alpha to be the rate-limiting step in the tautomerization, although with cysteine sulfinate, the formation of the external aldimine might contribute to the rate limitation. Accumulation of the ketimine in the reverse direction would indicate that the proton abstraction at C4' is rate-limiting in this half-reaction. The results demonstrate the feasibility of further structural investigations of true enzyme-substrate intermediates. PMID:1935964

  19. Characterization of the energy-dependent response of riometer absorption

    NASA Astrophysics Data System (ADS)

    Kellerman, A. C.; Shprits, Y. Y.; Makarevich, R. A.; Spanswick, E.; Donovan, E.; Reeves, G.

    2015-01-01

    Ground-based riometers provide an inexpensive means to continuously remote sense the precipitation of electrons in the dynamic auroral region of Earth's ionosphere. The energy-dependent relationship between riometer absorption and precipitating electrons is thus of great importance for understanding the loss of electrons from the Earth's magnetosphere. In this study, statistical and event-based analyses are applied to determine the energy of electrons to which riometers chiefly respond. Time-lagged correlation analysis of trapped to precipitating fluxes shows that daily averaged absorption best correlates with ˜60 keV trapped electron flux at zero-time lag, although large variability is observed across different phases of the solar cycle. High-time resolution statistical cross-correlation analysis between signatures observed by riometer stations, and assuming electron motion due to gradient and curvature drift, results in inferred energies of 10-100 keV, with a clear maximum in occurrence for 40-60 keV electrons. One event is considered in detail utilizing riometer absorption signatures obtained from several stations. The mean inferred energies for the initial rise time and peak of the absorption after correction for electric field effects were ˜70 keV and ˜60 keV, respectively. The analyses presented provide a means to characterize the energy of electrons to which riometers are responding in both a statistical sense and during the evolution of individual events.

  20. Comprehensive Spectroscopic Characterization of Model Aromatic Substituents of Lignin

    NASA Astrophysics Data System (ADS)

    Dean, Jacob C.; Vara, Vanesa Vaquero; Hotopp, Kelly M.; Dian, Brian C.; Zwier, Timothy S.

    2012-06-01

    2,6-Dimethoxyphenol (2,6-DMP) is a model compound with aromatic substitution similar to that in sinapyl alcohol, one of the three monomers that make up lignin. 2,6-DMP has been studied combining several spectroscopic techniques that span the microwave, infrared and ultraviolet regions. Spectra from laser-induced fluorescence excitation, IR-UV hole-burning, fluorescence dip IR, dispersed fluorescence and rotational spectra have allowed us to develop more insight to the structural details, intramolecular H-bonding and electronic excited states of this sinapyl alcohol analog. Coupling in the CH stretch region, broadening effects in the IR spectra and Coriolis coupling due to the OH tunneling coordinate in the rotational spectrum will be shown as we present this diverse set of experimental data involving transitions between different vibronic, vibrational and rotational levels of the molecule. These features will be compared to those in 2-methoxyphenol and 4-methyl-2,6-DMP during the discussion.

  1. Organometallic Synthesis and Spectroscopic Characterization of Manganese-Doped CdSe Nanocrystals

    E-print Network

    Griffin, Robert G.

    Organometallic Synthesis and Spectroscopic Characterization of Manganese-Doped CdSe Nanocrystals-VI semiconductor nanocrystals doped with transition metals has proved to be particularly difficult. In the case to the bulk material is the primary litmus test for doped nanocrystals. However, this emission only implies

  2. Biochemical and Spectroscopic Characterization of the Covalent Binding of Heme to Cytochrome b6

    E-print Network

    Biochemical and Spectroscopic Characterization of the Covalent Binding of Heme to Cytochrome b6 of the cytochrome b6f complex disclosed the unexpected presence of a new heme ci [Stroebel, D., Choquet, Y., Popot identify a Cys35-containing proteolytic fragment (Tyr25-Lys111) from cytochrome b6 as a peptide

  3. Photomask CD and LER characterization using Mueller matrix spectroscopic ellipsometry

    NASA Astrophysics Data System (ADS)

    Heinrich, A.; Dirnstorfer, I.; Bischoff, J.; Meiner, K.; Ketelsen, H.; Richter, U.; Mikolajick, T.

    2014-10-01

    Critical dimension and line edge roughness on photomask arrays are determined with Mueller matrix spectroscopic ellipsometry. Arrays with large sinusoidal perturbations are measured for different azimuth angels and compared with simulations based on rigorous coupled wave analysis. Experiment and simulation show that line edge roughness leads to characteristic changes in the different Mueller matrix elements. The influence of line edge roughness is interpreted as an increase of isotropic character of the sample. The changes in the Mueller matrix elements are very similar when the arrays are statistically perturbed with rms roughness values in the nanometer range suggesting that the results on the sinusoidal test structures are also relevant for "real" mask errors. Critical dimension errors and line edge roughness have similar impact on the SE MM measurement. To distinguish between both deviations, a strategy based on the calculation of sensitivities and correlation coefficients for all Mueller matrix elements is shown. The Mueller matrix elements M13/M31 and M34/M43 are the most suitable elements due to their high sensitivities to critical dimension errors and line edge roughness and, at the same time, to a low correlation coefficient between both influences. From the simulated sensitivities, it is estimated that the measurement accuracy has to be in the order of 0.01 and 0.001 for the detection of 1 nm critical dimension error and 1 nm line edge roughness, respectively.

  4. Vibrational spectroscopic characterization of wild growing mushrooms and toadstools

    NASA Astrophysics Data System (ADS)

    Moha?ek-Grošev, Vlasta; Božac, Romano; Puppels, Gerwin J.

    2001-12-01

    Recently, there has been increase of general interest in fungi because of the possible medical applications of their polysaccharide constituents called glucans, some of which are reported to have immunomodulatory properties. Since an extraction method can change the chemical composition of a substance, especially a delicate one such as fungal thallus, it is necessary and useful to know more about the studied matter in advance in order to choose the chemical procedure properly. We demonstrated the usefulness of vibrational spectroscopy in identifying different glucan types in various parts of intact fruiting bodies of Asco- and Basidiomycetes. Fourier transform-infrared (FT-IR) spectroscopy was used for obtaining vibrational spectra of spores and fruiting bodies of more than 70 species belonging to 37 different genera of wild growing mushrooms. The list of the bands in 750-950 cm -1 interval, assigned to ?- and ?-glucans, is provided for all species studied. Vibrational spectra in the interval 1000-1200 cm -1 could serve as an indicator of mushroom genus, although particular species cannot be identified spectroscopically. Great similarities in spectra of spores of the same genus, but different species, e.g. Tricholoma album and Trichloma sulphureum, were observed. On the other hand, spectra of cap, stalk and spores of the same mushroom show great differences, indicating variety in the chemical composition of different parts of the same fruiting body.

  5. New homotrinuclear lanthanide complexes: synthesis, characterization and spectroscopic study.

    PubMed

    Silva, Wagner E; Belian, Mônica Freire; Freire, Ricardo O; de Sá, Gilberto F; Alves, Severino

    2010-09-23

    This work presents the synthesis and spectroscopic study of new homotrinuclear (TRI) systems for photonics applications. The luminescence spectroscopy shows characteristics transitions of Eu(III) and Tb(III) ions. For the Gd(III) complexes, the triplets states were determined by phosphorescence measurement. The complexes’ coordination geometries were calculated using the Sparkle/AM1 model. For the europium systems, the Sparkle/AM1 geometries were used to calculate all details involved in the energy transfer process, and the theoretical quantum yields were determined. From an energy diagram, that estimates triplet levels, it was possible to understand some experimental phenomenon, such as weak luminescence for precursor complex (without heterocyclics ligands), and ligands emission in terbium complexes. Some of these observations can also be explained by the Jablonski diagrams that describe, based on theoretical calculations, all luminescent process. The synthesized complexes showed high values of quantum yield in ethanolic environment: 50% for EuTRIDipy, 26% EuTRITerpy, and 56% for EuTRIPhen complexes. PMID:20738128

  6. Thermal, spectroscopic, and ab initio structural characterization of carprofen polymorphs.

    PubMed

    Bruni, Giovanna; Gozzo, Fabia; Capsoni, Doretta; Bini, Marcella; Macchi, Piero; Simoncic, Petra; Berbenni, Vittorio; Milanese, Chiara; Girella, Alessandro; Ferrari, Stefania; Marini, Amedeo

    2011-06-01

    Commercial and recrystallized polycrystalline samples of carprofen, a nonsteroidal anti-inflammatory drug, were studied by thermal, spectroscopic, and structural techniques. Our investigations demonstrated that recrystallized sample, stable at room temperature (RT), is a single polymorphic form of carprofen (polymorph I) that undergoes an isostructural polymorphic transformation by heating (polymorph II). Polymorph II remains then metastable at ambient conditions. Commercial sample is instead a mixture of polymorphs I and II. The thermodynamic relationships between the two polymorphs were determined through the construction of an energy/temperature diagram. The ab initio structural determination performed on synchrotron X-Ray powder diffraction patterns recorded at RT on both polymorphs allowed us to elucidate, for the first time, their crystal structure. Both crystallize in the monoclinic space group type P2(1) /c, and the unit cell similarity index and the volumetric isostructurality index indicate that the temperature-induced polymorphic transformation I ? II is isostructural. Polymorphs I and II are conformational polymorphs, sharing a very similar hydrogen bond network, but with different conformation of the propanoic skeleton, which produces two different packing. The small conformational change agrees with the low value of transition enthalpy obtained by differential scanning calorimetry measurements and the small internal energy computed with density functional methods. PMID:21246561

  7. Spectroscopic Characterization of Plastic Optical Fibers Doped With Fluorene Oligomers

    Microsoft Academic Search

    MarÍa AsunciÓn Illarramendi; Joseba Zubia; Luca Bazzana; Gaizka Durana; Gotzon Aldabaldetreku; JosÉ RamÓn Sarasua

    2009-01-01

    The optical properties of four fluorene oligomers embedded in plastic optical fiber have been investigated by using steady-state luminescence technique. In particular, we study the dependence of the optical spectra with dopant oligofluorene, emission wavelength, excitation wavelength, and light propagation distance through the fiber. Using this information, we have characterized the optical loss in these doped optical fibers.

  8. Application of Spectroscopic Ellipsometry and Mueller Ellipsometry to Optical Characterization

    E-print Network

    Garcia-Caurel, Enric; Gaston, Jean-Paul; Yan, Li

    2012-01-01

    This article aims to provide a brief overview of both established and novel ellipsometry techniques, as well as their applications. Ellipsometry is an indirect optical technique in that information about the physical properties of a sample is obtained through modeling analysis. Standard ellipsometry is typically used to characterize optically isotropic bulk and/or layered materials. More advanced techniques like Mueller ellipsometry, also known as polarimetry in literature, are necessary for the complete and accurate characterization of anisotropic and/or depolarizing samples which occur in many instances, both in research and "real life" activities. In this article we cover three main areas of subject: basic theory of polarization, standard ellipsometry and Mueller ellipsometry. Section I is devoted to a short and pedagogical introduction of the formalisms used to describe light polarization. The following section is devoted to standard ellipsometry. The focus is on the experimental aspects, including both p...

  9. Spectroscopic characterization of a novel electronic brachytherapy system

    Microsoft Academic Search

    Derek Liu; Emily Poon; Magdalena Bazalova; Brigitte Reniers; Michael Evans; Thomas Rusch; Frank Verhaegen

    2008-01-01

    The Axxent developed by Xoft Inc. is a novel electronic brachytherapy system capable of generating x-rays up to 50 keV. These low energy photon-emitting sources merit attention not only because of their ability to vary the dosimetric properties of the radiation, but also because of the radiobiological effects of low energy x-rays. The objective of this study is to characterize

  10. Spectroscopic Characterization of Mineralogy Across Vesta: Evidence of Different Lithologies

    NASA Technical Reports Server (NTRS)

    De Sanotis, M. C.; Ammannito, E.; Filacchione, G.; Capria, M. T.; Tosi, F.; Capaccioni, F.; Zambon, F.; Carraro, F.; Fonte, S.; Frigeri, A.; Jaumann, R.; Magni, G.; Marchi, S.; McCord, T. B.; McFadden, L. A.; McSween, H. Y.; Mittlefehldt, D. W.; Nathues, A.; Palomba, E.; Pieters, C. M.; Raymond, C. A.; Russell, C. T.; Turrini, D.

    2012-01-01

    The average spectrum of Vesta, obtained by VIR in the range 0.25-5.1 microns, shows clear evidence of absorption bands due to pyroxenes and thermal emissions beyond 3.5 11m. Vesta shows considerable variability across its surface in terms of spectral reflectance and emission, band depths, bands widths and bands centers, reflecting a complex geological history. Vesta's average spectrum and inferred mineralogy resemble those of howardite meteorites. On a regional scale, significant deviations are seen: the south polar 500km Rheasilvia impact crater has a higher diogenitic component, and equatorial regions show a higher eucritic component. This lithologic distribution, with a concentration of Mg-pyroxenes in the Rheasilvia area, reinforces the hypothesis of a deeper diogenitic crust excavated by the impact that formed the Rheasilvia crater, and an upper eucritic crust, whose remnants are seen in the equatorial region. This scenario has implications for Vesta differentiation, consistent with magma ocean models. However, serial magmatism models could also have concentrated pyroxene cumulates in plutons emplaced within the lower crust,

  11. Spectroscopic Characterization of Oxime Ligands and Their Complexes

    Microsoft Academic Search

    Cumali Çelik; Zeynep Ulukanli; Mehmet Tümer; Selahattin Serin

    2003-01-01

    New imine–oxime ligands H3L–H3L have been obtained from reactions of the Schiff base ligands H2B–H2B with monochloroglyoxime. Mononuclear copper(II), cobalt(II), nickel(II), vanadyl(IV) and zinc(II) complexes of the imine–oxime ligands H3L–H3L have been prepared and characterized by elemental analyses, infrared and electronic spectra, magnetic moment and molar conductance data. The molar conductance data show that the complexes are non?electrolytes. When the

  12. NMR spectroscopic characterization of ?-cyclodextrin inclusion complex with vanillin

    NASA Astrophysics Data System (ADS)

    Pîrnau, Adrian; Bogdan, Mircea; Floare, Calin G.

    2009-08-01

    The inclusion of vanillin by ?-cyclodextrin was investigated by 1H NMR. The continuous variation technique was used to evidence the formation of soluble 1:1 complex in aqueous solution. The association constant of vanillin with ?-cyclodextrin has been obtained at 298 K by fitting the experimental chemical shifts differences, ??obs = ?free - ?obs of the observed guest and host protons, with a non-linear regression method. Besides the effective association constant, the fitting procedure allows a precise determination of all chemical shift parameters characterizing the pure complex. They can by used for an analysis of the geometry of the molecular complex in solution.

  13. Spectroscopic characterization of a novel electronic brachytherapy system.

    PubMed

    Liu, Derek; Poon, Emily; Bazalova, Magdalena; Reniers, Brigitte; Evans, Michael; Rusch, Thomas; Verhaegen, Frank

    2008-01-01

    The Axxent developed by Xoft Inc. is a novel electronic brachytherapy system capable of generating x-rays up to 50 keV. These low energy photon-emitting sources merit attention not only because of their ability to vary the dosimetric properties of the radiation, but also because of the radiobiological effects of low energy x-rays. The objective of this study is to characterize the x-ray source and to model it using the Geant4 Monte Carlo code. Spectral and attenuation curve measurements are performed at various peak voltages and angles and the source is characterized in terms of spectrum and half-value layers (HVLs). Also, the effects of source variation and source aging are quantified. Bremsstrahlung splitting, phase-space scoring and particle-tagging features are implemented in the Geant4 code, which is bench-marked against BEAMnrc simulations. HVLs from spectral measurements, attenuation curve measurements and Geant4 simulations mostly agree within uncertainty. However, there are discrepancies between measurements and simulations for photons emitted on the source transverse plane (90 degrees). PMID:18182687

  14. Crystal structure characterization as well as theoretical study of spectroscopic properties of novel Schiff bases containing pyrazole group

    NASA Astrophysics Data System (ADS)

    Guo, Jia; Ren, Tiegang; Zhang, Jinglai; Li, Guihui; Li, Weijie; Yang, Lirong

    2012-09-01

    A series of novel Schiff bases containing pyrazole group were synthesized using 1-aryl-3-methyl-4-benzoyl-5-pyrazolone and phenylenediamine as the starting materials. All as-synthesized Schiff bases were characterized by means of NMR, FT-IR, and MS; and the molecular geometries of two Schiff bases as typical examples were determined by means of single crystal X-ray diffraction. In the meantime, the ultraviolet-visible light absorption spectra and fluorescent spectra of various as-synthesized products were also measured. Moreover, the B3LYP/6-1G(d,p) method was used for the optimization of the ground state geometry of the Schiff bases; and the spectroscopic properties of the products were computed and compared with corresponding experimental data based on cc-pVTZ basis set of TD-B3LYP method. It has been found that all as-synthesized Schiff bases show a remarkable absorption peak in a wavelength range of 270-370 nm; and their maximum emission peaks are around 344 nm and 332 nm, respectively.

  15. Electronic absorption spectroscopic behavior and acidity constants of some new dinitrophenylhydrazone derivatives.

    PubMed

    Alizadeh, Kamal; Amraie, Abouzar

    2015-08-01

    In the present study, UV-visible electronic spectra of three new 2,4-dinitrophenylhydrazone derivatives (C1, C2 and C3) have been studied. Different bands observed have been assigned to the proper electronic transitions. The solvatochromic behaviors of these compounds were investigated by studying their electronic spectra in several organic solvents with different polarities. The longer wavelength band is assigned to an intermolecular charge transfer transition. The solvated H-bonding complexes formed between dimethylformamide and 2,4-dinitrophenylhydrazone derivatives were also investigated. ?G, and the Kf values of the molecular complexes formed in solution have been determined. Effects of temperature increase and concentration changes on the longer spectroscopic wavelength band of the studied compounds were investigated. In this work, the behavior of acidity constants of these compounds in different pH values is studied by a multiwavelength spectrophotometric method too. PMID:25827767

  16. Spectroscopic characterization of chrysotile asbestos from different regions

    NASA Astrophysics Data System (ADS)

    Risti?, Mira; Czakó-Nagy, Ilona; Musi?, Svetozar; Vértes, Attila

    2011-05-01

    Chrysotile asbestos from different geographic regions was characterized by 57Fe Mössbauer and FT-IR spectroscopies, and FE-SEM coupled with EDS. Mössbauer spectra showed incorporation of Fe(II) and Fe(III) into the crystal structure of chrysotile. The Fe(II)/Fe(III) ratios were calculated. The Fe(II) occupied the octahedral Mg(II) positions. Broadening of Mössbauer lines corresponding to the Fe(III) doublet indicated a possible presence of Fe(III) in tetrahedral and octahedral positions. In all samples magnetite (Fe 3-xO 4) was found as associated mineral. Changes in the FT-IR spectra of chrysotiles were assigned to structural incorporation of metal ions, such as iron or aluminium ions. The morphology of chrysotile asbestos was inspected by FE-SEM.

  17. GPI detailed spectroscopic and astrometric characterization of HR 8799cde.

    NASA Astrophysics Data System (ADS)

    Marois, Christian; Draper, Zack; Barman, Travis; Konopacky, Quinn; Patience, Jennifer; Ingraham, Patrick; Macintosh, Bruce; Lafreniere, David; Matthews, Brenda

    2014-08-01

    We are proposing deep high signal-to-noise ratio (SNR) Gemini Planet Imager (GPI) Y, J, H and K1/K2 spectroscopy/photometry of the three inner planets of HR 8799. With GPI's superior contrast, and our advanced data reduction and analysis pipeline, these observations will revolutionize our understanding of the system's planets by allowing, for the first time, detailed high-SNR near infrared spectroscopy of planet e, as well as complementary planet c and d spectroscopy at Y-, J-, H- and K-band. The data will also be used to derive highly accurate relative astrometry of the three planets, allowing for more precise orbital characterization and detection of acceleration, a key value to properly constrain the system&'s orbital configuration.

  18. X-ray absorption spectroscopic investigation of sulfur sites in coal: organic sulfur identification

    Microsoft Academic Search

    C. L. Spiro; J. Wong; F. W. Lytle; R. B. Greegor; D. H. Maylotte; S. H. Lamson

    1984-01-01

    High-resolution x-ray absorption spectroscopy was used to probe the chemical and structural environments of sulfur in coal. Measurement of the sulfur K-edge spectra down to 2472.0 electron volts under nonvacuum conditions was made possible in an all-helium path, and a Stern-Heald type ion chamber was used for fluorescence detection. For a number of selected sulfur-containing minerals and organic model compounds,

  19. Spectroscopic investigation of amber color silicate glasses and factors affecting the amber related absorption bands

    NASA Astrophysics Data System (ADS)

    Morsi, Morsi M.; El-sherbiny, Samya I.; Mohamed, Karam M.

    2015-06-01

    The effects of carbon, Fe2O3 and Na2SO4 contents on the amber color of glass with composition (wt%) 64.3 SiO2, 25.7 CaO, 10 Na2O were studied. The effect of some additives that could be found in glass batch or cullets on the amber related absorption band(s) was also studied. An amber related absorption band due to the chromophore Fe3+O3S2- was recorded at 420 nm with shoulder at 440 nm. A second amber related band recorded at 474 nm with shoulder at 483 nm was assigned to FeS. Increasing melting time at 1400 °C up to 6 h caused fainting of the amber color, decreases the intensities of the amber related bands and shifted the first band to 406 nm. Addition of ZnO, Cu2O and NaNO3 to the glass produced decolorizing effect and vanishing of the amber related bands. The effects of melting time and these additives were explained on the bases of destruction the amber chromophore and its conversion into Fe3+ in tetrahedral sites or ZnS. Addition of Se intensifies the amber related bands and may cause dark coloration due to the formation of Se° and polyselenide. Amber color can be monitored through measuring the absorption in the range 406-420 nm.

  20. Spectroscopic characterization of potential tunable solid state laser materials - Cr(3+)-doped germanium garnets

    Microsoft Academic Search

    S. R. Desjardins; L. J. Andrews; B. C. McCollum; W. J. Miniscalco

    1985-01-01

    A systematic characterization of the compounds Ca3M2(1-x)Cr2x(GeO4)3 where M = Ga, Al, Sc has been performed using emission, absorption and EPR spectroscopies. Unusual oxidation states were detected in the Ga and Al germanates. EPR spectra unmistakably point to the presence of some Ga(2+) or Ga(4+) and Al(2+) or Al(4+) ions, respectively, even in undoped samples. Optical absorption spectra further suggest

  1. Analytical and spectroscopic characterization of humic acids extracted from sewage sludge, manure, and worm compost

    Microsoft Academic Search

    S. Deiana; C. Gessa; B. Manunza; R. Seeber; R. Rausa

    1990-01-01

    Humic acids extracted from sewage sludges, manure, and worm compost have been characterized by chemical and spectroscopic methods. Meaningful differences in the composition were revealed by FTIR, ¹H, ¹³C NMR, and visible spectroscopies. These differences allow a differentiation among the products depending on the source from which they were obtained. Humic acid extracted from sewage sludges contains the highest percentage

  2. Spectroscopic techniques for characterization of high-mobility strained-Si CMOS

    Microsoft Academic Search

    Jens Schmidt; Günther Vogg; Frank Bensch; Stephan Kreuzer; Peter Ramm; Stefan Zollner; Ran Liu; Peter Wennekers

    2005-01-01

    The application of Raman spectroscopy and spectroscopic ellipsometry (SE) for characterization of strained silicon layers on SiGe virtual substrates is demonstrated. X-ray diffraction measurements (XRD) for calibration of Raman results have been carried out on strained Si\\/SiGe structures. For the composition-dependent shift of the Si–Si vibration in SiGe the relation ?Si–Si=520.6-68xGe is found, the strain shift coefficient for the longitudinal

  3. Flash spectroscopic characterization of photosynthetic electron transport in isolated heterocysts

    SciTech Connect

    Houchins, J.P.; Hind, G.

    1983-07-01

    Electron transport was studied in heterocysts of the filamentous cyanobacterium Anabaena 7120 using spectral and kinetic analysis of absorbance transients elicited by single turnover flashes. Consistent photosynthetic turnovers were observed only in the presence of an exogenous source of reductant; therefore measurements were routinely made under a gas phase containing H2. Prominent absorbance changes corresponding to the oxidation of cytochrome c (554 nm) and the reduction of cytochrome b563 (563 nm) were observed. Under the most reducing conditions (99% H2/1% O2) cytochrome b563 was partially reduced between flashes in a slow, dark reaction. At 10-15% O2, the slow, dark reduction of cytochrome b563 was eliminated. Cytochrome turnover ceased entirely at high O2 concentrations (30%) but was restored by the addition of 25 microM KCN, demonstrating an interaction between the photosynthetic and respiratory electron transfer chains. Strobilurin A slowed the re-reduction of cytochrome c and eliminated the appearance of reduced cytochrome b563 by blocking electron transfer between reduced plastoquinone and the cytochrome b/f complex. Inhibition at a second site was apparent with 2-(n-heptyl)-4-hydroxyquinoline N-oxide, which blocked the reoxidation of cytochrome b563 but had little effect on cytochrome c relaxation. In uncoupled heterocysts, the rates of cytochrome c re-reduction and cytochrome b563 reduction were equal. Additional unassigned absorbance changes at 475 nm, 515 nm, and 572 nm were partially characterized. No absorbance change corresponding to an electrochromic shift was observed.

  4. Synthesis and spectroscopic characterization of copper zinc aluminum nanoferrite particles.

    PubMed

    Lakshmi Reddy, S; Ravindra Reddy, T; Roy, Nivya; Philip, Reji; Montero, Ovidio Almanza; Endo, Tamio; Frost, Ray L

    2014-06-01

    Copper doped zinc aluminum ferrites CuxZn1-x.(AlxFe2-x)O4 are synthesized by the solid-state reaction route and characterized by XRD, TEM, EPR and non linear optical spectroscopy techniques. The average particle size is found to be from 35 to 90nm and the unit cell parameter "a" is calculated as from 8.39 to 8.89Å. The cation distributions are estimated from X-ray diffraction intensities of various planes. The XRD studies have verified the quality of the synthesis of compounds and have shown the differences in the positions of the diffraction peaks due to the change in concentration of copper ions. TEM pictures clearly indicating that fundamental unit is composed of octahedral and tetrahedral blocks and joined strongly. The selected area electron diffraction (SAED) of the ferrite system shows best crystallinity is obtained when Cu content is very. Some of the d-plane spacings are exactly coinciding with XRD values. EPR spectra is compositional dependent at lower Al/Cu concentration EPR spectra is due to Fe(3+) and at a higher content of Al/Cu the EPR spectra is due to Cu(2+). Absence of EPR spectra at room temperature indicates that the sample is perfectly ferromagnetic. EPR results at low temperature indicate that the sample is paramagnetic, and that copper is placed in the tetragonal elongation (B) site with magnetically non-equivalent ions in the unit cell having strong exchange coupling between them. This property is useful in industrial applications. Nonlinear optical properties of the samples studied using 5ns laser pulses at 532nm employing the open aperture z-scan technique indicate that these ferrites are potential candidates for optical limiting applications. PMID:24632431

  5. Spectroscopic and ultrasonic investigations on structural characterization of borate glass specimen doped with transition metal ions

    NASA Astrophysics Data System (ADS)

    Sathish, K.; Thirumaran, S.

    2015-08-01

    The present work describes the glass samples of composition (x% V2O5-(80-x)% B2O3-20% Na2CO3) VBS glass system and (x% MnO2-(80-x)% B2O3-20% Na2CO3) in MBS glass system with mol% ranging from x = 3, 6, 9, 12, 15 and 18 in steps of 3 mol% are prepared by melt quenching technique. For these prepared glass systems, sound velocity (longitudinal and shear velocities) and density have been measured. The sound velocity (longitudinal and shear) was measured by using pulse-echo technique at 5 MHz. The XRD study was carried to out to ascertain the amorphous nature of the glass specimen. Using these measured values, the elastic moduli, Poisson's ratio, Debye temperature, acoustic impedance and thermal expansion coefficient of the two glass systems were evaluated. The elastic and mechanical properties of the prepared glass systems are analyzed from ultrasonic study and the structural characterization from spectroscopic study. The effects due to the doping of transition metal ions with borate have been discussed. In the V2O5 doped glass system, (VBS glass system) the sound velocity, density and elastic moduli, steeply increases after 12 mol% comparatively with MnO2 doped glass system (VBS glass system). The present study critically observes the doping of V2O5 with borate enhances the strengthening of network linkage and hardening of the glassy network structure than MnO2. The IR spectral analysis reveals depolymerization of the borate network and conversion of BO3 or BO4 units with the formation of non-bridging oxygen. The FTIR spectral studies confirm the presence of various functional groups of the sample. FTIR spectrum of sample exhibits broad absorption bands indicating the wide distribution of borate structural units. The effect of Na2CO3, V2O5 and MnO2 contents on the structures of borate glass is evaluated from the FTIR spectra. The topological aspects of the prepared glass samples are exhaustively reported from SEM micrographs.

  6. Spectroscopic and Functional Characterization of Iron-Bound Forms of Azotobacter vinelandiiNifIscA†

    PubMed Central

    Mapolelo, Daphne T.; Zhang, Bo; Naik, Sunil G.; Huynh, Boi Hanh; Johnson, Michael K.

    2012-01-01

    The ability of Azotobacter vinelandii NifIscA to bind Fe has been investigated to assess the role of Fe-bound forms in NIF-specific Fe-S cluster biogenesis. NifIscA is shown to bind one Fe(III) or one Fe(II) per homodimer and the spectroscopic and redox properties of both the Fe(III)- and Fe(II)-bound forms have been characterized using the UV-visible absorption, CD and VTMCD, EPR, Mössbauer and resonance Raman spectroscopies. The results reveal a rhombic intermediate-spin (S = 3/2) Fe(III) center (E/D = 0.33, D = 3.5 ± 1.5cm?1) that is most likely 5-coordinate with two or three cysteinate ligands and a rhombic high spin (S = 2) Fe(II) center (E/D = 0.28, D = 7.6 cm?1) with properties similar to reduced rubredoxins or rubredoxin variants with three cysteinate and one or two oxygenic ligands. Iron-bound NifIscA undergoes reversible redox cycling between the Fe(III)/Fe(II) forms with a midpoint potential of +36 ±15 mV at pH 7.8 (versus NHE). L-cysteine is effective in mediating release of free Fe(II) from both the Fe(II)- and Fe(III)-bound forms of NifIscA. Fe(III)-bound NifIscA was also shown to a competent iron source for in vitro NifS-mediated [2Fe-2S] cluster assembly on the N-terminal domain of NifU, but the reaction occurs via cysteine-mediated release of free Fe(II) rather than direct iron transfer. The proposed roles of A-type proteins in storing Fe under aerobic growth conditions and serving as iron donors for cluster assembly on U-type scaffold proteins or maturation of biological [4Fe-4S] centers are discussed in light of these results. PMID:23003563

  7. X-ray absorption spectroscopic studies of cadmium and selenite adsorption on aluminum oxides

    SciTech Connect

    Papelis, C.; Brown, G.E. Jr.; Parks, G.A.; Leckie, J.O. [Stanford Univ., CA (United States)

    1995-06-01

    To enhance our understanding of trace element partitioning at oxide-water interfaces, we studied the local coordination environment of cadmium(II) and selenite complexes sorbed on aluminum oxides, in situ, using X-ray absorption spectroscopy (XAS). The adsorbents included porous, high surface area transition aluminas (ALCOA CP-5 and C-33) and the minerals corundum ({Alpha}-Al{sub 2}O{sub 3}) and gibbsite ({gamma}-Al(OH){sub 3}). Cadmium sorption densities ranged from 1.2 to 12.0 {mu}mol/m{sup 2} and selenite sorption densities ranged from 1.2 to 4.6 {mu}mol/m{sup 2}. X-ray absorption fine structure (XAFS) analysis of the selenite spectra indicates that Se is coordinated to three O atoms at 1.69 A, regardless of substrate, and that the complexes are mononuclear. XAFS analysis of low sorption density cadmium complexes suggests that cadmium is coordinated to six oxygens at 2.33 A and that the complexes are mononuclear. These results, in combination with sorption isotherm data, suggest that, under the conditions studied, cadmium and selenite diffuse into the pores of the transition aluminas and sorb as mononuclear complexes. These results have significant implications for the fate of trace elements in subsurface environments and the remediation of waters and groundwaters. 33 refs., 11 figs., 4 tabs.

  8. Spectroscopic characterization of alumina-supported bis(allyl)iridium complexes : site-isolation, reactivity, and decomposition studies.

    SciTech Connect

    Trovitch, R. J.; Guo, N.; Janicke, M. T.; Li, H.; Marshall, C. L.; Miller, J. T.; Sattelberger, A. P.; John, K. D.; Baker, R. T.; LANL; Univ. of Ottawa

    2010-01-01

    The covalent attachment of tris(allyl)iridium to partially dehydroxylated ?-alumina is found to proceed via surface hydroxyl group protonation of one allyl ligand to form an immobilized bis(allyl)iridium moiety, (?AlO)Ir(allyl)2, as characterized by CP-MAS 13C NMR, inductively coupled plasma-mass spectrometry, and Ir L3 edge X-ray absorption spectroscopy. Extended X-ray absorption fine-structure (EXAFS) measurements taken on unsupported Ir(allyl)3 and several associated tertiary phosphine addition complexes suggest that the ?3-allyl ligands generally account for an Ir-C coordination number of 2 rather than 3, with an average Ir-C distance of 2.16 A. Using this knowledge, combined EXAFS and X-ray absorption near-edge structure studies reveal that a small amount of Ir0 is also formed upon reaction of Ir(allyl)3 with the surface. It was found that the addition of either 2,6-dimethylphenyl isocyanide or carbon monoxide to the supported complex allows spectroscopic identification of the supported bis(allyl)iridium complexes, (?AlO)Ir(allyl)2(CNAr) [Ar = 2,6-(CH3)2C6H4] and (?AlO)Ir(allyl)2(CO)2, respectively. Although samples of the supported bis(allyl)iridium complex are active for the dehydrogenation of cyclohexane to benzene at temperatures between 180 and 220C, in situ temperature-programmed reaction XAFS and continuous-flow reactor studies suggest that Ir0 nanoparticles, rather than a well-defined Ir3+ complex, are responsible for the observed activity.

  9. Octahedral cation ordering in Mg, Fe2+-olivine: an optical absorption spectroscopic study

    NASA Astrophysics Data System (ADS)

    Taran, Michail N.; Koch-Müller, Monika

    2006-11-01

    Polarized optical absorption spectra of natural olivine, Fa10Fo90, were measured before and after annealing/quenching experiments performed at 650, 800, 1,000 and 1,200°C under controlled oxygen fugacity. It was found that the annealing induces weak but definite changes in the olivine spectra. The intensity of the spin-allowed Z > X-polarized band at 9,560 cm-1 and shoulder at ˜8,300 cm-1 attributed to Fe2+(M2), continuously decreases with annealing temperature, whereas a weaker band at ˜11,600 cm-1 assigned to electronic spin-allowed transitions of Fe2+(M1), increases. This evidently shows that annealing treatments cause a redistribution of Fe2+ from M2 to M1. The fractionation increases with increasing temperature. This observation is in good correspondence with many diffraction structural studies of natural and synthetic olivines, as well as with recent Raman and Mössbauer investigations by Kolesov and Geiger (Mitt Österr Mineral Ges 149:48, 2004) and Morozov et al. (Eur J Mineral 17:495 500, 2005) evidencing a weak tendency of Fe to order into the M1 site with increasing temperature. However, this deduction is incompatible with the results of the in situ neutron power diffraction study of synthetic FeMgSiO4 by Redfern et al. (Phys Chem Minerals 27:630 637, 2000). Polarization properties of the UV absorption edge, attributed to ligand-to-metal charge-transfer transitions in Fe3+, changes from Y > X ? Z in natural samples to a weak Y ? X ? Z-pleochroism in annealed ones. This may be due to redistribution of a small content of Fe3+ among M1 and M2 structural sites.

  10. In Situ Polarization Modulation Infrared Reflection Absorption Spectroscopic and Kinetic Investigations of Heterogeneous Catalytic Reactions 

    E-print Network

    Cai, Yun

    2010-01-14

    below the temperature previously reported. Characterizations of highly catalytically active Au films have also been carried out. Electronic and chemical properties of (1 x 1)- and (1 x 3)-Au/TiOx/Mo(112) films are investigated by PM-IRAS using CO as a...

  11. Resolution limits of laser spectroscopic absorption measurements with hollow glass waveguides.

    PubMed

    Chen, Jia; Hangauer, Andreas; Strzoda, Rainer; Amann, Markus Christian

    2010-10-01

    In this paper, resolution limits of laser spectroscopy absorption measurements with hollow capillary fibers are investigated. Furthermore, a concept of sensitive near-infrared sensing utilizing hollow fiber directly coupled with vertical-cavity surface-emitting lasers is developed. By performing wavelength modulation spectroscopy, the smallest absorbance that can be detected by the fiber sensor was determined to be 10(-4), limited by a random modulation of the fiber transmission function (modal noise). By mechanically vibrating the fiber, a sensor resolution of 10(-5) in absorbance is achieved. Because the random modulation on the fiber transmission function limits the detection sensitivity, its physical reasons are analyzed. One contribution is found to be the partial integration of the far field, and the amplitude of the spectral features is inversely proportional to the square root of the integrated speckle points number. Therefore, careful design of the fiber-detector outcoupling is necessary. It turned out that incoupling alignment is not of much influence with respect to the spectral background. The residual spectral background is caused by mode-dependent effects and can be lowered by vibrating the fiber mechanically. PMID:20885460

  12. Spectroscopic characterization of both aqueous and solid-state diacerhein/hydroxypropyl-?-cyclodextrin inclusion complexes

    NASA Astrophysics Data System (ADS)

    Petralito, Stefania; Zanardi, Iacopo; Spera, Romina; Memoli, Adriana; Travagli, Valter

    2014-06-01

    Diacerhein, a poorly water soluble antirheumatic prodrug, was spectroscopically characterized to form inclusion complexes with hydroxypropyl-?-cyclodextrin (HP?CD) in both aqueous solution and in solid phase. Complexation with the hydrophilic carriers was used to improve the solubility and dissolution rate of the compound. The kinetics of the prodrug degradation to the active rhein in aqueous buffer solution were also investigated as a function of HP?CD concentration. The solid complexes prepared by different methods such as physical mixture, kneading, co-evaporation method and freeze dried method in 1:1 M ratio, were characterized by DSC and FTIR. The dissolution profiles of solid complexes were determined and compared with diacerhein alone and their physical mixture, in the simulated intestinal fluid at 37 °C. The accurate molecular spectroscopic characterization of diacerhein in the presence of different amounts of aqueous cyclodextrins was essential to determine the correct binding constants for the diacerhein/HP?CD system. The binding constants were also validated by UV spectrometry and HPLC procedure in order to compare the values from the different methods. Higuchi-Connors phase solubility method has proved not suitable when either the free or/and the complexed prodrug degrade in aqueous solution.

  13. Mass spectroscopic characterization of the GeSe:GeI4 vapor transport system

    NASA Technical Reports Server (NTRS)

    Buchan, Nicholas I.; Rosenberger, Franz

    1987-01-01

    The GeSe:GeI4 vapor crystal growth system was characterized mass spectroscopically. A steady-state Knudsen effusion technique was developed to simulate the equilibrium conditions at one end of a vapor transport ampoule. It was found that the previously neglected equilibrium GeSe2(s) = GeSe(v) + 1/2Se2(v) reduces the Se2(v) concentration to an extent that sublimation/condensation of GeSe becomes the dominant transport mechanism. At total pressures near 1 atm the concentration of an additional Ge-Se-I vapor species becomes comparable to that of GeSe(v).

  14. Silver sulfadoxinate: Synthesis, structural and spectroscopic characterizations, and preliminary antibacterial assays in vitro

    NASA Astrophysics Data System (ADS)

    Zanvettor, Nina T.; Abbehausen, Camilla; Lustri, Wilton R.; Cuin, Alexandre; Masciocchi, Norberto; Corbi, Pedro P.

    2015-02-01

    The sulfa drug sulfadoxine (SFX) reacted with Ag+ ions in aqueous solution, affording a new silver(I) complex (AgSFX), which was fully characterized by chemical, spectroscopic and structural methods. Elemental, ESI-TOF mass spectrometric and thermal analyses of AgSFX suggested a [Ag(C12H13N4O2S)] empirical formula. Infrared spectroscopic measurements indicated ligand coordination to Ag(I) through the nitrogen atoms of the (deprotonated) sulfonamide group and by the pyrimidine ring, as well as through oxygen atom(s) of the sulfonamide group. These hypotheses were corroborated by 13C and 15N SS-NMR spectroscopy and by an unconventional structural characterization based on X-ray powder diffraction data. The latter showed that AgSFX crystallizes as centrosymmetric dimers with a strong Ag⋯Ag interaction of 2.7435(6) Å, induced by the presence of exo-bidentate N,N? bridging ligands and the formation of an eight-membered ring of [AgNCN]2 sequence, nearly planar. Participation of oxygen atoms of the sulfonamide residues generates in the crystal a 1D coordination polymer, likely responsible for its very limited solubility in all common solvents. Besides the analytical, spectroscopic and structural description, the antibacterial properties of AgSFX were assayed using disc diffusion methods against Escherichia coli and Pseudomonas aeruginosa (Gram-negative), and Staphylococcus aureus (Gram-positive) bacterial strains. The AgSFX complex showed to be active against Gram-positive and Gram-negative bacterial strains, being comparable to the activities of silver sulfadiazine.

  15. Reactivity of Chromium(III) Nutritional Supplements in Biological Media: An X-Ray Absorption Spectroscopic Study

    SciTech Connect

    Nguyen, A.; Mulyani, I.; Levina, A.; Lay, P.A.

    2009-05-22

    Chromium(III) nutritional supplements are widely used due to their purported ability to enhance glucose metabolism, despite growing evidence on low activity and the potential genotoxicity of these compounds. Reactivities of Cr(III) complexes used in nutritional formulations, including [Cr3O(OCOEt)6(OH2)3]+ (A), [Cr(pic)3] (pic) = 2-pyridinecarboxylato(-) (B), and trans-[CrCl2(OH2)4]+ (CrCl3 {center_dot} 6H2O; C), in a range of natural and simulated biological media (artificial digestion systems, blood and its components, cell culture media, and intact L6 rat skeletal muscle cells) were studied by X-ray absorption near-edge structure (XANES) spectroscopy. The XANES spectroscopic data were processed by multiple linear-regression analyses with the use of a library of model Cr(III) compounds, and the results were corroborated by the results of X-ray absorption fine structure spectroscopy and electrospray mass spectrometry. Complexes A and B underwent extensive ligand-exchange reactions under conditions of combined gastric and intestinal digestion (in the presence of a semisynthetic meal, 3 h at 310 K), as well as in blood serum and in a cell culture medium (1-24 h at 310 K), with the formation of Cr(III) complexes with hydroxo and amino acid/protein ligands. Reactions of compounds A-C with cultured muscle cells led to similar ligand-exchange products, with at least part of Cr(III) bound to the surface of the cells. The reactions of B with serum greatly enhanced its propensity to be converted to Cr(VI) by biological oxidants (H2O2 or glucose oxidase system), which is proposed to be a major cause of both the insulin-enhancing activity and toxicity of Cr(III) compounds (Mulyani, I.; Levina, A.; Lay, P. A. Angew. Chem. Int. Ed. 2004, 43, 4504-4507). This finding enhances the current concern over the safety of consumption of large doses of Cr(III) supplements, particularly [Cr(pic)3].

  16. Characterization of photon-counting detector responsivity for nonlinear two-photon absorption process

    Microsoft Academic Search

    S. E. Sburlan; W. H. Farr

    2011-01-01

    Sub-band absorption at 1550 nm has been demonstrated and characterized on silicon Geiger mode detectors, which normally would be expected to have no response at this wavelength. We compare responsivity measurements to single-photon absorption for wavelengths slightly above the band gap wavelength of silicon (~1100 mum). One application for this low efficiency sub-band absorption is in deep space optical communication

  17. Azocalixarenes: Synthesis, Characterization, Complexation, Extraction, Absorption Properties and Thermal Behaviours

    Microsoft Academic Search

    Hasalettin Deligöz

    2006-01-01

    Azocalixarenes, which have a conjugated chromophore azo (–N=N–) group in p-positions, are synthesized in “one-pot” procedures in satisfactory yields. Their structures in the solid and solution are elucidated by UV–vis, FT-IR, 1H and 13C NMR spectroscopic methods as well as elemental analysis techniques. Some of them are complexed with metal ions (alkali,\\u000a alkaline-earth and transition metal ions) under neutral conditions.

  18. Characterization of high reflecting coatings and optical materials by direct absorption and cavity ring down measurements

    Microsoft Academic Search

    Ch. Mühlig; G. Schmidl; J. Bergmann; W. Triebel

    2008-01-01

    At 193nm and 527 nm, the laser induced deflection (LID) technique is applied to measure directly and quantitatively residual absorptions in high reflecting optical coatings. In addition, combined measurements of absorption, transmission, reflectivity and scattering for HR mirrors at 193 nm reveal very good results for the energy balance. Cavity ring down (CRD) spectroscopy is a sensitive technique to characterize

  19. Spectroscopic characterization of 250-?m-selected hyper-luminous star-forming galaxies

    NASA Astrophysics Data System (ADS)

    Casey, C. M.; Chapman, S. C.; Smail, Ian; Alaghband-Zadeh, S.; Bothwell, M. S.; Swinbank, A. M.

    2011-03-01

    We present near-infrared (near-IR) spectroscopic observations from Very Large Telescope Infrared Spectrometer And Array Camera (ISAAC) of 13 250-?m luminous galaxies in the Chandra Deep Field-South, seven of which have confirmed redshifts which average to = 2.0 ± 0.4. Another two sources of the 13 have tentative z > 1 identifications. Eight of the nine redshifts were identified with H? detection in H and K bands, three of which are confirmed redshifts from previous spectroscopic surveys. We use their near-IR spectra to measure H? linewidths and luminosities, which average to 415 ± 20 km s-1 and 3 × 1035 W (implying SFR H?˜ 200 M ? yr-1), both similar to the H? properties of submillimetre galaxies (SMGs). Just like SMGs, 250-?m-luminous galaxies have large H? to far-infrared (FIR) extinction factors such that the H? star formation rates (SFRs) underestimate the FIR SFRs by approximately eight to 80 times. FIR photometric points observed from 24 to 870 ?m are used to constrain the spectral energy distributions even though uncertainty caused by FIR confusion in the Balloon-borne Large-Aperture Submillimeter Telescope (BLAST) bands is significant. The population has a mean dust temperature of Td= 52 ± 6 K, emissivity ?= 1.73 ± 0.13 and FIR luminosity LFIR= 3 × 1013 L?. Although selection at 250 ?m allows for the detection of much hotter dust-dominated hyper-luminous infrared galaxies (HyLIRGs) than SMG selection (at 850 ?m), we do not find any ?60-K 'hot-dust' HyLIRGs. We have shown that near-IR spectroscopy combined with good photometric redshifts is an efficient way to spectroscopically identify and characterize these rare, extreme systems, hundreds of which are being discovered by the newest generation of IR observatories including the Herschel Space Observatory.

  20. FT-IR spectroscopic, thermal analysis of human urinary stones and their characterization.

    PubMed

    Selvaraju, R; Raja, A; Thiruppathi, G

    2015-02-25

    In the present study, FT-IR, XRD, TGA-DTA spectral methods have been used to investigate the chemical compositions of urinary calculi. Multi-components of urinary calculi such as calcium oxalate, hydroxyl apatite, struvite and uric acid have been studied. The chemical compounds are identified by FT-IR spectroscopic technique. The mineral identification was confirmed by powder X-ray diffraction patterns as compared with JCPDS reported values. Thermal analysis techniques are considered the best techniques for the characterization and detection of endothermic and exothermic behaviors of the urinary stones. The percentages of each hydrate (COM and COD) are present together, in the presences of MAPH or UA. Finally, the present study suggests that the Urolithiasis is significant health problem in children, and is very common in some parts of the world, especially in India. So that present study is so useful and helpful to the scientific community for identification of latest human health problems and their remedies using spectroscopic techniques. PMID:25306135

  1. Characterization of non-Fickian moisture absorption in thermosetting polymers

    NASA Astrophysics Data System (ADS)

    Guloglu, Gorkem E.; Altan, M. Cengiz

    2015-05-01

    A recently developed moisture absorption model for thermosetting polymers that combines the non-Fickian, diffusion hindrance effects and three-dimensional anisotropy is introduced. The hindered diffusion model is shown to predict both short term Fickian and long term anomalous moisture absorption behavior often observed in thermosetting polymers and their composites. The salient characteristics of long term moisture uptake such as the equilibrium moisture content and the effect of non-Fickian phenomena are presented. Anomalous moisture concentration profiles predicted by the two-dimensional solution of hindered diffusion model are demonstrated for various cases, including the through-the-thickness moisture profile of a 40-ply, quartz/bismaleimide (BMI) composite laminate. The effects of diffusion hindrance and anisotropy on the two-dimensional, through-the-thickness concentration profiles are illustrated. The moisture absorption parameters for an EPON 862 epoxy laminate are recovered from the experimental moisture absorption data. The hindered diffusion model is shown to accurately predict the moisture uptake of EPON 862 over the complete absorption time period. The non-Fickian effects governed by the hindrance coefficient are identified for both EPON 862 and quartz/BMI composite laminate. It is shown that the quartz/BMI laminate displays significant non-Fickian behavior compared to EPON 862 epoxy resin.

  2. Chemical vapor deposition synthesis and Raman spectroscopic characterization of large-area graphene sheets.

    PubMed

    Liao, Chun-Da; Lu, Yi-Ying; Tamalampudi, Srinivasa Reddy; Cheng, Hung-Chieh; Chen, Yit-Tsong

    2013-10-01

    We present a chemical vapor deposition (CVD) method to catalytically synthesize large-area, transferless, single- to few-layer graphene sheets using hexamethyldisilazane (HMDS) on a SiO2/Si substrate as a carbon source and thermally evaporated alternating Ni/Cu/Ni layers as a catalyst. The as-synthesized graphene films were characterized by Raman spectroscopic imaging to identify single- to few-layer sheets. This HMDS-derived graphene layer is continuous over the entire growth substrate, and single- to trilayer mixed sheets can be up to 30 ?m in the lateral dimension. With the synthetic CVD method proposed here, graphene can be grown into tailored shapes directly on a SiO2/Si surface through vapor priming of HMDS onto predefined photolithographic patterns. The transparent and conductive HMDS-derived graphene exhibits its potential for widespread electronic and opto-electronic applications. PMID:23461419

  3. Spectroscopic characterization of a green copper site in a single-domain cupredoxin.

    PubMed

    Roger, Magali; Biaso, Frédéric; Castelle, Cindy J; Bauzan, Marielle; Chaspoul, Florence; Lojou, Elisabeth; Sciara, Giuliano; Caffarri, Stefano; Giudici-Orticoni, Marie-Thérèse; Ilbert, Marianne

    2014-01-01

    Cupredoxins are widespread copper-binding proteins, mainly involved in electron transfer pathways. They display a typical rigid greek key motif consisting of an eight stranded ?-sandwich. A fascinating feature of cupredoxins is the natural diversity of their copper center geometry. These geometry variations give rise to drastic changes in their color, such as blue, green, red or purple. Based on several spectroscopic and structural analyses, a connection between the geometry of their copper-binding site and their color has been proposed. However, little is known about the relationship between such diversity of copper center geometry in cupredoxins and possible implications for function. This has been difficult to assess, as only a few naturally occurring green and red copper sites have been described so far. We report herein the spectrocopic characterization of a novel kind of single domain cupredoxin of green color, involved in a respiratory pathway of the acidophilic organism Acidithiobacillus ferrooxidans. Biochemical and spectroscopic characterization coupled to bioinformatics analysis reveal the existence of some unusual features for this novel member of the green cupredoxin sub-family. This protein has the highest redox potential reported to date for a green-type cupredoxin. It has a constrained green copper site insensitive to pH or temperature variations. It is a green-type cupredoxin found for the first time in a respiratory pathway. These unique properties might be explained by a region of unknown function never found in other cupredoxins, and by an unusual length of the loop between the second and the fourth copper ligands. These discoveries will impact our knowledge on non-engineered green copper sites, whose involvement in respiratory chains seems more widespread than initially thought. PMID:24932914

  4. Synthesis, characterization and spectroscopic behavior of novel 2-oxo-1,4-disubstituted-1,2,5,6-tetrahydrobenzo[h]quinoline-3-carbonitrile dyes

    NASA Astrophysics Data System (ADS)

    Khan, Salman A.; Asiri, Abdullah M.; Al-Thaqafy, Saad H.; Faidallah, Hassan M.; El-Daly, Samy A.

    2014-12-01

    Two synthetic pathways were adopted to synthesize the target 2-oxo-1,4-disubstituted-1,2,5,6-tetrahydro-benzo[h]quinoline-3-carbonitriles. Structure of the synthesized compounds has been characterized based on FT-IR, 1H NMR, 13C NMR and elemental analyses. UV-Vis and fluorescence spectroscopy measurements provided that all compounds are good absorbent and fluorescent. Fluorescence polarity study demonstrated that these compounds were sensitive to the polarity of the microenvironment provided by different solvents. In addition, spectroscopic and physicochemical parameters, including singlet absorption, extinction coefficient, Stokes shift, oscillator strength and dipole moment were investigated in order to explore the analytical potential of synthesized compounds.

  5. Synthesis and spectroscopic characterization studies of low molecular weight light emitting PPV segmented copolymers

    NASA Astrophysics Data System (ADS)

    Ali, Basil; Jabar, Sattar; Salih, Whidad; Al Tamimi, Raed K.; Al Attar, Hameed; Monkman, Andy P.

    2009-12-01

    New tuneable segmented alternating copoly( p-phenylene vinylene) (PPV) derivatives were chemically synthesised via the Wittig polycondensation reaction. The chemical and optical properties in solution and in solid state were evaluated. The absorption and photoemission spectra show that incorporating an ethane dioxy spacer limits the conjugation length and produces a blue emitting copolymer, poly[1,2-ethane dioxy 2-methoxy-1,4-phenylene-vinyl 1,4-phenylene-vinyl 3-methoxy 1,4-phenylene] (EDO-PPV- 1) 1. A red shift in the copolymer emission was achieved by adding an electron-donating group, a hexoloxy-substituted PPV segment, poly[1,2-ethane dioxy 2-methoxy-1,4-phenylene-vinyl 2,5-dihexoloxy 1,4-phenylene-vinyl 3-methoxy 1,4-phenylene] (EDO-PPV- 2) 2. The photophysical properties of these block copolymers was compared with the fully conjugated copolymer poly[2-methoxy-5-(2'-ethyl-hexyloxy)-1,4-phenylene vinylene] (MEH-PPV) 3. The absorption band of the ? deloc- ?deloc? transition at 400-500 nm is limited in 1 and 2 indicating that the conjugation is effectively interrupted. The effect of torsional motions on the Stokes shift in these segmented copolymers is discussed. The photoluminescence (PL) efficiency and lifetime of 1 and 2 is different, indicating that the contribution from additional non-radiative decay channels due to interchain interactions is significant. The steady state and time-resolved photophysical characteristics of the thin film form of the copolymers indicates a high order of stacking in copolymer 1 and strong interchain interaction leading to strong excimer emission which may be ascribed to the low folding degree and planarity of the copolymers chemical structure. The spectroscopic time-resolved analysis confirms the interchain interaction.

  6. Spectroscopic characterization of effective components anthraquinones in Chinese medicinal herbs binding with serum albumins

    NASA Astrophysics Data System (ADS)

    Bi, Shuyun; Song, Daqian; Kan, Yuhe; Xu, Dong; Tian, Yuan; Zhou, Xin; Zhang, Hanqi

    2005-11-01

    The interactions of serum albumins such as human serum albumin (HSA) and bovine serum albumin (BSA) with emodin, rhein, aloe-emodin and aloin were assessed employing fluorescence quenching and absorption spectroscopic techniques. The results obtained revealed that there are relatively strong binding affinity for the four anthraquinones with HSA and BSA and the binding constants for the interactions of anthraquinones with HSA or BSA at 20 °C were obtained. Anthraquinone-albumin interactions were studied at different temperatures and in the presence of some metal ions. And the competition binding of anthraquinones with serum albumins was also discussed. The Stern-Volmer curves suggested that the quenching occurring in the reactions was the static quenching process. The binding distances and transfer efficiencies for each binding reactions were calculated according to the Föster theory of non-radiation energy transfer. Using thermodynamic equations, the main action forces of these reactions were also obtained. The reasons of the different binding affinities for different anthraquinone-albumin reactions were probed from the point of view of molecular structures.

  7. Spectroscopic characterization of LaAlO 3 crystal doped with Tm 3+ ions

    NASA Astrophysics Data System (ADS)

    Gocali?ska, A.; Dere?, P. J.; G?uchowski, P.; Goldner, Ph.; Guillot-Noël, O.

    2008-01-01

    This work presents the result of spectroscopic research on LaAlO 3 crystal doped with Tm 3+ ions. The host possesses perovskite structure. The investigated sample was single crystal, grown by the Czochralski method. Absorption and emission as well as decay profiles were measured in visible and the IR range at room and at low (77 K) temperature. Under excitation matching several excited states emission from the 1D 2 (27 700 cm -1), 1I 6 + 3P 0 (28 600 cm -1), 3H 4 (12 400 cm -1 and 6800 cm -1) and 3F 4 (5800 cm -1) levels was obtained together with theses strong bands other weaker transitions were registered. The decay times are short for the violet and blue emission and significantly longer for the red and IR emission (at the room temperatures values are 22 ?s and 5.8 ms for 1D 2 and 3F 4 levels, respectively). The system is discussed in terms of Tm 3+ energy levels structure. Further investigations are considered.

  8. Spectroscopic characterization of II-VI compounds and application to copper indium selenide-based solar cells

    Microsoft Academic Search

    Heriberto De Jesus Aguilar Juarez

    1999-01-01

    Structures consisting of CuInSe2 films, deposited on molybdenum-coated glass substrates and covered by CdS or ZnO thin films, for application in solar cells, have been characterized by spectroscopic ellipsometry, atomic force microscopy, photoluminescence and photovoltaic response. Computer aided simulations of the photovoltaic operation of these structures have been made to reinforce and complement the results of the characterization studies. The

  9. Solution properties and spectroscopic characterization of polymeric precursors to SiNCB and BN ceramic materials

    SciTech Connect

    Cortez, E.; Remsen, E; Chlanda, V. [Analytical Science Center, Monsanto Corporate Research, Monsanto Company, 800 North Lindbergh, St. Louis, Missouri 63167 (United States); Carrol, P. [Department of Chemistry and Laboratory for the Research on the Structure of Matter, University of Pennsylvania, Pennsylvania 19107-6323 (United States); Sneddon, L. [The Advanced Ceramics Program, Dow Corning Corporation, Midland, Michigan, 48686-0995 (United States)

    1998-06-01

    Boron Nitride, BN, and composite SiNCB ceramic fibers are important structural materials because of their excellent thermal and oxidative stabilities. Consequently, polymeric materials as precursors to ceramic composites are receiving increasing attention. Characterization of these materials requires the ability to evaluate simultaneous molecular weight and compositional heterogeneity within the polymer. Size exclusion chromatography equipped with viscometric and refractive index detection as well as coupled to a LC-transform device for infrared absorption analysis has been employed to examine these heterogeneities. Using these combined approaches, the solution properties and the relative amounts of individual functional groups distributed through the molecular weight distribution of SiNCB and BN polymeric precursors were characterized. {copyright} {ital 1998 American Institute of Physics.}

  10. [Chromatographic and spectroscopic characterization of phycocyanin and its subunits purified from Anabaena variabilis CCC421].

    PubMed

    Chakdar, N; Sakha, S; Pabbi, S

    2014-01-01

    Phycocyanin, a high value pigment was purified from diazotrophic cyanobacteria Anabaena variabilis CCC421 using a strategy involving ammonium sulfate precipitation, dialysis and anion exchange chromatography using DEAE-cellulose column. 36% phycocyanin with a purity of 2.75 was recovered finally after anion exchange chromatography. Purified phycocyanin was found to contain 2 subunits of 17 and 18 kDa which were identified as a-and (3 subunits by SDS-PAGE and MALDI-TOE HPLC method using a C5 column coupled with fluorescence or photodiode-based detection was also developed to separate and detect the A. variabilis CCC421 phycocyanin subunits. The fluorescence method was more sensitive than photodiode one. The purified phycocyanin from A. variabilis CCC421 as well as its subunits was characterized with respect to absorption and IR spectra. Spectral characterization of the subunits revealed that alpha and beta subunits contained one and two phycocyanobilin groups as chromophores, respectively. PMID:25272755

  11. Hafnium(IV) chloride complexes with chelating ?-ketiminate ligands: Synthesis, spectroscopic characterization and volatility study.

    PubMed

    Patil, Siddappa A; Medina, Phillip A; Antic, Aleks; Ziller, Joseph W; Vohs, Jason K; Fahlman, Bradley D

    2015-09-01

    The synthesis and characterization of four new ?-ketiminate hafnium(IV) chloride complexes dichloro-bis[4-(phenylamido)pent-3-en-2-one]-hafnium (4a), dichloro-bis[4-(4-methylphenylamido)pent-3-en-2-one]-hafnium (4b), dichloro-bis[4-(4-methoxyphenylamido)pent-3-en-2-one]-hafnium (4c), and dichloro-bis[4-(4-chlorophenylamido)pent-3-en-2-one]-hafnium (4d) are reported. All the complexes (4a-d) were characterized by spectroscopic methods ((1)H NMR, (13)C NMR, IR), and elemental analysis while the compound 4c was further examined by single-crystal X-ray diffraction, revealing that the complex is monomer with the hafnium center in octahedral coordination environment and oxygens of the chelating N-O ligands are trans to each other and the chloride ligands are in a cis arrangement. Volatile trends are established for four new ?-ketiminate hafnium(IV) chloride complexes (4a-d). Sublimation enthalpies (?Hsub) were calculated from thermogravimetric analysis (TGA) data, which show that, the dependence of ?Hsub on the molecular weight (4a-c) and inductive effects from chlorine (4d). PMID:25897715

  12. Biochemical and spectroscopic characterization of two new cytochromes isolated from Desulfuromonas acetoxidans.

    PubMed

    Bruschi, M; Woudstra, M; Guigliarelli, B; Asso, M; Lojou, E; Petillot, Y; Abergel, C

    1997-09-01

    The multimeric cytochromes described to date in sulfate- and sulfur-reducing bacteria are associated with diverse respiratory modes involving the use of elemental sulfur or oxidized sulfur compounds as terminal acceptors. They exhibit no structural similarity with the other cytochrome c classes and are characterized by a bis-histidinyl axial iron coordination and low redox potentials. We have purified two new cytochromes c with markedly different molecular masses (10 000 and 50 000) from the bacterium Desulfuromonas acetoxidans, which uses anaerobic sulfur respiration as its sole energy source. The characterization by electrochemistry and optical and EPR spectroscopies revealed the cytochrome c (Mr = 10 000) to be the first monohemic cytochrome c exhibiting a bis-histidinyl axial coordination and a low redox potential (-220 mV). The cytochrome c (Mr = 50 000) contains four hemes of low potential (-200, -210, -370, and -380 mV) with the same axial coordination. The N-terminal amino acid sequences were compared with that of the trihemic cytochrome c7, previously described in D. acetoxidans and which is related to tetrahemic cytochrome c3 from sulfate reducing bacteria. Some homology was found between cytochrome c (Mr = 10 000) and cytochrome c7. Both D. acetoxidans cytochromes c are located in the periplasmic space and their biochemical and spectroscopic properties indicate that they belong to the class III cytochromes. PMID:9271490

  13. Potentiometric, electronic, and transient absorptive spectroscopic properties of oxidized single-walled carbon nanotubes helically wrapped by ionic, semiconducting polymers in aqueous and organic media.

    PubMed

    Deria, Pravas; Olivier, Jean-Hubert; Park, Jaehong; Therien, Michael J

    2014-10-01

    We report the first direct cyclic voltammetric determination of the valence and conduction band energy levels for noncovalently modified (6,5) chirality enriched SWNTs [(6,5) SWNTs] in which an aryleneethynylene polymer monolayer helically wraps the nanotube surface at periodic and constant morphology. Potentiometric properties as well as the steady-state and transient absorption spectroscopic signatures of oxidized (6,5) SWNTs were probed as a function of the electronic structure of the aryleneethynylene polymer that helically wraps the nanotube surface, the solvent dielectric, and nanotube hole polaron concentration. These data: (i) highlight the utility of these polymer-SWNT superstructures in experiments that establish the potentiometric valence and conduction band energy levels of semiconducting carbon nanotubes; (ii) provide a direct measure of the (6,5) SWNT hole polaron delocalization length (2.75 nm); (iii) determine steady-state and transient electronic absorptive spectroscopic signatures that are uniquely associated with the (6,5) SWNT hole polaron state; and (iv) demonstrate that modulation of semiconducting polymer frontier orbital energy levels can drive spectral shifts of SWNT hole polaron transitions as well as regulate SWNT valence and conduction band energies. PMID:25211354

  14. Characterization of Spectral Absorption Properties of Aerosols Using Satellite Observations

    NASA Technical Reports Server (NTRS)

    Torres, O.; Jethva, H.; Bhartia, P. K.; Ahn, C.

    2012-01-01

    The wavelength-dependence of aerosol absorption optical depth (AAOD) is generally represented in terms of the Angstrom Absorption Exponent (AAE), a parameter that describes the dependence of AAOD with wavelength. The AAE parameter is closely related to aerosol composition. Black carbon (BC) containing aerosols yield AAE values near unity whereas Organic carbon (OC) aerosol particles are associated with values larger than 2. Even larger AAE values have been reported for desert dust aerosol particles. Knowledge of spectral AAOD is necessary for the calculation of direct radiative forcing effect of aerosols and for inferring aerosol composition. We have developed a satellitebased method of determining the spectral AAOD of absorbing aerosols. The technique uses high spectral resolution measurements of upwelling radiation from scenes where absorbing aerosols lie above clouds as indicated by the UV Aerosol Index. For those conditions, the satellite measured reflectance (rho lambda) is approximately given by Beer's law rho lambda = rho (sub 0 lambda) e (exp -mtau (sub abs lambda)) where rho(sub 0 lambda) is the cloud reflectance, m is the geometric slant path and tau (sub abs lambda) is the spectral AAOD. The rho (sub 0 lambda) term is determined by means of radiative transfer calculations using as input the cloud optical depth derived as described in Torres et al. [JAS, 2012] that accounts for the effects of aerosol absorption. In the second step, corrections for molecular and aerosol scattering effects are applied to the cloud reflectance term, and the spectral AAOD is then derived by inverting the equation above. The proposed technique will be discussed in detail and application results will be presented. The technique can be easily applied to hyper-spectral satellite measurements that include UV such as OMI, GOME and SCIAMACHY, or to multi-spectral visible measurements by other sensors provided that the aerosol-above-cloud events are easily identified.

  15. X-Ray Absorption Characterization of Diesel Exhaust Particulates

    SciTech Connect

    Nelson, A J; Ferreira, J L; Reynolds, J G; Roos, J W

    1999-11-18

    We have characterized particulates from a 1993 11.1 Detroit Diesel Series 60 engine with electronic unit injectors operated using fuels with and without methylcyclopentadienyl manganese tricarbonyl (MMT) and overbased calcium sulfonate added. X-ray photoabsorption (XAS) spectroscopy was used to characterize the diesel particulates. Results reveal a mixture of primarily Mn-phosphate with some Mn-oxide, and Ca-sulfate on the surface of the filtered particulates from the diesel engine.

  16. Synergic use of TOMS and Aeronet Observations for Characterization of Aerosol Absorption

    NASA Technical Reports Server (NTRS)

    Torres, O.; Bhartia, P. K.; Dubovik, O.; Holben, B.; Siniuk, A.

    2003-01-01

    The role of aerosol absorption on the radiative transfer balance of the earth-atmosphere system is one of the largest sources of uncertainty in the analysis of global climate change. Global measurements of aerosol single scattering albedo are, therefore, necessary to properly assess the radiative forcing effect of aerosols. Remote sensing of aerosol absorption is currently carried out using both ground (Aerosol Robotic Network) and space (Total Ozone Mapping Spectrometer) based observations. The satellite technique uses measurements of backscattered near ultraviolet radiation. Carbonaceous aerosols, resulting from the combustion of biomass, are one of the most predominant absorbing aerosol types in the atmosphere. In this presentation, TOMS and AERONET retrievals of single scattering albedo of carbonaceous aerosols, are compared for different environmental conditions: agriculture related biomass burning in South America and Africa and peat fires in Eastern Europe. The AERONET and TOMS derived aerosol absorption information are in good quantitative agreement. The most absorbing smoke is detected over the African Savanna. Aerosol absorption over the Brazilian rain forest is less absorbing. Absorption by aerosol particles resulting from peat fires in Eastern Europe is weaker than the absorption measured in Africa and South America. This analysis shows that the near UV satellite method of aerosol absorption characterization has the sensitivity to distinguish different levels of aerosol absorption. The analysis of the combined AERONET-TOMS observations shows a high degree of synergy between satellite and ground based observations.

  17. Spectroscopic characterization of high-energy and high fluence rate photon beams

    NASA Astrophysics Data System (ADS)

    Bartol, Laura J.

    High-energy, high fluence rate photon sources are used in radiation oncology for the treatment of a variety of disease sites. Common dosimetry methods for characterizing these sources use energy-integrating devices; however, the most descriptive characterization of these sources are performed with devices that preserve the energy-specific information in the source output. This work used Monte-Carlo- (MC-) and measurement-based spectroscopic methods to characterize two therapeutic-level megavoltage photon sources. MC simulations were performed using the MCNP5 transport code and measurements were performed with a Compton-scattering (CS) technique. Because MC was used extensively in this work, some general MCNP5 investigations were performed to benchmark the techniques used. Limitations in the advanced variance reduction techniques, Doppler-broadening model, and use of phase space files were investigated. Based on the results of these investigations, recommendations were made for using each technique. The validity of the CS technique for use with megavoltage systems was demonstrated using MC simulations of a 6 MV linear accelerator field and measurements of a high dose rate 192Ir source. Following these initial demonstrations, the spectrum of a 60Co teletherapy unit was characterized. Simulations were performed to determine the spectrum's sensitivity to the source model. Multiple measurements were completed using a reverse-electrode germanium (REGe) detector with the CS spectrometry technique. The CS spectra were corrected for detector response and the CS geometry using a novel detector response function that was calculated using MCNP5. The detector response was unfolded using the Gold deconvolution method. Comparisons of the simulated and measured spectra showed agreement in terms of the peak positions, mean spectrum energy, and relative fluences under specific portions of the spectra. The spectrum of a 6 MV photon field from a Varian Clinac iX linear accelerator was also characterized. Simulations were performed to determine the spectrum's sensitivity to changes in the primary electron source parameters of mean energy, spot size, and divergence. In addition, measurements were performed using the CS technique with the REGe detector. These measurements demonstrated that the linac spectrum was detectable above background, and the CS signal was dependent on field size.

  18. Chemical Characterization and Absorption of Phytochemicals From Mangifera indica L.

    E-print Network

    Krenek, Kimberly Ann

    2013-08-12

    polyphenolics, it was first necessary to chemically characterize the compounds present using HPLC-MSn analysis. Mango pulp and extracts were also incubated with a pectinase, cellulase, pectinase with ß-glucosidase activity, and a pure ß-glucosidase to learn...

  19. Absorption

    NSDL National Science Digital Library

    Katherine M Knudson (Polson Middle School)

    1998-04-01

    This activity can be used to allow students to explore the concept of absorption using a variety of materials. Extensions include exploring how Native Americans used absorbtion in a number of ways. This inquiry activity was developed by a K-12 science teacher in the American Physiological SocietyÂ?s 1998 Frontiers in Physiology Program. The NSES Standards addressed by this activity are current as of the year of development. For more information on the Frontiers in Physiology Program, please visit www.frontiersinphys.org.

  20. Spectroscopic ellipsometric characterization of Si/Si(1-x)Ge(x) strained-layer superlattices

    NASA Technical Reports Server (NTRS)

    Yao, H.; Woollam, J. A.; Wang, P. J.; Tejwani, M. J.; Alterovitz, S. A.

    1993-01-01

    Spectroscopic ellipsometry (SE) was employed to characterize Si/Si(1-x)Ge(x) strained-layer superlattices. An algorithm was developed, using the available optical constants measured at a number of fixed x values of Ge composition, to compute the dielectric function spectrum of Si(1-x)Ge(x) at an arbitrary x value in the spectral range 17 to 5.6 eV. The ellipsometrically determined superlattice thicknesses and alloy compositional fractions were in excellent agreement with results from high-resolution x ray diffraction studies. The silicon surfaces of the superlattices were subjected to a 9:1 HF cleaning prior to the SE measurements. The HF solution removed silicon oxides on the semiconductor surface, and terminated the Si surface with hydrogen-silicon bonds, which were monitored over a period of several weeks, after the HF cleaning, by SE measurements. An equivalent dielectric layer model was established to describe the hydrogen-terminated Si surface layer. The passivated Si surface remained unchanged for greater than 2 h, and very little surface oxidation took place even over 3 to 4 days.

  1. Spectroscopic and Electrochemical Characterization of Nanostructured Optically-Transparent Carbon Electrodes

    PubMed Central

    Benavidez, Tomas E.; Garcia, Carlos D.

    2013-01-01

    The present paper describes the results related to the optical and electrochemical characterization of thin carbon films fabricated by spin coating and pyrolysis of AZ P4330-RS photoresist. The goal of this paper is to provide comprehensive information allowing for the rational the selection of the conditions to fabricate optically-transparent carbon electrodes (OTCE) with specific electro-optical properties. According to our results, these electrodes could be appropriate choices as electrochemical transducers to monitor electrophoretic separations. At the core of this manuscript is the development and critical evaluation of a new optical model to calculate the thickness of the OTCE by variable angle spectroscopic ellipsometry (VASE). Such data was complemented with topography and roughness (obtained by AFM), electrochemical properties (obtained by cyclic voltammetry), electrical properties (obtained by electrochemical impedance spectroscopy), and structural composition (obtained by Raman spectroscopy). Although the described OTCE were used as substrates to investigate the effect of electrode potential on the real-time adsorption of proteins by ellipsometry, these results could enable the development of other biosensors that can be then integrated into various CE platforms. PMID:23595607

  2. Spectroscopic characterization of Cr2+ ions in ZnSe/ZnS crystals under visible excitation

    NASA Astrophysics Data System (ADS)

    Peppers, Jeremy M.; Fedorov, Vladimir V.; Mirov, Sergey B.

    2015-02-01

    Detailed spectroscopic characterization of Cr:ZnSe (Cr:ZnS) crystals under visible excitation into the charge transfer bands of Cr2+ impurities was performed. Middle infrared photoluminescence of Cr:ZnS under this excitation exhibits shorter rise time (~150ns) than that previously observed in Cr:ZnSe (~4-10 ?s). As a result the quantum yield of Cr:ZnS mid-IR photoluminescence under 10ns pulsed 416nm excitation into the charge transfer band was estimated at close to 100%, which contrasts with low (~14%) quantum yield measured in Cr:ZnSe under 532nm pulsed excitation, indicating the possibility of efficient excitation of the upper laser level of Cr:ZnS using this mechanism. The rise time can be caused by cascade relaxation from higher lying levels through the 3T1 metastable level, producing luminescence in the near-IR. Measurements of the temperature dependence of the middle- and near infrared photoluminescence signals are reported. These values indicated that more efficient pumping of Cr:ZnSe under 532nm excitation can be achieved at temperatures greater than 300 K. Results of high temperature laser experiments supporting this idea are presented.

  3. High-k dielectric characterization by VUV spectroscopic ellipsometry and X-ray reflection

    NASA Astrophysics Data System (ADS)

    Boher, P.; Evrard, P.; Piel, J. P.; Defranoux, C.; Fouere, J. C.; Bellandi, E.; Bender, H.

    2003-09-01

    In this study, we use vacuum UV spectroscopic ellipsometry (VUVSE) to characterize new high dielectric materials. Indeed, all the candidates for high k dielectrics become strongly absorbent when the wavelength is reduced down to 140nm. So, the correlation between thickness and refractive index is reduced in the VUV range and much more precise structural information can be deduced. HfO2, Al2O3 and mixed HfAlOx layers have been studied with and without thin SiO2 oxide at the interface. X-ray reflectometry (XRR) has been used to measure precisely the layer thickness and roughness. The two techniques are included in the same automated metrology system dedicated to 300mm technology which is also presented. We show in particular that VUVSE can detect the crystalline character of the layers and their composition can be measured in addition to the layer thickness. Results are compared to those obtained by transmission electron microscopy (TEM), x-ray fluorescence analysis (XRF) and x-ray photoemission (XPS).

  4. Structural and spectroscopic characterization of a thiosemicarbazidatodioxouranium(VI) complex: A combined experimental and DFT study

    NASA Astrophysics Data System (ADS)

    ?ahin, Musa; Özdemir, Nam?k; Bal-Demirci, Tülay; Ülküseven, Bahri; Dinçer, Muharrem; Soylu, Mustafa Serkan

    2015-01-01

    The title thiosemicarbazidatodioxouranium(VI) compound was synthesized and characterized by FT-IR, NMR and UV-vis spectroscopies. Solid-state structure of the compound was confirmed by X-ray crystallography. Besides, the molecular geometry, vibrational frequencies and gauge-independent atomic orbital (GIAO) 1H and 13C NMR chemical shift values of the compound in the ground state have been calculated using the density functional theory (DFT/B3LYP) method with the 6-311++G(d,p) basis set for the C, H, Cl, N, O, S atoms and SDD pseudo-potential for the U atom, and compared with the experimental data. Using the TD-DFT method, electronic absorption spectra of the compound have been predicted at same level. As a result, a good agreement is obtained between the experimental and theoretical ones.

  5. Valence fluctuation in Sm1-xEuxS system: An X-ray absorption spectroscopic study

    Microsoft Academic Search

    R. K. Singhal; K. B. Garg

    1992-01-01

    Sm1-xEuxS (x = 0.10 to 0.85) alloys have been investigated using XANES (X-ray absorption near-edge structure) technique to examine the question of intermediate valence of Sm and Eu. SmLIII absorption edge data point to the intermediate valence of Sm, and the Sm valence data clearly exhibits a continoous valence transition of Sm with increasing Eu content. On the other hand,

  6. Characterizing the structure of lipodisq nanoparticles for membrane protein spectroscopic studies.

    PubMed

    Zhang, Rongfu; Sahu, Indra D; Liu, Lishan; Osatuke, Anna; Comer, Raven G; Dabney-Smith, Carole; Lorigan, Gary A

    2015-01-01

    Membrane protein spectroscopic studies are challenging due to the difficulty introduced in preparing homogenous and functional hydrophobic proteins incorporated into a lipid bilayer system. Traditional membrane mimics such as micelles or liposomes have proved to be powerful in solubilizing membrane proteins for biophysical studies, however, several drawbacks have limited their applications. Recently, a nanosized complex termed lipodisq nanoparticles was utilized as an alternative membrane mimic to overcome these caveats by providing a homogeneous lipid bilayer environment. Despite all the benefits that lipodisq nanoparticles could provide to enhance the biophysical studies of membrane proteins, structural characterization in different lipid compositions that closely mimic the native membrane environment is still lacking. In this study, the formation of lipodisq nanoparticles using different weight ratios of POPC/POPG lipids to SMA polymers was characterized via solid-state nuclear magnetic resonance (SSNMR) spectroscopy and dynamic light scattering (DLS). A critical weight ratio of (1/1.25) for the complete solubilization of POPC/POPG vesicles has been observed and POPC/POPG vesicles turned clear instantaneously upon the addition of the SMA polymer. The size of lipodisq nanoparticles formed from POPC/POPG lipids at this weight ratio of (1/1.25) was found to be about 30 nm in radius. We also showed that upon the complete solubilization of POPC/POPG vesicles by SMA polymers, the average size of the lipodisq nanoparticles is weight ratio dependent, when more SMA polymers were introduced, smaller lipodisq nanoparticles were obtained. The results of this study will be helpful for a variety of biophysical experiments when specific size of lipid disc is required. Further, this study will provide a proper path for researchers working on membrane proteins to obtain pertinent structure and dynamic information in a physiologically relevant membrane mimetic environment. PMID:24853657

  7. A multi-epoch spectroscopic study of the BAL quasar APM 08279+5255: I. C IV absorption variability

    E-print Network

    Trevese, D; Vagnetti, F; Perna, M; Paris, D; Turriziani, S

    2013-01-01

    Broad Absorption Lines indicate gas outflows with velocities from thousands km/s to about 0.2 the speed of light, which may be present in all quasars and may play a major role in the evolution of the host galaxy. The variability of absorption patterns can provide informations on changes of the density and velocity distributions of the absorbing gas and its ionization status. We collected 23 photometrical and spectro-photometrical observations at the 1.82m Telescope of the Asiago Observatory since 2003, plus other 5 spectra from the literature. We analysed the evolution in time of the equivalent width of the broad absorption feature and two narrow absorption systems, the correlation among them and with the R band magnitude. We performed a structure function analysis of the equivalent width variations. We present an unprecedented monitoring of a broad absorption line quasar based on 28 epochs in 14 years. The shape of broad absorption feature shows a relative stability, while its equivalent width slowly decline...

  8. Combined use of X-ray reflectometry and spectroscopic ellipsometry for characterization of thin film optical properties

    NASA Astrophysics Data System (ADS)

    Cain, Jason P.; Robie, Stephen; Zhang, Qiaolin; Singh, Bhanwar; Emami, Iraj

    2006-03-01

    Accurate characterization of the optical properties of thin film materials used in semiconductor manufacturing is essential for many metrology applications in the fab, including film thickness measurement and scatterometry. The most common method for measuring these optical properties is spectroscopic ellipsometry. In this work X-ray reflectometry is used as a means of independently determining the thickness of a film to be characterized. This information is then used in the conventional analysis of spectroscopic ellipsometry data to extract the optical properties. In addition, the use of a Cauchy dispersion model fitted to the transparent region of the spectrum (if it exists) was used to determine the film thickness. Once the thickness was determined, a point-by-point regression was performed on the ellipsometry data to extract the optical properties. The results from these techniques were compared with each other and with conventional analysis of the ellipsometry data using common dispersion models.

  9. Characterization of fresh and aged natural ingredients used in historical ointments by molecular spectroscopic techniques: IR, Raman and fluorescence

    Microsoft Academic Search

    L. Brambilla; C. Riedo; C. Baraldi; A. Nevin; M. C. Gamberini; C. D’Andrea; O. Chiantore; S. Goidanich; L. Toniolo

    Natural organic materials used to prepare pharmaceutical mixtures including ointments and balsams have been characterized\\u000a by a combined non-destructive spectroscopic analytical approach. Three classes of materials which include vegetable oils (olive,\\u000a almond and palm tree), gums (Arabic and Tragacanth) and beeswax are considered in this study according to their widespread\\u000a use reported in ancient recipes. Micro-FTIR, micro-Raman and fluorescence spectroscopies

  10. Crystallographic and spectroscopic characterization and reactivities of a mononuclear non-haem iron(III)-superoxo complex.

    PubMed

    Hong, Seungwoo; Sutherlin, Kyle D; Park, Jiyoung; Kwon, Eunji; Siegler, Maxime A; Solomon, Edward I; Nam, Wonwoo

    2014-01-01

    Mononuclear non-haem iron(III)-superoxo species (Fe(III)-O2(-·)) have been implicated as key intermediates in the catalytic cycles of dioxygen activation by non-haem iron enzymes. Although non-haem iron(III)-superoxo species have been trapped and characterized spectroscopically in enzymatic and biomimetic reactions, no structural information has yet been obtained. Here we report the isolation, spectroscopic characterization and crystal structure of a mononuclear side-on (?(2)) iron(III)-superoxo complex with a tetraamido macrocyclic ligand. The non-haem iron(III)-superoxo species undergoes both electrophilic and nucleophilic oxidation reactions, as well as O2-transfer between metal complexes. In the O2-transfer reaction, the iron(III)-superoxo complex transfers the bound O2 unit to a manganese(III) analogue, resulting in the formation of a manganese(IV)-peroxo complex, which is characterized structurally and spectroscopically as a mononuclear side-on (?(2)) manganese(IV)-peroxo complex. The difference in the redox distribution between the metal ions and O2 in iron(III)-superoxo and manganese(IV)-peroxo complexes is rationalized using density functional theory calculations. PMID:25510711

  11. Chemical Characterization of Riverine Dissolved Organic Matter Using a Combination of Spectroscopic and Pyrolytic Methods

    NASA Astrophysics Data System (ADS)

    Templier, J.; Derenne, S.

    2006-12-01

    It is now well established that riverine dissolved organic matter (DOM) play a major role in environmental processes. However natural organic matter exhibit different properties depending on their sources and the fractions considered. As a result chemical characterization of DOM has appeared essential for a better understanding of their reactivity. The purpose of this work was to characterize all of the DOM at molecular level, including the non-hydrolysable fraction, which is a major part of this OM. To this aim a new analytical approach had to be considered. A combination of spectroscopic and pyrolytic methods has been applied to various fractions of DOM originating from different catchments (French and Amazonian rivers). The fractions were termed hydrophilic, transphilic and colloids according to the IHSS fractionation procedure, and account for at least 70% of the total dissolved organic carbon. Solid state 13C NMR and FTIR afford information on the nature and relative abundance of the chemical functions occurring in macromolecules. Differential thermogravimetric analysis allows to determine the thermal behaviour of the studied material and hence to optimize analytical pyrolysis conditions. Curie point pyrolysis combined to gas chromatography and mass spectrometry leads to identification of characteristic pyrolysis products, some of them being specific of a macromolecular source. Additional information can be provided by thermochemolysis with tetramethylammonium hydroxide (TMAH). TMAH was shown to allow an increase in the efficiency of the cracking of macromolecular structures and an enhancement of the detection of the polar pyrolysis products especially due to methylation of the alcohol, phenol and acid groups. The results obtained have established the importance of terrestrial contribution to DOM. Hydrophobic fractions mainly originate from lignin-derived units, whereas transphilic fractions mostly contain cellulose units together with lignin derived ones and substantial amount of nitrogen-containing moieties. Characterization of colloidal fraction has indicated the presence of compounds from bacterial origin, especially specific nitrogen-containing molecules that are characteristic pyrolysis products of peptidoglycans, along with lignin-derived units. However pyrolysis has revealed significant differences in the detection of nitrogen-containing molecules, which do not parallel nitrogen content of the fractions. Moreover in hydrophobic and transphilic fractions the molecular structure of these compounds, which are mainly nitrogen- and oxygen- containing molecules, has not allowed to ascertain their origin. As the major biological sources of organic nitrogen (proteins, amino sugars, or tetrapyrrole pigments) involve differences in the main nitrogen functionality, two additional spectroscopic methods, namely X-ray photoelectron spectroscopy (XPS) and solid state 15N NMR, have been used to determine the nitrogen functional groups (amide, amine, and N-heterocycle) present in the different fractions of DOM. The combination of these two methods has revealed the occurrence of different functionality of nitrogen, with relative contributions depending on the considered fraction. It has also appeared that Curie point pyrolysis does not account for the presence of nitrogen in macromolecules with the same efficiency depending on the functional group involved. This study has highlighted the importance of combining different analytical approaches to obtain a whole insight into chemical structure of OM and avoid biased information.

  12. Characterization of light absorption in thin-film silicon with periodic nanohole arrays.

    PubMed

    Yahaya, Nor Afifah; Yamada, Noboru; Kotaki, Yukio; Nakayama, Tadachika

    2013-03-11

    Light absorption in thin-film nanostructured monocrystalline silicon (c-Si) in a glass/Ag(0.2 µm)/c-Si(1 µm) stack is characterized using simulations and measurements. Nanohole (NH) arrays designed for a practical thin-film solar cell configuration experimentally exhibit a significant improvement of the light absorption in the 1-µm ultrathin c-Si layer that exceeds the theoretical Yablonovitch limit in the long wavelength range. Fabricated square-lattice and hexagonal NH arrays give relative improvements of 65 and 70%, respectively, in the total absorption compared to a nonpatterned stack. The effect of an indium-tin-oxide (ITO) coating is also simulated, and an empty NH configuration gives the lowest ITO parasitic absorption. PMID:23482160

  13. Development of Cellular Absorptive Tracers (CATs) for a Quantitative Characterization of Microbial Mass in Flow Systems

    SciTech Connect

    Saripalli, Prasad; Brown, Christopher F.; Lindberg, Michael J.

    2005-03-16

    We report on a new Cellular Absorptive Tracers (CATs) method, for a simple, non-destructive characterization of bacterial mass in flow systems. Results show that adsorption of a CAT molecule into the cellular mass results in its retardation during flow, which is a good, quantitative measure of the biomass quantity and distribution. No such methods are currently available for a quantitative characterization of cell mass.

  14. Growth and spectroscopic characterization of monolayer and few-layer hexagonal boron nitride on metal substrates.

    PubMed

    Feigelson, Boris N; Bermudez, Victor M; Hite, Jennifer K; Robinson, Zachary R; Wheeler, Virginia D; Sridhara, Karthik; Hernández, Sandra C

    2015-02-28

    Atomically thin two dimensional hexagonal boron nitride (2D h-BN) is one of the key materials in the development of new van der Waals heterostructures due to its outstanding properties including an atomically smooth surface, high thermal conductivity, high mechanical strength, chemical inertness and high electrical resistance. The development of 2D h-BN growth is still in the early stages and largely depends on rapid and accurate characterization of the grown monolayer or few layers h-BN films. This paper demonstrates a new approach to characterizing monolayer h-BN films directly on metal substrates by grazing-incidence infrared reflection absorption spectroscopy (IRRAS). Using h-BN films grown by atmospheric-pressure chemical vapor deposition on Cu and Ni substrates, two new sub-bands are found for the A2u out-of-plane stretching mode. It is shown, using both experimental and computational methods, that the lower-energy sub-band is related to 2D h-BN coupled with substrate, while the higher energy sub-band is related to decoupled (or free-standing) 2D h-BN. It is further shown that this newly-observed fine structure in the A2u mode can be used to assess, quickly and easily, the homogeneity of the h-BN-metal interface and the effects of metal surface contamination on adhesion of the layer. PMID:25640166

  15. Structural Characterization of Mixed Nanoferrites Using X-Ray Absorption Spectroscopy

    Microsoft Academic Search

    S. Calvin; B. Ravel; E. A. Carpenter; S. A. Morrison; V. G. Harris

    2002-01-01

    Structural characterization of mixed nanoferrite materials is often difficult, both because of the high degree of disorder which may be present and because the transition metals which are common constituents of these materials, such as manganese, iron, nickel, and zinc, exhibit similar atomic scattering factors. Extended x-ray absorption fine structure (EXAFS) spectroscopy is well-suited for investigation of these materials, since

  16. Spectroscopic characterization of the binding mechanism of fluorescein and carboxyfluorescein in human serum albumin

    NASA Astrophysics Data System (ADS)

    Sulaiman, Saba A. J.; Kulathunga, H. Udani; Abou-Zied, Osama K.

    2015-03-01

    Fluorescein (FL) and some of its precursors have proven to be effective fluorescent tracers in pharmaceutical and medical applications owing to their high quantum yield of fluorescence in physiological conditions and their high membrane permeability. In order to protect FL from metabolic effects during the process of its delivery, human serum albumin (HSA) has been used as a carrier because of its compatibility with the human body. In the present work, we used spectroscopic methods to characterize the binding mechanisms of FL and one of its derivatives, 5(6)- carboxyfluorescein (CFL), in the HSA protein. The absorbance change of the two ligands (FL and CFL) was quantified as a function of the HSA concentration and the results indicate a moderate binding strength for the two ligands inside HSA (1.00 +/- 0.12 x 104 M-1). The quenching effect of FL(CFL) on the fluorescence intensity of W214 (the sole tryptophan in HSA) indicates that FL and CFL occupy Site I in the protein which is known to bind several hydrophobic drugs. By performing site-competitive experiments, the location of the ligands is determined to be similar to that of the anticoagulant drug warfarin. At higher ratios of [ligand]/[HSA], we observed an upward curvature in the Stern-Volmer plots which indicates that the ligands occupy more pockets in Site I, close to W214. Our results indicate that both ligands bind in HSA with a moderate strength that should not affect their release when used as fluorescent reporters. The chemical and physical identities of the two ligands are also preserved inside the HSA binding sites.

  17. Absorption spectroscopic studies of carbon dioxide conversion in a low pressure glow discharge using tunable infrared diode lasers

    Microsoft Academic Search

    F. Hempel; J. Röpcke; F. Miethke; H.-E. Wagner

    2002-01-01

    The time and spatial dependence of the chemical conversion of CO2 to CO were studied in a closed glow discharge reactor (p = 50 Pa, I = 2-30 mA) consisting of a small plasma zone and an extended stationary afterglow. Tunable infrared diode laser absorption spectroscopy has been applied to determine the absolute ground state concentrations of CO and CO2.

  18. ?-MnO 2/polyaniline composites: Preparation, characterization, and applications in microwave absorption

    NASA Astrophysics Data System (ADS)

    Jianjun, Hu; Yuping, Duan; Jia, Zhang; Hui, Jing; Shunhua, Liu; Weiping, Li

    2011-05-01

    MnO 2/doped polyaniline (PANI) is prepared by an in situ polymerization method using ?-MnO 2 as the addition agent and hydrochloric acid as the doping agent. Products are characterized by FT-IR, UV-vis, XRD, and TEM. Conductivity, electromagnetic properties, and microwave absorption properties are first discussed on the basis of structural characterization. The as-prepared products of MnO 2/PANI are partially crystalline in nature and spherical in pattern with grain sizes of 50-70 nm. MnO 2 particles are successfully decorated with doped PANI. MnO 2/PANI displays moderate electric conduction, excellent dielectric losses, and microwave absorption capabilities. Compared to pure MnO 2, the dielectric and reflection loss properties of MnO 2/PANI composites exhibit significant improvements, with an effective absorption band at 5 GHz under -10 dB and maximum reflection loss of -21 dB at 13.56 GHz. Pure MnO 2 shows an effective absorption band of 3 GHz under -10 dB and a maximum reflection loss of -14.20 dB at 11.5 GHz. Thus, MnO 2/PANI composites are found to be a promising microwave absorption material.

  19. Spectroscopic characterization of PET glycolysis and surface molecular orientation of polymers

    NASA Astrophysics Data System (ADS)

    Weir, Michael David

    This dissertation seeks to develop novel polymer characterization techniques using UV and fluorescence spectroscopy. The first portion of the dissertation consists of monitoring the glycolytic depolymerization of poly(ethylene terephthalate), PET, using UV and fluorescence spectroscopy. The primary product of the glycolysis of PET is bis(hydroxyethyl) tereplithalate (BHET), along with other low molecular weight oligomers (degree of polymerization = 1--3). The UV absorption of the glycolized products occurs at 287 nm and is associated with the pi ? pi* transition of the tereplithalate moiety. This absorption band shows a linear increase with reaction time that corresponds to an increase in the concentration of glycolized products. BHET was selected as a model compound to represent the glycolized products and was used to calculate the concentration of glycolized products. When using excitation wavelengths of 300 nm and 340 nm, fluorescence emission spectra of the glycolized products were observed at 350 nm and 380 nm respectively. These emission bands also showed an increase in intensity corresponding to the concentration increase. Again, BHET was used as a model compound to simulate and calculate the concentration of the glycolized products. We determined the overall reaction to be second order and that the reaction rate is strongly dependent on the glycol concentration; an increase in the glycol concentration results in an increase in the reaction rate. The second portion of this dissertation consists of the characterization of surface molecular orientation of poly(ethylene terephthalate) (PET) and Kaptono films by UV reflection dichroism using a specular reflection accessory and a bifurcated fiber optic. The UV reflection peaks for PET and Kapton RTM occur at 257 nm and 310 nm respectively. The orientation function and dichroic ratio calculated using both specular reflection and the fiber optic agreed well with each other. Additionally, correct placement of the polarizer is essential in producing good results. When placed at either the source or detector side of the fiber, there was no evidence of orientation seen. However, placement at the common end shows good agreement with the results from the specular reflection accessory. These different results are a manifestation of the polarization/depolarization characteristics of the fiber optic.

  20. Synthesis, spectroscopic characterization and molecular modeling of a tetranuclear platinum(II) complex with thiazolidine-4-carboxylic acid

    NASA Astrophysics Data System (ADS)

    Corbi, Pedro P.; Formiga, André L. B.; Bonk, Fábio A.; Quintão, Frederico A.; Ferraresi, Diego K. D.; Lustri, Wilton R.; Massabni, Antonio C.

    2012-07-01

    The synthesis, spectroscopic characterization and molecular modeling of a novel tetranuclear platinum(II) complex with thiazolidine-4-carboxylic acid (THC) are described. Elemental analysis is consistent with the composition PtCl2C4H7NO2S·H2O. Infrared (IR) spectroscopic results and solid-state 13C and 15N nuclear magnetic resonance (NMR) data indicate coordination of the ligand to Pt(II) through the nitrogen and sulfur atoms. The square planar geometry of the platinum(II) complex is completed by chlorine atoms. Density functional theory (DFT) suggests the formation of a tetrameric cluster as the most probable structure, where each THC molecule bridges between two metal centers. The compound is insoluble in water.

  1. Spectroscopic method for Earth-satellite-Earth laser long-path absorption measurements using Retroreflector In Space (RIS)

    NASA Technical Reports Server (NTRS)

    Sugimoto, Nobuo; Minato, Atsushi; Sasano, Yasuhiro

    1992-01-01

    The Retroreflector in Space (RIS) is a single element cube-corner retroreflector with a diameter of 0.5 m designed for earth-satellite-earth laser long-path absorption experiments. The RIS is to be loaded on the Advanced Earth Observing System (ADEOS) satellite which is scheduled for launch in Feb. 1996. The orbit for ADEOS is a sun synchronous subrecurrent polar-orbit with an inclination of 98.6 deg. It has a period of 101 minutes and an altitude of approximately 800 km. The local time at descending node is 10:15-10:45, and the recurrent period is 41 days. The velocity relative to the ground is approximately 7 km/s. In the RIS experiment, a laser beam transmitted from a ground station is reflected by RIS and received at the ground station. The absorption of the intervening atmosphere is measured in the round-trip optical path.

  2. X-ray-absorption-spectroscopic evidence for a novel iron cluster in hydrogenase II from Clostridium pasteurianum.

    PubMed Central

    George, G N; Prince, R C; Stokley, K E; Adams, M W; Stockley, K E

    1989-01-01

    Hydrogenase II from Clostridium pasteurianum contains three different iron-sulphur clusters. Two are [4Fe-4S](2+.1+) clusters, whereas the other, which is thought to be the site of interaction with H2 and is known as the 'H cluster', is of unknown structure and possesses unusual spectroscopic properties. Analysis of the iron e.x.a.f.s. spectra shows that the H cluster contains iron co-ordinated mostly to sulphur and possesses 2.8 A (1 A = 0.1 nm) Fe--Fe separations when oxidized and 3.3 A Fe--Fe separations when reduced with H2. The data suggest that the reduced H cluster represents a new structural type of iron-sulphur cluster. PMID:2655584

  3. Nuclear Magnetic Resonance and X-Ray Absorption Spectroscopic Studies of Lithium Insertion in Silver Vanadium Oxide Cathodes

    Microsoft Academic Search

    N. D. Leifer; A. Colon; k. Martocci; S. G. Greenbaum; F. M. Alamgir; T. B. Reddy; N. R. Gleason; R. A. Leising; E. S. Takeuchi

    2007-01-01

    Structural studies have been carried out on AgVO (silver vanadium oxide, SVO) and LiAgVO, lithiated SVO with x=0.72, 2.13, and 5.59 using nuclear magnetic resonance (NMR) and X-ray absorption spectroscopy (XAS). Lithium-7 NMR indicates the formation of a solid electrolyte interphase layer on the x=0.72 sample and lithium intercalation into both octahedral and tetrahedral sites in the SVO lattice, and

  4. An X-ray absorption (EXAFS) spectroscopic study of aquated Ag + in hydrothermal solutions to 350°C

    Microsoft Academic Search

    T. M. Seward; C. M. B. Henderson; J. M. Charnock; B. R. Dobson

    1996-01-01

    The first direct measurements over a range of temperatures from 25–350°C are reported for cation-oxygen (water) distances in aqueous solutions at equilibrium saturated vapour pressures. The silver-oxygen (first shell water) bond lengths in AgNO3 and AgClO4 solutions were obtained using extended X-ray absorption fine structure (EXAFS) measurements on the silver K-edge. At 25°C and 1 bar, the Ag+ ion is

  5. X-ray absorption spectroscopic evidence for the complexation of Hg(II) by reduced sulfur in soil humic substances

    Microsoft Academic Search

    K. Xia; U. L. Skyllberg; W. F. Bleam; P. A. Helmke; P. R. Bloom; E. A. Nater

    1999-01-01

    Analysis of Hg(II) complexed by a soil humic acid (HA) using synchrotron-based X-ray absorption spectroscopy (XAS) revealed the importance of reduces sulfur functional groups (thiol (R-SH) and disulfide (R-SS-R)\\/disulfane (R-SSH)) in humic substances in the complexation of Hg(II). A two-coordinate binding environment with one oxygen atom and one sulfur atom at distances of 2.02 and 2.38 â«, respectively, was found

  6. [Three-dimensional excitation emission matrix fluorescence spectroscopic characterization of dissolved organic matter].

    PubMed

    Fu, Ping-Qing; Liu, Cong-Qiang; Wu, Feng-Chang

    2005-12-01

    Three-dimensional excitation emission matrix fluorescence spectroscopy (3DEEM) was applied to characterize the fluorescence properties of dissolved organic matter (DOM) in lakes, rivers, streams, and ground waters. The results showed that the 3DEEM of DOM in aquatic environments mainly have four fluorescence peaks: peak A and C was referred to as fulvic-like fluorescence, and peak B and D was referred to as protein-like fluorescence. Results of river water DOM typically showed strong fulvic-like fluorescence. Polluted river waters often showed strong protein-like fluorescence. Four peaks were also found in the 3DEEM of lake DOM, which can origin from terrestrial runoff or from sources within the lakes. In Lake Baihua, strong protein-like fluorescence was found owing to the pollution by municipal wastewaters. Groundwater DOM has relatively lower DOC concentrations at 0.56-0.85 mg x L(-1) and is characterized by fulvic-like fluorescence only if it was polluted by municipal wastewaters, and then it has strong protein-like fluorescence. The authors demonstrate that for all DOM samples, fluorescence intensity at peak C and absorption at 254 nm both showed a strong correlation with DOC concentrations (r2 = 0.82 and 0.95, respectively). Also a strong linear correlation between UV-fulvic-like fluorescence and visible fulvic-like fluorescence was found (r2 = 0.96). The fulvic-like fluorescence at peak A and C varied in accordance to each other with the pH of the DOM samples, and the maximum fluorescence occurred at pH 10, while the maximum value of protein-like fluorescence (peak B) occurred at pH around 8.5. PMID:16544498

  7. X-ray absorption spectroscopic studies of the active sites of nickel- and copper-containing metalloproteins

    SciTech Connect

    Tan, G.O.

    1993-06-01

    X-ray absorption spectroscopy (XAS) is a useful tool for obtaining structural and chemical information about the active sites of metalloproteins and metalloenzymes. Information may be obtained from both the edge region and the extended X-ray absorption fine structure (EXAFS) or post-edge region of the K-edge X-ray absorption spectrum of a metal center in a compound. The edge contains information about the valence electronic structure of the atom that absorbs the X-rays. It is possible in some systems to infer the redox state of the metal atom in question, as well as the geometry and nature of ligands connected to it, from the features in the edge in a straightforward manner. The EXAFS modulations, being produced by the backscattering of the ejected photoelectron from the atoms surrounding the metal atom, provide, when analyzed, information about the number and type of neighbouring atoms, and the distances at which they occur. In this thesis, analysis of both the edge and EXAFS regions has been used to gain information about the active sites of various metalloproteins. The metalloproteins studied were plastocyanin (Pc), laccase and nickel carbon monoxide dehydrogenase (Ni CODH). Studies of Cu(I)-imidazole compounds, related to the protein hemocyanin, are also reported here.

  8. Infrared spectroscopic, x-ray, and nanoscale characterization of strontium titanate thin films

    SciTech Connect

    Webb, J.D.; Moutinho, H.R.; Kazmerski, L.L. [National Renewable Energy Lab., Golden, CO (United States); Mueller, C.H.; Rivkin, T.V.; Treece, R.E. [Superconducting Core Technologies, Inc., Golden, CO (United States); Dalberth, M.; Rogers, C.T. [Colorado Univ., Boulder, CO (United States). Dept. of Physics

    1996-06-01

    Attenuated total reflectance (ATR) measurements were performed using Fourier transform infrared (FTIR) spectroscopy in the ATR mode with a thallium iodobromide (KRS-5) crystal to measure the frequencies of the v{sub 3} and v{sub 4} phonon absorption bands in thin Sr titanate films deposited on single-crystal Y-Ba Cu oxide (YBCO), La aluminate, Mg oxide, and Sr titanate substrates. The KRS-5 crystal enabled FTIR-ATR measurements at frequencies above 400 cm{sup -1}. Atomic force microscopy (AFM) and x-ray diffraction (XRD) measurements were also made to further characterize the films. The measurements were repeated on single-crystal specimens of Sr titanate and the substrates for comparison. Softening in the frequency of the v{sub 4} transverse optical phonon in the lattice-mismatched films below the established value of 544 cm{sup -1} is indicative of the highly textured, polycrystalline ceramic nature of the films and is consistent with the XRD and AFM results.

  9. Infrared spectroscopic, x-ray, and nanoscale characterization of strontium titanate thin films

    SciTech Connect

    Webb, J.D.; Moutinho, H.R.; Kazmerski, L.L. [National Renewable Energy Lab., Golden, CO (United States); Mueller, C.H.; Rivkin, T.V.; Treece, R.E. [Superconducting Core Technologies, Inc., Golden, CO (United States); Dalberth, M.; Rogers, C.T. [Colorado Univ., Boulder, CO (United States). Dept. of Physics

    1996-04-01

    Attenuated total reflectance (ATR) measurements were performed using Fourier transform infrared (FTIR) spectroscopy in the ATR mode with a thallium iodobromide (KRS-5) crystal to measure the frequencies of the {nu}{sub 3} and {nu}{sub 4} phonon absorption bands in thin strontium titanate films deposited on single-crystal yttrium-barium copper oxide (YBCO), lanthanum aluminate, magnesium oxide, and strontium titanate substrates. The KRS-5 crystal enabled FTIR-ATR measurements to be made at frequencies above 400 cm{sup {minus}1}. Atomic force microscopy (AFM) and X-ray diffraction (XRD) measurements were also made to further characterize the films. The measurements were repeated on single-crystal specimens of strontium titanate and the substrates for comparison. Softening in the frequency of the {nu}{sub 4} transverse optical phonon in the lattice- mismatched films below the established value of 544 cm{sup {minus}1} is indicative of the highly textured, polycrystalline ceramic nature of the films and is consistent with the XRD and AFM results.

  10. Infrared spectroscopic characterization of organic matter associated with microbial bioalteration textures in basaltic glass.

    PubMed

    Preston, L J; Izawa, M R M; Banerjee, N R

    2011-09-01

    Microorganisms have been found to etch volcanic glass within volcaniclastic deposits from the Ontong Java Plateau, creating micron-sized tunnels and pits. The fossil record of such bioalteration textures is interpreted to extend back ?3.5 billion years to include meta-volcanic glass from ophiolites and Precambrian greenstone belts. Bioalteration features within glass clasts from Leg 192 of the Ocean Drilling Program were investigated through optical microscopy and Fourier transform infrared (FTIR) spectroscopy of petrographic thin sections. Extended depth of focus optical microscopic imaging was used to identify bioalteration tubules within the samples and later combined with FTIR spectroscopy to study the organic molecules present within tubule clusters. The tubule-rich areas are characterized by absorption bands indicative of aliphatic hydrocarbons, amides, esters, and carboxylic groups. FTIR analysis of the tubule-free areas in the cores of glass clasts indicated that they were free of organics. This study further constrains the nature of the carbon compounds preserved within the tubules and supports previous studies that suggest the tubules formed through microbial activity. PMID:21848422

  11. X-ray absorption fine structure spectroscopic determination of plutonium speciation at the Rocky Flats environmental technology

    SciTech Connect

    Lezama-pacheco, Juan S [Los Alamos National Laboratory; Conradson, Steven D [Los Alamos National Laboratory; Clark, David L [Los Alamos National Laboratory

    2008-01-01

    X-ray Absorption Fine Structure spectroscopy was used to probe the speciation of the ppm level Pu in thirteen soil and concrete samples from the Rocky Flats Environmental Technology Site in support of the site remediation effort that has been successfully completed since these measurements. In addition to X-ray Absorption Near Edge Spectra, two of the samples yielded Extended X-ray Absorption Fine Structure spectra that could be analyzed by curve-fits. Most of these spectra exhibited features consistent with PU(IV), and more specificaJly, PuO{sub 2+x}-type speciation. Two were ambiguous, possibly indicating that Pu that was originally present in a different form was transforming into PuO{sub 2+x}, and one was interpreted as demonstrating the presence of an unusual Pu(VI) compound, consistent with its source being spills from a PUREX purification line onto a concrete floor and the resultant extreme conditions. These experimental results therefore validated models that predicted that insoluble PuO{sub 2+x} would be the most stable form of Pu in equilibrium with air and water even when the source terms were most likely Pu metal with organic compounds or a Pu fire. A corollary of these models' predictions and other in situ observations is therefore that the minimal transport of Pu that occurred on the site was via the resuspension and mobilization of colloidal particles. Under these conditions, the small amounts of diffusely distributed Pu that were left on the site after its remediation pose only a negligible hazard.

  12. Crystal structure, complexation, spectroscopic characterization and antimicrobial evaluation of 3,4-dihydroxybenzylidene isonicotinyl-hydrazone

    NASA Astrophysics Data System (ADS)

    Jeragh, Bakir; Ali, Mayada S.; El-Asmy, Ahmed A.

    2015-06-01

    A single crystal of 3,4-dihydroxybenzylidene isonicotinylhydrazone, HBINH, has been grown and solved by X-ray crystallography. The VO2+, Zr4+, Co2+, Ni2+, Cu2+, Zn2+, Cd2+, Hg2+ and Pd2+ complexes of HBINH have been prepared and spectroscopically characterized. The data confirmed the formulae [Co(HBINH)(H2O)Cl]Cl·H2O, [Pd(HBINH)Cl2], [Zn(HBINH)2Cl2], [Cd(HBINH)(H2O)2Cl2]·1½H2O, [(VO)2(HBINH-3H)(OH)(H2O)], [Ni2(HBINH)(H2O)6Cl2]Cl2, [Cu2(HBINH-3H)(H2O)2(OAc)]·3H2O, [Zr2(HBINH-3H)Cl4]Cl, [Hg2(HBINH)Cl4] and the dimer {[Cu(HBINH)Cl]Cl}2. Most of the complexes have intense colors and high melting points and some are electrolytes in DMSO solution. The ligand behaves as a neutral bidentate in the Co(II), Cu(II), Pd(II), Zn(II) and Cd(II) complexes; dibasic tetradentate in [Ni2(HBINH)(H2O)6Cl2]Cl2 and tribasic tetradentate in [Cu2(HBINH-3H)(OAc)]·5H2O, [(VO)2(HBINH-3H)(OH)(H2O)] and [Zr2(HBINH-3H)Cl4]Cl by the loss of 3H+ due to the deprotonation of the two hydroxyl groups and the enolization of the amide (Odbnd CNH) group. A tetrahedral geometry was proposed for the Co(II), Cu(II), Zn(II) and Hg(II) complexes; square-planar for the Pd(II) complex; square-pyramid for the VO2+ complex and octahedral for the Ni(II) and Cd(II) complexes. The complexes [Cd(HBINH)(H2O)2Cl2]·1½H2O, [(VO)2(HBINH-3H)(OH)(H2O)] and [Cu2(HBINH-3H)-(H2O)2(OAc)]·3H2O have activities against Bacillus sp. M3010, Candida albicans, Escherichia coli, Staphylococcus aureus and Slamonella sp. PA393.

  13. In vitro characterization of the intestinal absorption of methylmercury using a Caco-2 cell model.

    PubMed

    Vázquez, Marta; Vélez, Dinoraz; Devesa, Vicenta

    2014-02-17

    Methylmercury (CH3Hg) is one of the forms of mercury found in food, particularly in seafood. Exposure to CH3Hg is associated with neurotoxic effects during development. In addition, methylmercury has been classified by the International Agency for Research on Cancer as a possible human carcinogen. Although the diet is known to be the main source of exposure, few studies have characterized the mechanisms involved in the absorption of this contaminant. The present study examines the absorption process using the Caco-2 cell line as a model of the intestinal epithelium. The results indicate that transport across the intestinal cell monolayer in an absorptive direction occurs mainly through passive transcellular diffusion. This mechanism coexists with carrier-mediated transcellular transport, which has an active component. The participation of H(+)- and Na(+)-dependent transport was observed. Inhibition tests point to the possible participation of amino acid transporters (B(0,+) system, L system, and/or y(+)L system) and organic anion transporters (OATs). Our study suggests the participation in CH3Hg absorption of transporters that have already been identified as being responsible for the transport of this species in other systems, although further studies are needed to confirm their participation in intestinal absorption. It should be noted that CH3Hg experiences important cellular acumulation (48-78%). Considering the toxic nature of this contaminant, this fact could affect intestinal epithelium function. PMID:24397474

  14. Tissue characterization with ballistic photons: counting scattering and/or absorption centres

    NASA Astrophysics Data System (ADS)

    Corral, F.; Strojnik, M.; Paez, G.

    2015-03-01

    We describe a new method to separate ballistic from the scattered photons for optical tissue characterization. It is based on the hypothesis that the scattered photons acquire a phase delay. The photons passing through the sample without scattering or absorption preserve their coherence so they may participate in interference. We implement a Mach-Zehnder experimental setup where the ballistic photons pass through the sample with the delay caused uniquely by the sample indices of refraction. We incorporate a movable mirror on the piezoelectric actuator in the sample arm to detect the amplitude of the modulation term. We present the theory that predicts the path-integrated (or total) concentration of the scattering and absorption centres. The proposed technique may characterize samples with transmission attenuation of ballistic photons by a factor of 10-14.

  15. Quantification of point-source emissions of CO2 and CH4 using airborne absorption spectroscopic remote sensing

    NASA Astrophysics Data System (ADS)

    Bovensmann, H.; Gerilowski, K.; Krings, T.; Buchwitz, M.; Sachs, T.; Erzinger, J.; Burrows, J. P.

    2012-04-01

    Many natural and anthropogenic emissions of CO2 and CH4 occure on small to point scales. Examples are the CO2 release by volcanoes, power plants, steel and cement production, as well as CH4 release by mud volcanoes, large seeps, land fills or open coal mines and coal mine venting. Quantifying and verifying these emissions by independent, non-intrusive (here remote sensing) techniques is required in the context of a better understanding and management these sources. The data of airborne absorption spectrometer covering the relevant spectral absorptions of CO2 and CH4 has the potential to contribute to this research and application area. Recent achievements using the Methane Airborne MAPper (MAMAP) sensor - developed by the University of Bremen in cooperation with the GFZ Potsdam - show that CO2 as well as CH4 point source emissions can be derived from column averaged dry air mole fractions of CO2 and CH4 retrieved from airborne passive nadir remote sensing measurements. The developed techniques are also relevant in the context of future CO2 and CH4 satellite missions like OCO-2 and CarbonSat. The paper will present first results of two campaigns performed in 2011 covering anthropogenic as well as geologic point sources of CO2 and CH4. The potential and limitations for future applications will be discussed.

  16. Spectroscopic characterization of alumina-supported bis(allyl)iridium complexes : site-isolation, reactivity, and decomposition studies

    Microsoft Academic Search

    Ryan J. Trovitch; Neng Guo; Michael T. Janicke; Hongbo Li; Christopher L. Marshall; Jeffrey T. Miller; Alfred P. Sattelberger; Kevin D. John; R. Thomas Baker

    2010-01-01

    The covalent attachment of tris(allyl)iridium to partially dehydroxylated ?-alumina is found to proceed via surface hydroxyl group protonation of one allyl ligand to form an immobilized bis(allyl)iridium moiety, (?AlO)Ir(allyl)2, as characterized by CP-MAS 13C NMR, inductively coupled plasma-mass spectrometry, and Ir L3 edge X-ray absorption spectroscopy. Extended X-ray absorption fine-structure (EXAFS) measurements taken on unsupported Ir(allyl)3 and several associated tertiary

  17. New 1,2,4-triazole-based azo-azomethine dyes. Part I: Synthesis, characterization and spectroscopic studies

    NASA Astrophysics Data System (ADS)

    Khanmohammadi, Hamid; Erfantalab, Malihe

    2012-02-01

    Four new 1,2,4-triazole-based azo-azomethine dyes were synthesized via condensation of 3,5-diamino-1,2,4-triazole with azo-coupled o-vanillin precursors. The prepared dyes were characterized by IR, UV-vis and 1H NMR spectroscopic methods as well as elemental analyses. Thermal properties of the prepared dyes were examined by thermogravimetric analysis. Results indicated that the framework of the dyes was stable up to 225 °C. Also, the influence of various factors including time and mixed DMSO/EtOH solution on UV-vis spectra of the dyes were investigated.

  18. Infrared spectroscopic characterization of dehydration and accompanying phase transition behaviors in NAT-topology zeolites

    SciTech Connect

    Wang, Hsiu-Wen [ORNL; Bishop, David [ORNL

    2012-01-01

    Relative humidity (PH2O, partial pressure of water)-dependent dehydration and accompanying phase transitions in NAT-topology zeolites (natrolite, scolecite, and mesolite) were studied under controlled temperature and known PH2O conditions by in situ diffuse-reflectance infrared Fourier transform spectroscopy and parallel X-ray powder diffraction. Dehydration was characterized by the disappearance of internal H2O vibrational modes. The loss of H2O molecules caused a sequence of structural transitions in which the host framework transformation path was coupled primarily via the thermal motion of guest Na?/Ca2? cations and H2O molecules. The observation of different interactions of H2O molecules and Na?/Ca2? cations with host aluminosilicate frameworks under highand low-PH2O conditions indicated the development of different local strain fields, arising from cation H2O interactions in NAT-type channels. These strain fields influence the Si O/Al O bond strength and tilting angles within and between tetrahedra as the dehydration temperature is approached. The newly observed infrared bands (at 2,139 cm-1 in natrolite, 2,276 cm-1 in scolecite, and 2,176 and 2,259 cm-1 in mesolite) result from strong cation H2O Al Si framework interactions in NAT-type channels, and these bands can be used to evaluate the energetic evolution of Na?/Ca2? cations before and after phase transitions, especially for scolecite and mesolite. The 2,176 and 2,259 cm-1 absorption bands in mesolite also appear to be related to Na?/Ca2? order disorder that occur when mesolite loses its Ow4 H2O molecules.

  19. Spectroscopic determination of leaf biochemistry using band-depth analysis of absorption features and stepwise multiple linear regression

    USGS Publications Warehouse

    Kokaly, R.F.; Clark, R.N.

    1999-01-01

    We develop a new method for estimating the biochemistry of plant material using spectroscopy. Normalized band depths calculated from the continuum-removed reflectance spectra of dried and ground leaves were used to estimate their concentrations of nitrogen, lignin, and cellulose. Stepwise multiple linear regression was used to select wavelengths in the broad absorption features centered at 1.73 ??m, 2.10 ??m, and 2.30 ??m that were highly correlated with the chemistry of samples from eastern U.S. forests. Band depths of absorption features at these wavelengths were found to also be highly correlated with the chemistry of four other sites. A subset of data from the eastern U.S. forest sites was used to derive linear equations that were applied to the remaining data to successfully estimate their nitrogen, lignin, and cellulose concentrations. Correlations were highest for nitrogen (R2 from 0.75 to 0.94). The consistent results indicate the possibility of establishing a single equation capable of estimating the chemical concentrations in a wide variety of species from the reflectance spectra of dried leaves. The extension of this method to remote sensing was investigated. The effects of leaf water content, sensor signal-to-noise and bandpass, atmospheric effects, and background soil exposure were examined. Leaf water was found to be the greatest challenge to extending this empirical method to the analysis of fresh whole leaves and complete vegetation canopies. The influence of leaf water on reflectance spectra must be removed to within 10%. Other effects were reduced by continuum removal and normalization of band depths. If the effects of leaf water can be compensated for, it might be possible to extend this method to remote sensing data acquired by imaging spectrometers to give estimates of nitrogen, lignin, and cellulose concentrations over large areas for use in ecosystem studies.We develop a new method for estimating the biochemistry of plant material using spectroscopy. Normalized band depths calculated from the continuum-removed reflectance spectra of dried and ground leaves were used to estimate their concentrations of nitrogen, lignin, and cellulose. Stepwise multiple linear regression was used to select wavelengths in the broad absorption features centered at 1.73 ??m, 2.10 ??m, and 2.301 ??m that were highly correlated with the chemistry of samples from eastern U.S. forests. Band depths of absorption features at these wavelengths were found to also be highly correlated with the chemistry of four other sites. A subset of data from the eastern U.S. forest sites was used to derive linear equations that were applied to the remaining data to successfully estimate their nitrogen, lignin, and cellulose concentrations. Correlations were highest for nitrogen (R2 from 0.75 to 0.94). The consistent results indicate the possibility of establishing a single equation capable of estimating the chemical concentrations in a wide variety of species from the reflectance spectra of dried leaves. The extension of this method to remote sensing was investigated. The effects of leaf water content, sensor signal-to-noise and bandpass, atmospheric effects, and background soil exposure were examined. Leaf water was found to be the greatest challenge to extending this empirical method to the analysis of fresh whole leaves and complete vegetation canopies. The influence of leaf water on reflectance spectra must be removed to within 10%. Other effects were reduced by continuum removal and normalization of band depths. If the effects of leaf water can be compensated for, it might be possible to extend this method to remote sensing data acquired by imaging spectrometers to give estimates of nitrogen, lignin, and cellulose concentrations over large areas for use in ecosystem studies.

  20. Compressed shell conditions extracted from spectroscopic analysis of Ti K-shell absorption spectra with evaluation of line self-emission

    NASA Astrophysics Data System (ADS)

    Johns, H. M.; Mancini, R. C.; Hakel, P.; Nagayama, T.; Smalyuk, V. A.; Regan, S. P.; Delettrez, J.

    2014-08-01

    Ti-doped tracer layers embedded in the shell at varying distances from the fuel-shell interface serve as a spectroscopic diagnostic for direct-drive experiments conducted at OMEGA. Detailed modeling of Ti K-shell absorption spectra produced in the tracer layer considers n = 1-2 transitions in F- through Li-like Ti ions in the 4400-4800 eV range, both including and excluding line self-emission. Testing the model on synthetic spectra generated from 1-D LILAC hydrodynamic simulations reveals that the model including self-emission best reproduces the simulation, while the model excluding self-emission overestimates electron temperature Te and density Ne to a higher degree for layers closer to the core. The prediction of the simulation that the magnitude of Te and duration of Ti absorption will be strongly tied to the distance of the layer from the core is consistent with the idea that regions of the shell close to the core are more significantly heated by thermal transport out of the hot dense core, but more distant regions are less affected by it. The simulation predicts more time variation in the observed Te, Ne conditions in the compressed shell than is observed in the experiment, analysis of which reveals conditions remain in the range Te = 400-600 eV and Ne = 3.0-10.0 × 1024 cm-3 for all but the most distant Ti-doped layer, with error bars ˜5% Te value and ˜10% Ne on average. The Te, Ne conditions of the simulation lead to a greater degree of ionization for zones close to the core than occurs experimentally, and less ionization for zones far from the core.

  1. Optical properties of large-area polycrystalline chemical vapor deposited graphene by spectroscopic ellipsometry

    Microsoft Academic Search

    F. J. Nelson; V. K. Kamineni; T. Zhang; E. S. Comfort; J. U. Lee; A. C. Diebold

    2010-01-01

    Spectroscopic ellipsometry was used to characterize the complex refractive index of chemical vapor deposition (CVD) graphene grown on copper foils and transferred to glass substrates. Two ellipsometers, with respective wavelength ranges extending into the ultraviolet and infrared (IR), have been used to characterize the CVD graphene optical functions. The optical absorption follows the same relation to the fine structure constant

  2. Atomic absorption spectroscopic, conductometric and colorimetric methods for determination of fluoroquinolone antibiotics using ammonium reineckate ion-pair complex formation

    NASA Astrophysics Data System (ADS)

    Ragab, Gamal H.; Amin, Alaa S.

    2004-03-01

    Three accurate, rapid and simple atomic absorption spectrometric, conductometric and colorimetric methods were developed for the determination of norfloxacin (NRF), ciprofloxacin (CIP), ofloxacin (OFL) and enrofloxacin (ENF). The proposed methods depend upon the reaction of ammonium reineckate with the studied drugs to form stable precipitate of ion-pair complexes, which was dissolved in acetone. The pink coloured complexes were determined either by AAS or colorimetrically at ?max 525 nm directly using the dissolved complex. Using conductometric titration, the studied drugs could be evaluated in 50% (v/v) acetone in the range 5.0-65, 4.0-48, 5.0-56 and 6.0-72 ?g ml -1 of NRF, CPF, OFL and ENF, respectively. The optimizations of various experimental conditions were described. The results obtained showed good recoveries of 99.15±1.15, 99.30±1.40, 99.60±1.50, and 99.00±1.25% with relative standard deviations of 0.81, 1.06, 0.97, and 0.69% for NRF, CPF, OFL, and ENF, respectively. Applications of the proposed methods to representative pharmaceutical formulations are successfully presented.

  3. X-ray absorption spectroscopic study of sodium iodide and iodine mediators in a solid-state supercapacitor

    NASA Astrophysics Data System (ADS)

    Mansour, Azzam N.; Zhou, Juanjuan; Zhou, Xiangyang

    2014-01-01

    In situ X-ray absorption spectroscopy was used to provide the redox states of the NaI/I2 mediators in an all-solid-state mediator-enhanced supercapacitor during the charge/discharge processes. Results show that in the charge process from -0.08 (open-circuit voltage (OCV)) to 0.80 V at constant current of 5 mA, all of the I- ions were oxidized to I2. However, in the discharge process from +0.80 V to OCV at constant current of -5 mA, only I3- ions were detected indicating that the I2 molecules were reduced to I3- ions. Upon a negative polarization from OCV to -0.80 V at constant current of -5 mA, the I3- ions were reduced to I- ions. Based on combined in situ XAS and cyclic voltammetry data, we show that the I-/I2 redox couple proceeds via the formation of I3- ions as an intermediate step.

  4. X-ray absorption spectroscopic evidence for the complexation of Hg(II) by reduced sulfur in soil humic substances

    SciTech Connect

    Xia, K. [Kansas State Univ., Manhattan, KS (United States). Dept. of Agronomy] [Kansas State Univ., Manhattan, KS (United States). Dept. of Agronomy; Skyllberg, U.L. [Swedish Univ. of Agricultural Sciences, Umeaa (Sweden). Dept. of Forest Ecology] [Swedish Univ. of Agricultural Sciences, Umeaa (Sweden). Dept. of Forest Ecology; Bleam, W.F.; Helmke, P.A. [Univ. of Wisconsin, Madison, WI (United States). Dept. of Soil Science] [Univ. of Wisconsin, Madison, WI (United States). Dept. of Soil Science; Bloom, P.R.; Nater, E.A. [Univ. of Minnesota, St. Paul, MN (United States). Dept. of Soil, Water, and Climate] [Univ. of Minnesota, St. Paul, MN (United States). Dept. of Soil, Water, and Climate

    1999-01-15

    Analysis of Hg(II) complexed by a soil humic acid (HA) using synchrotron-based X-ray absorption spectroscopy (XAS) revealed the importance of reduces sulfur functional groups (thiol (R-SH) and disulfide (R-SS-R)/disulfane (R-SSH)) in humic substances in the complexation of Hg(II). A two-coordinate binding environment with one oxygen atom and one sulfur atom at distances of 2.02 and 2.38 {angstrom}, respectively, was found in the first coordination shell of Hg(II) complexed by humic acid. Model calculations show that a second coordination sphere could contain one carbon atom and a second sulfur atom at 2.78 and 2.93 {angstrom}, respectively. This suggests that in addition to thiol S, disulfide/disulfane S may be involved with the complexation of Hg(II) in soil organic matter. The appearance of carbon atom in the second coordination shell suggests that one O-containing ligand such as carboxyl and phenol ligands rather than H{sub 2}O molecule is bound to the Hg(II). The involvement of oxygen ligand in addition to the reduced S ligands in the complexation of Hg(II) is due to the low density of reduced S ligands in humic substances. The XAS results from this experiment provided direct molecular level evidence for the preference of reduced S functional groups over oxygen ligands by Hg(II) in the complexation with humic substances.

  5. Local structural studies of the cubic Cd1–xCaxO system through Cd K-edge extended X-ray absorption spectroscopic studies

    PubMed Central

    Srihari, Velaga; Sridharan, V.; Nomura, Masaharu; Sastry, V. Sankara; Sundar, C. S

    2012-01-01

    Cd K-edge extended X-ray absorption fine-structure spectroscopic studies were carried out on Cd1–xCaxO (0 ? x ?0.9) solid solutions and the first and second nearest neighbour (NN) distances and their mean square relative displacement ?2 were estimated. The first NN distance, d Cd–O(x), was found to be smaller than its expected value, a(x)/2, obtained from the X-ray diffraction measurements. It increases monotonically and non-linearly with a negative curvature, comparable with that of the a(x) value variation. The variation ?2 of the 1NN with x is consistent with a disordered solid solution model. The 2NN distances d Cd–Cd(x) and d Cd–Ca(x) are found to follow the average values obtained by X-ray diffraction with d Cd–Ca(x) > d Cd–Cd(x). From detailed analysis it is argued that the solid solution exhibits a bimodal distribution of the 1NN distances, d Cd–O(x) and d Ca–O(x), and that the system belongs to a persistent type. PMID:22713887

  6. Optical absorption of Zn(V,Al)O thin films studied by spectroscopic ellipsometry from 1 to 6 eV

    NASA Astrophysics Data System (ADS)

    Sayari, Amor; El Mir, Lassaad; Al-Heniti, Saleh; Al-Harbi, Talal; Yaghmour, Saud Jamil; Abdullah Al-Ghamdi, Ahmad

    2013-06-01

    Aerogel nanoparticles prepared with various Al concentrations were used as a target for the deposition of (V,Al) co-doped ZnO films by rf-magnetron sputtering on glass substrates. The influence of Al content on the structural and the optical properties of the Zn(V,Al)O films was investigated by X-ray diffraction and spectroscopic ellipsometry (SE). It is found that all films exhibit one high intensity (0 0 2) peak, indicating that they have c-axis preferred orientation due to self-texturing mechanism. SE measurements, used to determine the complex pseudo dielectric functions, were carried out at room temperature in the 1-6 eV photon energy region. The excitonic edge of the fundamental band gap (E0) transition in the imaginary part of the dielectric function of the Zn(V,Al)O films is observed around 3.5 eV and shows a dependence on the Al content. The E0 absorption edge of the Zn0.9-x V0.1AlxO alloys shows a blueshift from that of pure ZnO, reaching 389 meV for x = 0.02. This blueshift is interpreted by the Burstein-Moss effect. By analyzing the dielectric function, reduced effective mass m* of the Zn0.9-x V0.1AlxO alloy is extracted and shows good agreement with literature values.

  7. Anion pairs in room temperature ionic liquids predicted by molecular dynamics simulation, verified by spectroscopic characterization

    SciTech Connect

    Schwenzer, Birgit; Kerisit, Sebastien N.; Vijayakumar, M.

    2014-01-01

    Molecular-level spectroscopic analyses of an aprotic and a protic room-temperature ionic liquid, BMIM OTf and BMIM HSO4, respectively, have been carried out with the aim of verifying molecular dynamics simulations that predict anion pair formation in these fluid structures. Fourier-transform infrared spectroscopy, Raman spectroscopy and nuclear magnetic resonance spectroscopy of various nuclei support the theoretically-determined average molecular arrangements.

  8. Spectroscopic and laser characterization of emerald. Final report, April 1983April 1986

    Microsoft Academic Search

    S. T. Lai; B. H. Chai

    1986-01-01

    The spectroscopic characteristics and laser properties of emerald were investigated. The laser measurements showed that the emerald-laser tuning range was 720-842 nm and exhibited a high gain and high efficiency in the 760-790 nm range. Under a crystal growth development program, the laser loss was reduced from 11%\\/cm to 0.4%\\/cm. The limiting factor in the laser efficiency is the excited-state

  9. Surface spectroscopic characterization of the interaction between zinc ions and. gamma. -alumina

    Microsoft Academic Search

    B. R. Strohmeier; D. M. Hercules

    1094-01-01

    Interaction of zinc ions with ..gamma..-alumina has been investigated using the surface spectroscopic techniques of X-ray photoelectron spectroscopy (ESCA or XPS) and low energy ion scattering spectroscopy (ISS). In addition, the bulk techniques of laser Raman spectroscopy (LRS) and X-ray diffraction (XRD) were employed. Surface characteristics of Zn\\/AlâOâ catalysts are affected by both metal loading and calcination temperature. The Zn\\/Al

  10. Redox Chemisty of Tantalum Clusters on Silica Characterized by X-ray Absorption Spectroscopy

    SciTech Connect

    Nemana,S.; Gates, B.

    2006-01-01

    SiO{sub 2}-supported clusters of tantalum were synthesized from adsorbed Ta(CH{sub 2}Ph){sub 5} by treatment in H{sub 2} at 523 K. The surface species were characterized by X-ray absorption spectroscopy (extended X-ray absorption fine structure (EXAFS) spectroscopy and X-ray absorption near edge spectroscopy (XANES)) and ultraviolet-visible spectroscopy. The EXAFS data show that SiOO{sub 2}-supported tantalum clusters were characterized by a Ta-Ta coordination number of approximately 2, consistent with the presence of tritantalum clusters, on average. When these were reduced in H{sub 2} and reoxidized in O{sub 2}, the cluster nuclearity remained essentially unchanged, although reduction and oxidation occurred, respectively, as shown by XANES and UV-vis spectra; in the reoxidation, the tantalum oxidation state change was approximately two electronic charges per tritantalum cluster. The data demonstrate an analogy between the chemistry of group 5 metals on the SiO{sub 2} support and their chemistry in solution, as determined by the group of Cotton.

  11. An x-ray absorption spectroscopic study of the electronic structure and bonding of rare-earth orthoferrites

    NASA Astrophysics Data System (ADS)

    Hayes, J. R.; Grosvenor, A. P.

    2011-11-01

    Rare-earth orthoferrites, REFeO3 (RE=rare earth; Y), are tremendously adaptable compounds that are being investigated for use in a wide variety of applications including gas sensors, vehicle catalytic converters, and solid-oxide fuel cells. They also exhibit interesting magnetic properties such as high-temperature antiferromagnetism, making them useful for data storage applications. The compounds adopt a distorted perovskite-type structure where the tilt angle of the octahedra increases (Fe-O-Fe bond angle decreases) as the size of the rare-earth atom decreases. Despite intensive study of the physical properties of these compounds, very few studies have investigated how the bonding and electronic structure of these systems change with substitution of the RE. X-ray absorption near-edge spectroscopy (XANES) is a technique well-suited for such a study, and, in view of this, Fe L-, Fe K- and O K-edge spectra from a series of REFeO3 compounds (RE=La, Pr, Nd, Sm, Eu, Gd, Ho, Yb, Y) have been collected, and are presented here. Fe L-edge spectra show that Fe is octahedrally coordinated and that the Fe-centered octahedra do not appear to distort with changes in the identity of the RE. The Fe K-edge spectra contain an intersite hybrid peak, which is an ill-studied feature that is attributed to non-local transitions of 1s electrons to 3d states on the next-nearest-neighbor atom that are hybridized with 4p states on the absorbing atom through O 2p states. In this study, it is shown that the intensity of this feature is strongly dependent on the Fe-O-Fe bond angle; the lower the Fe-O-Fe bond angle, the less intense the intersite hybrid peak is.

  12. An x-ray absorption spectroscopic study of the electronic structure and bonding of rare-earth orthoferrites.

    PubMed

    Hayes, J R; Grosvenor, A P

    2011-11-23

    Rare-earth orthoferrites, REFeO? (RE D rare earth; Y), are tremendously adaptable compounds that are being investigated for use in a wide variety of applications including gas sensors, vehicle catalytic converters, and solid-oxide fuel cells. They also exhibit interesting magnetic properties such as high-temperature antiferromagnetism, making them useful for data storage applications. The compounds adopt a distorted perovskite-type structure where the tilt angle of the octahedra increases (Fe-O-Fe bond angle decreases) as the size of the rare-earth atom decreases. Despite intensive study of the physical properties of these compounds, very few studies have investigated how the bonding and electronic structure of these systems change with substitution of the RE. X-ray absorption near-edge spectroscopy (XANES) is a technique well-suited for such a study, and, in view of this, Fe L-, Fe K- and O K-edge spectra from a series of REFeO? compounds (RE D La, Pr, Nd, Sm, Eu, Gd, Ho, Yb, Y) have been collected, and are presented here. Fe L-edge spectra show that Fe is octahedrally coordinated and that the Fe-centered octahedra do not appear to distort with changes in the identity of the RE. The Fe K-edge spectra contain an intersite hybrid peak, which is an ill-studied feature that is attributed to non-local transitions of 1s electrons to 3d states on the next-nearest-neighbor atom that are hybridized with 4p states on the absorbing atom through O 2p states. In this study, it is shown that the intensity of this feature is strongly dependent on the Fe-O-Fe bond angle; the lower the Fe-O-Fe bond angle, the less intense the intersite hybrid peak is. PMID:22056809

  13. An x-ray absorption spectroscopic study of the electronic structure and bonding of rare-earth orthoferrites

    SciTech Connect

    Hayes, J.R.; Grosvenor, A.P. (Saskatchewan)

    2011-11-07

    Rare-earth orthoferrites, REFeO{sub 3} (RE=rare earth; Y), are tremendously adaptable compounds that are being investigated for use in a wide variety of applications including gas sensors, vehicle catalytic converters, and solid-oxide fuel cells. They also exhibit interesting magnetic properties such as high-temperature antiferromagnetism, making them useful for data storage applications. The compounds adopt a distorted perovskite-type structure where the tilt angle of the octahedra increases (Fe-O-Fe bond angle decreases) as the size of the rare-earth atom decreases. Despite intensive study of the physical properties of these compounds, very few studies have investigated how the bonding and electronic structure of these systems change with substitution of the RE. X-ray absorption near-edge spectroscopy (XANES) is a technique well-suited for such a study, and, in view of this, Fe L-, Fe K- and O K-edge spectra from a series of REFeO{sub 3} compounds (RE=La, Pr, Nd, Sm, Eu, Gd, Ho, Yb, Y) have been collected, and are presented here. Fe L-edge spectra show that Fe is octahedrally coordinated and that the Fe-centered octahedra do not appear to distort with changes in the identity of the RE. The Fe K-edge spectra contain an intersite hybrid peak, which is an ill-studied feature that is attributed to non-local transitions of 1s electrons to 3d states on the next-nearest-neighbor atom that are hybridized with 4p states on the absorbing atom through O 2p states. In this study, it is shown that the intensity of this feature is strongly dependent on the Fe-O-Fe bond angle; the lower the Fe-O-Fe bond angle, the less intense the intersite hybrid peak is.

  14. Nanoflaky MnO2/functionalized carbon nanotubes for supercapacitors: an in situ X-ray absorption spectroscopic investigation.

    PubMed

    Chang, Han-Wei; Lu, Ying-Rui; Chen, Jeng-Lung; Chen, Chi-Liang; Lee, Jyh-Fu; Chen, Jin-Ming; Tsai, Yu-Chen; Chang, Chien-Min; Yeh, Ping-Hung; Chou, Wu-Ching; Liou, Ya-Hsuan; Dong, Chung-Li

    2015-02-01

    The surfaces of acid- and amine-functionalized carbon nanotubes (C-CNT and N-CNT) were decorated with MnO2 nanoflakes as supercapacitors by a spontaneous redox reaction. C-CNT was found to have a lower edge plane structure and fewer defect sites than N-CNT. MnO2/C-CNT with a highly developed surface area exhibited favorable electrochemical performance. To determine the atomic/electronic structures of the MnO2/functionalized CNTs (MnO2/C-CNT and MnO/N-CNT) during the charge/discharge process, in situ X-ray absorption spectroscopy (XAS) measurements were made at the Mn K-edge. Both C-CNT and N-CNT are highly conductive. The effect of the scan rate on the capacitance behavior was also examined, revealing that the ?* state of CNT and the size of the tunnels in pseudo-capacitor materials (which facilitate conduction and the transport of electrolyte ions) are critical for the capacitive performance, and their role depends on the scan rate. In the slow charge/discharge process, MnO2/N-CNT has a more symmetrical rectangular cyclic voltammetry (CV) curve. In the fast charge/discharge process, MnO2/C-CNT with a highly developed surface provides fast electronic and ionic channels that support a reversible faradaic redox reaction between MnO2 nanoflakes and the electrolyte, significantly enhancing its capacitive performance over that of MnO2/N-CNT. The MnO2/C-CNT architecture has great potential for supercapacitor applications. The information that was obtained herein helps to elucidate CNT surface modification and the design of the MnO2/functionalized CNT interface with a view for the further development of supercapacitors. This work, and especially the combination of CV with in situ XAS measurements, will be of value to readers with an interest in nanomaterial, nanotechnology and their applications in energy storage. PMID:25511126

  15. Spectroscopic and Computational Characterization of Substrate-Bound Mouse Cysteine Dioxygenase: Nature of the Ferrous and Ferric Cysteine Adducts and Mechanistic Implications †

    PubMed Central

    Gardner, Jessica D.; Pierce, Brad S.; Fox, Brian G.; Brunold, Thomas C.

    2010-01-01

    Cysteine dioxygenase (CDO) is a mononuclear non-heme Fe-dependent dioxygenase that catalyzes the initial step of oxidative cysteine catabolism. Its active site consists of an Fe(II) ion ligated by three histidine residues from the protein, an interesting variation on the more common 2-His-1-carboxylate motif found in many other non-heme Fe(II)-dependent enzymes. Multiple structural and kinetic studies of CDO have been carried out recently, resulting in a variety of proposed catalytic mechanisms; however, many open questions remain regarding the structure/function relationships of this vital enzyme. In this study, resting and substrate-bound forms of CDO in the Fe(II) and Fe(III) states, both of which are proposed to have important roles in this enzyme’s catalytic mechanism, were characterized by utilizing various spectroscopic methods. The nature of the substrate/active-site interactions was also explored using the cysteine analog selenocysteine (Sec). Our electronic absorption, magnetic circular dichroism, and resonance Raman data exhibit features characteristic of direct S (or Se) ligation to both the high-spin Fe(II) and Fe(III) active-site ions. The resulting Cys (or Sec)-bound species were modeled and further characterized using density functional theory computations to generate experimentally validated geometric and electronic structure descriptions. Collectively, our results yield a more complete description of several catalytically relevant species and provide support for a reaction mechanism similar to that established for many structurally related 2-His-1-carboxylate Fe(II)-dependent dioxygenases. PMID:20397631

  16. Nanoflaky MnO2/functionalized carbon nanotubes for supercapacitors: an in situ X-ray absorption spectroscopic investigation

    NASA Astrophysics Data System (ADS)

    Chang, Han-Wei; Lu, Ying-Rui; Chen, Jeng-Lung; Chen, Chi-Liang; Lee, Jyh-Fu; Chen, Jin-Ming; Tsai, Yu-Chen; Chang, Chien-Min; Yeh, Ping-Hung; Chou, Wu-Ching; Liou, Ya-Hsuan; Dong, Chung-Li

    2015-01-01

    The surfaces of acid- and amine-functionalized carbon nanotubes (C-CNT and N-CNT) were decorated with MnO2 nanoflakes as supercapacitors by a spontaneous redox reaction. C-CNT was found to have a lower edge plane structure and fewer defect sites than N-CNT. MnO2/C-CNT with a highly developed surface area exhibited favorable electrochemical performance. To determine the atomic/electronic structures of the MnO2/functionalized CNTs (MnO2/C-CNT and MnO/N-CNT) during the charge/discharge process, in situ X-ray absorption spectroscopy (XAS) measurements were made at the Mn K-edge. Both C-CNT and N-CNT are highly conductive. The effect of the scan rate on the capacitance behavior was also examined, revealing that the ?* state of CNT and the size of the tunnels in pseudo-capacitor materials (which facilitate conduction and the transport of electrolyte ions) are critical for the capacitive performance, and their role depends on the scan rate. In the slow charge/discharge process, MnO2/N-CNT has a more symmetrical rectangular cyclic voltammetry (CV) curve. In the fast charge/discharge process, MnO2/C-CNT with a highly developed surface provides fast electronic and ionic channels that support a reversible faradaic redox reaction between MnO2 nanoflakes and the electrolyte, significantly enhancing its capacitive performance over that of MnO2/N-CNT. The MnO2/C-CNT architecture has great potential for supercapacitor applications. The information that was obtained herein helps to elucidate CNT surface modification and the design of the MnO2/functionalized CNT interface with a view for the further development of supercapacitors. This work, and especially the combination of CV with in situ XAS measurements, will be of value to readers with an interest in nanomaterial, nanotechnology and their applications in energy storage.The surfaces of acid- and amine-functionalized carbon nanotubes (C-CNT and N-CNT) were decorated with MnO2 nanoflakes as supercapacitors by a spontaneous redox reaction. C-CNT was found to have a lower edge plane structure and fewer defect sites than N-CNT. MnO2/C-CNT with a highly developed surface area exhibited favorable electrochemical performance. To determine the atomic/electronic structures of the MnO2/functionalized CNTs (MnO2/C-CNT and MnO/N-CNT) during the charge/discharge process, in situ X-ray absorption spectroscopy (XAS) measurements were made at the Mn K-edge. Both C-CNT and N-CNT are highly conductive. The effect of the scan rate on the capacitance behavior was also examined, revealing that the ?* state of CNT and the size of the tunnels in pseudo-capacitor materials (which facilitate conduction and the transport of electrolyte ions) are critical for the capacitive performance, and their role depends on the scan rate. In the slow charge/discharge process, MnO2/N-CNT has a more symmetrical rectangular cyclic voltammetry (CV) curve. In the fast charge/discharge process, MnO2/C-CNT with a highly developed surface provides fast electronic and ionic channels that support a reversible faradaic redox reaction between MnO2 nanoflakes and the electrolyte, significantly enhancing its capacitive performance over that of MnO2/N-CNT. The MnO2/C-CNT architecture has great potential for supercapacitor applications. The information that was obtained herein helps to elucidate CNT surface modification and the design of the MnO2/functionalized CNT interface with a view for the further development of supercapacitors. This work, and especially the combination of CV with in situ XAS measurements, will be of value to readers with an interest in nanomaterial, nanotechnology and their applications in energy storage. Electronic supplementary information (ESI) available. See DOI: 10.1039/c4nr06439a

  17. Spectroscopic characterization of a Ni-organic radical intermediate in the aerobic oxidation of methanol catalyzed by a Ni(II)(polyoximate) complex

    Microsoft Academic Search

    Sara E. Edison; Sean D. Conklin; Necati Kaval; Lionel E. Cheruzel; Jeanette A. Krause; Carl J. Seliskar; William R. Heineman; Robert M. Buchanan; Michael J. Baldwin

    2008-01-01

    In the aerobic oxidation of methanol catalyzed by a Ni(II)(TRISOX) complex [H3TRISOX=tris(1-propan-2-onyl oxime)amine], an intermediate is observed spectroscopically. The intensities of both the UV–Vis absorption and electron paramagnetic resonance (EPR) spectra associated with this intermediate maximize during the time period of maximum formaldehyde production, and decrease as the methanol oxidation activity decreases. The UV–Vis spectrum has prominent features at 350,

  18. Modified polyamines for CO{sub 2} absorption. Product preparation and characterization

    SciTech Connect

    De Filippis, P.; Giavarini, C.; Maggi, C.; Rinaldi, G.; Silla, R.

    2000-05-01

    Aliphatic polyamines easily absorb acidic gases but unfortunately are not suitable for industrial application because their solutions are difficult to regenerate. Molecular modification is of primary importance to reduce their basicity and to allow their use in acid gas recovery processes. Various modified polyamines were prepared by reacting tetraethylenepentamine (TEPA) with formaldehyde and formaldehyde/phenol in various molar ratios. The physical and chemical characterization of the synthesized products showed a general reduction of basicity; the modification of TEPA with formaldehyde and phenol gave products with high CO{sub 2} absorption capacity and easier regeneration; moreover, the heat of reaction during CO{sub 2} absorption was reduced. The selected compound had a TEPA/CH{sub 2}O/C{sub 6}H{sub 5}OH ratio equal to 1/0.5/0.4. This new product showed higher cyclic capacity, higher absorption rate, and lower degradation compared with diethanolamine under the same experimental conditions. The product is stable, constant in composition, and suitable for industrial scale-up.

  19. Characterization of a new modular decay total absorption gamma-ray spectrometer (DTAS) for FAIR

    SciTech Connect

    Montaner Piza, A.; Tain, J. L.; Agramunt, J.; Algora, A.; Guadilla, V.; Marin, E.; Rice, S.; Rubio, B. [Instituto de Fisica Corpuscular, CSIC-Univ. de Valencia, Apdo. Correos 22085, E-46071 Valencia (Spain)

    2013-06-10

    Beta-decay studies are one of the main goals of the DEcay SPECtroscopy experiment (DESPEC) to be installed at the future Facility for Antiproton and Ion Research (FAIR). DESPEC aims at the study of nuclear structure of exotic nuclei. A new modular Decay Total Absorption gamma-ray Spectrometer (DTAS) is being built at IFIC and is specially adapted to studies at fragmentation facilities such as the Super Fragment Separator (Super-FRS) at FAIR. The designed spectrometer is composed of 16 identical NaI(Tl) scintillation crystals. This work focuses on the characterization of these independent modules, as an initial step for the characterization of the full spectrometer. Monte Carlo simulations have been performed in order to understand the detector response.

  20. Synthesis, spectroscopic characterization and crystal structure of novel NNNN-donor ?-bis(bidentate) tetraaza acyclic Schiff base ligands.

    PubMed

    Habibi, Mohammad Hossein; Shojaee, Elahe; Nichol, Gary S

    2012-12-01

    Novel NNNN-donor ?-bis(bidentate) tetraaza acyclic Schiff base ligands with different substituents (CF(3), N(CH(3))(2) or OH groups) were synthesized by the condensation reaction of triethylenetetramine with 4-substituted benzaldehydes. Triethylenetetramine tris(4-trifluoromethylbenzylidene) (TTFMB), triethylenetetramine tris(4-dimethylaminobenzylidene) (TTDMB) and triethylenetetramine tris(2,4-dihydroxybenzylidene) (TTDHB) were formed as N(4) donor ligands. The formation of a five-membered imidazolidine ring from the ethylenediamine backbone as a spacer-cumbridging unit gives rise to a new type of imidazolidine ligand. The structure of the TTFMB and TTDMB were determined by single crystal X-ray crystallography. The synthesized ligands have been characterized on the basis of the results of cyclic voltammetry (CV) and spectroscopic studies viz. FT-IR spectroscopy (FT-IR), mass spectroscopy (MS) and UV-Vis spectroscopy (UV-Vis). PMID:23010628

  1. Potential approaches to the spectroscopic characterization of high performance polymers exposed to energetic protons and heavy ions

    NASA Technical Reports Server (NTRS)

    Suleman, Naushadalli K.

    1991-01-01

    A potential limitation to human activity on the lunar surface or in deep space is the exposure of the crew to unacceptably high levels of penetrating space radiations. The radiations of most concerns for such missions are high-energy protons emitted during solar flares, and galactic cosmic rays which are high-energy ions ranging from protons to iron. The development of materials for effective shielding from energetic space radiations will clearly require a greater understanding of the underlying mechanisms of radiation-induced damage in bulk materials. This can be accomplished in part by the detailed spectroscopic characterization of bulk materials that were exposed to simulated space radiations. An experimental data base thus created can then be used in conjunction with existing radiation transport codes in the design and fabrication of effective radiation shielding materials. Electron Paramagnetic Resonance Spectroscopy was proven very useful in elucidating radiation effects in polymers (high performance polymers are often an important components of structural composites).

  2. Low-temperature and time-resolved spectroscopic characterization of the LOV2 domain of Avena sativa phototropin

    SciTech Connect

    Gauden, Magdalena; Crosson, Sean; van Stokkum, I.H.; Grondelle, Rienkvan; Moffat, Keith; Kennis, John T. (UC)

    2004-12-13

    The phototropins are plant blue-light receptors that base their light-dependent action on the reversible formation of a covalent bond between a flavin mononucleotide (FMN) cofactor and a conserved cysteine residue in light, oxygen or voltage (LOV) domains. The spectroscopic properties of the LOV2 domain of phototropin 1 of Avena sativa (oat) have been investigated by means of low-temperature absorption and fluorescence spectroscopy and by time-resolved fluorescence spectroscopy. The low-temperature absorption spectrum of the LOV2 domain showed a fine structure around 473 nm, indicating heterogeneity in the flavin binding pocket. The fluorescence quantum yield of the flavin cofactor increased from 0.13 to 0.41 upon cooling the sample from room temperature to 77 K. A pronounced phosphorescence emission around 600 nm was observed in the LOV2 domain between 77 and 120 K, allowing for an accurate positioning of the flavin triplet state in the LOV2 domain at 16900 cm{sup -1}. Fluorescence from the cryotrapped covalent adduct state was extremely weak, with a fluorescence spectrum showing a maximum at 440 nm. Time-resolved fluorescence experiments utilizing a synchroscan streak camera revealed a singlet-excited state lifetime of the LOV2 domain of 2.4 ns. FMN dissolved in aqueous solution showed a pH-dependent lifetime ranging between 2.9 ns at pH 2.0 to 4.7 ns at pH 8.0. No spectral shifting of the flavin emission was observed in the LOV2 domain nor in FMN in aqueous solution.

  3. Low-temperature and time-resolved spectroscopic characterization of the LOV2 domain of Avena sativa phototropin 1

    NASA Astrophysics Data System (ADS)

    Gauden, Magdalena; Crosson, Sean; van Stokkum, I. H. M.; van Grondelle, Rienk; Moffat, Keith; Kennis, John T. M.

    2004-09-01

    The phototropins are plant blue-light receptors that base their light-dependent action on the reversible formation of a covalent bond between a flavin mononucleotide (FMN) cofactor and a conserved cysteine residue in light, oxygen or voltage (LOV) domains. The spectroscopic properties of the LOV2 domain of phototropin 1 of Avena sativa (oat) have been investigated by means of low-temperature absorption and fluorescence spectroscopy and by time-resolved fluorescence spectroscopy. The low-temperature absorption spectrum of the LOV2 domain showed a fine structure around 473 nm, indicating heterogeneity in the flavin binding pocket. The fluorescence quantum yield of the flavin cofactor increased from 0.13 to 0.41 upon cooling the sample from room temperature to 77 K. A pronounced phosphorescence emission around 600 nm was observed in the LOV2 domain between 77 and 120 K, allowing for an accurate positioning of the flavin triplet state in the LOV2 domain at 16900 cm-1. Fluorescence from the cryotrapped covalent adduct state was extremely weak, with a fluorescence spectrum showing a maximum at 440 nm. Time-resolved fluorescence experiments utilizing a synchroscan streak camera revealed a singlet-excited state lifetime of the LOV2 domain of 2.4 ns. FMN dissolved in aqueous solution showed a pH-dependent lifetime ranging between 2.9 ns at pH 2.0 to 4.7 ns at pH 8.0. No spectral shifting of the flavin emission was observed in the LOV2 domain nor in FMN in aqueous solution.

  4. Synthesis and Spectroscopic Characterization of Water-Soluble Fluorescent Ag Nanoclusters

    PubMed Central

    Zheng, Chengzhi; Wang, Huiping; Liu, Lingzhi; Zhang, Manjun; Liang, Jiangong; Han, Heyou

    2013-01-01

    Water-soluble fluorescent Ag nanoclusters (NCs) were synthesized at room temperature with sodium dodecyl sulfonate (SDS) as a protective agent. The effects of synthetic conditions on the fluorescence properties of Ag NCs were investigated. The results show that the fluorescence intensity of Ag NCs strongly depends on the synthetic conditions, such as the molar ratio of AgNO3 versus SDS and sodium borohydride (NaBH4), the reaction time, and the pH value of the reaction solution. Under the optimum conditions, the as-prepared Ag NCs exist in face-centered-cubic phase with an average size of 2?nm. Fluorescence spectra of Ag NCs show emission peaks at 365?nm for different excitation wavelength. Resonant absorptions are observed at 203?nm and 277?nm in the absorption spectrum, which can be used to establish the electronic levels in the Ag NCs system. PMID:23762779

  5. Spectroscopic characterization and quantitative determination of atorvastatin calcium impurities by novel HPLC method

    NASA Astrophysics Data System (ADS)

    Gupta, Lokesh Kumar

    2012-11-01

    Seven process related impurities were identified by LC-MS in the atorvastatin calcium drug substance. These impurities were identified by LC-MS. The structure of impurities was confirmed by modern spectroscopic techniques like 1H NMR and IR and physicochemical studies conducted by using synthesized authentic reference compounds. The synthesized reference samples of the impurity compounds were used for the quantitative HPLC determination. These impurities were detected by newly developed gradient, reverse phase high performance liquid chromatographic (HPLC) method. The system suitability of HPLC analysis established the validity of the separation. The analytical method was validated according to International Conference of Harmonization (ICH) with respect to specificity, precision, accuracy, linearity, robustness and stability of analytical solutions to demonstrate the power of newly developed HPLC method.

  6. Chemical and spectroscopic characterization of water extractable organic matter during vermicomposting of cattle dung.

    PubMed

    Lv, Baoyi; Xing, Meiyan; Yang, Jian; Qi, Wensheng; Lu, Yongsen

    2013-03-01

    This work illustrated the characteristics and transformation of water extractable organic matter (WEOM) during vermistabilization (Eisenia fetida) of cattle dung by means of chemical and spectroscopic methods. The independent experiment conducted in triplicate was sampled at the 0, 7, 14, 21, 35, 60 and 90days. Results showed that the DOC kept steady around 2.7gkg(-1) after day 60 and the DOC/DON ratio decreased from 19.77 to 5.26 till the end of vermicomposting. On the other hand, vermicomposting decreased the aliphatic, proteinaceous, carbohydrates components and increased the aromaticity and oxygen-containing functional groups in the WEOM. Moreover, fluorescence spectra and fluorescence regional integration (FRI) results indicated that protein-like groups were degraded and fulvic and humic acid-like compounds were evolved during the vermicomposting process. In all, this study suggested the suitability of WEOM for monitoring the organics transformation and assessing the maturity in the vermicomposting. PMID:23416619

  7. 1H NMR spectroscopic characterization of inclusion complexes of tolfenamic and flufenamic acids with ?-cyclodextrin

    NASA Astrophysics Data System (ADS)

    Floare, C. G.; Pirnau, A.; Bogdan, M.

    2013-07-01

    The complexation between the anionic forms of tolfenamic acid and flufenamic acid with ?-cyclodextrin was investigated in solution by 1D and 2D proton NMR spectroscopy. The stoichiometry of the complexes was determined by the method of continuous variation using the chemical induced shifts of both the host and guest protons. An analysis of the spectroscopic data revealed that simultaneous inclusion of both rings of tolfenamic and flufenamic acids occur, giving rise each to two isomeric 1:1 complexes. The view of a bimodal binding between these two drugs and ?-cyclodextrin was also supported by ROESY experiments. Using a rough approximation, we have estimated the association constants order of magnitude of the 1:1 complexes.

  8. XAFS spectroscopic characterization of elements in combustion ash and fine particulate matter

    Microsoft Academic Search

    Frank E. Huggins; Naresh Shah; Gerald P. Huffman; J. David Robertson

    2000-01-01

    X-ray absorption fine structure (XAFS) spectroscopy is a powerful non-destructive, direct technique for determining the speciation of environmentally important elements in products derived from combustion of fossil fuels. Such information is potentially important (i) for assessing the threat to human health posed by specific forms and oxidation states of such elements in combustion products (ash) or in combustion-derived airborne particulate

  9. Green preparation and spectroscopic characterization of plasmonic silver nanoparticles using fruits as reducing agents

    PubMed Central

    Ærøe Hyllested, Jes; Espina Palanco, Marta; Hagen, Nicolai; Mogensen, Klaus Bo

    2015-01-01

    Summary Chemicals typically available in plants have the capability to reduce silver and gold salts and to create silver and gold nanoparticles. We report the preparation of silver nanoparticles with sizes between 10 and 300 nm from silver nitrate using fruit extract collected from pineapples and oranges as reducing agents. The evolvement of a characteristic surface plasmon extinction spectrum in the range of 420 nm to 480 nm indicates the formation of silver nanoparticles after mixing silver nitrate solution and fruit extract. Shifts in plasmon peaks over time indicate the growth of nanoparticles. Electron microscopy shows that the shapes of the nanoparticles are different depending on the fruit used for preparation. The green preparation process can result in individual nanoparticles with a very poor tendency to form aggregates with narrow gaps even when aggregation is forced by the addition of NaCl. This explains only modest enhancement factors for near-infrared-excited surface enhanced Raman scattering. In addition to the surface plasmon band, UV–visible absorption spectra show features in the UV range which indicates also the presence of small silver clusters, such as Ag4 2+. The increase of the plasmon absorption correlates with the decrease of absorption band in the UV. This confirms the evolution of silver nanoparticles from silver clusters. The presence of various silver clusters on the surface of the “green” plasmonic silver nanoparticles is also supported by a strong multicolor luminesce signal emitted by the plasmonic particles during 473 nm excitation. PMID:25821667

  10. Green preparation and spectroscopic characterization of plasmonic silver nanoparticles using fruits as reducing agents.

    PubMed

    Ærøe Hyllested, Jes; Espina Palanco, Marta; Hagen, Nicolai; Mogensen, Klaus Bo; Kneipp, Katrin

    2015-01-01

    Chemicals typically available in plants have the capability to reduce silver and gold salts and to create silver and gold nanoparticles. We report the preparation of silver nanoparticles with sizes between 10 and 300 nm from silver nitrate using fruit extract collected from pineapples and oranges as reducing agents. The evolvement of a characteristic surface plasmon extinction spectrum in the range of 420 nm to 480 nm indicates the formation of silver nanoparticles after mixing silver nitrate solution and fruit extract. Shifts in plasmon peaks over time indicate the growth of nanoparticles. Electron microscopy shows that the shapes of the nanoparticles are different depending on the fruit used for preparation. The green preparation process can result in individual nanoparticles with a very poor tendency to form aggregates with narrow gaps even when aggregation is forced by the addition of NaCl. This explains only modest enhancement factors for near-infrared-excited surface enhanced Raman scattering. In addition to the surface plasmon band, UV-visible absorption spectra show features in the UV range which indicates also the presence of small silver clusters, such as Ag4 (2+). The increase of the plasmon absorption correlates with the decrease of absorption band in the UV. This confirms the evolution of silver nanoparticles from silver clusters. The presence of various silver clusters on the surface of the "green" plasmonic silver nanoparticles is also supported by a strong multicolor luminesce signal emitted by the plasmonic particles during 473 nm excitation. PMID:25821667

  11. Biological activity studies on metal complexes of novel tridentate Schiff base ligand. Spectroscopic and thermal characterization

    Microsoft Academic Search

    Gehad G. Mohamed; M. M. Omar; Amr A. Ibrahim

    2009-01-01

    Metal complexes of novel Schiff base (HL) ligand, prepared via condensation of 4-aminoantipyrine and 2-aminophenol, are prepared. The ligand is characterized based on elemental analysis, mass, IR and 1H NMR spectra. Metal complexes are reported and characterized based on elemental analyses, IR, 1H NMR, solid reflectance, magnetic moment, molar conductance, ESR spectra and thermal analyses (TG, DTG and DTA). From

  12. Spectroscopic characterization of water extractable organic matter during composting of municipal solid waste

    Microsoft Academic Search

    Xiaosong He; Beidou Xi; Zimin Wei; Xujing Guo; Mingxiao Li; Da An; Hongliang Liu

    2011-01-01

    This paper aims to characterize the evolution of water extractable organic matter (WEOM) during the composting of municipal solid waste (MSW), and investigate the correlation between maturity and WEOM characteristics. WEOM was extracted at different stages of MSW composting (0, 7, 14, 21, and 51d) and characterized by FTIR, UV–Vis, and fluorescence spectroscopy. The results obtained show that the composting

  13. Applied quantum chemistry: Spectroscopic detection and characterization of the F2BS and Cl2BS free radicals in the gas phase.

    PubMed

    Jin, Bing; Sheridan, Phillip M; Clouthier, Dennis J

    2015-03-28

    In this and previous work [D. J. Clouthier, J. Chem. Phys. 141, 244309 (2014)], the spectroscopic signatures of the X2BY (X = H, halogen, Y = O, S) free radicals have been predicted using high level ab initio theory. The theoretical results have been used to calculate the electronic absorption and single vibronic level (SVL) emission spectra of the radicals under typical jet-cooled conditions. Using these diagnostic predictions, the previously unknown F2BS and Cl2BS free radicals have been identified and characterized. The radicals were prepared in a free jet expansion by subjecting precursor mixtures of BF3 or BCl3 and CS2 vapor to an electric discharge at the exit of a pulsed molecular beam valve. The B?(2)A1-X?(2)B2 laser-induced fluorescence spectra were found within 150 cm(-1) of their theoretically predicted positions with vibronic structure consistent with our Franck-Condon simulations. The B?(2)A1 state emits down to the ground state and to the low-lying A?(2)B1 excited state and the correspondence between the observed and theoretically derived SVL emission Franck-Condon profiles was used to positively identify the radicals and make assignments. Excited state Coriolis coupling effects complicate the emission spectra of both radicals. In addition, a forbidden component of the electronically allowed B?-X? band system of Cl2BS is evident, as signaled by the activity in the b2 modes in the spectrum. Symmetry arguments indicate that this component gains intensity due to a vibronic interaction of the B?(2)A1 state with a nearby electronic state of (2)B2 symmetry. PMID:25833573

  14. Synthesis, spectroscopic characterization, photochemical and photophysical properties and biological activities of ruthenium complexes with mono- and bi-dentate histamine ligand.

    PubMed

    Cardoso, Carolina R; de Aguiar, Inara; Camilo, Mariana R; Lima, Márcia V S; Ito, Amando S; Baptista, Maurício S; Pavani, Christiane; Venâncio, Tiago; Carlos, Rose M

    2012-06-14

    The monodentate cis-[Ru(phen)(2)(hist)(2)](2+)1R and the bidentate cis-[Ru(phen)(2)(hist)](2+)2A complexes were prepared and characterized using spectroscopic ((1)H, ((1)H-(1)H)COSY and ((1)H-(13)C)HSQC NMR, UV-vis, luminescence) techniques. The complexes presented absorption and emission in the visible region, as well as a tri-exponential emission decay. The complexes are soluble in aqueous and non-aqueous solution with solubility in a buffer solution of pH 7.4 of 1.14 × 10(-3) mol L(-1) for (1R + 2A) and 6.43 × 10(-4) mol L(-1) for 2A and lipophilicity measured in an aqueous-octanol solution of -1.14 and -0.96, respectively. Photolysis in the visible region in CH(3)CN converted the starting complexes into cis-[Ru(phen)(2)(CH(3)CN)(2)](2+). Histamine photorelease was also observed in pure water and in the presence of BSA (1.0 × 10(-6) mol L(-1)). The bidentate coordination of the histamine to the ruthenium center in relation to the monodentate coordination increased the photosubstitution quantum yield by a factor of 3. Pharmacological studies showed that the complexes present a moderate inhibition of AChE with an IC(50) of 21 ?mol L(-1) (referred to risvagtini, IC(50) 181 ?mol L(-1) and galantamine IC(50) 0.006 ?mol L(-1)) with no appreciable cytotoxicity toward to the HeLa cells (50% cell viability at 925 ?mol L(-1)). Cell uptake of the complexes into HeLa cells was detected by fluorescence confocal microscopy. Overall, the observation of a luminescent complex that penetrates the cell wall and has low cytotoxicity, but is reactive photochemically, releasing histamine when irradiated with visible light, are interesting features for application of these complexes as phototherapeutic agents. PMID:22539182

  15. Spectroscopic characterization of metal complexes of novel Schiff base. Synthesis, thermal and biological activity studies

    Microsoft Academic Search

    M. M. Omar; Gehad G. Mohamed; Amr A. Ibrahim

    2009-01-01

    Novel Schiff base (HL) ligand is prepared via condensation of 4-aminoantipyrine and 2-aminobenzoic acid. The ligand is characterized based on elemental analysis, mass, IR and 1H NMR spectra. Metal complexes are reported and characterized based on elemental analyses, IR, 1H NMR, solid reflectance, magnetic moment, molar conductance and thermal analyses (TGA, DrTGA and DTA). The molar conductance data reveal that

  16. Spectroscopic Ellipsometry Characterization of Variable Cu Concentration in Copper Indium Gallium di-Selenide Photovoltaic Films

    NASA Astrophysics Data System (ADS)

    Verley, J. C.; Furtak, T. E.

    2000-03-01

    Copper indium gallium di-selenide (CIGS) is among the most promising thin-film photovoltaic (PV) materials. Solar cells, using CIGS as an absorber layer, have achieved greater than 18 percent power conversion efficiencies on the laboratory scale. The best CIGS based photovoltaics have been created by utilizing the so-called three-stage process for the growth of the absorber layer. Standard substrates consist of soda-lime glass coated with Mo, which serves as the back contact. Despite their successful performance, the characteristics of CIGS films are poorly understood. The relative amount of Cu in the absorber layer during and after growth is an important variable in the creation of high quality PV material. We have investigated the properties of PV quality CIGS films using spectroscopic, variable angle ellipsometry, which is sensitive to the films’ band-edge and graded profile optical characteristics. The films were prepared with various mid-growth and post-growth Cu concentrations, following the standard procedures described above.

  17. Evaluation of optical parameters and characterization of ultrasonically sprayed MgO films by spectroscopic ellipsometry

    NASA Astrophysics Data System (ADS)

    Kurtaran, S.; Akyuz, I.; Atay, F.

    2013-01-01

    MgO is a chemically stable buffer layer and a good candidate with its unique optical and structural characteristics such as low refractive index and good lattice matching for the deposition of technologically important materials. In this work, we have produced MgO films by a low cost ultrasonic spray pyrolysis technique and tried to improve their characteristics by thermal annealing. MgO films have been obtained on glass substrates at 325 ± 5 °C and annealed at two different temperatures as 500 °C and 600 °C for 2 h. Elemental analyses have been made by energy-dispersive X-ray spectroscopy. Thicknesses, refractive indices and extinction coefficient values have been determined by spectroscopic ellipsometry technique using Cauchy-Urbach model. Band gap values of the films have been calculated using the absorbance spectra and optical method. X-ray diffraction patterns have been used to investigate the structural properties and to calculate lattice parameters. Atomic force microscope images have been taken to see the effect of thermal annealing on surface morphology. Electrical resistivity values of the films have been determined using a four-point probe set-up. As a result, annealing temperature has a strong effect on the mentioned properties and a low cost ultrasonic spray pyrolysis technique allows the production of new and alternative MgO buffer layers for technological applications.

  18. Molecular structure and spectroscopic characterization of Carbamazepine with experimental techniques and DFT quantum chemical calculations.

    PubMed

    Suhasini, M; Sailatha, E; Gunasekaran, S; Ramkumaar, G R

    2015-04-15

    A systematic vibrational spectroscopic assignment and analysis of Carbamazepine has been carried out by using FT-IR, FT-Raman and UV spectral data. The vibrational analysis were aided by electronic structure calculations - ab initio (RHF) and hybrid density functional methods (B3LYP) performed with standard basis set 6-31G(d,p). Molecular equilibrium geometries, electronic energies, natural bond order analysis, harmonic vibrational frequencies and IR intensities have been computed. A detailed interpretation of the vibrational spectra of the molecule has been made on the basis of the calculated Potential Energy Distribution (PED) by VEDA program. UV-visible spectrum of the compound was also recorded and the electronic properties, such as HOMO and LUMO energies and ?max were determined by HF/6-311++G(d,p) Time-Dependent method. The thermodynamic functions of the title molecule were also performed using the RHF and DFT methods. The restricted Hartree-Fock and density functional theory-based nuclear magnetic resonance (NMR) calculation procedure was also performed, and it was used for assigning the (13)C and (1)H NMR chemical shifts of Carbamazepine. PMID:25682215

  19. Surface spectroscopic characterization of the interaction between zinc ions and. gamma. -alumina

    SciTech Connect

    Strohmeier, B.R.; Hercules, D.M.

    1984-04-01

    Interaction of zinc ions with ..gamma..-alumina has been investigated using the surface spectroscopic techniques of X-ray photoelectron spectroscopy (ESCA or XPS) and low energy ion scattering spectroscopy (ISS). In addition, the bulk techniques of laser Raman spectroscopy (LRS) and X-ray diffraction (XRD) were employed. Surface characteristics of Zn/Al/sub 2/O/sub 3/ catalysts are affected by both metal loading and calcination temperature. The Zn/Al intensity ratio was examined as a function of zinc content and calcination temperature. Plots of both ESCA and ISS intensity ratios (Zn/Al) vs metal loading show changes in slope at high loadings, indicating a change in surface structure. ESCA, LRS, and XRD all show the ability to distinguish between ZnO and ZnAl/sub 2/O/sub 4/. Results indicate that at low zinc loadings (<20%), a strong interaction occurs between zinc and ..gamma..-alumina resulting in the formation of an aluminate type phase (i.e., a surface spinel). This interaction involves diffusion of zinc ions into the tetrahedral lattice sites of the support. At higher loadings, bulk-like ZnO segregates on top of the interaction species and the support. ESCA has also been used to study the effects of reduction and sulfiding on the catalysts.

  20. Synthesis and Spectroscopic Characterization of Some New Axially Ligated Indium(III) Macrocyclic Complexes and Their Biological Activities

    PubMed Central

    Bajju, Gauri D.; Gupta, Deepmala; Kapahi, Ashu

    2014-01-01

    The synthesis and spectroscopic characterization of new axially ligated indium(III) porphyrin complexes were reported. Chloroindium(III) porphyrin (TPPIn-Cl) was obtained in good yield by treating the corresponding free base with indium trichloride. The action of the different phenols on chloroderivatives (TPPIn-Cl) led to the corresponding phenolato complexes (TPPIn-X). These derivatives were characterized on the basis of mass spectrometry, 1H-NMR, IR, and UV-visible data. The separation and isolation of these derivatives have been achieved through chromatography. The spectral properties of free base porphyrin and its corresponding metallated and axially ligated indium(III) porphyrin compounds were compared with each other. A detailed analysis of UV-Vis, 1H-NMR, and IR suggested the transformation from free base porphyrin to indium(III) porphyrin. Besides, 13C-NMR and fluorescence spectra were also reported and interpreted. The stability of these derivatives has also been studied through thermogravimetry. The complexes were also screened for anticancerous activities. Among all the complexes, 4-MePhO-InTPP shows highest anticancerous activity. The title complexe, TPPIn-X (where X = different phenolates), represents a five-coordinate indium(III) porphyrin complex in a square-pyramidal geometry with the phenolate anion as the axial ligand. PMID:25140121

  1. Synthesis, spectroscopic, structural and thermal characterizations of vanadyl(IV) adenine complex prospective as antidiabetic drug agent.

    PubMed

    El-Megharbel, Samy M; Hamza, Reham Z; Refat, Moamen S

    2015-01-25

    The vanadyl(IV) adenine complex; [VO(Adn)2]?SO4; was synthesized and characterized. The molar conductivity of this complex was measured in DMSO solution that showed an electrolyte nature. Spectroscopic investigation of the green solid complex studied here indicate that the adenine acts as a bidentate ligand, coordinated to vanadyl(IV) ions through the nitrogen atoms N7 and nitrogen atom of amino group. Thus, from the results presented the vanadyl(IV) complex has square pyramid geometry. Further characterizations using thermal analyses and scanning electron techniques was useful. The aim of this paper was to introduce a new drug model for the diabetic complications by synthesized a novel mononuclear vanadyl(IV) adenine complex to mimic insulin action and reducing blood sugar level. The antidiabetic ability of this complex was investigated in STZ-induced diabetic mice. The results suggested that VO(IV)/adenine complex has antidiabetic activity, it improved the lipid profile, it improved liver and kidney functions, also it ameliorated insulin hormone and blood glucose levels. The vanadyl(IV) complex possesses an antioxidant activity and this was clear through studying SOD, CAT, MDA, GSH and methionine synthase. The current results support the therapeutic potentiality of vanadyl(IV)/adenine complex for the management and treatment of diabetes. PMID:25150436

  2. Characterization of magnetic materials by low-field microwave absorption techniques

    NASA Astrophysics Data System (ADS)

    Valenzuela, R.; Alvarez, G.; Montiel, H.; Gutiérrez, M. P.; Mata-Zamora, M. E.; Barrón, F.; Sánchez, A. Y.; Betancourt, I.; Zamorano, R.

    A low-field non-resonant microwave absorption has recently been observed in a variety of magnetically ordered materials at low DC fields (-1000 Oe ? HDC?+1000 Oe), which is known as low-field microwave absorption (LFA). It has been shown that LFA is essentially similar to giant magnetoimpedance (GMI), and clearly different from ferromagnetic resonance (FMR). LFA strongly depends on the anisotropy field of the sample. In contrast with FMR (which can be described as the homogeneous precession of spins in the saturated state), LFA can be thought as a spin rotation process occurring during the magnetic saturation. In this work, we present a detailed study of the basic features of LFA in several types of materials: ferrites and amorphous microwires and ribbons; in particular the effects sample shape, temperature up to the Curie transition, the influence of easy axis and the effects of annealings. These examples show that once LFA is fully understood, it can become a powerful characterization tool.

  3. Comparison and investigation of bovine hemoglobin binding to dihydroartemisinin and 9-hydroxy-dihydroartemisinin: Spectroscopic characterization

    NASA Astrophysics Data System (ADS)

    Xiao, Mengsi; Han, Lina; Zhou, Lin; Zhou, Yanhuai; Huang, Xiaoqin; Ge, Xuefeng; Wei, Shaohua; Zhou, Jiahong; Wu, Heming; Shen, Jian

    The UV-vis absorption, steady state/time resolved fluorescence spectroscopy and synchronous fluorescence, circular dichroism (CD) spectroscopy are used to investigate the interaction mechanisms of dihydroartemisinin (DHA) and 9-hydroxy-dihydroartemisinin (9-OH DHA), respectively. The UV-vis studies present that DHA and 9-OH DHA can disturb the structure of bovine hemoglobin (BHb). Steady state/time resolved and synchronous fluorescence spectroscopy reveal that the binding constant of DHA with BHb is bigger than 9-OH DHA. CD spectra indicate DHA and 9-OH DHA can change the conformation of BHb. The comparison results suggest that the binding of BHb with DHA is more stable and stronger than 9-OH DHA.

  4. Spectroscopic investigation and optical characterization of Eu3+ ions in K-Nb-Si glasses

    NASA Astrophysics Data System (ADS)

    Murali Mohan, M.; Rama Moorthy, L.; Ramachari, D.; Jayasankar, C. K.

    2014-01-01

    This paper reports on the effect of concentration of Eu3+ ions in K2O-Nb2O5-SiO2-Eu2O3 (KNbSiEu) glasses prepared by the melt quenching technique. By using the Judd-Ofelt (JO) theory, the intensity parameters ?? (? = 2, 4, 6) have been determined from the absorption and emission spectra of Eu3+ ions under different constraints. The radiative properties of some of the excited states of Eu3+ ions have been calculated. The decay curves of 5D0 level exhibited single exponential for all the Eu3+ ions concentrations. From these results, it is suggested that the strong red emission at 616 nm corresponding to the 5D0 ? 7F2 transition could be used for the development of optical display devices.

  5. Design and spectroscopic characterization of novel series of near infrared indocyanine dyes

    NASA Astrophysics Data System (ADS)

    Abd-El-Aziz, Alaa S.; Strohm, Elizabeth A.; Okasha, Rawda M.

    2015-07-01

    A novel series of near infrared heptamethine indocyanine dyes bearing various aromatic chromophores has been synthesized. The synthetic methodology was achieved via ester condensation reactions of heptamethine indocyanine parent dye with carboxylic moiety and aromatic compounds such as anthracene, pyrene and thiophene derivatives. Structural analysis of the newly prepared dyes was accomplished using one- and two-dimensional nuclear magnetic resonance, infrared spectroscopy and electrospray ionization mass spectrometry. These dyes exhibited high molar absorptivity based on the UV-visible/near-infrared spectral data. Fluorescence emission spectral data was used to determine the relative quantum yield. The new dyes displayed formation of H-aggregates in water at low concentrations, while this behavior was not observed in methanol.

  6. Structural characterization of electrodeposited copper hexacyanoferrate films by using a spectroscopic multi-technique approach.

    PubMed

    Giorgetti, Marco; Guadagnini, Lorella; Tonelli, Domenica; Minicucci, Marco; Aquilanti, Giuliana

    2012-04-28

    A deep structural investigation predominantly by X-ray spectroscopic techniques is conducted on films of copper hexacyanoferrate (CuHCF) deposited under different conditions, aimed at establishing structure-properties relationships. We show that the potentiodynamic electrosynthesis of CuHCF on carbon-based surfaces produces a highly disordered material, with a variable amount of Prussian Blue (PB). The subsequent Cu(2+) intercalation induces the partial conversion of PB into CuHCF, which explains the improved electrocatalytic properties after the intercalation process. Both Cu and Fe K-edge data have been recorded. For the sample with the lower amount of PB, we could perform a multiple edge data analysis to determine the local atomic environment around both metal centres using the same set of structural parameters. The presence of high multiplicity Cu-N-C-Fe linear chains has allowed us to determine accurately the local environment of Fe while fitting the Cu K-edge data only. Using this approach we have retrieved structural information around Fe for those samples in which the concomitant presence of PB would have made impossible the analysis of the Fe K-edge. The Fe-C, C-N and Cu-N bond distances have been found in agreement with those of the bulk structures, but higher values of [Fe(CN)(6)] vacancies for the building blocks have been evidenced, reaching a value of ~45% in one sample. XANES, Raman and SEM data agree with the model proposed for each studied electrode. PMID:22422097

  7. Theoretical spectroscopic characterization at low temperatures of S-methyl thioformate and O-methyl thioformate

    SciTech Connect

    Senent, M. L., E-mail: senent@iem.cfmac.csic.es [Departamento de Química y Física Teóricas, Instituto de Estructura de la Materia, IEM-C.S.I.C., Serrano 121, Madrid 28006 (Spain); Puzzarini, C., E-mail: cristina.puzzarini@unibo.it [Dipartimento di Chimica G. Ciamician, Università di Bologna, Via F. Selmi 2, I-40126 Bologna (Italy); Hochlaf, M., E-mail: hochlaf@univ-mlv.fr [Laboratoire de Modélisation et Simulation Multi Echelle, Université Paris-Est, MSME UMR 8208 CNRS, 5 boulevard Descartes, 77454 Marne-la-Vallée (France); Domínguez-Gómez, R., E-mail: rosa.dominguez@upm.es [Departamento de Ingeniería Civil, Cátedra de Química, E.U.I.T. Obras Públicas, Universidad Politécnica de Madrid, Madrid (Spain); Carvajal, M., E-mail: miguel.carvajal@dfa.uhu.es [Departamento de Física Aplicada, Facultad de Ciencias Experimentales, Unidad Asociada IEM-CSIC-U.Huelva, Universidad de Huelva, 21071 Huelva (Spain)

    2014-09-14

    Highly correlated ab initio methods are employed to determine spectroscopic properties at low temperatures of two S-analogs of methyl formate: S-methyl thioformate CH{sub 3}-S-CHO (MSCHO) and O-methyl thioformate CH{sub 3}-O-CHS (MOCHS). Both species are detectable and they are expected to play an important role in Astrochemistry. Molecular properties are compared with those of the O-analog, methyl formate. Both isomers present two conformers cis and trans. cis-CH{sub 3}-S-CHO represents the most stable structure lying 4372.2 cm{sup ?1} below cis-CH{sub 3}-O-CHS. The energy difference between the cis and trans forms is drastically lower for MSCHO (1134 cm{sup ?1}) than for MOCHS (1963.6 cm{sup ?1}). Harmonic and anharmonic fundamentals and the corresponding intensities, as well as the rotational constants for the ground vibrational and first excited torsional states and the centrifugal distortions constants, are provided. Low torsional energy levels have been obtained by solving variationally a two dimensional Hamiltonian expressed in terms of the two torsional degrees of freedom. The corresponding 2D potential energy surfaces have been computed at the CCSD(T)/aug-cc-pVTZ level of theory. The methyl torsional barriers V{sub 3}(cis) are determined to be 139.7 cm{sup ?1} (CH{sub 3}-S-CHO) and 670.4 cm{sup ?1} (CH{sub 3}-O-CHS). The A/E splitting of ground torsional state has been estimated to be 0.438 cm{sup ?1} for CH{sub 3}-S-CHO and negligible for CH{sub 3}-O-CHS.

  8. Terahertz broadband spectroscopic investigations of amino acid

    NASA Astrophysics Data System (ADS)

    Zhu, De-chong; Zhang, Liang-liang; Zhong, Hua; Zhang, Cun-lin

    2011-08-01

    We present an experimental terahertz (THz) spectroscopic investigation of amino acid using an air-breakdown-coherent detection (ABCD) system. The strong and ultra-broadband (0.1 to 10THz) terahertz radiations generated by two-color laser induced air plasma and measured by coherent heterodyne detection. The broadband THz reflection spectra of L-Lysine (C6H14N2O2) and L-Arginine (C6H14N2O2) are obtained. To solve the phase-retrieval problem in RTDS, the absorption signatures of the materials are extracted directly from the first derivative of the relative reflectance with respect to frequency. The absorption features of the two amino acids are characterized in the 0.5~6 THz region. It is found that both the two amino acids have an absorption peak at 1.10 THz.

  9. MR imaging and proton MR spectroscopic studies in Sjogren-Larsson syndrome: characterization of the leukoencephalopathy

    Microsoft Academic Search

    Michel A. A. P. Willemsen; Marinette van der Graaf; Marjo S. van der Knaap; Arend Heerschap; Peter H. M. F. van Domburg; F. J. M. Gabreëls; Jan J. Rotteveel

    2004-01-01

    BACKGROUND AND PURPOSE: Sjogren-Larsson syndrome (SLS) is a neurocutaneous syndrome caused by a genetic enzyme deficiency in lipid metabolism. Our purpose was to characterize the nature of the cerebral involvement in SLS. METHODS: MR imaging was performed in 18 patients (aged 5 months to 45 years) and repeated in 14. Single-voxel proton MR spectra were acquired from cerebral white matter

  10. Spectroscopic characterization of the chemical composition of the potent sweetener Vartamil

    NASA Astrophysics Data System (ADS)

    Kolosova, T. E.; Prokhodchenko, L. K.; Pilipenko, V. V.; Suboch, V. P.

    2008-03-01

    The chemical composition of the potent sweetener Vartamil was characterized using spectral methods. It was demonstrated that Vartamil is a mixture of saccharose chloro derivatives, the main one of which is 4,1',6'-trichloro-4,1',6'-trideoxygalactosaccharose (Sucralose).

  11. Spectroscopic characterization and structural modeling of prolamin from maize and pearl millet

    Microsoft Academic Search

    Milton Roque Bugs; Lucimara Aparecida Forato; Raquel Kely Bortoleto-Bugs; Hannes Fischer; Yvonne Primerano Mascarenhas; Richard John Ward; Luiz Alberto Colnago

    2004-01-01

    Biophysical methods and structural modeling techniques have been used to characterize the prolamins from maize ( Zea mays) and pearl millet ( Pennisetum americanum). The alcohol-soluble prolamin from maize, called zein, was extracted using a simple protocol and purified by gel filtration in a 70% ethanol solution. Two protein fractions were purified from seed extracts of pearl millet with molecular

  12. Steady state and time-resolved fluorescence spectroscopic characterization of normal and cancerous urine

    NASA Astrophysics Data System (ADS)

    Rajasekaran, Ramu; Aruna, Prakasa Rao; Balu David, Munusamy; Koteeswaran, Dornadula; Muthuvelu, Kulandaivel; Rai, R.; Ganesan, Singaravelu

    2013-03-01

    Urine is one of the diagnostically important bio fluids, as it has many metabolites and some of them are native fluorophores. There may be a variation in the distribution and the physiochemical properties of the fluorophores during any metabolic change and pathologic conditions. Native fluorescence spectroscopy has been considered as a promising tool to characterize the fluorophores present in the urine. In this study, we aimed at characterizing the urine of both normal and patients with confirmed cancer using steady state and time-resolved fluorescence spectroscopy at 280 nm and 350 nm excitation. It is observed that the metabolites indoxyl sulphate and neopterin and its derivatives are responsible for altered spectral signatures at 280 nm, and 350 nm excitation. The overall spectral data were subjected to Principal Component Analysis and the resultant components were used as input in the linear discriminant analysis. As a total, 84% and 81.8% of samples were correctly classified at 280 nm and 350 nm respectively.

  13. Metal Complexes of Phenylpiperazine?Based Dithiocarbamate Ligands. Synthesis, Characterization, Spectroscopic, Thermal, and Antimicrobial Activity Studies

    Microsoft Academic Search

    Veysel T. Yilmaz; Turan K. Yaz?c?lar; Hasan Cesur; Resit Ozkanca; Fatma Z. Maras

    2003-01-01

    Potassium salts of phenylpiperazine (Phpzdtc), fluorophenylpiperazine (F?Phpzdtc) and nitrophenylpiperazine (N?Phpzdtc) dithiocarbamates and their manganese(II), iron(II), cobalt(II), nickel(II), copper(II) and zinc(II) complexes have been synthesized and characterized by elemental analyses, IR, UV?VIS, magnetic moment measurements and thermal analysis techniques. On the basis of experimental data, the dithiocarbamates (dtcs) have been observed to coordinate to the metal ions via both sulphur atoms

  14. Synthesis, crystal structures and spectroscopic characterizations of two difluoroboradiaza- s-indacene dyes

    NASA Astrophysics Data System (ADS)

    Yu, Yan-Hong; Shen, Zhen; Xu, Hai-Yun; Wang, Yan-Wei; Okujima, Tetsuo; Ono, Noboru; Li, Yi-Zhi; You, Xiao-Zeng

    2007-02-01

    Two new 8-(4-dimethylaminophenyl) substituted boron-dipyrromethene (BDP) dyes: 1,2,6,7-tetraethyl-4,4-difluoro-3,5-dimethyl-8-(4-dimethylaminophenyl)-4-bora-3 a,4 a-diaza- s-indacene (5) and 4,4-difluoro-1,2,3,5,6,7-hexamethyl-8-(4-dimethylaminophenyl)-4-bora-3 a,4 a-diaza- s-indacene (6) have been synthesized and their crystal structures are determined by X-ray diffraction analysis. The torsion angles of 8-phenyl ring and the indacene plane are 79.61° for 5 and 87.56° for 6, respectively. The absorption and steady-state fluorescence properties in different solvents have been investigated. The fluorescence quantum yields of the two dyes are lower in more polar solvents, which can be ascribed to the intramolecular charge transfer from the aniline to the BDP unit. Protonation of the aniline moiety at low pH in MeOH-H 2O (1:1 v/v) solution causes a large fluorescence enhancement. The p Ka values calculated from the pH dependent fluorescence emission spectra are 3.14 for 5 and 3.09 for 6, respectively. They are suitable as pH probes excitable with visible light.

  15. Spectroscopic characterization of C2Hx intermediates in the dissociation of vinyl iodide on Pt(111)

    NASA Astrophysics Data System (ADS)

    Ren, Yuan; Waluyo, Iradwikanari; Yin, Jun; Trenary, Michael

    2015-07-01

    The thermal decomposition of vinyl iodide on Pt(111) was studied using reflection absorption infrared spectroscopy (RAIRS). Some of the vinyl iodide molecularly desorbs at 160 K and the remainder decomposes via scission of the C-I bond to form vinyl. In this way, the vibrational signature of vinyl on Pt(111) is directly determined by RAIRS. At 190 K, vinyl starts to convert to di-? bonded ethylene. The ethylene undergoes further reaction at 230 K to hydrogenate to ethylidene, possibly by way of a vinyl intermediate. Upon annealing the surface to 300 K, ethylidene is converted to ethylidyne. Hydrogen pre-adsorption promotes the cleavage of the C-I bond of vinyl iodide and the formation of vinyl, which subsequently leads to an increase in the amount of di-? bonded ethylene formed. The surface hydrogen enhances the formation of ethylidyne, possibly by removal of excess ethylidene by hydrogenation, as ethylidene was not observed when hydrogen was pre-adsorbed on the surface.

  16. Characterization of the interactions between tetracycline antibiotics and microbial extracellular polymeric substances with spectroscopic approaches.

    PubMed

    Song, Chao; Sun, Xue-Fei; Xing, Su-Fang; Xia, Peng-Fei; Shi, Yi-Jing; Wang, Shu-Guang

    2014-02-01

    The antibiotics have attracted global attentions for their impact on aquatic ecosystem. The knowledge about the fate of antibiotics encountering extracellular polymeric substances (EPS) is, however, limited. In this study, we investigated the interacting mechanisms of tetracycline (TC) to EPS extracted from aerobic activated sludge. The contributions of the main components of EPS, extracellular proteins, and polysaccharides were evaluated using bovine serum albumin and alginate sodium, respectively. Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, and nuclear magnetic resonance indicated that hydroxyl, carboxyl, and amino groups were the domain chemical groups involved in the interaction between TC and EPS, and the binding of TC onto EPS changed the structure of these chemical groups, thus causing shifts in their UV-visible absorption spectra. In addition, we found that extracellular proteins, rather than polysaccharides, were the major active contents involved in the interaction. Three-dimensional excitation-emission matrix fluorescence spectroscopy showed that the fluorophores in EPS were clearly quenched by TC and the static quenching process was observed, implying the complex formation of TC and EPS. Furthermore, thermodynamic analysis indicated that the binding of TC with EPS is spontaneous and dominated by electrostatic forces. PMID:23979850

  17. Characterization of interaction of calf thymus DNA with gefitinib: Spectroscopic methods and molecular docking.

    PubMed

    Shi, Jie-Hua; Liu, Ting-Ting; Jiang, Min; Chen, Jun; Wang, Qi

    2015-06-01

    The binding interaction of gefitinib with calf thymus DNA (ct-DNA) under the simulated physiological pH condition was studied employing UV absorption, fluorescence, circular dichroism (CD), viscosity measurement and molecular docking methods. The experimental results revealed that gefitinib preferred to bind to the minor groove of ct-DNA with the binding constant (Kb) of 1.29×10(4)Lmol(-1) at 298K. Base on the signs and magnitudes of the enthalpy change (?H(0)=-60.4kJmol(-1)) and entropy change (?S(0)=-124.7Jmol(-1)K(-1)) in the binding process and the results of molecular docking, it can be concluded that the main interaction forces between gefitinib and ct-DNA in the binding process were van der Waals force and hydrogen bonding interaction. The results of CD experiments revealed that gefitinib did not disturb native B-conformation of ct-DNA. And, the significant change in the conformation of gefitinib in gefitinib-ct-DNA complex was observed from the molecular docking results and the change was close relation with the structure of B-DNA fragments, indicating that the flexibility of gefitinib molecule also plays an important role in the formation of the stable gefitinib-ct-DNA complex. PMID:25839749

  18. Characterization of protein immobilization at silver surfaces bynear edge x-ray absorption fine structure spectroscopy

    SciTech Connect

    Liu, X.; Jang, C.-H.; Zheng, F.; J rgensen, A.; Denlinger, J.D.; Dickson, K.A.; Raines, R.T.; Abbott, N.L.; Himpsel, F.J.

    2006-06-21

    Ribonuclease A (RNase A) is immobilized on silver surfacesin oriented and random form via self-assembled monolayers (SAMs) ofalkanethiols. The immobilization process is characterized step-by-stepusing chemically selective near-edge X-ray absorption fine structurespectroscopy (NEXAFS) at the C, N, and S K-edges. Causes of imperfectimmobilization are pinpointed, such as oxidation and partial desorptionof the alkanethiol SAMs and incomplete coverage. The orientation of theprotein layer manifests itself in an 18 percent polarization dependenceof the NEXAFS signal from the N 1s to pi* transition of the peptide bond,which is not seen for a random orientation. The S 1s to C-S sigma*transition exhibits an even larger polarization dependence of 41 percent,which is reduced to 5 percent for a random orientation. A quantitativemodel is developed that explains the sign and magnitude of thepolarization dependence at both edges. The results demonstrate thatNEXAFS is able to characterize surface reactions during theimmobilization of proteins and to provide insight into their orientationson surfaces.

  19. Synthesis and spectroscopic characterization of a fluorescent pyrrole derivative containing electron acceptor and donor groups

    NASA Astrophysics Data System (ADS)

    Almeida, A. K. A.; Monteiro, M. P.; Dias, J. M. M.; Omena, L.; da Silva, A. J. C.; Tonholo, J.; Mortimer, R. J.; Navarro, M.; Jacinto, C.; Ribeiro, A. S.; de Oliveira, I. N.

    2014-07-01

    The synthesis and fluorescence characterization of a new pyrrole derivative (PyPDG) containing the electron donor-acceptor dansyl substituent is reported. The effects of temperature and solvent polarity on the steady-state fluorescence of this compound are investigated. Our results show that PyPDG exhibits desirable fluorescent properties which makes it a promising candidate to be used as the photoactive material in optical thermometry and thermography applications. Further, the electrochemical and emission properties of polymeric films obtained from the oxidation polymerization of PyPDG are also analyzed.

  20. SULFUR CHEMISTRY. Gas phase observation and microwave spectroscopic characterization of formic sulfuric anhydride.

    PubMed

    Mackenzie, Rebecca B; Dewberry, Christopher T; Leopold, Kenneth R

    2015-07-01

    We report the observation of a covalently bound species, formic sulfuric anhydride (FSA), that is produced from formic acid and sulfur trioxide under supersonic jet conditions. FSA has been structurally characterized by means of microwave spectroscopy and further investigated by using density functional theory and ab initio calculations. Theory indicates that a ?2 + ?2 + ?2 cycloaddition reaction between SO3 and HCOOH is a plausible pathway to FSA formation and that such a mechanism would be effectively barrierless. We speculate on the possible role that FSA may play in the Earth's atmosphere. PMID:26138972

  1. Theoretical spectroscopic characterization at low temperatures of methyl hydroperoxide and three S-analogs.

    PubMed

    Dalbouha, S; Senent, M L; Komiha, N

    2015-02-21

    The low temperature spectra of the detectable species methyl hydroperoxide (CH3OOH) and three sulfur analogs, the two isomers of methanesulfenic acid (CH3SOH and CH3OSH) and the methyl hydrogen disulfide (CH3SSH), are predicted from highly correlated ab initio methods (CCSD(T) and CCSD(T)-F12). Rotational parameters, anharmonic frequencies, torsional energy barriers, torsional energy levels, and their splittings are provided. Our computed parameters should help for the characterization and the identification of these organic compounds in laboratory and in the interstellar medium. PMID:25702012

  2. Synthesis, characterization and multi-spectroscopic DNA interaction studies of a new platinum complex containing the drug metformin

    NASA Astrophysics Data System (ADS)

    Shahabadi, Nahid; Heidari, Leila

    2014-07-01

    A new platinum(II) complex; [Pt(Met)(DMSO)Cl]Cl in which Met = metformin and DMSO: dimethylsulfoxide, was synthesized and characterized by 1H NMR, IR, UV-Vis spectra, molar conductivity and computational methods. Binding interaction of this complex with calf thymus (CT) DNA has been investigated by using absorption, emission, circular dichroism, viscosity measurements, differential pulse voltammetry and cleavage studies by agarose gel electrophoresis. UV-Vis absorption studies showed hyperchromism. CD studies showed less perturbation on the base stacking and helicity bands in the CD spectrum of CT-DNA (B ? C structural transition). In fluorimeteric studies, the Pt(II) complex can bind with DNA-NR complex and forms a new non-fluorescence adduct. The anodic peak current in the differential pulse voltammogram of the Pt(II) complex decreased gradually with the addition of DNA. Cleavage experiments showed that the Pt(II) complex does not induce any cleavage under the experimental setup. Finally all results indicated that Pt(II) complex interact with DNA via groove binding mode.

  3. Synthesis, characterization and multi-spectroscopic DNA interaction studies of a new platinum complex containing the drug metformin.

    PubMed

    Shahabadi, Nahid; Heidari, Leila

    2014-07-15

    A new platinum(II) complex; [Pt(Met)(DMSO)Cl]Cl in which Met = metformin and DMSO: dimethylsulfoxide, was synthesized and characterized by (1)H NMR, IR, UV-Vis spectra, molar conductivity and computational methods. Binding interaction of this complex with calf thymus (CT) DNA has been investigated by using absorption, emission, circular dichroism, viscosity measurements, differential pulse voltammetry and cleavage studies by agarose gel electrophoresis. UV-Vis absorption studies showed hyperchromism. CD studies showed less perturbation on the base stacking and helicity bands in the CD spectrum of CT-DNA (B?C structural transition). In fluorimeteric studies, the Pt(II) complex can bind with DNA-NR complex and forms a new non-fluorescence adduct. The anodic peak current in the differential pulse voltammogram of the Pt(II) complex decreased gradually with the addition of DNA. Cleavage experiments showed that the Pt(II) complex does not induce any cleavage under the experimental setup. Finally all results indicated that Pt(II) complex interact with DNA via groove binding mode. PMID:24682051

  4. Structural and spectroscopic characterization of Mo 1-xW xO 3- ? mixed oxides

    NASA Astrophysics Data System (ADS)

    Morandi, S.; Paganini, M. C.; Giamello, E.; Bini, M.; Capsoni, D.; Massarotti, V.; Ghiotti, G.

    2009-12-01

    Mo 1-xW xO 3 oxides with different cationic fraction ( x=0.2, 0.5 and 0.8) and, for comparison purposes, pure MoO 3 and WO 3 were prepared. Along with textural and structural characterizations, absorbance FT-IR, diffuse reflectance UV-vis-NIR and EPR spectroscopies were employed to study the changes in the electronic properties of these materials passing from Mo 1-xW xO 3 in oxidizing atmosphere to Mo 1-xW xO 3-? in reducing conditions. XRD analysis showed that the Mo-W mixed oxides are constituted by two or three crystalline phases, whose abundance and composition are well characterized by structural refinement with the Rietveld method. Only the sample with the highest Mo content ( x=0.2) shows a predominant mixed phase and also a superior ability to lose oxygen with respect to the other mixed oxides. The oxygen loss in the reduced oxides induces the formation of defects with electronic levels in the band gap of the material, in particular, electrons trapped in oxygen vacancies and/or at cationic sites (polarons). While the nature of defect sites induced in the mixed and in the pure oxides is similar, the photo-ionization energies, the ratio between surface and bulk defects and the stability of the defects in oxygen at increasing temperature are peculiar of each mixed oxide.

  5. Synthesis and characterization of low-OH?fluor-chlorapatite: A single-crystal XRD and NMR spectroscopic study

    SciTech Connect

    McCubbin, Francis M.; Mason, Harris E.; Park, Hyunsoo; Phillips, Brian L.; Parise, John B.; Nekvasil, Hanna; Lindsley, Donald H. (SBU)

    2008-12-12

    Los-OH apatite of the compositional range Ca{sub 4.99-5.06}(PO{sub 4}){sub 2.98-3.00}F{sub 0.51-0.48}Cl{sub 0.38-0.36}OH{sub 0.14-0.12} was synthesized and characterized structurally by synchrotron-based single-crystal X-ray diffraction (XRD), and multiple nuclear magnetic resonance (NMR) spectroscopic techniques. the average structure is hexagonal with space group P6{sub 3}/m. The presence of scattering in the single-crystal diffraction data set, which is incommensurate within the average hexagonal structure, suggests the presence of localized short-range monoclinic domains. Complex lineshapes in the {sup 31}P and {sup 19}F MAS NMR spectra are also consistent with the presence of an incommensurate phase. No evidence was detected for splitting of the Ca2 site into two distinct sites (as had been previously reported for hexagonal ternary apatities). Structure refinement and {sup 19}F{l_brace}{sup 35}Cl{r_brace} TRAPDOR NMR experiments verified intercolumnal neighboring of F and Cl atoms (inter-column distance of 2.62 {angstrom}) within this low-OH{sup -} apatite suggesting that long-range neighboring of F and Cl within the apatite anion channels is feasible.

  6. Spectroscopic characterization of intermetallic catalysts and correlations with methanation activity and laser mass spectrometry of organic compounds

    SciTech Connect

    Dang, T.A.

    1983-01-01

    Spectroscopic techniques such as electron spectroscopy for chemical analysis (ESCA), Auger electron spectroscopy (AES), secondary ion mass spectrometry (SIMS), ion scattering spectroscopy (ISS), scanning electron microscopy (SEM) and energy dispersive x-ray analysis (EDX) were used to characterize a number of intermetallic catalytic systems: Th/sub x/Ni/sub y/, Th/sub x/Co/sub y/ and Th Ni/sub x/Fe/sub 5-x/. The results are discussed in relation to methanation activity. Laser mass spectra (LMS) obtained for diquaternary ammonium salts do not show emission of doubly charged molecular ions. Instead, characteristic ions are formed by dehydrogenation (M-H)/sup +/ or dealkylation (M-CH/sub 3/)/sup +/ from the dication. In the case where coulombic repulsion between the two positive charges in the molecule is large, the charge separation process, M/sup 2 +/ ..-->.. M/sub 1//sup +/ + M/sub 2//sup +/, is favored over dehydrogenation and dealkylation. Emission of cluster ions occurs during laser irradiation of substituted pyridines even at threshold laser power density. The clusters generated include dimers and trimers, and appear in both positive ion and negative ion laser mass spectra.

  7. Americium characterization by X-ray fluorescence and absorption spectroscopy in plutonium uranium mixed oxide

    SciTech Connect

    Degueldre, Claude, E-mail: claude.degueldre@psi.ch; Cozzo, Cedric; Martin, Matthias; Grolimund, Daniel; Mieszczynski, Cyprian

    2013-06-01

    Plutonium uranium mixed oxide (MOX) fuels are currently used in nuclear reactors. The actinides in these fuels need to be analyzed after irradiation for assessing their behaviour with regard to their environment and the coolant. In this work the study of the atomic structure and next-neighbour environment of Am in the (Pu,U)O? lattice in an irradiated (60 MW d kg?¹) MOX sample was performed employing micro-X-ray fluorescence (µ-XRF) and micro-X-ray absorption fine structure (µ-XAFS) spectroscopy. The chemical bonds, valences and stoichiometry of Am (~0.66 wt%) are determined from the experimental data gained for the irradiated fuel material examined in its peripheral zone (rim) of the fuel. In the irradiated sample Am builds up as Am³? species within an [AmO?]¹³? coordination environment (e.g. >90%) and no (<10%) Am(IV) or (V) can be detected in the rim zone. The occurrence of americium dioxide is avoided by the redox buffering activity of the uranium dioxide matrix. - Graphical abstract: Americium LIII XAFS spectra recorded for the irradiated MOX sub-sample in the rim zone for a 300 ?m×300 ?m beam size area investigated over six scans of 4 h. The records remain constant during multi-scan. The analysis of the XAFS signal shows that Am is found as trivalent in the UO? matrix. This analytical work shall open the door of very challenging analysis (speciation of fission product and actinides) in irradiated nuclear fuels. - Highlights: • Americium was characterized by microX-ray absorption spectroscopy in irradiated MOX fuel. • The americium redox state as determined from XAS data of irradiated fuel material was Am(III). • In the sample, the Am³? face an AmO?¹³?coordination environment in the (Pu,U)O? matrix. • The americium dioxide is reduced by the uranium dioxide matrix.

  8. Spectroscopic characterization of discharge products in Li-Air cells with aprotic carbonate electrolytes

    SciTech Connect

    Veith, Gabriel M [ORNL; Nanda, Jagjit [ORNL; Howe, Jane Y [ORNL; Dudney, Nancy J [ORNL

    2011-01-01

    Raman, infrared and X-ray photoelectron spectroscopies were used to characterize the thick coating of reaction products on carbon and MnO2 coated carbon cathodes produced during discharge of Li-air cells. The results show that neither Li2O2 or Li2O are major components of the insoluble discharge products; instead the products are largely composed of fluorine, lithium, and carbon, with surprisingly little oxygen. The complex reaction chemistry also appears to involve the formation of ethers or alkoxide products at the expense of the carbonate solvent molecules (ethylene carbonate and dimethylcarbonate). The irreversible discharge reaction is likely electrochemically promoted with Li-anion species and dissolved oxygen. Exactly how the molecular O2 participates in the reaction is unclear and requires further study. The addition of a conformal coating of MnO2 on the carbon lowers the cell s operating voltage, but does not alter the overall discharge chemistry.

  9. Spectroscopic characterization of a masterpiece: the Manueline foral charter of Sintra.

    PubMed

    Manso, Marta; Le Gac, Agnès; Longelin, Stéphane; Pessanha, Sofia; Frade, José Carlos; Guerra, Mauro; Candeias, António José; Carvalho, Maria Luísa

    2013-03-15

    The foral charter attributed by D. Manuel I of Portugal, in 1514, to the village of Sintra was studied using Energy Dispersive X-ray Fluorescence spectrometry, Raman and Infrared micro-spectroscopies. A complete characterization of the pictorial materials used in the production of this masterpiece allowed the identification of iron gall inks used in the written text; pigments such as malachite, azurite, lead white, cinnabar, yellow ochre, gold, silver and carbon black in the illuminations and letterings; filler and binder used in the production of coloring materials and inks. Gum and calcium carbonate were the most recurrent binder and filler identified in this study. Silvering and gilding were mostly obtained by applying ground silver and gold on parchment. PMID:23318772

  10. Spectroscopic characterization of a masterpiece: The Manueline foral charter of Sintra

    NASA Astrophysics Data System (ADS)

    Manso, Marta; Gac, Agnès Le; Longelin, Stéphane; Pessanha, Sofia; Frade, José Carlos; Guerra, Mauro; Candeias, António José; Carvalho, Maria Luísa

    2013-03-01

    The foral charter attributed by D. Manuel I of Portugal, in 1514, to the village of Sintra was studied using Energy Dispersive X-ray Fluorescence spectrometry, Raman and Infrared micro-spectroscopies. A complete characterization of the pictorial materials used in the production of this masterpiece allowed the identification of iron gall inks used in the written text; pigments such as malachite, azurite, lead white, cinnabar, yellow ochre, gold, silver and carbon black in the illuminations and letterings; filler and binder used in the production of coloring materials and inks. Gum and calcium carbonate were the most recurrent binder and filler identified in this study. Silvering and gilding were mostly obtained by applying ground silver and gold on parchment.

  11. Synthesis and spectroscopic characterization of gallic acid and some of its azo complexes

    NASA Astrophysics Data System (ADS)

    Masoud, Mamdouh S.; Hagagg, Sawsan S.; Ali, Alaa E.; Nasr, Nessma M.

    2012-04-01

    A series of gallic acid and azo gallic acid complexes were prepared and characterized by elemental analysis, IR, electronic spectra and magnetic susceptibility. The complexes were of different geometries: Octahedral, Tetrahedral and Square Planar. ESR was studied for copper complexes. All of the prepared complexes were of isotropic nature. The thermal analyses of the complexes were studied by DTA and DSC techniques. The thermodynamic parameters and the thermal transitions, such as glass transitions, crystallization and melting temperatures for some ligands and their complexes were evaluated and discussed. The entropy change values, ?S#, showed that the transition states are more ordered than the reacting complexes. The biological activities of some ligands and their complexes are tested against Gram positive and Gram negative bacteria. The results showed that some complexes have a well considerable activity against different organisms.

  12. Structural and spectroscopic characterizations of tetra-nuclear niobium(V) complexes of quinolinol derivatives

    NASA Astrophysics Data System (ADS)

    Amini, Mostafa M.; Fazaeli, Yousef; Mohammadnezhad, Gholamhossein; Khavasi, Hamid Reza

    2015-06-01

    Reactions between niobium ethoxide and 8-hydroxy-2-methylquinoline or 5-chloro-8-hydroxyquinoline have been explored. Two new tetranuclear heteroleptic niobium complexes containing oxo, ethoxo, and quinolinate chelate rings have been synthesized and characterized by 1H, 13C and 93Nb NMR, UV-Vis, and FT-IR spectroscopies, and single-crystal X-ray diffraction. The molecular structures of the niobium complexes, [Nb4(?-O)4(?-OEt)2(ONC10H8)2(OEt)8] (I) and [Nb4(?-O)4(?-OEt)2(ONC9H5Cl)2(OEt)8] (II), are composed of a pair of edge-sharing bioctahedral moieties in which connected via two almost linear oxo-bridges, with a large difference in the NbO distances. Single-crystal structures showed both complexes are centrosymmetric and contain two distinct Nb centers, and results confirmed by observation of two niobium signals in the 93Nb NMR spectra of complexes.

  13. Synthesis, spectroscopic characterization and pH dependent photometric and electrochemical fate of Schiff bases.

    PubMed

    Rauf, Abdur; Shah, Afzal; Abbas, Saghir; Rana, Usman Ali; Khan, Salah Ud-Din; Ali, Saqib; Zia-Ur-Rehman; Qureshi, Rumana; Kraatz, Heinz-Bernhard; Belanger-Gariepy, Francine

    2015-03-01

    A new Schiff base, 1-((4-bromophenylimino) methyl) naphthalen-2-ol (BPIMN) was successfully synthesized and characterized by (1)H NMR, (13)C NMR, FTIR and UV-Vis spectroscopy. The results were compared with a structurally related Schiff base, 1-((4-chlorophenylimino) methyl) naphthalen-2-ol (CPIMN). The photometric and electrochemical fate of BPIMN and CPIMN was investigated in a wide pH range. The experimental findings were supported by quantum mechanical approach. The redox mechanistic pathways were proposed on the basis of results obtained electrochemical techniques. Moreover, pH dependent UV-Vis spectroscopy of BPIMN and CPIMN was carried out and the appearance of isosbestic points indicated the existence of these compounds in different tautomeric forms. PMID:25437845

  14. Synthesis, spectroscopic characterization and DFT calculations of ?-O-4 type lignin model compounds

    NASA Astrophysics Data System (ADS)

    Mostaghni, Fatemeh; Teimouri, Abbas; Mirshokraei, Seyed Ahmad

    2013-06-01

    ?-O-4 type lignin model compounds with the title of Erythro-2-(2-methoxyphenoxy)-1-(3,4,5-trimethoxyphenyl)-1,3-propanediol and Erythro-2-(2-methoxyphenoxy)-1-(4-Hydroxy-3,5-dimethoxyphenyl)-1,3-propanediol were synthesised and some modifications and improvements on them were introduced. These compounds were characterized by IR, Mass and NMR spectroscopy. Density functional theory (DFT) calculations were performed for the title compounds using the standard 6-31G* basis set. IR, 13C and 1H NMR of the title compounds were calculated at the DFT-B3LYP level of theory using the 6-31G* basis set. In this work comparison between the experimental and the theoretical results indicates that the DFT-B3LYP method is able to provide satisfactory results for predicting the properties of the considered compounds.

  15. Molecular modelling, spectroscopic characterization and biological studies of tetraazamacrocyclic metal complexes

    NASA Astrophysics Data System (ADS)

    Rathi, Parveen; Sharma, Kavita; Singh, Dharam Pal

    2014-09-01

    Macrocyclic complexes of the type [MLX]X2; where L is (C30H28N4), a macrocyclic ligand, M = Cr(III) and Fe(III) and X = Cl-, CH3COO- or NO3-, have been synthesized by template condensation reaction of 1,8-diaminonaphthalene and acetylacetone in the presence of trivalent metal salts in a methanolic medium. The complexes have been formulated as [MLX]X2 due to 1:2 electrolytic nature of these complexes. The complexes have been characterized with the help of elemental analyses, molar conductance measurements, magnetic susceptibility measurements, electronic, infrared, far infrared, Mass spectral studies and molecular modelling. Molecular weight of these complexes indicates their monomeric nature. On the basis of all these studies, a five coordinated square pyramidal geometry has been proposed for all these complexes. These metal complexes have also been screened for their in vitro antimicrobial activities.

  16. Spectroscopic characterization of magnetic Fe3O4@Au core shell nanoparticles

    NASA Astrophysics Data System (ADS)

    Fouad, Dina M.; El-Said, Waleed A.; Mohamed, Mona B.

    2015-04-01

    The magnetic nanoparticles iron oxide (Fe3O4) nanoparticles and iron oxide/gold core-shell (Fe3O4/Au) nanoparticles were synthesized and their catalytic photo-degradation activity towards malathion as example of organophosphorus pesticides were reported. Iron oxide (Fe3O4) magnetic nanoparticle was successfully prepared through co-precipitation method by the reduction of ferric chloride (FeCl3) using ascorbic acid. The morphology of the prepared nanoparticles was characterized by the TEM and XRD (X-ray diffraction) techniques. Degradation of 10 ppm of malathion in the presence of these nanoparticles under UV radiation was monitored using (HPLC) and UV-visible spectra. Fe3O4/Au nanoparticles showed higher efficiency in photo-degradation of malathion than Fe3O4 ones.

  17. Molecular modelling, spectroscopic characterization and biological studies of tetraazamacrocyclic metal complexes.

    PubMed

    Rathi, Parveen; Sharma, Kavita; Singh, Dharam Pal

    2014-09-15

    Macrocyclic complexes of the type [MLX]X2; where L is (C30H28N4), a macrocyclic ligand, M=Cr(III) and Fe(III) and X=Cl-, CH3COO- or NO3-, have been synthesized by template condensation reaction of 1,8-diaminonaphthalene and acetylacetone in the presence of trivalent metal salts in a methanolic medium. The complexes have been formulated as [MLX]X2 due to 1:2 electrolytic nature of these complexes. The complexes have been characterized with the help of elemental analyses, molar conductance measurements, magnetic susceptibility measurements, electronic, infrared, far infrared, Mass spectral studies and molecular modelling. Molecular weight of these complexes indicates their monomeric nature. On the basis of all these studies, a five coordinated square pyramidal geometry has been proposed for all these complexes. These metal complexes have also been screened for their in vitro antimicrobial activities. PMID:24769359

  18. A new heterometallic (Ni 2+ and Cr 3+) complex – Crystal structure and spectroscopic characterization

    Microsoft Academic Search

    Marijana Juric; Pavica Planinic; Dijana Žili?; Boris Rakvin; Biserka Prugovecki; Dubravka Matkovic-Calogovic

    2009-01-01

    A new heterometallic complex, of the composition [Ni(bpy)3]2[Cr(C2O4)3]NO3·10H2O (bpy=2,2?-bipyridine) (1), was synthesized and characterized by elemental and TG\\/DTA analyses, IR, UV\\/vis and EPR spectroscopy and by a single-crystal X-ray diffraction study. The compound crystallizes in the monoclinic P21\\/c space group, with the unit cell parameters: a=23.201(7), b=13.562(4), c=22.350(7)Å, ?=92.782(5)°, V=7024(4)Å3 and Z=4. The molecular structure of 1 consists of two

  19. Structural and spectroscopic characterization of E- and Z-isomers of azobenzene.

    PubMed

    Duarte, Luís; Fausto, Rui; Reva, Igor

    2014-08-28

    Monomers of azobenzene were isolated in argon matrices at 15 K and characterized by infrared spectroscopy and theoretical calculations. When the equilibrium vapors existing over the azobenzene crystals at room temperature were trapped in the matrix, only the thermodynamically most stable E-azobenzene was detected. In an attempt to convert E-azobenzene into the Z isomer, the matrix-isolated E-monomers were irradiated either by broad-band or narrow-band UV-visible light of different wavelengths, in the 600-200 nm range. However, no E-to-Z transformation was observed under these conditions. In an alternative experiment, E-azobenzene was irradiated by UV-visible broad-band light in the gas phase prior to trapping in a matrix. In this case, the E-to-Z photoisomerization occurred, and both E- and Z-azobenzene monomers were detected in the matrix sample. Subsequent irradiation of the matrix with narrow-band tunable visible or UV light (? < 550 nm) resulted in back conversion of Z-azobenzene into the E-form. The observed photoinduced E-to-Z isomerizations allowed for the reliable vibrational characterization of both azobenzene isomers. The two-dimensional potential energy surfaces of Z- and E-azobenzene were explored as functions of the torsional movement of the two phenyl rings. They exhibit large flat areas around the minima, for both isomers, allowing for large-amplitude zero-point torsional vibrations. For the Z-form, these vibrations were found to be responsible for significant changes in the equilibrium NN bond length (up to 0.3 pm). This also allowed to explain the experimentally observed frequency smearing of the N=N stretching vibration in this isomer. PMID:24647717

  20. Laboratory studies of spectroscopic markers for the characterization of surface erosion by plasmas

    SciTech Connect

    Manos, D.M.; Bennett, T.; Herzer, M.; Schwarzmann, J.

    1992-01-01

    The erosion rates in portions of fusion plasma devices like the ITER tokamak are sufficiently high that nearly real-time information on cumulative removal is needed for control and machine safety. We are developing a digitally--encoded scheme to indicate the depth of erosion at numerous poloidal and toroidal locations around ITER. The scheme uses materials embedded in the walls and divertors, which, when uncovered, present remotely detectable signals. This paper reports laboratory experiments on prototype markers consisting of combinations of up to 5 elements (Au,Pd,Ag,In,Ga) along with Au,Pt, and Ta pure metals. The markers were bonded to 4-D carbon-carbon composite of the type proposed for use in the ITER first wall, and placed in the lower-hybrid-driven plasma of the atomic beam facility at PPL. The paper describes this device Light emission was characterized using a 1 meter Czerny-Turner vacuum ultraviolet monochromator. The samples were characterized both before and after plasma exposure by Auger spectroscopy. We report the time-dependent behavior of the spectra of the visible and ultraviolet light emitted by the plasma when the markers are uncovered by the erosion showing emission lines of the marker elements which are easily distinguished from the background plasma lines. The dependence of the light intensity on bias voltage is compared to the known sputtering yields of the elements. The optical detection method allows exploration of the threshold dependence of these multi-element targets. An exponential dependence of yield above threshold was observed for all of the elements studied.

  1. Laboratory studies of spectroscopic markers for the characterization of surface erosion by plasmas

    SciTech Connect

    Manos, D.M.; Bennett, T.; Herzer, M.; Schwarzmann, J.

    1992-06-01

    The erosion rates in portions of fusion plasma devices like the ITER tokamak are sufficiently high that nearly real-time information on cumulative removal is needed for control and machine safety. We are developing a digitally--encoded scheme to indicate the depth of erosion at numerous poloidal and toroidal locations around ITER. The scheme uses materials embedded in the walls and divertors, which, when uncovered, present remotely detectable signals. This paper reports laboratory experiments on prototype markers consisting of combinations of up to 5 elements (Au,Pd,Ag,In,Ga) along with Au,Pt, and Ta pure metals. The markers were bonded to 4-D carbon-carbon composite of the type proposed for use in the ITER first wall, and placed in the lower-hybrid-driven plasma of the atomic beam facility at PPL. The paper describes this device Light emission was characterized using a 1 meter Czerny-Turner vacuum ultraviolet monochromator. The samples were characterized both before and after plasma exposure by Auger spectroscopy. We report the time-dependent behavior of the spectra of the visible and ultraviolet light emitted by the plasma when the markers are uncovered by the erosion showing emission lines of the marker elements which are easily distinguished from the background plasma lines. The dependence of the light intensity on bias voltage is compared to the known sputtering yields of the elements. The optical detection method allows exploration of the threshold dependence of these multi-element targets. An exponential dependence of yield above threshold was observed for all of the elements studied.

  2. Theoretical spectroscopic characterization at low temperatures of detectable sulfur-organic compounds: Ethyl mercaptan and dimethyl sulfide

    NASA Astrophysics Data System (ADS)

    Senent, M. L.; Puzzarini, C.; Domínguez-Gómez, R.; Carvajal, M.; Hochlaf, M.

    2014-03-01

    Highly correlated ab initio methods are used for the spectroscopic characterization of ethyl mercaptan (CH3CH232SH, ETSH) and dimethyl sulfide (CH332SCH3, DMS), considering them on the vibrational ground and excited torsional states. Since both molecules show non-rigid properties, torsional energy barriers and splittings are provided. Equilibrium geometries and the corresponding rotational constants are calculated by means of a composite scheme based on CCSD(T) calculations that accounts for the extrapolation to the complete basis set limit and core-correlation effects. The ground and excited states rotational constants are then determined using vibrational corrections obtained from CCSD/cc-pVTZ force-field calculations, which are also employed to determine anharmonic frequencies for all vibrational modes. CCSD(T) and CCSD force fields are employed to predict quartic and sextic centrifugal-distortion constants, respectively. Equilibrium rotational constants are also calculated using CCSD(T)-F12. The full-dimensional anharmonic analysis does not predict displacements of the lowest torsional excited states due to Fermi resonances with the remaining vibrational modes. Thus, very accurate torsional transitions are calculated by solving variationally two-dimensional Hamiltonians depending on the CH3 and SH torsional coordinates of ethyl mercaptan or on the two methyl groups torsions of dimethyl-sulfide. For this purpose, vibrationally corrected potential energy surfaces are computed at the CCSD(T)/aug-cc-pVTZ level of theory. For ethyl mercaptan, calculations show large differences between the gauche (g) and trans (t) conformer spectral features. Interactions between rotating groups are responsible for the displacements of the g-bands with respect to the t-bands that cannot therefore be described with one-dimensional models. For DMS, the CCSD(T) potential energy surface has been semi-empirically adjusted to reproduce experimental data. New assignments are suggested for the methyl torsion bands of ETSH and a reassignment is proposed for the infrared bands of DMS (0 3 ? 0 4 and 1 0 ? 1 1). Our accurate spectroscopic data should be useful for the analysis of the microwave and far infrared spectra of ETSH and DMS recorded, at low temperatures, either in laboratory or in the interstellar medium.

  3. Theoretical spectroscopic characterization at low temperatures of detectable sulfur-organic compounds: ethyl mercaptan and dimethyl sulfide.

    PubMed

    Senent, M L; Puzzarini, C; Domínguez-Gómez, R; Carvajal, M; Hochlaf, M

    2014-03-28

    Highly correlated ab initio methods are used for the spectroscopic characterization of ethyl mercaptan (CH3CH2 (32)SH, ETSH) and dimethyl sulfide (CH3 (32)SCH3, DMS), considering them on the vibrational ground and excited torsional states. Since both molecules show non-rigid properties, torsional energy barriers and splittings are provided. Equilibrium geometries and the corresponding rotational constants are calculated by means of a composite scheme based on CCSD(T) calculations that accounts for the extrapolation to the complete basis set limit and core-correlation effects. The ground and excited states rotational constants are then determined using vibrational corrections obtained from CCSD/cc-pVTZ force-field calculations, which are also employed to determine anharmonic frequencies for all vibrational modes. CCSD(T) and CCSD force fields are employed to predict quartic and sextic centrifugal-distortion constants, respectively. Equilibrium rotational constants are also calculated using CCSD(T)-F12. The full-dimensional anharmonic analysis does not predict displacements of the lowest torsional excited states due to Fermi resonances with the remaining vibrational modes. Thus, very accurate torsional transitions are calculated by solving variationally two-dimensional Hamiltonians depending on the CH3 and SH torsional coordinates of ethyl mercaptan or on the two methyl groups torsions of dimethyl-sulfide. For this purpose, vibrationally corrected potential energy surfaces are computed at the CCSD(T)/aug-cc-pVTZ level of theory. For ethyl mercaptan, calculations show large differences between the gauche (g) and trans (t) conformer spectral features. Interactions between rotating groups are responsible for the displacements of the g-bands with respect to the t-bands that cannot therefore be described with one-dimensional models. For DMS, the CCSD(T) potential energy surface has been semi-empirically adjusted to reproduce experimental data. New assignments are suggested for the methyl torsion bands of ETSH and a reassignment is proposed for the infrared bands of DMS (0 3 ? 0 4 and 1 0 ? 1 1). Our accurate spectroscopic data should be useful for the analysis of the microwave and far infrared spectra of ETSH and DMS recorded, at low temperatures, either in laboratory or in the interstellar medium. PMID:24697436

  4. Aggregation numbers and microstructure characterization of self-assembled aggregates of poly(ethylene oxide) surfactants and related block-copolymers, studied by spectroscopic methods

    Microsoft Academic Search

    Marilena Vasilescu; Agneta Caragheorgheopol; Horia Caldararu

    2001-01-01

    This review presents typical examples of micellar size measurements and structural characterization of self-assembled systems as determined with spectroscopic methods, selected from our representative results accumulated in recent years of systematic studies. The choice of examples has aimed at emphasizing the potentiality of the methods used in the study of poly(ethylene oxide) (PEO) surfactants. By using the time-resolved fluorescence quenching

  5. Spectroscopic characterization of extracellular polymeric substances from a mixed culture dominated by ammonia-oxidizing bacteria.

    PubMed

    Yin, Cuiqin; Meng, Fangang; Chen, Guang-Hao

    2015-01-01

    Extracellular polymeric substances (EPS) of aerobic (AerAOB) and anaerobic ammonium-oxidizing bacteria (AnAOB) are expected to have a significant impact on the performance of autotrophic nitrogen removal in engineered systems. However, there are a few investigations of the EPS of AerAOB and AnAOB, and the results are contradictory. In this study, photometric measurements indicated that the EPS of AerAOB- (31.74 ± 1.48 mg/g-VSS, volatile suspended solids) and AnAOB-enriched cultures (30.12 ± 1.52 mg/g-VSS) contained more polysaccharides than did conventional activated sludge from a municipal wastewater treatment facility (10.76 ± 0.83 mg/g-VSS). In addition, the EPS of the AnAOB-enriched culture was dominated by proteins, leading to a considerably higher protein/polysaccharide ratio (2.64 ± 0.12) than those of the AerAOB-enriched culture (0.56 ± 0.03) and conventional activated sludge (1.96 ± 0.09). Characterization using Fourier transform infrared spectroscopy (FTIR) revealed the dominance of amide bands and/or polysaccharide-associated bands in the EPS of AnAOB and AerAOB. These results corroborate the data from the photometric measurements. In addition, the EPS of AnAOB (23.1% ± 1.2%) and AerAOB (21.9% ± 1.1%) had a higher portion of ?-helices, which is the key protein secondary structure that determines flocculation or cell aggregation, in the amide I band than that of activated sludge (16.7% ± 0.8%). X-ray photoelectron spectroscopy (XPS) characterization also revealed significantly different functionalities among the EPS of the three mixed cultures; e.g., O-(C,H), which indicates the presence of polysaccharides, was richer in the EPS of AerAOB, whereas protonated amines, which are commonly found in amino acids and amino sugars, accounted for a large portion of the EPS of AnAOB. The results of this study can potentially expand our knowledge of the microbial aggregates responsible for autotrophic nitrogen removal. PMID:25462778

  6. Minor groove binding of the food colorant carmoisine to DNA: spectroscopic and calorimetric characterization studies.

    PubMed

    Basu, Anirban; Kumar, Gopinatha Suresh

    2014-01-01

    The interaction of the food additive carmoisine with herring testes DNA was studied by multifaceted biophysical techniques. Carmoisine exhibited hypochromic effects in absorbance, whereas in fluorescence the intensity enhanced upon complexation with DNA. Energy transfer from the DNA base pairs to carmoisine molecules occurred upon complexation. A groove binding model of interaction was envisaged for carmoisine-DNA complexation from 4',6-diamidino-2-phenylindole (DAPI) and Hoechst displacement studies. The binding of carmoisine stabilized the DNA structure against thermal denaturation. The binding induced moderate conformational perturbations in the B-form structure of DNA. The binding affinity (10(4) M(-1)) values, calculated from absorbance and fluorescence data, and calorimetry titrations were in close agreement with each other. The binding was characterized to be exothermic and favored by small negative enthalpic and large positive entropic contributions. Salt-dependent calorimetric studies revealed that the binding reaction was dominated by nonpolyelectrolytic forces. The negative heat capacity value suggested the role of hydrophobic effect in the interaction. PMID:24328331

  7. Infrared spectroscopic characterization of carbonated apatite: a combined experimental and computational study.

    PubMed

    Ren, Fuzeng; Ding, Yonghui; Leng, Yang

    2014-02-01

    A combined experimental and computational approach was employed to investigate the feasibility and effectiveness of characterizing carbonated apatite (CAp) by infrared (IR) spectroscopy. First, an experimental comparative study was conducted to identify characteristic IR vibrational bands of carbonate substitution in the apatite lattice. The IR spectra of pure hydroxyapatite (HA), carbonate adsorbed on the HA surface, a physical mixture of HA and sodium carbonate monohydrate, a physical mixture of HA and calcite, synthetic CAps prepared using three methods (precipitation method, hydrothermal route, and solid-gas reaction at high temperature) and biological apatites (human enamel, human cortical bone, and two animal bones) were compared. Then, the IR vibrational bands of carbonate in CAp were calculated with density functional theory. The experimental study identified characteristic IR bands of carbonate that cannot be generated from surface adsorption or physical mixtures and the results show that the bands at ?880, 1413, and 1450 cm(-1) should not be used as characteristic bands of CAp since they could result from carbonate adsorbed on the apatite crystals surface or present as a separate phase. The combined experimental and computational study reveals that the carbonate v3 bands at ?1546 and 1465 cm(-1) are, respectively, the IR signature bands for type A CAp and type B CAp. PMID:23533194

  8. Spectroscopic characterization of B/KNO3 diode-laser induced combustion.

    PubMed

    Sivan, J; Haas, Y

    2013-11-21

    The combustion of a B/KNO3 pyrotechnic mixture was characterized by its chemiluminescence for the first time. The reaction was initiated by a continuous wave (cw) diode laser inside a novel multipurpose reaction cell, whose design and construction are described. As in the case of the extensively studied oxidation of boron by O2, the most intense luminescence, recorded in the 400-600 nm range, is assigned to BO2. Its appearance delay time (10(-2) to 10(-1) s) equals that measured for the pressure increase and is shortened as the laser power is increased. A band observed at 355 nm appears at longer delay times than the BO2 bands. The band, and some weaker ones, may be assigned to BO, although some bands expected for BO (based on reaction between B atoms and O2) are absent from the spectra. This observation is discussed in the text, and possible emission from BN is discussed. If the band is assigned to BO, the absence of known bands may be due to specific E-V resonance energy transfer. Possible oxidation mechanisms consistent with the different delay ignition times are discussed. PMID:23679891

  9. Synthesis, spectroscopic and thermal characterization of some transition metal complexes of folic acid.

    PubMed

    El-Wahed, M G Abd; Refat, M S; El-Megharbel, S M

    2008-09-01

    Compounds having general formula: [M(FO)(Cl)x(H2O)y]x zH2O, where (M=Mn(II), Fe(III), Co(II), Ni(II), Cu(II), Zn(II), Cd(II) and Hg(II), FO=folate anion, x=2 or 4, y=2 or 4 and z=0, 1, 2, 3, 5 or 15) were prepared. The obtained compounds were characterized by elemental analysis, infrared as well as electronic spectra, thermogravimetric analysis and the conductivity measurements. The results suggested that all folate complexes were formed by 2:1 molar ratio (metal:folic acid) as a bidentate through both of the two carboxylic groups. The molar conductance measurements proved that the folate complexes are electrolytes. The kinetic thermodynamic parameters such as: E*, DeltaH*, DeltaS* and DeltaG* were estimated from the DTG curves. The antibacterial evaluation of the folic acid and their complexes was also done against some Gram positive/negative bacteria as well as fungi. PMID:18024191

  10. Structural characterization of humic-like substances with conventional and surface-enhanced spectroscopic techniques

    NASA Astrophysics Data System (ADS)

    Carletti, Paolo; Roldán, Maria Lorena; Francioso, Ornella; Nardi, Serenella; Sanchez-Cortes, Santiago

    2010-10-01

    Emission-excitation, synchronous fluorescence spectroscopy and surface-enhanced Raman scattering (SERS) combined with surface-enhanced fluorescence (SEF) were applied to aqueous solutions of a humic-like substance (HLS) extracted from earthworm faeces. All measurements were acquired in a wide range of pH (4-12) and analysed by the linear regression analysis. Diffuse Reflectance Infrared Fourier Transform (DRIFT) spectra were also acquired to assist in the structural characterization of this HLS. The emission and excitation spectra allowed the identification of two main fluorophores in the analysed sample. Moreover, a close correlation between fluorescence intensities of each fluorophore with pH variation was observed. SERS and SEF, in agreement with the fluorescence spectroscopy, showed that the HLS at low pH values exists in an aggregated and coiled molecular structure while it is dispersed and uncoiled at alkaline conditions. The obtained spectra also evidenced that different conditions modify the functional groups exposed to the surrounding aqueous environment.

  11. New copper(II) complexes with dopamine hydrochloride and vanillymandelic acid: Spectroscopic and thermal characterization

    NASA Astrophysics Data System (ADS)

    Mohamed, Gehad G.; Nour El-Dien, F. A.; El-Nahas, R. G.

    2011-10-01

    The dopamine derivatives participate in the regulation of wide variety of physiological functions in the human body and in medication life. Increase and/or decrease in the concentration of dopamine in human body reflect an indication for diseases such as Schizophrenia and/or Parkinson diseases. The Cu(II) chelates with coupled products of dopamine hydrochloride (DO.HCl) and vanillymandelic acid (VMA) with 4-aminoantipyrine (4-AAP) are prepared and characterized. Different physico-chemical techniques namely IR, magnetic and UV-vis spectra are used to investigate the structure of these chelates. Cu(II) forms 1:1 (Cu:DO) and 1:2 (Cu:VMA) chelates. DO behave as a uninegative tridentate ligand in binding to the Cu(II) ion while VMA behaves as a uninegative bidentate ligand. IR spectra show that the DO is coordinated to the Cu(II) ion in a tridentate manner with ONO donor sites of the phenolic- OH, -NH and carbonyl- O, while VMA is coordinated with OO donor sites of the phenolic- OH and -NH. Magnetic moment measurements reveal the presence of Cu(II) chelates in octahedral and square planar geometries with DO and VMA, respectively. The thermal decomposition of Cu(II) complexes is studied using thermogravimetric (TG) and differential thermal analysis (DTA) techniques. The activation thermodynamic parameters, such as, energy of activation, enthalpy, entropy and free energy change of the complexes are evaluated and the relative thermal stability of the complexes are discussed.

  12. Preparation, spectroscopic characterization and crystal structures of ferrocenylalkanediols and derived acetates

    NASA Astrophysics Data System (ADS)

    Lapi?, Jasmina; Bili?, Josipa; Cetina, Mario; Djakovi?, Senka; Rapi?, Vladimir

    2011-01-01

    ( meso, dl)-3-(Ferrocenylmethyl)pentane-2,4-diol ( 3) was synthesized by reduction of 3-(ferrocenylmethyl)pentane-2,4-dione ( 2) with LiAlH 4 in a good yield and corresponding monoacetate 4 and diacetate 5 were prepared. Newly prepared compounds are characterized by elemental analysis, IR and NMR spectroscopy and will be used as a substrate or standards for lipase mediated desymmetrization. The structures of 3-(ferrocenylmethyl)pentane-2,4-diol ( 3) and 2-(ferrocenylmethyl)propane-1,3-diol diacetate ( 8), which is derived from prochiral 2-(ferrocenylmethyl)propane-1,2-diol ( 6), were determined by X-ray crystal structure analysis. The conformation of the cyclopentadienyl rings is eclipsed in 3 and almost halfway between eclipsed and staggered in 8. One O-H⋯O hydrogen bond links the molecules of diol 3 into chains, while one weak C-H⋯? interaction self-assembles the molecules of diacetate 8 into dimers.

  13. Synchronous fluorescence spectroscopic characterization of DMBA-TPA-induced squamous cell carcinoma in mice

    NASA Astrophysics Data System (ADS)

    Diagaradjane, Parmeswaran; Yaseen, Mohammad A.; Yu, Jie; Wong, Michael S.; Anvari, Bahman

    2006-01-01

    While initially confined to the epidermis, squamous cell carcinoma can eventually penetrate into the underlying tissue if not diagnosed early and treated. The noninvasive early detection of the carcinoma is important to achieve a complete treatment of the disease. Of the various non-invasive optical techniques, the synchronous fluorescence (SF) technique is considered to provide a simplified spectral profile with more sharp spectral signatures of the endogenous fluorophores in complex systems. The potential use of the SF technique in the characterization of the sequential tissue transformation in 7,12-dimethylbenz(a)anthracene-12-O-tetradecanoylphorbol-13-acetate (DMBA-TPA)-induced mouse skin tumor model in conjunction with simple statistical analysis is explored. The SF spectra show distinct differences during the earlier weeks of the tumor-induction period. Intensity ratio variables are calculated and used in three discriminant analyses. All the discriminant analyses show better classification results with accuracy greater than 80%. From the observed differences in the spectral characteristics and the ratio variables that resulted in better classification between groups, it is concluded that tryptophan, collagen, and NADH are the key fluorophores that undergo changes during tissue transformation process and hence they can be targeted as tumor markers to diagnose normal from abnormal tissues using the SF technique.

  14. Characterization of green copper phase pigments in Egyptian artifacts with X-ray absorption spectroscopy and principal components analysis

    NASA Astrophysics Data System (ADS)

    Lau, Deborah; Kappen, Peter; Strohschnieder, Marika; Brack, Narelle; Pigram, Paul J.

    2008-11-01

    The characterization of materials in historical artifacts can contribute significantly to their preservation and understanding; however, sampling and characterization are ideally performed using non-destructive approaches. The analysis of green pigments from Egyptian artifacts presents a further challenge as responses to laboratory based techniques have proven unsuccessful in many cases. An alternative approach is the use of non-destructive X-ray absorption near-edge structure spectroscopy, which was performed on a reference set of copper-containing green minerals and other compounds. Data projection using principal component analysis was used to explore the spectral data structures and to illustrate the relationship between the spectra and copper speciation, resulting in a calibration or training set of the reference materials used. Data from the training set were compared with samples from Egyptian artifacts. The combination of X-ray absorption spectroscopy with principal components analysis provides a novel approach in archeometry and the characterization of objects of cultural heritage.

  15. Fluorescence spectroscopic characterization of dissolved organic matter fractions in soils in soil aquifer treatment.

    PubMed

    Xue, Shuang; Zhao, Qingliang; Wei, Liangliang; Song, Youtao; Tie, Mei

    2013-06-01

    This work investigated the effect of soil aquifer treatment (SAT) operation on the fluorescence characteristics of dissolved organic matter (DOM) fractions in soils through laboratory-scale soil columns with a 2-year operation. The resin adsorption technique (with XAD-8 and XAD-4 resins) was employed to characterize the dissolved organic matter in soils into five fractions, i.e., hydrophobic acid (HPO-A), hydrophobic neutral (HPO-N), transphilic acid (TPI-A), transphilic neutral (TPI-N), and hydrophilic fraction (HPI). The synchronous fluorescence spectra revealed the presence of soluble microbial byproduct- and humic acid-like components and polycyclic aromatic compounds in DOM in soils, and SAT operation resulted in the enrichment of these fluorescent materials in all DOM fractions in the surface soil (0-12.5 cm). More importantly, the quantitative method of fluorescence regional integration was used in the analysis of excitation-emission matrix (EEM) spectra of DOM fractions in soils. The cumulative EEM volume (? T, n ) results showed that SAT operation led to the enrichment of more fluorescent components in HPO-A and TPI-A, as well as the dominance of less fluorescent components in HPO-N, TPI-N, and HPI in the bottom soil (75-150 cm). Total ? T, n values, which were calculated as [Formula: see text], suggested an accumulation of fluorescent organic matter in the upper 75 cm of soil as a consequence of SAT operation. The distribution of volumetric fluorescence among five regions (i.e., P i, n ) results revealed that SAT caused the increased content of humic-like fluorophores as well as the decreased content of protein-like fluorophores in both HPO-A and TPI-A in soils. PMID:23054268

  16. Spectroscopic characterization and structural modeling of prolamin from maize and pearl millet.

    PubMed

    Bugs, Milton Roque; Forato, Lucimara Aparecida; Bortoleto-Bugs, Raquel Kely; Fischer, Hannes; Mascarenhas, Yvonne Primerano; Ward, Richard John; Colnago, Luiz Alberto

    2004-07-01

    Biophysical methods and structural modeling techniques have been used to characterize the prolamins from maize ( Zea mays) and pearl millet ( Pennisetum americanum). The alcohol-soluble prolamin from maize, called zein, was extracted using a simple protocol and purified by gel filtration in a 70% ethanol solution. Two protein fractions were purified from seed extracts of pearl millet with molecular weights of 25.5 and 7 kDa, as estimated by SDS-PAGE. The high molecular weight protein corresponds to pennisetin, which has a high alpha-helical content both in solution and the solid state, as demonstrated by circular dichroism and Fourier transform infrared spectra. Fluorescence spectroscopy of both fractions indicated changes in the tryptophan microenvironments with increasing water content of the buffer. Low-resolution envelopes of both fractions were retrieved by ab initio procedures from small-angle X-ray scattering data, which yielded maximum molecular dimensions of about 14 nm and 1 nm for pennisetin and the low molecular weight protein, respectively, and similar values were observed by dynamic light scattering experiments. Furthermore, (1)H nuclear magnetic resonance spectra of zein and pennisetin do not show any signal below 0.9 ppm, which is compatible with more extended solution structures. The molecular models for zein and pennisetin in solution suggest that both proteins have an elongated molecular structure which is approximately a prolate ellipsoid composed of ribbons of folded alpha-helical segments with a length of about 14 nm, resulting in a structure that permits efficient packing within the seed endosperm. PMID:14508615

  17. Synthesis, structure, and spectroscopic characterization of three uranyl phosphates with unique structural units

    NASA Astrophysics Data System (ADS)

    Wylie, Ernest M.; Dawes, Colleen M.; Burns, Peter C.

    2012-12-01

    Single crystals of Zn4(OH)2[(UO2)(PO4)2(OH)2(H2O)] (UZnP), Cs[(UO2)(HPO4)NO3] (UCsP), and In3[(UO2)2(PO4)4OH(H2O)6].2H2O (UInP) were obtained from hydrothermal reactions and have been structurally and chemically characterized. UZnP crystallizes in space group Pbcn, a=8.8817(7), b=6.6109(5), c=19.569(1) Å; UCsP crystallizes in P-1, a=7.015(2), b=7.441(1), c=9.393(2) Å, ?=72.974(2), ?=74.261(2), ?=79.498(2); and UInP crystallizes in P-1, a=7.9856(5), b=9.159(1), c=9.2398(6) Å ?=101.289(1), ?=114.642(1), ?=99.203(2). The U6+ cations are present as (UO2)2+ uranyl ions coordinated by five O atoms to give pentagonal bipyramids. The structural unit in UZnP is a finite cluster containing a uranyl pentagonal bipyramid that shares corners with two phosphate tetrahedra. The structural unit in UCsP is composed of uranyl pentagonal bipyramids with one chelating nitrate group that are linked into chains by three bridging hydrogen phosphate tetrahedra. In UInP, the structural unit contains pairs of edge-sharing uranyl pentagonal bipyramids with two chelating phosphate tetrahedra that are linked into chains through two bridging phosphate tetrahedra. Indium octahedra link these uranyl phosphate chains into a 3-dimensional framework. All three compounds exhibit unique structural units that deviate from the typical layered structures observed in uranyl phosphate solid-state chemistry.

  18. A New, Longitudinally Resolved, Spectroscopic Characterization of Quaoar’s Surface

    NASA Astrophysics Data System (ADS)

    Dalle Ore, Cristina M.; Barucci, Maria A.; Perna, Davide; Doressoundiram, Alain; Alvarez-Candal, Alvaro; Nitschelm, Christian; Cruikshank, Dale P.

    2014-11-01

    (50000) Quaoar, one of the largest Trans-neptunian objects, is comparable in size to Pluto’s moon Charon. However, while Charon’s surface is rich almost exclusively in H2O ice, Quaoar‘s surface is characterized by ices of CH4, N2, as well as C2H6, a product of irradiation of CH4 (Dalle Ore et al. 2009). Because of its distance from the Sun, Quaoar is expected to have preserved, to a degree, its original composition, however, its relatively small size did not make it a prime candidate for presence of volatile ices in the study by Schaller and Brown (2007). Furthermore, based on the Brown et al. (2011) study its red coloration points to CH3OH as the ice which, when irradiated, might have produced the red material. We present new visible to near-infrared (0.3-2.48?m) spectro-photometric data obtained with the XSHOOTER (Vernet et al. 2011) instrument at the VLT-ESO facility at four different longitudes on the surface of Quaoar. The data are complemented by previously published photometric observations obtained in the near-infrared (3.6, 4.5?m) with the Spitzer Space Telescope, which provide an extra set of constraints in the model calculation process in spite of the different observing times that preclude establishing the spatial consistency between the two sets.For each of the four spectra we perform spectral modeling of the entire wavelength range -from 0.3 to 4.5?m- by means of a code based on the Shkuratov radiative transfer formulation of the slab model. We obtain spatially resolved compositional information for the surface of Quaoar supporting the presence of CH4 and C2H6, as previously reported, along with evidence for N2 and NH3OH. The albedo at the two Spitzer bands indicates the likely presence of CO and CO2. CH3OH, predicted on the basis of Quaoar’s coloration (Brown et al. 2011), is not found at any of the four longitudes, implying that the presence of this ice is a sufficient, but not necessary condition for reddening of TNO surfaces. Other ices, in particular CH4 (Brunetto et al. 2006), have been shown to be plausible precursors for reddening of TNO surfaces.

  19. De novo design and spectroscopic characterization of Cu(II)-binding peptides based upon the blue copper protein plastocyanin

    E-print Network

    Daugherty, Roxanne Gail

    2002-01-01

    Blue copper proteins have long held the interest of inorganic chemists, partially because of the interesting spectroscopic properties of the proteins and partially because of the difficulty in synthesizing an inorganic model complex that mimics...

  20. Fourier transform infrared and Raman spectroscopic characterization of homogeneous solution concentration gradients near a container wall at different temperatures

    NASA Technical Reports Server (NTRS)

    Loo, B. H.; Burns, D. H.; Lee, Y. G. L.; Emerson, M. T.

    1991-01-01

    Fourier transform infrared (FTIR) and Raman spectroscopic techniques were used to study the solution concentration gradient in succino nitrile-rich and water-rich homogeneous solutions. The spectroscopic data shows significant concentration dependency. Although FTIR-attenuated total reflectance could not yield surface spectra since the evanescent infrared wave penetrated deep into the bulk solution, it showed that water-rich clusters were decreased at higher temperatures. This result is consistent with the calorimetric results reported earlier.

  1. Characterization of Functionalized Self-Assembled Monolayers and Surface-Attached Interlocking Molecules Using Near-Edge X-ray Absorption Fine Structure Spectroscopy

    SciTech Connect

    Willey, T; Willey, T

    2004-03-24

    Quantitative knowledge of the fundamental structure and substrate binding, as well as the direct measurement of conformational changes, are essential to the development of self-assembled monolayers (SAMs) and surface-attached interlocking molecules, catenanes and rotaxanes. These monolayers are vital to development of nano-mechanical, molecular electronic, and biological/chemical sensor applications. This dissertation investigates properties of functionalized SAMs in sulfur-gold based adsorbed molecular monolayers using quantitative spectroscopic techniques including near-edge x-ray absorption fine structure spectroscopy (NEXAFS) and x-ray photoelectron spectroscopy (XPS). The stability of the gold-thiolate interface is addressed. A simple model SAM consisting of dodecanethiol adsorbed on Au(111) degrades significantly in less than 24 hours under ambient laboratory air. S 2p and O 1s XPS show the gold-bound thiolates oxidize to sulfinates and sulfonates. A reduction of organic material on the surface and a decrease in order are observed as the layer degrades. The effect of the carboxyl vs. carboxylate functionalization on SAM structure is investigated. Carboxyl-terminated layers consisting of long alkyl-chain thiols vs. thioctic acid with short, sterically separated, alkyl groups are compared and contrasted. NEXAFS shows a conformational change, or chemical switchability, with carboxyl groups tilted over and carboxylate endgroups more upright. Surface-attached loops and simple surface-attached rotaxanes are quantitatively characterized, and preparation conditions that lead to desired films are outlined. A dithiol is often insufficient to form a molecular species bound at each end to the substrate, while a structurally related disulfide-containing polymer yields surface-attached loops. Similarly, spectroscopic techniques show the successful production of a simple, surface-attached rotaxane that requires a ''molecular riveting'' step to hold the mechanically attached crown ether rings in place until disulfides in the molecules adsorb onto the gold. Finally, by introducing an aldehyde into the crown ether portion of this well-characterized surface-attached rotaxane, conformational changes are directly measured when the aldehyde is reacted with aniline. These fundamental results have implications for the creation of nanoscale functional surfaces using molecular monolayers.

  2. Observation of a cw Dark-Field Signal in an Absorption Spectroscopic Experiment Using a Phase Locked Free-Electron Laser

    NASA Astrophysics Data System (ADS)

    Szarmes, Eric B.; Madey, John M. J.; Straub, Karl D.

    2000-03-01

    We introduce a technique for ultrasensitive absorption spectroscopy using the GHz-rate pulse train from a phase-locked free-electron laser (FEL), in which the fractional power absorbed from one or more laser lines reappears as a signal on the dark background between the pulses emerging from the sample. Preliminary absorption experiments in 15 Torr cm of methane at 3.25 ?m, using phase-locked pulses from the Mark III FEL, clearly reveal an interpulse beat signal due to absorption by adjacent molecular rotational lines which is generated only in the presence of interpulse phase coherence.

  3. Observation of a cw dark-field signal in an absorption spectroscopic experiment using a phase locked free-electron laser

    PubMed

    Szarmes; Madey; Straub

    2000-03-27

    We introduce a technique for ultrasensitive absorption spectroscopy using the GHz-rate pulse train from a phase-locked free-electron laser (FEL), in which the fractional power absorbed from one or more laser lines reappears as a signal on the dark background between the pulses emerging from the sample. Preliminary absorption experiments in 15 Torr cm of methane at 3.25 &mgr;m, using phase-locked pulses from the Mark III FEL, clearly reveal an interpulse beat signal due to absorption by adjacent molecular rotational lines which is generated only in the presence of interpulse phase coherence. PMID:11018958

  4. Isolation, characterization, spectroscopic properties and quantum chemical computations of an important phytoalexin resveratrol as antioxidant component from Vitis labrusca L. and their chemical compositions

    NASA Astrophysics Data System (ADS)

    Güder, Aytaç; Korkmaz, Halil; Gökce, Halil; Alpaslan, Yelda Bingöl; Alpaslan, Gökhan

    2014-12-01

    In this study, isolation and characterization of trans-resveratrol (RES) as an antioxidant compound were carried out from VLE, VLG and VLS. Furthermore, antioxidant activities were evaluated by using six different methods. Finally, total phenolic, flavonoid, ascorbic acid, anthocyanin, lycopene, ?-carotene and vitamin E contents were carried out. In addition, the FT-IR, 13C and 1H NMR chemical shifts and UV-vis. spectra of trans-resveratrol were experimentally recorded. Quantum chemical computations such as the molecular geometry, vibrational frequencies, UV-vis. spectroscopic parameters, HOMOs-LUMOs energies, molecular electrostatic potential (MEP), natural bond orbitals (NBO) and nonlinear optics (NLO) properties of title molecule have been calculated by using DFT/B3PW91 method with 6-311++G(d,p) basis set in ground state for the first time. The obtained results show that the calculated spectroscopic data are in a good agreement with experimental data.

  5. Observation of a cw Dark-Field Signal in an Absorption Spectroscopic Experiment Using a Phase Locked Free-Electron Laser

    Microsoft Academic Search

    Eric B. Szarmes; John M. J. Madey; Karl D. Straub

    2000-01-01

    We introduce a technique for ultrasensitive absorption spectroscopy using the GHz-rate pulse train from a phase-locked free-electron laser (FEL), in which the fractional power absorbed from one or more laser lines reappears as a signal on the dark background between the pulses emerging from the sample. Preliminary absorption experiments in 15 Torr cm of methane at 3.25 mum, using phase-locked

  6. Characterization of ovalbumin absorption pathways in the rat intestine, including the effects of aspirin.

    PubMed

    Yokooji, Tomoharu; Nouma, Hitomi; Matsuo, Hiroaki

    2014-01-01

    Ingested proteins are absorbed from the intestinal lumen via the paracellular and/or transcellular pathways, depending on their physicochemical properties. In this study, we investigated the absorption pathway(s) of ovalbumin (OVA), an egg white-allergen, as well as the mechanisms of aspirin-facilitated OVA absorption in rats. In situ intestinal re-circulating perfusion experiments showed that the absorption rate of fluorescein isothiocyanate (FITC)-labeled OVA in the distal intestine was higher than that for a marker of non-specific absorption, FITC-dextran (FD-40), and that colchicine, a general endocytosis inhibitor, suppressed OVA absorption. In the distal intestine, bafiromycin A1 and phenylarsine oxide inhibited the OVA absorption rate, whereas mehyl-?-cyclodextrin exerted no significant effects. Thus, OVA is preferentially absorbed from the distal intestine via the paracellular and receptor- and clathrin-mediated endocytic pathways. Furthermore, aspirin increased OVA absorption in the presence or absence of colchicine, indicating that aspirin facilitated OVA absorption by inducing intestinal barrier disruption and paracellular permeability. PMID:25087958

  7. Chemical characterization of tribochemical and thermal films generated from neutral and basic ZDDPs using X-ray absorption spectroscopy

    Microsoft Academic Search

    Marina Fuller; Zhanfeng Yin; Masoud Kasrai; G. Michael Bancroft; Elaine S. Yamaguchi; P. Ray Ryason; Pierre A. Willermet; Kim H. Tan

    1997-01-01

    X-ray absorption near edge structure (XANES) spectroscopy at the phosphorus L-edge and sulphur L-edge has been used to characterize the chemical nature of tribochemical and thermally generated films from several ZDDP antiwear agents in the neutral and basic forms. Using the P and S L-edge XANES spectra of model compounds with known structure as fingerprints, the chemical structures of P

  8. Absorption spectroscopy using quantum cascade laser

    Microsoft Academic Search

    Simin Cai

    1999-01-01

    Characteristic molecular and atomic absorption spectra in the middle infrared region are extensively used for chemical analysis and spectroscopic detection of gases. The absorption of electromagnetic radiation in this so- called ``fingerprint'' spectral region is due to the vibration-rotational bands of molecular structures. Various techniques have been developed for high resolution and high sensitivity absorption spectroscopic detection. In this dissertation,

  9. New opportunities in trace elements structural characterization: high-energy X-ray absorption near-edge structure spectroscopy.

    PubMed

    Chaboy, J; Cotallo, E; Quartieri, S; Boscherini, F

    2002-03-01

    Garnets in lower crustal mafic and ultramafic rocks usually contain rare-earth elements (REE) in trace concentrations. Direct characterization of REE at trace levels in natural garnets is not available in the literature because of the difficulty of obtaining structural information by means of conventional diffraction methods. Here, the characterization of Nd at trace levels (176-1029 p.p.m.) in a set of natural garnets performed by means of Nd K-edge X-ray absorption near-edge structure spectroscopy is presented, showing the capability of high-energy XANES for REE in trace structural determinations. PMID:11872928

  10. Seismic and spectroscopic characterization of the solar-like pulsating CoRoT target HD 49385

    NASA Astrophysics Data System (ADS)

    Deheuvels, S.; Bruntt, H.; Michel, E.; Barban, C.; Verner, G.; Régulo, C.; Mosser, B.; Mathur, S.; Gaulme, P.; Garcia, R. A.; Boumier, P.; Appourchaux, T.; Samadi, R.; Catala, C.; Baudin, F.; Baglin, A.; Auvergne, M.; Roxburgh, I. W.; Pérez Hernández, F.

    2010-06-01

    Context. The star HD 49385 is the first G-type solar-like pulsator observed in the seismology field of the space telescope CoRoT. The satellite collected 137 days of high-precision photometric data on this star, confirming that it presents solar-like oscillations. HD 49385 was also observed in spectroscopy with the NARVAL spectrograph in January 2009. Aims: Our goal is to characterize HD 49385 using both spectroscopic and seismic data. Methods: The fundamental stellar parameters of HD 49385 are derived with the semi-automatic software VWA, and the projected rotational velocity is estimated by fitting synthetic profiles to isolated lines in the observed spectrum. A maximum likelihood estimation is used to determine the parameters of the observed p modes. We perform a global fit, in which modes are fitted simultaneously over nine radial orders, with degrees ranging from ? = 0 to ? = 3 (36 individual modes). Results: Precise estimates of the atmospheric parameters (Teff, [M/H], log g) and of the ? sin i of HD 49385 are obtained. The seismic analysis of the star leads to a clear identification of the modes for degrees ? = 0,1,2. Around the maximum of the signal (? ? 1013 ?Hz), some peaks are found significant and compatible with the expected characteristics of ? = 3 modes. Our fit yields robust estimates of the frequencies, linewidths and amplitudes of the modes. We find amplitudes of ~5.6 ± 0.8 ppm for radial modes at the maximum of the signal. The lifetimes of the modes range from one day (at high frequency) to a bit more than two days (at low frequency). Significant peaks are found outside the identified ridges and are fitted. They are attributed to mixed modes. Based on data obtained from the CoRoT (Convection, Rotation and planetary Transits) space mission, developed by the French Space agency CNES in collaboration with the Science Programs of ESA, Austria, Belgium, Brazil, Germany and Spain.Based on data obtained using the Télescope Bernard Lyot at Observatoire du Pic du Midi, CNRS and Université Paul Sabatier, France.

  11. Spectroscopic characterization of the coordination chemistry and hydrolysis of gallium(III) in the presence of aquatic organic matter

    NASA Astrophysics Data System (ADS)

    Hagvall, Kristoffer; Persson, Per; Karlsson, Torbjörn

    2014-12-01

    Interactions between metals and natural organic matter (NOM) are of great environmental importance and one of the key factors influencing hydrolysis, solubility, and speciation of the metals. However, studying geochemically relevant metals like Al, Fe, and Cu is sometimes associated with analytical problems; for example Fe and Cu are both redox active. Gallium (Ga) is a non-redox active metal that usually occurs at very low concentrations in environmental samples and therefore a wide concentration range of metal(III)-NOM species can be explored by adding Ga(III) to such samples. This makes Ga(III) a good probe and analogue for other metal ions, in particular Al. In addition, due to the increased usage of Ga in society, a better understanding of how Ga interacts with NOM is of importance but such studies are scarce. In this work, Ga(III) interactions with two different organic materials (Suwannee River natural organic matter and Suwannee River fulvic acid) were studied using infrared (IR) and extended X-ray absorption fine structure (EXAFS) spectroscopy in a large experimental range (101-84,076 ?g Ga g-1 dry weight; pH 3-8). Our IR spectroscopic results showed that Ga(III) is bonded mainly to carboxylic functional groups and suggested that only a fraction of the total number of carboxylic sites in the samples was actively involved in the bonding. Modeling of the EXAFS data revealed that Ga(III) formed mononuclear chelate complexes with NOM that strongly suppressed the hydrolysis and polymerization of Ga(III). At low Ga(III) concentrations (1675-16,649 ?g g-1) organic complexes, consisting of 1-3 chelate ring structures, were the dominating species in the entire pH range while at higher concentrations (67,673-84,076 ?g g-1, pH 3.0-7.0) we detected mixtures of mononuclear organic Ga(III) complexes, Ga(III) (hydr)oxide, and free Ga(III) (here defined as the hydrated Ga(III) ion and its soluble hydrolysis products). Moreover, the EXAFS results showed significantly higher contribution from second-shell C atoms (9-11) for the Ga(III)-organic complexes at the lowest concentration (101-125 ?g g-1, pH 4.9-5.1), indicating formation of cage-like structures similar to Ga(III)-EDTA. Our combined results showed that Ga(III)-NOM interactions can be of importance for the solubility and speciation of Ga in environmental systems. Furthermore, the similarities between Ga(III) and previous Fe(III) results demonstrate that Ga(III) can be utilized as a probe for metal(III)-NOM interactions over an extended experimental range (e.g., pH and metal concentration) and thereby improve our knowledge about these interactions in general.

  12. Non-ionic surfactants as novel intranasal absorption enhancers: in vitro and in vivo characterization.

    PubMed

    Li, Ying; Li, Jinfeng; Zhang, Xin; Ding, Jiaojiao; Mao, Shirui

    2014-10-27

    Abstract Objective: To explore the potential of non-ionic surfactants as novel intranasal absorption enhancers. Methods: Taking sumatriptan succinate (SMS) as a model drug, influence of different non-ionic surfactants, including laurate sucrose ester (SE), cremophor EL and poloxamer 188, on the intranasal absorption of SMS was investigated using an in situ nasal perfusion technique in rats. Ciliotoxicity of the non-ionic surfactants was evaluated using an in situ toad palate model. In vivo behavior of the selected formulations was studied in rats. Results: All the non-ionic surfactants investigated increased the intranasal absorption of SMS remarkably but with varied extent and trend. Moreover, it was revealed that at the same concentration, laurate SE had better permeation-enhancing effect than that of cremophor EL and poloxamer 188. The ciliotoxicity results showed that all the non-ionic surfactants were regarded as safe at selected concentrations. Based on the in situ absorption data and ciliotoxicity results, the following three samples, 0.5% laurate SE, 0.1% cremophor EL and 0.5% poloxamer 188 were selected for in vivo absorption studies in rats. Among them, 0.5% laurate SE group presented the highest enhancing effect, followed by 0.1% cremophor EL and 0.5% poloxamer 188 group, with absolute bioavailability 29.99%, 22.64% and 20.90%, respectively. Conclusions: Laurate SE is a promising intranasal absorption enhancer. PMID:25347689

  13. Nd3+-doped Lu2O3 transparent sesquioxide ceramics elaborated by the Spark Plasma Sintering (SPS) method. Part 1: Structural, thermal conductivity and spectroscopic characterization

    NASA Astrophysics Data System (ADS)

    Alombert-Goget, G.; Guyot, Y.; Guzik, M.; Boulon, G.; Ito, A.; Goto, T.; Yoshikawa, A.; Kikuchi, M.

    2015-03-01

    We report the detailed analysis of both structural characterization by SEM, thermal conductivity of high value and high resolution spectroscopic properties of Nd3+-doped Lu2O3 transparent ceramics fabricated by the non-conventional SPS method. The emission spectra of the main C2 site shows two close 4F3/2 ? 4I11/2 laser lines at 1076.3 and 1080.5 nm, respectively. The optical properties of the two C2 and C3i sites and of C2-C3i and C2-C2 Nd3+ pairs have especially been analyzed.

  14. Two complexes of Co(II) and Pd(II) formed in reaction with a mono-oxazoline derivative. Spectroscopic characterization and cytotoxic evaluation

    NASA Astrophysics Data System (ADS)

    Alexandru, Maria-Gabriela; Cirkovic Velickovic, Tanja; Krstic, Maja; Hrubaru, Madalina-Marina; Draghici, Constantin

    2013-06-01

    Two coordination compounds obtained from 2-(4-ethoxyphenyl)-4,5-dihydro-1H-oxazole, L, [CoCl2(L)2] (1) and [OHsbnd CH2sbnd CH2sbnd NH3]2·[PdCl4] (2) were synthesized and characterized through elemental analysis, spectroscopic methods (FTIR, UV-Vis, 1H NMR) and X-ray diffraction. Cytotoxicity tests on PBMC and HeLa cells were performed in order to evaluate the potential applications of these compounds in medicine. Also, compound (2) exhibits ligand assisted luminescent properties that were determined in solid state.

  15. Cinoxacin complexes with divalent metal ions. Spectroscopic characterization. Crystal structure of a new dinuclear Cd(II) complex having two chelate-bridging carboxylate groups. Antibacterial studies

    Microsoft Academic Search

    M Ru??z; L Perelló; J Server-Carrió; R Ortiz; S Garc??a-Granda; M. R D??az; E Cantón

    1998-01-01

    Several cinoxacin (HCx) complexes with divalent metal ions have been prepared and characterized by spectroscopic techniques. The crystal structure of [Cd2(Cx)4(H2O)2]·10H2O has been determined by X-ray diffraction. The complex is triclinic, space group P1? with unit-cell dimensions: a=10.412(2), b=11.119(2), c=13.143(6)Å, ?=76.78(4)°, ?=74.59(3)°, ?=77.12(3)°, V=1406.0(8) Å3. In this complex each cadmium atom is heptacoordinated; the metal environment is formed by two

  16. CD-ROM Spectroscope: A Simple and Inexpensive Tool for Classroom Demonstrations on Chemical Spectroscopy

    Microsoft Academic Search

    Fumitaka Wakabayashi; Kiyohito Hamada; Kozo Sone

    1998-01-01

    Construction of a handy spectroscope using a compact disk (CD) or a CD-ROM and its application to the observation of emission and absorption spectra are described. Using this simple cardboard-made spectroscope, one can readily observe line emission spectra of fluorescent lamps, gas discharge tubes, etc. The spectroscope is also used to observe the absorption spectra of colored solutions; the absorption

  17. Optical characterization of metalorganic vapor-phase epitaxy-grown GaAs 1- xN x alloys using spectroscopic ellipsometry

    NASA Astrophysics Data System (ADS)

    Matsumoto, S.; Yaguchi, H.; Kashiwase, S.; Hashimoto, T.; Yoshida, S.; Aoki, D.; Onabe, K.

    2000-12-01

    We have measured complex dielectric functions, ?1+ i?2, of GaAs 1- xN x alloys using spectroscopic ellipsometry to investigate higher-energy band gaps. The E1 gap-related peak height for ?2 decreases with increasing N concentration, indicating that the optical absorption at the E1 gap decreases. On the contrary, the E2 gap transition does not change so much with varying N concentration. These results are consistent with the theoretical study, which predicts that the lowest conduction band is mostly a combination of the ? and L states. The bowing parameters of the E1 and E2 gaps are rather large but much smaller than the bowing parameter of the E0 gap.

  18. Spectroscopic characterization of II-VI compounds and application to copper indium selenide-based solar cells

    NASA Astrophysics Data System (ADS)

    Aguilar Juarez, Heriberto De Jesus

    Structures consisting of CuInSe2 films, deposited on molybdenum-coated glass substrates and covered by CdS or ZnO thin films, for application in solar cells, have been characterized by spectroscopic ellipsometry, atomic force microscopy, photoluminescence and photovoltaic response. Computer aided simulations of the photovoltaic operation of these structures have been made to reinforce and complement the results of the characterization studies. The optical properties of CuInSe2, CdS and ZnO films over ranges of photon energies from 1.0 through 4.0 eV were determined. The measured optical bandgaps, 0.96 eV for CuInSe2, 2.35 eV for CdS and 3.33 eV for ZnO, are in good agreement with the values reported in the literature for bulk samples of those materials. In the case of CuInSe2, a second transition photon energy was detected at 1.02 eV. This transition was assumed to be due to gallium content in the CuInSe 2 film near the Mo interface. Depth structure profiles of the films were generated. The one for as-deposited CuInSe2 was found to include a surface layer (ODC layer) about 230 nm thick which exhibited optical properties considerably different from those of the bulk of the film. In the case of US (as might be expected for films grown by the chemical bath deposition technique) it was found that the films consist of two layers: a very compact one, about 29 nm thick, at the bottom of the film; and a much thicker and porous one, about 127 nm thick, on top. CdS/CuInSe2 and ZnO/CuInSe2 test cells were fabricated from substrates with as-deposited CuInSe2 and CuInSe2 from which a layer had been removed by etching. Test cells with CdS buffer layers on etched CuInSe2 exhibited degraded performance compared to cells fabricated on as-deposited CuInSe2. These results suggest that some interaction between US and the absorber material occurs in the case of etched absorbers. Thus, CdS may play a greater role than simply providing protection for the absorber layer during deposition of the TCO (top contact) layer. Photoluminescence measurements from plain CuInSe2 films, compared with similar measurements taken for CdS- or ZnO-coated films, showed an increase in the photoluminescence emission in the later cases, indicative of a reduction of nonradiative recombination caused by a passivating effect of the buffer layers on the interface. Numerical simulations of the operation of CuInSe2-based solar cells disclosed a mechanism by which the resistivity of the buffer layer may enhance the performance of the cells, and one that would promote inflected current-voltage characteristics. A comparison between the simulated performance of devices with experimentally determined results revealed the effects of a process-related connection between the resistivity of buffer layers and the electronic properties of the absorber, which have an impact on the conversion efficiencies of solar cells.

  19. The crystalline nanocluster phase as a medium for structural and spectroscopic studies of light absorption of photosensitizer dyes on semiconductor surfaces.

    PubMed

    Benedict, Jason B; Coppens, Philip

    2010-03-10

    The crystalline nanocluster phase, in which nanoscale metal oxide clusters are self-assembled in three-dimensional periodic arrays, is described. The crystalline assembly of nanoparticles functionalized with technologically relevant ligands offers the opportunity to obtain unambiguous structural information that can be combined with theoretical calculations based on the known geometry and used to interpret spectroscopic and other information. A series of Ti/O clusters up to approximately 2.0 nm in diameter have been synthesized and functionalized with the adsorbents catechol and isonicotinic acid. Whereas the isonicotinate is always adsorbed in a bridging monodentate mode, four different adsorption modes of catechol have been identified. The particles show a significantly larger variation of the Ti-O distances than observed in the known TiO(2) phases and exhibit both sevenfold overcoordination and five- and fourfold undercoordination of the Ti atoms. Theoretical calculations show only a moderate dependence of the catecholate net charge on the geometry of adsorption. All of the catechol-functionalized clusters have a deep-red color due to penetration of the highest occupied catechol levels into the band gap of the Ti/O particles. Spectroscopic measurements of the band gap of the Ti(17) cluster are in good agreement with the theoretical values and show a blue shift of approximately 0.22 eV relative to those reported for anatase nanoparticles. PMID:20146516

  20. Spectroscopic ellipsometry characterization of SiN x antireflection films on textured multicrystalline and monocrystalline silicon solar cells

    Microsoft Academic Search

    M. F. Saenger; J. Sun; M. Schädel; J. Hilfiker; M. Schubert; J. A. Woollam

    2010-01-01

    We present a spectroscopic ellipsometry study of silicon nitride based antireflection films deposited on chemically textured multi- and monocrystalline silicon wafers. The ellipsometric parameters were measured from the near infrared to the ultra violet spectral region. We report the effective thickness and complex index of refraction parameters of the antireflection films from all studied surfaces, regardless of their microscopic morphology.

  1. Biochemical, Kinetic, and Spectroscopic Characterization of Ruegeria pomeroyi DddW—A Mononuclear Iron-Dependent DMSP Lyase

    PubMed Central

    Brummett, Adam E.; Schnicker, Nicholas J.; Crider, Alexander; Todd, Jonathan D.; Dey, Mishtu

    2015-01-01

    The osmolyte dimethylsulfoniopropionate (DMSP) is a key nutrient in marine environments and its catabolism by bacteria through enzymes known as DMSP lyases generates dimethylsulfide (DMS), a gas of importance in climate regulation, the sulfur cycle, and signaling to higher organisms. Despite the environmental significance of DMSP lyases, little is known about how they function at the mechanistic level. In this study we biochemically characterize DddW, a DMSP lyase from the model roseobacter Ruegeria pomeroyi DSS-3. DddW is a 16.9 kDa enzyme that contains a C-terminal cupin domain and liberates acrylate, a proton, and DMS from the DMSP substrate. Our studies show that as-purified DddW is a metalloenzyme, like the DddQ and DddP DMSP lyases, but contains an iron cofactor. The metal cofactor is essential for DddW DMSP lyase activity since addition of the metal chelator EDTA abolishes its enzymatic activity, as do substitution mutations of key metal-binding residues in the cupin motif (His81, His83, Glu87, and His121). Measurements of metal binding affinity and catalytic activity indicate that Fe(II) is most likely the preferred catalytic metal ion with a nanomolar binding affinity. Stoichiometry studies suggest DddW requires one Fe(II) per monomer. Electronic absorption and electron paramagnetic resonance (EPR) studies show an interaction between NO and Fe(II)-DddW, with NO binding to the EPR silent Fe(II) site giving rise to an EPR active species (g = 4.29, 3.95, 2.00). The change in the rhombicity of the EPR signal is observed in the presence of DMSP, indicating that substrate binds to the iron site without displacing bound NO. This work provides insight into the mechanism of DMSP cleavage catalyzed by DddW. PMID:25993446

  2. Spectroscopic Characterization of AN Alkyl-Substituted Criegee Intermediate CH_{3}CHOO and its OH Radical Products

    NASA Astrophysics Data System (ADS)

    Beames, Joseph M.; Liu, Fang; Lu, Lu; Lester, Marsha I.

    2013-06-01

    In the atmosphere, cycloaddition of ozone to the double bond of alkenes produces energized Criegee intermediates, which undergo subsequent decay processes to yield OH radicals. In this laboratory, a simple alkyl-substituted Criegee intermediate CH_{3}CHOO is produced by 248 nm photolysis of CH_{3}CHI_{2} and subsequent reaction of CH_{3}CHI with O_{2} in a quartz capillary tube reactor, following the same approach utilized for CH_{2}OO. The CH_{3}CHOO intermediate (m/z=60) and other products are detected following supersonic expansion using 118 nm VUV ionization in a time-of-flight mass spectrometer. The OH radical products from decomposition of the CH_{3}CHOO intermediate are also directly detected at m/z=17 using a new UV+VUV ionization scheme, combining UV excitation on the OH A ^2?^+-X ^2? (1,0) transition with fixed-frequency VUV at 118 nm, or alternatively by UV laser-induced fluorescence on the OH A-X transition; OH products are also observed from CH_{2}OO. The CH_{3}CHOO intermediate is characterized by a strong B ^1A'-X ^1A' electronic transition, in which UV excitation near the peak of a broad absorption profile centered at 320 nm results in significant depletion of the CH_{3}CHOO photoionization signal. The mechanism proposed for OH generation from energized CH_{3}CHOO and many larger Criegee intermediates is a 1,4 H-atom shift to form vinylhydroperoxide species that decay to produce OH. This reaction scheme provides a non-photolytic source of OH radicals in the atmosphere during night and winter times. J. M. Beames, F. Liu, L. Lu, and M. I. Lester, J. Am. Chem. Soc. {134}, 20045 (2012). J. M. Beames, F. Liu, M. I. Lester and C. Murray, J. Chem. Phys. {134}, 241102 (2011).

  3. Identification and Characterization of Visible Absorption Components in Aqueous Methylglyoxal-Ammonium Sulfate Mixtures

    NASA Astrophysics Data System (ADS)

    McGivern, W. S.; Allison, T. C.; Radney, J. G.; Zangmeister, C. D.

    2014-12-01

    The aqueous reaction of methylglyoxal (MG) with ammonium sulfate has been suggested as a source of atmospheric ``brown carbon.'' We have utilized high-performance liquid chromatography coupled to ultraviolet-visible spectroscopy and tandem mass spectrometry to study the products of this reaction at high concentrations. The overall product spectrum shows a large number of distinct components; however, the visible absorption from this mixture is derived a very small number of components. The largest contributor is an imine-substituted (C=N-H) product of aldol condensation/facile dehydration reaction between the parent MG and a hydrated product of the MG + ammonia reaction. The asymmetric nature of this compound relative to the aldol condensation of two MG results in a sufficiently large redshift of the UV absorption spectrum that absorption of visible radiation can occur in the long-wavelength tail. The simplicity of the imine products is a result of a strong bias toward ketimine products due to the extensive hydration of the aldehydic moiety in the parent in aqueous solution. In addition, a strong pH dependence of the absorption cross section was observed with significantly greater absorption under more basic conditions. We have performed time-dependent density functional theory calculations to evaluate the absorption spectra of all of the possible condensation products and their respective ions, and the results are consistent with the experimental observations. We have also observed smaller concentrations of other condensation products of the imine-substituted parent species that do not contribute significantly to the visible absorption but have not been previously discussed.

  4. Local structure and speciation of platinum in fresh and road-aged North American sourced vehicle emissions catalysts: an X-ray absorption spectroscopic study.

    PubMed

    Ash, Peter W; Boyd, David A; Hyde, Timothy I; Keating, Jonathan L; Randlshofer, Gabriele; Rothenbacher, Klaus; Sankar, Gopinathan; Schauer, James J; Shafer, Martin M; Toner, Brandy M

    2014-04-01

    Given emerging concerns about the bioavailability and toxicity of anthropogenic platinum compounds emitted into the environment from sources including vehicle emission catalysts (VEC), the platinum species present in selected North American sourced fresh and road-aged VEC were determined by Pt and Cl X-ray absorption spectroscopy. Detailed analysis of the Extended X-ray Absorption Fine Structure at the Pt L3 and L2 edges of the solid phase catalysts revealed mainly oxidic species in the fresh catalysts and metallic components dominant in the road-aged catalysts. In addition, some bimetallic components (Pt-Ni, Pt-Pd, Pt-Rh) were observed in the road-aged catalysts from supporting Ni-, Pd-, and Rh-K edge XAS studies. These detailed analyses allow for the significant conclusion that this study did not find any evidence for the presence of chloroplatinate species in the investigated solid phase of a Three Way Catalyst or Diesel Oxidation Catalysts. PMID:24568168

  5. Sulfur KEdge X-Ray Absorption Spectroscopy: A Spectroscopic Tool to Examine the Redox State of S-Containing Metabolites in vivo

    Microsoft Academic Search

    Annette Rompel; Roehl M. Cinco; Mathew J. Latimer; Ann E. McDermott; R. D. Guiles; Alexandre Quintanlha; Ronald M. Krauss; Kenneth Sauer; Vittal K. Yachandra; Melvin P. Klein

    1998-01-01

    The sulfur K-edge x-ray absorption spectra for the amino acids cysteine and methionine and their corresponding oxidized forms cystine and methionine sulfoxide are presented. Distinct differences in the shape of the edge and the inflection point energy for cysteine and cystine are observed. For methionine sulfoxide the inflection point energy is 2.8 eV higher compared with methionine. Glutathione, the most

  6. In situ X-ray absorption near-edge spectroscopic study of the cathodic reduction of artificial iron oxide passive films

    Microsoft Academic Search

    Patrik Schmuki; S. a b Virtanen; A. J. a Davenport; C. M. a Vitus

    1996-01-01

    Galvanostatic reduction of Fe2O3 and Fe3O4 sputter-deposited thin films was investigated as a model for reduction of the passive film on iron. X-ray absorption near-edge spectroscopy was used to perform in situ measurements of the valence state and dissolution (thinning rate) of the films during reduction. In borate buffer, the reduction of Fe2O3 takes place in two stages. The first

  7. Cerium oxide nanoparticles coated by surfactant sodium bis(2-ethylhexyl) sulphosuccinate (AOT): local atomic structures and x-ray absorption spectroscopic studies

    Microsoft Academic Search

    Zhonghua Wu; Lin Guo; Huanjun Li; Robert E. Benfield; Qinglin Yang; Didier Grandjean; Qianshu Li; Hesun Zhu

    2001-01-01

    Cerium oxide nanoparticles coated by sodium bis(2-ethylhexyl) sulphosuccinate (AOT) were prepared by using a microemulsion method. Transmission electron microscopy revealed an average particle size of 2-3 nm. X-ray diffraction showed that the cerium oxide nanoparticles retain the CeF2-type cubic structures like the bulk crystal. The intermediate valence of formally tetravalent compounds had been detected by x-ray-absorption near-edge structure (XANES) spectra

  8. Spectroscopic Study of Solvent Effects on the Electronic Absorption Spectra of Flavone and 7-Hydroxyflavone in Neat and Binary Solvent Mixtures

    PubMed Central

    Sancho, Matias I.; Almandoz, Maria C.; Blanco, Sonia E.; Castro, Eduardo A.

    2011-01-01

    The solvatochromic characteristics of flavone and 7-hydroxyflavone were investigated in neat and binary solvent mixtures. The spectral shifts of these solutes were correlated with the Kamlet and Taft parameters (?, ? and ?*) using linear solvation energy relationships. The multiparametric analysis indicates that both specific hydrogen bond donor ability and non-specific dipolar interactions of the solvents play an important role in absorption maxima of flavone in pure solvents. The hydrogen bond acceptor ability of the solvent was the main parameter affecting the absorption maxima of 7-hydroxyflavone. The simulated absorption spectra using a TD-DFT method were in good agreement with the experimental ones for both flavones. Index of preferential solvation was calculated as a function of solvent composition. Preferential solvation by ethanol was detected in cyclohexane-ethanol and acetonitrile-ethanol mixtures for flavone and in acetonitrile-ethanol mixtures for 7-hydroxyflavone. These results indicate that intermolecular hydrogen bonds between solute and solvent are responsible for the non-linear variation of the solvatochromic shifts on the mole fraction of ethanol in the analyzed binary mixtures. PMID:22272110

  9. Time-dependent X-ray absorption spectroscopic (XAS) study on the transformation of zinc basic salt into bis(N-oxopyridine-2-thionato) zinc (II).

    PubMed

    Paek, Seung-Min; Jo, Won-Young; Park, Man; Choy, Jin-Ho

    2007-11-01

    Solid transchelation reaction was established for the synthesis of bis(N-oxopyridine-2-thionato) zinc (II), commonly known as zinc pyrithione (ZPT), to control particle size using zinc basic salt (ZBS) and aqueous sodium pyrithione solution. Distinguished from ZPT particles prepared by usual precipitation reaction, the obtained ZPT nanoparticles exhibited very narrow size distribution. X-ray absorption spectroscopy (XAS) at Zn K-edge was systematically examined to elucidate time-dependent local structural evolution during solid transchelation reaction. X-ray absorption near edge structure (XANES) analysis clearly revealed that local environment around zinc atoms transformed into pentahedron as reaction proceeded. Based on quantitative X-ray diffraction and XANES analysis, we made structural models. Theoretical XAS spectrum calculated with FEFF code could reproduce experimental one, suggesting that XAS analysis could be very powerful tool to probe phase transformation. Furthermore, according to extended X-ray absorption fine structure (EXAFS) fitting results, Zn-O distance in reaction products gradually increased from 1.96 to 2.07 angstroms, suggesting that zinc atoms bounded with oxygen ones in ZBS were transchelated with pyrithione ligands. This study could be a strong evidence for the usefulness of XAS to study time-dependent structural transformation of nanocrystalline materials. PMID:18047076

  10. Aqueous Cadmium Chalcogenide Quantum Dots: Synthesis, Characterization, Spectroscopic Investigation of Electron Transfer Properties and Photovoltaic Device Performance

    NASA Astrophysics Data System (ADS)

    Coughlin, Kathleen M.

    The research presented in this thesis will focus on (1) synthesis and characterization of aqueous CdSe quantum dots (QDs) as alternatives to organic QDs; (2) the roles that linkers and capping groups play on the physical and optical properties of aqueous QDs; (3) performance of QD-sensitized solar cells (QDSSC) incorporating magic-sized clusters (MSCs) vs regular QDs (RQDs) and as a function of the molecular linkers between QDs and TiO2; and (4) the effect of the polysulfide electrolyte on QD-functionalized TiO 2 films and their performance in QDSSCs. The use of QDs as light harvesters has grown over the last few decades due to their unique properties. Water-dispersible QDs are of increasing interest because their syntheses are straightforward, environmentally-benign and more cost-effective. CdSe and CdS QDs were synthesized at room temperature under ambient conditions, by combining a Cd precursor and either Na2SeSO3 (for CdSe) or Na2S2O3 (for CdS), in basic aqueous reaction mixtures. Three different ligands were utilized as capping groups (cysteinate (Cys), mercaptopropionate (MP), and mercaptosuccinate (MS)). Changing the capping-agent, the reagent concentrations and the temperature changed the photophysical properties of the QDs. When Cys was used as the capping-agent, MSCs were formed. When high concentrations of Cys were used or when the reaction mixture was heated, RQDs were formed. When MP and MS were used in the synthesis of CdSe, RQDs were formed. In the synthesis of CdS, MS caused the formation of RQDs, and MP caused formation of a mixture of RQDs and MSCs. Transient absorption spectroscopy and photoelectrochemical experiments were performed to understand the influence of capping-agent and electronic properties (MSCs vs. RQDs) on the efficiency of electron transfer from photoexcited QDs to TiO2. The Cys-CdSe-functionalized TiO2 exhibited more efficient electron injection and/or slower recombination, leading to improved efficiency of QDSSCs. Devices made with Cys-CdSe RQDs exhibited higher efficiencies than QDSSCs with Cys-CdSe MSCs, indicating that the presence of Cys induces greater efficiency in QDSSCs. For QDSSCs, a polysulfide electrolyte is commonly used instead of I-/I3-. Effects of the polysulfide electrolyte and Na2S on CdSe-functionalized TiO2 films were explored to elucidate the chemistry that occurs when CdSe is exposed to the electrolyte in the QDSSCs. Photophysical changes to the CdSe-functionalized films occurred when exposed to the polysulfide electrolyte. Upon immersion of CdSe-functionalized TiO¬2 films into solutions of Na2S, an initial red shift in the absorption spectrum was observed, followed by a decrease and blue shift of the band. Based on XPS analysis of the films, it was determined that the S within the electrolyte (1) replaced Se or (2) bound to the CdSe-functionalized film without replacing Se. Photoelectrochemical measurements were acquired to analyze device performance with varying [S] within the electrolyte. Upon increase of S, the efficiency of the device increased and gave rise to a better fill factor in the photocurrent-photovoltage data collected.

  11. X-ray fluorescence mapping and micro-XANES spectroscopic characterization of exhaust particulates emitted from auto engines burning MMT-added gasoline.

    PubMed

    Mölders, N; Schilling, P J; Wong, J; Roos, J W; Smith, I L

    2001-08-01

    The elemental distribution and compositional homogeneity in auto exhaust particulates emitted from methylcyclopentadienyl manganese tricarbonyl-(MMT-)added gasoline engines have been investigated using a newly installed synchrotron X-ray microprobe. Two representative groups of exhaust particulate matter, as defined in a recent bulk X-ray absorption fine structure (XAFS) spectroscopic study at the Mn K-edge, were studied. The micro-X-ray absorption near-edge structure (XANES) spectra indicate a relatively homogeneous distribution of phases within a given particulate sample, down to a spatial extent of 40 microm (the resolution of microprobe). The micro-XANES also enabled analysis of several areas which displayed compositions different from the bulk sample, supporting the general theory describing manganese species formation in the exhaust. The ability to evaluate small regions also enabled direct verification of manganese sulfate from the S XANES despite the vast excess of sulfur present in other forms. The presence of a chloride compound, introduced through the sample dilution air and engine intake air, was also revealed. The study demonstrates the value of the combined X-ray microfluorescence with excitation by polychromatic radiation for elemental mapping and micro-XANES spectroscopy for chemical speciation in the study of dilute environmental materials containing low-Z constituents such as Cl, S, and P. PMID:11505987

  12. Characterization of sputtered and annealed niobium oxide films using spectroscopic ellipsometry, Rutherford backscattering spectrometry and X-ray diffraction

    Microsoft Academic Search

    M. Serenyi; T. Lohner; P. Petrik; Z. Zolnai; Z. E. Horváth; N. Q. Khánh

    2008-01-01

    Niobium oxide films were prepared by radio frequency sputtering using Nb2O5 crystalline powder. The thickness and the complex dielectric functions of the as-prepared films were determined by spectroscopic ellipsometry using the Tauc–Lorentz oscillator model. The as-deposited films were amorphous, their refractive index varies between 2.26 and 2.30 at wavelength of 550 nm and the optical band gap varies between 3.29 and

  13. Feasibility of Spectroscopic Characterization of Algal Lipids: Chemometric Correlation of NIR and FTIR Spectra with Exogenous Lipids in Algal Biomass

    Microsoft Academic Search

    Lieve M. L. Laurens; Edward J. Wolfrum

    2011-01-01

    A large number of algal biofuels projects rely on a lipid screening technique for selecting a particular algal strain with\\u000a which to work. We have developed a multivariate calibration model for predicting the levels of spiked neutral and polar lipids\\u000a in microalgae, based on infrared (both near-infrared (NIR) and Fourier transform infrared (FTIR)) spectroscopy. The advantage\\u000a of an infrared spectroscopic

  14. Direct characterization and removal of interfering absorption trends in two-layer turbid media

    E-print Network

    Berger, Andrew J.

    a physiologically relevant range of optical properties and varying the absorption coefficients due to bottom a priori knowledge of the optical properties present in the model. An ana- lytical approximation), positron emission tomog- raphy (PET), magnetoencephalography (MEG), and func- tional magnetic resonance

  15. Spectroscopic characterization of 78 DENIS ultracool dwarf candidates in the solar neighborhood and the Upper Scorpii OB association

    NASA Astrophysics Data System (ADS)

    Martín, E. L.; Phan-Bao, N.; Bessell, M.; Delfosse, X.; Forveille, T.; Magazzù, A.; Reylé, C.; Bouy, H.; Tata, R.

    2010-07-01

    Aims: We search for new ultracool dwarfs and report here our observations of 78 ultracool dwarf candidates that have been photometrically selected using the DENIS survey point source catalogue. We analyze low-resolution optical spectroscopic observations to estimate spectral types of all candidates. Methods: We derive spectral types for each object using measurements of the PC3 spectral index as defined in Martín et al. They range from M6 to L3. The H? emission and NaI subordinate doublet (818.3 nm and 819.9 nm) equivalent widths are measured in the spectra to identify young stellar objects. Spectroscopic indices of TiO, VO, CrH, and FeH molecular features are also reported. Results: A rule-of-thumb criterion for selecting young very low-mass objects using the NaI doublet equivalent width is given. It is used to confirm seven new members of the Upper Sco OB association and two new members of the R Cr-A star-forming region. Four of our field objects are also classified as very young, but are not members of any known nearby young association. The frequency of lower-gravity young objects in our field ultracool sample is 8.5%. Our results provide the first spectroscopic classification for 42 ultracool dwarfs in the solar vicinity with spectrophotometric distances in the range 17 pc to 65 pc (3 of them being new L dwarfs within 20 pc).

  16. Spectroscopic characterization of 78 DENIS ultracool dwarf candidates in the solar neighborhood and the Upper Sco OB association

    E-print Network

    Martin, E L; Bessell, M; Delfosse, X; Forveille, T; Magazzu, A; Reyle, C; Bouy, H; Tata, R

    2010-01-01

    Aims: Low-resolution optical spectroscopic observations for 78 very low-mass star and brown dwarf candidates that have been photometrically selected using the DENIS survey point source catalogue. Methods: Spectral types are derived for them using measurements of the PC3 index. They range from M6 to L4. H_alpha emission and NaI subordinate doublet (818.3 nm and 819.9 nm) equivalent widths are measured in the spectra. Spectroscopic indices of TiO, VO, CrH and FeH molecular features are also reported. Results: A rule-of-thumb criterion to select young very low-mass objects using the NaI doublet equivalent width is given. It is used to confirm seven new members of the Upper Sco OB association and two new members of the R Cr-A star-forming region. Four of our field objects are also classified as very young, but are not members of any known nearby young association. The frequency of lower-gravity young objects in our field ultracool sample is 8.5%. Our results provide the first spectroscopic classification for 38 u...

  17. Organic matter characterization by infrared spectroscopic methods in lake sediment records from boreal and subarctic Sweden: Implications for long-term carbon cycling

    NASA Astrophysics Data System (ADS)

    Meyer-Jacob, Carsten; Rosén, Peter; Bindler, Richard

    2013-04-01

    Freshwater systems play an important role in the global carbon cycle. In this dynamic system, inorganic and organic carbon can be incorporated into biota, effluxed to the atmosphere or accumulated in sediments. The amount and composition of the carbon, derived from both aquatic and terrestrial sources, accumulated in sediments depend on the climatic and environmental conditions present in the lake and its catchment, and are thus sensitive to changes in, e.g., temperature, precipitation, vegetation and hydrological flow patterns. In this study, we show the application of infrared spectroscopic methods to qualitatively and quantitatively characterize organic matter stored in lake sediments with a focus on changes in the source of terrestrial-derived organic matter. Infrared spectroscopic methods facilitate a fast, cost-efficient and non-destructive analysis of minerogenic as well as organic sediment components. We applied three different infrared spectroscopic analyses - visible-near infrared spectroscopy (VNIRS; 25000-4000 cm-1), Fourier-transform infrared spectroscopy in the mid-IR region (FTIR; 3750-400 cm-1) and a combined Fourier-transformed infrared - thermal programmed desorption technique (FTIR-TPD; 3750-400 cm-1) - to Holocene sediment records from two Swedish lakes, Lång-Älgsjön and Lake Koukkel, to reconstruct past changes in the organic matter composition. The infrared spectral information of these records indicate sections of different organic matter composition reflecting varying stages of the lake and landscape development. An early-Holocene mire development around the boreal lake Lång-Älgsjön led to an increased input of organic matter from the catchment into the lake initiating an early natural lake acidification, whereas the subarctic Lake Koukkel has been affected by mire and potentially late-Holocene permafrost dynamics, which caused an increased and less variable input of allochthonous organic matter. Overall, variations in organic matter composition seem mainly driven by changes in the landscape rather than any direct effects of successive climate changes. Our findings emphasize that infrared spectroscopic methods are a promising tool for the fast and cost-effective characterization of organic matter in sediment samples, particularly with regard to the detection of qualitative differences between samples. An improved understanding of past variations in the organic matter composition and the related processes driving these changes is essential to further understand the interactions in the carbon cycle between the terrestrial and aquatic systems.

  18. Absorption and emission spectroscopic characterisation of the LOV2-domain of phot from Chlamydomonas reinhardtii fused to a maltose binding protein

    NASA Astrophysics Data System (ADS)

    Holzer, W.; Penzkofer, A.; Susdorf, T.; Álvarez, M.; Islam, Sh. D. M.; Hegemann, P.

    2004-07-01

    The absorption and emission behaviour of flavin mononucleotide (FMN) in the wild-type light, oxygen and voltage-sensitive (LOV) domain LOV2 of the photoreceptor phot from the green alga Chlamydomonas reinhardtii is studied at pH 8. Actually a LOV2-MBP-fusion protein (MBP=maltose binding protein) expressed in an Escherichia coli strain is investigated. For fresh samples stored in the dark an initial fluorescence quantum yield of ?F=0.08±0.01 is determined. Blue-light photo-excitation generates a non-fluorescent intermediate photoproduct (flavin-C(4a)-cysteinyl adduct with absorption peak at 390 nm). In the aqueous solutions studied approximately seven percent of the FMN molecules are not bound to the protein (free FMN in oxidized form) and about seven percent of the non-covalently bound FMN are not convertible to an adduct. Approximately two thirds of the intermediate photoproduct recovers with a time constant of 41 ± 1 s, while approximately one third recovers with a time constant of about 7 min. The photo-adduct formation is thought to proceed via singlet excited-state electron transfer and triplet formation.

  19. Halo-substituted thiosemicarbazones and their copper(II), nickel(II) complexes: Detailed spectroscopic characterization and study of antitumour activity against HepG2 human hepatoblastoma cells

    NASA Astrophysics Data System (ADS)

    Jagadeesh, M.; Kalangi, Suresh K.; Sivarama Krishna, L.; Reddy, A. Varada

    2014-01-01

    Copper(II) and nickel(II) complexes of two different halogen substituted thiosemicarbazone ligands were synthesized. The ligands 3,4-difluoroacetophenone thiosemicarbazone (1) and 2-bromo-4'-chloroacetophenone thiosemicarbazone (2) were characterized and confirmed spectroscopically by FT-IR, FT-Raman, UV-vis and fluorescence spectral analysis, while the respective copper(II) complexes [Cu(C9H9N3F2S)2Cl2] (1a), [Cu(C9H9N3ClBrS)2Cl2] (2a) and nickel(II) complexes [Ni(C9H9N3F2S)2] (1b), [Ni(C9H9N3ClBrS)2] (2b) were characterized by FT-IR, UV-vis and electron paramagnetic spectroscopy (EPR). The EPR spectra of the Cu(II) complexes provided the rhombic octahedral and axial symmetry of the complexes 1a and 2a respectively. For the complex 1a, the g values calculated as g1 = 2.1228, g2 = 2.0706 and g3 = 2.001 between 2900 and 3300 G. While for the complex 2a, a set of two resonance absorptions were observed. The synthesized compounds were tested for antitumor activity and showed that the ability to kill liver cancer cells significantly. Out of all the synthesized compounds, copper(II) complexes 1a and 2a showed high cytotoxic effect on liver cancer cells with 67.51% and 42.77% of cytotoxicity respectively at 100 ?M.

  20. Spectroscopic Observations

    NSDL National Science Digital Library

    This is a series of three activities about light and spectra. First, learners will construct their own spectroscope, observe common light sources, record the observed spectra, and compare their findings. Next, learners will use their spectroscopes to observe the spectra from different gas tubes and compare each observed spectrum to known spectra. Finally, they will observe a solar spectrum created by a prism, view a solar spectrum on paper, and attempt to determine the elements present in the Sun. This activity requires spectroscope posters and gratings available from the Stanford Solar Center (http://solar-center.stanford.edu/posters/), fluorescent and incandescent light sources, and emission lamps and power sources. This activity is from the Stanford Solar Center's All About the Sun: Sun and Stars activity guide for Grades 5-8 and can also accompany the Stanford Solar Center's Build Your Own Spectroscope activity.

  1. Preformulation characterization and in vivo absorption in beagle dogs of JFD, a novel anti-obesity drug for oral delivery.

    PubMed

    Fan, Yunzhou; Yang, Meiyan; Wang, Yuli; Li, Yanyou; Zhou, Yuanda; Chen, Xiaoping; Shan, Li; Wei, Jun; Gao, Chunsheng

    2015-05-01

    JFD (N-isoleucyl-4-methyl-1,1-cyclopropyl-1-(4-chlorine)phenyl-2-amylamine·HCl) is a novel investigational anti-obesity drug without obvious cardiotoxicity. The objective of this study was to characterize the key physicochemical properties of JFD, including solution-state characterization (ionization constant, partition coefficient, aqueous and pH-solubility profile), solid-state characterization (particle size, thermal analysis, crystallinity and hygroscopicity) and drug-excipient chemical compatibility. A supporting in vivo absorption study was also carried out in beagle dogs. JFD bulk powders are prismatic crystals with a low degree of crystallinity, particle sizes of which are within 2-10??m. JFD is highly hygroscopic, easily deliquesces to an amorphous glass solid and changes subsequently to another crystal form under an elevated moisture/temperature condition. Similar physical instability was also observed in real-time CheqSol solubility assay. pKa (7.49?±?0.01), log?P (5.10?±?0.02) and intrinsic solubility (S0) (1.75??g/ml) at 37?°C of JFD were obtained using potentiometric titration method. Based on these solution-state properties, JFD was estimated to be classified as BCS II, thus its dissolution rate may be an absorption-limiting step. Moreover, JFD was more chemically compatible with dibasic calcium phosphate, mannitol, hypromellose and colloidal silicon dioxide than with lactose and magnesium stearate. Further, JFD exhibited an acceptable pharmacokinetic profiling in beagle dogs and the pharmacokinetic parameters Tmax, Cmax, AUC0-t and absolute bioavailability were 1.60?±?0.81?h, 0.78?±?0.47??g/ml, 3.77?±?1.85??g·h/ml and 52.30?±?19.39%, respectively. The preformulation characterization provides valuable information for further development of oral administration of JFD. PMID:24694186

  2. Light Absorption Properties of Brown Carbon from Fresh and Aged Biomass Burning Aerosols Characterized in a Smog Chamber

    NASA Astrophysics Data System (ADS)

    Saleh, R.; Chuang, W.; Hennigan, C.; McMeeking, G. R.; Coe, H.; Donahue, N. M.; Robinson, A. L.

    2011-12-01

    Black carbon is an important particulate phase light absorber in the atmosphere. Recent studies have shown that some organic matter also absorb visible light, especially at short wavelengths. These organic compounds are referred to as "brown carbon". Biomass burning is a major contributor to brown carbon in atmospheric particulate matter; however, its optical properties are poorly characterized. We have conducted smog chamber experiments to investigate light absorption properties of brown carbon in primary and aged biomass burning emissions, namely the imaginary refractive index. The aging was performed in a smog chamber, where dilute emissions were exposed to UV lights to initiate photo-oxidation, which often produced substantial secondary organic aerosol. The experiments took place at Carnegie Mellon University (CMU) and at the US Fire Science Laboratory in Missoula, MT as part of the Fire Lab at Missoula field campaign (FLAME 2009). The CMU experiments simulated household wood burning (oak), and the FLAME experiments simulated wildland fires with fuels including gallberry, lodgepole pine, black spruce and ponderosa pine. Absorption coefficients were measured using an Aethalometer (Magee Scientific) at 7 different wavelengths ranging between 370 nm and 950 nm. The black carbon size distributions were measured using a Single Particle Soot Photometer (SP2, DMT), and total aerosol size distributions were measured using a Scanning Mobility Particle Sizer (SMPS, TSI). The absorption coefficients of both the fresh and aged aerosol were significantly larger, and had stronger wavelength dependence than what would be expected for black carbon alone, and for a black carbon core with a non-absorbing shell. This indicates that biomass burning organic aerosol should be classified as brown carbon. A (black carbon) core - (brown carbon) shell absorption model based on Mie theory was optimized to determine the shell imaginary refractive index which produces model outputs that fit measured absorption coefficients. The fresh and aged aerosol had similar optical properties, with shell imaginary refractive index ranging between 0.2 and 0.4 at 550 nm, and wavelength dependence between ?-2 and ?-3. These values correspond to absorption efficiencies comparable to black carbon at short visible wavelengths. Assuming a clear (non-absorbing) shell overestimates the single scattering albedo by up to a factor of 2, and underestimates the simple forcing efficiency by up to an order of magnitude.

  3. Time-resolved characterization of a filamentary argon discharge at atmospheric pressure in a capillary using emission and absorption spectroscopy

    NASA Astrophysics Data System (ADS)

    Schröter, Sandra; Pothiraja, Ramasamy; Awakowicz, Peter; Bibinov, Nikita; Böke, Marc; Niermann, Benedikt; Winter, Jörg

    2013-11-01

    An argon/nitrogen (0.999/0.001) filamentary pulsed discharge operated at atmospheric pressure in a quartz tube is characterized using voltage-current measurements, microphotography, optical emission spectroscopy (OES) and absorption spectroscopy. Nitrogen is applied as a sensor gas for the purpose of OES diagnostic. The density of argon metastable atoms Ar(3P2) is determined using tunable diode laser absorption spectroscopy (TDLAS). Using a plasma chemical model the measured OES data are applied for the characterization of the plasma conditions. Between intense positive pulses the discharge current oscillates with a damped amplitude. It is established that an electric current flows in this discharge not only through a thin plasma filament that is observed in the discharge image but also through the whole cross section of the quartz tube. A diffuse plasma fills the quartz tube during a time between intense current pulses. Ionization waves are propagating in this plasma between the spike and the grounded area of the tube producing thin plasma channels. The diameter of these channels increases during the pause between the propagation of ionization waves probably because of thermal expansion and diffusion. Inside the channels electron densities of ˜2 × 1013 cm-3, argon metastable densities ˜1014 cm-3 and a reduced electric field about 10 Td are determined.

  4. The X-ray absorption spectroscopic model of the copper(II) imidazole complex ion in liquid aqueous solution: a strongly solvated square pyramid.

    PubMed

    Frank, Patrick; Benfatto, Maurizio; Hedman, Britt; Hodgson, Keith O

    2012-02-20

    Cu K-edge extended X-ray absorption fine structure (EXAFS) and Minuit X-ray absorption near-edge structure (MXAN) analyses were combined to evaluate the structure of the copper(II) imidazole complex ion in liquid aqueous solution. Both methods converged to the same square-pyramidal inner coordination sphere [Cu(Im)(4)L(ax)](2+) (L(ax) indeterminate) with four equatorial nitrogen atoms at EXAFS, 2.02 ± 0.01 Å, and MXAN, 1.99 ± 0.03 Å. A short-axial N/O scatterer (L(ax)) was found at 2.12 ± 0.02 Å (EXAFS) or 2.14 ± 0.06 Å (MXAN). A second but very weak axial Cu-N/O interaction was found at 2.9 ± 0.1 Å (EXAFS) or 3.0 ± 0.1 Å (MXAN). In the MXAN fits, only a square-pyramidal structural model successfully reproduced the doubled maximum of the rising K-edge X-ray absorption spectrum, specifically excluding an octahedral model. Both EXAFS and MXAN also found eight outlying oxygen scatterers at 4.2 ± 0.3 Å that contributed significant intensity over the entire spectral energy range. Two prominent rising K-edge shoulders at 8987.1 and 8990.5 eV were found to reflect multiple scattering from the 3.0 Å axial scatterer and the imidazole rings, respectively. In the MXAN fits, the imidazole rings took in-plane rotationally staggered positions about copper. The combined (EXAFS and MXAN) model for the unconstrained cupric imidazole complex ion in liquid aqueous solution is an axially elongated square-pyramidal core, with a weak nonbonded interaction at the second axial coordination position and a solvation shell of eight nearest-neighbor water molecules. This core square-pyramidal motif has persisted through [Cu(H(2)O)(5)](2+), [Cu(NH(3))(4)(NH(3),H(2)O)](2+), (1, 2) and now [Cu(Im)(4)L(ax))](2+) and appears to be the geometry preferred by unconstrained aqueous-phase copper(II) complex ions. PMID:22316238

  5. Characterization of SEI layers on LiMn2O4 cathodes with in-situ spectroscopic ellipsometry

    SciTech Connect

    Lei, Jinglei; Li, Lingjie; Kostecki, Robert; Muller, Rolf; McLarnon, Frank

    2004-08-30

    In situ spectroscopic ellipsometry was employed to study the initial stage of SEI layer formation on thin-film LiMn{sub 2}O{sub 4} electrodes. It was found that the SEI layer formed immediately upon exposure of the electrode to EC/DMC (1:1 by vol) 1.0 M LiPF{sub 6} electrolyte. The SEI layer thickness then increased in proportion to a logarithmic function of elapsed time. In comparison, the SEI layer thickness on a cycled electrode increased in proportion to a linear function of the number of cycles.

  6. X-ray absorption spectroscopic studies of the dinuclear iron center in methane monooxygenase and the sulfure and chlorine centers in photographic materials

    SciTech Connect

    DeWitt, J.G.

    1992-12-01

    The dinuclear iron center of the hydroxylase component of soluble methane monooxygenase (MMO) from Methylococcus capsulatus and Methylosinus trichosporiwn has been studied by X-ray absorption spectroscopy. Analysis of the Fe K-edge EXAFS revealed that the first shell coordination of the Fe(HI)Fe(IH) oxidized state of the hydroxylase from M. capsulatus consists of approximately 6 N and 0 atoms at an average distance of 2.04 [Angstrom]. The Fe-Fe distance was determined to be 3.4 [Angstrom]. No evidence for the presence of a short oxo bridge in the iron center of the oxidized hydroxylase was found, suggesting that the active site of MMO is significantly different from the active sites of the dinuclear iron proteins hemery and ribonucleotide reductase. In addition, the results of the first shell fits suggest that there are more oxygen than nitrogen donor ligands.

  7. X-ray absorption spectroscopic studies of the dinuclear iron center in methane monooxygenase and the sulfure and chlorine centers in photographic materials

    SciTech Connect

    DeWitt, J.G.

    1992-12-01

    The dinuclear iron center of the hydroxylase component of soluble methane monooxygenase (MMO) from Methylococcus capsulatus and Methylosinus trichosporiwn has been studied by X-ray absorption spectroscopy. Analysis of the Fe K-edge EXAFS revealed that the first shell coordination of the Fe(HI)Fe(IH) oxidized state of the hydroxylase from M. capsulatus consists of approximately 6 N and 0 atoms at an average distance of 2.04 {Angstrom}. The Fe-Fe distance was determined to be 3.4 {Angstrom}. No evidence for the presence of a short oxo bridge in the iron center of the oxidized hydroxylase was found, suggesting that the active site of MMO is significantly different from the active sites of the dinuclear iron proteins hemery and ribonucleotide reductase. In addition, the results of the first shell fits suggest that there are more oxygen than nitrogen donor ligands.

  8. A novel strategy for site-directed chemical reactions in single stranded DNA--absorption and NMR spectroscopic studies of model compounds.

    PubMed Central

    Asseline, U; Rozelle, T; Lancelot, G; Thuong, N T

    1992-01-01

    A new and simple model enabling a chemical species to be brought to a preselected site in single strand DNA is reported. Two oligonucleotides containing a propanediol linkage were hybridized to their complementary sequences with an extra-base opposite the propanediol derivative. Absorption studies results shown that the addition of a bisacridine derivative strongly increased the stabilities of both duplexes when added in a 1:1 ratio. NMR studies on one of these duplexes brought evidence of the intercalation of the bisacridine at the position involving the propanediol linkage. These results suggest that this system could be used to target a specific reaction at a preselected position using the bisacridine derivative as carrier for the reactive species. PMID:1408782

  9. Glutamine/Glutamate Metabolism Studied with Magnetic Resonance Spectroscopic Imaging for the Characterization of Adrenal Nodules and Masses

    PubMed Central

    Goldman, Suzan M.; Nunes, Thiago F.; Melo, Homero J. F.; Dalavia, Claudio; Szejnfeld, Denis; Kater, Claudio; Andreoni, Cassio; Szejnfeld, Jacob; Ajzen, Sergio A.

    2013-01-01

    Purpose. To assess glutamine/glutamate (Glx) and lactate (Lac) metabolism using proton magnetic resonance spectroscopic imaging (1H-MRS) in order to differentiate between adrenal gland nodules and masses (adenomas, pheochromocytomas, carcinomas, and metastases). Materials and Methods. Institutional review board approval and informed consent were obtained. A total of 130 patients (47 men) with 132 adrenal nodules/masses were prospectively assessed (54 ± 14.8 years). A multivoxel system was used with a two-dimensional point-resolved spectroscopy/chemical-shift imaging sequence. Spectroscopic data were interpreted by visual inspection and peak amplitudes of lipids (Lip), choline (Cho), creatine (Cr), Lac, and Glx. Lac/Cr and Glx/Cr were calculated. Glx/Cr was assessed in relation to lesion size. Results. Statistically significant differences were observed in Glx/Cr results between adenomas and pheochromocytomas (P < 0.05), however, with a low positive predictive value (PPV). Glx levels were directly proportional to lesion size in carcinomas. A cutoff point of 1.44 was established for the differentiation between carcinomas larger versus smaller than 4?cm, with 75% sensitivity, 100% specificity, 100% PPV, and 80% accuracy. Lac/Cr results showed no differences across lesions. A cutoff point of ?6.5 for Lac/Cr was established for carcinoma diagnosis. Conclusion. Glx levels are directly proportional to lesion size in carcinomas. A cutoff point of ?6.5 Lac/Cr differentiates carcinomas from noncarcinomas. PMID:24199200

  10. Establishment and Characterization of an Omasal Epithelial Cell Model Derived from Dairy Calves for the Study of Small Peptide Absorption

    PubMed Central

    Xu, Qingbiao; Wu, Yueming; Liu, Hongyun; Xie, Yingming; Huang, Xinbei; Liu, Jianxin

    2014-01-01

    The objective of this study was to establish a primary culture of omasal epithelial cells (OECs) derived from dairy calves and to characterize its function in small peptide absorption. Bovine omasal tissues were obtained from newborn Chinese Holstein calves and digested with a 2.5% trypsin solution to obtain OECs. The isolated cells were later cultured in DMEM containing 10% fetal bovine serum, 5 ?g/ml insulin, 10 ng/ml epidermal growth factor, 100 U/ml penicillin, 100 ?g/ml streptomycin, 50 ?g/ml gentamycin and 2.5 ?g/ml amphotericin B. Hematoxylin and eosin staining of omasal tissue after digestion indicated that the cultured cells originated from the epithelial strata. Pure epithelial cells displayed an epithelial cell-like morphology, similar to cobblestone, with few visible fibroblasts and were cytokeratin 18-positive according to immunocytochemical analyses. The OECs were morphologically characterized with desmosomes, tight junctions and microvilli. These cells exhibited normal growth properties, as assessed using a cell growth curve, and were stably cultured for 10 passages. The OECs expressed the peptide transporter 1 (PEPT1) mRNA and absorbed intact glycylsarcosine (Gly-Sar). The uptake of Gly-Sar by OECs was pH-dependent with an optimal pH of 5.5–6.5. Furthermore, the uptake of Gly-Sar was also time-dependent, concentration-dependent and temperature-dependent. Moreover, PEPT1 was saturated with Gly-Sar at a concentration of 2.5 mM. The uptake via PEPT1 was higher compared with that via passive route at low substrate concentrations (<1.5 mM). This result suggested that PEPT1 contributed more to total small peptide absorption at low concentrations. In addition, this uptake could be competitively inhibited by methionine-glycine. Taken together, these data suggested that PEPT1 contributes to small peptide absorption in OECs. Thus, OECs may serve as a useful culture model for the study of the absorption of small peptides in bovine omasum. PMID:24633419

  11. Constraining the N2O5 UV absorption cross section from spectroscopic trace gas measurements in the tropical mid-stratosphere

    NASA Astrophysics Data System (ADS)

    Kritten, L.; Butz, A.; Chipperfield, M. P.; Dorf, M.; Dhomse, S.; Hossaini, R.; Oelhaf, H.; Prados-Roman, C.; Wetzel, G.; Pfeilsticker, K.

    2014-09-01

    The absorption cross section of N2O5, ?N2O5(?, T), which is known from laboratory measurements with the uncertainty of a factor of 2 (Table 4-2 in (Jet Propulsion Laboratory) JPL-2011; the spread in laboratory data, however, points to an uncertainty in the range of 25 to 30%, Sander et al., 2011), was investigated by balloon-borne observations of the relevant trace gases in the tropical mid-stratosphere. The method relies on the observation of the diurnal variation of NO2 by limb scanning DOAS (differential optical absorption spectroscopy) measurements (Weidner et al., 2005; Kritten et al., 2010), supported by detailed photochemical modelling of NOy (NOx(= NO + NO2) + NO3 + 2N2O5 + ClONO2 + HO2NO2 + BrONO2 + HNO3) photochemistry and a non-linear least square fitting of the model result to the NO2 observations. Simulations are initialised with O3 measured by direct sun observations, the NOy partitioning from MIPAS-B (Michelson Interferometer for Passive Atmospheric Sounding - Balloon-borne version) observations in similar air masses at night-time, and all other relevant species from simulations of the SLIMCAT (Single Layer Isentropic Model of Chemistry And Transport) chemical transport model (CTM). Best agreement between the simulated and observed diurnal increase of NO2 is found if the ?N2O5(?, T) is scaled by a factor of 1.6 ± 0.8 in the UV-C (200-260 nm) and by a factor of 0.9 ± 0.26 in the UV-B/A (260-350 nm), compared to current recommendations. As a consequence, at 30 km altitude, the N2O5 lifetime against photolysis becomes a factor of 0.77 shorter at solar zenith angle (SZA) of 30° than using the recommended ?N2O5(?, T), and stays more or less constant at SZAs of 60°. Our scaled N2O5 photolysis frequency slightly reduces the lifetime (0.2-0.6%) of ozone in the tropical mid- and upper stratosphere, but not to an extent to be important for global ozone.

  12. An X-ray absorption spectroscopic study of the metal site preference in Al{sub 1-x}Ga{sub x}FeO{sub 3}

    SciTech Connect

    Walker, James D.S. [Department of Chemistry, University of Saskatchewan, Saskatoon, Saskatchewan, S7N 5C9 (Canada); Grosvenor, Andrew P., E-mail: andrew.grosvenor@usask.ca [Department of Chemistry, University of Saskatchewan, Saskatoon, Saskatchewan, S7N 5C9 (Canada)

    2013-01-15

    Magnetoelectric materials have potential for being introduced into next generation technologies, especially memory devices. The AFeO{sub 3} (Pna2{sub 1}; A=Al, Ga) system has received attention to better understand the origins of magnetoelectric coupling. The magnetoelectric properties this system exhibits depend on the amount of anti-site disorder present, which is affected by the composition and the method of synthesis. In this study, Al{sub 1-x}Ga{sub x}FeO{sub 3} was synthesized by the ceramic method and studied by X-ray absorption spectroscopy. Al L{sub 2,3}-, Ga K-, and Fe K-edge spectra were collected to examine how the average metal coordination number changes with composition. Examination of XANES spectra from Al{sub 1-x}Ga{sub x}FeO{sub 3} indicate that with increasing Ga content, Al increasingly occupies octahedral sites while Ga displays a preference for occupying the tetrahedral site. The Fe K-edge spectra indicate that more Fe is present in the tetrahedral site in AlFeO{sub 3} than in GaFeO{sub 3}, implying more anti-site disorder is present in AlFeO{sub 3}. - Graphical abstract: Al{sub 1-x}Ga{sub x}FeO{sub 3} has been investigated by XANES. Through examination of Al L{sub 2,3}-, Ga K-, and Fe K-edge XANES spectra, it was found that more anti-site disorder of the Fe atoms is present in AlFeO{sub 3} compared to in GaFeO{sub 3}. Highlights: Black-Right-Pointing-Pointer Al{sub 1-x}Ga{sub x}FeO{sub 3} was investigated by X-ray absorption spectroscopy. Black-Right-Pointing-Pointer Ga prefers to occupy the tetrahedral site in Al{sub 1-x}Ga{sub x}FeO{sub 3}. Black-Right-Pointing-Pointer Fe prefers to occupy the octahedral sites in Al{sub 1-x}Ga{sub x}FeO{sub 3} as x increases. Black-Right-Pointing-Pointer More anti-site disorder is present in AlFeO{sub 3} compared to in GaFeO{sub 3.}.

  13. Spectroscopic characterization of Co3O4 catalyst doped with CeO2 and PdO for methane catalytic combustion.

    PubMed

    Jod?owski, P J; J?drzejczyk, R J; Rogulska, A; Wach, A; Ku?trowski, P; Sitarz, M; ?ojewski, T; Ko?odziej, A; ?ojewska, J

    2014-10-15

    The study deals with the XPS, Raman and EDX characterization of a series of structured catalysts composed of cobalt oxides promoted by palladium and cerium oxides. The aim of the work was to relate the information gathered from spectroscopic analyses with the ones from kinetic tests of methane combustion to establish the basic structure-activity relationships for the catalysts studied. The most active catalyst was the cobalt oxide doped with little amount of palladium and wins a confrontation with pure palladium oxide catalyst which is commercially used in converters for methane. The analyses Raman and XPS analyses showed that this catalyst is composed of a cobalt spinel and palladium oxide. The quantitative approach to the composition of the catalysts by XPS and EDX methods revealed that the surface of palladium doped cobalt catalyst is enriched with palladium oxide which provides a great number of active centres for methane combustion indicated by kinetic parameters. PMID:24913565

  14. Spectroscopic characterization of Co3O4 catalyst doped with CeO2 and PdO for methane catalytic combustion

    NASA Astrophysics Data System (ADS)

    Jod?owski, P. J.; J?drzejczyk, R. J.; Rogulska, A.; Wach, A.; Ku?trowski, P.; Sitarz, M.; ?ojewski, T.; Ko?odziej, A.; ?ojewska, J.

    2014-10-01

    The study deals with the XPS, Raman and EDX characterization of a series of structured catalysts composed of cobalt oxides promoted by palladium and cerium oxides. The aim of the work was to relate the information gathered from spectroscopic analyses with the ones from kinetic tests of methane combustion to establish the basic structure-activity relationships for the catalysts studied. The most active catalyst was the cobalt oxide doped with little amount of palladium and wins a confrontation with pure palladium oxide catalyst which is commercially used in converters for methane. The analyses Raman and XPS analyses showed that this catalyst is composed of a cobalt spinel and palladium oxide. The quantitative approach to the composition of the catalysts by XPS and EDX methods revealed that the surface of palladium doped cobalt catalyst is enriched with palladium oxide which provides a great number of active centres for methane combustion indicated by kinetic parameters.

  15. Absorption spectra and photovoltaic characterization of chlorophyllins as sensitizers for dye-sensitized solar cells.

    PubMed

    Calogero, Giuseppe; Citro, Ilaria; Crupi, Cristina; Di Marco, Gaetano

    2014-11-11

    Dye-sensitized solar cells (DSSCs) based on Chlorine-e6 (Chl-e6), a Chlorophyll a derivative, and Chl-e6 containing Cu, have been investigated by carrying out incident photon to current efficiency (IPCE) and current-voltage (I-V) measurements. The effect of the metallic ion and the influence of the solvent polarity on the dye aggregation and their absorption bands have been analysed by performing electronic absorption measurements. The dependence of the photoelectrochemical parameters of these DSSCs on the electrolyte by the addition of pyrimidine and/or pyrrole has been discussed in details. For the first time I-V curves for a DSSC based on copper Chl-e6 dye have been shown and compared with Zn based chlorophyllin. Furthermore, the performance of a Cu-Chl-e6 based DSSC has been deeply improved by a progressive optimization of the TiO2 multilayer photoanode overcoming the best data reported in literature so far for this dye. It's worth to emphasize that, the analysis reported in this paper supplies very useful information which paves the way to further detailed studies turned to the employment of natural pigments as sensitizers for solar cells. PMID:24892526

  16. Absorption spectra and photovoltaic characterization of chlorophyllins as sensitizers for dye-sensitized solar cells

    NASA Astrophysics Data System (ADS)

    Calogero, Giuseppe; Citro, Ilaria; Crupi, Cristina; Di Marco, Gaetano

    2014-11-01

    Dye-sensitized solar cells (DSSCs) based on Chlorine-e6 (Chl-e6), a Chlorophyll a derivative, and Chl-e6 containing Cu, have been investigated by carrying out incident photon to current efficiency (IPCE) and current-voltage (I-V) measurements. The effect of the metallic ion and the influence of the solvent polarity on the dye aggregation and their absorption bands have been analysed by performing electronic absorption measurements. The dependence of the photoelectrochemical parameters of these DSSCs on the electrolyte by the addition of pyrimidine and/or pyrrole has been discussed in details. For the first time I-V curves for a DSSC based on copper Chl-e6 dye have been shown and compared with Zn based chlorophyllin. Furthermore, the performance of a Cu-Chl-e6 based DSSC has been deeply improved by a progressive optimization of the TiO2 multilayer photoanode overcoming the best data reported in literature so far for this dye. It's worth to emphasize that, the analysis reported in this paper supplies very useful information which paves the way to further detailed studies turned to the employment of natural pigments as sensitizers for solar cells.

  17. Combination of chiroptical, absorption and fluorescence spectroscopic methods reveals multiple, hydrophobicity-driven human serum albumin binding of the antimalarial atovaquone and related hydroxynaphthoquinone compounds.

    PubMed

    Zsila, Ferenc; Fitos, Ilona

    2010-11-01

    High-affinity human serum albumin (HSA) binding of the C3-substituted antimalarial 2-hydroxy-1,4-naphthoquinone derivative atovaquone (ATQ) has been demonstrated and studied by circular dichroism (CD), UV/VIS absorption, fluorescence spectroscopy and affinity chromatography methods. The analysis of induced CD data generated upon HSA binding of ATQ revealed two high-affinity binding sites (K(a) ? 2 × 10(6) M(-1)). CD interaction studies and displacement of specific fluorescent and radioactive marker ligands indicated the contribution of both principal drug binding sites of HSA to complexation of ATQ, and also suggested the possibility of simultaneous binding of ATQ and some other drugs (e.g. warfarin, phenylbutazone, diazepam). Comparison of UV/VIS spectra of ATQ measured in aqueous solutions indicated the prevalence of the anionic species formed by dissociation of the 2-hydroxyl group. HSA binding of related natural hydroxynaphthoquinones, lapachol and lawsone also induces similar CD spectra. The much weaker binding affinity of lawsone (K(a) ? 10(4) M(-1)) bearing no C3 substituent highlights the importance of hydrophobic interactions in the strong HSA binding of ATQ and lapachol. Since neither drug exhibited significant binding to serum ?(1)-acid glycoprotein, HSA must be the principal plasma protein for the binding and transportation of 2-hydroxy-1,4-naphthoquinone-type compounds which are ionized at physiological pH values. PMID:20737064

  18. Absorption spectroscopic and FTIR studies on EDA complexes between TNT (2,4,6-trinitrotoluene) with amines in DMSO and determination of the vertical electron affinity of TNT.

    PubMed

    Sharma, S P; Lahiri, S C

    2008-06-01

    TNT (2,4,6-trinitrotoluene) formed deep red 1:1 CT complexes with chromogenic agents like isopropylamine, ethylenediamine, bis(3-aminopropyl)amine and tetraethylenepentamine in DMSO. The complexes were also observed in solvents like methanol, acetone, etc. when the amines were present in large excess. The isopropylamine, complex showed three absorption peaks (at 378, 532 and 629 nm) whereas higher amines showed four peaks (at 370, 463, 532 and 629 nm). The peak at 463 nm vanished rapidly. The peak of the complexes near 530 nm required about 8-10 min to develop and the complexes were stable for about an hour but the peak slowly shifted towards 500 nm and the complexes were found to be stable for more than 24 h. The evidence of complex formation was obtained from distinct spots in HPTLC plates and from the shifts in frequencies and formation of new peaks in FTIR spectra. The peaks near 460 nm (transient) and 530 nm may be due to Janovsky reaction but could not be established. The extinction coefficients of the complexes were determined directly which enabled the accurate determination of the association constants KDA with TNT and amines in stoichiometric ratios. The results were verified using iterative method. The quantification of TNT was made using epsilon value of the complex with ethylenediamine. The vertical electron affinity (EA) of TNT was calculated using the method suggested by Mulliken. PMID:17765603

  19. Absorption spectroscopic and FTIR studies on EDA complexes between TNT (2,4,6-trinitrotoluene) with amines in DMSO and determination of the vertical electron affinity of TNT

    NASA Astrophysics Data System (ADS)

    Sharma, S. P.; Lahiri, S. C.

    2008-06-01

    TNT (2,4,6-trinitrotoluene) formed deep red 1:1 CT complexes with chromogenic agents like isopropylamine, ethylenediamine, bis(3-aminopropyl)amine and tetraethylenepentamine in DMSO. The complexes were also observed in solvents like methanol, acetone, etc. when the amines were present in large excess. The isopropylamine, complex showed three absorption peaks (at 378, 532 and 629 nm) whereas higher amines showed four peaks (at 370, 463, 532 and 629 nm). The peak at 463 nm vanished rapidly. The peak of the complexes near 530 nm required about 8-10 min to develop and the complexes were stable for about an hour but the peak slowly shifted towards 500 nm and the complexes were found to be stable for more than 24 h. The evidence of complex formation was obtained from distinct spots in HPTLC plates and from the shifts in frequencies and formation of new peaks in FTIR spectra. The peaks near 460 nm (transient) and 530 nm may be due to Janovsky reaction but could not be established. The extinction coefficients of the complexes were determined directly which enabled the accurate determination of the association constants KDA with TNT and amines in stoichiometric ratios. The results were verified using iterative method. The quantfication of TNT was made using ? value of the complex with ethylenediamine. The vertical electron affinity ( EA) of TNT was calculated using the method suggested by Mulliken.

  20. The Time Domain Spectroscopic Survey: Spectroscopic Variability Investigations Within SDSS-IV/eBOSS

    NASA Astrophysics Data System (ADS)

    Green, Paul J.; Anderson, Scott F.; Morganson, Eric; Eracleous, Michael; Shen, Yue; Brandt, W. Niel; Ruan, John J.; Schmidt, Sarah J.; Badenes, Carles; West, Andrew A.; Ju, Wenhua; Greene, Jenny E.; Tdss, Panstarrs-1, Sdss-Iv

    2015-01-01

    The Time Domain Spectroscopic Survey (TDSS) is an SDSS-IV subproject that began summer 2014 and will continue for 4-6 years. Besides its main program to obtain initial characterization spectra of about 220,000 optical variables selected from PanSTARRS-1, the TDSS includes 9 separate smaller programs to study spectroscopic variability. We describe each of these Few-Epoch Spectroscopy (FES) programs, which target objects with existing SDSS spectroscopy amongst classes of quasars and stars of particular astrophysical interest. These include, in approximate order of decreasing sample size: Broad Absorption Line Quasars (BALQSOs), the most photometrically variable ("HyperVariable") quasars, high S/N normal broad line quasars, quasars with double-peaked or very asymmetric broad emission line profiles, Hypervariable stars, active ultracool (late-M and L-type) dwarf stars with Halpha emission, dwarf carbon stars, white dwarf/M dwarf spectroscopic binaries with Halpha emission, and binary supermassive black hole candidates from MgII broad line velocity shift analysis. We summarize herein the unique and diverse astrophysical investigations facilitated by these TDSS FES programs.

  1. Spectroscopic characterization of different structural forms of the new promising energetic material FOX-7 in different solvents

    NASA Astrophysics Data System (ADS)

    Šimková, Ludmila; Šoral, Michal; Lušpai, Karol; Ludvík, Ji?í

    2015-03-01

    UV-vis, IR and NMR spectroscopy were utilized as direct monitoring techniques for structure changes of a new promising energetic material FOX-7 in different protic and aprotic solvents. The dissolved FOX-7 indicates changes in molecular structure as compared with that in solid-state. The push-pull properties of the molecule together with the effects of solvents result in charge separated zwitterion formed in solution. By combination of different spectroscopic techniques, structural changes of charge-separated molecule of FOX-7 were described in dependence on the solvent properties, temperature, proton activity and concentration. From the analytical point of view, the lowest detectable concentration of FOX-7 using UV-vis spectra was determined to approximately 6 × 10-7 mol L-1.

  2. Recent advances in characterization of CaCu3Ti4O12 thin films by spectroscopic ellipsometric metrology.

    PubMed

    Lo Nigro, Raffaella; Malandrino, Graziella; Toro, Roberta G; Losurdo, Maria; Bruno, Giovanni; Fragalà, Ignazio L

    2005-10-12

    CaCu3Ti4O12 (CCTO) thin films were successfully grown on LaAlO3(100) and Pt/TiO2/SiO2/Si(100) substrates by a novel MOCVD approach. Epitaxial CCTO(001) thin films have been obtained on LaAlO3(100) substrates, while polycrystalline CCTO films have been grown on Pt/TiO2/SiO2/Si(100) substrates. Surface morphology and grain size of the different nanostructured deposited films were examined by AFM, and spectroscopic ellipsometry has been used to investigate the electronic part of the dielectric constant (epsilon2). Looking at the epsilon2 curves, it can be seen that by increasing the film structural order, a greater dielectric response has been obtained. The measured dielectric properties accounted for the ratio between grain volumes and grain boundary areas, which is very different in the different structured films. PMID:16201781

  3. The PtAl{sup ?} and PtAl{sub 2}{sup ?} anions: Theoretical and photoelectron spectroscopic characterization

    SciTech Connect

    Zhang, Xinxing; Ganteför, Gerd; Bowen, Kit H., E-mail: kbowen@jhu.edu, E-mail: ana@chem.ucla.edu [Departments of Chemistry and Materials Science, Johns Hopkins University, Baltimore, Maryland 21218 (United States); Alexandrova, Anastassia N., E-mail: kbowen@jhu.edu, E-mail: ana@chem.ucla.edu [Department of Chemistry and Biochemistry, University of California, Los Angeles, Los Angeles, California 90095-1569, USA and California NanoSystems Institute, 570 Westwood Plaza, Building 114, Los Angeles, California 90095 (United States)

    2014-04-28

    We report a joint photoelectron spectroscopic and theoretical study of the PtAl{sup ?} and PtAl{sub 2}{sup ?} anions. The ground state structures and electronic configurations of these species were identified to be C{sub ?v}, {sup 1}?{sup +} for PtAl{sup ?}, and C{sub 2v}, {sup 2}B{sub 1} for PtAl{sub 2}{sup ?}. Structured anion photoelectron spectra of these clusters were recorded and interpreted using ab initio calculations. Good agreement between theory and experiment was found. All experimental features were successfully assigned to one-electron transitions from the ground state of the anions to the ground or excited states of the corresponding neutral species.

  4. Mapping tropical biodiversity using spectroscopic imagery : characterization of structural and chemical diversity with 3-D radiative transfer modeling

    NASA Astrophysics Data System (ADS)

    Feret, J. B.; Gastellu-Etchegorry, J. P.; Lefèvre-Fonollosa, M. J.; Proisy, C.; Asner, G. P.

    2014-12-01

    The accelerating loss of biodiversity is a major environmental trend. Tropical ecosystems are particularly threatened due to climate change, invasive species, farming and natural resources exploitation. Recent advances in remote sensing of biodiversity confirmed the potential of high spatial resolution spectroscopic imagery for species identification and biodiversity mapping. Such information bridges the scale-gap between small-scale, highly detailed field studies and large-scale, low-resolution satellite observations. In order to produce fine-scale resolution maps of canopy alpha-diversity and beta-diversity of the Peruvian Amazonian forest, we designed, applied and validated a method based on spectral variation hypothesis to CAO AToMS (Carnegie Airborne Observatory Airborne Taxonomic Mapping System) images, acquired from 2011 to 2013. There is a need to understand on a quantitative basis the physical processes leading to this spectral variability. This spectral variability mainly depends on canopy chemistry, structure, and sensor's characteristics. 3D radiative transfer modeling provides a powerful framework for the study of the relative influence of each of these factors in dense and complex canopies. We simulated series of spectroscopic images with the 3D radiative model DART, with variability gradients in terms of leaf chemistry, individual tree structure, spatial and spectral resolution, and applied methods for biodiversity mapping. This sensitivity study allowed us to determine the relative influence of these factors on the radiometric signal acquired by different types of sensors. Such study is particularly important to define the domain of validity of our approach, to refine requirements for the instrumental specifications, and to help preparing hyperspectral spatial missions to be launched at the horizon 2015-2025 (EnMAP, PRISMA, HISUI, SHALOM, HYSPIRI, HYPXIM). Simulations in preparation include topographic variations in order to estimate the robustness of image processing methods for mountainous ecosystems.

  5. Characterization of Cr3+ doped mixed alkali ions effect in zinc borate glasses - Physical and spectroscopic investigations

    NASA Astrophysics Data System (ADS)

    Rama Sundari, G.; Pushpa Manjari, V.; Raghavendra Rao, T.; Satish, D. V.; Rama Krishna, Ch.; Venkata Reddy, Ch.; Ravikumar, R. V. S. S. N.

    2014-06-01

    The physical and structural properties of Cr3+ doped 19.9 ZnO + xLi2O + (30 - x) Na2O + 50B2O3 (5 ? x ? 25) (ZLNB) glasses have been studied. Powder X-ray diffraction patterns indicated the amorphous nature of the glass samples. The physical parameters of all the glasses were also evaluated with respect to the composition. They exhibit the non-linearity providing the evidence for mixed alkali ions effect. The infrared spectra of the glasses in the range 400-4000 cm-1 showed the presence of BO3 and BO4 local structures in all the glass systems. No boroxol ring formation was observed in the structure of these glasses. Optical absorption and electron paramagnetic resonance studies were carried out at room temperature. From the optical absorption data various optical parameters such as optical band gap, Urbach energy were evaluated. Crystal field and Racah parameters are evaluated from optical absorption spectra. The EPR spectra of Cr3+ doped ZLNB glasses exhibited resonance signals at g = 4.066 and g = 1.9779 characteristic of Cr3+ ions. The evaluated bonding parameters suggest the covalent nature.

  6. Constraining the N2O5 UV absorption cross-section from spectroscopic trace gas measurements in the tropical mid-stratosphere

    NASA Astrophysics Data System (ADS)

    Kritten, L.; Butz, A.; Chipperfield, M. P.; Dorf, M.; Dhomse, S.; Hossaini, R.; Oelhaf, H.; Prados-Roman, C.; Wetzel, G.; Pfeilsticker, K.

    2014-02-01

    The absorption cross-section of N2O5, ?N2O5(?, T), which is known from laboratory measurements with the uncertainty of a factor of 2 (Table 4-2 in JPL-2011, Sander et al., 2011), was investigated by balloon-borne observations of the relevant trace gases in the tropical mid-stratosphere. The method relies on the observation of the diurnal variation of NO2 supported by detailed photochemical modelling of NOy (NOx(= NO + NO2) + NO3 + 2N2O5 + ClONO2 + HO2NO2 +BrONO2 + HNO3) photochemistry. Simulations are initialised with O3 measured by direct sun observations, the NOy partitioning from MIPAS-B (Michelson Interferometer for Passive Atmospheric Sounding-Balloon) observations in similar air masses at nighttime, and all other relevant species from simulations of the SLIMCAT chemical transport model (CTM). Best agreement between the simulated and observed diurnal increase of NO2 is found if the ?N2O5(?, T) is scaled by a factor of 1.6 ± 0.8 in the UV-C (200-260 nm) and by a factor of 0.9 ± 0.26 in the UV-B/A (260-350 nm), compared to current recommendations. In consequence, at 30 km altitude, the N2O5 lifetime against photolysis becomes a factor of 0.77 shorter at solar zenith angle (SZA) of 30° than using the recommended ?N2O5 (?, T), and stays more or less constant at SZAs of 60°. Our scaled N2O5 photolysis frequency slightly reduces the lifetime (0.2-0.6%) of ozone in the tropical mid- and upper stratosphere, but not to an extent to be important for global ozone.

  7. Spectroscopic remote sensing of plant stress at leaf and canopy levels using the chlorophyll 680 nm absorption feature with continuum removal

    NASA Astrophysics Data System (ADS)

    Sanches, Ieda Del'Arco; Souza Filho, Carlos Roberto; Kokaly, Raymond Floyd

    2014-11-01

    This paper explores the use of spectral feature analysis to detect plant stress in visible/near infrared wavelengths. A time series of close range leaf and canopy reflectance data of two plant species grown in hydrocarbon-contaminated soil was acquired with a portable spectrometer. The ProSpecTIR-VS airborne imaging spectrometer was used to obtain far range hyperspectral remote sensing data over the field experiment. Parameters describing the chlorophyll 680 nm absorption feature (depth, width, and area) were derived using continuum removal applied to the spectra. A new index, the Plant Stress Detection Index (PSDI), was calculated using continuum-removed values near the chlorophyll feature centre (680 nm) and on the green-edge (560 and 575 nm). Chlorophyll feature's depth, width and area, the PSDI and a narrow-band normalised difference vegetation index were evaluated for their ability to detect stressed plants. The objective was to analyse how the parameters/indices were affected by increasing degrees of plant stress and to examine their utility as plant stress indicators at the remote sensing level (e.g. airborne sensor). For leaf data, PSDI and the chlorophyll feature area revealed the highest percentage (67-70%) of stressed plants. The PSDI also proved to be the best constraint for detecting the stress in hydrocarbon-impacted plants with field canopy spectra and airborne imaging spectroscopy data. This was particularly true using thresholds based on the ASD canopy data and considering the combination of higher percentage of stressed plants detected (across the thresholds) and fewer false-positives.

  8. Chemical modification of TiO2 surfaces with methylsilanes and characterization by infrared absorption spectroscopy

    NASA Technical Reports Server (NTRS)

    Finklea, H. O.; Vithanage, R.

    1982-01-01

    Infrared absorption spectra of methylsilanes bonded to a TiO2 powder were obtained. The reacting silanes include Me sub (4-n)SiX sub n (n=1-4; X=Cl, OMe) and hexamethyldisilazane (HMDS). Reactions were performed on hydroxylated-but-anhydrous TiO2 surfaces in the gas phase. IR spectra confirm the presence of a bonded silane layer. Terminal surface OH groups are found to react more readily than bridging OH groups. By-products of the modification adsorp tenaciously to the surface. The various silanes show only small differences in their ability to sequester surface OH groups. Following hydrolysis in moist air, Si-OH groups are observed only for the tetrafunctional silanes.

  9. Optical characterization of the nematic lyotropic chromonic liquid crystals: light absorption, birefringence, and scalar order parameter.

    PubMed

    Nastishin, Yu A; Liu, H; Schneider, T; Nazarenko, V; Vasyuta, R; Shiyanovskii, S V; Lavrentovich, O D

    2005-10-01

    We report on the optical properties of the nematic (N) phase formed by lyotropic chromonic liquid crystals (LCLCs) in well aligned planar samples. LCLCs belong to a broad class of materials formed by one-dimensional molecular self-assembly and are similar to other systems such as "living polymers" and "wormlike micelles." We study three water soluble LCLC forming materials: disodium chromoglycate, a derivative of indanthrone called Blue 27, and a derivative of perylene called Violet 20. The individual molecules have a planklike shape and assemble into rodlike aggregates that form the phase once the concentration exceeds about 0.1 M. The uniform surface alignment of the N phase is achieved by buffed polyimide layers. According to the light absorption anisotropy data, the molecular planes are on average perpendicular to the aggregate axes and thus to the nematic director. We determined the birefringence of these materials in the N and biphasic N-isotropic (I) regions and found it to be negative and significantly lower in the absolute value as compared to the birefringence of typical thermotropic low-molecular-weight nematic materials. In the absorbing materials Blue 27 and Violet 20, the wavelength dependence of birefringence is nonmonotonic because of the effect of anomalous dispersion near the absorption bands. We describe positive and negative tactoids formed as the nuclei of the new phase in the biphasic N-I region (which is wide in all three materials studied). Finally, we determined the scalar order parameter of the phase of Blue 27 and found it to be relatively high, in the range 0.72-0.79, which puts the finding into the domain of general validity of the Onsager model. However, the observed temperature dependence of the scalar order parameter points to the importance of factors not accounted for in the athermal Onsager model, such as interaggregate interactions and the temperature dependence of the aggregate length. PMID:16383406

  10. Optical characterization of the nematic lyotropic chromonic liquid crystals: Light absorption, birefringence, and scalar order parameter

    NASA Astrophysics Data System (ADS)

    Nastishin, Yu. A.; Liu, H.; Schneider, T.; Nazarenko, V.; Vasyuta, R.; Shiyanovskii, S. V.; Lavrentovich, O. D.

    2005-10-01

    We report on the optical properties of the nematic (N) phase formed by lyotropic chromonic liquid crystals (LCLCs) in well aligned planar samples. LCLCs belong to a broad class of materials formed by one-dimensional molecular self-assembly and are similar to other systems such as “living polymers” and “wormlike micelles.” We study three water soluble LCLC forming materials: disodium chromoglycate, a derivative of indanthrone called Blue 27, and a derivative of perylene called Violet 20. The individual molecules have a planklike shape and assemble into rodlike aggregates that form the N phase once the concentration exceeds about 0.1M . The uniform surface alignment of the N phase is achieved by buffed polyimide layers. According to the light absorption anisotropy data, the molecular planes are on average perpendicular to the aggregate axes and thus to the nematic director. We determined the birefringence of these materials in the N and biphasic N -isotropic (I) regions and found it to be negative and significantly lower in the absolute value as compared to the birefringence of typical thermotropic low-molecular-weight nematic materials. In the absorbing materials Blue 27 and Violet 20, the wavelength dependence of birefringence is nonmonotonic because of the effect of anomalous dispersion near the absorption bands. We describe positive and negative tactoids formed as the nuclei of the new phase in the biphasic N-I region (which is wide in all three materials studied). Finally, we determined the scalar order parameter of the N phase of Blue 27 and found it to be relatively high, in the range 0.72-0.79, which puts the finding into the domain of general validity of the Onsager model. However, the observed temperature dependence of the scalar order parameter points to the importance of factors not accounted for in the athermal Onsager model, such as interaggregate interactions and the temperature dependence of the aggregate length.

  11. Characterization of esterase and alcohol dehydrogenase activity in skin. Metabolism of retinyl palmitate to retinol (vitamin A) during percutaneous absorption.

    PubMed

    Boehnlein, J; Sakr, A; Lichtin, J L; Bronaugh, R L

    1994-08-01

    Retinyl palmitate, a widely used ingredient in cosmetic products, is promoted for its beneficial effects on the appearance of skin. Previous studies suggest that enzymes are available in skin to metabolize this ingredient during skin absorption. Esterase activity hydrolyzes retinyl palmitate to retinol (vitamin A), which is oxidized in many tissues to retinoic acid primarily by alcohol dehydrogenase. The activities of esterase and alcohol dehydrogenase were characterized in hairless guinea pig skin by using flow-through diffusion cells and radiolabeled model compounds (methyl salicylate and benzyl alcohol) previously shown to be metabolized by these enzymes. Methyl salicylate was hydrolyzed by esterase to a greater extent in viable skin than in nonviable skin. Glycine conjugation of salicylic acid and benzoic acid occurred only in viable skin. The metabolism of methyl salicylate and benzyl alcohol occurred to a greater extent in male guinea pig skin than in female guinea pig skin. The percutaneous absorption of both radiolabeled compounds was similar in viable and nonviable skin. About 30 and 18% of topically applied retinyl palmitate were absorbed from an acetone vehicle by hairless guinea pig skin and human skin, respectively. Less than 1% of the applied dose of this lipophilic compound diffused from skin into the receptor fluid. Retinol was the only detectable metabolite of retinyl palmitate in both hairless guinea pig and human skin. In human skin, 44% of the absorbed retinyl palmitate was hydrolyzed to retinol. The use of retinyl palmitate in cosmetic formulations may result in significant delivery of retinol into the skin. PMID:7971717

  12. Characterization of selective binding of alkali cations with carboxylate by x-ray absorption spectroscopy of liquid microjets

    SciTech Connect

    Saykally, Richard J; Uejio, Janel S.; Schwartz, Craig P.; Duffin, Andrew M.; Drisdell, Walter S.; Cohen, Ronald C.; Saykally, Richard J.

    2008-01-08

    We describe an approach for characterizing selective binding between oppositely charged ionic functional groups under biologically relevant conditions. Relative shifts in K-shell x-ray absorption spectra of aqueous cations and carboxylate anions indicate the corresponding binding strengths via perturbations of carbonyl antibonding orbitals. XAS spectra measured for aqueous formate and acetate solutions containing lithium, sodium, and potassium cations reveal monotonically stronger binding of the lighter metals, supporting recent results from simulations and other experiments. The carbon K-edge spectra of the acetate carbonyl feature centered near 290 eV clearly indicate a preferential interaction of sodium versus potassium, which was less apparent with formate. These results are in accord with the Law of Matching Water Affinities, relating relative hydration strengths of ions to their respective tendencies to form contact ion pairs. Density functional theory calculations of K-shell spectra support the experimental findings.

  13. Observation of x-ray absorption magnetic circular dichroism in well-characterized iron-cobalt-platinum multilayers

    SciTech Connect

    Jankowski, A.F.; Waddill, G.D.; Tobin, J.G.

    1993-04-01

    Magnetic circular dichroism in the Fe 2p x-ray absorption is observed in multilayers of(Fe9.5{Angstrom}/Pt9.5{Angstrom}){sub 92}. The magnetization and helicity are both in the plane of this multilayer which is prepared by magnetron sputter deposition. This sample is part of a study to examine magnetization in the ternary multilayer system of FeCo/Pt. Lattice and layer pair spacings are measured using x-ray scattering. The atomic concentration profiles of the multilayer films are characterized using Auger electron spectroscopy coupled with depth profiling. Conventional and high resolution transmission electron microscopy are used to examine the thin film, growth morphology and atomic structure.

  14. Wells-Dawson Polyoxometelates [HP2W18-nMonO62]Fe2.5, xH2O; n = 0, 6: Synthesis, spectroscopic characterization and catalytic application for dyes

    E-print Network

    Paris-Sud XI, Université de

    1 Wells-Dawson Polyoxometelates [HP2W18-nMonO62]Fe2.5, xH2O; n = 0, 6: Synthesis, spectroscopic characterizations of a new Wells- Dawson-type heteropolyanions which contains iron HFe2.5P2W18O62, 23H2O and HFe2.5P studied. Keywords: heteropolyanions, Wells- Dawson-type, synthesis, characterizations, dyes, hydrogen

  15. Monothiol Glutaredoxins Can Bind Linear [Fe3S4]+ and [Fe4S4]2+ Clusters in Addition to [Fe2S2]2+ Clusters: Spectroscopic Characterization and Functional Implications

    PubMed Central

    Zhang, Bo; Bandyopadhyay, Sibali; Shakamuri, Priyanka; Naik, Sunil G.; Huynh, Boi Hanh; Couturier, Jérémy; Rouhier, Nicolas; Johnson, Michael K.

    2013-01-01

    Saccharomyces cerevisiae mitochondrial glutaredoxin 5 (Grx5) is the archetypical member of a ubiquitous class of monothiol glutaredoxins with a strictly conserved CGFS active-site sequence that has been shown to function in biological [Fe2S2]2+ cluster trafficking. In this work, we show that recombinant S. cerevisiae Grx5 purified aerobically after prolonged exposure of the cell-free extract to air or after anaerobic reconstitution in the presence of glutathione, predominantly contains a linear [Fe3S4]+ cluster. The excited state electronic properties and ground state electronic and vibrational properties of the linear [Fe3S4]+ cluster have been characterized using UV-visible absorption/CD/MCD, EPR, Mössbauer and resonance Raman spectroscopies. The results reveal a rhombic S = 5/2 linear [Fe3S4]+ cluster with properties similar to those reported for synthetic linear [Fe3S4]+ clusters and the linear [Fe3S4]+ clusters in purple aconitase. Moreover, the results indicate that the Fe-S cluster content previously reported for many monothiol Grxs has been misinterpreted exclusively in terms of [Fe2S2]2+ clusters, rather than linear [Fe3S4]+ clusters or mixtures of linear [Fe3S4]+ and [Fe2S2]2+ clusters. In the absence of GSH, anaerobic reconstitution of Grx5 yields a dimeric form containing one [Fe4S4]2+ cluster that competent for in vitro activation of apo-aconitase, via intact cluster transfer. The ligation of the linear [Fe3S4]+ and [Fe4S4]2+ clusters in Grx5 has been assessed by spectroscopic, mutational and analytical studies. Potential roles for monothiol Grx5 in scavenging and recycling linear [Fe3S4]+ clusters released during protein unfolding under oxidative stress conditions and in maturation of [Fe4S4]2+ cluster-containing proteins are discussed in light of these results. PMID:24032439

  16. CD Spectroscope

    NSDL National Science Digital Library

    2012-06-26

    In this activity, learners use an old CD to construct a spectroscope, a device that separates light into its component colors. Learners will hold it up to various light sources to examine how different light has different color strengths. Use this activity to introduce learners to the color spectrum and the tools scientists use to study it.

  17. Color discrimination in halobacteria: spectroscopic characterization of a second sensory receptor covering the blue-green region of the spectrum.

    PubMed Central

    Wolff, E K; Bogomolni, R A; Scherrer, P; Hess, B; Stoeckenius, W

    1986-01-01

    Halobacterium halobium is attracted by green and red light and repelled by blue-green and shorter wavelength light. a photochromic, rhodopsin-like protein in the cell membrane, sensory rhodopsin sR587, has been identified as the receptor for the long-wavelength and near-UV stimuli. Discrepancies between the action spectrum for the repellent effect of blue light and the absorption spectrum of sR587 and its photocycle intermediate S373 strongly suggest the existence of an additional photoreceptor for the blue region of the spectrum. Transient light-induced absorbance changes in intact cells and cell membranes show, in addition to sR587, the presence of a second photoactive pigment with maximal absorption near 480 nm. It undergoes a cyclic photoreaction with a half-time of 150 msec. One intermediate state with maximal absorption near 360 nm has been resolved. The spectral properties of the new pigment are consistent with a function as the postulated photoreceptor for the repellent effect of blue light. The phototactic reactions and both pigments are absent when retinal synthesis is blocked; both can be restored by the addition of retinal. These results confirm and extend similar observations by Takahashi et al. [Takahashi, T., Tomioka, H., Kamo, N. & Kobatake, Y. (1985) FEMS Microbiol. Lett. 28, 161-164]. The archaeobacterium H. halobium thus uses two different mechanisms for color discrimination; it uses two rhodopsin-like receptors with different spectral sensitivities and also the photochromicity of at least one of these receptors to distinguish between three regions covering the visible and near-UV spectrum. PMID:3463965

  18. Characterization of the Electronic Structure of Silicon Nanoparticles Using X-ray Absorption and Emission

    SciTech Connect

    Vaverka, A M

    2008-07-15

    Resolving open questions regarding transport in nanostructures can have a huge impact on a broad range of future technologies such as light harvesting for energy. Silicon has potential to be used in many of these applications. Understanding how the band edges of nanostructures move as a function of size, surface termination and assembly is of fundamental importance in understanding the transport properties of these materials. In this thesis work I have investigated the change in the electronic structure of silicon nanoparticle assemblies as the surface termination is changed. Nanoparticles are synthesized using a thermal evaporation technique and sizes are determined using atomic force microscopy (AFM). By passivating the particles with molecules containing alcohol groups we are able to modify the size dependent band edge shifts. Both the valence and conduction bands are measured using synchrotron based x-ray absorption spectroscopy (XAS) and soft x-ray fluorescence (SXF) techniques. Particles synthesized via recrystallization of amorphous silicon/SiO{sub 2} multilayers of thicknesses below 10 nm are also investigated using the synchrotron techniques. These samples also show quantum confinement effects but the electronic structure is different from those synthesized via evaporation methods. The total bandgap is determined for all samples measured. The origins of these differences in the electronic structures are discussed.

  19. Characterization of the electronic structure of silicon nanoparticles using x-ray absorption and emission

    NASA Astrophysics Data System (ADS)

    Montoya Vaverka, April Susan

    Resolving open questions regarding transport in nanostructures can have a huge impact on a broad range of future technologies such as light harvesting for energy. Silicon has potential to be used in many of these applications. Understanding how the band edges of nanostructures move as a function of size, surface termination and assembly is of fundamental importance in understanding the transport properties of these materials. In this thesis work I have investigated the change in the electronic structure of silicon nanoparticle assemblies as the surface termination is changed. Nanoparticles are synthesized using a thermal evaporation technique and sizes are determined using atomic force microscopy (AFM). By passivating the particles with molecules containing alcohol groups we are able to modify the size dependent band edge shifts. Both the valence and conduction bands are measured using synchrotron based x-ray absorption spectroscopy (XAS) and soft x-ray fluorescence (SXF) techniques. Particles synthesized via recrystallization of amorphous silicon/SiO2 multilayers of thicknesses below 10 rim are also investigated using the synchrotron techniques. These samples also show quantum confinement effects but the electronic structure is different from those synthesized via evaporation methods. The total bandgap is determined for all samples measured. The origins of these differences in the electronic structures are discussed.

  20. Fourier transform infrared absorption spectroscopy characterization of gaseous atmospheric pressure plasmas with 2 mm spatial resolution

    NASA Astrophysics Data System (ADS)

    Laroche, G.; Vallade, J.; Bazinette, R.; van Nijnatten, P.; Hernandez, E.; Hernandez, G.; Massines, F.

    2012-10-01

    This paper describes an optical setup built to record Fourier transform infrared (FTIR) absorption spectra in an atmospheric pressure plasma with a spatial resolution of 2 mm. The overall system consisted of three basic parts: (1) optical components located within the FTIR sample compartment, making it possible to define the size of the infrared beam (2 mm × 2 mm over a path length of 50 mm) imaged at the site of the plasma by (2) an optical interface positioned between the spectrometer and the plasma reactor. Once through the plasma region, (3) a retro-reflector module, located behind the plasma reactor, redirected the infrared beam coincident to the incident path up to a 45° beamsplitter to reflect the beam toward a narrow-band mercury-cadmium-telluride detector. The antireflective plasma-coating experiments performed with ammonia and silane demonstrated that it was possible to quantify 42 and 2 ppm of these species in argon, respectively. In the case of ammonia, this was approximately three times less than this gas concentration typically used in plasma coating experiments while the silane limit of quantification was 35 times lower. Moreover, 70% of the incoming infrared radiation was focused within a 2 mm width at the site of the plasma, in reasonable agreement with the expected spatial resolution. The possibility of reaching this spatial resolution thus enabled us to measure the gaseous precursor consumption as a function of their residence time in the plasma.

  1. Fourier transform infrared absorption spectroscopy characterization of gaseous atmospheric pressure plasmas with 2 mm spatial resolution.

    PubMed

    Laroche, G; Vallade, J; Bazinette, R; van Nijnatten, P; Hernandez, E; Hernandez, G; Massines, F

    2012-10-01

    This paper describes an optical setup built to record Fourier transform infrared (FTIR) absorption spectra in an atmospheric pressure plasma with a spatial resolution of 2 mm. The overall system consisted of three basic parts: (1) optical components located within the FTIR sample compartment, making it possible to define the size of the infrared beam (2 mm × 2 mm over a path length of 50 mm) imaged at the site of the plasma by (2) an optical interface positioned between the spectrometer and the plasma reactor. Once through the plasma region, (3) a retro-reflector module, located behind the plasma reactor, redirected the infrared beam coincident to the incident path up to a 45° beamsplitter to reflect the beam toward a narrow-band mercury-cadmium-telluride detector. The antireflective plasma-coating experiments performed with ammonia and silane demonstrated that it was possible to quantify 42 and 2 ppm of these species in argon, respectively. In the case of ammonia, this was approximately three times less than this gas concentration typically used in plasma coating experiments while the silane limit of quantification was 35 times lower. Moreover, 70% of the incoming infrared radiation was focused within a 2 mm width at the site of the plasma, in reasonable agreement with the expected spatial resolution. The possibility of reaching this spatial resolution thus enabled us to measure the gaseous precursor consumption as a function of their residence time in the plasma. PMID:23126767

  2. Americium characterization by X-ray fluorescence and absorption spectroscopy in plutonium uranium mixed oxide

    NASA Astrophysics Data System (ADS)

    Degueldre, Claude; Cozzo, Cedric; Martin, Matthias; Grolimund, Daniel; Mieszczynski, Cyprian

    2013-06-01

    Plutonium uranium mixed oxide (MOX) fuels are currently used in nuclear reactors. The actinides in these fuels need to be analyzed after irradiation for assessing their behaviour with regard to their environment and the coolant. In this work the study of the atomic structure and next-neighbour environment of Am in the (Pu,U)O2 lattice in an irradiated (60 MW d kg-1) MOX sample was performed employing micro-X-ray fluorescence (µ-XRF) and micro-X-ray absorption fine structure (µ-XAFS) spectroscopy. The chemical bonds, valences and stoichiometry of Am (˜0.66 wt%) are determined from the experimental data gained for the irradiated fuel material examined in its peripheral zone (rim) of the fuel. In the irradiated sample Am builds up as Am3+ species within an [AmO8]13- coordination environment (e.g. >90%) and no (<10%) Am(IV) or (V) can be detected in the rim zone. The occurrence of americium dioxide is avoided by the redox buffering activity of the uranium dioxide matrix.

  3. Equipment for hydrogen absorption-desorption cycling characterization of hydride forming materials.

    PubMed

    Meyer, G; Arneodo Larochette, P; Baruj, A; Castro, F J; Lacharmoise, P; Zacur, E; Talagañis, B A

    2007-02-01

    Hydrogen storage materials suffer different degradation processes when they are cycled, forming and decomposing their associated hydride phases. In order to study these processes, we have designed and built an automated apparatus specifically developed for cycling samples of hydride forming materials by changing the external hydrogen pressure. Instead of the standard open configuration involving a high-pressure, high-quality gas bottle and a vacuum pump, the equipment uses another hydride forming material (in our case LaNi5) as a source and sink of hydrogen. The resulting closed-loop configuration eliminates hydrogen waste and ensures that extremely high purity gas is used during the whole experiment, thanks to the purifying properties of the selected hydride as source/sink. Hydrogen pressure is set by changing the source/sink temperature. Cycles can be performed as fast as one cycle every 5 min, a period comparable with typical good hydride forming material kinetics. An example of application of the apparatus is given for 1000 absorption/ desorption cycles on a Mm0.8Ca0.2Ni5 sample. PMID:17578119

  4. One protein, two chromophores: comparative spectroscopic characterization of 6,7-dimethyl-8-ribityllumazine and riboflavin bound to lumazine protein.

    PubMed

    Paulus, Bernd; Illarionov, Boris; Nohr, Daniel; Roellinger, Guillaume; Kacprzak, Sylwia; Fischer, Markus; Weber, Stefan; Bacher, Adelbert; Schleicher, Erik

    2014-11-20

    We investigated the lumazine protein from Photobacterium leiognathi in complex with its biologically active cofactor, 6,7-dimethyl-8-ribityllumazine, at different redox states and compared the results with samples containing a riboflavin cofactor. Using anaerobic photoreduction, we were able to record optical absorption kinetics from both cofactors in similar protein environments. It could be demonstrated that the protein is able to stabilize a neutral ribolumazine radical with ?35% yield. The ribolumazine radical state was further investigated by W-band continuous-wave EPR and X-band pulsed ENDOR spectroscopy. Here, both the principal values of the g-tensor and an almost complete mapping of the proton hyperfine couplings (hfcs) could be obtained. Remarkably, the g-tensor's principal components are similar to those of the respective riboflavin-containing protein; however, the proton hfcs show noticeable differences. Comparing time-resolved optical absorption and fluorescence data from ribolumazine-containing samples, solely fluorescence but no signs of any intermediate radical or a triplet state could be identified. This is in contrast to lumazine protein samples containing the riboflavin cofactor, for which a high yield of the photogenerated triplet state and some excited flavin radical could be detected using time-resolved spectroscopy. These results clearly demonstrate that ribolumazine is a redox-active molecule and could, in principle, be employed as a cofactor in other enzymatic reactions. PMID:25325849

  5. Molecular structure, spectroscopic characterization of (S)-2-Oxopyrrolidin-1-yl Butanamide and ab initio, DFT based quantum chemical calculations

    NASA Astrophysics Data System (ADS)

    Ramya, T.; Gunasekaran, S.; Ramkumaar, G. R.

    2015-10-01

    The experimental and theoretical spectra of (S)-2-Oxopyrrolidin-1-yl Butanamide (S2OPB) were studied. FT-IR and FT-Raman spectra of S2OPB in the solid phase were recorded and analyzed in the range 4000-450 and 5000-50 cm-1 respectively. The structural and spectroscopic analyses of S2OPB were calculated using ab initio Hartree Fock (HF) and density functional theory calculations (B3PW91, B3LYP) with 6-31G(d,p) basis set. A complete vibrational interpretation has been made on the basis of the calculated Potential Energy Distribution (PED). The HF, B3LYP and B3PW91 methods based NMR calculation has been used to assign the 1H NMR and 13C NMR chemical shift of S2OPB. Comparative study on UV-Vis spectral analysis between the experimental and theoretical (B3PW91, B3LYP) methods and the global chemical parameters and local descriptor of reactivity through the Fukui function were performed. Finally the thermodynamic properties of S2OPB were calculated at different temperatures and the corresponding relations between the properties and temperature were also studied.

  6. Spectroscopic characterization of the oxyferrous complex of prostacyclin synthase in solution and in trapped sol–gel matrix

    PubMed Central

    Yeh, Hui-Chun; Hsu, Pei-Yung; Tsai, Ah-Lim; Wang, Lee-Ho

    2010-01-01

    Prostacyclin synthase (PGIS) is a member of the cytochrome P450 family in which the oxyferrous complexes are generally labile in the absence of substrate. At 4 °C, the on-rate constants and off-rate constants of oxygen binding to PGIS in solution are 5.9 × 105 m?1 ·s?1 and 29 s?1, respectively. The oxyferrous complex decays to a ferric form at a rate of 12 s?1. We report, for the first time, a stable oxyferrous complex of PGIS in a transparent sol–gel monolith. The encapsulated ferric PGIS retained the same spectroscopic features as in solution. The binding capabilities of the encapsulated PGIS were demonstrated by spectral changes upon the addition of O-based, N-based and C-based ligands. The peroxidase activity of PGIS in sol–gel was three orders of magnitude slower than that in solution owing to the restricted diffusion of the substrate in sol–gel. The oxyferrous complex in sol–gel was observable for 24 h at room temperature and displayed a much red-shifted Soret peak. Stabilization of the ferrous–carbon monoxide complex in sol–gel was observed as an enrichment of the 450-nm species over the 420-nm species. This result suggests that the sol–gel method may be applied to other P450s to generate a stable intermediate in the di-oxygen activation. PMID:18397321

  7. Some new [(thione)2Au(diamine)]Cl3 complexes: Synthesis, spectroscopic characterization, computational and in vitro cytotoxic studies

    NASA Astrophysics Data System (ADS)

    Al-Maythalony, Bassem A.; Monim-ul-Mehboob, M.; Altaf, Muhammad; Wazeer, Mohammed I. M.; Isab, Anvarhusein A.; Altuwaijri, Saleh; Ahmed, Ayesha; Dhuna, Vikram; Bhatia, Gaurav; Dhuna, Kshitija; Kamboj, Sukhdev Singh

    2013-11-01

    Recent advances in oncology are focused on developing new complexes of gold(III) with various ligands that show augmented anti-proliferative potential and reduced toxicity as compared to cis-platin. In this study, new Au(III) complexes of the type [(thione)2Au(diamine)]Cl3 are reported, where thione = 1,3-imidazolidine-2-thione (Imt), 1,3-Diazinane-2-thione (Diaz) and diamine = 1,2-diaminoethane (en), 1,3-diaminopropane (pn) or 1,4-diaminobutane (bn). The solid state IR as well as 13C and 15N NMR data indicate that Au(III) center is bonded via sulfur of thiocarbonyl Sdbnd Crbond2 site of the thiones and also chelated by the diamines from the trans side of coordinated thiones. Spectroscopic data are evaluated by comparisons with calculated data from the built and optimized structure by GAUSSIAN 09 at the RB3LYP level with LanL2DZ bases set. These new Au(III) complexes based on mixed thione and diamine ligands are very similar to the square planar structure of tetracoordinate [Au(en)2]Cl3complex. In this study, cytotoxicity data for these gold(III) complexes against C6 glioma cell lines are also reported, and the results indicate some complexes have cytotoxicity comparable to cis-platin.

  8. Portuguese tin-glazed earthenware from the 16th century: A spectroscopic characterization of pigments, glazes and pastes

    NASA Astrophysics Data System (ADS)

    Vieira Ferreira, L. F.; Ferreira Machado, I.; Ferraria, A. M.; Casimiro, T. M.; Colomban, Ph.

    2013-11-01

    Sherds representative of the Portuguese faience production of the early-16th century from the "Mata da Machada" kiln and from an archaeological excavation on a small urban site in the city of Aveiro (from late 15th to early 16th century) were studied with the use of non-invasive spectroscopies, namely: ground state diffuse reflectance absorption (GSDR), micro-Raman, Fourier-transform infrared (FT-IR) and proton induced X-ray (PIXE). These results were compared with the ones obtained for two Spanish productions, from Valencia and Seville, both from same period (late 15th century and 16th century), since it is well know that Portugal imported significant quantities of those goods from Spain at that time.

  9. Direct Imaging and Spectroscopic Characterization of Stimulus-Responsive Syuji Fujii,*, Steven P. Armes, Tohru Araki,*, and Harald Ade

    E-print Network

    drug delivery,2 chemical separations,3 sensors,4 catalysis,5 dynamically tunable microlenses,6 templates for synthesis of inorganic nano- particles,7 water purification,8 viscosity modifiers9 for characterizing solvated microgels include dynamic light scat- tering (DLS), 1H NMR, small-angle neutron

  10. Combined UHV/high-pressure catalysis setup for depth-resolved near-surface spectroscopic characterization and catalytic testing of model catalysts

    SciTech Connect

    Mayr, Lukas; Klötzer, Bernhard; Penner, Simon [Institute of Physical Chemistry, University of Innsbruck, Innrain 52a, 6020 Innsbruck (Austria)] [Institute of Physical Chemistry, University of Innsbruck, Innrain 52a, 6020 Innsbruck (Austria); Rameshan, Raffael [Institute of Physical Chemistry, University of Innsbruck, Innrain 52a, 6020 Innsbruck (Austria) [Institute of Physical Chemistry, University of Innsbruck, Innrain 52a, 6020 Innsbruck (Austria); Department of Inorganic Chemistry, Fritz Haber Institute of the Max Planck Society, Faradayweg 4-6, 14195 Berlin (Germany); Rameshan, Christoph [Institute of Physical Chemistry, University of Innsbruck, Innrain 52a, 6020 Innsbruck (Austria) [Institute of Physical Chemistry, University of Innsbruck, Innrain 52a, 6020 Innsbruck (Austria); Institute of Materials Chemistry, Vienna University of Technology, Getreidemarkt 9/BC/01, 1060 Vienna (Austria)

    2014-05-15

    An ultra-high vacuum (UHV) setup for “real” and “inverse” model catalyst preparation, depth-resolved near-surface spectroscopic characterization, and quantification of catalytic activity and selectivity under technologically relevant conditions is described. Due to the all-quartz reactor attached directly to the UHV-chamber, transfer of the catalyst for in situ testing without intermediate contact to the ambient is possible. The design of the UHV-compatible re-circulating batch reactor setup allows the study of reaction kinetics under close to technically relevant catalytic conditions up to 1273 K without contact to metallic surfaces except those of the catalyst itself. With the attached differentially pumped exchangeable evaporators and the quartz-microbalance thickness monitoring equipment, a reproducible, versatile, and standardised sample preparation is possible. For three-dimensional near-surface sample characterization, the system is equipped with a hemispherical analyser for X-ray photoelectron spectroscopy (XPS), electron-beam or X-ray-excited Auger-electron spectroscopy, and low-energy ion scattering measurements. Due the dedicated geometry of the X-ray gun (54.7°, “magic angle”) and the rotatable sample holder, depth analysis by angle-resolved XPS measurements can be performed. Thus, by the combination of characterisation methods with different information depths, a detailed three-dimensional picture of the electronic and geometric structure of the model catalyst can be obtained. To demonstrate the capability of the described system, comparative results for depth-resolved sample characterization and catalytic testing in methanol steam reforming on PdGa and PdZn near-surface intermetallic phases are shown.

  11. Microscopic and Spectroscopic Characterization of Calcified Microorganisms at the Nanometer-Scale in Experimental and Field Samples

    Microsoft Academic Search

    K. Benzerara; T. Yoon; N. Menguy; T. Tyliszczak; G. E. Brown

    2004-01-01

    Calcium phosphates and calcium carbonates are the most prevalent minerals involved in microbial fossilization. Structural characterization of both the organic and mineral components in such samples is, however, usually difficult at the appropriate spatial resolution, i.e., at the submicrometer scale. We have used a combination of Scanning Transmission X-ray microscopy (STXM), a synchrotron-based technique, and High-Resolution Transmission Electron Microscopy (HRTEM)

  12. Spectroscopic characterization of heme iron–nitrosyl species and their role in NO reductase mechanisms in diiron proteins†

    PubMed Central

    Moënne-Loccoz, Pierre

    2010-01-01

    Nitric oxide (NO) plays an important role in cell signalling and in the mammalian immune response to infection. On its own, NO is a relatively inert radical, and when it is used as a signalling molecule, its concentration remains within the picomolar range. However, at infection sites, the NO concentration can reach the micromolar range, and reactions with other radical species and transition metals lead to a broad toxicity. Under aerobic conditions, microorganisms cope with this nitrosative stress by oxidizing NO to nitrate (NO3?). Microbial hemoglobins play an essential role in this NO-detoxifying process. Under anaerobic conditions, detoxification occurs via a 2-electron reduction of two NO molecules to N2O. In many bacteria and archaea, this NO-reductase reaction is catalyzed by diiron proteins. Despite the importance of this reaction in providing microorganisms with a resistance to the mammalian immune response, its mechanism remains ill-defined. Because NO is an obligatory intermediate of the denitrification pathway, respiratory NO reductases also provide resistance to toxic concentrations of NO. This family of enzymes is the focus of this review. Respiratory NO reductases are integral membrane protein complexes that contain a norB subunit evolutionarily related to subunit I of cytochrome c oxidase (CcO). NorB anchors one high-spin heme b3 and one non-heme iron known as FeB, i.e., analogous to CuB in CcO. A second group of diiron proteins with NO-reductase activity is comprised of the large family of soluble flavoprotein A found in strict and facultative anaerobic bacteria and archaea. These soluble detoxifying NO reductases contain a non-heme diiron cluster with a Fe–Fe distance of 3.4 Å and are only briefly mentioned here as a promising field of research. This article describes possible mechanisms of NO reduction to N2O in denitrifying NO-reductase (NOR) proteins and critically reviews recent experimental results. Relevant theoretical model calculations and spectroscopic studies of the NO-reductase reaction in heme/copper terminal oxidases are also overviewed. PMID:17534533

  13. Spectroscopic Characterization of a Multiband Complex Oxide: Insulating and Conducting Cement 12CaO·7Al?O?

    SciTech Connect

    McLeod, John A.; Buling, A.; Kurmaev, Ernst Z.; Sushko, Petr V.; Neumann, N.; Finkelstein, L. D.; Kim, S. W.; Hosono, H.; Moewes, Alexander

    2012-01-13

    Natural 12CaO·7Al?O? (C12A7) is a wide band gap insulator, but conductivity can be realized by introducing oxygen deficiency. Currently, there are two competing models explaining conductivity in oxygen-deficient C12A7, one involving the electron transfer via a “cage conduction band” inside the nominal band gap, the other involving electron hopping along framework lattice sites. To help resolve this debate, we probe insulating and conducting C12A7 with x-ray emission, x-ray absorption, and x-ray photoemission spectroscopy, which provide a full picture of both the valence and conduction band edges in these materials. Thesemeasurements suggest the existence of a narrow conduction band between themain conduction and valence bands common in both conducting and insulating C12A7 and support the theory that free electrons in oxygen-deficient C12A7 occupy the low-energy states of this narrow band. Our measurements are corroborated with density functional theory calculations.

  14. Purification and characterization of troponin C from pike muscle: a comparative spectroscopic study with rabbit skeletal muscle troponin C.

    PubMed

    McCubbin, W D; Oikawa, K; Sykes, B D; Kay, C M

    1982-11-01

    The conformation of troponin C (TN-C) isolated from the white muscle of pike (Esox lucius), in the Ca2+ and metal-free states, was studied by circular dichroism, absorption difference spectroscopy, solvent perturbation difference spectroscopy, intrinsic fluorescence, thiol titration, and 1H nuclear magnetic resonance spectroscopy. In addition, the molecular weight of the protein was determined by sedimentation equilibrium and polyacrylamide gel electrophoresis in the presence of sodium dodecyl sulfate. The composition of the protein was established by amino acid analysis. The resulting data were compared with those from the widely studied analogue isolated from rabbit skeletal muscle. The results indicate near equivalence in many of the properties of pike and rabbit TN-C, such as molecular weight, the magnitude of the calcium-induced conformational change, and urea- or thermal-induced denaturability. However, the pike protein has five additional potential carboxyl groups, and there is good evidence from NMR, solvent perturbation, and fluorescence studies for the presence of a buried tyrosine residue in the apo state. PMID:7150538

  15. Bis(oxalato)dioxovanadate(V) and bis(oxalato)oxoperoxo-vanadate(V) complexes: spectroscopic characterization and biological activity.

    PubMed

    León, Ignacio E; Etcheverry, Susana B; Parajón-Costa, Beatriz S; Baran, Enrique J

    2013-11-01

    Two structurally related vanadium(V) complexes, K3[VO2(C2O4)2] · 3H2O and K3[VO(O2)(C2O4)2] · 1/2H2O, were thoroughly characterized by infrared, Raman, and electronic spectroscopies. The effect of both complexes on the viability of the human MG-63 osteosarcoma cells was tested using the MTT assay. The monoperoxo complex shows a very strong antiproliferative activity (at 100-?M concentration, this complex diminished the cell viability ca. 80 %), whereas the dioxo complex was inactive. PMID:24026441

  16. Epiafzelechin from the root bark of Cassia sieberiana: detection by DART mass spectrometry, spectroscopic characterization, and antioxidant properties.

    PubMed

    Kpegba, Kafui; Agbonon, Amegnona; Petrovic, Ana G; Amouzou, Etchri; Gbeassor, Messanvi; Proni, Gloria; Nesnas, Nasri

    2011-03-25

    The root bark of Cassia sieberiana was analyzed using direct analysis in real time mass spectrometry, and a main flavonoid component with an [M + H](+) mass of 275 was identified. The flavonoid, epiafzelechin, was isolated and fully characterized with the concerted use of NMR spectroscopy, circular dichroism, and optical rotation. Electronic circular dichroism and optical rotation TDDFT calculations were also performed, and their agreement with the experimental results confirmed the enantiomeric identity of the isolated natural product. The antioxidant activity of the compound was also investigated. PMID:21070009

  17. Synthesis and spectroscopic characterization of monometallic molybdenum (VI) complexes derived from bis(2-hydroxy-1-naphthaldehyde)succinoyldihydrazone

    NASA Astrophysics Data System (ADS)

    Kumar, A.; Koch, A.; Borthakur, R.; Chakraborty, M.; De, A. K.; Phukan, A.; Bez, G.; Lal, R. A.

    2014-04-01

    Molybdenum complexes [(?2-O)2(MoO2)2(H4nsh)2]·2A·2C2H5OH (where A = O (1), py (2), 2-pic (3), 4-pic (4) and 5-pic (5)) have been synthesized in absolute ethanol from bis(2-hydroxy-1-naphthaldehyde)succinoyldihydrazone. The composition of the complexes has been deduced on the basis of the data obtained from elemental analyses and thermo-analytical data. All complexes are non-electrolyte in DMSO solution as evident from low value of molar conductance in the range 2.2-3.3 ?-1 cm2 mol-1. The complexes are diamagnetic and have molybdenum in +6 oxidation state. The dihydrazone coordinates to the molybdenum centre as a neutral bidentate ligand through two azomethine nitrogen atoms only. This is revealed by the downfield shift of ?(sbnd CHdbnd Nsbnd ) signals by 0.16-0.44 ppm as compared to that in the free dihydrazone. The carbon atoms closer to azomethine nitrogen atoms downfield shift confirming the coordination of azomethine nitrogen atoms. The ?(Cdbnd N) stretching vibrations also shift to lower frequency in the IR spectra of the complexes. Apart from the intra ligand bands, the complexes show a new absorption band in the region 421-423 nm attributed to charge-transfer transition from dihydrazone ligand to molybdenum centre. The dihydrazone is present in anti-cis conformation in all of the complexes. The complexes develop a new kind of intramolecular hydrogen bonding between naphtholic sbnd OH groups of coordinated dihydrazone.

  18. Thermal analysis and vibrational spectroscopic characterization of the boro silicate mineral datolite - CaBSiO4(OH).

    PubMed

    Frost, Ray L; Xi, Yunfei; Scholz, Ricardo; Lima, Rosa Malena Fernandes; Horta, Laura Frota Campos; Lopez, Andres

    2013-11-01

    The objective of this work is to determine the thermal stability and vibrational spectra of datolite CaBSiO4(OH) and relate these properties to the structure of the mineral. The thermal analysis of datolite shows a mass loss of 5.83% over a 700-775°C temperature range. This mass loss corresponds to 1 water (H2O) molecules pfu. A quantitative chemical analysis using electron probe was undertaken. The Raman spectrum of datolite is characterized by bands at 917 and 1077cm(-1) assigned to the symmetric stretching modes of BO and SiO tetrahedra. A very intense Raman band is observed at 3498cm(-1) assigned to the stretching vibration of the OH units in the structure of datolite. BOH out-of-plane vibrations are characterized by the infrared band at 782cm(-1). The vibrational spectra are based upon the structure of datolite based on sheets of four- and eight-membered rings of alternating SiO4 and BO3(OH) tetrahedra with the sheets bonded together by calcium atoms. PMID:23867640

  19. Spectroscopic characterization of polyaniline formed by using copper(II) in homogeneous and MCM-41 molecular sieve media.

    PubMed

    Izumi, Celly M S; Constantino, Vera R L; Temperini, Marcia L A

    2005-12-01

    This work emphasizes the important role of the synthetic parameters in the structure of the polymeric material obtained in the aniline polymerization. The polymers formed by the oxidative polymerization of aniline by copper(II) ions in acidic aqueous solution, acetonitrile/water medium, and also copper(II) acetate complex encapsulated into MCM-41 molecular sieve were characterized by resonance Raman spectroscopy using three exciting laser lines and other techniques such as UV-vis, FTIR, and XANES (Nitrogen K edge). Additionally the products were investigated by thermogravimetric analysis and powder X-ray diffraction. When Cu(II) ions in acidic aqueous medium are used, emeraldine salt (ES-PANI) is formed through the usual head-to-tail polymerization mechanism, while in acetonitrile/water medium a polymer is observed having mainly phenazine-like rings, quinonediimine, and/or phenylenediamine segments in the chains, suggesting that a distinct mechanism is operating. The average molecular weights of the free polymers synthesized in water and in acetronile/water were, respectively, ca. 37 300 and 16 900 Da. The encapsulated polymer synthesized in Cu(II)-MCM-41 is a polymeric mixture of (i) ES-PANI and (ii) the polymer obtained when this metal cation was used as oxidant in acetonitrile/water medium. All the characterization data were compared to those ones obtained for standard free polyaniline and also for the encapsulated polymer into mesoporous MCM-41 formed by using persulfate in acidic aqueous medium as oxidant. PMID:16853880

  20. Surface spectroscopic characterization of hydrodesulfurization catalysts, molybdenum-alumina catalysts, and Ni-W/Al/sub 2/O/sub 3/ catalysts, and molybdenum-titania catalysts

    SciTech Connect

    Li, C.P.

    1984-01-01

    X-ray photoelectron spectroscopy (ESCA), ion scattering spectroscopy (ISS), and x-ray diffraction have been used to characterize a series of sulfided and reduced MoO/sub 3//..gamma..-Al/sub 2/O/sub 3/ catalysts. ESCA and ISS have identified the presence of both MoS/sub 2/ and Mo(V) on a sulfided MoO/sub 3//..gamma..-Al/sub 2/O/sub 3/ catalyst. The octahedrally and tetrahedrally coordinated molybdenum on an oxidic MoO/sub 3//..gamma..-Al/sub 2/O/sub 3/ precursor catalyst show different sulfidation behavior. The distribution of nickel species on Ni/Al/sub 2/O/sub 3/ and Ni-W/Al/sub 2/O/sub 3/ catalysts have been studied using ESCA and ISS. Increases in the peak width asymmetry of an Ni 2p photoelectron spectra were observed for Ni/Al/sub 2/O/sub 3/ when the nickel content was increased. These changes were minimized when the tungsten concentration was increased from 15 to 24% WO/sub 3/. The surface structure of MoO/sub 3//TiO/sub 2/ catalysts have been investigated using several spectroscopic techniques: ESCA, ISS, x-ray diffraction, IR and Raman spectroscopy. Up to the concentration of 10wt% MoO/sub 3/, two types of molybdenum-titania surface interaction species are produced in roughly a 2:1 proportion.

  1. ZnO nanocrystals on SiO{sub 2}/Si surfaces thermally cleaned in ultrahigh vacuum and characterized using spectroscopic photoemission and low energy electron microscopy

    SciTech Connect

    Ericsson, Leif K. E.; Magnusson, Kjell O.; Zakharov, Alexei A. [Department of Physics, Karlstad University, Karlstad S-651 88 (Sweden); Maxlab, Lund University, Lund S-221 00 (Sweden)

    2010-05-15

    Thermal cleaning in ultrahigh vacuum of ZnO nanocrystals distributed on SiO{sub 2}/Si surfaces has been studied using spectroscopic photoemission and low energy electron microscopy (SPELEEM). This study thus concern weakly bound ZnO nanocrystals covering only 5%-10% of the substrate. Chemical properties, crystallinity, and distribution of nanocrystals are used to correlate images acquired with the different techniques showing excellent correspondence. The nanocrystals are shown to be clean enough after thermal cleaning at 650 deg. C to be imaged by LEEM and x-ray PEEM as well as chemically analyzed by site selective x-ray photoelectron spectroscopy ({mu}-XPS). {mu}-XPS shows a sharp Zn 3d peak and resolve differences in O 1s states in oxides. The strong LEEM reflections together with the obtained chemical information indicates that the ZnO nanocrystals were thermally cleaned, but do not indicate any decomposition of the nanocrystals. {mu}-XPS was also used to determine the thickness of SiO{sub 2} on Si. This article is the first to our knowledge where the versatile technique SPELEEM has been used to characterize ZnO nanocrystals.

  2. Cinoxacin complexes with divalent metal ions. Spectroscopic characterization. Crystal structure of a new dinuclear Cd(II) complex having two chelate-bridging carboxylate groups. Antibacterial studies.

    PubMed

    Ruíz, M; Perelló, L; Server-Carrió, J; Ortiz, R; García-Granda, S; Díaz, M R; Cantón, E

    1998-03-01

    Several cinoxacin (HCx) complexes with divalent metal ions have been prepared and characterized by spectroscopic techniques. The crystal structure of [Cd2(Cx)4(H2O)2].10H2O has been determined by X-ray diffraction. The complex is triclinic, space group P1 with unit-cell dimensions: a = 10.412(2), b = 11.119(2), c = 13.143(6)A, chi== 76.78(4) degrees, beta = 74.59(3) degrees, gamma = 77.12(3) degrees, V = 1406.0(8) A3. In this complex each cadmium atom is heptacoordinated: the metal environment is formed by two Oketo and two Ocarbox atoms from two different cinoxacinate monoanions, two carboxylate oxygen atoms from a third cinoxacinate ligand and by one water oxygen atom on the seventh position. Two of the cinoxacinate ions act as tridentate chelate and bridging ligands and the other one as a bidentate chelate ligand. In the bridging monoanions the carboxylate group is behaving as a chelate ligand. All the complexes were screened for their activity against several bacteria, showing activity similar to that of cinoxacin. Additionally, the number of bacteria killed after 3 h of incubation with cinoxacin, [Cu(Cx)2].2H2O and [Co(Cx)3]Na.10H2O complexes was determined against E. coli ATCC 25922; the copper compound presents paradoxical effect which has been described and related to the mechanism of action of quinolones. PMID:9654749

  3. Spectroscopic detection

    DOEpatents

    Woskov, Paul P. (Bedford, MA); Hadidi, Kamal (Cambridge, MA)

    2003-01-01

    In embodiments, spectroscopic monitor monitors modulated light signals to detect low levels of contaminants and other compounds in the presence of background interference. The monitor uses a spectrometer that includes a transmissive modulator capable of causing different frequency ranges to move onto and off of the detector. The different ranges can include those with the desired signal and those selected to subtract background contributions from those with the desired signal. Embodiments of the system are particularly useful for monitoring metal concentrations in combustion effluent.

  4. Fused-ring derivatives of quinoxalines: spectroscopic characterization and photoinduced processes investigated by EPR spin trapping technique.

    PubMed

    Barbieriková, Zuzana; Dvoranová, Dana; Bella, Maroš; Milata, Viktor; Czímerová, Adriana; Brezová, Vlasta

    2014-01-01

    10-Ethyl-7-oxo-7,10-dihydropyrido[2,3-f]quinoxaline derivatives, synthesized as promising biologically/photobiologically active compounds were characterized by UV/vis, FT-IR and fluorescent spectroscopy. Photoinduced processes of these derivatives were studied by EPR spectroscopy, monitoring in situ the generation of reactive intermediates upon UVA (?max=365 nm) irradiation. The formation of reactive oxygen species and further oxygen- and carbon-centered radical intermediates was detected and possible reaction routes were suggested. To quantify the investigated processes, the quantum yields of the superoxide radical anion spin-adduct and 4-oxo-2,2,6,6-tetramethylpiperidine N-oxyl generation were determined, reflecting the activation of molecular oxygen by the excited state of the quinoxaline derivative. PMID:25120058

  5. Synthesis, spectroscopic characterization and computational studies of 2-(4-bromophenyl)-2-oxoethyl 3-methylbenzoate by density functional theory

    NASA Astrophysics Data System (ADS)

    Diwaker; Chidan Kumar, C. S.; Kumar, Ashish; Chandraju, Siddegowda; Fun, Hoong-Kun; Quah, Ching Kheng

    2015-07-01

    The title compound, 2-(4-bromophenyl)-2-oxoethyl 3-methylbenzoate, has been synthesized and characterized using experimental FTIR, 1H and 13C NMR, single crystal XRD and various theoretical methods (FTIR, NMR, electronic and band gap studies). The compound crystallizes in monoclinic space group P21/c with a = 8.176 (2) Å, b = 7.82 (2) Å, c = 2.952 (6) Å, ? = 91.330 (4)° and Z = 4. The initial coordinate geometry obtained by XRD is further used to obtain the optimized ground state geometry of the investigated compound using HF and DFT/B3LYP/6-311++G(2d,2p) level of theory. Geometrical parameters, vibrational frequencies, (GIAO) 1H and 13C NMR chemical shifts have been calculated theoretically using the optimized ground state geometry. Apart from this, density of states of different atoms, total density of states and band gap studies have also been successfully studied using theoretical models.

  6. {sup 13}C-METHYL FORMATE: OBSERVATIONS OF A SAMPLE OF HIGH-MASS STAR-FORMING REGIONS INCLUDING ORION-KL AND SPECTROSCOPIC CHARACTERIZATION

    SciTech Connect

    Favre, Cécile; Bergin, Edwin A.; Crockett, Nathan R.; Neill, Justin L. [Department of Astronomy, University of Michigan, 500 Church Street, Ann Arbor, MI 48109 (United States); Carvajal, Miguel [Dpto. Física Aplicada, Unidad Asociada CSIC, Facultad de Ciencias Experimentales, Universidad de Huelva, E-21071 Huelva (Spain); Field, David [Department of Physics and Astronomy, University of Aarhus, Ny Munkegade 120, DK-8000 Aarhus C (Denmark); Jørgensen, Jes K.; Bisschop, Suzanne E. [Centre for Star and Planet Formation, Niels Bohr Institute, University of Copenhagen, Juliane Maries Vej 30, DK-2100 Copenhagen Ø (Denmark); Brouillet, Nathalie; Despois, Didier; Baudry, Alain [Univ. Bordeaux, LAB, UMR 5804, F-33270, Floirac (France); Kleiner, Isabelle [Laboratoire Interuniversitaire des Systèmes Atmosphériques (LISA), CNRS, UMR 7583, Université de Paris-Est et Paris Diderot, 61, Av. du Général de Gaulle, F-94010 Créteil Cedex (France); Margulès, Laurent; Huet, Thérèse R.; Demaison, Jean, E-mail: cfavre@umich.edu, E-mail: miguel.carvajal@dfa.uhu.es [Laboratoire de Physique des Lasers, Atomes et Molécules, UMR CNRS 8523, Université Lille I, F-59655 Villeneuve d'Ascq Cedex (France)

    2015-01-01

    We have surveyed a sample of massive star-forming regions located over a range of distances from the Galactic center for methyl formate, HCOOCH{sub 3}, and its isotopologues H{sup 13}COOCH{sub 3} and HCOO{sup 13}CH{sub 3}. The observations were carried out with the APEX telescope in the frequency range 283.4-287.4 GHz. Based on the APEX observations, we report tentative detections of the {sup 13}C-methyl formate isotopologue HCOO{sup 13}CH{sub 3} toward the following four massive star-forming regions: Sgr B2(N-LMH), NGC 6334 IRS 1, W51 e2, and G19.61-0.23. In addition, we have used the 1 mm ALMA science verification observations of Orion-KL and confirm the detection of the {sup 13}C-methyl formate species in Orion-KL and image its spatial distribution. Our analysis shows that the {sup 12}C/{sup 13}C isotope ratio in methyl formate toward the Orion-KL Compact Ridge and Hot Core-SW components (68.4 ± 10.1 and 71.4 ± 7.8, respectively) are, for both the {sup 13}C-methyl formate isotopologues, commensurate with the average {sup 12}C/{sup 13}C ratio of CO derived toward Orion-KL. Likewise, regarding the other sources, our results are consistent with the {sup 12}C/{sup 13}C in CO. We also report the spectroscopic characterization, which includes a complete partition function, of the complex H{sup 13}COOCH{sub 3} and HCOO{sup 13}CH{sub 3} species. New spectroscopic data for both isotopomers H{sup 13}COOCH{sub 3} and HCOO{sup 13}CH{sub 3}, presented in this study, have made it possible to measure this fundamentally important isotope ratio in a large organic molecule for the first time.

  7. Depth Profile Characterization of Spin-Coated Poly(3,4-ethylenedioxythiophene):Poly(styrene sulfonic acid) Films for Thin-Film Solar Cells during Argon Plasma Etching by Spectroscopic Ellipsometry

    Microsoft Academic Search

    Tomohisa Ino; Tatsuya Hayashi; Keiji Ueno; Hajime Shirai

    2011-01-01

    Depth profiles of the optical constants, carrier mobility, and carrier density of spin-coated poly(3,4-ethylenedioxythiophene):poly(styrene sulfonic acid) (PEDOT:PSS) films were investigated by real-time characterization by spectroscopic ellipsometry (SE) during argon plasma etching at atmospheric pressure. Spectral analysis revealed that homogeneous etching occurred within 10--15 nm of the top surface, followed by the appearance of a conductive PEDOT phase and surface roughening,

  8. Structural Characterization of Fe/Pd/Fe/GaAs(001) Thin Films by X-Ray Absorption Fine Structure Spectroscopy

    NASA Astrophysics Data System (ADS)

    Budnik, Petr S.

    The small lateral dimensions of spintronic devices and high density memory bits require the employment of magnetic ultrathin metallic film structures. Understanding the structure of such films is a critical component of developing the correct interpretation of their magnetic behaviour. The Molecular Beam Epitaxy facility, MBE-1, was developed for use on the undulator beamline of the Pacific Northwest Consortium Collaborative Access Team at the Advanced Photon Source to permit in situ epitaxial growth of metal films and their structural characterization by synchrotron radiation techniques. In this thesis it was used to characterize the trilayer system iron/palladium/iron on GaAs(001). Three categories of samples were prepared and examined in situ. Iron films were deposited on the 4x6-reconstructed surface of GaAs(001) with thicknesses ranging from 0.5 to 38.5 monolayers. Palladium films were deposited on iron as follows: 1 monolayer palladium on 9 monolayers of iron, and 3.5 and 7 monolayers palladium on 38.5 monolayers of iron. Finally, iron films 4 and 10 monolayers thick were deposited on 7 monolayers of palladium on 38.5 monolayers of iron. The polarization-dependent X-ray absorption fine structure (XAFS) technique in total reflection mode was employed to examine the samples and compare in-plane to out-of-plane structure in these films. This technique allows extracting identities of nearest neighbours, nearest neighbour radial distances, coordination numbers, and mean square relative displacement to characterize the probed system. Iron and palladium K-edge spectra were obtained both above and below the critical angle for total reflection. Near 4 monolayers for iron films on GaAs(001), a transition from island to layer-by-layer growth modes is accompanied by the observation of a body-centered tetragonal structure with a c/a ratio of 1.030(8), with no thickness dependence observed up to 38.5 monolayers. The intermediate palladium layer shows a face-centered tetragonal structure. Alloying at the interface with the underlying iron is restricted to a depth of 0.5-1.0 monolayers. The upper layer of iron shows tetragonal distortion similar to the layers of iron grown on GaAs(001)-4x6. There is also evidence of alloy formation at the interface involving the underlying palladium with the thickness of the alloy region being 1.5-2.0 monolayers.

  9. Polyoxometalates Functionalized by Bisphosphonate Ligands: Synthesis, Structural, Magnetic and Spectroscopic Characterizations and Activity on Tumor Cell Lines

    PubMed Central

    Moll, Hani El; Zhu, Wei; Oldfield, Eric; Albelo, L. Marleny Rodriguez; Mialane, Pierre; Marrot, Jérôme; Vila, Neus; Mbomekallé, Israel Martyr; Rivière, Eric; Duboc, Carole; Dolbecq, Anne

    2012-01-01

    We report the synthesis and characterization of eight new Mo, W, or V-containing polyoxometalate (POM) bisphosphonate complexes with metal nuclearities ranging from 1 to 6. The compounds were synthesized in water by treating MoVI, WVI, VIV or VV precursors with biologically active bisphosphonates H2O3PCR(OH)PO3H2 (R = C3H6NH2, Ale; R = CH2S(CH3)2, Sul and R = C4H5N2, Zol, where Ale=alendronate, Sul=(2-Hydroxy-2,2-bis-phosphono-ethyl)-dimethyl-sulfonium and Zol=zoledronate.). Mo6(Sul)2 and Mo6(Zol)2 contain two trinuclear MoVI cores which can rotate around a central oxo group while Mo(Ale)2 and W(Ale)2 are mononuclear species. In V5(Ale)2 and V5(Zol)2 a central VIV ion is surrounded by two VV dimers bound to bisphosphonate ligands. V6(Ale)4 can be viewed as the condensation of one V5(Ale)2 with one additional VIV ion and two Ale ligands, while V3(Zol)3 is a triangular VIV POM. These new POM bisphosphonates complexes were all characterized by single-crystal X-ray diffraction. The stability of the Mo and W POMs was studied by 31P NMR spectroscopy and showed that all compounds except the mononuclear Mo(Ale)2 and W(Ale)2 were stable in solution. EPR measurements performed on the vanadium derivatives confirmed the oxidation state of the V ions and evidenced their stability in aqueous solution. Electrochemical studies on V5(Ale)2 and V5(Zol)2 showed reduction of VV to VIV and magnetic susceptibility investigations on V3(Zol)3 enabled a detailed analysis of the magnetic interactions. The presence of zoledronate or vanadium correlated with the most potent activity (IC50~1–5 ?M) against three human tumor cell lines. PMID:22725619

  10. Mono- and dinuclear manganese(III) complexes showing efficient catechol oxidase activity: syntheses, characterization and spectroscopic studies.

    PubMed

    Banu, Kazi Sabnam; Chattopadhyay, Tanmay; Banerjee, Arpita; Mukherjee, Madhuparna; Bhattacharya, Santanu; Patra, Goutam Kumar; Zangrando, Ennio; Das, Debasis

    2009-10-28

    Four side-off compartmental ligands L1-L4 [L1 = N,N'-ethylenebis(3-formyl-5-methyl-salicylaldimine), L2 = N,N'-1-methylethylenebis(3-formyl-5-methylsalicylaldimine), L3 = N,N'-1,1-dimethylethylenebis(3-formyl-5-methylsalicylaldimine) and L4= N,N'-cyclohexenebis(3-formyl-5-methylsalicylaldimine)] having two binding sites, N2O2 and O4, have been chosen to synthesize mononuclear and dinuclear manganese(III) complexes with the aim to study their catecholase activity using 3,5-di-tert-butylcatechol (3,5-DTBC) as substrate in the presence of molecular oxygen. In all cases only mononuclear manganese complexes (1-4) were obtained, with manganese coordination taking place at the N2O2 binding site only, irrespective of the amount of manganese salt used. All these complexes have been characterized by routine physico-chemical techniques. Complex MnL2Cl.4H2O (2) has further been structurally characterized by X-ray single crystal structure analysis. Four dinuclear manganese complexes, 5-8, were obtained after condensing the two pending formyl groups on each ligand (L1-L4) with aniline followed by reaction with MnCl2 to put the second Mn atom onto another N2O2 site. The catalytic activity of all complexes 1-8 has been investigated following the oxidation of 3,5-di-tert-butylcatechol (3,5-DTBC) to 3,5-di-tert-butylbenzoquinone (3,5-DTBQ) with molecular oxygen in two different solvents, methanol and acetonitrile. The study reveals that the catalytic activity is influenced by the solvent and to a significant extent by the backbone of the diamine and the behavior seems to be related mainly to steric rather than electronic factors. Experimental data suggest that a correlation, the lower the E(1/2) value the higher the catalytic activity, can be drawn between E(1/2) and Vmax of the complexes in a particular solvent. The EPR measurements suggest that the catalytic property of the complexes is related to the metal center(s) participation rather than to a radical mechanism. PMID:19809751

  11. Spectroscopic Infrared Ellipsometry

    E-print Network

    Eindhoven, Technische Universiteit

    Spectroscopic Infrared Ellipsometry: Components, Calibration, and Application #12;CIP-DATA KONINKLIJKE BIBLIOTHEEK, DEN HAAG Boer, Johannes Henricus Wilhelmus Gerardus den Spectroscopic Infrared in Dutch. ISBN 90 386 0017 8 Subject headings: spectroscopy ellipsometry infrared. #12;Spectroscopic

  12. EPR Spectroscopic and Computational Characterization of the Hydroxyethylidene-Thiamine Pyrophosphate Radical Intermediate of Pyruvate:Ferredoxin Oxidoreductase †

    PubMed Central

    Mansoorabadi, Steven O.; Seravalli, Javier; Furdui, Cristina; Krymov, Vladimir; Gerfen, Gary J.; Begley, Tadhg P.; Melnick, Jonathan; Ragsdale, Stephen W.; Reed, George H.

    2008-01-01

    The radical intermediate of pyruvate:ferredoxin oxidoreductase (PFOR) from Moorella thermoacetica was characterized using electron paramagnetic resonance (EPR) spectroscopy at X-band and D-band microwave frequencies. EPR spectra obtained with various combinations of isotopically labeled substrate (pyruvate) and coenzyme (thiamine pyrophosphate (TPP)), were analyzed by spectral simulations. Parameters obtained from the simulations were compared with those predicted from electronic structure calculations on various radical structures. The g-values and 14N/15N-hyperfine splittings obtained from the spectra are consistent with a planar, hydroxyethylidene-thiamine pyrophosphate (HE-TPP) ?-radical, in which spin is delocalized onto the thiazolium sulfur and nitrogen atoms. The 1H-hyperfine splittings from the methyl group of pyruvate and the 13C-hyperfine splittings from C2 of both pyruvate and TPP are consistent with a model in which the pyruvate-derived oxygen atom of the HE-TPP radical forms a hydrogen bond. The hyperfine splitting constants and g-values are not compatible with those predicted for a non-planar, ?/n-type cation radical. PMID:16752902

  13. [Three-dimensional excitation emission matrix fluorescence spectroscopic characterization of loosely bound and tightly bound extracellular polymeric substances of sludge].

    PubMed

    Ouyang, Er-ming; Wang, Wei; Long, Neng; Li, Huai

    2009-05-01

    Three-dimensional excitation emission matrix fluorescence spectroscopy (3DEEM)was applied to characterize the loosely bound extracellular polymeric substances (LB-EPS) and tightly bound extracellular polymeric substances (TB-EPS) extracted from aerobic sludge in wastewater treatment. The results showed that three fluorescence peaks were identified in threedimensional excitation emission matrix fluorescence spectra of the LB-REPS and TB-EPS: peak B (lamda ex/ lamda em = 270-280 nm/345-360 nm), peak C (lamda ex/ lamda em = 330-340 nm/410-430 nm)and peak D (lamda ex/ lamda em = 390 nm/450-470 nm). The peak B was attributed to the protein-like fluorophores, peak C to the visible fulvic-like fluorophore and peak D to the humic-like fluorophore. Results of the peak intensity showed that the major component of the LB-EPS and TB-EPS is protein-like organic matter, then followed by (from high to low): fulvic-like organic matter and humic-like organic matter. The effects of both pH and concentration were significant to the 3DEEMs of LB-EPS and TB-EPS, but the degree is not the same. LB-EPS has the particular chemical structures which are different from the TB-EPS. PMID:19650479

  14. [Three-dimensional excitation emission matrix fluorescence spectroscopic characterization of the complexation between mercury (II) and dissolved organic matter].

    PubMed

    Fu, Ping-qing; Liu, Cong-qiang; Wu, Feng-chang

    2004-11-01

    With the development of fluorescence technique, three-dimensional excitation emission matrix fluorescence spectroscopy (3DEEM) was widely applied to characterize the nature of dissolved organic matter (DOM) in natural waters since the last decade. 3DEEM and fluorescence quenching titration were used to study the interaction between Hg(II) and DOM. The results show that a general decrease in intensity for individual peak A, B and C was found as concentrations of Hg(II) increased. pH is the main parameter that strongly influences the Hg(II)-DOM complexation. The addition of Cl- ion to the Hg(II)-DOM system caused an increase in fluorescence intensity. The results also show that the addition of Ca(II) solution strongly enhanced the fluorescence intensity for humic-like fluorescence, while the protein-like fluorescence only slightly enhanced. On the contrary, no fluorescence enhancement was found in the Hg(II)-DOM system after the addition of Mg(II) ion. A decrease in fluorescence emission intensity was found after the addition of Cu(II) ion to the Hg(II)-DOM solution. PMID:15759899

  15. EPR spectroscopic and computational characterization of the hydroxyethylidene-thiamine pyrophosphate radical intermediate of pyruvate:ferredoxin oxidoreductase.

    PubMed

    Mansoorabadi, Steven O; Seravalli, Javier; Furdui, Cristina; Krymov, Vladimir; Gerfen, Gary J; Begley, Tadhg P; Melnick, Jonathan; Ragsdale, Stephen W; Reed, George H

    2006-06-13

    The radical intermediate of pyruvate:ferredoxin oxidoreductase (PFOR) from Moorella thermoacetica was characterized using electron paramagnetic resonance (EPR) spectroscopy at X-band and D-band microwave frequencies. EPR spectra, obtained with various combinations of isotopically labeled substrate (pyruvate) and coenzyme (thiamine pyrophosphate (TPP)), were analyzed by spectral simulations. Parameters obtained from the simulations were compared with those predicted from electronic structure calculations on various radical structures. The g-values and 14N/15N-hyperfine splittings obtained from the spectra are consistent with a planar, hydroxyethylidene-thiamine pyrophosphate (HE-TPP) pi-radical, in which spin is delocalized onto the thiazolium sulfur and nitrogen atoms. The 1H-hyperfine splittings from the methyl group of pyruvate and the 13C-hyperfine splittings from C2 of both pyruvate and TPP are consistent with a model in which the pyruvate-derived oxygen atom of the HE-TPP radical forms a hydrogen bond. The hyperfine splitting constants and g-values are not compatible with those predicted for a nonplanar, sigma/n-type cation radical. PMID:16752902

  16. Spectroscopic characterization of X-ray emitting young stars associated with the Sh 2-296 nebula

    E-print Network

    Fernandes, B; Montmerle, T; Rojas, G

    2015-01-01

    We studied a sample of stars associated with the Sh 2-296 nebula, part of the reflection nebulae complex in the region of Canis Major (CMa R1). Our sample corresponds to optical counterparts of X-ray sources detected from observations with the XMM-Newton satellite, which revealed dozens of possible low-mass young stars not yet known in this region. A sample of 58 young star candidates were selected based on optical spectral features, mainly H{\\alpha} and lithium lines, observed with multi-objects spectroscopy performed by the Gemini South telescope. Among the candidates, we find 41 confirmed T Tauri and 15 very likely young stars. Based on the H{\\alpha} emission, the T Tauri stars were distinguished between classical (17%) and weak-lined (83%), but no significant difference was found in the age and mass distribution of these two classes. The characterization of the sample was complemented by near- and mid-infrared data, providing an estimate of ages and masses from the comparison with pre-main-sequence evolut...

  17. Comparative studies, synthesis, spectroscopic and characterization of N-methylisatin-3-Girard's T and P hydrazone complexes

    NASA Astrophysics Data System (ADS)

    Azhari, Shaker J.; Salah, Sabah; Farag, Rabei S.; Mostafa, Mohsen M.

    2015-02-01

    Different types of complexes derived from the reactions of N-methylisatin Girard's T hydrazone, N,N,N-trimethyl-2-[(2z)-2-(1-methyl-2-oxo-1,2-dihydro-3H-indole-3-ylidene) hydrazino]-2-oxo-ethan ammonium chloride (MIGT) and N-methylisatin Girard's P hydrazone, 1-{2-(2z)-2-[(1-methyl-2-oxo-1,2-dihydro-3H-indole-3-ylidene) hydrazino]-2-oxoethyl}pyridinium chloride (MIGP) with Fe3+, Al3+, Sb3+ and Sn2+ salts were synthesized. The isolated complexes were characterized by elemental analyses, molar conductivities, spectral (IR, UV-Vis., 1H NMR, mass), magnetic moments and thermal measurements. The values of conductance suggest that the complexes are conducting in polar solvents (EtOH, H2O and DMF). The IR spectra suggest that the ligands coordinate in a bidentate and/or tridentate manner via the carbonyl groups of both N-methylisatin and Girard's T and/or P and the (Cdbnd N) group. The solvents inside and outside the coordination sphere were determined by weight loss and TGA methods. The octahedral geometry of the complexes is confirmed using spectral, magnetic and DFT method from DMOL3 calculations. The ligands and their metal complexes were tested against different strains of bacteria and fungi.

  18. Synthesis and characterization of CdS doped TiO{sub 2} nanocrystalline powder: A spectroscopic study

    SciTech Connect

    Thakur, Priya [Department of Chemistry, University of Pune, Pune 411007 (India)] [Department of Chemistry, University of Pune, Pune 411007 (India); Chadha, Ridhima; Biswas, Nandita; Sarkar, Sisir K.; Mukherjee, Tulsi [Radiation and Photochemistry Division, Bhabha Atomic Research Centre, Mumbai 400085 (India)] [Radiation and Photochemistry Division, Bhabha Atomic Research Centre, Mumbai 400085 (India); Joshi, Satyawati S., E-mail: ssjoshi@chem.unipune.ac.in [Department of Chemistry, University of Pune, Pune 411007 (India); Kapoor, Sudhir, E-mail: sudhirk@barc.gov.in [Radiation and Photochemistry Division, Bhabha Atomic Research Centre, Mumbai 400085 (India)] [Radiation and Photochemistry Division, Bhabha Atomic Research Centre, Mumbai 400085 (India)

    2012-07-15

    Graphical abstract: Raman spectra of TiO{sub 2} sample doped with 50% CdS and annealed at 600 °C. Highlights: ? Transformation from anatase to rutile is prohibited in doped TiO{sub 2}. ? FTIR study indicates that TiO{sub 2} lattice has been modified in the presence of CdS. ? Raman spectroscopy is found to be more sensitive as compared to XRD. -- Abstract: This report aimed to study the effect of CdS doping in TiO{sub 2} on the phase transformation of TiO{sub 2} from anatase to rutile using X-ray diffraction (XRD) and Raman spectroscopy. CdS-doped TiO{sub 2} nanocomposites have been prepared and characterized using Fourier transform infrared spectroscopy (FTIR) and transmission electron microscopy (TEM). We have observed that contrary to bare TiO{sub 2}, phase transformation of TiO{sub 2} from anatase to rutile is hindered when doped with CdS at high temperature. Raman spectroscopy is found to be more sensitive for detection of the surface of TiO{sub 2} as compared to XRD.

  19. Spectroscopic planetary detection

    NASA Technical Reports Server (NTRS)

    Deming, Drake

    1991-01-01

    One of the most promising methods for the detection of extra-solar planets is the spectroscopic method, where a small Doppler shift (approx. 10 meter/sec) in the spectrum of the parent star reveals the presence of planetary companions. However, solar type stars may show spurious Doppler shifts due to surface activity. If these effects are periodic, as is the solar activity cycle, then they may masquerade as planetary companions. The goal of this study was to determine whether the solar cycle affects the Doppler stability of integrated sunlight. Observations of integrated sunlight were made in the near infrared (approx. 2 micron), using the Kitt Peak McMath Fourier transform spectrometer, with a N2O gas absorption cell for calibration. An accuracy of approx. 5 meter/sec was achieved.

  20. Analytical studies on the charge transfer complexes of loperamide hydrochloride and trimebutine drugs. Spectroscopic and thermal characterization of CT complexes.

    PubMed

    Elqudaby, Hoda M; Mohamed, Gehad G; El-Din, Ghada M G

    2014-08-14

    Charge transfer complexes of loperamide hydrochloride (LOP.HCl) and trimebutine (TB) drugs as electron donor with 2,3-dichloro-5,6-dicyano-p-benzoquinone (DDQ), tetracyanoethylene (TCNE) and 7,7,8,8-tetracyanoquinodimethane (TCNQ) as ?-acceptors in acetonitrile were investigated spectrophotometrically to determine the cited drugs in pure and dosage forms. The reaction gives highly coloured complex species which are measured spectrophotometrically at 460, 415 and 842nm in case of LOP.HCl and at 455, 414 and 842nm in case of TB using DDQ, TCNE and TCNQ reagents, respectively. The optimum experimental conditions have been studied carefully and optimized. Beer's law was obeyed over the concentration ranges of 47.70-381.6, 21.50-150.5 and 10.00-100.0?gmL(-1) for LOP.HCl and 37.85-264.9, 38.75-310.0 and 7.75-155.0?gmL(-1) for TB using DDQ, TCNE and TCNQ reagents, respectively. Sandell sensitivity, standard deviation, relative standard deviation, limit of detection and quantification were calculated. The obtained data refer to high accuracy and precision of the proposed method. These results are also confirmed by inter and intra-day precision with percent recovery of 99.18-101.1% and 99.32-101.4% in case of LOP.HCl and 98.00-102.0% and 97.50-101.4% in case of TB using DDQ, TCNE and TCNQ reagents for intra- and inter-day, respectively. These data were compared with those obtained using official methods for the determination of the cited drugs. The stability constants of the CT complexes were determined. The final products of the reaction were isolated and characterized using FT-IR, (1)H NMR, elemental analysis and thermogravimetric analysis (TG). The stoichiometry and apparent formation constant of the complexes formed were determined by applying the conventional spectrophotometric molar ratio method. PMID:24727166

  1. Analytical studies on the charge transfer complexes of loperamide hydrochloride and trimebutine drugs. Spectroscopic and thermal characterization of CT complexes

    NASA Astrophysics Data System (ADS)

    Elqudaby, Hoda M.; Mohamed, Gehad G.; El-Din, Ghada M. G.

    2014-08-01

    Charge transfer complexes of loperamide hydrochloride (LOP.HCl) and trimebutine (TB) drugs as electron donor with 2,3-dichloro-5,6-dicyano-p-benzoquinone (DDQ), tetracyanoethylene (TCNE) and 7,7,8,8-tetracyanoquinodimethane (TCNQ) as ?-acceptors in acetonitrile were investigated spectrophotometrically to determine the cited drugs in pure and dosage forms. The reaction gives highly coloured complex species which are measured spectrophotometrically at 460, 415 and 842 nm in case of LOP.HCl and at 455, 414 and 842 nm in case of TB using DDQ, TCNE and TCNQ reagents, respectively. The optimum experimental conditions have been studied carefully and optimized. Beer’s law was obeyed over the concentration ranges of 47.70-381.6, 21.50-150.5 and 10.00-100.0 ?g mL-1 for LOP.HCl and 37.85-264.9, 38.75-310.0 and 7.75-155.0 ?g mL-1 for TB using DDQ, TCNE and TCNQ reagents, respectively. Sandell sensitivity, standard deviation, relative standard deviation, limit of detection and quantification were calculated. The obtained data refer to high accuracy and precision of the proposed method. These results are also confirmed by inter and intra-day precision with percent recovery of 99.18-101.1% and 99.32-101.4% in case of LOP.HCl and 98.00-102.0% and 97.50-101.4% in case of TB using DDQ, TCNE and TCNQ reagents for intra- and inter-day, respectively. These data were compared with those obtained using official methods for the determination of the cited drugs. The stability constants of the CT complexes were determined. The final products of the reaction were isolated and characterized using FT-IR, 1H NMR, elemental analysis and thermogravimetric analysis (TG). The stoichiometry and apparent formation constant of the complexes formed were determined by applying the conventional spectrophotometric molar ratio method.

  2. Native fluorescence spectroscopic characterization of DMBA induced carcinogenesis in mice skin for the early detection of tissue transformation.

    PubMed

    Ebenezar, Jeyasingh; Aruna, Prakasa Rao; Ganesan, Singaravelu

    2015-06-21

    The objective of the study is to characterize the endogenous porphyrin fluorescence in a dimethylbenz(a)anthracene (DMBA) induced mouse skin tumor model using native fluorescence emission and excitation spectroscopy. Two intensity ratio parameters I580/I635 and I420/I515 were selected to represent the key fluorophore of endogenous porphyrins from emission and excitation spectra recorded in vivo from 31 DMBA treated animals and 5 control animals. In the emission spectrum, the endogenous porphyrin was elevated at 635 nm in different transformation lesions such as hyperplasia, papilloma, dysplasia, ESCC and WDSCC. This is corroborated by the endogenous porphyrin elevation at 420, 515, 550 and 588 nm in the WDSCC lesions from the excitation spectra. The elevation of endogenous porphyrin, probably protoporphyrin IX (PpIX), is due to biochemical and metabolic alterations in epithelial cells during tissue transformation. The loss of ferrochelatase activity might be responsible for enhanced PpIX in the transformed tissues. The sensitivity and specificity were determined for different lesion pairs from the scatter plot based on the discrimination value by validation with histopathological results. The emission intensity ratio I580/I635 at 405 nm excitation was selected to discriminate normal from hyperplasia, hyperplasia from papilloma, papilloma from dysplasia, dysplasia from early squamous cell carcinoma (ESCC), and ESCC from well differentiated squamous cell carcinoma (WDSCC) with specificities of 100%, 88%, 100%, 86%, and 100% and sensitivities of 100%, 80%, 100%, 100% and 100% respectively. Similarly, the excitation intensity ratio I420/I515 for 635 nm emission used to discriminate between WDSCC lesions and normal tissue gives 100% specificity and 100% sensitivity. PMID:25909647

  3. Spectroscopic characterization and biological activity of dihydrazone transition metal complexes: Crystal structure of 2,3-butanedione bis(isonicotinylhydrazone)

    NASA Astrophysics Data System (ADS)

    El-Sayed, Ahmed E. M.; Al-Fulaij, O. A.; Elaasar, A. A.; El-Defrawy, M. M.; El-Asmy, A. A.

    2015-01-01

    Metal complexes of the chloride, nitrate and acetate salts of Co(II), Ni(II) Cu(II), Zn(II), Cd(II) or Hg(II) with 2,3-butanedione bis(isonicotinylhydrazone) [BBINH] have been synthesized and structurally characterized. The crystal of BBINH was solved to crystallize as monoclinic system with space group of P121/c14. The formulae of the complexes were assigned based on the elemental analysis and mass spectra. The formation of BBINH complexes depend on the metal anion used. All complexes are nonelectrolytes except for the complexes 2, 3, 4 are (1:1) and 13 and 14 which are 1:2 electrolytes. BBINH behaves as a neutral tetradentate (N2O2) in the chloride complexes of Ni(II), Cu(II), Zn(II), Cd(II) and Hg(II). In [Co2(BBINH)(H2O)Cl3]Cl?H2O, BBINH has the same dentate but with the two Co(II) ions. In the acetate complexes, [Ni2(BBINH-2H)(H2O)2(OAc)2]?3H2O and [Cu2(BBINH-2H)(OAc)2]?5H2O, BBINH acts as a binegative tetradentate with the two metal ions. The ligand in the nitrate complexes acts as a neutral bidentate via the two hydrazone azomethine Cdbnd NHy; the nitrate ions are ionic in the Cd(II) and Zn(II) complexes and covalent in the Ni(II) complex. The data are supported by NMR (1H and 13C) spectra. The magnetic moments and electronic spectra of all complexes provide tetrahedral, square planar and/or octahedral structure. The decomposition of the complexes revealed the outer and inner solvents as well as the remaining residue based on TGA. The complexes have variable activities against some bacteria and fungi. The ligand is inactive against all tested organisms. The activity of Cd(II) and Hg(II) may be related to the geometry of the complexes.

  4. Substrate specificity, metal binding properties, and spectroscopic characterization of the DapE-encoded N-succinyl-L,L-diaminopimelic acid desuccinylase from Haemophilus influenzae.

    PubMed

    Bienvenue, David L; Gilner, Danuta M; Davis, Ryan S; Bennett, Brian; Holz, Richard C

    2003-09-16

    The catalytic and structural properties of divalent metal ion cofactor binding sites in the dapE-encoded N-succinyl-L,L-diaminopimelic acid desuccinylase (DapE) from Haemophilus influenzae were investigated. Co(II)-substituted DapE enzyme was 25% more active than the Zn(II)-loaded form of the enzyme. Interestingly, Mn(II) can activate DapE, but only to approximately 20% of the Zn(II)-loaded enzyme. The order of the observed k(cat) values are Co(II) > Zn(II) > Cd(II) > Mn(II) >Ni(II) approximately equal Cu(II) approximately equal Mg(II). DapE was shown to only hydrolyze L,L-N-succinyl-diaminopimelic acid (L,L-SDAP) and was inactive toward D,L-, L,D-, and D,D-SDAP. DapE was also inactive toward several acetylated amino acids as well as D,L-succinyl aminopimelate, which differs from the natural substrate, L,L-SDAP, by the absence of the amine group on the amino acid side chain. These data imply that the carboxylate of the succinyl moiety and the amine form important interactions with the active site of DapE. The affinity of DapE for one versus two Zn(II) ions differs by nearly 2.2 x 10(3) times (K(d1) = 0.14 microM vs K(d2) = 300 microM). In addition, an Arrhenius plot was constructed from k(cat) values measured between 16 and 35 degrees C and was linear over this temperature range. The activation energy for [ZnZn(DapE)] was found to be 31 kJ/mol with the remaining thermodynamic parameters calculated at 25 degrees C being DeltaG(++) = 64 kJ/mol, DeltaH(++) = 28.5 kJ/mol, and DeltaS(++) = -119 J mol(-1) K(-1). Electronic absorption and EPR spectra of [Co_(DapE)] and [CoCo(DapE)] indicate that the first Co(II) binding site is five-coordinate, while the second site is octahedral. In addition, any spin-spin interaction between the two Co(II) ions in [CoCo(DapE)] is very weak. The kinetic and spectroscopic data presented herein suggest that the DapE from H. influenzae has similar divalent metal binding properties to the aminopeptidase from Aeromonas proteolytica (AAP), and the observed divalent metal ion binding properties are discussed with respect to their catalytic roles in SDAP hydrolysis. PMID:12962500

  5. Physiological Characterization of Root Zn2+ Absorption and Translocation to Shoots in Zn Hyperaccumulator and Nonaccumulator Species of Thlaspi.

    PubMed

    Lasat, M. M.; Baker, AJM.; Kochian, L. V.

    1996-12-01

    Radiotracer techniques were employed to characterize 65Zn2+ influx into the root symplasm and translocation to the shoot in Thlaspi caerulescens, a Zn hyperaccumulator, and Thlaspi arvense, a nonaccumulator. A protocol was developed that allowed us to quantify unidirectional 65Zn2+ influx across the root-cell plasma membrane (20 min of radioactive uptake followed by 15 min of desorption in a 100 [mu]M ZnCl2 + 5 mM CaCl2 solution). Concentration-dependent Zn2+ influx in both Thlaspi species yielded nonsaturating kinetic curves that could be resolved into linear and saturable components. The linear kinetic component was shown to be cell-wall-bound Zn2+ remaining in the root after desorption, and the saturable component was due to Zn2+ influx across the root-cell plasma membrane. This saturable component followed Michaelis-Menten kinetics, with similar apparent Michaelis constant values for T. caerulescens and T. arvense (8 and 6 [mu]M, respectively). However, the maximum initial velocity for Zn2+ influx in T. caerulescens root cells was 4.5-fold higher than for T. arvense, indicating that enhanced absorption into the root is one of the mechanisms involved in Zn hyperaccumulation. After 96 h 10-fold more 65Zn was translocated to the shoot of T. caerulescens compared with T. arvense. This indicates that transport sites other than entry into the root symplasm are also stimulated in T. caerulescens. We suggest that although increased root Zn2+ influx is a significant component, transport across the plasma membrane and tonoplast of leaf cells must also be critical sites for Zn hyperaccumulation in T. caerulescens. PMID:12226473

  6. CHARACTERIZING THE CIRCUMGALACTIC MEDIUM OF NEARBY GALAXIES WITH HST/COS AND HST/STIS ABSORPTION-LINE SPECTROSCOPY

    SciTech Connect

    Stocke, John T.; Keeney, Brian A.; Danforth, Charles W.; Shull, J. Michael; Froning, Cynthia S.; Green, James C.; Penton, Steven V. [Center for Astrophysics and Space Astronomy, Department of Astrophysical and Planetary Sciences, University of Colorado, 389 UCB, Boulder, CO 80309 (United States)] [Center for Astrophysics and Space Astronomy, Department of Astrophysical and Planetary Sciences, University of Colorado, 389 UCB, Boulder, CO 80309 (United States); Savage, Blair D., E-mail: john.stocke@colorado.edu [Department of Astronomy, University of Wisconsin, Madison, WI 53706 (United States)

    2013-02-15

    The circumgalactic medium (CGM) of late-type galaxies is characterized using UV spectroscopy of 11 targeted QSO/galaxy pairs at z {<=} 0.02 with the Hubble Space Telescope Cosmic Origins Spectrograph (COS) and {approx}60 serendipitous absorber/galaxy pairs at z {<=} 0.2 with the Space Telescope Imaging Spectrograph. CGM warm cloud properties are derived, including volume filling factors of 3%-5%, cloud sizes of 0.1-30 kpc, masses of 10-10{sup 8} M {sub Sun }, and metallicities of {approx}0.1-1 Z {sub Sun }. Almost all warm CGM clouds within 0.5 R {sub vir} are metal-bearing and many have velocities consistent with being bound, 'galactic fountain' clouds. For galaxies with L {approx}> 0.1 L*, the total mass in these warm CGM clouds approaches 10{sup 10} M {sub Sun }, {approx}10%-15% of the total baryons in massive spirals and comparable to the baryons in their parent galaxy disks. This leaves {approx}> 50% of massive spiral-galaxy baryons 'missing'. Dwarfs (<0.1 L*) have smaller area covering factors and warm CGM masses ({<=}5% baryon fraction), suggesting that many of their warm clouds escape. Constant warm cloud internal pressures as a function of impact parameter (P/k {approx} 10 cm{sup -3} K) support the inference that previous COS detections of broad, shallow O VI and Ly{alpha} absorptions are of an extensive ({approx}400-600 kpc), hot (T Almost-Equal-To 10{sup 6} K), intra-cloud gas which is very massive ({>=}10{sup 11} M {sub Sun }). While the warm CGM clouds cannot account for all the 'missing baryons' in spirals, the hot intra-group gas can, and could account for {approx}20% of the cosmic baryon census at z {approx} 0 if this hot gas is ubiquitous among spiral groups.

  7. Synthesis, characterization and applications of pyrocatechol modified amberlite XAD-2 resin for preconcentration and determination of metal ions in water samples by flame atomic absorption spectrometry (FAAS)

    Microsoft Academic Search

    Pankaj Kumar Tewari; Ajai Kumar Singh

    2001-01-01

    A new chelating resin is prepared by coupling Amberlite XAD-2 with pyrocatechol through an azo spacer, characterized (by elemental analysis, IR and TGA) and studied for preconcentrating Cd(II), Co(II), Cu(II), Fe(III), Ni(II) and Zn(II) using flame atomic absorption spectrometry (FAAS) for metal monitoring. The sorption is quantitative in the pH range 3.0–6.5, whereas quantitative desorption occurs instantaneously with 2 M

  8. Spectroscopic and functional characterization of cyanobacterium Synechocystis PCC 6803 mutants on the cytoplasmic-side of cytochrome b559 in photosystem II.

    PubMed

    Chiu, Yi-Fang; Chen, Yung-Han; Roncel, Mercedes; Dilbeck, Preston L; Huang, Jine-Yung; Ke, Shyue-Chu; Ortega, José M; Burnap, Robert L; Chu, Hsiu-An

    2013-04-01

    We performed spectroscopic and functional characterization on cyanobacterium Synechocystis PCC6803 with mutations of charged residues of the cytoplasmic side of cytochrome (Cyt) b559 in photosystem II (PSII). All of the mutant cells grew photoautotrophically and assembled stable PSII. However, R7E?, R17E? and R17L? mutant cells grew significantly slower and were more susceptible to photoinhibition than wild-type cells. The adverse effects of the arginine mutations on the activity and the stability of PSII were in the following order (R17L?>R7E?>R17E? and R17A?). All these arginine mutants exhibited normal period-four oscillation in oxygen yield. Thermoluminescence characteristics indicated a slight decrease in the stability of the S3QB(-)/S2QB(-) charge pairs in the R7E? and R17L? mutant cells. R7E? and R17L? PSII core complexes contained predominantly the low potential form of Cyt b559. EPR results indicated the displacement of one of the two axial ligands to the heme of Cyt b559 in R7E? and R17L? mutant reaction centers. Our results demonstrate that the electrostatic interactions between these arginine residues and the heme propionates of Cyt b559 are important to the structure and redox properties of Cyt b559. In addition, the blue light-induced nonphotochemical quenching was significantly attenuated and its recovery was accelerated in the R7L? and R17L? mutant cells. Furthermore, ultra performance liquid chromatography-mass spectrometry results showed that the PQ pool was more reduced in the R7E? and R17L? mutant cells than wild-type cells in the dark. Our data support a functional role of Cyt b559 in protection of PSII under photoinhibition conditions in vivo. PMID:23399490

  9. Interactions of metal ions with two quinolone antimicrobial agents (cinoxacin and ciprofloxacin). Spectroscopic and X-ray structural characterization. Antibacterial studies.

    PubMed

    López-Gresa, M P; Ortiz, R; Perelló, L; Latorre, J; Liu-González, M; García-Granda, S; Pérez-Priede, M; Cantón, E

    2002-09-30

    Several novel metal-quinolone compounds have been synthesized and characterized by analytical, spectroscopic and X-ray diffraction methods. The crystal structure of the four compounds, Na(2)[(Cd(Cx)3)(Cd(Cx)3(H2O))].12H2O, [Co(Cp)2(H2O)2].9H2O, [Zn(Cp)2(H2O)2].8H2O and [Cd(HCp)2(Cl)2].4H2O, is presented and discussed: HCx=1-ethyl-1,4-dihydro-4-oxo(1,3)-dioxolo(4,5-g)cinnoline-3-carboxylic acid and HCp=1-cyclopropyl-6-fluoro-1,4-dihydro-4-oxo-7-(1-piperazinyl)-3-quinoline carboxylic acid. In all these compounds the quinolone acts as a bidentate chelate ligand that binds through one carboxylate oxygen atom and the exocyclic carbonyl oxygen atom. Complexes of ciprofloxacin were screened for their activity against several bacteria, showing activity similar to that of the ligand. In addition, the number of bacteria killed after 3 h of incubation with the ligand, [Co(Cp)2(H2O)2].9H2O, Ni(Cp)2.10H2O and Cu(Cp)2.6H2O, was determined against S. aureus ATCC25923. There is a direct relationship between the growth rate and the lethal rate. Against growing bacteria, the ligand is the most bactericidal and Cu(Cp)2.6H2O is the less bactericidal. On the contrary, against non-dividing bacteria, the complexes were more bactericidal than the ligand, with Cu(Cp)(2).6H(2)O the most bactericidal compound. PMID:12230989

  10. Spectroscopic characterization of the chiral structure of individual single-walled carbon nanotubes and the edge structure of isolated graphene nanoribbons.

    PubMed

    Zhang, Daqi; Yang, Juan; Li, Yan

    2013-04-22

    The chiral structure of single-walled carbon nanotubes (SWNTs) and the edge structure of graphene nanoribbons (GNRs) play an important role in determining their electronic and phonon structures. Spectroscopic methods, which require simple sample preparation and cause minimal sample damage, are the most commonly utilized techniques for determining the structures of SWNTs and graphene. In this review the current status of various spectroscopic methods are presented in detail, including resonance Raman, photoluminescence (PL), and Rayleigh scattering spectroscopies, for determination of the chiral structure of individual SWNTs and the edge structure of isolated graphene, especially of graphene nanoribbons. The different photophysical processes involved in each spectroscopic method are reviewed to achieve a comprehensive understanding of the electronic and phonon properties of SWNTs and graphene. The advantages and limitations of each spectroscopic method as well as the challenges in this area are discussed. PMID:23529997

  11. Genesis of a Cerium Oxide-Supported Gold Catalyst for CO Oxidation: Transformation of Mononuclear Gold Complexes into Clusters as Characterized by X-Ray Absorption Spectroscopy

    SciTech Connect

    Aguilar-Guerrero, V.; Lobo-Lapidus, R; Gates, B

    2009-01-01

    CeO{sub 2}-supported mononuclear gold species synthesized from Au(CH{sub 3}){sub 2}(acac) catalyzed CO oxidation at 353 K, with a turnover frequency of 6.5 x 10{sup -3} molecules of CO (Au atom s){sup -1} at CO and O{sub 2} partial pressures of 1.0 and 0.5 kPa, respectively. As the catalyst functioned in a flow reactor, the activity increased markedly so that within about 10 h the conversion of CO had increased from about 1% to almost 100%. Activated catalyst samples were characterized by X-ray absorption spectroscopy and found to incorporate clusters of gold, which increased in size, undergoing reduction, with increasing time of operation. The X-ray absorption near-edge structure spectrum of the catalyst used for the longest period was indistinguishable from that characterizing gold foil. Extended X-ray absorption fine structure data characterizing the catalyst after the longest period of operation indicated the presence of clusters of approximately 30 Au atoms each, on average. The evidence that the catalytic activity increased as the clusters grew is contrasted with earlier reports pointing to increasing activity of supported gold clusters as they were made smallerin a cluster size range largely exceeding ours.

  12. Soliton absorption spectroscopy

    PubMed Central

    Kalashnikov, V. L.; Sorokin, E.

    2010-01-01

    We analyze optical soliton propagation in the presence of weak absorption lines with much narrower linewidths as compared to the soliton spectrum width using the novel perturbation analysis technique based on an integral representation in the spectral domain. The stable soliton acquires spectral modulation that follows the associated index of refraction of the absorber. The model can be applied to ordinary soliton propagation and to an absorber inside a passively modelocked laser. In the latter case, a comparison with water vapor absorption in a femtosecond Cr:ZnSe laser yields a very good agreement with experiment. Compared to the conventional absorption measurement in a cell of the same length, the signal is increased by an order of magnitude. The obtained analytical expressions allow further improving of the sensitivity and spectroscopic accuracy making the soliton absorption spectroscopy a promising novel measurement technique. PMID:21151755

  13. Resolving Spectral Lines with a Periscope-Type DVD Spectroscope

    ERIC Educational Resources Information Center

    Wakabayashi, Fumitaka

    2008-01-01

    A new type of DVD spectroscope, the periscope type, is described and the numerical analysis of the observed emission and absorption spectra is demonstrated. A small and thin mirror is put inside and an eighth part of a DVD is used as a grating. Using this improved DVD spectroscope, one can observe and photograph visible spectra more easily and…

  14. Characterization of nonlinear absorption of InN epitaxial films with femtosecond pulsed transmission Z-scan measurements

    NASA Astrophysics Data System (ADS)

    Tsai, Tsong-Ru; Wu, Tsung-Han; Liao, Jung-Cheng; Wei, Tai-Huei; Chiang, Hai-Pang; Hwang, Jih-Shang; Tsai, Din-Ping; Chen, Yang-Fang

    2009-03-01

    The femtosecond pulsed Z-scan measurements of the resonant nonlinear optical absorption of the InN epitaxial films in the range of 720-790nm were reported. The absorption saturation behavior was found to gradually decrease with increasing photon energy. The nonlinear optical absorption cross sections of the InN films were estimated and the values are found to be in good agreement with the calculations based on the band-filling model. These results are relevant for the future development of nonlinear optical devices based on InN.

  15. X-ray photoelectron, Cu L3MM Auger and X-ray absorption spectroscopic studies of Cu nanoparticles produced in aqueous solutions: The effect of sample preparation techniques

    NASA Astrophysics Data System (ADS)

    Saikova, Svetlana; Vorobyev, Sergey; Likhatski, Maxim; Romanchenko, Alexander; Erenburg, Simon; Trubina, Svetlana; Mikhlin, Yuri

    2012-08-01

    Stable sols of copper nanoparticles from 10 nm to 50 nm in diameter synthesized in aqueous solutions using several reducing agents and immobilized on pyrographite were characterized by XPS, Cu L3MM Auger and X-ray absorption spectroscopy (Cu L-edge TEY XANES and Cu K-edge XANES and EXAFS in transmission mode) along with UV-vis spectroscopy, AFM, TEM. It was found that the nanoparticles produced in the hydrazine hydrate and sodium borohydride assisted synthesis are composed of surface Cu(II) oxyhydroxides, and the shells formed by cuprite Cu2O and distorted Cu(I) oxide, which showed the Cu L-edge peak shifted to higher energies, above the metallic core. The relative amount of cuprite was usually larger in the hydrazine systems, but it depended on the sample preparation protocol. The nanoparticles prepared using ascorbic acid as a reactant consisted of rather thick Cu(II) overlayer and largely distorted Cu(I) oxide underneath. The post-synthetic sample handling notably affected the results; in particular, sedimentation (instead of drying of the colloidal solution) favored reduction of the oxide layers to metallic copper and agglomeration of the Cu particles in the precipitate, even in the case of ascorbic acid, while the colloidal particles in the supernatant were oxidized.

  16. Optical absorption and fluorescence properties of Dy3+: SFB glasses

    Microsoft Academic Search

    D. Uma Maheswari; J. Suresh Kumar; T. Sasikala; A. Mohan Babu; K. Pavani; Kiwan Jang; L. Rama Moorthy

    2009-01-01

    This paper presents the preparation and spectroscopic characterization of Dy3+-doped sodium fluoroborate (SFB) glasses of the type (50-x) B2O3 + 25 Na2O + 10 CaF2 + 10 AlF3 + 5 LaF3 + x DyF3 (x = 0.01, 0.1, 0.5,1.0, 2.0 and 4.0 mol%). By measuring the area under absorption bands, the experimental oscillator strengths are determined. The Judd-Ofelt (J-O) intensity

  17. Raman Spectroscopic Characterization of Graphene

    Microsoft Academic Search

    Bo Tang; Hu Guoxin; Hanyang Gao

    2010-01-01

    The recent progress using Raman spectroscopy and imaging of graphene is reviewed. The intensity of the G band increases with increased graphene layers, and the shape of 2D band evolves into four peaks of bilayer graphene from a single peak of monolayer graphene. The G band will blue shift and become narrow with both electron and hole doping, whereas the

  18. Vibrational spectroscopic characterization of fluoroquinolones

    Microsoft Academic Search

    U. Neugebauer; A. Szeghalmi; M. Schmitt; W. Kiefer; J. Popp; U. Holzgrabe

    2005-01-01

    Quinolones are important gyrase inhibitors. Even though they are used as active agents in many antibiotics, the detailed mechanism of action on a molecular level is so far not known. It is of greatest interest to shed light on this drug–target interaction to provide useful information in the fight against growing resistances and obtain new insights for the development of

  19. Preparation and characterization of novel glass-ceramic tile with microwave absorption properties from iron ore tailings

    NASA Astrophysics Data System (ADS)

    Yao, Rui; Liao, SongYi; Dai, ChangLu; Liu, YuChen; Chen, XiaoYu; Zheng, Feng

    2015-03-01

    A novel glass-ceramic tile consisting of one glass-ceramic layer (GC) attaining microwave absorption properties atop ceramic substrate was prepared through quench-heat treatment route derived from iron ore tailings (IOTs) and commercial raw materials (purity range 73-99%). X-ray diffraction (XRD), SEM, Energy dispersive X-ray spectroscopy (EDS), Fourier transform infrared spectroscopy (FTIR), Physical property measurement system (PPMS) and Vector network analyzer (VNA) measurements were carried out to investigate phase, microstructure, magnetic and microwave absorption aspects of the glass-ceramic layer. Roughly 80.6±1.7 wt% borosilicate glass and 19.4±1.7 wt% spinel ferrite with chemical formula of (Zn2+0.17Fe3+0.83)[Fe3+1.17Fe2+0.06Ni2+0.77]O4 were found among the tested samples. Absorption of Electromagnetic wave by 3 mm thick glass-ceramic layer at frequency of 2-18 GHz reached peak reflection loss (RL) of -17.61 dB (98.27% microwave absorption) at 10.31 GHz. Altering the thickness of the glass-ceramic layer can meet the requirements of different level of microwave absorption.

  20. Gradient Moment Compensated Magnetic Resonance Spectroscopic Imaging

    PubMed Central

    Kim, Dong-Hyun; Gu, Meng; Spielman, Daniel M.

    2010-01-01

    Spectroscopic imaging applications outside of the brain can suffer from artifacts due to inherent long scan times and susceptibility to motion. A fast spectroscopic imaging sequence has been devised with reduced sensitivity to motion. The sequence uses oscillating readout gradients and acquires k-space data in a spiral out–in fashion, which allows fast k-space coverage. We show that a spiral out–in readout acquisition is characterized by small gradient moments, reducing sensitivity to motion-induced artifacts. Data are acquired comparing the sequence to normal phase encoded spectroscopic imaging and conventional spiral spectroscopic imaging protocols. In addition, in vivo data are acquired from the liver, demonstrating potential usage as a multivoxel fat/water spectroscopic imaging tool. Results indicate that in the presence of motion, ghosting effects are reduced while metabolite signal increases of approximately 10% can be achieved. PMID:19161164

  1. Cationic cobalt(III) complex as anion receptor: Synthesis, spectroscopic characterization, single-crystal X-ray structure determination and packing analyses of [Co(phen) 2CO 3](4-aminobenzenesulphonate).6H 2O

    Microsoft Academic Search

    Raj Pal Sharma; Ajnesh Singh; Thammarat Aree; Paloth Venugopalan

    2009-01-01

    To explore the potential of [Co(phen)2CO3]+ as anion receptor, the complex salt [Co(phen)2CO3](4-aminobenzenesulphonate).6H2O was synthesized and characterized by X-ray crystallography, elemental analyses, spectroscopic studies (IR, UV\\/Visible, 1H, 13C and 59Co NMR), solubility product and conductance measurements. The complex salt crystallizes in the triclinic space group P1¯ with unit cell constants: a=10.803(2), b=11.758(2), c=15.190(3) Å, ?=99.66(3)°, ?=103.53(3)°, ?=113.54(3)°. X-ray structure determination

  2. Synthesis and spectroscopic characterization of site-specific 2-amino-1-methyl-6-phenylimidazo[4,5-b]pyridine oligodeoxyribonucleotide adducts

    PubMed Central

    Brown, Karen; Guenther, Elizabeth A.; Dingley, Karen H.; Cosman, Monique; Harvey, Chris A.; Shields, Sharon J.; Turteltaub, Kenneth W.

    2001-01-01

    The aim of the present study is to determine the chemical structure and conformation of DNA adducts formed by incubation of the bioactive form of 2-amino-1-methyl-6-phenylimidazo[4,5-b]pyridine (PhIP), N-acetoxy-PhIP, with a single-stranded 11mer oligodeoxyribonucleotide. Using conditions optimized to give the C8-dG-PhIP adduct as the major product, sufficient material was synthesized for NMR solution structure determination. The NMR data indicate that in duplex DNA this adduct exists in equilibrium between two different conformational states. In the main conformer, the covalently bound PhIP molecule intercalates in the helix, whilst in the minor conformation the PhIP ligand is probably solvent exposed. In addition to the C8-dG-PhIP adduct, at least eight polar adducts are found after reaction of N-acetoxy-PhIP with the oligonucleotide. Three of these were purified for further characterization and shown to exhibit lowest energy UV absorption bands in the range 342–347 nm, confirming the presence of PhIP or PhIP derivative. Accurate mass determination of two of the polar adducts by negative ion MALDI-TOF MS revealed ions consistent with a spirobisguanidino-PhIP derivative and a ring-opened adduct. The third adduct, which has the same mass as the C8-dG-PhIP oligonucleotide adduct, may contain PhIP bound to the N2 position of guanine. PMID:11328879

  3. Spectroscopic and Computational Characterization of the NO Adduct of Substrate-Bound Fe(II) Cysteine Dioxygenase: Insights into the Mechanism of O2 Activation

    PubMed Central

    Blaesi, Elizabeth J.; Gardner, Jessica D.; Fox, Brian G.; Brunold, Thomas C.

    2013-01-01

    Cysteine dioxygenase (CDO) is a mononuclear non-heme iron(II)-dependent enzyme critical for maintaining appropriate cysteine (Cys) and taurine levels in eukaryotic systems. Since CDO possesses both an unusual 3-His facial ligation sphere to the iron center and a rare Cys-Tyr crosslink near the active site, the mechanism by which it converts Cys and molecular oxygen to cysteine sulfinic acid is of broad interest. However, as of yet direct experimental support for any of the proposed mechanisms is still lacking. In this study, we have used NO as a substrate analogue for O2 to prepare a species that mimics the geometric and electronic structures of an early reaction intermediate. The resultant unusual S=1/2 {FeNO}7 species was characterized by magnetic circular dichroism, electron paramagnetic resonance, and electronic absorption spectroscopies, as well as computational methods including density functional theory and semi-empirical calculations. The NO adducts of Cys- and selenocysteine (Sec)-bound Fe(II)CDO exhibit virtually identical electronic properties; yet, CDO is unable to oxidize Sec. To explore the differences in reactivity between Cys- and Sec-bound CDO, the geometries and energies of viable O2-bound intermediates were evaluated computationally, and it was found that a low-energy quintet-spin intermediate on the Cys reaction pathway adopts a different geometry for the Sec-bound adduct. The absence of a low-energy O2 adduct for Sec-bound CDO is consistent with our experimental data and may explain why Sec does not act as a substrate for CDO. PMID:23906193

  4. Characterization of Esterase and Alcohol Dehydrogenase Activity in Skin. Metabolism of Retinyl Palmitate to Retinol (Vitamin A) During Percutaneous Absorption

    Microsoft Academic Search

    James Boehnlein; Adel Sakr; J. Leon Lichtin; Robert L. Bronaugh

    1994-01-01

    Retinyl palmitate, a widely used ingredient in cosmetic products, is promoted for its beneficial effects on the appearance of skin. Previous studies suggest that enzymes are available in skin to metabolize this ingredient during skin absorption. Esterase activity hydrolyzes retinyl palmitate to retinol (vitamin A), which is oxidized in many tissues to retinoic acid primarily by alcohol dehydrogenase. The activities

  5. Employing Multiple Spectroscopic Techniques Simultaneously to Observe Protein Unfolding

    NASA Astrophysics Data System (ADS)

    Crowe, Michael; Kelty, Ben; Link, Justin

    2015-03-01

    A protein's function is directly related to its native, folded structure. In order to study the structure of proteins, the unfolding process may be characterized. In our study, by using the spectroscopic techniques of circular dichroism (CD), absorption, and fluorescence simultaneously, we examined the unfolding of horse heart cytochrome c, a well-studied, model protein by gradually increasing the concentration of the chemical denaturant, guanidine hydrochloride. The signal changes from these modalities over the course of the unfolding reaction provides some of the thermodynamic properties like Gibbs free energy for insight into the stability of the protein. This allows us to compare the three techniques under the exact same conditions. The objective of this session is to present recent work in developing a protocol to observe the unfolding of cytochrome c using fluorescence, absorbance, and CD simultaneously.

  6. Surface gravity analysis of the NIRSPEC Brown Dwarf Spectroscopic Survey

    NASA Astrophysics Data System (ADS)

    Martin, Emily; McLean, Ian S.; Mace, Gregory N.; Logsdon, Sarah E.; Rice, Emily L.

    2015-01-01

    We present an analysis of J band spectra for over two hundred M, L, and T dwarfs obtained from the Brown Dwarf Spectroscopic Survey (BDSS) using NIRSPEC on the Keck II Telescope. This R~2000 sample includes spectra presented in McLean et al. (2003), as well as many new, unpublished spectra observed for the BDSS, more than doubling the size of the original survey. We determine surface gravity-sensitive spectral indices from the literature, which probe K I and FeH absorption, and we estimate uncertainties using a Monte Carlo iterative method. With these indices we characterize surface gravities of our targets in order to disentangle temperature and age of brown dwarfs and low mass stars of various masses.

  7. X-ray diffraction, spectroscopic characterization and quantum chemical calculations by DFT and HF of novel 2-hydroxy-12-(4-hydroxyphenyl)-9,9-dimethyl-9,10-dihydro-8H-benzo[a]xanthen-11(12H)-one

    NASA Astrophysics Data System (ADS)

    Aggarwal, Komal; Khurana, Jitender M.

    2015-01-01

    In this paper, the title compound, 2-hydroxy-12-(4-hydroxyphenyl)-9,9-dimethyl-9,10-dihydro-8H-benzo[a]xanthen-11(12H)-one (2HBX), has been characterized by using MS, FTIR, 1H and 13C NMR spectroscopic, and X-ray crystallographic techniques. X-ray studies revealed the presence of intermolecular hydrogen bonding and ?-? stacking interactions. Quantum chemical calculations have also been performed on the title compound to calculate the molecular geometry and vibrational frequencies in the ground state using density functional theory (B3LYP) and Hartree-Fock (HF) methods with the 6-311G(d,p) basis set. The calculated results show that the optimized geometry parameters can well reproduce the crystal structure, and the theoretical vibrational frequency values show good agreement with experimental values. Application of scaling factors for FTIR frequency predictions showed good agreement with experimental values. In addition, Mulliken atomic charges of the title compound were calculated and discussed. 1H NMR analysis also shows good agreement with experimental observations. Stability of the molecule arising from hyperconjugative interactions and charge delocalization has been analyzed using natural bond orbital (NBO) analysis. TDDFT calculations were used to compare the experimental and theoretical absorption spectra. The calculated HOMO and LUMO energies show that charge transfer occurs within the molecule. In addition, the molecular electrostatic potential (MEP) analysis of the title compound was investigated using theoretical calculations.

  8. Spectroscopic and Computational Studies of a Series of High-Spin Ni(II) Thiolate Complexes

    PubMed Central

    Van Heuvelen, Katherine M.; Cho, Jaeheung; Dingee, Timothy; Riordan, Charles G.; Brunold, Thomas C.

    2010-01-01

    The electronic structures of a series of high-spin Ni(II)-thiolate complexes of the form [PhTttBu]Ni(SR) (R = CPh3, 2; C6F5, 3; C6H5, 4; PhTttBu = phenyltris((tert-butylthio)methyl)borate) have been characterized using a combined spectroscopic and computational approach. Resonance Raman (rR) spectroscopic data reveal that the ?Ni–SR vibrational feature occurs between 404 and 436 cm?1 in these species. The corresponding rR excitation profiles display a striking de-enhancement behavior due to interference effects involving energetically proximate electronic excited states. These data were analyzed in the framework of time-dependent Heller theory to obtain quantitative insight into excited state nuclear distortions. The electronic absorption and magnetic circular dichroism spectra of 2 – 4 are characterized by numerous charge transfer (CT) transitions. The dominant absorption feature, which occurs at ~18,000 cm?1 in all three complexes, is assigned as a thiolate-to-Ni CT transition involving molecular orbitals that are of ?-symmetry with respect to the Ni–S bond, reminiscent of the characteristic absorption feature of blue copper proteins. Density functional theory computational data provide molecular orbital descriptions for 2 – 4 and allow for detailed assignments of the key spectral features. A comparison of the results obtained in this study to those reported for similar Ni-thiolate species reveals that the supporting ligand plays a secondary role in determining the spectroscopic properties, as the electronic structure is primarily determined by the metal–thiolate bonding interaction. PMID:20565082

  9. Characterization of raw, delignified and bleached jute fibres by study of absorption of moisture and some mechanical properties

    Microsoft Academic Search

    Kh. M. Mannan; M. A. I. Talukder

    1997-01-01

    This paper describes the response to moisture absorption and some mechanical properties of jute fibres (Corchorus capsularis) on dewaxing, delignification, bleaching and treatment with jute batch oil-in-emulsion. On dewaxing the dimension of the capillaries expand from 100 Å for raw fibres to 107 Å. On scouring with detergent, the capillaries contract slightly. On treatment with jute batch (JB) oil-in-emulsion the

  10. Characterization of the aramid\\/epoxy interfacial properties by means of pull-out test and influence of water absorption

    Microsoft Academic Search

    Kazuto Tanaka; Kohji Minoshima; Witold Grela; Kenjiro Komai

    2002-01-01

    Single fiber pull-out tests were carried out to investigate the influence of water absorption on the interfacial properties of aramid\\/epoxy composite. The fiber\\/matrix interfacial strength was severely decreased between 4 and 7 week immersion time in deionized water at 80 °C, and thereafter showed a plateau. This change with immersion time did not correspond with that of the water gain of

  11. Characterization of cryogenic materials by x-ray absorption methods. [Ta, Zr additions in Nb/sub 3/Sn

    SciTech Connect

    Heald, S.M.; Tranquada, J.M.

    1985-01-01

    X-ray absorption techniques have in recent years been developed into powerful probes of the electronic and structural properties of materials difficult to study by other techniques. In particular, the extended x-ray absorption fine structure (EXAFS) technique can be applied to a variety of cryogenic materials. Three examples are used to demonstrate the power of the technique. The first is the determination of the lattice location of dilute alloying additions such as Ta and Zr in Nb/sub 3/Sn. The Ta additions are shown to reside predominately in Nb lattice sites, while Zr is not uniquely located at either Nb or Sn sites. In addition to structural information, temperature dependent EXAFS studies can be used to determine the rms deviations of atomic bond lengths, providing information about the temperature dependence of interatomic force constants. For Nb/sub 3/Sn deviations are found from simple harmonic behavior at low temperatures which indicate a softening of the Nb-Sn bond strength. The final example is the study of interfacial properties in thin film systems. This is accomplished by making x-ray absorption measurements under conditions of total external reflection of the incident x-rays. As some examples show, this technique has great potential for studying interfacial reactions, a process used in the fabrication of many superconducting materials.

  12. Application of spectroscopic techniques for the study of paper documents: A survey

    NASA Astrophysics Data System (ADS)

    Manso, M.; Carvalho, M. L.

    2009-06-01

    For many centuries paper was the main material for recording cultural achievements all over the world. Paper is mostly made from cellulose with small amounts of organic and inorganic additives, which allow its identification and characterization and may also contribute to its degradation. Prior to 1850, paper was made entirely from rags, using hemp, flax and cotton fibres. After this period, due to the enormous increase in demand, wood pulp began to be commonly used as raw material, resulting in rapid degradation of paper. Spectroscopic techniques represent one of the most powerful tools to investigate the constituents of paper documents in order to establish its identification and its state of degradation. This review describes the application of selected spectroscopic techniques used for paper characterization and conservation. The spectroscopic techniques that have been used and will be reviewed include: Fourier-Transform Infrared spectroscopy, Raman spectroscopy, Nuclear Magnetic Resonance spectroscopy, X-Ray spectroscopy, Laser-based Spectroscopy, Inductively Coupled Mass Spectroscopy, Laser ablation, Atomic Absorption Spectroscopy and X-Ray Photoelectron Spectroscopy.

  13. X-ray Absorption Spectroscopy Characterization of Zn Underpotential Deposition on Au(111) from Phosphate Supporting Electrolyte

    SciTech Connect

    Lee, J R; O'Malley, R L; O'Connell, T J; Vollmer, A; Rayment, T

    2009-12-11

    Zn K-edge X-ray absorption spectroscopy (XAS) has been used to investigate the structure of Zn monolayers prepared on Au(111) electrodes via underpotential deposition (UPD) from phosphate supporting electrolyte. Theoretical modeling of the XAS data indicates that the Zn adatoms adopt a commensurate ({radical}3x{radical}3)R30{sup o} ({mu}{sub sc} = 0.33) adlayer structure and reside within the 3-fold hollow sites of the Au(111) surface. Meanwhile, phosphate counter-ions co-adsorb on the UPD adlayer and bridge between the Zn adatoms in a ({radical}3x{radical}3)R30{sup o} ({mu}{sub sc} = 0.33) configuration, with each phosphorous atom residing above a vacant 3-fold hollow site of the Au(111). Significantly, this surface structure is invariant between the electrochemical potential for UPD adlayer formation and the onset of bulk Zn electrodeposition. Analysis of the Zn K-edge absorption onset also presents the possibility that the Zn adatoms do not fully discharge during the process of UPD, which had been proposed in prior voltammetric studies of the phosphate/Zn(UPD)/Au(111) system.

  14. Advanced elemental characterization during Pt-In catalyst formation by wavelet transformed X-ray absorption spectroscopy.

    PubMed

    Filez, Matthias; Redekop, Evgeniy A; Poelman, Hilde; Galvita, Vladimir V; Marin, Guy B

    2015-03-17

    Complementary to conventional X-ray absorption near edge structure (XANES) and Fourier transformed (FT) extended X-ray absorption fine structure (EXAFS) analysis, the systematic application of wavelet transformed (WT) XAS is shown to disclose the physicochemical mechanisms governing Pt-In catalyst formation. The simultaneous k- and R-space resolution of the WT XAS signal allows for the efficient allocation of the elemental nature to each R-space peak. Because of its elemental discrimination capacity, the technique delivers structural models which can subsequently serve as an input for quantitative FT EXAFS modeling. The advantages and limitations of applying WT XAS are demonstrated (1) before and (2) after calcination to 650 °C of a Pt(acac)2 impregnated Mg(In)(Al)Ox support and (3) after subsequent H2 reduction to 650 °C. Combined XANES, FT, and WT XAS analysis shows that the acac ligands of the Pt precursor decompose during calcination, leading to atomically dispersed Pt(4+) cations on the Mg(In)(Al)Ox support. H2 reduction treatment eventually results in the formation of 1.5 nm Pt-In alloyed nanoparticles. Widespread use and systematic application of wavelet-based XAS can potentially reveal in greater detail the intricate mechanisms involved in catalysis, chemistry, and related fields. PMID:25704379

  15. Spectroscopic measurement of radiation of high-pressure mercury discharge lamps

    SciTech Connect

    Fu Ling; Leutz, Ralf; Ries, Harald [Physics Department, Philipps-University, Renthof 5, 35037 Marburg (Germany)

    2005-06-15

    Compact size and high efficiency are important features for projection systems. As the most often used sources for projection optics, short arc lamps are characterized by their impressive economy and the ability to produce extremely bright light from small dimensional sources. In this contribution the old principle of back reflection towards the sources is applied to a high-pressure mercury discharge lamp with a reflector to improve the radiance of the source by 35% at a certain reduced solid angle. Increasing the optical thickness of sources is equivalent to reducing the total phase space (etendue) of emitted radiation by the same factor, which is very useful for compacting sources. In addition, by comparing the forward radiation and the back-reflected radiation obtained from spectroscopic measurements, we calculate the absorptivity, emissivity, absorption, and emission coefficients of the plasma of the arc lamp based on Kirchhoff's Law and Planck's equation which is necessary for determining its temperature and pressure.

  16. Joint spectroscopic and theoretical investigations of transition metal complexes involving non-innocent ligands.

    PubMed

    Ray, Kallol; Petrenko, Taras; Wieghardt, Karl; Neese, Frank

    2007-04-28

    A series of transition metal complexes involving non-innocent o-dithiolene and o-phenylenediamine ligands has been characterized in detail by various spectroscopic methods like magnetic circular dichroism (MCD), absorption (abs), resonance Raman (rR), electron paramagnetic resonance (EPR), and sulfur K-edge X-ray absorption spectroscopies. A computational model for the electronic structure of the complexes is then proposed based on the density functional theory (DFT) or ab-initio methods, which can successfully account for the observed trends in the experimental spectra (MCD, rR, and abs) of the complexes. Based on these studies, the innocent vs non-innocent nature of the ligands in a given transition metal complex is found to be dependent on the position of the central metal ion in the periodic table, its effective nuclear charge in interplay with relativistic effects. PMID:17426855

  17. Characterizing phosphorus speciation of Chesapeake Bay sediments using chemical extraction, 31P NMR, and X-ray absorption fine structure spectroscopy.

    PubMed

    Li, Wei; Joshi, Sunendra R; Hou, Guangjin; Burdige, David J; Sparks, Donald L; Jaisi, Deb P

    2015-01-01

    Nutrient contamination has been one of the lingering issues in the Chesapeake Bay because the bay restoration is complicated by temporally and seasonally variable nutrient sources and complex interaction between imported and regenerated nutrients. Differential reactivity of sedimentary phosphorus (P) pools in response to imposed biogeochemical conditions can record past sediment history and therefore a detailed sediment P speciation may provide information on P cycling particularly the stability of a P pool and the formation of one pool at the expense of another. This study examined sediment P speciation from three sites in the Chesapeake Bay: (i) a North site in the upstream bay, (ii) a middle site in the central bay dominated by seasonally hypoxic bottom water, and (iii) a South site at the bay-ocean boundary using a combination of sequential P extraction (SEDEX) and spectroscopic techniques, including (31)P NMR, P X-ray absorption near edge structure spectroscopy (XANES), and Fe extended X-ray absorption fine structure (EXAFS). Results from sequential P extraction reveal that sediment P is composed predominantly of ferric Fe-bound P and authigenic P, which was further confirmed by solid-state (31)P NMR, XANES, and EXAFS analyses. Additionally, solution (31)P NMR results show that the sediments from the middle site contain high amounts of organic P such as monoesters and diesters, compared to the other two sites, but that these compounds rapidly decrease with sediment depth indicating remineralized P could have precipitated as authigenic P. Fe EXAFS enabled to identify the changes in Fe mineral composition and P sinks in response to imposed redox condition in the middle site sediments. The presence of lepidocrocite, vermiculite, and Fe smectite in the middle site sediments indicates that some ferric Fe minerals can still be present along with pyrite and vivianite, and that ferric Fe-bound P pool can be a major P sink in anoxic sediments. These results provide improved insights into sediment P dynamics, particularly the rapid remineralization of organic P and the stability of Fe minerals and the ferric Fe-bound P pool in anoxic sediments in the Chesapeake Bay. PMID:25469633

  18. Spectroscopic characterization of various Yb3+ doped laser materials at cryogenic temperatures for the development of high energy class diode pumped solid state lasers

    NASA Astrophysics Data System (ADS)

    Jambunathan, Venkatesan; Koerner, Joerg; Sikocinski, Pawel; Divoky, Martin; Sawicka, Magdalena; Lucianetti, Antonio; Hein, Joachim; Mocek, Tomas

    2013-05-01

    Precise values of absorption, emission and gain cross-sections of Yb:YAG, Yb:LuAG, Yb:CaF2 and Yb:FP15-glass at cryogenic temperatures are presented. To obtain the emission cross-sections two theoretical approaches were used. The first is the McCumber or reciprocity method (RM) which is based on the absorption spectra. The second is the Fuchtbauer-Ladenburg (FL) method using fluorescence spectra. From the results of cross-sections one can expect significant impact on laser performance on these materials especially in the case of high energy class diode pumped solid state lasers.

  19. Portable sample preparation and analysis system for micron and sub-micron particle characterization using light scattering and absorption spectroscopy

    DOEpatents

    Stark, Peter C. (Los Alamos, NM); Zurek, Eduardo (Barranquilla, CO); Wheat, Jeffrey V. (Fort Walton Beach, FL); Dunbar, John M. (Santa Fe, NM); Olivares, Jose A. (Los Alamos, NM); Garcia-Rubio, Luis H. (Temple Terrace, FL); Ward, Michael D. (Los Alamos, NM)

    2011-07-26

    There is provided a method and device for remote sampling, preparation and optical interrogation of a sample using light scattering and light absorption methods. The portable device is a filtration-based device that removes interfering background particle material from the sample matrix by segregating or filtering the chosen analyte from the sample solution or matrix while allowing the interfering background particles to be pumped out of the device. The segregated analyte is then suspended in a diluent for analysis. The device is capable of calculating an initial concentration of the analyte, as well as diluting the analyte such that reliable optical measurements can be made. Suitable analytes include cells, microorganisms, bioparticles, pathogens and diseases. Sample matrixes include biological fluids such as blood and urine, as well as environmental samples including waste water.

  20. The HITRAN 2008 Molecular Spectroscopic Database

    NASA Technical Reports Server (NTRS)

    Rothman, Laurence S.; Gordon, Iouli E.; Barbe, Alain; Benner, D. Chris; Bernath, Peter F.; Birk, Manfred; Boudon, V.; Brown, Linda R.; Campargue, Alain; Champion, J.-P.; Chance, Kelly V.; Coudert, L. H.; Sung, K.; Toth, R. A.

    2009-01-01

    This paper describes the status of the 2008 edition of the HITRAN molecular spectroscopic database. The new edition is the first official public release since the 2004 edition, although a number of crucial updates had been made available online since 2004. The HITRAN compilation consists of several components that serve as input for radiative-transfer calculation codes: individual line parameters for the microwave through visible spectra of molecules in the gas phase; absorption cross-sections for molecules having dense spectral features, i.e., spectra in which the individual lines are not resolved; individual line parameters and absorption cross sections for bands in the ultra-violet; refractive indices of aerosols, tables and files of general properties associated with the database; and database management software. The line-by-line portion of the database contains spectroscopic parameters for forty-two molecules including many of their isotopologues.

  1. Effects of low-temperature catalytic pretreatments on coal structure and reactivity in liquefaction. Final technical report, Volume 2 - hydrogenative and hydrothermal pretreatments and spectroscopic characterization using pyrolysis-GC-MS, CPMAS {sup 13}C NMR and FT-IR

    SciTech Connect

    Chunshan Song; Hatcher, P.G.; Saini, A.K.; Wenzel, K.A.

    1998-01-01

    It has been indicated by DOE COLIRN panel that low-temperature catalytic pretreatment is a promising approach to the development of an improved liquefaction process. This work is a fundamental study on effects of pretreatments on coal structure and reactivity in liquefaction. The main objectives of this project are to study the coal structural changes induced by low-temperature catalytic and thermal pretreatments by using spectroscopic techniques; and to clarify the pretreatment-induced changes in reactivity or convertibility of coals. As the second volume of the final report, here we summarize our work on spectroscopic characterization of four raw coals including two subbituminous coals and two bituminous coals, tetrahydrofuran (THF)-extracted but unreacted coals, the coals (THF-insoluble parts) that have been thermally pretreated. in the absence of any solvents and in the presence of either a hydrogen-donor solvent or a non-donor solvent, and the coals (THF-insoluble parts) that have been catalytically pretreated in the presence of a dispersed Mo sulfide catalyst in the absence of any solvents and in the presence of either a hydrogen-donor solvent or a non-donor solvent.

  2. Characterization of fine particulate matter in ambient air by combining TEM and multiple spectroscopic techniques--NMR, FTIR and Raman spectroscopy.

    PubMed

    Ji, Zhurun; Dai, Rucheng; Zhang, Zengming

    2015-03-01

    This paper reports a systematic study of the microstructures and spectroscopic characteristics of PM2.5 and its potential sources in Beijing by combining transmission electron microscopy and multiple spectroscopic techniques: nuclear magnetic resonance, Fourier transform infrared and Raman spectroscopy. TEM images showed that dominant components of PM2.5 are airborne organic substances with many trace metal elements which are associated with combustion sources. NMR spectra precisely determined the percentage of carbonaceous speciation in both PM2.5 (with spatial and temporal distribution) and its potential sources, and distinguished the similarities and differences among them. In FTIR spectra, a remarkable peak at 1390 cm(-1) that appeared only in PM2.5 samples was attributed to NH4NO3, representing the occurrence of secondary processes. Raman spectra revealed certain inorganic compounds including sulfate and nitrate ions. Based on the analysis of the decomposition of Raman spectra, spectral parameters provided structural information and helped to find potential sources of PM2.5. In the space of carbon aromaticity index and ID1/IG, PM2.5 points followed a linear distribution which may also be useful in source tracing. The result shows that the combined non-destructive methods are efficient to trace the sources of PM2.5. PMID:25597896

  3. Mn L{sub 2,3}-edge X-ray absorption spectroscopic studies on charge-discharge mechanism of Li{sub 2}MnO{sub 3}

    SciTech Connect

    Kubobuchi, Kei, E-mail: kubobuchi@nissan-arc.co.jp [NISSAN ARC Ltd., 1 Natsushima, Yokosuka 237-0061 (Japan); Institute of Industrial Science, The University of Tokyo, 4-6-1 Komaba, Meguro, Tokyo 153-8505, Japan. (Japan); Mogi, Masato; Imai, Hideto [NISSAN ARC Ltd., 1 Natsushima, Yokosuka 237-0061 (Japan); Ikeno, Hidekazu [Osaka Prefecture University, 1-2 Gakuen-cho, Naka-ku, Sakai, Osaka 599-8570 (Japan); Tanaka, Isao [Department of Materials Science and Engineering, Kyoto University, Yoshida-Honmachi, Sakyo-ku, Kyoto 606-8501 (Japan); Mizoguchi, Teruyasu, E-mail: teru@iis.u-tokyo.ac.jp [Institute of Industrial Science, The University of Tokyo, 4-6-1 Komaba, Meguro, Tokyo 153-8505, Japan. (Japan)

    2014-02-03

    The redox reaction of Mn in Li{sub 2}MnO{sub 3} was studied by X-ray absorption spectroscopy and ab initio multiplet calculation. Associated with the de-intercalation of Li-ion, small but clear spectral changes were observed in Mn-L{sub 2,3} X-ray absorption near edge structure (XANES). The systematic ab initio multiplet calculations of Mn-L{sub 2,3} XANES revealed that the spectral changes in the experiment could not simply be ascribed to the change of the valency from Mn{sup 4+} to Mn{sup 5+} but can be explained well by the changes of local atomic structures around Mn{sup 4+} due to the Li de-intercalation. Our results suggest that the electronic state of oxygen should change during charging in Li{sub 2}MnO{sub 3}.

  4. Spectroscopic planetary detection

    NASA Technical Reports Server (NTRS)

    Deming, Drake

    1988-01-01

    One of the most promising methods for the detection of extra-solar planets is the spectroscopic method, where a small Doppler shift (approximately 10 meters/sec) in the spectrum of the parent star reveals the presence of planetary companions. However, solar-type stars may show spurious Doppler shifts due to surface activity. If these effects are periodic, as is the solar activity cycle, then they may masquerade as planetary companions. The goal of this investigation is to determine whether the solar cycle affects the Doppler stability of integrated sunlight. Observations of integrated sunlight are made in the near infrared (approximately 2 micrometer), using the Kitt Peak McMath Fourier transform spectrometer, with an N2O gas absorption cell for calibration. Researchers currently achieve an accuracy of approximately 5 meters/sec. Solar rotation velocities vary by plus or minus 2000 meters/sec across the solar disk, and imperfect optical integration of these velocities is the principal source of error. We have been monitoring the apparent velocity of integrated sunlight since 1983. They initially saw a decrease of approximately 30 meters/sec in the integrated light velocity from 1983 through 1985, but in 1987 to 1988 the integrated light velocity returned to its 1983 level. It is too early to say whether these changes are solar-cycle related. Although the FTS, unlike a slit spectrograph, has a large field of view, researchers are always looking for ways to improve the optical integration of the solar disk. They recently made an improvement in the method used to optically collimate the FTS, and this has reduced the error level, eliminating some systematic effects seen earlier.

  5. Characterization of radiation damage at the Nb site in natural pyrochlores and samarskites by x-ray absorption spectroscopy

    SciTech Connect

    Greegor, R.B.; Lytle, F.W.; Chakoumakos, B.C.; Lumpkin, G.R.; Warner, J.K.; Ewing, R.C.

    1988-01-01

    X-ray absorption spectroscopy has been used to investigate the Nb B-site in pyrochlores (A/sub 1-2/B/sub 2/O/sub 6/Y/sub 0-1/, Fd3m, Z = 8) and samarskites (A/sub 3/B/sub 5/O/sub 16/) in both metamict and annealed condition. The XANES and EXAFS measurements indicate significant changes in pyrochlore and smaller changes in samarskite as a result of radiation damage. In the metamict state the Nb site in both pyrochlores and samarskites is similar to Nb in Nb/sub 2/O/sub 5/. Short Nb-O (1.65/angstrom/) bonds are not disrupted by alpha-decay/recoil-nuclei events as much as longer bonds (2.00/angstrom/). This increases the asymmetry and static disorder at the local Nb site while long range order is greatly diminished resulting in considerable distribution in Nb-M distances and bond angles. 23 refs., 5 figs., 1 tab.

  6. Spectroscope, Hand-Held (ChemPages Lab)

    NSDL National Science Digital Library

    Spectroscope, Hand-Held: this is a resource in the collection "ChemPages Laboratory Resources". A hand-held spectroscope contains a diffraction grating that separates electromagnetic radiation into its component wavelengths. The spectroscope can observe either absorption or emission spectra. The ChemPages Laboratory Resources are a set of web pages that include text, images, video, and self check questions. The topics included are those that are commonly encountered in the first-year chemistry laboratory. They have been put together for use as both a pre-laboratory preparation tool and an in-laboratory reference source.

  7. Characterization of Oxygen Containing Functional Groups on Carbon Materials with Oxygen K-edge X-ray Absorption Near Edge Structure Spectroscopy

    SciTech Connect

    K Kim; P Zhu; L Na; X Ma; Y Chen

    2011-12-31

    Surface functional groups on carbon materials are critical to their surface properties and related applications. Many characterization techniques have been used to identify and quantify the surface functional groups, but none is completely satisfactory especially for quantification. In this work, we used oxygen K-edge X-ray absorption near edge structure (XANES) spectroscopy to identify and quantify the oxygen containing surface functional groups on carbon materials. XANES spectra were collected in fluorescence yield mode to minimize charging effect due to poor sample conductivity which can potentially distort XANES spectra. The surface functional groups are grouped into three types, namely carboxyl-type, carbonyl-type, and hydroxyl-type. XANES spectra of the same type are very similar while spectra of different types are significantly different. Two activated carbon samples were analyzed by XANES. The total oxygen contents of the samples were estimated from the edge step of their XANES spectra, and the identity and abundance of different functional groups were determined by fitting of the sample XANES spectrum to a linear combination of spectra of the reference compounds. It is concluded that oxygen K-edge XANES spectroscopy is a reliable characterization technique for the identification and quantification of surface functional groups on carbon materials.

  8. Synthesis and characterization of Bi{sub 2}S{sub 3} composite nanoparticles with high X-ray absorption

    SciTech Connect

    Huang, Huan-Huan; Chen, Jun; Meng, Yuan-Zheng; Yang, Xiao-Quan; Zhang, Ming-Zhen; Yu, Yong; Ma, Zhi-Ya; Zhao, Yuan-Di, E-mail: zydi@mail.hust.edu.cn

    2013-10-15

    Graphical abstract: - Highlights: • Uniform Bi{sub 2}S{sub 3} nanorods were prepared via a hot injection method. • Bi{sub 2}S{sub 3} nanorods were coated with TEOS and PEG for surface modification. • CT images of Bi{sub 2}S{sub 3}@SiO{sub 2}-PEG are much higher than clinical iobitridol when they have the same concentration. • Cellular toxicity of Bi{sub 2}S{sub 3}@SiO{sub 2}-PEG is low when the probes were directly in contact with tissue fluid. - Abstract: Owing to the high X-ray absorption, Bi{sub 2}S{sub 3} nanocrystals are widely used as CT contrast agents. Here, we prepared uniform Bi{sub 2}S{sub 3} nanorods via a hot injection method using bismuth (III) chloride, sulfur and oleyl amine. The resulting nanocrystals were coated with tetraethylorthosilicate (TEOS) and 2-[methoxy(polyethyleneoxy)propyl]yrimethoxysilane (PEG-silane) for the biological utility. X-ray diffraction (XRD) and transmission electron microscopy (TEM) results showed that the Bi{sub 2}S{sub 3} nanorods had an orthorhombic structure with the length of 14 nm and the diameter of 7 nm, respectively. Composite nanoparticles (0.0226 M) gave a CT number at 550 (HU), which was higher than that of the commercial available iobitridol CT contrast agent. Furthermore, cell experiments revealed that Bi{sub 2}S{sub 3} composite nanoparticles had a low cytotoxicity with a concentration up to 0.01 M of Bi for 24 h.

  9. Picosecond flash spectroscopic studies on ultraviolet stabilizers and stabilized polymers

    NASA Technical Reports Server (NTRS)

    Scott, G. W.

    1982-01-01

    Spectroscopic and excited state decay kinetics are reported for monomeric and polymeric forms of ultraviolet stabilizers in the 2-(2'-hydroxyphenyl)-benzotriazole and 2-hydroxybenzophenone classes. For some of these molecules in various solvents at room temperature, (1) ground state absorption spectra, (2) emission spectra, (3) picosecond time-resolved transient absorption spectra, (4) ground state absorption recovery kinetics, (5) emission kinetics, and (6) transient absorption kinetics are reported. In the solid state at low temperatures, emission spectra and their temperature dependent kinetics up to approximately 200K as well as, in one case, the 12K excitation spectra of the observed dual emission are also reported.

  10. Spectroscopic study of major components of dissolved organic matter naturally occurring in water

    SciTech Connect

    Patsayeva, S. [Moscow State Univ. (Russian Federation). Physics Dept.; Reuter, R. [Univ. of Oldenburg (Germany). Physics Dept.

    1995-12-31

    Natural organic compounds are present in significant concentration in all types of water. Many organic chemicals found in natural waters can be regarded as products of both biosynthesis and biodegradation. Until now not more than 30% of the dissolved organic matter (DOM) have been chemically characterized. The characterized fraction includes compound classes as carbohydrates, amino acids, hydrocarbons, fatty acids, phenolic compounds and others. The spectroscopic study of dissolved organic matter and its major components is important for applications of lidar remote sensing techniques for water quality measurements. In this paper, fluorescence emission and excitation spectra, as well as absorption spectra for commercially available analogues of major components of gelbstoff are analyzed and compared with spectra of natural water samples of different origin.

  11. Quest for Environmentally-Benign Ligands for Actinide Separations: Thermodynamic, Spectroscopic, and Structural Characterization of U(VI) Complexes with Oxa-Diamide and Related Ligands

    Microsoft Academic Search

    Guoxin Tian; Linfeng Rao; Simon J. Teat; Guokui Liu

    2009-01-01

    Complexation of U(VI) with N,N,N,N-tetramethyl-3-oxa-glutaramide (TMOGA) and N,N-dimethyl-3-oxa-glutaramic acid (DMOGA) was studied in comparison with their dicarboxylate analog, oxydiacetic acid (ODA). Thermodynamic parameters, including stability constants, enthalpy and entropy of complexation, were determined by spectrophotometry, potentiometry and calorimetry. Single-crystal X-ray diffractometry, EXAFS spectroscopy, FT-IR absorption and laser-induced luminescence spectroscopy were used to obtain structural information on the U(VI) complexes. Like

  12. Synthesis, characterization and application of a new chelating resin for on-line separation, preconcentration and determination of Ag(I) by flame atomic absorption spectrometry.

    PubMed

    Da?ba?i, Teslima; Saçmaci, Serife; Sahan, Serkan; Kartal, Senol; Ulgen, Ahmet

    2013-01-15

    A simple and reliable on-line separation/preconcentration procedure was developed for the determination of trace levels of Ag(I) by flame atomic absorption spectrometry. Poly[N-(3-methyl-1H-indol-1-yl)-2-methacrylamide-co-2-acrylamido-2-methyl-1-propane sulfonic acid-co-divinylbenzene] was synthesized and characterized as a new chelating resin for the first time. Ag(I) was sorbed on the chelating resin, from which it could be eluted with 3 mol L(-1) HCl and then introduced directly to the nebulizer-burner system for flame atomic absorption spectrometry. The parameters influential on the determination of Ag(I) ions such as the pH of the sample solution, amount of resin, eluent type, interfering ions and flow variables were studied. Under the optimum conditions, the calibration graph obtained was linear over the concentration range of 2-20 ?g L(-1). The detection limit of the method (3?) was 0.3 ?g L(-1) while precision was 1.5% (n=25) at the level of 10 ?g L(-1) Ag(I). The limit of quantification for the method, based on 20 ?, was 2.0 ?g L(-1). The enrichment factor was found to be 65 while the optimized sample volume was 13.6 mL. The accuracy of the method was performed by analyzing certified reference materials. The developed method was applied successfully for the determination of silver in different water samples with satisfactory results. PMID:23200350

  13. Synthesis and reactivity of dimethyl gold complexes supported on MgO: characterization by infrared and X-ray absorption spectroscopies.

    PubMed

    Guzman, Javier; Anderson, Bruce G; Vinod, C P; Ramesh, Kanaparthi; Niemantsverdriet, J W; Gates, Bruce C

    2005-04-12

    Dimethyl gold complexes bonded to partially dehydroxylated MgO powder calcined at 673 K were synthesized by adsorption of Au(CH3)2(acac) (acac is C5H7O2) from n-pentane solution. The synthesis and subsequent decomposition of the complexes by treatment in He or H2 were characterized with diffuse reflectance Fourier transform infrared (DRIFT), X-ray absorption near edge structure (XANES), and extended X-ray absorption fine structure (EXAFS) spectroscopies. The XANES results identify Au(III) in the supported complexes, and the EXAFS and DRIFTS data indicate mononuclear dimethyl gold complexes as the predominant surface gold species, consistent with the lack of Au-Au contributions in the EXAFS spectrum and the presence of nu(as)(CH3) and nu(s)(CH3) bands in the IR spectrum. EXAFS data show that each complex is bonded to two oxygen atoms of the MgO surface at an Au-O distance of 2.16 angstroms. The DRIFT spectra show that reaction of Au(CH3)2(acac) with MgO at room temperature also formed Mg(acac)2 and H(acac) species on the support. Treatment of the dimethyl gold complexes in He or H2 at increasing temperatures varying from 373 to 573 K removed CH3 ligands and caused aggregation forming zerovalent gold nanoclusters of increasing size, ultimately with an average diameter of about 30 angstroms. Analysis of the gas-phase products during the genesis of the gold clusters indicated formation of CH4 (consistent with removal of CH3 groups) and CO2 at 473-573 K, associated with decomposition of the organic ligands derived from acac species. O2 and CO2 were also formed in the decomposition of ubiquitous carbonates present on the surface of the MgO support. PMID:15807620

  14. X-ray absorption spectroscopic study of chemically and electrochemically Li ion extracted Li{sub y}Co{sub 0.85}Al{sub 0.15}O{sub 2} compounds

    SciTech Connect

    Kim, M.G.; Yo, C.H. [Yonsei Univ., Seoul (Korea, Republic of). Dept. of Chemistry] [Yonsei Univ., Seoul (Korea, Republic of). Dept. of Chemistry

    1999-08-05

    The local structure refinements for chemically and electrochemically Li ion extracted Li{sub y}Co{sub 0.85}Al{sub 0.15}O{sub 2} compounds have been investigated by Co K-edge X-ray absorption spectroscopy. In the X-ray absorption near-edge structure (XANES), the 1s {r_arrow} 3d transition at {approximately} 7,709.9 eV and 1s {r_arrow} 4p transition at {approximately} 7,727.8 eV for the pristine LiCo{sub 0.85}Al{sub 0.15}O{sub 2} have shifted effectively to higher energy regions of {approximately} 0.6 eV and {approximately} 2.5 eV for the higher Li ion extraction, respectively, which shows that the average oxidation state of Co ion increases gradually with the extraction. The systematic variations of peak intensities for the 1s {r_arrow} 3d transition and 1s {r_arrow} 4p transition result from Co 3d and 4p orbital mixing by the local structure distortion around Co atoms. In particular, the abrupt decrease of peak intensity for 1s {r_arrow} 4p transition with shakedown process by ligand to metal charge transfer (LMCT) represents the transfer of the hole state from the oxygen to Co atom and the localization at the Co atomic site as a form of Co{sup IV} ion by structural distortion. The XANES features for the electrochemical extraction have shown that the electrochemical redox reaction is always not reversible in the Li ion extraction/insertion process. From the extended X-ray absorption fine structure (EXAFS) refinement, the interatomic distances of bond pairs decrease for the Li ion extraction. The chemical and electrochemical extractions have a significant effect on Fourier transform (FT) magnitude, which decreases linearly with the extraction. Since single and multiple scatterings with Co atoms have predominantly contributed to the FT magnitudes, the systematic decrease of FT magnitude is closely related to the static disorder of two different oxidative Co{sup III} and Co{sup IV} ions. This fact is consistent with the increase of the Debye-Waller factor for each bond pair.

  15. Spectroscopic and chirooptical properties of doped sillenite crystals. I. Absorption and circular-dichroism spectra of Bi{sub 12}SiO{sub 20} and Bi{sub 12}TiO{sub 20} crystals doped with phosphorus and vanadium

    SciTech Connect

    Burkov, V.I.; Zubovich, N.Yu. [Moscow Physicotechnical Institute (Russian Federation); Kargin, Yu.F.; Volkov, V.V. [Kurnakov Institute of General and Inorganic Chemistry, Moscow (Russian Federation)

    1994-08-01

    In the absorption spectra of undoped crystals of bismuth titanate Bi{sub 12}TiO{sub 20} (BTO), an inflection was found to occur at the edge of fundamental absorption; this inflection was most distinctly pronounced when the optical density was plotted on a logarithmic scale. Accordingly, in the spectrum of circular dichroism (CD) of the crystal exhibiting positive rotation, a band (peaked at 2.95 eV, {lambda} = 0.42 {mu}m) of positive sign, which coincides with the CD sign of the interband transition, is observed. In the {Delta}{epsilon}c scale, the intensity of this band attains a value of 18 x 10{sup {minus}2} cm{sup {minus}1} with 10-15-% scattering for different samples. For Al{sub 2}O{sub 3{minus}}, Ga{sub 2}O{sub 3{minus}}, and ZnO-doped bismuth titanate crystals, this band shifts to shorter wavelengths; the intensity of the long-wavelength band in the CD spectrum decreases proportionally with the dopant concentration, and, at a certain dopant concentration, this band vanishes altogether. The value of the optical rotation by the doped crystals (as compared to the undoped ones) changed noticeably only in the vicinity of the edge of fundamental absorption; however, the sign (positive) of the optical rotation remain unchanged. In this paper, the authors report on the chirooptical parameters of Bi{sub 12}SiO{sub 20} (BSO) and BTO crystals doped with V{sub 2}O{sub 5} (0.1-1.0 wt%) and P{sub 2}O{sub 5} (0.1-0.5 wt%). In experiments, the absorption and CD spectra as well as the dispersion of optical rotation (DOR) for bismuth titanate crystals doped with phosphorus and vanadium were measured; for comparison, similar data obtained for bismuth silicate crystals doped with vanadium are also presented. As compared with the undoped crystals, the spectroscopic and chirooptical characteristics of the doped crystals changed markedly at relatively low concentrations of dopants.

  16. Spectroscopic studies of tantalum doped borate glasses

    NASA Astrophysics Data System (ADS)

    Sharada, M.; Suresh Babu, D.

    2012-10-01

    Glasses with formula 30Li2O 60B2O3xTa2O5 (10-x) Bi2O3 for x=0, 2, 4, 6 and 8 were prepared via normal melt quenching technique and characterized by refractive index and MDSC. Refractive index (?) and glass transition temperature (Tg) are found to increase with increase in dopant concentration. Impedance spectra of the samples were recorded in the frequency range 100 Hz-5 MHz in the temperature range 175-275 °C. The plots are typical of those recorded for disordered systems. Conductivities and relaxation times are found to follow Arrhenius type of relation and activation energies are calculated. Optical absorption spectra were recorded in the wavelength range 200-900 nm range from which cutoff wavelength (?c) and optical band gap energy (Eg) are evaluated. ?c is found to decrease while Eg to increase with increase in composition. FTIR spectra of the samples were recorded in the frequency range 400-1500 cm-1 which exhibit characteristic bands corresponding to BO3, BO4 stretching vibrations and BO bending vibration. Tightening of the structure is indicated by increase in the vibration of BO3 at the cost of BO4 for 8 mol% of Ta2O5. This is in support of the highest value of Tg for this sample among the series. Raman spectra of the samples were recorded in the frequency range 200-1200 cm-1. With successive addition of Ta2O5, increase in the vibration of Ta-O groups TaO6 groups to be responsible for observed increase in ? and Tg. An attempt is made to prepare tantalum doped borate glasses and study them by spectroscopic techniques.

  17. Electronic structure, orbital symmetry and bonding topology of Ba(Fe{sub 1-x}Co{sub x}){sub 2}As{sub 2} superconductors probed with x-ray absorption spectroscop.

    SciTech Connect

    Cheney, C. P.; Bondino, F.; Callcott, T. A.; Vilmercati, P.; Ederer, D.; Magnano, E.; Malvestuto, M.; Parmigiani, F.; Sefat, A. S.; McGuire, M. A.; Jin, R.; Sales, B. C.; Mandrus, D.; Singh, D. J.; Freeland, J. W.; Mannella, N. (X-Ray Science Division); ( PSC-USR); (Univ. of TN); (CNR-INFM, Lab. Nazionale TASC); (Tulane Univ.); (Sincrotrone Trieste S.C.p.A.); (Univ. degli Studi di Trieste); (ORNL)

    2010-01-01

    The orbital symmetries of electron-doped iron-arsenide superconductors Ba(Fe{sub 1-x}Co{sub x}){sub 2}As{sub 2} have been measured with x-ray absorption spectroscopy. The data reveal signatures of Fe d electron itinerancy, weak electronic correlations, and a high degree of Fe-As hybridization related to the bonding topology of the Fe d{sub xz+yz} states, which are found to contribute substantially at the Fermi level. The energies and detailed orbital character of Fe and As derived unoccupied s and d states are found to be in remarkably good agreement with the predictions of standard density-functional theory.

  18. Synthesis, spectroscopic and structural characterization of 5-benzoyl-4-phenyl-2-methylthio-1H-pyrimidine with theoretical calculations using density functional theory

    NASA Astrophysics Data System (ADS)

    ?nkaya, Ersin; Dinçer, Muharrem; ?ahan, Emine; Y?ld?r?m, ?smail

    2013-10-01

    In this paper, we will report a combined experimental and theoretical investigation of the molecular structure and spectroscopic parameters (FT-IR, 1H NMR, 13C NMR) of 5-benzoyl-4-phenyl-2-methylthio-1H-pyrimidine. The compound crystallizes in the triclinic space group P-1 with Z = 2. The molecular geometry was also optimized using density functional theory (DFT/B3LYP) method with the 6-311G(d,p) and 6-311++G(d,p) basis sets in ground state and compared with the experimental data. All the assignments of the theoretical frequencies were performed by potential energy distributions using VEDA 4 program. Information about the size, shape, charge density distribution and site of chemical reactivity of the molecules has been obtained by mapping electron density isosurface with electrostatic potential (ESP). Also, non-linear optical properties of the title compound were performed at B3LYP/6-311++G(d,p) level. The theoretical results showed an excellent agreement with the experimental values.

  19. Raman and infrared spectroscopic characterization of the phosphate mineral paravauxite Fe2+Al2(PO4)2(OH)2?8H2O

    NASA Astrophysics Data System (ADS)

    Frost, Ray L.; Scholz, Ricardo; Lópes, Andrés; Xi, Yunfei; Gobac, Željka Žigove?ki; Horta, Laura Frota Campos

    2013-12-01

    We have undertaken a vibrational spectroscopic study of paravauxite the Siglo XX mine, Bustillo Province, northern of Potosí department, Bolivia. This mine is important source for rare and unusual secondary phosphate minerals and is the type locality for a number of rare phosphates such as vauxite, sigloite, metavauxite and for jeanbandyite. The chemical formula of the studied sample was determined as Fe0.952+,(Al0.07)?1.02(Al)2.09(PO4)1.97(OH)1.98·7.90(H2O). The Raman spectrum is dominated by an intense Raman band at 1020 cm-1 assigned to the PO43-?1 symmetric stretching mode. Low intensity Raman bands found at 1058, 1115 and 1148 cm-1 are assigned to the PO43-?3 antisymmetric stretching vibrations. Raman bands of paravauxite at 537, 570, 609 and 643 cm-1 are assigned to the ?4PO43- bending modes whilst the Raman bands at 393 and 420 cm-1 are due to the ?2PO43- bending modes. The Raman spectral profile of paravauxite in the hydroxyl stretching region is broad with component bands resolved at 3086, 3215, 3315, 3421, 3505 and 3648 cm-1. Vibrational spectroscopy enables the assessment of the molecular structure of paravauxite to be undertaken.

  20. Characterization and quantification of amorphous material in milled and spray-dried salbutamol sulfate: a comparison of thermal, spectroscopic, and water vapor sorption approaches.

    PubMed

    Grisedale, Louise C; Jamieson, Matthew J; Belton, Peter S; Barker, Susan A; Craig, Duncan Q M

    2011-08-01

    A study has been undertaken using a range of established and novel approaches to examine the effects of milling on the structure and crystallization behavior of salbutamol sulfate. A combination of modulated temperature differential scanning calorimetry, attenuated total reflectance Fourier-transform infrared spectroscopy, powder X-ray diffraction, and gravimetric vapor sorption analysis have been employed, with a particular view to examining the validity of using spray-dried material as a comparator. Although the expected increase in amorphization with milling time was observed, several unexpected observations were made including an apparently anomalous relationship between glass transition temperature and water content; this was used as the basis for the development of a novel method of quantifying amorphous content. Reasonable agreement was found between the data obtained from the spectroscopic and thermal methods, particularly those latter approaches that do not rely on recrystallization for quantification. The activation energy for the onset process was determined and found to be similar for all materials studied. The study has indicated that when using spray-dried material as a standard, the associated limitations must be appreciated, particularly in terms of the assumption of comparability of the recrystallization process between materials that is embedded in many quantification techniques. PMID:21456029

  1. Speciation and characterization of arsenic in gold ores and cyanidation tailings using X-ray absorption spectroscopy

    USGS Publications Warehouse

    Paktunc, D.; Foster, A.; Heald, S.; Laflamme, G.

    2004-01-01

    The knowledge of mineralogy and molecular structure of As is needed to better understand the stability of As in wastes resulting from processing of gold ores. In this study, optical microscopy, scanning electron microscopy, electron microprobe, X-ray diffraction and X-ray absorption fine structure (XAFS) spectroscopy (including both XANES and EXAFS regimes) were employed to determine the mineralogical composition and local coordination environment of As in gold ores and process tailings from bench-scale tests designed to mimic a common plant practice. Arsenic-bearing minerals identified in the ores and tailings include iron (III) oxyhydroxides, scorodite (FeAsO4??2H2O), ferric arsenates, arseniosiderite (Ca2Fe3 (AsO4)3O2??3H2O), Ca-Fe arsenates, pharmacosiderite (KFe4 (AsO4)3(OH)4??6-7H2O), jarosite (K2Fe6(SO4)4 (OH)12) and arsenopyrite (FeAsS). Iron (III) oxyhydroxides contain variable levels of As from trace to about 22 wt% and Ca up to approximately 9 wt%. Finely ground ore and tailings samples were examined by bulk XAFS and selected mineral grains were analyzed by microfocused XAFS (micro-EXAFS) spectroscopy to reconcile the ambiguities of multiple As sources in the complex bulk EXAFS spectra. XANES spectra indicated that As occurs as As5+in all the samples. Micro-EXAFS spectra of individual iron (III) oxyhydroxide grains with varying As concentrations point to inner-sphere bidentate-binuclear arsenate complexes as the predominant form of As. There are indications for the presence of a second Fe shell corresponding to bidentate-mononuclear arrangement. Iron (III) oxyhydroxides with high As concentrations corresponding to maximum adsorption densities probably occur as nanoparticles. The discovery of Ca atoms around As in iron (III) oxyhydroxides at interatomic distances of 4.14-4.17 A?? and the coordination numbers suggest the formation of arseniosiderite-like nanoclusters by coprecipitation rather than simple adsorption of Ca onto iron (III) oxyhydroxides. Correlation of Ca with As in iron (III) oxyhydroxides as determined by electron microprobe analysis supports the coprecipitate origin for the presence of Ca in iron (III) oxyhydroxides. The samples containing higher abundances of ferric arsenates released higher As concentrations during the cyanidation tests. The presence of highly soluble ferric arsenates and Ca-Fe arsenates, and relatively unstable iron (III) oxyhydroxides with Fe/As molar ratios of less than 4 in the ore and process tailings suggests that not only the tailings in the impoundment will continue to release As, but also there is the potential for mobilization of As from the natural sources such as the unmined ore. ?? 2004 Elsevier Ltd.

  2. Spectroscopic properties of Sm3+-doped oxy-fluoride powders with various Sm3+ concentration and sintering temperature

    NASA Astrophysics Data System (ADS)

    Liu, Fangchao; Han, Qun; Liu, Tiegen; Yao, Yunzhi; Chen, Yaofei; Du, Yang

    2015-07-01

    Sm3+-doped oxy-fluoride (OFSm) powders are prepared by the melt quenching technique and characterized using FE-SEM, optical absorption and emission techniques. Spectroscopic properties of Sm3+-doped oxy-fluoride powders with different Sm3+ concentration and sintering temperature are presented and discussed by using the absorption, emission measurements. The Judd-Ofelt intensity (J-O) parameters (??, where ? = 2, 4 and 6), measured from the experimental oscillator strengths of the absorption spectra, are used to evaluate the radiative parameters of the fluorescence transitions. Intense orange emission can be obtained when excited with 325 nm wavelength by increasing the sintering temperature to 1400 °C. Ratio of fluorescence intensities arising from the two closing lying 4F3/2 and 4G5/2 levels is studied, concentration quenching has been noticed beyond 2 mol% of Sm3+ ions concentration. The excellent spectroscopic properties along with the outstanding thermal stability suggest that the OFSm03 powders may become an attractive laser material to exhibit efficient visible lasing emission in the orange spectral region.

  3. Sulfur X-Ray Absorption And Vibrational Spectroscopic Study of Sulfur Dioxide, Sulfite, And Sulfonate Solutions And of the Substituted Sulfonate Ions X(3)CSO(3-)(X = H, Cl, F)

    SciTech Connect

    Risberg, E.Damian; Eriksson, L.; Mink, J.; Pettersson, L.G.M.; Skripkin, M.Yu.; Sandstrom, M.

    2009-06-02

    Sulfur K-edge X-ray absorption near-edge structure (XANES) spectra have been recorded and the S(1s) electron excitations evaluated by means of density functional theory-transition potential (DFT-TP) calculations to provide insight into the coordination, bonding, and electronic structure. The XANES spectra for the various species in sulfur dioxide and aqueous sodium sulfite solutions show considerable differences at different pH values in the environmentally important sulfite(IV) system. In strongly acidic (pH < {approx}1) aqueous sulfite solution the XANES spectra confirm that the hydrated sulfur dioxide molecule, SO{sub 2}(aq), dominates. The theoretical spectra are consistent with an OSO angle of {approx}119{sup o} in gas phase and acetonitrile solution, while in aqueous solution hydrogen bonding reduces the angle to {approx}116{sup o}. The hydration affects the XANES spectra also for the sulfite ion, SO{sub 3}{sup 2-}. At intermediate pH (4) the two coordination isomers, the sulfonate (HSO{sub 3{sup -}}) and hydrogen sulfite (SO{sub 3}H{sup -}) ions with the hydrogen atom coordinated to sulfur and oxygen, respectively, could be distinguished with the ratio HSO{sub 3{sup -}}:SO{sub 3}H{sup -} about 0.28:0.72 at 298 K. The relative amount of HSO{sub 3{sup -}} increased with increasing temperature in the investigated range from 275 to 343 K. XANES spectra of sulfonate, methanesulfonate, trichloromethanesulfonate, and trifluoromethanesulfonate compounds, all with closely similar S-O bond distances in tetrahedral configuration around the sulfur atom, were interpreted by DFT-TP computations. The energy of their main electronic transition from the sulfur K-shell is about 2478 eV. The additional absorption features are similar when a hydrogen atom or an electron-donating methyl group is bonded to the -SO{sub 3} group. Significant changes occur for the electronegative trichloromethyl (Cl{sub 3}C-) and trifluoromethyl (F{sub 3}C-) groups, which strongly affect the distribution especially of the {pi} electrons around the sulfur atom. The S-D bond distance 1.38(2) {angstrom} was obtained for the deuterated sulfonate (DSO{sub 3{sup -}}) ion by Rietveld analysis of neutron powder diffraction data of CsDSO{sub 3}. Raman and infrared absorption spectra of the CsHSO{sub 3}, CsDSO{sub 3}, H{sub 3}CSO{sub 3}Na, and Cl{sub 3}CSO{sub 3}Na{center_dot}H{sub 2}O compounds and Raman spectra of the sulfite solutions have been interpreted by normal coordinate calculations. The C-S stretching force constant for the trichloromethanesulfonate ion obtains an anomalously low value due to steric repulsion between the Cl{sub 3}C- and -SO{sub 3} groups. The S-O stretching force constants were correlated with corresponding S-O bond distances for several oxosulfur species.

  4. Spectroscopic characterization of zirconium(IV) and hafniumf(IV) gallate phthalocyanines in monolithic silica gels obtained by sol gel method

    NASA Astrophysics Data System (ADS)

    Gerasymchuk, Y. S.; Chernii, V. Ya.; Tomachynski, L. A.; Legendziewicz, J.; Radzki, St.

    2005-07-01

    The Zr(IV) and Hf(IV) phthalocyanines, with gallate as axial ligand coordinated to the central metal atom of phthalocyanine, were incorporated in silica gels during sol-gel process with using tetraethyl orthosilicate (TEOS) as precursor. The obtained mixed inorganic-organic composites were transparent and homogeneous. The absorption and emission properties of these materials in comparison with the spectra of the Zr(IV) and Hf(IV) phthalocyanines in various solvents were investigated. The spectra were correlated with various stage of the sol-gel process. It was established that in the gels concurrence of the monomer and dimer form is different in sol, alco-, hydro- and xerogels. The intensive 700-725 nm fluorescence emission upon relatively long-wavelength excitation and unusually large (about 45 nm) Stokes shift in the Q region, suggest that Zr(IV) and Hf(IV) phthalocyanines could be considered as photosensitizers in the PDT method (photodynamic therapy).

  5. 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 ?(FeNO) and ?(NO) that are only marginally distinct from those reported for native myoglobin. However, binding of FeII at the FeB site shifts the heme ?(FeNO) by +17 cm-1 and the ?(NO) by -50 cm-1 to 1549 cm-1. This low ?(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 ?(NO) in the ZnII-loaded protein supports this interpretation. PMID:21634416

  6. New diorganotin(IV) complexes with 3-(2-hydroxy-5-methylphenylamino)-1,3-diphenylprop-2-en-1-one: Synthesis, spectroscopic characterization, structural studies and antibacterial activity

    NASA Astrophysics Data System (ADS)

    Sedaghat, Tahereh; Naseh, Mohamad; Bruno, Giuseppe; Amiri Rudbari, Hadi; Motamedi, Hossein

    2012-10-01

    New organotin(IV) complexes, Ph2SnL (1) and Me2SnL (2), have been synthesized from reaction of corresponding diorganotin(IV) dichlorides with a Schiff base, 3-(2-hydroxy-5-methylphenylamino)-1,3-diphenylprop-2-en-1-one (H2L), derived from condensation of 2-amino-4-methylphenol with dibenzoylmethane. The synthesized compounds have been investigated by elemental analysis and IR, 1H NMR, and 119Sn NMR spectroscopy. Spectroscopic studies show that the Schiff base acts as a tridentate dianionic ligand and coordinates via the nitrogen and phenolic and enolic oxygen atoms. The structures of H2L and 2 have been also confirmed by X-ray crystallography. Schiff base exists as the keto-amine tautomeric form in solid state with two intramolecular hydrogen bonds of the Nsbnd H⋯O type and also intermolecular hydrogen bonds of Osbnd H⋯O type that create a dimer. In the structure of 2, tin center is surrounded by two O and one N atoms from the ligand and two C atoms of methyl groups and the sixth coordination site is occupied by phenolic oxygen atom of another molecule, thus a dimeric molecule with a Sn2O2 four-membered ring is formed. The in vitro antibacterial activity of ligand and complexes has been evaluated against Gram-positive (Bacillus cereus and Staphylococcus aureus) and Gram-negative (Escherichia coli and Pseudomonas aeruginosa) bacteria. H2L showed no activity but the diphenyltin(IV) complex exhibited good activities along with the standard antibacterial drugs.

  7. Building a Spectroscope

    NSDL National Science Digital Library

    Students learn about the variations of white light in this Moveable Museum unit, in which they build a pocket-sized spectroscope from readily available materials and examine different light sources in school, at home, and around their town or city. The seven-page PDF guide includes suggested general background readings for educators, activity and safety notes, step-by-step directions, and a spectroscope template.

  8. Network vs Molecular Structural Characteristics of Ge-Doped Arsenic Sulfide Glasses: A Combined Neutron/X-ray Diffraction, Extended X-ray Absorption Fine Structure, and Raman Spectroscopic Study

    SciTech Connect

    Soyer-Uzun, S.; Sen, S; Aitken, B

    2009-01-01

    Combined neutron/X-ray diffraction, Ge and As K-edge extended X-ray absorption fine structure analysis, and Raman spectroscopy are employed to study the compositional dependence of the short- and intermediate-range structures of As-rich GexAsyS100-x-y glasses with a constant Ge:As atomic ratio of 1:17.3. The structures of glasses with compositions near stoichiometry (35 ? x + y ? 43) are dominated by the presence of a predominantly heteropolar-bonded As2S3 network. However, an increasing metal content (x + y = 55) results in a novel glass consisting predominantly of As4S3 molecules, held together by van der Waals forces. The formation of this 'molecular' glass implies an apparently anomalous situation of near-zero connectivity and dimensionality with increasing average coordination number. A further increase in metal content (60 ? x + y ? 65) results in the formation of As-As homopolar-bonded structural regions that coexist with As4S3 molecules. Such unusual evolution of intermediate-range order is shown to be closely related to the compositional variation of thermophysical properties and density fluctuation in these glasses

  9. Fourier-transformed infrared absorption spectroscopy: a tool to characterize the chemical composition of Ar-NH3-SiH4 dielectric barrier discharge

    NASA Astrophysics Data System (ADS)

    Vallade, Julien; Massines, Françoise

    2013-11-01

    This study brings initial insight into the characterization of the gas chemical composition in a dielectric barrier discharge (DBD) by Fourier-transformed infrared absorption spectroscopy. Capitalizing on a double path of the IR beam, measurements were performed in 5 cm long, 2 mm gap plasma. As the IR beam cross-section in the plasma was 2 × 2 mm2, a translation system was used to scan the plasma along the direction of the gas flow with a 2 mm spatial resolution. In the case of Ar-SiH4(67 ppm)-NH3(133 ppm) glow-mode DBD, all IR spectra peaks from 6000 to 800 cm-1 are related to vibrations of Si-H from SiH4 and N-H from NH3. Here, the N-H vibration is observable but non-quantifiable. At 50 kHz excitation, the absolute concentration of SiH4 was measured at different positions and different power values in continuous and modulated modes. In the absence of powder formation in the plasma and for an initial density of 1.6 × 1015 cm-3, all the measurements are fitted by the same exponential decay leading to an energy of 38 eV per dissociated molecule of SiH4. The presence of powders in the plasma reduces SiH4 dissociation rate by a factor larger than 4.

  10. Characterization of Pd-Based FCC CO/NO(X) Control Additives By in Situ FTIR And Extended X-Ray Absorption Fine Structure Spectroscopies

    SciTech Connect

    Alexeev, O.S.; Krishnamoorthy, S.; Ziebarth, M.S.; Yaluris, G.; Roberie, T.G.; Amiridis, M.D.

    2009-05-28

    Pd n{sup +}/Ce n{sup +}/Na{sup +}/{gamma}-Al{sub 2}O{sub 3}-type materials used as FCC additives for CO/NO{sub x} control were characterized by extended x-ray absorption fine structure (EXAFS) spectroscopy and in situ FTIR. The EXAFS data indicate that in freshly prepared samples palladium is present in the form of high dispersed PdO species. Reduction with H{sub 2} at 500{sup o}C leads to the formation of small Pd clusters incorporating on average approximately six to eight metal atoms at a Pd-Pd bond distances of 2.76 {angstrom}. All components of these materials can interact with NO and promote the formation of nitrate/nitrite species, essentially 'trapping' NO{sub x} species on the catalyst surface. However, the Na{sup +} species dominate the surface chemistry and readily form sodium nitrates with a characteristic IR band at 1370--1385 cm{sup -1}. Finally, hydroxyls from the support are also actively participating in the formation of HNO{sub x} type compounds with characteristic stretching vibrations in the 3500-3572 cm{sup -1} region.

  11. Characterization of Pd-based FCC CO/NOx Control Additives by in situ FTIR and Extended X-ray Absorption Fine Structure Spectrscopies

    SciTech Connect

    Alexeev,O.; Krishnamoorthy, S.; Ziebarth, M.; Yaluris, G.; Roberie, T.; Amiridis, M.

    2007-01-01

    Pd{sup n+}/Ce{sup n+}/Na{sup +}/{gamma}-Al{sub 2}O{sub 3}-type materials used as FCC additives for CO/NO{sub x} control were characterized by extended X-ray absorption fine structure (EXAFS) spectroscopy and in situ FTIR. The EXAFS data indicate that in freshly prepared samples palladium is present in the form of highly dispersed PdO species. Reduction with H{sub 2} at 500 C leads to the formation of small Pd clusters incorporating on average approximately six to eight metal atoms at a Pd-Pd bond distance of 2.76 {angstrom}. All components of these materials can interact with NO and promote the formation of nitrate/nitrite species, essentially 'trapping' NO{sub x} species on the catalyst surface. However, the Na{sup +} species dominate the surface chemistry and readily form sodium nitrates with a characteristic IR band at 1370-1385 cm{sup -1}. Finally, hydroxyls from the support are also actively participating in the formation of HNO{sub x} type compounds with characteristic stretching vibrations in the 3500-3572 cm{sup -1} region.

  12. Exo-S: A Probe-scale Space Mission to Directly Image and Spectroscopically Characterize Exoplanetary Systems Using a Starshade and Telescope System

    NASA Astrophysics Data System (ADS)

    Seager, Sara; Cash, Webster C.; Kasdin, N. Jeremy; Sparks, William B.; Turnbull, Margaret C.; Kuchner, Marc J.; Roberge, Aki; Domagal-Goldman, Shawn; Shaklan, Stuart; Thomson, Mark; Lisman, Doug; Martin, Suzanne; Cady, Eric; Webb, David

    2014-06-01

    "Exo-S" is NASA's first directed community study of a starshade and telescope system for space-based discovery and characterization of exoplanets by direct imaging. Under a cost cap of $1B, Exo-S will use a modestly sized starshade (also known as an "external occulter") and a modest aperture space telescope for high contrast observations of exoplanetary systems. The Exo-S will obtain spectra of a subset of its newly discovered exoplanets as well as already known Jupiter-mass exoplanets. Exo-S will be capable of reaching down to the discovery of Earth-size planets in the habitable zones of twenty sun-like stars, with a favorable few accessible for spectral characterization. We present highlights of the science goals, the mission design, and technology milestones already reached. At the study conclusion in 2015, NASA will evaluate the Exo-S concept for potential development at the end of this decade.

  13. ADVANCED SPECTROSCOPIC AND MICRO-SCOPIC CHARACTERISATION TECHNIQUES -

    E-print Network

    Sparks, Donald L.

    - 1 - ADVANCED SPECTROSCOPIC AND MICRO- SCOPIC CHARACTERISATION TECHNIQUES - TOOLS TO ENLIGHTEN wide time scales. Ex- situ batch and flow techniques offer high elemental sensitivity, but their time-situ synchrotron-based, quick scanning X-ray absorption spectroscopy (Q-XAS) and attenuated total reflectance

  14. Arsenate Adsorption On Ruthenium Oxides: A Spectroscopic And Kinetic Investigation

    EPA Science Inventory

    Arsenate adsorption on amorphous (RuO2?1.1H2O) and crystalline (RuO2) ruthenium oxides was evaluated using spectroscopic and kinetic methods to elucidate the adsorption mechanism. Extended X-ray absorption fine structure spectroscopy (EXAFS) was ...

  15. Spectroscopic Characterization and 3-MICROMETER CW Laser Operation of ERBIUM(3+):GADOLINIUM(3) GALLIUM(5) OXYGEN(12) and ERBIUM(3+):YTTRIUM(3) SCANDIUM(2) GALLIUM(3) OXYGEN(12)

    NASA Astrophysics Data System (ADS)

    Dinerman, Bradley Jay

    The spectroscopic and 3-?m laser properties of rm Er^{3+ }{:}Gd_3Ga_5O_{12 } and rm Er^{3+} {:}Y_3Sc_2Ga_3O_{12 } are investigated. The Judd-Ofelt Theory is applied to calculate radiative lifetimes, branching ratios, and radiative quantum efficiencies. The results reveal radiative lifetimes significantly longer than those actually observed for the ^4I_ {11/2}, ^4I_{9/2} , and ^4S_{3/2 } states, which indicate that strong quenching processes operate in these media. Radiative quantum efficiencies of 24% and 32% are observed from the ^4I _{11/2} state for GGG and YSGG, respectively. The role of upconversion is examined in an experiment in which the luminescence which occurs from the ^4S_{3/2} and ^4I_{9/1} states following chopped, cw pumping is analyzed in two time domains: that resulting from direct excitation and that resulting following upconversion-induced excitation. The ratio of upconversion-induced luminescence to pump-induced luminscence is quantified and applied to a simplified rate model, from which values of the ^4I_ {13/2} and ^4I _{11/2} upconversion coefficients, alpha_1 and alpha _2, are calculated. The calculated alpha_1 is typically larger than the calculated alpha_2, which partially explains the mechanism by which cw laser oscillation occurs. The 3-?m laser properties of Er:GGG and Er:YSGG are investigated using monolithic laser resonators. The lasers are pumped directly into the ^4I_{11/2} upper state near 0.97 ?m by either a Ti:sapphire or InGaAs diode laser. Greater than 0.5-W of 2.79-?m laser emission and nearly 0.3-W of 2.82-?m emission are observed from diode-pumped Er:YSGG and Er:GGG, respectively. The efficiencies and properties of the two host materials are typically very similar, yet YSGG categorically operates more efficiently than GGG. The spectral and spatial characteristics of the emission are also observed. The lasers typically operate on four or five longitudinal modes. Tunable, single-frequency emission is demonstrated from Er:YAG at 2.94-mu m. TEM_{00}-mode operation from GGG and YSGG is observed under Ti:sapphire -pumped conditions; multimode operation is observed from the diode-pumped system.

  16. Infrared and Raman spectroscopic characterization of the borate mineral colemanite - CaB3O4(OH)3·H2O - implications for the molecular structure

    NASA Astrophysics Data System (ADS)

    Frost, Ray L.; Xi, Yunfei; Scholz, Ricardo; Belotti, Fernanda Maria; Cândido Filho, Mauro

    2013-04-01

    Colemanite CaB3O4(OH)3·H2O is a secondary borate mineral formed from borax and ulexite in evaporate deposits of alkaline lacustrine sediments. The basic structure of colemanite contains endless chains of interlocking BO2(OH) triangles and BO3(OH) tetrahedrons with the calcium, water and extra hydroxide units interspersed between these chains. The Raman spectra of colemanite is characterized by an intense band at 3605 cm-1 assigned to the stretching vibration of OH units and a series of bands at 3182, 3300, 3389 and 3534 cm-1 assigned to water stretching vibrations. Infrared bands are observed in similar positions. The BO stretching vibrations of the trigonal and tetrahedral boron are characterized by Raman bands at 876, 1065 and 1084 cm-1. The OBO bending mode is defined by the Raman band at 611 cm-1. It is important to characterize the very wide range of borate minerals including colemanite because of the very wide range of applications of boron containing minerals.

  17. Synthesis and spectroscopic characterization of 3,4-difluoroacetophenone-thiosemicarbazone and its palladium(II) complex: Evaluation of antimicrobial and antitumour activity

    NASA Astrophysics Data System (ADS)

    Jagadeesh, M.; Rashmi, H. K.; Subba Rao, Y.; Sreenath Reddy, A.; Prathima, B.; Uma Maheswari Devi, P.; Reddy, A. Varada

    2013-11-01

    A new cis-palladium(II)diaqua(3,4-difluoroacetophenonethiosemicarbazone complex (Pd(II) complex) is synthesized using 3,4-difluoroacetophenonethiosemicarbazone(L). The L and its Pd(II) complex are characterized and confirmed by elemental analyses, electrochemical analyses, FT-IR, FT-Raman, UV-Vis, HRMS and LC-MS techniques. Ligand L is further characterized by 1H, 13C and 19F NMR spectroscopy. The crystal structure of L is unambiguously characterized by single X-ray crystallography. The ligand (L) belongs to monoclinic system with P2(1)/C space group and the unit cell parameters are a(Å) = 9.1144(7), b(Å) = 13.7928(7), c(Å) = 8.4174(5), ?(°) = 90, ?(°) = 100.715, ?(°) = 90 and volume V(A3) = 1039.73(11). The Raman bands observed for the L and its Pd(II) complex are in good agreement with the FT-IR spectral data. The Pd(II) complex is found to be highly efficient in inhibiting the growth of human pathogens like Salmonella typhimurium and Klebsiella pneumonia with MIC value 10.0 ?g/mL whose inhibition zones are almost comparable with the standard antibiotic. The synthesized compounds have shown antiproliferative activity against the human breast cancer cell lines MDA-MB231 by intermitting the regular pathway of ribonucleotidereductase.

  18. A cavity type absorption cell for double resonance microwave spectroscopy.

    NASA Technical Reports Server (NTRS)

    Lee, M. C.; White, W. F.

    1972-01-01

    Description of an experimental dual resonant cavity absorption cell for observing microwave spectroscopic double-resonance effects. The device is composed of two Fabry-Perot interferometers excited by independent microwave sources and mounted at right angles in a suitable vacuum enclosure. The pumping transition is modulated by one source and the modulation induced on the rf absorption in the orthogonal cavity is detected.

  19. Utilization of charge-transfer complexation for the detection of carcinogenic substances in foods: Spectroscopic characterization of ethyl carbamate with some traditional ?-acceptors

    NASA Astrophysics Data System (ADS)

    Adam, Abdel Majid A.; Refat, Moamen S.; Saad, Hosam A.

    2013-04-01

    The study of toxic and carcinogenic substances in foods represents one of the most demanding areas in food safety, due to their repercussions for public health. One potentially toxic compound for humans is ethyl carbamate (EC). EC is a multi-site genotoxic carcinogen of widespread occurrence in fermented foods and alcoholic beverages. Structural and thermal stability of charge-transfer complexes formed between EC as a donor with quinol (QL), picric acid (PA), chloranilic acid (CLA), p-chloranil (p-CHL) and 1,3-dinitrobenzene (DNB) as acceptors were reported. Elemental analysis (CHN), electronic absorption spectra, photometric titration, IR, and 1H NMR spectra show that the interaction between EC and acceptors was stabilized by hydrogen bonding, via a 1:1 stoichiometry. Thermogravimetric (TG) analysis indicates that the formation of molecular CT complexes was stable, exothermic and spontaneous. Finally, the CT complexes were screened for their antibacterial and antifungal activities. The results indicated that the [(EC)(QL)] complex exhibited strong antimicrobial activities against various bacterial and fungal strains compared with standard drugs.

  20. Structural and spectroscopic characterizations on the charge-transfer interactions of the second generation poly(propylene amine) dendrimers with iodine and picric acid acceptors

    NASA Astrophysics Data System (ADS)

    El-Sayed, Mohamed Y.; Refat, Moamen S.

    2015-02-01

    Herein, this study was focused to get a knowledge about the intermolecular charge transfer complexes between the second generation of poly(propylene amine) dendrimer (PPD2) with picric acid (PA) and iodine (I2) as ? and ?-acceptors. The charge-transfer interaction of the PPD2 electron donor and the PA acceptor has been studied in CHCl3. The resulted data refereed to the formation of the new CT-complex with the general formula [(PPD2)(PA)4]. The 1:4 stoichiometry of the reaction was discussed upon the on elemental analysis and photometric titration. On the other hand, the 1:3½ iodine-PPD2 heptaiodide (I7-) charge-transfer complex has been studied spectrophotometrically in chloroform at room temperature with general formula [(PPD2)]+I7-. The electronic absorption bands of 2I2·I3- (I7-) are observed at 358 and 294 nm. Raman laser spectrum of the brown solid heptaiodide complex has two clearly vibration bands at 155 and 110 cm-1 due to symmetric stretching ?s(Isbnd I) outer and inner bonds, respectively. The 1H NMR spectra and differential scanning calorimetry (DSC) data of PPD2 charge-transfer complexes were discussed.

  1. Supercritical hydrothermal synthesis of Cu{sub 2}O(SeO{sub 3}): Structural characterization, thermal, spectroscopic and magnetic studies

    SciTech Connect

    Larranaga, Aitor [Departamento de Mineralogia y Petrologia, Facultad de Ciencia y Tecnologia, Universidad del Pais Vasco/EHU, Apdo. 644, E-48080 Bilbao (Spain); Mesa, Jose L. [Departamento de Quimica Inorganica, Facultad de Ciencia y Tecnologia, Universidad del Pais Vasco/EHU, Apdo. 644, E-48080 Bilbao (Spain)], E-mail: joseluis.mesa@ehu.es; Lezama, Luis [Departamento de Quimica Inorganica, Facultad de Ciencia y Tecnologia, Universidad del Pais Vasco/EHU, Apdo. 644, E-48080 Bilbao (Spain); Pizarro, Jose L.; Arriortua, Maria I. [Departamento de Mineralogia y Petrologia, Facultad de Ciencia y Tecnologia, Universidad del Pais Vasco/EHU, Apdo. 644, E-48080 Bilbao (Spain); Rojo, Teofilo [Departamento de Quimica Inorganica, Facultad de Ciencia y Tecnologia, Universidad del Pais Vasco/EHU, Apdo. 644, E-48080 Bilbao (Spain)

    2009-01-08

    Cu{sub 2}O(SeO{sub 3}) has been synthesized in supercritical hydrothermal conditions, using an externally heated steel reactor with coupled hydraulic pump for the application of high pressure. The compound crystallizes in the P2{sub 1}3 cubic space group. The unit cell parameter is a = 9.930(1) A with Z = 12. The crystal structure has been refined by the Rietveld method. The limit of thermal stability is, approximately, 490 deg. C. Above this temperature the compound decomposes to SeO{sub 2}(g) and CuO(s). The IR spectrum shows the characteristic bands of the (SeO{sub 3}){sup 2-} oxoanion. In the diffuse reflectance spectrum two intense absorptions characteristic of the Cu(II) cations in five-coordination are observed. The ESR spectra are isotropic from room temperature to 5 K, with g = 2.11(2). The thermal evolution of the intensity and line width of the signals suggest a ferromagnetic transition in the 50-45 K range. Magnetic measurements, at low temperatures, confirm the existence of a ferromagnetic transition with a critical temperature of 55 K.

  2. Analyzing Water's Optical Absorption

    NASA Technical Reports Server (NTRS)

    2002-01-01

    A cooperative agreement between World Precision Instruments (WPI), Inc., and Stennis Space Center has led the UltraPath(TM) device, which provides a more efficient method for analyzing the optical absorption of water samples at sea. UltraPath is a unique, high-performance absorbance spectrophotometer with user-selectable light path lengths. It is an ideal tool for any study requiring precise and highly sensitive spectroscopic determination of analytes, either in the laboratory or the field. As a low-cost, rugged, and portable system capable of high- sensitivity measurements in widely divergent waters, UltraPath will help scientists examine the role that coastal ocean environments play in the global carbon cycle. UltraPath(TM) is a trademark of World Precision Instruments, Inc. LWCC(TM) is a trademark of World Precision Instruments, Inc.

  3. Interfacial spectroscopic characterization of organic/ferromagnet hetero-junction of 3,4,9,10-perylene-teracarboxylic dianhydride-based organic spin valves

    NASA Astrophysics Data System (ADS)

    Hong, Jhen-Yong; Ou Yang, Kui-Hon; Wang, Bo-Yao; Li, Kai-Shin; Shiu, Hung-Wei; Chen, Chia-Hao; Chan, Yuet-Loy; Wei, Der-Hsin; Chang, Fan-Hsiu; Lin, Hong-Ji; Chiang, Wen-Chung; Lin, Minn-Tsong

    2014-02-01

    We report interfacial characterization of 3,4,9,10-perylene-teracarboxylic dianhydride (PTCDA)-based organic spin valves (OSV) dusted with a thin layer of partially oxidized alumina at the organic semiconductor (OSC)/ferromagnet (FM) interfaces. Up to 13.5% magnetoresistance is achieved at room temperature. X-ray photoelectron spectroscopy measurements reveal interfacial electronic interaction between PTCDA and FM while the application of a thin alumina layer at the PTCDA/FM interfaces prevents the electronic hybridization and effectively preserves the spin injection into the OSC spacer. This finding demonstrates the critical effect of interfacial structure on magnetotransport behavior in OSV.

  4. Interfacial spectroscopic characterization of organic/ferromagnet hetero-junction of 3,4,9,10-perylene-teracarboxylic dianhydride-based organic spin valves

    SciTech Connect

    Hong, Jhen-Yong; Ou Yang, Kui-Hon; Li, Kai-Shin [Department of Physics, National Taiwan University, 10617 Taipei, Taiwan (China); Wang, Bo-Yao [Department of Physics, National Taiwan University, 10617 Taipei, Taiwan (China); Department of Physics, National Changhua University of Education, Changhua 500, Taiwan (China); Shiu, Hung-Wei; Chen, Chia-Hao; Chan, Yuet-Loy; Wei, Der-Hsin; Chang, Fan-Hsiu; Lin, Hong-Ji [National Synchrotron Radiation Research Center, 30076 Hsinchu, Taiwan (China); Chiang, Wen-Chung, E-mail: wchiang@faculty.pccu.edu.tw [Department of Physics, Chinese Culture University, 11114 Taipei, Taiwan (China); Lin, Minn-Tsong, E-mail: mtlin@phys.ntu.edu.tw [Department of Physics, National Taiwan University, 10617 Taipei, Taiwan (China); Institute of Atomic and Molecular Sciences, Academia Sinica, 10617 Taipei, Taiwan (China)

    2014-02-24

    We report interfacial characterization of 3,4,9,10-perylene-teracarboxylic dianhydride (PTCDA)-based organic spin valves (OSV) dusted with a thin layer of partially oxidized alumina at the organic semiconductor (OSC)/ferromagnet (FM) interfaces. Up to 13.5% magnetoresistance is achieved at room temperature. X-ray photoelectron spectroscopy measurements reveal interfacial electronic interaction between PTCDA and FM while the application of a thin alumina layer at the PTCDA/FM interfaces prevents the electronic hybridization and effectively preserves the spin injection into the OSC spacer. This finding demonstrates the critical effect of interfacial structure on magnetotransport behavior in OSV.

  5. Molecular structure, spectroscopic characterization (FT-IR, FT-Raman, UV and NMR), HOMO and LUMO analysis of 3-ethynylthiophene with DFT quantum chemical calculations.

    PubMed

    Karabacak, Mehmet; Bilgili, Sibel; Mavis, Tugba; Eskici, Mustafa; Atac, Ahmet

    2013-11-01

    In this work, FT-IR, FT-Raman, UV and NMR spectra of 3-ethynylthiophene (3-ETP, C6H4S) were carried out by using density functional theory DFT/B3LYP method with the 6-311++G(d,p), 6-311+G(d,p), 6-311G(d,p), 6-31++G(d,p), 6-31+G(d,p), 6-31G(d,p) basis sets. FT-IR and FT-Raman spectra were recorded in the regions of 3500-400cm(-1) and 3500-50cm(-1), respectively. The geometrical parameters, energies and wavenumbers were obtained and 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 and PQS program. The (1)H, (13)C and HMQC ((1)H-(13)C correlation) NMR spectra in chloroform (CDCl3) were recorded and calculated. The UV spectrum of investigated compound were recorded in the region of 200-400nm in ethanol solution. The electronic properties, such as excitation energies, absorption wavelengths, HOMO and LUMO energies were performed by DFT/B3LYP approach and the results were compared with experimental observations. The thermodynamic properties such zero-point vibrational energy, thermal energy, specific heat capacity, rotational constants, entropy, and dipole moment of the studied compound were calculated. As a result, the calculated results were compared with the observed data and found to be in good agreement. PMID:23886506

  6. Molecular structure, spectroscopic characterization (FT-IR, FT-Raman, UV and NMR), HOMO and LUMO analysis of 3-ethynylthiophene with DFT quantum chemical calculations

    NASA Astrophysics Data System (ADS)

    Karabacak, Mehmet; Bilgili, Sibel; Mavis, Tugba; Eskici, Mustafa; Atac, Ahmet

    2013-11-01

    In this work, FT-IR, FT-Raman, UV and NMR spectra of 3-ethynylthiophene (3-ETP, C6H4S) were carried out by using density functional theory DFT/B3LYP method with the 6-311++G(d,p), 6-311+G(d,p), 6-311G(d,p), 6-31++G(d,p), 6-31+G(d,p), 6-31G(d,p) basis sets. FT-IR and FT-Raman spectra were recorded in the regions of 3500-400 cm-1 and 3500-50 cm-1, respectively. The geometrical parameters, energies and wavenumbers were obtained and 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 and PQS program. The 1H, 13C and HMQC (1H-13C correlation) NMR spectra in chloroform (CDCl3) were recorded and calculated. The UV spectrum of investigated compound were recorded in the region of 200-400 nm in ethanol solution. The electronic properties, such as excitation energies, absorption wavelengths, HOMO and LUMO energies were performed by DFT/B3LYP approach and the results were compared with experimental observations. The thermodynamic properties such zero-point vibrational energy, thermal energy, specific heat capacity, rotational constants, entropy, and dipole moment of the studied compound were calculated. As a result, the calculated results were compared with the observed data and found to be in good agreement.

  7. Cu(II), Co(II) and Ni(II) complexes of new Schiff base ligand: Synthesis, thermal and spectroscopic characterizations

    NASA Astrophysics Data System (ADS)

    Refat, Moamen S.; El-Sayed, Mohamed Y.; Adam, Abdel Majid A.

    2013-04-01

    Cu(II), Co(II), and Ni(II) complexes were synthesized from 2-[(5-o-chlorophenylazo-2-hydroxybenzylidin)amino]-phenol Schiff base (H2L). Metal ions coordinate in a tetradentate or hexadentate features with these O2N donor ligand, which are characterized by elemental analyses, magnetic moments, infrared, Raman laser, electronic, and 1H NMR spectral studies. The elemental analysis suggests the stoichiometry to be 1:1 (metal:ligand). Reactions with Cu(II), Co(II) and Ni(II), resulted [Cu(H2L)(H2O)2(Cl)]Cl, [Co(H2L)(H2O)3]Cl2?3H2O and [Ni(H2L)(H2O)2]Cl2?6H2O. The thermal decomposition behavior of H2L complexes has been investigated by thermogravimetric analysis (TG/DTG) at a heating rate of 10 °C min-1 under nitrogen atmosphere. The brightness side in this study is to take advantage for the preparation and characterizations of single phases of CuO, CoO and NiO nanoparticles using H2L complexes as precursors via a solid-state decomposition procedure. The crystalline structures of products using X-ray diffractometer (XRD), morphology of particles by scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDX) were investigated.

  8. Microstructural and optical investigations of sol-gel derived ferroelectric BaTiO3 nanocrystalline films determined by spectroscopic ellipsometry

    Microsoft Academic Search

    Z. G. Hu; Y. W. Li; M. Zhu; Z. Q. Zhu; J. H. Chu

    2008-01-01

    Ferroelectric BaTiO3 nanocrystalline films (BTNFs) with the crystalline sizes of about 30 nm were grown on Pt\\/Ti\\/SiO2\\/Si substrates by a modified sol-gel method. Spectroscopic ellipsometry (SE) was used to characterize the films in the photon energy range of 1.5-5.0 eV with a five-phase layered model (air\\/surface rough layer\\/BaTiO3\\/interface layer\\/Pt). The optical properties in the transparent and absorption regions have been

  9. Microstructural and optical investigations of sol–gel derived ferroelectric BaTiO 3 nanocrystalline films determined by spectroscopic ellipsometry

    Microsoft Academic Search

    Z. G. Hu; Y. W. Li; M. Zhu; Z. Q. Zhu; J. H. Chu

    2008-01-01

    Ferroelectric BaTiO3 nanocrystalline films (BTNFs) with the crystalline sizes of about 30 nm were grown on Pt\\/Ti\\/SiO2\\/Si substrates by a modified sol–gel method. Spectroscopic ellipsometry (SE) was used to characterize the films in the photon energy range of 1.5–5.0 eV with a five-phase layered model (air\\/surface rough layer\\/BaTiO3\\/interface layer\\/Pt). The optical properties in the transparent and absorption regions have been

  10. Synthesis, characterization and applications of pyrocatechol modified amberlite XAD-2 resin for preconcentration and determination of metal ions in water samples by flame atomic absorption spectrometry (FAAS).

    PubMed

    Tewari, P K; Singh, A K

    2001-01-01

    A new chelating resin is prepared by coupling Amberlite XAD-2 with pyrocatechol through an azo spacer, characterized (by elemental analysis, IR and TGA) and studied for preconcentrating Cd(II), Co(II), Cu(II), Fe(III), Ni(II) and Zn(II) using flame atomic absorption spectrometry (FAAS) for metal monitoring. The sorption is quantitative in the pH range 3.0-6.5, whereas quantitative desorption occurs instantaneously with 2 M HCl or HNO(3) The sorption capacity has been found to be in the range 0.023-0.092 mmol g(-1) of resin. The loading half time (t(1/2)) is 1.4, 4.8, 1.6, 3.2, 2.3 and 1.8 min, respectively for Cd, Co, Cu, Fe, Ni and Zn. The tolerance limits of electrolytes NaCl, NaBr, NaNO(3), Na(2)SO(4) and Na(3)PO(4) in the sorption of all the six metal ions (0.2 mug ml(-1)) are reported. The Mg(II) and Ca(II) are tolerable with each of them (0.2 mug ml(-1)) up to a concentration level of 0.01-1.0 M. The enrichment factor has been found to be 200 except for Fe and Cu for which the values are 80 and 100, respectively. The lowest concentration of metal ion for quantitative recovery is 5, 10, 20, 25, 10 and 10 mug l(-1) for Cd, Co, Cu, Fe, Ni and Zn, respectively. The simultaneous determination of all these metal ions is possible and the method has been applied to determine all the six metal ions in tap and river water samples (RSD

  11. Nearly Uniform Decaosmium Clusters Supported on MgO: Characterization by X-ray Absorption Spectroscopy and Scanning Transmission Electron Microscopy

    SciTech Connect

    Kulkarni, A.; Mehraeen, S; Reed, B; Okamoto, N; Browning, N; Gates, B

    2009-01-01

    Samples containing small, nearly uniform clusters of a heavy metal, Os, were prepared on a high-area porous support consisting of light atoms, MgO, to provide an opportunity for a critical assessment of estimates of cluster size determined by extended X-ray absorption fine structure (EXAFS) spectroscopy and high-angle annular dark field scanning transmission electron microscopy (HAADF-STEM). Supported carbonyl clusters approximated as decaosmium were prepared by reductive carbonylation of adsorbed Os3(CO)12 at 548 K and 1 bar. Infrared (IR) spectra of the clusters resemble those attributed in earlier work to supported clusters similar to [Os10C(CO)24]2-, consistent with the EXAFS data. The spectra indicate a molar yield of decaosmium carbonyl clusters of about 65-70%. As these clusters were treated in flowing H2, they were partially decarbonylated, as shown by IR and EXAFS spectra. The rms (root-mean-square) radii of the undecarbonylated and partially decarbonylated clusters were found by HAADF-STEM to be 3.11 {+-} 0.09 and 3.06 {+-} 0.05 A, respectively, and the close agreement between these values is consistent with the inference that the cluster frame was essentially the same in each. The average rms radius of the undecarbonylated clusters, estimated on the basis of EXAFS data, was 2.94 {+-} 0.07 A, calculated on the basis of the assumption that the osmium frame matched that of [Os10C(CO)24]2-. EXAFS analysis of the data characterizing the partially decarbonylated sample, aided by the STEM results, showed, consistent with the STEM results, that the partial decarbonylation did not lead to a significant change in the rms radius of the metal frame.

  12. Exo-C: a Probe-Scale Space Mission to Directly Image and Spectroscopically Characterize Exoplanetary Systems Using an Internal Coronagraph

    NASA Technical Reports Server (NTRS)

    Stapelfeldt, Karl R.; Brenner, Michael P.; Warfield, Keith R.; Dekens, Frank G.; Belikov, Ruslan; Brugarolas, Paul B.; Bryden, Geoffrey; Cahoy, Kerri L.; Chakrabarti, Supriya; Dubovitsky, Serge; Effinger, Robert T.; Hirsch, Brian; Kissil, Andrew; Krist, John E.; Lang, Jared J.; Marley, Mark S.; McElwain, Michael W.; Meadows, Victoria S.; Nissen, Joel; Oseas, Jeffrey M.; Serabyn, Eugene; Sunada, Eric; Trauger, John T.; Unwin, Stephen C.

    2014-01-01

    "Exo-C" is NASA's first community study of a modest aperture space telescope designed for high contrast observations of exoplanetary systems. The mission will be capable of taking optical spectra of nearby exoplanets in reflected light, discover previously undetected planets, and imaging structure in a large sample of circumstellar disks. It will obtain unique science results on planets down to super-Earth sizes and serve as a technology pathfinder toward an eventual flagship-class mission to find and characterize habitable exoplanets. We present the mission/payload design and highlight steps to reduce mission cost/risk relative to previous mission concepts. At the study conclusion in 2015, NASA will evaluate it for potential development at the end of this decade. Keywords: Exoplanets, high contrast imaging, optical astronomy, space mission concepts

  13. Structural and spectroscopic characterization of Mo{sub 1-x}W{sub x}O{sub 3-{delta}} mixed oxides

    SciTech Connect

    Morandi, S.; Paganini, M.C.; Giamello, E. [Department of Inorganic, Physical and Materials Chemistry and NIS Center of Excellence, University of Torino, Via P. Giuria 7-9, 10125 Torino (Italy); Bini, M.; Capsoni, D.; Massarotti, V. [Department of Physical Chemistry 'M. Rolla' and IENI-CNR, University of Pavia, Viale Taramelli 16, 27100 Pavia (Italy); Ghiotti, G., E-mail: giovanna.ghiotti@unito.i [Department of Inorganic, Physical and Materials Chemistry and NIS Center of Excellence, University of Torino, Via P. Giuria 7-9, 10125 Torino (Italy)

    2009-12-15

    Mo{sub 1-x}W{sub x}O{sub 3} oxides with different cationic fraction (x=0.2, 0.5 and 0.8) and, for comparison purposes, pure MoO{sub 3} and WO{sub 3} were prepared. Along with textural and structural characterizations, absorbance FT-IR, diffuse reflectance UV-vis-NIR and EPR spectroscopies were employed to study the changes in the electronic properties of these materials passing from Mo{sub 1-x}W{sub x}O{sub 3} in oxidizing atmosphere to Mo{sub 1-x}W{sub x}O{sub 3-{delta}} in reducing conditions. XRD analysis showed that the Mo-W mixed oxides are constituted by two or three crystalline phases, whose abundance and composition are well characterized by structural refinement with the Rietveld method. Only the sample with the highest Mo content (x=0.2) shows a predominant mixed phase and also a superior ability to lose oxygen with respect to the other mixed oxides. The oxygen loss in the reduced oxides induces the formation of defects with electronic levels in the band gap of the material, in particular, electrons trapped in oxygen vacancies and/or at cationic sites (polarons). While the nature of defect sites induced in the mixed and in the pure oxides is similar, the photo-ionization energies, the ratio between surface and bulk defects and the stability of the defects in oxygen at increasing temperature are peculiar of each mixed oxide. - Graphical abstract: The combined use of different techniques provides new insight into structural, optical and electronic properties of semiconductor Mo{sub 1-x}W{sub x}O{sub 3-{delta}} mixed oxides.

  14. In vivo determination of the absorption and scattering spectra of the human prostate during photodynamic therapy

    PubMed Central

    Finlay, Jarod C.; Zhu, Timothy C; Dimofte, Andreea; Stripp, Diana; Malkowicz, S. Bruce; Whittington, Richard; Miles, Jeremy; Glatstein, Eli; Hahn, Stephen M.

    2015-01-01

    A continuing challenge in photodynamic therapy is the accurate in vivo determination of the optical properties of the tissue being treated. We have developed a method for characterizing the absorption and scattering spectra of prostate tissue undergoing PDT treatment. Our current prostate treatment protocol involves interstitial illumination of the organ via cylindrical diffusing optical fibers (CDFs) inserted into the prostate through clear catheters. We employ one of these catheters to insert an isotropic white light point source into the prostate. An isotropic detection fiber connected to a spectrograph is inserted into a second catheter a known distance away. The detector is moved along the catheter by a computer-controlled step motor, acquiring diffuse light spectra at 2 mm intervals along its path. We model the fluence rate as a function of wavelength and distance along the detector’s path using an infinite medium diffusion theory model whose free parameters are the absorption coefficient µa at each wavelength and two variables A and b which characterize the reduced scattering spectrum of the form µ’s = A??b. We analyze our spectroscopic data using a nonlinear fitting algorithm to determine A, b, and µa at each wavelength independently; no prior knowledge of the absorption spectrum or of the sample’s constituent absorbers is required. We have tested this method in tissue simulating phantoms composed of intralipid and the photosensitizer motexafin lutetium (MLu). The MLu absorption spectrum recovered from the phantoms agrees with that measured in clear solution, and µa at the MLu absorption peak varies linearly with concentration. The µ’s spectrum reported by the fit is in agreement with the known scattering coefficient of intralipid. We have applied this algorithm to spectroscopic data from human patients sensitized with MLu (2 mg kg?1) acquired before and after PDT. Before PDT, the absorption spectra we measure include the characteristic MLu absorption peak. Using our phantom data as a calibration, we have determined the pre-treatment MLu concentration to be approximately 2 to 8 mg kg?1. After PDT, the concentration is reduced to 1 to 2.5 mg kg?1, an indication of photobleaching induced by irradiation. In addition, absorption features corresponding to the oxygenated and deoxygenated forms of hemoglobin indicate a reduction in tissue oxygenation during treatment.

  15. Characterization of industrial explosives based on the determination of metal oxides in the identification particles by microwave digestion and atomic absorption spectrometry method.

    PubMed

    Husáková, Lenka; Srámková, Jitka; Stanková, Jirina; Nemec, Petr; Vecera, Miroslav; Krejcová, Anna; Stancl, Miroslav; Akstein, Zbynek

    2008-07-01

    Identification particles used for the purpose of the post-blast identification of explosives have a coding system based on the combination of metal oxides and their various concentrations. These materials are composed of the polymeric matrix, iron powder (ferromagnetic properties), UV light active dyestuff and various metal oxides in a various ratios. A suitable analytical method has to be used for an accurate characterization of these metal components in the particles in order to find the required information, i.e. to determine the place and the year of production and as the case may be, also the production batch of misused explosives. In this work, the method of microwave digestion and flame atomic absorption spectrometry (F-AAS) was developed for an accurate determination of Zn, Mg, Cu and Pb in a few novel types of identification particles and applied to their characterization. When using specific sample treatment (digestion with a mixture of nitric acid with hydrochloric or hydrofluoric acid), the 3 sigma limits of detection (LODs) for the determination of Zn, Mg, Cu and Pb in 5mg original samples were 1.9, 0.2, 1.3 and 2.4 mg g(-1), respectively. The signal suppression due to the presence of HNO3+HCl or HNO3+HF was observed for Zn; therefore, the calibration solutions had to be prepared exactly with the same acids as those used for the sample mineralization. The determination of Mg, Cu and Pb was free of interferences; hence a simple calibration curve method could be adopted for attaining accurate results. The accuracy was checked by comparison of the results with those obtained by means of independent inductively coupled plasma optical emission spectrometry (ICP-OES). Good precision values, as relative standard deviation, in the range of 1-5% were obtained. A total number of 71 samples was analysed and classified by multivariate methods to prove the suitability of the procedure proposed for the purpose of the identification of explosives. PMID:18440172

  16. Resonant X-Ray Scattering and Absorption for the Global and Local Structures of Cu-modified Metallothioneins in Solution

    Microsoft Academic Search

    Meiyi Li; Yu-Shan Huang; U-Ser Jeng; I-Jui Hsu; YewChung Sermon Wu; Ying-Huang Lai; Chiu-Hun Su; Jyh-Fu Lee; Yu Wang; Chia-Ching Chang

    2009-01-01

    With Cd and Zn metal ions removed from the native rabbit-liver metallothionein upon unfolding, Cu-modified metallothioneins (Cu-MTs) were obtained during refolding in solutions containing CuI or CuII ions. X-ray absorption near-edge spectroscopic results confirm the respectively assigned oxidation states of the copper ions in CuI-MT and CuII-MT. Global and local structures of the Cu-MTs were subsequently characterized by anomalous small-angle

  17. Total absorption of light in sub-wavelength metallic waveguides

    NASA Astrophysics Data System (ADS)

    Ghossoub, Marc G.; Sinha, Sanjiv

    2013-12-01

    Resonance cavity modes enhance optical transmission through sub-wavelength metallic apertures but their role in absorption remains unclear. Here, we use full field simulation and a semi-analytical model to report absorption and transmission enhancement in transmission gratings under transverse electric illumination. The fundamental cavity mode of the sub-wavelength grating cavities is the major contributor to absorption. We demonstrate the possibility of tailoring such cavity resonances to induce total absorption in reflection gratings. Our method advances the understanding of transmittance and absorption enhancing mechanisms in metallic nanostructures which constitute fundamental components in energy harvesting, sensing, and spectroscopic applications.

  18. Hetarylazoindoles 2. Spectroscopic and structural investigation of new benzothiazolylazo indole dyes

    NASA Astrophysics Data System (ADS)

    Sefero?lu, Zeynel; Kaynak, Filiz Betül; Ertan, Nermin; Özbey, Süheyla

    2013-09-01

    Synthesis of new benzothiazolylazo indole dyes were carried out by diazotization of 2-aminobenzothiazole, 6- and 5,6-disubstituted 2-aminobenzothiazoles using with nitrosyl sulfuric acid and coupling with various 2- and 1,2-disubstituted indole derivatives. The structures of the dyes were characterized by UV-vis, FT-IR, 1H NMR, mass spectroscopic techniques and elemental analysis. Their solvatochromic properties in different solvents were investigated and their absorption spectra were found to be solvent dependent. The azo-hydrazone tautomerism was discussed in relation to solvent and substituent effects. In addition, acid-base effect on this equilibrium was also evaluated. To determine the most tautomeric form of the prepared dyes in solid state, X-ray data for 2-Methyl-3-(6-methoxybenzothiazol-2-yldiazenyl)-1H-indole were recorded in different solvents. The X-ray results showed that the dye was stable as azo tautomer in the solid state.

  19. Spectroscopic studies on gallic acid and its azo derivatives and their iron(III) complexes.

    PubMed

    Masoud, Mamdouh S; Ali, Alaa E; Haggag, Sawsan S; Nasr, Nessma M

    2014-01-01

    Azo gallic derivatives and their iron(III) complexes were synthesized and characterized. The stereochemistry and the mode of bonding of the complexes were achieved based on elemental analysis, UV-Vis and IR. The thermal behaviors of the complexes were studied. The effect of pH on the electronic absorption spectra of gallic acid and its azo derivatives are discussed. Different spectroscopic methods (molar ratio, straight line method, continuous variation, slope ratio and successive method) are applied for determination of stoichiometry and pK values for the complex formation of gallic acid with iron(III) in aqueous media. Iron(III) complexes of gallic acid is formed with different ratio: 1:1, 1:2, 1:3 and 1:4 (M:L). PMID:24211811

  20. Spectroscopic and structural studies of L-arginine doped Potassium Dihydrogen Phosphate crystals

    NASA Astrophysics Data System (ADS)

    Govani, Jayesh; Botez, Cristian; Durrer, William; Manciu, Felicia

    2009-03-01

    We report in this study the spectroscopic and structural characterization of standard and L-arginine doped potassium dihydrogen phosphate crystals synthesized by a solution growth technique. The infrared absorption and Raman results demonstrate chemical functionalization between the amino (NH3^+) groups of the organic material and the phosphate units of the inorganic crystals. This affirmation, which also implies the achievement of successful doping, is supported by the existence of extra vibrational lines in the IR and Raman spectra of L-arginine doped potassium dihydrogen phosphate crystals; these vibrational lines exhibit shifting towards lower frequencies as compared with the characteristic bands of L-arginine. Incorporation of the amino acid into the structure of the inorganic material is revealed by X-ray diffraction results also, where the shifting of diffraction lines and the appearance of a new one are observed.

  1. Spectroscopic characterization and mechanistic investigation of P-methyl transfer by a radical SAM enzyme from the marine bacterium Shewanella denitrificans OS217.

    PubMed

    Allen, Kylie D; Wang, Susan C

    2014-09-16

    Natural products containing carbon-phosphorus bonds elicit important bioactivity in many organisms. l-Phosphinothricin contains the only known naturally-occurring carbon-phosphorus-carbon bond linkage. In actinomycetes, the cobalamin-dependent radical S-adenosyl-l-methionine (SAM) methyltransferase PhpK catalyzes the formation of the second C-P bond to generate the complete C-P-C linkage in phosphinothricin. Here we use electron paramagnetic resonance and nuclear magnetic resonance spectroscopies to characterize and demonstrate the activity of a cobalamin-dependent radical SAM methyltransferase denoted SD_1168 from Shewanella denitrificans OS217, a marine bacterium that has not been reported to synthesize phosphinothricin. Recombinant, refolded, and reconstituted SD_1168 binds a four-iron, four-sulfur cluster that interacts with SAM and cobalamin. In the presence of SAM, a reductant, and methylcobalamin, SD_1168 surprisingly catalyzes the P-methylation of N-acetyl-demethylphosphinothricin and demethylphosphinothricin to produce N-acetyl-phosphinothricin and phosphinothricin, respectively. In addition, this enzyme is active in the absence of methylcobalamin if the strong reductant titanium (III) citrate and hydroxocobalamin are provided. When incubated with [methyl-(13)C] cobalamin and titanium citrate, both [methyl-(13)C] and unlabeled N-acetylphosphinothricin are produced. Our results suggest that SD_1168 catalyzes P-methylation using radical SAM-dependent chemistry with cobalamin as a coenzyme. In light of recent genomic information, the discovery of this P-methyltransferase suggests that S. denitrificans produces a phosphinate natural product. PMID:25224746

  2. Synthesis, Spectroscopic and Physicochemical Characterization and Biological Activity of Co(II) and Ni(II) Coordination Compounds with 4-Aminoantipyrine Thiosemicarbazone

    PubMed Central

    2005-01-01

    We describe the synthesis and characterization of cobalt(II) and nickel(II) coordination compounds of 4[N-(furan-2’-aldimine)amino]antipyrine thiosemicarbazone (FFAAPTS) and 4[N-(4'-nitrobenzalidene) amino]antipyrine thiosemicarbazone (4'-NO2BAAPTS). All the isolated compounds have the general composition MX2(L)(H2O) (M = Co2+ or Ni2+; X = Cl, Br, NO3, NCS or CH3COO; L = FFAAPTS or 4'-NO2BAAPTS) and M(ClO4)2(L)2 (M = Co2+ or Ni2+; L = FFAAPTS or 4'-NO2BAAPTS). Infrared spectral studies indicate that both the thiosemicarbazones coordinate in their neutral form and they act as {N,N,S} tridentate chelating ligands. Room temperature magnetic measurements and electronic spectral studies suggest the distorted octahedral geometries of the prepared complexes. Thermogravimetric studies are also reported and the possible structures of the complexes are proposed. Antibacterial and antifungal properties of these metal-coordination compounds have also been studied. PMID:18365104

  3. The spectroscopic characterization, photochromism of cadmium(II)-iodo complexes of 1-alkyl-2-(arylazo)imidazoles and DFT computation of representative complexes

    NASA Astrophysics Data System (ADS)

    Sen, Chandana; Nandi, Avijit; Mallick, Debashis; Mondal, Sudipa; Sarker, Kamal Krishna; Sinha, Chittaranjan

    2015-02-01

    [Cd(Raai-CnH2n+1)(?-I)I]2 and [Cd(Raai-CnH2n+1)2I2] are synthesized by the reaction of CdI2 with 1-alkyl-2-(arylazo)imidazole (Raai-CnH2n+1, n = 4, 6, 8) in MeOH in 1:1 and 1:2 M ratio of salt and ligands, respectively. The complexes have been characterized by spectral data (UV-Vis, IR, 1H NMR, Mass). The coordinated Raai-CnH2n+1 shows photochromism, E(trans)-to-Z(cis) isomerisation, upon UV light irradiation. The reverse process, Z-to-E, is very slow in visible light irradiation process while the reaction is sensitive to change of reaction temperature. The quantum yields (?E?Z) for E-to-Z and the activation energy (Ea) of Z-to-E isomerisation are calculated and found that the complexes show subordinate results compared to free ligand. DFT computations of two representative complexes were carried out to explain the spectral and photochromic phenomena.

  4. Synthesis, spectroscopic characterization and quantum chemical computational studies on 1-acetyl-3,5-di(4-methylphenyl)-1H-pyrazole

    NASA Astrophysics Data System (ADS)

    ?nkaya, Ersin; Dinçer, Muharrem; Korkusuz, Elif; Y?ld?r?m, ?smail; Büyükgüngör, Orhan

    2012-11-01

    The pyrazole compound 1-acetyl-3,5-di(4-methylphenyl)-1H-pyrazole, (C19H18N2O), was characterized by X-ray single crystal diffraction technique, IR-NMR spectroscopy and quantum chemical computational methods as both experimental and theoretically. The compound crystallizes in the monoclinic space group C 2/c with a = 32.5334 (1) Å, b = 5.8060 (1) Å, c = 23.6519 (8) Å, ? = 134.572 (2)°, and Z = 8. The molecular geometry was also optimized using the Hartree-Fock (HF) and density functional theory (DFT/B3LYP) methods with the 6-311G(d,p) basis set and compared with the experimental data. To determine conformational flexibility, molecular energy profile of the tittle compound was obtained by semi-empirical (AM1) with respect to selected degree of torsional freedom, which was varied from -180° to +180° in steps 10°. From the optimized geometry of the molecule, vibrational frequencies, gauge-independent atomic orbital (GIAO) 1H and 13C NMR chemical shift values, molecular electrostatic potential (MEP) distribution, non-linear optical properties, frontier molecular orbitals (FMOs) of the title compound have been calculated in the ground state theoretically. The theoretical result showed good agreement with the experimental values.

  5. Spectroscopic characterization and solubility investigation on the effects of As(V) on mineral structure tooeleite (Fe?(AsO?)?SO?(OH)?·H?O).

    PubMed

    Liu, Jing; Deng, Shiming; Zhao, Fenghua; Cheng, Hongfei; Frost, Ray L

    2015-01-01

    Tooeleite is an unique ferric arsenite sulfate mineral, which has the potential significance of directly fixing As(III) as mineral trap. The tooeleite and various precipitates were hydrothermally synthesized under the different of initial As(III)/As(V) molar ratios and characterized by XRD, FTIR, XPS and SEM. The crystallinity of tooeleite decreases with the amount of As(V). The precipitate is free of any crystalline tooeleite at the level of that XRD could detect when the ratio of As(III)/As(V) of 7:3 and more. The characteristic bands of tooeleite are observed in 772, 340, 696 and 304 cm(-1), which are assigned to the ??, ??, ?? and ?? vibrations of AsO?(3-). These intensities of bands gradually decreases with the presence of As(V) and its increasing. An obviously wide band is observed in 830 cm(-1), which is the ?? vibration of AsO?. The result of XPS reveals that the binding energies of As?d increase from 44.0 eV to 45.5 eV, which indicates that the amount of As(V) in the precipitates increases. The concentrations of arsenic released of these precipitates are 350-650 mg/L. The stability of tooeleite decreases by comparison when the presence of coexisting As(V) ions. PMID:25025316

  6. Synthesis and Characterization of Ba(Zr{sub x}Ti{sub 1-x})O{sub 3} Solid Solutions Using Impedance Spectroscopic Techniques

    SciTech Connect

    Bajpai, P. K.; Mohan, C. R. K. [Advanced Material Research Laboratory Department of Pure and Applied Physics Guru Ghasidas Vishwavidyalaya, Bilaspur-495009 (India)

    2011-11-22

    Technologically important solid solutions of Ba(Zr{sub x}Ti{sub 1-x})O{sub 3} are synthesized using conventional solid state route. Relatively dense and single phase ceramics are confirmed using X-ray diffraction. Homogeneous and micron size grain growth is characterized using SEM. Impedance spectroscopy is used to study the electrical properties of ceramics. Broad and diffuse impedance loss peak is observed above 250 deg. C, which shifts towards higher frequency with increase in temperature. The distribution of relaxation frequency may be associated with the B-site cationic disorder due to the random distribution of (Zr{sup 4+}/Ti{sup +4}) having different ionic radii. Impedance relaxation obeys the Arrhenius relation with activation energy, E{tau} is 0.31 eV and 0.48 eV for BZT compositions with x = 0.10 and 0.15 respectively. Equivalent circuit representation using two RC element coupled in parallel is used to analyse the impedance response.

  7. Preparation and spectroscopic characterization of novel cyclodiphosph(V)azane of N1-2-pyrimidinylsulfanilamide complexes . Magnetic, thermal and biological activity studies

    NASA Astrophysics Data System (ADS)

    Sharaby, Carmen M.; Mohamed, Gehad G.; Omar, M. M.

    2007-04-01

    Hexachlorocyclophosph(V)azane of sulfadiazine, (sulfupyrimidine) [ N1-2-pyrimidinylsulfanilamide] (H 2L 1), was prepared and reacted with sulfur and glycine to give (H 2L 2) and (H 2L 3) ligands, respectively. The prepared ligands; H 2L 1, H 2L 2 and H 2L 3, react in 1:2 [ligands]:[metal ions] molar ratio with transition metals to give coloured complexes in a relatively good yields. The complexes were characterized using different physicochemical techniques, namely elemental analyses, IR, UV-vis, mass, 1H NMR, molar conductance, magnetic, solid reflectance and thermal analysis. The spectral data reveal that all the ligands behave as neutral bidentate ligands and coordinated to the metal ions via pyrimidine-N and enolic sulfonamide OH. The molar conductance data reveal that the complexes are non-electrolytes while UV-vis, solid reflectance and magnetic moment data have been shown that the complexes have octahedral geometry. The thermal behaviour of the complexes is studied and the thermodynamic activation parameters are calculated. The ligands and their complexes show high to moderate bactericidal activity.

  8. Synthesis, spectroscopic characterization and quantum chemical computational studies on 4-(3-methyl-3-phenylcyclobutyl)-2-(2-undecylidenehydrazinyl)thiazole

    NASA Astrophysics Data System (ADS)

    ?en, Fatih; Dinçer, Muharrem; Cukurovali, Alaaddin

    2014-11-01

    The Schiff base compound, 4-(3-methyl-3-phenylcyclobutyl)-2-(2-undecylidenehydrazinyl)thiazole, (C25H37N3S), was synthesized and characterized combining several experimental techniques (X-ray, 1H NMR and 13C NMR) and theoretical methods. The compound crystallizes in the monoclinic space group P 21/c with a = 16.2306 (6) Å, b = 6.728 (2) Å, c = 26.1834 (10) Å, ? = 120.687 (3), and Z = 4. The initial molecular geometry (X-ray coordinates) was optimized using Hartree-Fock (HF) and Density Functional Theory (DFT/B3LYP) method with the 6-31+G(d, p) basis set in ground state. From the optimized geometry of the molecule, geometric parameters, vibrational frequencies, gauge-independent atomic orbital (GIAO) 1H and 13C NMR chemical shift values of the title compound have been calculated theoretically and compared with the experimental data. Data from theoretical calculations show excellent consistency with experimental results. Besides, molecular electrostatic potential (MEP) distribution, frontier molecular orbitals (FMOs) and non-linear optical (NLO) properties of the title molecule were investigated by theoretical calculations.

  9. Purification and spectroscopic characterization of Ctb, a group III truncated hemoglobin implicated in oxygen metabolism in the food-borne pathogen Campylobacter jejuni†

    PubMed Central

    Wainwright, Laura M.; Wang, Yinghua; Park, Simon F.; Yeh, Syun-Ru; Poole, Robert K.

    2008-01-01

    Campylobacter jejuni is a foodborne bacterial pathogen that possesses two distinct hemoglobins, encoded by the ctb and cgb genes. The former codes for a truncated hemoglobin (Ctb) in group III, an assemblage of uncharacterized globins in diverse clinically- and technologically-significant bacteria. Here, we show that Ctb purifies as a monomeric, predominantly oxygenated species. Optical spectra of ferric, ferrous, O2- and CO-bound forms resemble those of other hemoglobins. However, resonance Raman analysis shows Ctb to have an atypical ?Fe-CO stretching mode at 514 cm-1, compared to the other truncated hemoglobins that have been characterized so far. This implies unique roles in ligand stabilisation for TyrB10, HisE7 and TrpG8, residues highly conserved within group III truncated hemoglobins. Since C. jejuni is a microaerophile, and a ctb mutant exhibits O2-dependent growth defects, one of the hypothesised roles of Ctb is in the detoxification, sequestration or transfer of O2 The midpoint potential (Eh) of Ctb was found to be ?33 mV, but no evidence was obtained in vitro to support the hypothesis that Ctb is reducible by NADH or NADPH. This truncated hemoglobin may function in the facilitation of O2 transfer to one of the terminal oxidases of C. jejuni or instead facilitate O2 transfer to Cgb for NO detoxification. PMID:16681372

  10. Microscopic and Spectroscopic Characterization of Aluminosilicate Waste Form with Cs/Sr/Ba Loading Using Scanning Electron Microscopy, Transmission Electron Microscopy, and X-Ray Diffraction

    NASA Astrophysics Data System (ADS)

    Cerefice, Gary; Ma, Longzhou; Kaminski, Michael

    2009-12-01

    An aluminosilicate waste form has been proposed for the storage and disposal of cesium and strontium isolated from recycled nuclear fuel. To examine the impact of sintering temperature on the waste form product, thermal analysis (thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC)) was used to identify key transition temperature ranges. Samples were produced in each temperature range to examine the impact on phase formation and microstructure. Examination of the synthesized materials by X-ray diffraction (XRD) confirmed the formation of the expected Cs- and Sr-aluminosilicate crystalline phases. However, microscopic characterization by scanning electron microscopy (SEM) revealed a spongelike, glassy morphology with high porosity and no observed crystallinity. This discrepancy was investigated by transmission electron microscopy (TEM) and high-resolution TEM (HRTEM), which identified the presence of discrete, submicron, crystalline phases within the bulk amorphous matrix. Elemental analysis by energy-dispersive X-ray (EDX) indicated that the strontium and barium were incorporated into the crystalline phase, while the cesium was incorporated into the amorphous matrix. Further analysis of samples synthesized without barium or strontium allowed for the identification of submicron crystalline phases within the amorphous matrix, identifying the source of the cesium aluminosilicate crystal peaks in the XRD patterns, with elemental analysis showing that the cesium was present in both the crystalline inclusions and the amorphous bulk phase.

  11. Synthesis, characterization and spectroscopic investigations of novel nano multi-metal oxide Co3O4·CeO2·ZnO

    NASA Astrophysics Data System (ADS)

    Subhan, Md Abdus; Ahmed, Tanzir

    2014-08-01

    A novel multi-metal nanocomposite, Co3O4·CeO2·ZnO has been prepared by co-precipitation of their carbonates from aqueous solutions of the metal nitrates following calcining and annealing 5 h at 450 °C and 10 h at 950 °C. Co3O4·CeO2·ZnO has been characterized by XRD, SEM, EDS, IR and PL spectra. The crystallite size of the as-synthesized sample varies in the range of 9-33 nm and those of the annealed sample in the range of 19-42 nm. Emissions of Co3O4·CeO2·ZnO were observed in UV and visible region at different excitations. Excitation wavelength dependent PL behavior of Co3O4·CeO2·ZnO has been observed in acetone. This PL property is contrary to the well-known Kasha’s rule of excitation wavelength dependence of emission spectrum.

  12. Ni(II) and Zn(II) complexes of 2-((thiophen-2-ylmethylene)amino)benzamide: Synthesis, spectroscopic characterization, thermal, DFT and anticancer activities

    NASA Astrophysics Data System (ADS)

    Tyagi, Prateek; Chandra, Sulekh; Saraswat, B. S.

    2015-01-01

    The paper presents the synthesis of Ni(II) and Zn(II) complexes of general composition M(L)X2 and M(L)2X2 (M = Ni(II), Zn(II), X = Cl-1, OAc-1) with Schiff base obtained through the condensation of 2-aminobenzamide with thiophene-2-carbaldehyde. The characterization of newly formed complexes was done by 1H NMR, UV-VIS, TGA, IR, mass spectrophotometry and molar conductivity studies. The thermal studies suggested that the complexes are more stable as compared to ligand. In DFT studies the geometries of Schiff's base and metal complexes were fully optimized with respect to the energy using the 6-31+g(d,p) basis set. On the basis of the spectral studies a distorted octahedral geometry has been assigned for Ni(II) complexes and tetrahedral geometry for Zn(II) complexes. The effect of these complexes on proliferation of human breast cancer cell line (MCF-7) and human hepatocellular liver carcinoma cell line (HepG2) were studied and compared with those of free ligand.

  13. Ni(II) and Zn(II) complexes of 2-((thiophen-2-ylmethylene)amino)benzamide: synthesis, spectroscopic characterization, thermal, DFT and anticancer activities.

    PubMed

    Tyagi, Prateek; Chandra, Sulekh; Saraswat, B S

    2015-01-01

    The paper presents the synthesis of Ni(II) and Zn(II) complexes of general composition M(L)X? and M(L)?X? (M=Ni(II), Zn(II), X=Cl(-1), OAc(-1)) with Schiff base obtained through the condensation of 2-aminobenzamide with thiophene-2-carbaldehyde. The characterization of newly formed complexes was done by (1)H NMR, UV-VIS, TGA, IR, mass spectrophotometry and molar conductivity studies. The thermal studies suggested that the complexes are more stable as compared to ligand. In DFT studies the geometries of Schiff's base and metal complexes were fully optimized with respect to the energy using the 6-31+g(d,p) basis set. On the basis of the spectral studies a distorted octahedral geometry has been assigned for Ni(II) complexes and tetrahedral geometry for Zn(II) complexes. The effect of these complexes on proliferation of human breast cancer cell line (MCF-7) and human hepatocellular liver carcinoma cell line (HepG2) were studied and compared with those of free ligand. PMID:25014642

  14. Synthesis, spectroscopic characterization, thermal studies, catalytic epoxidation and biological activity of chromium and molybdenum hexacarbonyl bound to a novel N 2O 2 Schiff base

    NASA Astrophysics Data System (ADS)

    Abdel Aziz, Ayman A.

    2010-08-01

    Complexes of M(CO) 6 (M = Cr and Mo) with novel Schiff base N,N'-bis(salicylidene)4,5-dichloro-1,2-phenylenediamine (H 2L) were prepared in benzene in two different conditions: (i) under reduced pressure resulting the dicarbonyl precursors [Cr(CO) 2(H 2L)] and [Mo(CO) 2(L)] and (ii) in air resulting the oxo complex [Cr(O)(L)] and the dioxo complex [Mo(O) 2(L)]. The complexes were characterized by elemental analysis, IR, 1H NMR, mass spectrometry, and magnetic measurement. Thermal behaviors of the complexes were also studied by using thermogravimetric analysis (TGA). The catalytic activity of the novel complexes in the epoxidation of cyclooctene, cyclohexene, 1-octene and 1-hexene with tert-butyl-hydroperoxide (TBHP) in methylene chloride was investigated. The antimicrobial activities of the ligand and their complexes have been screened against various strains of bacteria and fungi and the results have been compared with some known antibiotics.

  15. Spectroscopic analysis of moss (Ceratodon purpureus and Physcomitrella patens) recombinant non-symbiotic hemoglobins

    PubMed Central

    Vázquez-Limón, Consuelo; Castro-Bustos, Saraí; Arredondo-Peter, Raúl

    2012-01-01

    Non-symbiotic hemoglobins (nsHbs) are O2-binding proteins widely distributed in land plants, including primitive bryophytes. Little is known about the properties of bryophyte nsHbs. Here, we report the spectroscopic characterization of two moss recombinant nsHbs, CerpurnsHb of Ceratodon purpureus and PhypatnsHb of Physcomitrella patens. Spectra showed that the absorption maxima of the ferrous and ferric forms of recombinant CerpurnsHb are located at 418, 531 and 557 nm and 407, 537, 569 (shoulder) and 632 (shoulder) nm, respectively, and of PhypatnsHb are located at 422, 529 and 557 nm and 407, 531, 571 (shoulder) and 647 (shoulder) nm, respectively. These absorption maxima are similar to those of rice Hb1. Also, the absorption maxima of the oxygenated ferrous form of recombinant CerpurnsHb and PhypatnsHb are located at 412, 541 and 575 nm and 414, 541 and 574 nm, respectively, similar to those of oxygenated rice Hb1 and cowpea leghemoglobin II. This evidence indicates that CerpurnsHb and PhypatnsHb are mostly hexacoordinate and that they bind O2. PMID:23336017

  16. Spectroscopic analysis of moss (Ceratodon purpureus and Physcomitrella patens) recombinant non-symbiotic hemoglobins.

    PubMed

    Vázquez-Limón, Consuelo; Castro-Bustos, Saraí; Arredondo-Peter, Raúl

    2012-11-01

    Non-symbiotic hemoglobins (nsHbs) are O(2)-binding proteins widely distributed in land plants, including primitive bryophytes. Little is known about the properties of bryophyte nsHbs. Here, we report the spectroscopic characterization of two moss recombinant nsHbs, CerpurnsHb of Ceratodon purpureus and PhypatnsHb of Physcomitrella patens. Spectra showed that the absorption maxima of the ferrous and ferric forms of recombinant CerpurnsHb are located at 418, 531 and 557 nm and 407, 537, 569 (shoulder) and 632 (shoulder) nm, respectively, and of PhypatnsHb are located at 422, 529 and 557 nm and 407, 531, 571 (shoulder) and 647 (shoulder) nm, respectively. These absorption maxima are similar to those of rice Hb1. Also, the absorption maxima of the oxygenated ferrous form of recombinant CerpurnsHb and PhypatnsHb are located at 412, 541 and 575 nm and 414, 541 and 574 nm, respectively, similar to those of oxygenated rice Hb1 and cowpea leghemoglobin II. This evidence indicates that CerpurnsHb and PhypatnsHb are mostly hexacoordinate and that they bind O(2). PMID:23336017

  17. Spectroscopic Studies of Carotenoid-to-Bacteriochlorophyll Energy Transfer in LHRC Photosynthetic Complex from Roseiflexus castenholzii

    SciTech Connect

    Niedzwiedzki, Dariusz; Collins, Aaron M.; LaFountain, Amy M; Enriquez, Miriam M; Frank, Harry A; Blankenship, R. E.

    2010-01-01

    Carotenoids present in the photosynthetic light-harvesting reaction center (LHRC) complex from chlorosome lacking filamentous anoxygenic phototroph, Roseiflexus castenholzii were purified and characterized for their photochemical properties. The LHRC from anaerobically grown cells contains five different carotenoids, methoxy-keto-myxocoxanthin, ?-carotene, and its three derivatives, whereas the LHRC from aerobically grown cells contains only three carotenoid pigments with methoxy-keto-myxocoxanthin being the dominant one. The spectroscopic properties and dynamics of excited singlet states of the carotenoids were studied by steady-state absorption, fluorescence and ultrafast time-resolved optical spectroscopy in organic solvent and in the intact LHRC complex. Time-resolved transient absorption spectroscopy performed in the near-infrared (NIR) on purified carotenoids combined with steady-state absorption spectroscopy led to the precise determination of values of the energies of the S{sub 1}(2{sup 1}A{sub g}{sup ?}) excited state. Global and single wavelength fitting of the ultrafast spectral and temporal data sets of the carotenoids in solvents and in the LHRC revealed the pathways of de-excitation of the carotenoid excited states.

  18. Fluorescence spectroscopic studies to characterize the internal environment of tetraethyl-orthosilicate derived sol-gel bulk and thin films with aging.

    PubMed

    Gupta, R; Mozumdar, S; Chaudhury, N K

    2005-01-15

    Characterization of the internal environment of a sol-gel matrix is an important area of investigation in optical biosensors. In the present study, different sol-gel compositions were prepared by varying the water (H2O) to tetraethyl-orthosilicate (TEOS) ratio (R) from 1 to 16 and the changes in the internal environment of the sol-gel both in bulk and thin films as a function of aging (storage) were investigated using fluorescence spectroscopy. We focussed on the fluorescence characteristics , viz. emission and excited state lifetime of Hoechst 33258 (H258), a bisbenzimidazole derivative, which was used as fluorescence probe entrapped in the TEOS derived sol-gel bulk and thin films. These sols were prepared at a low pH (approximately 2.0) and the thin films were coated by dip coating technique at withdrawal speeds of 1 cm/min and 0.1cm/min. Usually, uniform thin films were obtained at a high speed (1 cm/min) and partially cracked film at a low speed (0.1 cm/min) as observed by fluorescence microscope. These observations did not change during aging. On the contrary, three months long observations on steady-state fluorescence emission measurements on H258 depicted a blue shift from 535 nm to 508 nm at R = 1 in the sol-gel bulk, whereas at higher ratios this was not prominent. At all ratios, dual emission bands were observed in thin films. This may be due to faster sol-gel to xerogel transition during aging depending on the ratio (R). Analysis of the excited state decay profiles of H258 revealed a double exponential fitting having a short (tau1) and a long (tau2) component in both fresh and during aging, in the sol-gel bulk and thin films, indicating heterogeneity in the internal environment. The value of tau1 increased from 0.4 ns to 1.2 ns whereas tau2 attained a value from 3.0 ns to 3.6 ns at R = 1 upon aging in the sol-gel bulk. The corresponding values of tau1 and tau2 in thin films were 0.3 ns and 3.5 ns, respectively. The values of these decay components in thin films did not alter much due to storage, but their relative contributions showed more systematic changes in the thin films. The observed changes could be correlated to rigidification in the bulk depending on the ratio (R). This process was very slow at R > or = 4. The heterogeneity in the internal environment of bulk and thin films upon aging appeared to be different as revealed from analysis of excited-state lifetime. Thus, the bisbenzimidazole derivative H258 appears to be very useful probe for characterizing the internal environment of both the sol-gel bulk and thin films. PMID:15590290

  19. Atomic oxygen effects on thin film space coatings studied by spectroscopic ellipsometry, atomic force microscopy, and laser light scattering

    NASA Technical Reports Server (NTRS)

    Synowicki, R. A.; Hale, Jeffrey S.; Woollam, John A.

    1992-01-01

    The University of Nebraska is currently evaluating Low Earth Orbit (LEO) simulation techniques as well as a variety of thin film protective coatings to withstand atomic oxygen (AO) degradation. Both oxygen plasma ashers and an electron cyclotron resonance (ECR) source are being used for LEO simulation. Thin film coatings are characterized by optical techniques including Variable Angle Spectroscopic Ellipsometry, Optical spectrophotometry, and laser light scatterometry. Atomic Force Microscopy (AFM) is also used to characterize surface morphology. Results on diamondlike carbon (DLC) films show that DLC degrades with simulated AO exposure at a rate comparable to Kapton polyimide. Since DLC is not as susceptible to environmental factors such as moisture absorption, it could potentially provide more accurate measurements of AO fluence on short space flights.

  20. Synthesis, spectroscopic characterization, crystal structure, DNA interaction study and invitro biological screenings of 4-(5-chloro-2-hydroxyphenylamino)-4-oxobut-2-enoic acid

    NASA Astrophysics Data System (ADS)

    Sirajuddin, Muhammad; Nooruddin; Ali, Saqib; McKee, Vickie; Khan, Shahan Zeb; Malook, Khan

    2015-01-01

    The titled compound, 4-(5-chloro-2-hydroxyphenylamino)-4-oxobut-2-enoic acid was synthesized and characterized by various techniques like elemental analyses, FT-IR, NMR (1H, and 13C) and single crystal X-ray structural analysis. The appearance of the OH peak of the carboxylic acid in the FT-IR and NMR spectra conform the formation of the compound. A good agreement was found between the calculated values of C, H, N and found values in elemental analysis that show the purity of the compound. Protons H2 and H3 are in cis conformation with each other as conformed both from 1H NMR as well as from single crystal X-ray analysis. The molecular structure of the title compound, C10H10NO3Cl, is stabilized by short intramolecular Osbnd H- - -O hydrogen bonds within the molecule. In the crystal structure, intermolecular Nsbnd H- - -O hydrogen bonds link molecules into zigzag chains resulting in a dendrimer like structure. The title compound was screened for biological activities like interaction with DNA, cytotoxicity, antitumor and antioxidant activities. DNA interaction study reveals that the binding mode of interaction of the compound with SS-DNA is intercalative as it results in hypochromism along with significant red shift of 5 nm. It was also found to be effective antioxidant of 2,2-diphenyl-1-picrylhydrazyl radical (DPPH) and show almost comparable antioxidant activity to that of the standard and known antioxidant, ascorbic acid, at higher concentration. The antitumor activity data of the compound shows that it can be used as potent antitumor agent.