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Sample records for absorption spectroscopic characterization

  1. X-Ray Absorption Spectroscopic Characterization of the Molybdenum Site of 'Escherichia Coli' Dimethyl Sulfoxide Reductase

    SciTech Connect

    George, G.N.; Doonan, C.J.; Rothery, R.A.; Boroumand, N.; Weiner, J.H.; /Saskatchewan U. /Alberta U.

    2007-07-09

    Structural studies of dimethyl sulfoxide (DMSO) reductases were hampered by modification of the active site during purification. We report an X-ray absorption spectroscopic analysis of the molybdenum active site of Escherichia coli DMSO reductase contained within its native membranes. The enzyme in these preparations is expected to be very close to the form found in vivo. The oxidized active site was found to have four Mo-S ligands at 2.43 angstroms, one Mo=O at 1.71 angstroms, and a longer Mo-O at 1.90 angstroms. We conclude that the oxidized enzyme is a monooxomolybdenum(VI) species coordinated by two molybdopterin dithiolenes and a serine. The bond lengths determined for E. coli DMSO reductase are very similar to those determined for the well-characterized Rhodobacter sphaeroides DMSO reductase, suggesting similar active site structures for the two enzymes. Furthermore, our results suggest that the form found in vivo is the monooxobis(molybdopterin) species.

  2. Absorption and fluorescence spectroscopic characterization of BLUF domain of AppA from Rhodobacter sphaeroides

    NASA Astrophysics Data System (ADS)

    Zirak, P.; Penzkofer, A.; Schiereis, T.; Hegemann, P.; Jung, A.; Schlichting, I.

    2005-08-01

    The BLUF domain of the transcriptional anti-repressor protein AppA from the non-sulfur anoxyphototrophic purple bacterium Rhodobacter sphaeroides was characterized by absorption and emission spectroscopy. The BLUF domain constructs AppA 148 (consisting of amino-acid residues 1-148) and AppA 126 (amino-acid residues 1-126) are investigated. The cofactor of the investigated domains is found to consist of a mixture of the flavins riboflavin, FMN, and FAD. The dark-adapted domains exist in two different active receptor conformations (receptor states) with different sub-nanosecond fluorescence lifetimes (BLUF r,f and BLUF r,sl) and a small non-interacting conformation (BLUF nc). The active receptor conformations are transformed to putative signalling states (BLUF s,f and BLUF s,sl) of low fluorescence efficiency and picosecond fluorescence lifetime by blue-light excitation (light-adapted domains). In the dark at room temperature both signalling states recover back to the initial receptor states with a time constant of about 17 min. A quantum yield of signalling state formation of about 25% was determined by intensity dependent transmission measurements. A photo-cycle scheme is presented including photo-induced charge transfer complex formation, charge recombination, and protein binding pocket reorganisation.

  3. Spectroscopic characterization of Nd:Y2O3: application toward a differential absorption lidar system for remote sensing of ozone

    NASA Astrophysics Data System (ADS)

    Walsh, Brian M.; McMahon, John M.; Edwards, William C.; Barnes, Norman P.; Equall, Randy W.; Hutcheson, Ralph L.

    2002-12-01

    Neodymium-doped yttria (Nd:Y2O3) is investigated as a solid-state laser material for frequency-tripled generation of ultraviolet laser wavelengths for use in remote sensing of ozone. Emphasis is placed both on the spectroscopy of the fundamental wavelengths at ~0.914 μm and ~0.946 μm to assess their feasibility for laser oscillation and on the absorption spectroscopy in the 0.8-μm wavelength region for determination of suitable pump sources. The temperature dependence of the emission and absorption characteristics of Nd:Y2O3 are examined, since aggressive cooling may be required for efficient ~0.914-μm lasing due to its quasi four-level nature. Data for flash-lamp-pumped laser performance on the 4F3/2-->4I11/2 is presented for Nd:Y2O3 and compared with Nd:YAG. Diode-pumped threshold-fluence and threshold-pump energy estimates for Nd:Y2O3 lasing on the 4F3/2-->4I9/2 at 0.914 μm and 0.946 μm are calculated based on the data presented here. The measurements presented here for the Nd:Y2O3 indicate favorable absorption and emission properties. Favorable absorption properties in the ~0.8-μm pump wavelength are compatible with a variety of potential pump sources. Favorable emission properties at reduced temperatures near 150 K indicate that Nd:Y2O3 operating at 0.914 μm and 0.946 μm will have normal-mode laser thresholds similar to that of room-temperature Nd:YAG operating at 0.946 μm. In Q-switched operation, however, Nd:Y2O3 is predicted to exceed the performance of Nd:YAG due to the lower 1.06/0.94 cross-section ratio, which helps to limit amplified spontaneous-emission effects. Although Nd:Y2O3 is not a new material, it has not been the topic of study due to growth problems associated with its high melting point. New advances in growth techniques and the favorable spectroscopic features of Nd:Y2O3 have inspired a new examination of this material.

  4. Absorption and emission spectroscopic characterization of photo-dynamics of photoactivated adenylyl cyclase mutant bPAC-Y7F of Beggiatoa sp.

    PubMed

    Penzkofer, Alfons; Stierl, Manuela; Mathes, Tilo; Hegemann, Peter

    2014-11-01

    The photoactivated cyclase bPAC of the microbial mats bacterium Beggiatoa sp. consists of a BLUF domain and an adenylyl cyclase domain. It has strong activity of photo-induced cyclic adenylyl monophosphate (cAMP) formation and is therefore an important optogenetic tool in neuroscience applications. The SUMO-bPAC-Y7F mutant where Tyr-7 is replaced by Phe-7 in the BLUF domain has lost the typical BLUF domain photo-cycle dynamics. Instead, the investigated SUMO-bPAC-Y7F mutant consisted of three protein conformations with different triplet based photo-dynamics: (i) reversible flavin quinone (Fl) cofactor reduction to flavin semiquinone (FlH), (ii) reversible violet/near ultraviolet absorbing flavin photoproduct (FlA) formation, and (iii) irreversible red absorbing flavin photoproduct (FlC) formation. Absorption and emission spectroscopic measurements on SUMO-bPAC-Y7F were carried out before, during and after light exposure. Flavin photo-dynamics schemes are developed for the SUMO-bPAC-Y7F fractions performing photo-induced FlH, FlA, and FlC formation. Quantitative parameters of the flavin cofactor excitation, relaxation and recovery dynamics in SUMO-bPAC-Y7F are determined. PMID:25154810

  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. 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.

  7. Absorption and fluorescence spectroscopic characterisation of a phenothiazine flavin dyad

    NASA Astrophysics Data System (ADS)

    Shirdel, J.; Penzkofer, A.; Procházka, R.; Shen, Z.; Daub, J.

    2007-07-01

    The phenothiazine-phenylene-isoalloxazine dyad, 3-methyl-10-[4-(10-heptyl-10 H-phenothiazin-3-yl)-phenyl]-10 H-benzo[ g]pteridine-2,4-dione, dissolved in either dichloromethane or acetonitrile is characterized by absorption and emission spectroscopy. Absorption cross-section spectra, stimulated emission cross-section spectra, fluorescence quantum distributions, fluorescence quantum yields, and degrees of fluorescence polarisation are determined. The fluorescence decay is determined by time-resolved measurements. The dye photo-stability is investigated by observation of absorption spectral changes due to prolonged blue-light excitation. The absorption spectrum of the dyad resembles the superposition of the absorption of the isoalloxazine (flavin) moiety and of the phenylphenothiazine moiety. Photo-excitation of the flavin moiety causes fluorescence quenching by ground-state reductive electron transfer from phenylphenothiazine to isoalloxazine followed by charge recombination. Photo-excitation of the phenothiazine moiety causes (i) efficient excited-state oxidative electron transfer from phenothiazine to isoalloxazine with successive recombination, and (ii) moderate energy transfer followed by ground-state phenothiazine electron transfer and recombination.

  8. Characterization of semicrystalline polymers after nanoimprint by spectroscopic ellipsometry

    NASA Astrophysics Data System (ADS)

    Wang, Si; Rond, Johannes; Steinberg, Christian; Papenheim, Marc; Scheer, Hella-Christin

    2016-02-01

    Semicrystalline Reg-P3HT (regio-regular poly-3-hexylthiophene) is a promising material for organic electronics. It features relatively high charge mobility and enables easy preparation because of its solubility. Due to its high optical and electrical anisotropy, the size, number and orientation of the ordered domains are important for applications. To control these properties without limitation from crystalline domains existing after spin coating, thermal nanoimprint is performed beyond the melting point. The state of the art of measurement to analyze the complex morphology is X-ray diffraction (XRD). We address an alternative measurement method to characterize the material by its optical properties, spectroscopic ellipsometry. It provides information on the degree of order from the typical fingerprint absorption spectrum. In addition, when the material is modeled as a uniaxial layer, an anisotropy factor can be derived. The results obtained from spectroscopic ellipsometry are in accordance with those from XRD. In particular, spectroscopic ellipsometry is able to distinguish between order along the backbone and order in π- π stacking direction, which is important with respect to conductivity.

  9. 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.

  10. Spectroscopic characterization of genetically modified flax fibers

    NASA Astrophysics Data System (ADS)

    Dymińska, L.; Gągor, A.; Hanuza, J.; Kulma, A.; Preisner, M.; Żuk, M.; Szatkowski, M.; Szopa, J.

    2014-09-01

    The principal goal of this paper is an analysis of flax fiber composition. Natural and genetically modified flax fibers derived from transgenic flax have been analyzed. Development of genetic engineering enables to improve the quality of fibers. Three transgenic plant lines with different modifications were generated based on fibrous flax plants as the origin. These are plants with: silenced cinnamyl alcohol dehydrogenase (CAD) gene; overexpression of polygalacturonase (PGI); and expression of three genes construct containing β-ketothiolase (phb A), acetoacetyl-CoA reductase (phb B), and poly-3-hydroxybutyric acid synthase (phb C). Flax fibers have been studied by FT-IR spectroscopy. The integral intensities of the IR bands have been used for estimation of the chemical content of the normal and transgenic flaxes. The spectroscopic data were compared to those obtained from chemical analysis of flax fibers. X-ray studies have been used to characterize the changes of the crystalline structure of the flax cellulose fibers.

  11. Spectroscopic characterization of uranium in evaporation basin sediments

    SciTech Connect

    Duff, M.C.; Morris, D.E.; Hunter, D.B.; Bertsch, P.M.

    2000-05-01

    Evaporation ponds in the San Joaquin Valley (SJV), CA, used for the containment of irrigation drainage waters contain elevated levels of uranium (U) resulting from the extensive leaching by carbonate-rich irrigation waters of the local agricultural soils that contain low levels of naturally-occurring U. The SJV ponds are subjected to changes in redox chemistry with cycles of drying and flooding. Past studies have shown that U in the SJV Pont 14 surface sediments is present as mostly the oxidized and soluble form, U(VI). However, the authors were uncertain whether the U in the soil was only present as a U oxide of mixed stoichiometry, such as U{sub 3}O{sub 8(s)} (pitchblende) or other species. Here they present characterization information, which includes wet chemical and in situ spectroscopic techniques (X-ray absorption near-edge structure (XANES) and low temperature time-resolved luminescence spectroscopies) for samples from two SJV Pond sediments. Surface sediments from SJV Pont 16 were characterized for average oxidation state of U with XANES spectroscopy. The wet chemical extractions and in situ spectroscopic techniques provided fundamental and basic knowledge about the fraction of U(IV) to U(VI), the speciation of luminescent U(VI), and the susceptibility of the sediment U species to leaching.

  12. Surface spectroscopic characterization of titanium implant materials

    NASA Astrophysics Data System (ADS)

    Lausmaa, Jukka; Kasemo, Bengt; Mattsson, Håkan

    1990-04-01

    Titanium is one of the most commonly used biomaterials for dental and orthopedic applications. Its excellent tissue compatibility is mainly due to the properties of the stable oxide layer which is present on the surface. This paper reports a detailed spectroscopic characterization of the surface composition of non-alloyed Ti implant materials, prepared according to procedures commonly used in clinical practice (machining, ultrasonic cleaning and sterilization). The main methods of characterization are XPS and AES, and complementary information is obtained by SIMS, EDX and NMA (nuclear microanalysis). The surface of the implants is found to consist of a thin surface oxide which is covered by a carbon-dominated contamination layer. By comparison with reference spectra from single crystal TiO 2 (rutile) the composition of the surface oxide is shown to be mainly TiO 2, with minor amounts of suboxides and TiN x. The thickness of the surface oxides is 2-6 nm, depending on the method of sterilization. The surface contamination layer is found to vary considerably from sample to sample and consists of mainly hydrocarbons with trace amounts of Ca, N, S, P, Cl. Some differences in surface composition between directly prepared surfaces, and some possible contamination sources, are identified and discussed shortly.

  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 presence of chlorophyll, and hence, confirm the presence of Mg. This study provides evidence of Mg- and Zn-related inhibition of urinary calculi formation with the addition of RAL herbal extract, contributing, from the spectroscopic point of view, to an intricate subject. Our present investigation might serve as an important source of information on this tantalizing and multifaceted problem, which is not yet completely understood. (Abstract shortened by UMI.)

  14. Spectroscopic remote sensing for material identification, vegetation characterization, and mapping

    USGS Publications Warehouse

    Kokaly, Raymond F.

    2012-01-01

    Identifying materials by measuring and analyzing their reflectance spectra has been an important procedure in analytical chemistry for decades. Airborne and space-based imaging spectrometers allow materials to be mapped across the landscape. With many existing airborne sensors and new satellite-borne sensors planned for the future, robust methods are needed to fully exploit the information content of hyperspectral remote sensing data. A method of identifying and mapping materials using spectral feature analyses of reflectance data in an expert-system framework called MICA (Material Identification and Characterization Algorithm) is described. MICA is a module of the PRISM (Processing Routines in IDL for Spectroscopic Measurements) software, available to the public from the U.S. Geological Survey (USGS) at http://pubs.usgs.gov/of/2011/1155/. The core concepts of MICA include continuum removal and linear regression to compare key diagnostic absorption features in reference laboratory/field spectra and the spectra being analyzed. The reference spectra, diagnostic features, and threshold constraints are defined within a user-developed MICA command file (MCF). Building on several decades of experience in mineral mapping, a broadly-applicable MCF was developed to detect a set of minerals frequently occurring on the Earth's surface and applied to map minerals in the country-wide coverage of the 2007 Afghanistan HyMap data set. MICA has also been applied to detect sub-pixel oil contamination in marshes impacted by the Deepwater Horizon incident by discriminating the C-H absorption features in oil residues from background vegetation. These two recent examples demonstrate the utility of a spectroscopic approach to remote sensing for identifying and mapping the distributions of materials in imaging spectrometer data.

  15. Spectroscopic remote sensing for material identification, vegetation characterization, and mapping

    NASA Astrophysics Data System (ADS)

    Kokaly, Raymond F.

    2012-06-01

    Identifying materials by measuring and analyzing their reflectance spectra has been an important procedure in analytical chemistry for decades. Airborne and space-based imaging spectrometers allow materials to be mapped across the landscape. With many existing airborne sensors and new satellite-borne sensors planned for the future, robust methods are needed to fully exploit the information content of hyperspectral remote sensing data. A method of identifying and mapping materials using spectral feature analyses of reflectance data in an expert-system framework called MICA (Material Identification and Characterization Algorithm) is described. MICA is a module of the PRISM (Processing Routines in IDL for Spectroscopic Measurements) software, available to the public from the U.S. Geological Survey (USGS) at http://pubs.usgs.gov/of/2011/1155/. The core concepts of MICA include continuum removal and linear regression to compare key diagnostic absorption features in reference laboratory/field spectra and the spectra being analyzed. The reference spectra, diagnostic features, and threshold constraints are defined within a user-developed MICA command file (MCF). Building on several decades of experience in mineral mapping, a broadly-applicable MCF was developed to detect a set of minerals frequently occurring on the Earth's surface and applied to map minerals in the country-wide coverage of the 2007 Afghanistan HyMap data set. MICA has also been applied to detect sub-pixel oil contamination in marshes impacted by the Deepwater Horizon incident by discriminating the C-H absorption features in oil residues from background vegetation. These two recent examples demonstrate the utility of a spectroscopic approach to remote sensing for identifying and mapping the distributions of materials in imaging spectrometer data.

  16. Opto-nanomechanical spectroscopic material characterization

    SciTech Connect

    Tetard, Laurene; Passian, Ali; Farahi, R. H.; Thundat, Thomas; Davison, Brian H.

    2015-08-10

    Cellulosic ethanol is a biofuel of considerable potential in the search for sustainable and renewable bioenergy [1,2]. However, while rich in carbohydrates [3], the plant cell walls exhibit a natural resistance to complex phenotype treatments such as enzymatic microbial deconstruction, heat and acid treatments that can remove the lignin polymers from cellulose before hydrolysis [5]. Noninvasive physical and chemical characterization of the cell walls and the effect of such treatments on biomass are challenging but necessary to understand and overcome such resistance [6]. Although lacking chemical recognition in their traditional forms, the various emerging modalities of nano-mechanical [7] and opto-nano-mechanical [8] force microscopies [9,10] provide a superb window into the needed nanoscale material characterization [6]. Infrared absorption spectroscopy is a powerful, non- destructive and ultra-sensitive technique that can provide the needed molecular fingerprinting but the photothermal channel is delocalized and thus lacks spatial resolution. Utilizing the emerging dynamic concepts of mode synthesizing atomic force microscopy (MSAFM) [11] and virtual resonance [12], we introduce a hybrid photonic and nanomechanical force microscopy (hp-MSAFM) with molecular recognition and characterize the extraction, holopulping and acid treatment of biomass. We present spatially and spectrally resolved cell wall images that reveal both the morphological and the compositional alterations of the cell walls. The measured biomolecular traits are in agreement with chemical maps obtained with infrared and confocal Raman micro-spectroscopies of the same samples. The presented findings should prove highly relevant in fields such as cancer research [13], nanotoxicity [14], energy storage and production [15], where morphological, chemical and subsurface studies of nanocomposites [16], nanoparticle uptake by cells [14], and nanoscale quality control [17] are in demand.

  17. Opto-nanomechanical spectroscopic material characterization

    DOE PAGESBeta

    Tetard, Laurene; Passian, Ali; Farahi, R. H.; Thundat, Thomas; Davison, Brian H.

    2015-08-10

    Cellulosic ethanol is a biofuel of considerable potential in the search for sustainable and renewable bioenergy [1,2]. However, while rich in carbohydrates [3], the plant cell walls exhibit a natural resistance to complex phenotype treatments such as enzymatic microbial deconstruction, heat and acid treatments that can remove the lignin polymers from cellulose before hydrolysis [5]. Noninvasive physical and chemical characterization of the cell walls and the effect of such treatments on biomass are challenging but necessary to understand and overcome such resistance [6]. Although lacking chemical recognition in their traditional forms, the various emerging modalities of nano-mechanical [7] and opto-nano-mechanicalmore » [8] force microscopies [9,10] provide a superb window into the needed nanoscale material characterization [6]. Infrared absorption spectroscopy is a powerful, non- destructive and ultra-sensitive technique that can provide the needed molecular fingerprinting but the photothermal channel is delocalized and thus lacks spatial resolution. Utilizing the emerging dynamic concepts of mode synthesizing atomic force microscopy (MSAFM) [11] and virtual resonance [12], we introduce a hybrid photonic and nanomechanical force microscopy (hp-MSAFM) with molecular recognition and characterize the extraction, holopulping and acid treatment of biomass. We present spatially and spectrally resolved cell wall images that reveal both the morphological and the compositional alterations of the cell walls. The measured biomolecular traits are in agreement with chemical maps obtained with infrared and confocal Raman micro-spectroscopies of the same samples. The presented findings should prove highly relevant in fields such as cancer research [13], nanotoxicity [14], energy storage and production [15], where morphological, chemical and subsurface studies of nanocomposites [16], nanoparticle uptake by cells [14], and nanoscale quality control [17] are in demand.« less

  18. Absorption and emission spectroscopic characterisation of 8-amino-riboflavin

    NASA Astrophysics Data System (ADS)

    Tyagi, A.; Zirak, P.; Penzkofer, A.; Mathes, T.; Hegemann, P.; Mack, M.; Ghisla, S.

    2009-10-01

    The flavin dye 8-amino-8-demethyl- D-riboflavin (AF) in the solvents water, DMSO, methanol, and chloroform/DMSO was studied by absorption and fluorescence spectroscopy. The first absorption band is red-shifted compared to riboflavin, and blue-shifted compared to roseoflavin (8-dimethylamino-8-demethyl-D-riboflavin). The fluorescence quantum yield of AF in the studied solvents varies between 20% and 50%. The fluorescence lifetimes were found to be in the 2-5 ns range. AF is well soluble in DMSO, weakly soluble in water and methanol, and practically insoluble in chloroform. The limited solubility causes AF aggregation, which was seen in differences between measured absorption spectra and fluorescence excitation spectra. Light scattering in the dye absorption region is discussed and approximate absorption cross-section spectra are determined from the combined measurement of transmission and fluorescence excitation spectra. The photo-stability of AF was studied by prolonged light exposure. The photo-degradation routes of AF are discussed.

  19. Spectroscopic characterization of indian standard sand

    NASA Astrophysics Data System (ADS)

    Anbalagan, G.; Prabakaran, A. R.; Gunasekaran, S.

    2010-03-01

    The characterization of Indian standard sand (IS650:1991 as per B.I.S. approval) was performed by X-ray diffraction, IR and Raman spectroscopy, and nuclear magnetic resonance techniques. The principal reflections occurring at the d-spacings of 4.2408, 3.3440, and 1.8292 Å confirm the presence of α-quartz crystalline structure in the sample. The calculated unit cell parameters are: a = 4.9294 Å, c = 5.4093 Å, and V = 113.832 Å3. Mid-IR spectrum shows the characteristic doublet for α-quartz at 797 and 778 cm-1. The Al/Al+Si ratio has been calculated from the position of the absorption band at 1100 cm-1. Raman spectrum of the sample has two strong peaks at 203 cm-1 and at 462 cm-1 for A1 vibrational mode characteristic of α-quartz. Two bands at 1410 and 1930 nm in near-IR spectrum indicate the presence of both molecular water and an OH group. A broad double band centered near 1210 nm and a weak band at 1050 nm attest the presence of Fe2+ and Fe3+ respectively in the sample. The signal near g ˜ 4 is characteristic of isolated Fe3+ ions in the distorted octahedral or tetrahedral crystalline field. 29Si NMR spectrum shows a strong signal at -107 ppm corresponding to quartz.

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

    SciTech Connect

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

    2015-01-12

    We report real-time detection of hydrogen (H) absorption in metallic palladium (Pd) nano-contacts immersed in liquid H{sub 2} using inelastic electron spectroscopy (IES). After introduction of liquid H{sub 2}, 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.

  1. Spectroscopic observations of magnesium absorption gradients in six elliptical galaxies

    NASA Astrophysics Data System (ADS)

    Couture, Jean; Hardy, Eduardo

    1988-09-01

    The authors present Mg2 absorption strengths for six early-type galaxies obtained with Mont Mgantic's long-slit spectrograph and a panoramic photon-counting detector system. The gradients have been measured to more than one effective radius for NGC 1052, 3379, 4365, 4406, 4621, and 7332 along the major axis and, in three cases, also along the minor axis. The data are presented in tabular and graphical form. The spectral variations have been mapped in two different adimensional radial coordinate systems. The gradients were found to be very similar for a given representation for all galaxies studied. The gradients are also similar to those derived from a representation of the available published data in the same coordinate systems. Using the currently available abundance versus Mg2 strength calibrations, the authors confirm that abundance varies by a factor ?2 within one effective radius for giant early-type galaxies.

  2. Spectroscopic characterization of isomerization transition states.

    PubMed

    Baraban, Joshua H; Changala, P Bryan; Mellau, Georg Ch; Stanton, John F; Merer, Anthony J; Field, Robert W

    2015-12-11

    Transition state theory is central to our understanding of chemical reaction dynamics. We demonstrate a method for extracting transition state energies and properties from a characteristic pattern found in frequency-domain spectra of isomerizing systems. This pattern-a dip in the spacings of certain barrier-proximal vibrational levels-can be understood using the concept of effective frequency, ω(eff). The method is applied to the cis-trans conformational change in the S1 state of C2H2 and the bond-breaking HCN-HNC isomerization. In both cases, the barrier heights derived from spectroscopic data agree extremely well with previous ab initio calculations. We also show that it is possible to distinguish between vibrational modes that are actively involved in the isomerization process and those that are passive bystanders. PMID:26659051

  3. Spectroscopic characterization of isomerization transition states

    NASA Astrophysics Data System (ADS)

    Baraban, Joshua H.; Changala, P. Bryan; Mellau, Georg Ch.; Stanton, John F.; Merer, Anthony J.; Field, Robert W.

    2015-12-01

    Transition state theory is central to our understanding of chemical reaction dynamics. We demonstrate a method for extracting transition state energies and properties from a characteristic pattern found in frequency-domain spectra of isomerizing systems. This pattern—a dip in the spacings of certain barrier-proximal vibrational levels—can be understood using the concept of effective frequency, ωeff. The method is applied to the cis-trans conformational change in the S1 state of C2H2 and the bond-breaking HCN-HNC isomerization. In both cases, the barrier heights derived from spectroscopic data agree extremely well with previous ab initio calculations. We also show that it is possible to distinguish between vibrational modes that are actively involved in the isomerization process and those that are passive bystanders.

  4. 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

  5. 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…

  6. Catalog of Narrow Mg II Absorption Lines in the Baryon Oscillation Spectroscopic Survey

    NASA Astrophysics Data System (ADS)

    Chen, Zhi-Fu; Gu, Qiu-Sheng; Chen, Yan-Mei

    2015-12-01

    Using the Data Release 9 Quasar spectra from the Baryonic Oscillation Spectroscopic Survey, which does not include quasar spectra from the Sloan Digital Sky Survey Data Release 7, we detect narrow Mg ii λλ2796, 2803 absorption doublets in the spectral data redward of 1250 Å (quasar rest frame) until the red wing of the Mg ii λ2800 emission line. Our survey is limited to quasar spectra with a median signal-to-noise ratio < {{S}}/{{N}}> ≥slant 4 pixel-1 in the surveyed spectral region, resulting in a sample that contains 43,260 quasars. We have detected a total of 18,598 Mg ii absorption doublets with 0.2933 ≤ zabs ≤ 2.6529. About 75% of absorbers have an equivalent width at rest frame of {W}rλ 2796≥slant 1 \\mathringA . About 75% of absorbers have doublet ratios ({DR}={W}rλ 2796/{W}rλ 2803) in the range of 1 ≤ DR ≤ 2, and about 3.2% lie outside the range of 1 - σDR ≤ DR ≤ 2 + σDR. We characterize the detection false positives/negatives by the frequency of detected Mg ii absorption doublets in the limits of the S/N of the spectral data. The S/N = 4.5 limit is assigned a completeness fraction of 53% and tends to be complete when the S/N is greater than 4.5. The redshift number densities of all of the detected Mg ii absorbers moderately increase from z ≈ 0.4 to z ≈ 1.5, which parallels the evolution of the cosmic star formation rate density. Limiting our investigation to those quasars whose emission redshift can be determined from narrow emission lines, the relative velocities (β) of Mg ii absorbers have a complex distribution which probably consists of three classes of Mg ii absorbers: (1) cosmologically intervening absorbers; (2) environmental absorbers that reside within the quasar host galaxies or galaxy clusters; (3) quasar outflow absorbers. After subtracting contributions from cosmologically intervening absorbers and environmental absorbers, the β distribution of the Mg iiabsorbers might mainly be contributed by the quasar outflow absorbers and peaks at υ ≈ 1500 km s-1. This peak velocity is lower than the value of 2000 km s-1 found in statistical analysis of C iv absorbers.

  7. Methodical study on plaque characterization using integrated vascular ultrasound, strain and spectroscopic photoacoustic imaging

    NASA Astrophysics Data System (ADS)

    Graf, Iulia M.; Su, Jimmy; Yeager, Doug; Amirian, James; Smalling, Richard; Emelianov, Stanislav

    2011-03-01

    Carotid atherosclerosis has been identified as a potential risk factor for cerebrovascular events, but information about its direct effect on the risk of recurrent stroke is limited due to incomplete diagnosis. The combination of vascular ultrasound, strain rate and spectroscopic photoacoustics could improve the timely diagnosis of plaque status and risk of rupturing. Current ultrasound techniques can noninvasively image the anatomy of carotid arteries. The spatio-temporal variation in displacement of different regions within the arterial wall can be derived from ultrasound radio frequency data; therefore an ultrasound based strain rate imaging modality can be used to reveal changes in arterial mechanical properties. Additionally, spectroscopic photoacoustic imaging can provide information on the optical absorption properties of arterial tissue and it can be used to identify the location of specific tissue components, such as lipid pools. An imaging technique combining ultrasound, strain rate and spectroscopic photoacoustics was tested on an excised atherosclerotic rabbit aorta. The ultrasound image illustrates inhomogeneities in arterial wall thickness, the strain rate indicates the arterial segment with reduced elasticity and the spectroscopic photoacoustic image illustrates the accumulation of lipids. The results demonstrated that ultrasound, strain rate and spectroscopic photoacoustic imaging are complementary. Thus the integration of the three imaging modalities advances the characterization of atherosclerotic plaques.

  8. Spectroscopic characterization of natural calcite minerals

    NASA Astrophysics Data System (ADS)

    Gunasekaran, S.; Anbalagan, G.

    2007-11-01

    The FT-IR, FT-Raman, NMR spectral data of ten different limestone samples have been compared. FT-IR and FT-Raman spectral data show that calcium carbonate in limestone, principally in the form of calcite, as identified by its main absorption bands at 1426, 1092, 876 and 712 cm -1. The sharp diffractions at the d-spacings, 3.0348, 1.9166 and 1.8796 confirm the presence of calcite structure and the calculated lattice parameters are: a = 4.9781 Å, c = 17.1188 Å. The range of 13C chemical shifts for different limestone samples is very small, varying from 198.38 to 198.42 ppm. The observed chemical shifts are consistent with the identical C-O bonding in different limestone samples. 27Al MAS NMR spectra of the samples exhibit a central line at 1 ppm and another line at 60 ppm corresponding to octahedral and tetrahedral Al ions, respectively. The five component resonances were observed in 29Si MAS NMR spectrum of limestone and these resonances were assigned to Si (4 Al), Si (3 Al), Si (2 Al), Si (1 Al) and Si (0 Al) from low field to high field.

  9. Opto-nanomechanical spectroscopic material characterization

    NASA Astrophysics Data System (ADS)

    Tetard, L.; Passian, A.; Farahi, R. H.; Thundat, T.; Davison, B. H.

    2015-10-01

    The non-destructive, simultaneous chemical and physical characterization of materials at the nanoscale is an essential and highly sought-after capability. However, a combination of limitations imposed by Abbe diffraction, diffuse scattering, unknown subsurface, electromagnetic fluctuations and Brownian noise, for example, have made achieving this goal challenging. Here, we report a hybrid approach for nanoscale material characterization based on generalized nanomechanical force microscopy in conjunction with infrared photoacoustic spectroscopy. As an application, we tackle the outstanding problem of spatially and spectrally resolving plant cell walls. Nanoscale characterization of plant cell walls and the effect of complex phenotype treatments on biomass are challenging but necessary in the search for sustainable and renewable bioenergy. We present results that reveal both the morphological and compositional substructures of the cell walls. The measured biomolecular traits are in agreement with the lower-resolution chemical maps obtained with infrared and confocal Raman micro-spectroscopies of the same samples. These results should prove relevant in other fields such as cancer research, nanotoxicity, and energy storage and production, where morphological, chemical and subsurface studies of nanocomposites, nanoparticle uptake by cells and nanoscale quality control are in demand.

  10. Crystallographic and X-ray absorption spectroscopic characterization of Helicobacter pylori UreE bound to Ni²⁺ and Zn²⁺ reveals a role for the disordered C-terminal arm in metal trafficking.

    PubMed

    Banaszak, Katarzyna; Martin-Diaconescu, Vlad; Bellucci, Matteo; Zambelli, Barbara; Rypniewski, Wojciech; Maroney, Michael J; Ciurli, Stefano

    2012-02-01

    The survival and growth of the pathogen Helicobacter pylori in the gastric acidic environment is ensured by the activity of urease, an enzyme containing two essential Ni²⁺ ions in the active site. The metallo-chaperone UreE facilitates in vivo Ni²⁺ insertion into the apoenzyme. Crystals of apo-HpUreE (H. pylori UreE) and its Ni⁺- and Zn⁺-bound forms were obtained from protein solutions in the absence and presence of the metal ions. The crystal structures of the homodimeric protein, determined at 2.00 Å (apo), 1.59 Å (Ni²⁺) and 2.52 Å (Zn²⁺) resolution, show the conserved proximal and solvent-exposed His¹⁰² residues from two adjacent monomers invariably involved in metal binding. The C-terminal regions of the apoprotein are disordered in the crystal, but acquire significant ordering in the presence of the metal ions due to the binding of His¹⁵². The analysis of X-ray absorption spectral data obtained using solutions of Ni²⁺- and Zn²⁺-bound HpUreE provided accurate information of the metal-ion environment in the absence of solid-state effects. These results reveal the role of the histidine residues at the protein C-terminus in metal-ion binding, and the mutual influence of protein framework and metal-ion stereo-electronic properties in establishing co-ordination number and geometry leading to metal selectivity. PMID:22010876

  11. Precision Radial Velocities of Double-lined Spectroscopic Binaries with an Iodine Absorption Cell

    NASA Astrophysics Data System (ADS)

    Konacki, Maciej

    2005-06-01

    A spectroscopic technique employing an iodine absorption cell (I2) to superimpose a reference spectrum onto a stellar spectrum is currently the most widely adopted approach to obtain precision radial velocities of solar-type stars. It has been used to detect ~80 extrasolar planets out of ~130 known. Yet in its original version, it only allows us to measure precise radial velocities of single stars. In this paper, we present a novel method employing an I2 absorption cell that enables us to accurately determine radial velocities of both components of double-lined binaries. Our preliminary results, based on the data from the Keck I telescope and HIRES spectrograph, demonstrate that 20-30 m s-1 radial velocity precision can be routinely obtained for ``early'' type binaries (F3-F8). For later type binaries, the precision reaches ~10 m s-1. We discuss applications of the technique to stellar astronomy and searches for extrasolar planets in binary systems. In particular, we combine the interferometric data collected with the Palomar Testbed Interferometer with our preliminary precision velocities of the spectroscopic double-lined binary HD 4676 to demonstrate that with such a combination one can routinely obtain masses of the binary components accurate at least at the level of 1.0%.

  12. Novel dipodal Schiff base compounds: Synthesis, characterization and spectroscopic studies

    NASA Astrophysics Data System (ADS)

    Obali, Aslihan Yilmaz; Ucan, Halil Ismet

    2015-02-01

    Two novel dipodal Schiff base compounds 1,2-benzyloxy-bis-[2-(benzylideneamino)phenol, L1 and 1,2-benzyloxy-bis[3-(benzylideneamino)pyridine], L2 were synthesized. Their sensing actions were confirmed by UV-Vis absorbance and emission spectroscopic studies in presence of Cr(III), Mn(II), Fe(III), Co(II), Ni(II), Cu(II), Zn(II), Sn(II), Cd(II) and Pb(II) in methanol medium (1 × 10-4 M). It was found that the dipodal compounds can selectively bind to Cu(II) and Pb(II) metal ions with a significant change in its emission and absorption spectra, while the addition of other metal ions (Cr(III), Mn(II), Fe(III), Co(II), Ni(II), Cu(II), Zn(II), Sn(II), Cd(II) and Pb(II)) produces insignificant or minor changes. The host-guest complexes formed were determined by Job's plot method. As a chemosensor, L1 and L2 dipodal Schiff base compounds shows a specific selectivity towards Cu(II) and Pb(II) ions in according to all spectroscopic data.

  13. Accurate dimensional characterization of periodic structures by spectroscopic Mueller polarimetry

    NASA Astrophysics Data System (ADS)

    Foldyna, M.; De Martino, A.; Cattelan, D.; Bogeat, F.; Licitra, C.; Foucher, J.; Barritault, P.; Hazart, J.

    2008-11-01

    The potential of spectroscopic Mueller polarimetry for the dimensional characterization of periodic structures has already been discussed in several instances. With respect to standard scatterometry; the added value of the technique is related to the information contained in the 16 elements of the Mueller matrix, while usual scatterometry provides only two. The additional information can prove useful to decorrelate dimensional or optical parameters, and to assess the adequacy of the model describing the profiles to be reconstructed: if the model is adequate, the optimal values of the dimensional parameters must remain stable when the measurement conditions, and thus the input data, are varied. This issue has been addressed for a series of 1D gratings etched in bulk Si and characterized by a spectroscopic polarimeter operating in the visible (Horiba Jobin Yvon MM-16), as well as CD-SEM and state-of-the art CD-AFM. With the usual lamellar or trapezoidal models both the CD and thickness values exhibit up to 10 nm systematic variations with measurement conditions. In contrast, with an original model taking into account the non-flatness of the open areas between adjacent lines the parameters become consistent to within 2 nm, well below typical tool-to-tool offsets. The corresponding profiles are also compatible with the CD-AFM images.

  14. Characterization of cytochrome c as marker for retinal cell degeneration by uv/vis spectroscopic imaging

    NASA Astrophysics Data System (ADS)

    Hollmach, Julia; Schweizer, Julia; Steiner, Gerald; Knels, Lilla; Funk, Richard H. W.; Thalheim, Silko; Koch, Edmund

    2011-07-01

    Retinal diseases like age-related macular degeneration have become an important cause of visual loss depending on increasing life expectancy and lifestyle habits. Due to the fact that no satisfying treatment exists, early diagnosis and prevention are the only possibilities to stop the degeneration. The protein cytochrome c (cyt c) is a suitable marker for degeneration processes and apoptosis because it is a part of the respiratory chain and involved in the apoptotic pathway. The determination of the local distribution and oxidative state of cyt c in living cells allows the characterization of cell degeneration processes. Since cyt c exhibits characteristic absorption bands between 400 and 650 nm wavelength, uv/vis in situ spectroscopic imaging was used for its characterization in retinal ganglion cells. The large amount of data, consisting of spatial and spectral information, was processed by multivariate data analysis. The challenge consists in the identification of the molecular information of cyt c. Baseline correction, principle component analysis (PCA) and cluster analysis (CA) were performed in order to identify cyt c within the spectral dataset. The combination of PCA and CA reveals cyt c and its oxidative state. The results demonstrate that uv/vis spectroscopic imaging in conjunction with sophisticated multivariate methods is a suitable tool to characterize cyt c under in situ conditions.

  15. Thermal, optical and spectroscopic characterizations of borate laser crystals

    SciTech Connect

    Chavoutier, M.; Jubera, V.; Veber, P.; Velazquez, M.; Viraphong, O.; Hejtmanek, J.; Decourt, R.; Debray, J.; Menaert, B.; Segonds, P.; Adamietz, F.; Rodriguez, V.; Manek-Hoenninger, I.; Fargues, A.; Descamps, D.; Garcia, A.

    2011-02-15

    The Yb-content Li{sub 6}Ln(BO{sub 3}){sub 3} (Ln: Gd, Y) solid solution has been investigated. Crystal growth has been successful for several compositions. A 22% molar content of ytterbium ions was determined by chemical analysis (ICP). Physical properties relevant to laser operation like mechanical hardness, thermal expansion and thermal conductivity were measured on single crystals. Optical measurements, including refractive index and low temperature spectroscopy, were also performed. Finally, the effect of the Y/Gd ratio is discussed. -- Graphical abstract: Several solid solutions of a rare earth borate were studied. The figure illustrates one of these single crystals obtained by Czochralski and shows thermal behaviour and absorption spectra at low temperature. Display Omitted Research highlights: {yields} We have grown by Czochralski method five Li{sub 6}Ln(BO{sub 3}){sub 3} (Ln=Y, Gd,Yb) single crystals. {yields} Chemical, physical and spectroscopic characteristics are reported. {yields} Data relevant to laser operation are listed.

  16. Synthesis, characterization and spectroscopic investigation of a novel phenylhydrazone Schiff base with solvatochromism.

    PubMed

    Li, Mingtian; Huang, Jun; Zhou, Xuan; Luo, Hong

    2010-02-01

    A novel Schiff base of 4,5-diazafluorene-9-p-nitrophenylhydrazone (DAFND) has been synthesized and characterized. The crystal structures of DAFND and its analogue 4,5-diazafluorene-9-phenylhydrazone (DAFPD) were determined by single crystal X-ray diffraction method. X-ray analyses reveal that DAFPD comprise of a nonplanar molecule and all atoms of DAFND are essentially coplanar. The color of DAFND changes from brown to blue when heated, so called thermochromism and the spectroscopic properties of the two compounds are investigated by electronic absorption spectra, showing DAFND possess solvatochromism, while DAFPD does not have thermochromic and solvatochromic properties. The lambda(max) of DAFND within various pure solvents are different ranging from 370 nm in toluene to 614 nm in pyridine. The imaginable mechanisms of thermochromism and solvatochromism are proposed. PMID:20031480

  17. Synthesis, characterization and spectroscopic investigation of a novel phenylhydrazone Schiff base with solvatochromism

    NASA Astrophysics Data System (ADS)

    Li, Mingtian; Huang, Jun; Zhou, Xuan; Luo, Hong

    2010-02-01

    A novel Schiff base of 4,5-diazafluorene-9- p-nitrophenylhydrazone (DAFND) has been synthesized and characterized. The crystal structures of DAFND and its analogue 4,5-diazafluorene-9-phenylhydrazone (DAFPD) were determined by single crystal X-ray diffraction method. X-ray analyses reveal that DAFPD comprise of a nonplanar molecule and all atoms of DAFND are essentially coplanar. The color of DAFND changes from brown to blue when heated, so called thermochromism and the spectroscopic properties of the two compounds are investigated by electronic absorption spectra, showing DAFND possess solvatochromism, while DAFPD does not have thermochromic and solvatochromic properties. The λmax of DAFND within various pure solvents are different ranging from 370 nm in toluene to 614 nm in pyridine. The imaginable mechanisms of thermochromism and solvatochromism are proposed.

  18. 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.

  19. 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

  20. 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.

  1. Spectroscopic detection, characterization and dynamics of free radicals relevant to combustion processes

    SciTech Connect

    Miller, Terry

    2015-06-04

    Combustion chemistry is enormously complex. The chemical mechanisms involve a multitude of elementary reaction steps and a comparable number of reactive intermediates, many of which are free radicals. Computer simulations based upon these mechanisms are limited by the validity of the mechanisms and the parameters characterizing the properties of the intermediates and their reactivity. Spectroscopy can provide data for sensitive and selective diagnostics to follow their reactions. Spectroscopic analysis also provides detailed parameters characterizing the properties of these intermediates. These parameters serve as experimental gold standards to benchmark predictions of these properties from large-scale, electronic structure calculations. This work has demonstrated the unique capabilities of near-infrared cavity ringdown spectroscopy (NIR CRDS) to identify, characterize and monitor intermediates of key importance in complex chemical reactions. Our studies have focussed on the large family of organic peroxy radicals which are arguably themost important intermediates in combustion chemistry and many other reactions involving the oxidation of organic compounds. Our spectroscopic studies have shown that the NIR Ã - ˜X electronic spectra of the peroxy radicals allows one to differentiate among chemical species in the organic peroxy family and also determine their isomeric and conformic structure in many cases. We have clearly demonstrated this capability on saturated and unsaturated peroxy radicals and β-hydroxy peroxy radicals. In addition we have developed a unique dual wavelength CRDS apparatus specifically for the purpose of measuring absolute absorption cross section and following the reaction of chemical intermediates. The utility of the apparatus has been demonstrated by measuring the cross-section and self-reaction rate constant for ethyl peroxy.

  2. 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.

  3. Chromium(V) peptide complexes: synthesis and spectroscopic characterization.

    PubMed

    Barnard, Peter J; Levina, Aviva; Lay, Peter A

    2005-02-21

    A series of stable Cr(V) model complexes that mimic the binding of Cr(V) to peptide backbones at the C-terminus of proteins have been prepared for N,N-dimethylurea derivatives of the tripeptides Aib3-DMF, AibLAlaAib-DMF, and AibDAlaAib-DMF (Aib = 2-amino-2-methylpropanoic acid, DMF = N,N-dimethylformamide). The Cr(ll) precursor complexes were synthesized by the initial deprotonation of the amide and acid groups of the peptide ligands in DMF with potassium tert-butoxide in the presence of CrCl2. The Cr(II) intermediates thus formed were then immediately oxidized to Cr(V) using tert-butyl hydroperoxide. Spectroscopic and mass-spectrometric analyses of the Cr(V) complexes showed that a new metal-directed organic transformation of the ligand had occurred. This involved a DMF solvent molecule becoming covalently bound to the amine group of the peptide ligand, yielding a urea group, and a third coordinated deprotonated urea nitrogen donor. A metal-directed oxidative coupling has been proposed as a possible mechanism for the organic transformation. The Cr(V/IV) reduction potential was determined for the three Cr(V) complexes using cyclic voltammetry, and in all cases it was quasi-reversible. These are the first isolated and fully characterized Cr(V) complexes with non-sulfur-containing peptide ligands. PMID:15859285

  4. Direct imaging and spectroscopic characterization of habitable planets with ELTs

    NASA Astrophysics Data System (ADS)

    Guyon, Olivier; Jovanovic, Nemanja; Lozi, Julien

    2015-12-01

    While the ~1e10 reflected light contrast between Earth-like planets and Sun-like stars is extremely challenging to overcome for ground-based telescopes, habitable planets around lower-mass stars can be "only" a 10 million times fainter than their host stars. Thanks to the small angular resolution offered by upcoming extremely large telescopes (ELTs) and recent advances in wavefront control and coronagraphic techniques, direct imaging and spectroscopic characterization of habitable planets will be possible around nearby M-type stars. Deep (~1e-8) contrast can be achieved by combining (1) sensitive fast visible light wavefront sensing (extreme-AO) with (2) kHz speckle control in the near-IR and (3) high efficiency coronagraphy. Spectroscopy will measure abundances of water, oxygen and methane, measure the planet rotation period, orbit, and identify main surface features through time-domain spectrophotometry.The Subaru Coronagraphic Extreme AO (SCExAO) system is a technology precursor to such a habitable planet imager for ELTs, and is currently under active development. By combining small inner working angle coronagraphy, visible-WFS based extreme-AO and fast speckle control, it will include the key elements of a future ELT system able to image and characterize habitable planets. We describe a technical plan to evolve SCExAO into a habitable planet imager for the Thirty Meter Telescope (TMT), which is aimed at providing such scientific capability during the 2020 decade, and inform the design, deployment and scientific operation of a more capable Extreme-AO instrument.

  5. 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

  6. 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 ...

  7. 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

  8. 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

  9. Theoretical modeling of the spectroscopic absorption properties of luciferin and oxyluciferin: A critical comparison with recent experimental studies

    NASA Astrophysics Data System (ADS)

    Anselmi, Massimiliano; Marocchi, Simone; Aschi, Massimiliano; Amadei, Andrea

    2012-01-01

    Firefly luciferin and its oxidated form, oxyluciferin, are two heterocyclic compounds involved in the enzymatic reaction, catalyzed by redox proteins called luciferases, which provides the bioluminescence in a wide group of arthropods. Whereas the electronic absorption spectra of D-luciferin in water at different pHs are known since 1960s, only recently reliable experimental electronic spectra of oxyluciferin have become available. In addition oxyluciferin is involved in a triple chemical equilibria (deprotonation of the two hydroxyl groups and keto-enol tautomerism of the 4-hydroxythiazole ring), that obligates to select during an experiment a predominant species, tuning pH or solvent polarity besides introducing chemical modifications. In this study we report the absorption spectra of luciferin and oxyluciferin in each principal chemical form, calculated by means of perturbed matrix method (PMM), which allowed us to successfully introduce the effect of the solvent on the spectroscopic absorption properties, and compare the result with available experimental data.

  10. Spectroscopic and Computational Characterization of the Base-off Forms of Cob(II)alamin

    PubMed Central

    Liptak, Matthew D.; Fleischhacker, Angela S.; Matthews, Rowena G.; Telser, Joshua; Brunold, Thomas C.

    2011-01-01

    The one-electron reduced form of vitamin B12, cob(II)alamin (Co2+Cbl), is found in several essential human enzymes, including the cobalamin-dependent methionine synthase (MetH). In this work, experimentally validated electronic structure descriptions for two “base-off” Co2+Cbl species have been generated by using a combined spectroscopic and computational approach, so as to obtain definitive clues as to how these and related enzymes catalyze the thermodynamically challenging reduction of Co2+Cbl to cob(I)alamin (Co1+Cbl). Specifically, electron paramagnetic resonance (EPR), electronic absorption (Abs), and magnetic circular dichroism (MCD) spectroscopic techniques have been employed as complementary tools to characterize the two distinct forms of base-off Co2+Cbl that can be trapped in the H759G variant of MetH, one possessing a five-coordinate and the other a four-coordinate, square-planar Co2+ center. Accurate spin Hamiltonian parameters for these low-spin Co2+ centers have been determined by collecting EPR data using both X- and Q-Band microwave frequencies, while Abs and MCD spectroscopic techniques have been employed to probe the corrin-centered π → π* and Co-based d → d excitations, respectively. By using these spectroscopic data for evaluating electronic structure calculations, it was found that density functional theory provides a reasonable electronic structure description for the five-coordinate form of base-off Co2+Cbl. However, it was necessary to resort to a multireference ab initio treatment to generate a more realistic description of the electronic structure of the four-coordinate form. Consistent with this finding, our computational data indicate that in the five-coordinate Co2+Cbl species, the unpaired spin density is primarily localized in the Co 3dz2-based molecular orbital, as expected, whereas in the four-coordinate form, extensive Co 3d orbital mixing, configuration-interaction, and spin-orbit coupling cause the unpaired electron to delocalize over several Co 3d orbitals. These results provide important clues with regards to the mechanism of enzymatic Co2+Cbl → Co1+Cbl reduction. PMID:19298066

  11. Transient absorption characterization of Cu- and Zn-metallized derivatives of meso-tetrakis(4-caynophenyl) N-confused porphyrin

    NASA Astrophysics Data System (ADS)

    Ao, Guanghong; Xiao, Zhengguo; Wang, Yuxiao; Zhang, Xueru; Song, Yinglin

    2015-10-01

    Meso-tetrakis(4-cyanophenyl)N-confused porphyrin [NCTPP(CN)4] and its two metallized derivatives with Cu2+ and Zn2+ ligand in the central position of the macrocycle are synthesized and spectroscopically characterized. Their excited-state dynamics are investigated with transient absorption (TA) spectroscopy upon excitation by 190 fs laser pulses at 420 nm within their Soret band region. A global and target analysis for the TA spectra of each porphyrin is performed via a four-level model including singlet (S) and triplet (T) states to extract the photophysical parameters at a variety of absorption wavelengths. Furthermore the corresponding excited-state lifetimes are extracted and discussed.

  12. Absorption properties of type-II InAs/InAsSb superlattices measured by spectroscopic ellipsometry

    SciTech Connect

    Webster, P. T.; Riordan, N. A.; Liu, S.; Zhang, Y.-H.; Johnson, S. R.; Steenbergen, E. H.

    2015-02-09

    Strain-balanced InAs/InAsSb superlattices offer access to the mid- to long-wavelength infrared region with what is essentially a ternary material system at the GaSb lattice constant. The absorption coefficients of InAs/InAsSb superlattices grown by molecular beam epitaxy on (100)-oriented GaSb substrates are measured at room temperature over the 30 to 800 meV photon energy range using spectroscopic ellipsometry, and the miniband structure of each superlattice is calculated using a Kronig-Penney model. The InAs/InAsSb conduction band offset is used as a fitting parameter to align the calculated superlattice ground state transition energy to the measured absorption onset at room temperature and to the photoluminescence peak energy at low temperature. It is observed that the ground state absorption coefficient and transition strength are proportional to the square of the wavefunction overlap and the ground state absorption coefficient approaches a maximum value of around 5780 cm{sup −1} as the wavefunction overlap approaches 100%. The absorption analysis of these samples indicates that the optical joint density of states is weakly dependent on the period thickness and Sb content of the superlattice, and that wavefunction overlap is the principal design parameter in terms of obtaining strong absorption in these structures.

  13. Spectroscopic characterization of nanocrystalline chromium nitride (CrN).

    PubMed

    Mangamma, G; Sairam, T N; Dash, S; Rajalakshmi, M; Kamruddin, M; Mittal, V K; Narasimhan, S V; Arora, A K; Sundar, C S; Tyagi, A K; Raj, Baldev

    2007-03-01

    Nanocrystalline chromiuim nitride has been synthesised by direct gas phase nitridation of nanocrystalline chromia at 1100 degrees C in ammonia-atmosphere. XRD of this material showed formation of single phase CrN with particle size around 20 nm. AFM studies showed particle distribution along with some soft agglomerated nanostructures. Nanocrystalline Cr2O3 and partially-as well as fully--converted nanocrystalline CrN were also investigated using various spectroscopic techniques like XPS, FT-IR, and Raman for gaining insight into the conversion pathways. Spectroscopic investigations of these materials clearly indicate that complete conversion of CrN occurs by nitriding at 1100 degrees C for 4 hrs. The salient spectroscopic features of these nanocrystalline materials with respect to their microcrystalline counterparts are discussed. PMID:17450861

  14. Possibilities and limitations of imaging spectroscopic reflectometry in optical characterization of thin films

    NASA Astrophysics Data System (ADS)

    Ohlídal, Miloslav; Ohlidal, Ivan; Nečas, David; Vodák, Jiří; Franta, Daniel; Nádaský, Pavel; Vižd'a, František

    2015-09-01

    It is possible to encounter thin films exhibiting various defects in practice. One of these defects is area non-uniformity in optical parameters (e.g. in thickness). Therefore it is necessary to have methods for an optical characterization of nonuniform thin films. Imaging spectroscopic reflectometry provides methods enabling us to perform an efficient optical characterization of such films. It gives a possibility to determine spectral dependencies of a local reflectance at normal incidence of light belonging to small areas (37 μm × 37 μm in our case) on these non-uniform films. The local reflectance is measured by individual pixels of a CCD camera serving as a detector of an imaging spectroscopic reflectometer. It is mostly possible to express the local reflectance using formulas corresponding to a uniform thin film. It allows a relatively simple treatment of the experimental data obtained by imaging spectroscopic reflectometry. There are three methods for treating these experimental data in the special case of thickness non-uniformity, i.e. in the case of the same optical constants within a certain area of the film - single pixel imaging spectroscopic reflectometry method, combination of single-pixel imaging spectroscopic reflectometry method and conventional methods (conventional single spot spectroscopic ellipsometry and spectrophotometry), and multi-pixel imaging spectroscopic reflectometry method. These methods are discussed and examples of the optical characterization of thin films non-uniform in thickness corresponding to these methods are presented in this contribution.

  15. Spectroscopic characterization of iron-doped II-VI compounds for laser applications

    NASA Astrophysics Data System (ADS)

    Martinez, Alan

    The middle Infrared (mid-IR) region of the electromagnetic spectrum between 2 and 15 ?m has many features which are of interest to a variety of fields such as molecular spectroscopy, biomedical applications, industrial process control, oil prospecting, free-space communication and defense-related applications. Because of this, there is a demand for broadly tunable, laser sources operating over this spectral region which can be easily and inexpensively produced. II-VI semiconductor materials doped with transition metals (TM) such as Co 2+, Cr2+, or Fe2+ exhibit highly favorable spectroscopic characteristics for mid-IR laser applications. Among these TM dopants, Fe2+ has absorption and emission which extend the farthest into the longer wavelength portion of the mid-IR. Fe2+:II-VI crystals have been utilized as gain elements in laser systems broadly tunable over the 3-5.5 microm range [1] and as saturable absorbers to Q -switch [2] and mode-lock [3] laser cavities operating over the 2.7-3 microm. TM:II-VI laser gain elements can be fabricated inexpensively by means of post-growth thermal diffusion with large homogeneous dopant concentration and good optical quality[4,5]. The work outlined in this dissertation will focus on the spectroscopic characterization of TM-doped II-VI semiconductors. This work can be categorized into three major thrusts: 1) the development of novel laser materials, 2) improving and extending applications of TM:II-VI crystals as saturable absorbers, and 3) fabrication of laser active bulk crystals. Because current laser sources based on TM:II-VI materials do not cover the entire mid-IR spectral region, it is necessary to explore novel laser sources to extend available emissions toward longer wavelengths. The first objective of this dissertation is the spectroscopic characterization of novel ternary host crystals doped with Fe2+ ions. Using crystal field engineering, laser materials can be prepared with emissions placed in spectral regions not currently covered by available sources while maintaining absorption which overlaps with available pump sources. Because optimization of these materials requires extensive experimentation, a technique to fabricate and characterize novel crystals in powder form was developed, eliminating the need for the crystal growth. Powders were characterized using Raman, photoluminescence studies, and kinetics of luminescence. The first demonstration of random lasing of Fe:ZnCdTe powder at 6 microm was reported. These results show promise for the development of these TM-doped ternary II-VI compounds as laser gain media operating at 6 microm and longer. The second major objective was to study the performance of TM:II-VI elements as saturable absorber Q-switches and mode-lockers in flash lamp pumped Er:YAG and Er:Cr:YSGG cavities. Different cavity schemes were arranged to eliminate depolarization losses and improve Q-switching performance in Er:YAG and the first use of Cr:ZnSe to passively Q -switch an Er:Cr:YSGG cavity was demonstrated. While post-growth thermal diffusion is an effective way to prepare large-scale highly doped TM:II-VI laser elements, the diffusion rate of some ions into II-VI semiconductors is too low to make this method practical for large crystals. The third objective was to improve the rate of thermal diffusion of iron into II-VI semiconductor crystals by means of gamma-irradiation during the diffusion process. When exposed to a dose rate of 44 R/s during the diffusion process, the diffusion coefficient for Fe into ZnSe showed improvement of 60% and the diffusion coefficient of Fe into ZnS showed improvement of 30%.

  16. White-light continuum probed femtosecond time-resolved absorption spectroscopic measurement of β-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 β-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. Nanofluid optical property characterization: towards efficient direct absorption solar collectors

    PubMed Central

    2011-01-01

    Suspensions of nanoparticles (i.e., particles with diameters < 100 nm) in liquids, termed nanofluids, show remarkable thermal and optical property changes from the base liquid at low particle loadings. Recent studies also indicate that selected nanofluids may improve the efficiency of direct absorption solar thermal collectors. To determine the effectiveness of nanofluids in solar applications, their ability to convert light energy to thermal energy must be known. That is, their absorption of the solar spectrum must be established. Accordingly, this study compares model predictions to spectroscopic measurements of extinction coefficients over wavelengths that are important for solar energy (0.25 to 2.5 μm). A simple addition of the base fluid and nanoparticle extinction coefficients is applied as an approximation of the effective nanofluid extinction coefficient. Comparisons with measured extinction coefficients reveal that the approximation works well with water-based nanofluids containing graphite nanoparticles but less well with metallic nanoparticles and/or oil-based fluids. For the materials used in this study, over 95% of incoming sunlight can be absorbed (in a nanofluid thickness ≥10 cm) with extremely low nanoparticle volume fractions - less than 1 × 10-5, or 10 parts per million. Thus, nanofluids could be used to absorb sunlight with a negligible amount of viscosity and/or density (read: pumping power) increase. PMID:21711750

  18. 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.

  19. Synthesis and spectroscopic characterization of a new (aryl-SCN)n polymer: Polythiocyanatohydroquinone

    NASA Astrophysics Data System (ADS)

    Baryshnikov, Gleb V.; Galagan, Rostislav L.; Shepetun, Ludmila P.; Litvin, Valentina A.; Minaev, Boris F.

    2015-09-01

    In the present work we have demonstrated the first synthesis of the polythiocyanogen-like (aryl-SCN)n compound (polythiocyanatohydroquinone) from the initial 1,4-benzoquinone and NH4SCN reagents under the normal conditions in the glacial acetic acid medium. The synthesized amorphous polymer was characterized experimentally by the FT-IR and UV-vis spectroscopic methods accompanied with theoretical assignments by the density functional theory (DFT) and time-dependent DFT calculations. The transmission electron microscopy and the XRD pattern analysis were used to indicate the amorphous structure of the synthesized polymer. The DFT geometry optimization of a number of oligomers (n = 4-8) permit us to predict the possible structure of polythiocyanatohydroquinone and to assign the observed bands in IR and UV-vis absorption spectra. It was found that the synthesized polythiocyanatohydroquinone powder has a complicated structure which can be represented as a branched polymer constructed from the mono- and doubly-SCN-substituted benzene-1,4-diol moieties. This new material demonstrates a good stabilizing effect in respect to colloidal solutions of Ag and Au nanoparticles. Additionally, polythiocyanatohydroquinone is predicted to be a promising candidate for creation of metal-containing composite materials. Its application as a framework for the Pt electrode closing is found very useful.

  20. Synthesis, characterization, spectroscopic properties, theoretical calculation, and antimicrobial activity of new aryldisulfonamides

    NASA Astrophysics Data System (ADS)

    Alyar, Saliha; Zengin, Hüseyin; Özbek, Neslihan; Karacan, Nurcan

    2011-04-01

    New aryldisulfonamides were synthesized and characterized by FTIR, 1H NMR, 13C NMR, HETCOR, COSY, LC-MS and elemental analysis techniques. The compounds gave intense emissions, where λmax = 405, 379 and 402 nm, upon irradiation by Ultra-Violet light. The photoluminescence quantum yields and long excited-state lifetimes of the compounds were calculated and were found to have photoluminescence quantum yields 39 ± 1.8%, 45 ± 2.2% and 34 ± 1.4% and long excited-state lifetimes of 3.65 ± 0.16, 4.17 ± 0.20 and 3.15 ± 0.12 ns, respectively. The photoluminescence intensities and quantum yields of compounds varied with the position of substituent on the ring and the chain length between aromatic rings. These novel compounds may be of interest as organic emitting materials for electroluminescent devices. The visible absorption maxima were calculated using time-depended density-functional theory (TD-DFT) and Zerner's intermediate neglect of differential overlap/spectroscopic (ZINDO/S) method in the gas phase. Further, the compounds were evaluated for in vitro antimicrobial activity against various microorganisms by microdilution and disk diffusion methods.

  1. Spectroscopic characterizations of rare earth doped ceramics, nanocrystals, nanocrystal embedded polymeric hosts and their potential applications

    NASA Astrophysics Data System (ADS)

    Nash, Kelly Latrice

    Trivalent rare earth (RE3+) ions have been used as an activator in laser host materials and in a wide variety of photonic applications. Of the competing hosts, one of the most well studied and successful host has been yttrium aluminum garnet Y3Al5O12 (YAG). In comparison to YAG, yttrium oxide (Y2O3) has shown promise as a potential laser medium due to its excellent optical, thermal and mechanical properties. As single crystals, Y2O3 system can be extremely difficult to grow due to the high melting temperature (2200C) of the host. Alternatively, ceramic and nanocrystalline forms of Y2O3 have contributed to renewed interest in the material as laser host and more recently in biological and other photonic applications due to simplicity of fabrication. This work focuses on four RE 3+ ions, namely erbium, neodymium, holmium, europium doped into Y 2O3 and are selected due to their multi-frequency absorption properties and visible to near infrared emission characteristics. The chosen nanocrystalline material are embedded or coated in polymers that are biocompatible resulting in visible to near infrared fluorescent polymers. These materials are characterized through morphology studies and spectroscopic analyses of the absorption and emission spectra. Judd-Ofelt (J-O) and Crystal-Field (CF) techniques are applied to the systems and the results are compared to single crystal and ceramic forms and in some cases these analyses are reported for the first time for this host. Results of these analyses show that the addition of near infrared emitting rare earth nanocrystals to these polymers offers an attractive application to their existing biological applications.

  2. Spectroscopic characterization of novel multilayer mirrors intended for astronomical and laboratory applications

    NASA Astrophysics Data System (ADS)

    Ragozin, Eugene N.; Mednikov, Konstantin N.; Pertsov, Andrei A.; Pirozhkov, Alexander S.; Reva, Anton A.; Shestov, Sergei V.; Ul'yanov, Artem S.; Vishnyakov, Eugene A.

    2009-05-01

    We report measurements of the reflection spectra of (i) concave (spherical and parabolic) Mo/Si, Mg/Si, and Al/Zr multilayer mirrors (MMs) intended for imaging solar spectroscopy in the framework of the TESIS/CORONAS-FOTON Satellite Project and of (ii) an aperiodic Mo/Si MM optimized for maximum uniform reflectivity in the 125-250 Å range intended for laboratory applications. The reflection spectra were measured in the configuration of a transmission grating spectrometer employing the radiation of a tungsten laser-driven plasma as the source. The function of detectors was fulfilled by backside-illuminated CCDs coated with Al or Zr/Si multilayer absorption filters. High-intensity second-order interference reflection peaks at wavelengths of about 160 Å were revealed in the reflection spectra of the 304-Å Mo/Si MMs. By contrast, the second-order reflection peak in the spectra of the new-generation narrow-band (~12 Å FWHM) 304-Å Mg/Si MMs is substantially depressed. Manifestations of the NEXAFS structure of the L2, 3 absorption edges of Al and Al2O3 were observed in the spectra recorded. The broadband Mo/Si MM was employed as the focusing element of spectrometers in experiments involving (i) the charge exchange of multiply charged ions with the donor atoms of a rare-gas jet; (ii) the spectroscopic characterization of a debris-free soft X-ray radiation source excited by Nd laser pulses in a Xe jet (iii) near-IR-to-soft-X-ray frequency conversion (double Doppler effect) occurring in the retroreflection from the relativistic electron plasma wake wave (flying mirror) driven by a multiterawatt laser in a pulsed helium jet.

  3. Spectroscopic Characterizations of Nonamphiphilic 2,5-BIS (5-TERT-BUTYL-BENZOXAZOLYL)-THIOPHENE Molecules at the Air-Water Interface and in Langmuir-Blodgett Films

    NASA Astrophysics Data System (ADS)

    Biswas, S.; Hussain, Syed Arshad; Bhattacharjee, D.

    This paper reports the π-A isotherm and spectroscopic characterizations of mixed Langmuir and Langmuir-Blodgett films of a nonamphiphilic thiophene derivative, namely, 2,5-Bis (5-tert-butyl-benzoxazolyl)-thiophene (BBOT) molecules, mixed with polymethyl methacrylate (PMMA) and stearic acid (SA). The π-A isotherms and molefraction vs. area per molecule studies indicate some repulsive interaction between sample (BBOT) and matrix (PMMA or SA) molecules. At higher surface pressure in the SA mixed BBOT Langmuir monolayer, a phase transition occurs, which has been revealed by π-A isotherm studies. UV-vis absorption and fluorescence spectroscopic studies confirm this phase transition and closer association of BBOT molecules. Spectroscopic studies of LB films lifted at higher surface pressure clearly confirm the presence of dimmers and higher-order n-meric sites.

  4. Life Finder Detectors; Detector Needs and Status for Spectroscopic Biosignature Characterization

    NASA Astrophysics Data System (ADS)

    Rauscher, Bernard J.; Bolcar, Matthew R.; Clampin, Mark; Domagal-Goldman, Shawn; McElwain, Michael W.; Moseley, Samuel H.; Stahle, Carl; Stark, Christopher C.; Thronson, Harley A.

    2016-01-01

    The search for life on other worlds looms large in NASA's future. Outside our solar system, direct spectroscopic biosignature characterization using very large UV-Optical-IR telescopes with coronagraphs or starshades is a core technique to both AURA's High Definition Space Telescope (HDST) concept and NASA's 30-year strategic plan. These giant space observatories require technological advancements in several areas, one of which is detectors. In this presentation, we review the detector requirements for spectroscopic biosignature characterization and discuss the status of some existing and proposed detector technologies for meeting them.

  5. Characterizing caged molecules through flash photolysis and transient absorption spectroscopy.

    PubMed

    Kao, Joseph P Y; Muralidharan, Sukumaran

    2013-01-01

    Caged molecules are photosensitive molecules with latent biological activity. Upon exposure to light, they are rapidly transformed into bioactive molecules such as neurotransmitters or second messengers. They are thus valuable tools for using light to manipulate biology with exceptional spatial and temporal resolution. Since the temporal performance of the caged molecule depends critically on the rate at which bioactive molecules are generated by light, it is important to characterize the kinetics of the photorelease process. This is accomplished by initiating the photoreaction with a very brief but intense pulse of light (i.e., flash photolysis) and monitoring the course of the ensuing reactions through various means, the most common of which is absorption spectroscopy. Practical guidelines for performing flash photolysis and transient absorption spectroscopy are described in this chapter. PMID:23494372

  6. 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.

  7. SPECTROSCOPIC CHARACTERIZATION AND DETECTION OF ETHYL MERCAPTAN IN ORION

    SciTech Connect

    Kolesniková, L.; Alonso, J. L.; Daly, A. M.; Tercero, B.; Cernicharo, J.; Gordon, B. P.; Shipman, S. T. E-mail: jlalonso@qf.uva.es E-mail: terceromb@cab.inta-csic.es E-mail: brittany.gordon@ncf.edu

    2014-03-20

    New laboratory data of ethyl mercaptan, CH{sub 3}CH{sub 2}SH, in the millimeter- and submillimeter-wave domains (up to 880 GHz) provided very precise values of the spectroscopic constants that allowed the detection of gauche-CH{sub 3}CH{sub 2}SH toward Orion KL. This identification is supported by 77 unblended or slightly blended lines plus no missing transitions in the range 80-280 GHz. A detection of methyl mercaptan, CH{sub 3}SH, in the spectral survey of Orion KL is reported as well. Our column density results indicate that methyl mercaptan is ≅ 5 times more abundant than ethyl mercaptan in the hot core of Orion KL.

  8. Spectroscopic characterization of naturally and chemically oxidized silicon surfaces

    NASA Astrophysics Data System (ADS)

    Tsunoda, Kazuaki; Ohashi, Emiko; Adachi, Sadao

    2003-11-01

    We have determined the thicknesses of naturally and chemically grown oxides on HF-cleaned silicon surfaces in ambient air and in NH4OH/H2O2/H2O solution, respectively, using spectroscopic ellipsometry. The naturally grown oxide thickness versus air-exposure time plots yield a rate constant of 3.5±0.5 Å/decade in ambient air. Chemical oxidation occurs immediately upon immersing the sample in the chemical solution and leaves the sample surface terminated with ˜6 Å of a chemical oxide. Photoreflectance intensity is found to be strongly dependent on such surface processing, and results are explained by the different degree of surface (interface) states.

  9. Application of spectroscopic ellipsometry to characterization of optical thin films

    NASA Astrophysics Data System (ADS)

    Woollam, John A.; Bungay, Corey L.; Yan, Li; Thompson, Daniel W.; Hilfiker, James N.

    2003-05-01

    Spectroscopic ellipsometry is used to determine optical constants, layer thicknesses in multilayer stacks, and microstructure (voids, alloy fraction, or mixed phase composition), and is a well-developed technique for analysis of optical thin films. Ellipsometers now cover from 140 nm (~ 9 eV) in the vacuum-ultraviolet to 200 microns (50cm-1) in the far infrared. Generalized anisotropy and depolarization are measurable using rotating compensator ellipsometers or controlled retarders for partial Mueller Matrix analysis. Rotating compensator ellipsometers allow accurate and rapid in situ diagnostics, including window birefringence calibration. Steady progress has been made in both ex situ and in situ ellipsometry hardware, software, and applications. These advances are reviewed and examples given.

  10. Characterization of used mineral oil condition by spectroscopic techniques.

    PubMed

    Vanhanen, Jarmo; Rinkiö, Marcus; Aumanen, Jukka; Korppi-Tommola, Jouko; Kolehmainen, Erkki; Kerkkänen, Tuula; Törmä, Päivi

    2004-08-20

    Optical absorption, fluorescence, and quantitative 13C NMR spectroscopy have been used to study the degradation of mineral gearbox oil. Samples of used oil were collected from field service. Measured absorption, fluorescence, and quantitative 13C NMR spectra of used oils show characteristic changes from the spectra of a fresh oil sample. A clearly observable, approximately 20-nm blueshift of the fluorescence emission occurs during the early stages of oil use and correlates with changes in intensity of some specific 13C NMR resonance lines. These changes correlate with oil age because of the connection between the blueshift and breaking of the larger conjugated hydrocarbons of oil as a result of use. PMID:15352397

  11. Synthesis and spectroscopic characterization of nanostructured thermoelectric materials

    NASA Astrophysics Data System (ADS)

    Reppert, Jason Brooks

    Bismuth in the bulk form is a semimetal with a rhombohedral structure. It has a small band overlap between the conduction and valence bands and a highly anisotropic electron effective-mass tensor. Thermoelectric materials, in which one of the three dimensions is in the nanometer regime, exhibit unique quantum confinement properties and have generated much interest in recent years. Theoretical investigations have suggested that nanowires with diameters ≤ 10 nm will possess a figure-of-merit ZT > 2. Prior to this study, it has been shown that Bi nanowires with small enough diameters (˜10 nm), prepared via the pulsed laser vaporization method, undergo a transition from a semimetal with a small band overlap to a semiconductor with a small indirect band gap. Infrared absorption and UV-visible measurements were used to confirm this semimetal-to-semiconductor phase transition. In this thesis, we report the synthesis and optical characteristics of a variety of various potential thermoelectric materials including bismuth, nickel sulfide and cadmium sulfide. The infrared absorption in our Bi nanorods is blue-shifted in energy when compared to the corresponding spectra in bulk Bi, and when cooled down to liquid nitrogen temperatures, group theory suggests a strong temperature dependence in the Bi band structure. We also find that the Bi nanorod suspension displays excellent optical limiting properties at both 532 and 1064 nm excitations in the nanosecond laser pulse regime. We have also synthesized nickel sulfide nanoparticles with an average size of 5 nm by a one-step solid phase reaction. The intensity-dependent nonlinear transmission study was carried out using a 7 ns Nd:YAG laser at 532nm using Z-scan, and the nonlinear scattering was found to be the dominant mechanism for the observed response. Importantly, the modified Z-scan method allowed us to measure two competing mechanisms simultaneously - the optical limiting and saturable absorption in surface-modified nickel sulfide nanoparticles suspensions.

  12. 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.

  13. Impedance spectroscopic characterization of gadolinium substituted cobalt ferrite ceramics

    SciTech Connect

    Rahman, Md. T. Ramana, C. V.

    2014-10-28

    Gadolinium (Gd) substituted cobalt ferrites (CoFe{sub 2−x}Gd{sub x}O{sub 4}, referred to CFGO) with variable Gd content (x = 0.0–0.4) have been synthesized by solid state ceramic method. The crystal structure and impedance properties of CFGO compounds have been evaluated. X-ray diffraction measurements indicate that CFGO crystallize in the inverse spinel phase. The CFGO compounds exhibit lattice expansion due to substitution of larger Gd ions into the crystal lattice. Impedance spectroscopy analysis was performed under a wide range of frequency (f = 20 Hz–1 MHz) and temperature (T = 303–573 K). Electrical properties of Gd incorporated Co ferrite ceramics are enhanced compared to pure CoFe{sub 2}O{sub 4} due to the lattice distortion. Impedance spectroscopic analysis illustrates the variation of bulk grain and grain-boundary contributions towards the electrical resistance and capacitance of CFGO materials with temperature. A two-layer heterogeneous model consisting of moderately conducting grain interior (ferrite-phase) regions separated by insulating grain boundaries (resistive-phase) accurately account for the observed temperature and frequency dependent electrical characteristic of CFGO ceramics.

  14. Isomerism of Cyanomethanimine: Accurate Structural, Energetic, and Spectroscopic Characterization.

    PubMed

    Puzzarini, Cristina

    2015-11-25

    The structures, relative stabilities, and rotational and vibrational parameters of the Z-C-, E-C-, and N-cyanomethanimine isomers have been evaluated using state-of-the-art quantum-chemical approaches. Equilibrium geometries have been calculated by means of a composite scheme based on coupled-cluster calculations that accounts for the extrapolation to the complete basis set limit and core-correlation effects. The latter approach is proved to provide molecular structures with an accuracy of 0.001-0.002 Å and 0.05-0.1° for bond lengths and angles, respectively. Systematically extrapolated ab initio energies, accounting for electron correlation through coupled-cluster theory, including up to single, double, triple, and quadruple excitations, and corrected for core-electron correlation and anharmonic zero-point vibrational energy, have been used to accurately determine relative energies and the Z-E isomerization barrier with an accuracy of about 1 kJ/mol. Vibrational and rotational spectroscopic parameters have been investigated by means of hybrid schemes that allow us to obtain rotational constants accurate to about a few megahertz and vibrational frequencies with a mean absolute error of ∼1%. Where available, for all properties considered, a very good agreement with experimental data has been observed. PMID:26529434

  15. Vibrational spectroscopic characterization of wild growing mushrooms and toadstools

    NASA Astrophysics Data System (ADS)

    Mohaček-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 α- and β-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.

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

    NASA Astrophysics Data System (ADS)

    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. ΔG, 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.

  17. X-ray absorption spectroscopic studies of mononuclear non-heme iron enzymes

    SciTech Connect

    Westre, T.E.

    1996-01-01

    Fe-K-edge X-ray absorption spectroscopy (XAS) has been used to investigate the electronic and geometric structure of the iron active site in non-heme iron enzymes. A new theoretical extended X-ray absorption fine structure (EXAFS) analysis approach, called GNXAS, has been tested on data for iron model complexes to evaluate the utility and reliability of this new technique, especially with respect to the effects of multiple-scattering. In addition, a detailed analysis of the 1s{yields}3d pre-edge feature has been developed as a tool for investigating the oxidation state, spin state, and geometry of iron sites. Edge and EXAFS analyses have then been applied to the study of non-heme iron enzyme active sites.

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

    PubMed

    Morsi, Morsi M; El-Sherbiny, Samya I; Mohamed, Karam M

    2015-06-15

    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 Fe(3+)O3S(2-) 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 6h 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 Fe(3+) 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. PMID:25795612

  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. Detailed Spectroscopic Characterization of an Expanding Flashboard Plasma

    NASA Astrophysics Data System (ADS)

    Tsigutkin, K.; Arad, R.; Ralchenko, Yu. V.; Maron, Y.

    1998-11-01

    Spectroscopic investigations of the plasma properties in a 400 ns, 160 kA Plasma Opening Switch (POS) are performed. A flashboard plasma source driven by a 100 kA current pulse is positioned 3 cm above the planar anode. By locally doping the plasma with various gases and observing characteristic emission from the doped gas beam we obtain results that are local in 3D. We measured the spatial distribution of the electron density as a function of time from Stark broadening of hydrogen lines. The density at the beginning of POS pulse (1.2 ? s after the flashboard discharge) was found to be 7 10^14 cm-3 near the anode and 3 10^14 cm-3 near the cathode. The electron temperature and the composition are studied from line intensities and collisional-radiative calculations. The temperature was found to drop in time from 12 2 eV to 6 1 eV at t=1.2 ? s. Analysis of the plasma composition shows, that initially the plasma consists only of protons with an expansion velocity of 1-1.5 10^7 cm/s. At the moment of POS operation the density of carbon (mainly CIV) is substantial only near the anode (? 20%). The expansion velocity of carbon ions is 3-4 10^6 cm/s. The density of other impurities such as oxygen, silicon, iron, copper and nickel is negligible at that time. Also, investigations of the magnetic field distribution from Zeeman splitting, the electron density from line intensities, and ion velocities from Doppler shifts during the POS conduction and opening phases will be presented.

  1. Spectroscopic characterization of ion-irradiated multi-layer graphenes

    NASA Astrophysics Data System (ADS)

    Tsukagoshi, Akira; Honda, Shin-ichi; Osugi, Ryo; Okada, Hiraku; Niibe, Masahito; Terasawa, Mititaka; Hirase, Ryuji; Izumi, Hirokazu; Yoshioka, Hideki; Niwase, Keisuke; Taguchi, Eiji; Lee, Kuei-Yi; Oura, Masaki

    2013-11-01

    Low-energy Ar ions (0.5-2 keV) were irradiated to multi-layer graphenes and the damage process, the local electronic states, and the degree of alignment of the basal plane, and the oxidation process upon ion irradiation were investigated by Raman spectroscopy, soft X-ray absorption spectroscopy (XAS) and in situ X-ray photoelectron spectroscopy (XPS). By Raman spectroscopy, we observed two stages similar to the case of irradiated graphite, which should relate to the accumulations of vacancies and turbulence of the basal plane, respectively. XAS analysis indicated that the number of sp2-hybridized carbon (sp2-C) atoms decreased after ion irradiation. Angle-resolved XAS revealed that the orientation parameter (OP) decreased with increasing ion energy and fluence, reflecting the turbulence of the basal plane under irradiation. In situ XPS shows the oxidation of the irradiated multi-layer graphenes after air exposure.

  2. ACCURATE SPECTROSCOPIC CHARACTERIZATION OF PROTONATED OXIRANE: A POTENTIAL PREBIOTIC SPECIES IN TITAN’S ATMOSPHERE

    PubMed Central

    Puzzarini, Cristina; Ali, Ashraf; Biczysko, Malgorzata; Barone, Vincenzo

    2015-01-01

    An accurate spectroscopic characterization of protonated oxirane has been carried out by means of state-of-the-art computational methods and approaches. The calculated spectroscopic parameters from our recent computational investigation of oxirane together with the corresponding experimental data available were used to assess the accuracy of our predicted rotational and IR spectra of protonated oxirane. We found an accuracy of about 10 cm−1 for vibrational transitions (fundamentals as well as overtones and combination bands) and, in relative terms, of 0.1% for rotational transitions. We are therefore confident that the spectroscopic data provided herein are a valuable support for the detection of protonated oxirane not only in Titan’s atmosphere but also in the interstellar medium. PMID:26543241

  3. Accurate spectroscopic characterization of protonated oxirane: a potential prebiotic species in Titan's atmosphere

    SciTech Connect

    Puzzarini, Cristina; Ali, Ashraf; Biczysko, Malgorzata; Barone, Vincenzo

    2014-09-10

    An accurate spectroscopic characterization of protonated oxirane has been carried out by means of state-of-the-art computational methods and approaches. The calculated spectroscopic parameters from our recent computational investigation of oxirane together with the corresponding experimental data available were used to assess the accuracy of our predicted rotational and IR spectra of protonated oxirane. We found an accuracy of about 10 cm{sup –1} for vibrational transitions (fundamentals as well as overtones and combination bands) and, in relative terms, of 0.1% for rotational transitions. We are therefore confident that the spectroscopic data provided herein are a valuable support for the detection of protonated oxirane not only in Titan's atmosphere but also in the interstellar medium.

  4. Characterization of female breasts in vivo by time-resolved and spectroscopic measurements in the near infrared spectroscopy

    NASA Astrophysics Data System (ADS)

    Heusmann, Hans; Koelzer, Jochen G.; Mitic, Gerhard

    1996-10-01

    Time-resolved and spectroscopic in vivo measurements were performed to determine the optical properties of the female breast in transmission. The time-resolved measurements were carried out at different positions on the female breast with a Ti:sapphire laser using as synchroscan steak camera. A diffusion model was used to calculate the absorption coefficient (mu) A and the reduced scattering coefficient. In addition, spectroscopic in vivo measurements of more than 100 patients were performed in a wavelength range between 650 and 1000 nm. A variety of pathological alterations could be characterized by measuring patients of different ages, different breast sizes, and at carrying locations on the breast. The results indicate that besides the pure detection of the amount of blood in the neovascular network, the volume concentrations of water and fat model was developed that takes the volume percentages of fat and water, the concentration and oxygenation of hemoglobin, and the relevant optical parameters into account. Experiments were carried out with volunteers and patients in a clinical environment: typical observations are presented and analyzed statistically.

  5. 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,

  6. Characterization of Sorolla's gouache pigments by means of spectroscopic techniques

    NASA Astrophysics Data System (ADS)

    Roldán, Clodoaldo; Juanes, David; Ferrazza, Livio; Carballo, Jorgelina

    2016-02-01

    This paper presents the characterization of the Joaquín Sorolla's gouache sketches for the oil on canvas series "Vision of Spain" commissioned by A. M. Huntington to decorate the library of the Hispanic Society of America in New York. The analyses were focused on the identification of the elemental composition of the gouache pigments by means of portable EDXRF spectrometry in a non-destructive mode. Additionally, SEM-EDX and FTIR analyses of a selected set of micro-samples were carried out to identify completely the pigments, the paint technique and the binding media. The obtained results have confirmed the identification of lead and zinc white, vermillion, earth pigments, ochre, zinc yellow, chrome yellow, ultramarine, Prussian blue, chromium based and copper-arsenic based green pigments, bone black and carbon based black pigments, and the use of gum arabic as binding media in the gouache pigments.

  7. X-ray absorption spectroscopic studies on novel microporous copper containing catalytic systems

    NASA Astrophysics Data System (ADS)

    Bhargava, Suresh K.; Akolekar, Deepak B.; Foran, Garry

    2006-11-01

    Novel copper metal modified microporous aluminosilicate and aluminophosphate catalysts with the high phase purity were synthesized and characterized. CuK-edge XAS measurements were carried out over a series of copper containing SAPO-34 and ZSM-5 catalysts. EXAFS technique was used to obtain specific climacteric information related to the copper atomic distances, coordination and near neighbour environments. EXAFS studies indicated the presence of different of Cu species on ZSM-5/SAPO34 catalysts.

  8. Spectroscopic characterization of silicalite-1 and titanium silicalite-1

    SciTech Connect

    Astorino, E.; Peri, J.B.; Willey, R.J.

    1995-12-01

    Titanium silicalite samples were prepared by two different procedures. A titanium-free sample (silicalite-1) was also prepared. The samples were characterized by XRD, SEM, skeletal FT-FIR and FT-Raman, UV-vis FT-IR of hydroxy-groups and of adsorbed ammonia. The skeletal spectra have been analyzed on the basis of a general interpretation of the vibrational structure of tetrahedra-based silica polymorphs. This leads to a partial modification of the traditional assignments of the skeletal vibrations of zeolites. Framework Ti is found to be responsible for a band near 960 cm{sup -1}, in both IR and Raman spectra, and for a shoulder near 510 cm{sup -1} in the IR spectra, as well as for other weak perturbations of the silicalite spectra. The two main features have been assigned to the asymmetric stretching and to the rocking modes of Si-O-Ti bridges. Framework Ti is found to act as a Lewis acid center, being able to coordinate ammonia from gas-phase. Extraframework Ti is observed in the form of anatase in samples prepared with the procedure 1 only with Ti content above 2%, while TiO{sub 2} is found in all samples prepared with the procedure 2. Both series of samples are active catalysts of phenol hydroxylation by H{sub 2}O{sub 2}. 57 refs., 13 figs., 2 tabs.

  9. Spectroscopic and morphologic characterization of the dentin/adhesive interface

    NASA Astrophysics Data System (ADS)

    Lemor, R. M.; Kruger, Michael B.; Wieliczka, David M.; Swafford, Jim R.; Spencer, Paulette

    1999-04-01

    The potential environmental risks associated with dental amalgams have forced many European countries to ban their use and turn to alternative materials, composite resins. The purpose of this study was to correlate morphologic characterization of the dentin/adhesive bond with chemical analyses using micro-FTIR and micro-Raman spectroscopy. A commercial dental adhesive was placed on dentin substrates cut from extracted, unerupted human third molars. Sections of the dentin/adhesive interface were investigated using IR radiation produced at the Aladdin synchrotron source; visible radiation from Kr+ laser was used for the micro-Raman spectroscopy and through the use of differentially staining in conjunction with light microscopy. Due to its limited spatial resolution and the unknown samples thickness the IR results cannot be used quantitatively in determining the extent of diffusion. The result from the micro-Raman spectroscopy and light microscopy indicate exposed protein at the dentin/adhesive interface. Using a laser that reduces background fluorescence, the micro-Raman spectroscopy provides quantitative chemical and morphologic information on the dentin/adhesive interface. The staining procedure is sensitive to sites of pure protein and complements the Raman results.

  10. Spectroscopic and morphologic characterization of the dentin/adhesive interface

    NASA Astrophysics Data System (ADS)

    Lemor, R. M.; Kruger, Michael B.; Wieliczka, David M.; Swafford, Jim R.; Spencer, Paulette

    1999-01-01

    The potential environmental risks associated with mercury release have forced many European countries to ban the use of dental amalgam. Alternative materials such as composite resins do not provide the clinical function for the length of time characteristically associated with dental amalgam. The weak link in the composite restoration is the dentin/adhesive bond. The purpose of this study was to correlate morphologic characterization of the dentin/adhesive bond with chemical analyses using micro- Fourier transform infrared and micro-Raman spectroscopy. A commercial dental adhesive was placed on dentin substrates cut from extracted, unerupted human third molars. Sections of the dentin/adhesive interface were investigated using infrared radiation produced at the Aladdin synchrotron source; visible radiation from a Kr+ laser was used for the micro-Raman spectroscopy. Sections of the dentin/adhesive interface, differentially stained to identify protein, mineral, and adhesive, were examined using light microscopy. Due to its limited spatial resolution and the unknown sample thickness the infrared results cannot be used quantitatively in determining the extent of diffusion. The results from the micro-Raman spectroscopy and light microscopy indicate exposed protein at the dentin/adhesive interface. Using a laser that reduces background fluorescence, the micro-Raman spectroscopy provides quantitative chemical and morphologic information on the dentin/adhesive interface. The staining procedure is sensitive to sites of pure protein and thus, complements the Raman results.

  11. Spectroscopic Studies on the Characterization of a Persian Playing Card.

    PubMed

    Holakooei, Parviz; Niknejad, Maryam; Vaccaro, Carmela

    2016-01-01

    This paper presents the results of our investigations on a playing card preserved at The Mūzih-i Āynih va Rushanāī in Yazd, Iran. Conducting micro X-ray fluorescence spectrometry (μ-XRF), micro-Raman spectroscopy (μ-Raman), infrared reflectography (IRR), ultraviolet fluorescence photography, radiography, and optical microscopy, various paints applied on the playing card were identified. According to our analytical studies, red, green, blue, black, and gold-like metallic paints were identified to be a red monoazo pigment (β-naphthol PR 53:1), chrome green, artificial ultramarine blue, carbon black, and brass powder (Dutch metal powder), respectively, dating the playing card to 1895 onward based on the manufacturing date of the red monoazo pigment. Barite was also shown to be mixed with the pigments as an extender. On the other hand, the portrait's face of the playing card was peculiarly blackened. Our analytical approach toward characterizing the blackened face showed that the black paint was achieved by carbon black and, in other words, the face was not blackened due to the darkening of Pb-bearing pigments. Moreover, it was shown that there was no underdrawing under the black face and the black paint was most probably executed in the same time with the other paints. Considering the possible use of the playing card, it was suggested not to remove the blackened face in the cleaning process since the black paint was a part of the integrity of the playing card. PMID:26767645

  12. Behavioral mutants of Euglena gracilis: functional and spectroscopic characterization.

    PubMed

    Lebert, M; Hader, D P

    1997-08-01

    Three mutant strains of the phytoflagellate Euglena gracilis Z have been characterized in order to analyze the signal perception and signal transduction pathways involved in photo- and gravitaxis. Using the fluorescence of the chromophoric groups believed to be involved in photoperception (flavins and pterins) a method was developed for an in situ and in vivo detection of the paraxonemal body, the proposed location of the photoreceptor molecules. Two of the mutant strains, 1224-5/9f and 1224-5/1f, do not possess a stigma and also lack a paraxonemal body, as indicated by fluorescence measurements. The third strain, FB, has a small stigma, but only some cells contain a paraxonemal body. In contrast to the present hypothesis on photoorientation of Euglena, all strains were able to orient with respect to the light direction. However, the mutant strains did not show any orientation at low irradiances. At medium and high irradiances the strains 1224-5/9f and 1224-5/1f oriented perpendicular to the light direction (diaphototaxis) while cells of strains of FB showed partly negative phototaxis and partly diaphototaxis. Diaphototaxis was never observed in the wild type strain. Strains 1224-5/9f and 1224-5/1f showed normal graviresponses compared with the wild type. Astasia longa, a nonphtototactic relative of E. gracilis, as well as strain FB were both negative and positive gravitactic at all culture ages tested. This result confirmed the hypothesis that the paraxonemal body is not directly involved in graviperception. PMID:11540955

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

    NASA Astrophysics Data System (ADS)

    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 90 nm and the unit cell parameter “a” is calculated as from 8.39 to 8.89 Å. 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 Fe3+ and at a higher content of Al/Cu the EPR spectra is due to Cu2+. 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 5 ns laser pulses at 532 nm employing the open aperture z-scan technique indicate that these ferrites are potential candidates for optical limiting applications.

  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. A mononuclear nonheme iron(III)-superoxo complex: Crystallographic and spectroscopic characterization and reactivities

    PubMed Central

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

    2016-01-01

    Mononuclear nonheme iron(III)-superoxo species (FeIII-O2−•) have been implicated as key intermediates in the catalytic cycles of dioxygen activation by nonheme iron enzymes. Although nonheme 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 for the first time the isolation, spectroscopic characterization, and crystal structure of a mononuclear side-on (η2) iron(III)-superoxo complex with a tetraamido macrocyclic ligand (TAML), [FeIII (TAML) (O2)]2− (1). The nonheme iron(III)-superoxo species undergoes both electrophilic and nucleophilic oxidation reactions as well as O2-transfer between metal complexes. In the O2-transfer reaction, 1 transfers the bound O2 unit to a manganese(III) analogue, resulting in the formation of a manganese(IV)-peroxo complex, [MnIV(TAML)(O2)]2− (2); 2 is characterized structurally and spectroscopically as a mononuclear side-on (η2) manganese(IV)-peroxo complex. The difference in the redox distribution between the metal ions and O2 in 1 and 2 is rationalized using density functional theory calculations. PMID:25510711

  16. Quaoar: New, Longitudinaly Resolved, Spectroscopic Characterization of Its Surface

    NASA Technical Reports Server (NTRS)

    Ore, C. M. Dalle; Barucci, M. A.; Cruikshank, D. P.; Alunni, Antonella

    2014-01-01

    (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 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 (Brown, Schaller, & Fraser, 2011. A Hypothesis for the Color Diversity of the Kuiper Belt. ApJL, 739, L60) 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 micrometers) spectro-photometric data obtained with the XSHOOTER (Vernet et al. 2011, A&A, 536A, 105 ) 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 micrometers) 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 micrometers- 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.

  17. Spectroscopic characterization of dissolved organic matter in coking wastewater during bio-treatment: full-scale plant study.

    PubMed

    Xu, Ronghua; Ou, Huase; Yu, Xubiao; He, Runsheng; Lin, Chong; Wei, Chaohai

    2015-01-01

    This paper taking a full-scale coking wastewater (CWW) treatment plant as a case study aimed to characterize removal behaviors of dissolved organic matter (DOM) by UV spectra and fluorescence excitation-emission matrix-parallel factor analysis (PARAFAC), and investigate the correlations between spectroscopic indices and water quality parameters. Efficient removal rates of chemical oxygen demand (COD), dissolved organic carbon (DOC) and total nitrogen (TN) after the bio-treatment were 91.3%, 87.3% and 69.1%, respectively. UV270 was proven to be a stable UV absorption peak of CWW that could reflect the mixture of phenols, heterocyclics, polynuclear aromatic hydrocarbons and their derivatives. Molecular weight and aromaticity were increased, and also the content of polar functional groups was greatly reduced after bio-treatment. Three fluorescent components were identified by PARAFAC: C1 (tyrosine-like), C2 (tryptophan-like) and C3 (humic-like). The removal rate of protein-like was higher than that of humic-like and C1 was identified as biodegradable substance. Correlation analysis showed UV270 had an excellent correlation with COD (r=0.921, n=60, P<0.01) and DOC (r=0.959, n=60, P<0.01) and significant correlation (r=0.875, n=60, P<0.01) was also found between C2 and TN. Therefore, spectroscopic characterization could provide novel insights into removal behaviors of DOM and potential to monitor water quality real-time during CWW bio-treatment. PMID:26465313

  18. 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.

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

    PubMed

    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. PMID:25841150

  20. Absorption-line-shape recovery beyond the detection-bandwidth limit: Application to the precision spectroscopic measurement of the Boltzmann constant

    NASA Astrophysics Data System (ADS)

    Rohart, F.; Mejri, S.; Sow, P. L. T.; Tokunaga, S. K.; Chardonnet, C.; Darquié, B.; Dinesan, H.; Fasci, E.; Castrillo, A.; Gianfrani, L.; Daussy, C.

    2014-10-01

    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 that 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 midinfrared. 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.

  1. 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.

  2. 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].

  3. Spectroscopic ellipsometry characterization of silicon/silicon-dioxide superlattices for photoluminescence and electroluminescence

    NASA Astrophysics Data System (ADS)

    Creazzo, Tim; Prather, Lindsay; Redding, Brandon; Shi, Shouyuan; Prather, Dennis

    2008-02-01

    Silicon based light emitting materials are of particular interest for integrating electric and photonic devices into an allsilicon platform. The progress of nano-scale fabrication has led to the ability to realize silicon emitters based on quantum confinement mechanisms. Quantum confinement in nano-structured silicon overcomes the indirect bandgap present in bulk silicon allowing for radiative emissions. Silicon/silicon dioxide superlattices employ two-dimensional confinement leading to light emission. Strong photoluminescence (PL) has been demonstrated in Si/SiO II superlattices, confirming the presence of quantum confinement effects. Our super lattice structures are grown using plasma enhanced chemical vapor deposition (PECVD) with alternating layers of silicon and silicon dioxide. Sub-10 nanometer periods are confirmed via transmission electron microscopy (TEM) and x-ray reflectivity (XRR) studies. However, consistent and predictable PL and electroluminescence (EL) relies on precise measurement and characterization of the deposition process. Spectroscopic ellipsometry (SE) offers a non-destructive extremely sensitive method of optical characterization which provides us with the required control. We present characterization of our superlattice structures using spectroscopic ellipsometry. The ellipsometer allows us to measure optical properties of the individual layers of ultra-thin silicon as a part of Si/SiO II superlattices. We demonstrate the change in the imaginary part of the dielectric function and the bandgap for a-Si. We also generate deposition rate curves for very specific PECVD recipes and apply this information to further SE characterization and modeling of multi-period superlattice structures.

  4. Spectroscopic characterization approach to study surfactants effect on ZnO 2 nanoparticles synthesis by laser ablation process

    NASA Astrophysics Data System (ADS)

    Drmosh, Q. A.; Gondal, M. A.; Yamani, Z. H.; Saleh, T. A.

    2010-05-01

    Zinc peroxide nanoparticles having grain size less than 5 nm were synthesized using pulsed laser ablation in aqueous solution in the presence of different surfactants and solid zinc target in 3% H 2O 2. The effect of surfactants on the optical and structure of ZnO 2 was studied by applying different spectroscopic techniques. Structural properties and grain size of the synthesized nanoparticles were studied using XRD method. The presence of the cubic phase of zinc peroxide in all samples was confirmed with XRD, and the grain sizes were 4.7, 3.7, 3.3 and 2.8 nm in pure H 2O 2, and H 2O 2 mixed with SDS, CTAB and OGM respectively. For optical characterization, FTIR transmittance spectra of ZnO 2 nanoparticles prepared with and without surfactants show a characteristic ZnO 2 absorption at 435-445 cm -1. FTIR spectrum revealed that the adsorbed surfactants on zinc peroxide disappeared in case of CTAB and OGM while it appears in case of SDS. This could be due to high critical micelles SDS concentration comparing with others which is attributed to the adsorption anionic nature of this surfactant. Both FTIR and UV-vis spectra show a red shift in the presence of SDS and blue shift in the presence of CTAB and OGM. The blue shift in the absorption edge indicates the quantum confinement property of nanoparticles. The zinc peroxide nanoparticles prepared in additives-free media was also characterized by Raman spectra which show the characteristic peaks at 830-840 and 420-440 cm -1.

  5. Characterizing the collision of potassium atoms with a siloxane coated glass surface using spectroscopic methods

    NASA Astrophysics Data System (ADS)

    Morgus, Tyler Christophe

    2001-07-01

    We have developed a series of three experiments to characterize the collisions between potassium atoms and a siloxane coated non-stick surface on a glass substrate. The first experiment looks at the aggregate effect of multiple collisions of the potassium atoms with the surface. The atoms are observed spectroscopically. The spectroscopic information allows for the calculation of the flux, average velocity, and density of the potassium atoms. These quantities are also calculated with a computer model. The parameters of the model are the probability that a potassium atom will stick to the surface during a collision, and the probabilities that the collision is specular or diffuse. The second experiment uses the photo-desorption effect to create a spatially peaked non-equilibrium density distribution. The rate of decay of this distribution is fit with a computer model whose free parameter is proportional to the probability that an atom will stick to the siloxane coated wall during a collision. The third experiment is designed to observe the results of a single collision with a siloxane coated surface. Again, the potassium atoms are observed spectroscopically, the Doppler effect providing velocity resolution. The intensity of the fluorescence is related to the velocity-density distribution. The density is then theoretically modeled using the same simple kernel, accounting for contributions to the density from the potassium source, specular collisions, and diffuse collisions.

  6. Spectroscopic characterization of biological agents using FTIR, normal Raman and surface-enhanced Raman spectroscopies

    NASA Astrophysics Data System (ADS)

    Luna-Pineda, Tatiana; Soto-Feliciano, Kristina; De La Cruz-Montoya, Edwin; Pacheco Londoño, Leonardo C.; Ríos-Velázquez, Carlos; Hernández-Rivera, Samuel P.

    2007-04-01

    FTIR, Raman spectroscopy and Surface Enhanced Raman Scattering (SERS) requires a minimum of sample allows fast identification of microorganisms. The use of this technique for characterizing the spectroscopic signatures of these agents and their stimulants has recently gained considerable attention due to the fact that these techniques can be easily adapted for standoff detection from considerable distances. The techniques also show high sensitivity and selectivity and offer near real time detection duty cycles. This research focuses in laying the grounds for the spectroscopic differentiation of Staphylococcus spp., Pseudomonas spp., Bacillus spp., Salmonella spp., Enterobacter aerogenes, Proteus mirabilis, Klebsiella pneumoniae, and E. coli, together with identification of their subspecies. In order to achieve the proponed objective, protocols to handle, cultivate and analyze the strains have been developed. Spectroscopic similarities and marked differences have been found for Spontaneous or Normal Raman spectra and for SERS using silver nanoparticles have been found. The use of principal component analysis (PCA), discriminate factor analysis (DFA) and a cluster analysis were used to evaluate the efficacy of identifying potential threat bacterial from their spectra collected on single bacteria. The DFA from the bacteria Raman spectra show a little discrimination between the diverse bacterial species however the results obtained from the SERS demonstrate to be high discrimination technique. The spectroscopic study will be extended to examine the spores produced by selected strains since these are more prone to be used as Biological Warfare Agents due to their increased mobility and possibility of airborne transport. Micro infrared spectroscopy as well as fiber coupled FTIR will also be used as possible sensors of target compounds.

  7. Processing of High Level Waste: Spectroscopic Characterization of Redox Reactions in Supercritical Water - Final Report

    SciTech Connect

    Arrington Jr., C. A.

    2000-11-15

    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 oxidation reactions at subcritical and supercritical temperatures are being followed by Raman spectroscopy using a high temperature stainless steel cell with diamond windows. In these reactions both hydrogen peroxide and nitrate anions are used as the oxidizing species with Cr(III) compounds and organic compounds as reducing agents.

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

    SciTech Connect

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

    1990-07-01

    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, {sup 1}H, {sup 13}C 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 of aliphatic carbon, associated with polysaccharides and proteinaceous structures, and has characteristics close to those of aquatic humic acids. On the other hand, humic acids from manure and worm compost are similar to the humic acids originating from soil.

  9. Dinitrosyl iron complexes (DNICs): from biomimetic synthesis and spectroscopic characterization toward unveiling the biological and catalytic roles of DNICs.

    PubMed

    Tsai, Ming-Li; Tsou, Chih-Chin; Liaw, Wen-Feng

    2015-04-21

    Dinitrosyl iron complexes (DNICs) have been recognized as storage and transport agents of nitric oxide capable of selectively modifying crucial biological targets via its distinct redox forms (NO(+), NO(•) and NO(-)) to initiate the signaling transduction pathways associated with versatile physiological and pathological responses. For decades, the molecular geometry and spectroscopic identification of {Fe(NO)2}(9) DNICs ({Fe(NO)x}(n) where n is the sum of electrons in the Fe 3d orbitals and NO π* orbitals based on Enemark-Feltham notation) in biology were limited to tetrahedral (CN = 4) and EPR g-value ∼2.03, respectively, due to the inadequacy of structurally well-defined biomimetic DNICs as well as the corresponding spectroscopic library accessible in biological environments. The developed synthetic methodologies expand the scope of DNICs into nonclassical square pyramidal and trigonal bipyramidal (CN = 5) and octahedral (CN = 6) {Fe(NO)2}(9) DNICs, as well as two/three accessible redox couples for mononuclear {Fe(NO)2}(9/10) and dinuclear [{Fe(NO)2}(9/10)-{Fe(NO)2}(9/10)] DNICs with biologically relevant S/O/N ligation modes. The unprecedented molecular geometries and electronic states of structurally well-defined DNIC models provide the foundation to construct a spectroscopic library for uncovering the identity of DNICs in biological environments as well as to determine the electronic structures of the {Fe(NO)2} core in qualitative and quantitative fashions by a wide range of spectroscopic methods. On the basis of (15)N NMR, electron paramagnetic resonance (EPR), IR, cyclic voltammetry (CV), superconducting quantum interference device (SQUID) magnetometry, UV-vis, single-crystal X-ray crystallography, and Fe/S K-edge X-ray absorption and Fe Kβ X-ray emission spectroscopies, the molecular geometry, ligation modes, nuclearity, and electronic states of the mononuclear {Fe(NO)2}(9/10) and dinuclear [{Fe(NO)2}(9/10)-{Fe(NO)2}(9/10)] DNICs could be characterized and differentiated. In addition, Fe/S K-edge X-ray absorption spectroscopy of tetrahedral DNICs deduced the qualitative assignment of Fe/NO oxidation states of {Fe(NO)2}(9) DNICs as a resonance hybrid of {Fe(II)((•)NO)(NO(-))}(9) and {Fe(III)(NO(-))2}(9) electronic states; the quantitative NO oxidation states of [(PhS)3Fe(NO)](-), [(PhS)2Fe(NO)2](-), and [(PhO)2Fe(NO)2](-) were further achieved by newly developed valence to core Fe Kβ X-ray emission spectroscopy as -0.58 ± 0.18, -0.77 ± 0.18, and -0.95 ± 0.18, respectively. The in-depth elaborations of electronic structures provide credible guidance to elucidate (a) the essential roles of DNICs modeling the degradation and repair of [Fe-S] clusters under the presence of NO, (b) transformation of DNIC into S-nitrosothiol (RSNO)/N-nitrosamine (R2NNO) and NO(+)/NO(•)/NO(-), (c) nitrite/nitrate activation producing NO regulated by redox shuttling of {Fe(NO)2}(9) and {Fe(NO)2}(10) DNICs, and (d) DNICs as H2S storage and cellular permeation pathway of DNIC/Roussin's red ester (RRE) for subsequent protein S-nitrosylation. The consolidated efforts on biomimetic synthesis, inorganic spectroscopy, chemical reactivity, and biological functions open avenues to the future designs of DNICs serving as stable inorganic NO(+)/NO(•)/NO(-) donors for pharmaceutical applications. PMID:25837426

  10. 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.

  11. Synthesis, structural characterization, Hirshfeld surface analysis and spectroscopic studies of cadmium (II) chloride complex with 4-hydroxy-1-methylpiperidine

    NASA Astrophysics Data System (ADS)

    Soudani, S.; Ferretti, V.; Jelsch, C.; Lefebvre, F.; Nasr, C. Ben

    2016-05-01

    The chemical preparation, crystal structure, Hirshfeld surface analysis and spectroscopic characterization of the novel cadmium (II) 4-hydroxy-1-methylpiperidine complex, Cd4Cl10(C6H14NO)2·2H2O, have been reported. The atomic arrangement can be described as built up by an anionic framework, formed by edge sharing CdCl6 and CdCl5O octahedral linear chains spreading along the a-axis. These chains are interconnected by water molecules via O-H⋯Cl and O-H⋯O hydrogen bonds to form layers parallel to (011) plane. The organic cations are inserted between layers through C-H⋯Cl hydrogen bonds. Investigation of intermolecular interactions and crystal packing via Hirshfeld surface analysis reveals that the HC⋯Cl and HC⋯HC intermolecular interactions are the most abundant contacts of the organic cation in the crystal packing. The statistical analysis of crystal contacts reveals the driving forces in the packing formation. The 13C and 15N CP-MAS NMR spectra are in agreement with the X-ray structure. The vibrational absorption bands were identified by infrared spectroscopy. DFT calculations allowed the attribution of the NMR peaks and of the IR bands.

  12. Spectroscopic characterization of 2-amino-N-hexadecyl-benzamide (AHBA), a new fluorescence probe for membranes.

    PubMed

    Marquezin, Cássia Alessandra; Hirata, Izaura Yoshico; Juliano, Luiz; Ito, Amando Siuiti

    2006-11-20

    We report the results of investigation on the spectroscopic properties of a new fluorescent lipophylic probe. The fluorophore o-aminobenzoic acid was covalently bound to the acyl chain hexadecylamine, producing the compound 2-amino-N-hexadecyl-benzamide. The behavior of the probe was dependent on the polarity of the medium: absorption and emission spectral position, quantum yield and lifetime decay indicate distinct behavior in water compared to ethanol and cyclohexane. The probe dissolves in the organic solvents, as indicated by the very low value of steady state fluorescence anisotropy and the short rotational correlation times obtained from fluorescence anisotropy decay measurements. On the other hand, the probe has low solubility in water, leading to the formation of aggregates in aqueous medium. The complex absorption spectrum in water was interpreted as originating from different forms of aggregation, as deduced from the wavelength dependence of anisotropy parameters. The probe interacts with surfactants in pre-micellar and micellar forms, as observed in experiments in the presence of sodium n-dodecylsulphate (SDS), n-cetyltrimethylammonium bromide (CTAB); 3-(dodecyl-dimethylammonium) propane-1-sulphonate (DPS) and 3-(hexadecyl-dimethylammonium) propane-1-sulphonate (HPS), and with vesicles of the phospholipid dimiristoyl-phosphatidylcholine (DMPC). The results demonstrate that AHBA is able to monitor properties like surface electric potential and phase transition of micelles and vesicles. PMID:16831508

  13. 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.

  14. Atomic Beam Density Characterization by Diode Laser Absorption Spectroscopy

    NASA Astrophysics Data System (ADS)

    Oxley, Paul; Wihbey, Joseph

    2015-05-01

    Atomic beams are used in many atomic physics experiments, and one of the key parameters of the beam is its density. We present experimental and theoretical details of a technique to determine absolute line-integrated beam densities based on resonant laser absorption. In our experiment a thermal lithium beam is chopped and a lockin amplifier detects the laser absorption signal at the chop frequency. This method is sensitive enough to allow detection of beams with densities as low as 5×105 atoms/cc, for a 9 mm beam thickness. We also explore the possibility of extending our method by using the related technique of wavelength modulation spectroscopy. This will reduce noise in the absorption signal, allow the beam density to be determined more rapidly, and will not require the atomic beam to be chopped. We anticipate improvements of up to a factor of 100 reduction in noise and up to a factor of 1000 increase in speed.

  15. Hard and soft X-ray absorption spectroscopic investigation of aqueous Fe(III)-hydroxamate siderophore complexes.

    PubMed

    Edwards, David C; Myneni, Satish C B

    2005-11-17

    Microorganisms release organic macromolecules, such as siderophores, to obtain Fe(III) from natural systems. While the relative stabilities of Fe(III)-siderophore complexes are well-studied, the structural environments of Fe(III) and ligands in the complex are not well-understood. Using the X-ray absorption spectroscopy (XAS) at the Fe- and N-K absorption edges, we characterized the nature of Fe(III) interactions with a hydroxamate siderophore, desferrioxamine B (desB), and its small structural analogue, acetohydroxamic acid (aHa), as a function of pH (1.4-11.4). These experimental studies are complemented with DFT calculations. The Fe-XAS studies suggest that Fe(aHa)3 is the dominant species in aqueous solutions in the pH range of 2.8-10.1, consistent with thermochemical information. However, the N-XAS and resonance Raman studies show that the chemical state of the ligand in the Fe(aHa)3 complex changes significantly with pH, and these variations are correlated with further deprotonation of the Fe(aHa)3 complex. The N-XAS studies also indicate that the overlap of Fe 3d orbitals with the molecular orbitals of the hydroxamate group is significant. The Fe- and N-XAS studies of Fe(III)-desB complexes indicated that Fe(desB)+ is the dominant species between pH values of 1.4 and 11.4, consistent with predicted stability constants. This information is useful in understanding the role of iron in bacterial transport, siderosis treatment, and actinide sequestration at contaminated sites. This is the first N-XAS study of aqueous metal ligand complexes, which demonstrates the applications of soft-XAS in studying the electronic structure of metal complexes of organic macromolecules in aqueous solutions. PMID:16833318

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

    PubMed

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

    2016-08-01

    Isophthalic acid (C6H4(CO2H)2) is a noteworthy organic compound widely used in coating and synthesis of resins and the production of commercially important polymers such as drink plastic bottles. The effects of isophthalic acid (IPA) on human health, toxicology, and biodegradability are the main focus of many researchers. Because structural and spectroscopic investigation of molecules provides a deep understanding of interactional behaviors of compounds, this study stands for exploring those features. Therefore, the spectroscopic, structural, electronic, and thermodynamical properties of IPA were thoroughly studied in this work experimentally using UV-Vis, (1)H and (13)C NMR, FT-IR, FT-Raman and theoretically via DFT and TD-DFT calculations. The UV-Vis absorption spectrum in water was taken in the region 200-400nm. The NMR chemical shifts ((1)H and (13)C) were recorded in DMSO solution. The infrared and Raman spectra of the solid IPA were recorded in the range of 4000-400cm(-1) and 3500-50cm(-1), respectively. DFT and TD-DFT calculations were performed at the level of B3LYP/6-311++G(d,p) in determination of geometrical structure, electronic structure analysis and normal mode. The (13)C and (1)H nuclear magnetic resonance (NMR) spectra were estimated by using the gauge-invariant atomic orbital (GIAO) method. The scaled quantum mechanics (SQM) method was used to determine the total energy distribution (TED) to assign the vibrational modes accurately. Weak interactions such as hydrogen bonding and Van der Walls were analyzed via reduced density gradient (RDG) analysis in monomeric and dimeric forms. Furthermore, the excitation energies, density of state (DOS) diagram, thermodynamical properties, molecular electro-static potential (MEP), and nonlinear optical (NLO) properties were obtained. PMID:27107533

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

    NASA Astrophysics Data System (ADS)

    Selvaraju, R.; Raja, A.; Thiruppathi, G.

    2015-02-01

    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.

  18. Chemical and spectroscopic characterization of a suite of Mars soil analogs

    NASA Technical Reports Server (NTRS)

    Coyne, L. M.; Banin, A.; Orenberg, J. B.; Carle, G. C.; Chang, S.; Scattergood, T. W.

    1987-01-01

    The National Aeronautics and Space Administration has begun preparations for the flight of the Mars Observer Mission in the early 1990s. An advanced ground-based study is being conducted on a usefully limited suite of Mars Soil Analog Materials (MarSAM) intended to simulate the aeolian material covering the surface of Mars. A series of variably proportioned iron/calcium smectite clays were prepared from a typical montmorillonite clay using the Banin method. The effect of increasing iron on a diverse set of chemical and spectroscopic properties of the suite of clays is discussed. In order to chemically characterize the MarSAM and compare them with the Martian soil studied by Viking, the clays were analyzed for their major and minor elemental compositions by X-ray fluorescence and ion-coupled plasma techniques. It was concluded that the surface iron has a complex and hitherto uninvestigated impact on the catalytic and spectroscopic properties of clays and on the ability of these material to store energy.

  19. Characterization of ultrathin gate dielectrics using combined grazing x-ray reflectance and spectroscopic ellipsometry

    NASA Astrophysics Data System (ADS)

    Boher, Pierre; Piel, Jean-Philippe; Evard, Patrick; Defranoux, Christophe; Stehle, Jean-Louis P.

    2001-04-01

    Precise characterization of high k gate dielectrics becomes a challenging task due to the very thin thicknesses (< 3 - 4 nm), which will be needed in the next generation integrated circuits. Conventional techniques such as spectroscopic ellipsometry in the visible range becomes difficult to use alone because of the great correlation between thickness and optical indices. To overcome this problem the following strategy is applied. First, grazing x- ray reflectance is used on all the samples to extract the different layer thickness using a simple model. Second, spectroscopic ellipsometry is applied and the results fitted with the structural models deduced from the x-ray results. In this conditions a precise structural model is built which can take into account the interface and surface behavior all factors that become critical for this range of thickness. This approach is applied to various types of oxide nitride gate dielectrics and ZrO2 films. In the fist case, the nitrogen content of the films can be precisely determined and also the inhomogeneity in depth of the layers in some cases. Interface problems can also be detected on ZrO2 films. Results are compared to x-ray photo-emission measurement in some cases.

  20. Characterization of trace metal desorption using electrothermal atomic absorption spectroscopy

    SciTech Connect

    Fonseca, R.W.

    1993-01-01

    The desorption characteristics of several metals have been studied using electrothermal atomic absorption spectroscopy (ETAAS). Activation energies and orders of release obtained from the atomic absorption profiles provided the main tools to draw conclusions about the different systems. Different factors affecting the absorption profiles were studied. Vaporization was carried out from different substrates including graphite, Ta and alumina. Different heating rates, drying temperatures and thermal pretreatment temperatures were studied. Chemisorption of gases onto the graphite prior to the sample deposition and roughening of the substrates surface using abrasives were also evaluated. ETAAS data provides information concerning the degree of metal-substrate interaction which is elemental dependent. Changes in activation energies as a result of variations in the thermal treatment of the sample revealed changes in the distribution of the analyte on the surface. The metal geometry and its distribution on the surface was also affected by changes in the substrate. Metals such as Ag and Au seemed to move on the surface and disperse to smaller particles when the temperature of the substrate reached the Tammann temperature for the respective metal. Given the potential of ETAAS to provide surface information a tube-in-tube atomizer was designed to make the technique more amenable for this type of investigation. Metal migration into different types of graphite was studied. Metals appeared to migrate several microns through imperfections on the substrate surface. The main effect of this migration on the atomic absorption profiles seemed to be an increase in tailing of the back edge. Finally, several methods used to evaluate kinetic parameters from ETAAS data were compared. One of the methods does not seem to discriminate order of release different than unity. However, the others did yield reasonable results for the metals studied with good correlations among them.

  1. Optical characterization of ferroelectric PZT thin films by variable angle spectroscopic ellipsometry

    NASA Astrophysics Data System (ADS)

    Rahman, Md. Shafiqur; Garcia, Carlos D.; Bhalla, Amar; Guo, Ruyan

    2014-09-01

    Ferroelectric thin films are used as high dielectric constant capacitors, infrared detectors, piezoelectric transducers, optical modulators, optical waveguides, and nonvolatile memory chips for dynamic random access memory (DRAM) etc. While ferroelectric and dielectric properties of these films have been extensively investigated, their optical properties have been comparatively less studied and of limited use in quantitative evaluation of multilayer thin films. In this work we explored the variable angle spectroscopic ellipsometry (VASE) technique for its effectiveness in physical property characterization. The VASE combined with its computer modeling tool enables nondestructive, nonintrusive, and contactless optical means for optical characterization. Crystalline Lead Zirconium Titanate PbZr0.52Ti0.48O3 (PZT) thin films, fabricated on SrTiO3 layer atop of Si substrates, were characterized using VASE (J.A. Woollam; Lincoln, NE, USA) by determining the ellipsometric parameters Ψ and Δ as a function of wavelengths (200-1000 nm) and incident angles (65°, 70°,75°) at room temperature. A physical representation of the multilayer system was constructed by a six layer model (analysis software WVASE32, J.A. Woollam) through a step-by-step method. Other physical properties characterized by several well-known techniques on structure, morphology and topographical features correspond well with the models developed using VASE alone. The technique and the methodology developed have shown promises in identifying the respective thickness and optical properties of multilayer thin film system, with limited input of processing or composition information.

  2. Synthesis, spectroscopic characterization and biological analysis of a new palladium(II) complex with methionine sulfoxide

    NASA Astrophysics Data System (ADS)

    Corbi, Pedro P.; Cagnin, Flávia; Sabeh, Lilian P. B.; Massabni, Antonio C.; Costa-Neto, Claudio M.

    2007-04-01

    A new palladium(II) complex with methionine sulfoxide was synthesized and characterized by a set of chemical and spectroscopic techniques. Elemental and mass spectrometry analyses of the solid complex fit to the composition [Pd(C 5H 10NO 3S) 2]·H 2O. 13C NMR, [ 1H- 15N] NMR and infrared spectra indicate coordination of the amino acid to Pd(II) through the carboxylate and amino groups in a square planar geometry. The complex is soluble in water. Biological activity was evaluated by cytotoxic analysis using HeLa cells. Determination of cell death was assessed using a tetrazolium salt colorimetric assay, which reflects the cells viability. After incubation for 48 h, 20% of cell death was achieved at a concentration of 200 μmol L -1 of the complex.

  3. ATLAST Detector Needs for Direct Spectroscopic Biosignature Characterization in the Visible and Near-IR

    NASA Technical Reports Server (NTRS)

    Rauscher, Bernard J.; Bolcar, Matthew R.; Clampin, Mark; Domagal-Goldman, Shawn D.; McElwain, Michael W.; Moseley, S. H.; Stahle, Carl; Stark, Christopher C.; Thronson, Harley A.

    2015-01-01

    Are we alone? Answering this ageless question will be a major focus for astrophysics in coming decades. Our tools will include unprecedentedly large UV-Optical-IR space telescopes working with advanced coronagraphs and starshades. Yet, these facilities will not live up to their full potential without better detectors than we have today. To inform detector development, this paper provides an overview of visible and near-IR (VISIR; lambda = 0.4 - 1.8 micrometers) detector needs for the Advanced Technology Large Aperture Space Telescope (ATLAST), specifically for spectroscopic characterization of atmospheric biosignature gasses. We also provide a brief status update on some promising detector technologies for meeting these needs in the context of a passively cooled ATLAST.

  4. Zinc acetylacetonate hydrate adducted with nitrogen donor ligands: Synthesis, spectroscopic characterization, and thermal analysis

    NASA Astrophysics Data System (ADS)

    Brahma, Sanjaya; Shivashankar, S. A.

    2015-12-01

    We report synthesis, spectroscopic characterization, and thermal analysis of zinc acetylacetonate complex adducted by nitrogen donor ligands, such as pyridine, bipyridine, and phenanthroline. The pyridine adducted complex crystallizes to monoclinic crystal structure, whereas other two adducted complexes have orthorhombic structure. Addition of nitrogen donor ligands enhances the thermal property of these complexes as that with parent metal-organic complex. Zinc acetylacetonate adducted with pyridine shows much higher volatility (106C), decomposition temperature (202C) as that with zinc acetylacetonate (136C, 220C), and other adducted complexes. All the adducted complexes are thermally stable, highly volatile and are considered to be suitable precursors for metal organic chemical vapor deposition. The formation of these complexes is confirmed by powder X-ray diffraction, Fourier transform infrared spectroscopy, mass spectroscopy, and elemental analysis. The complexes are widely used as starting precursor materials for the synthesis of ZnO nanostructures by microwave irradiation assisted coating process.

  5. Electrochemical and resonance Raman spectroscopic characterization of polyaniline and polyaniline-metalloporphyrin electrode films

    SciTech Connect

    Macor, K.A.; Su, Y.O.; Miller, L.A.; Spiro, T.G.

    1987-08-12

    Characteristics of electropolymerized aniline and metallotetrakis(2-aminophenyl)porphine (metallo-2-TAPP) films are described. Aniline polymerized from methylene chloride solution by oxidative cycling at a platinum electrode shows characteristic two-wave or one-wave cycle voltammograms when scanned in pH 1 aqueous solution, depending on the positive potential sweep limit. Similar CV's are produced when the solution contains metallo-TAPP's, except that additional waves associated with metalloporphyrin redox processes are superimposed. The absorption spectra of the films formed on transparent SnO/sub 2/ electrodes showed characteristic metalloporphyrin Soret absorption bands, with red shifts relative to the solution spectra, due to axial coordination and/or excitonic effects. Raman spectra are reported for films polymerized from aniline, aniline-/sup 15/N, aniline-N,N-d/sub 2/, and aniline-d/sub 5/. The replacement of strong aniline bands at 1000 and 1029 cm/sup -1/ with bands in the films at 1190 and 1200 cm/sup -1/ is diagnostic for para-substituted aniline units in the polymer. The films show a strong /sup 15/N-sensitive band at 1525 cm/sup -1/, which is absent in aniline but present in p-phenylenediamine. Thus the electrochemical and spectroscopic characteristics of the TAPP films are fully consistent with unmodified porphyrin units contained within a polyaniline polymer. Porphyrin radical cation formation is insufficient to induce polymerization if the potential is lower than that required for aniline oxidation. Films containing Mn(2-TAPP) show a Mn/sup 3+/2+/ wave at approx.-0.2 V, negative of the polyaniline redox waves, when the electrode is in contact with nonaqueous or aqueous electrolyte. The metalloporphyrin redox process does not require electronic conduction through the polyaniline framework. 21 references. 8 figures.

  6. 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.

  7. Spectroscopic Characterization of a Green Copper Site in a Single-Domain Cupredoxin

    PubMed Central

    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 β-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

  8. 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.

  9. Spectroscopic characterizations of Er doped LaPO4 submicron phosphors prepared by homogeneous precipitation method

    NASA Astrophysics Data System (ADS)

    Saltmarsh, N.; Kumar, G. A.; Kailasnath, M.; Shenoy, Vittal; Santhosh, C.; Sardar, D. K.

    2016-03-01

    Hexagonal shaped LaPO4 submicron particles doped with various concentrations of Er were successfully prepared by homogenous precipitation method using metal nitrates and ammonium phosphate. Particles of approximate particle size 125 nm and size distribution of 85 nm are obtained with good crystallinity. After heat treatment at 1200 °C for 2 h, the particles are characterized for their various optical properties such as absorption, emission, fluorescence decay and optical band gap. Optical absorption and emission data are numerically analyzed with the help of Judd-Ofelt model to evaluate various radiative spectral properties such as radiative decay rates, radiative quantum yield, emission cross-section and fluorescence branching ratios of various emission transitions. Though the radiative quantum yield of 1554 nm emission approaches the theoretical limit of 100%, the experimentally measured quantum yield is only 11% at 12 W/cm2 at 980 nm excitation power density in 2% Er doped LaPO4.

  10. 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.

  11. Optical and spectroscopic characterization of Er3+-Yb3+co-doped tellurite glasses and fibers

    NASA Astrophysics Data System (ADS)

    Narro-García, R.; Desirena, H.; Chillcce, E. F.; Barbosa, L. C.; Rodriguez, E.; De la Rosa, E.

    2014-04-01

    Optical and spectroscopic properties of Er3+-Yb3+ co-doped TeO2-WO3-Nb2O5-Na2O-Al2O3 glasses and fibers were investigated. Emission spectra and fluorescence lifetimes of 4I13/2 level of Er3+ion as a function of rare earth concentration and fiber length were measured in glasses. Results show that the self-absorption effect broadens the spectral bandwidth of 4I13/2→4I15/2 transition and lengthens the lifetime significantly from 3.5 to 4.6 ms. Fibers were fabricated by the rod-in-tube technique using a Heathway drawing tower. The emission power of these Er3+-Yb3+ co-doped Step Index Tellurite Fibers (SITFs; lengths varying from 2 to 60 cm) were generated by a 980 nm diode laser pump and then the emission power spectra were acquired with an OSA. The maximum emission power spectra, within the 1530-1560 nm region, were observed for fiber lengths ranging from 3 to 6 cm. The highest bandwidth obtained was 108 nm for 8 cm fiber length around 1.53 µm.

  12. Transient Spectroscopic Characterization of the Genesis of a Ruthenium Complex Catalyst Supported on Zeolite Y

    SciTech Connect

    Ogino, Isao; Gates, Bruce C.

    2010-01-12

    A mononuclear ruthenium complex anchored to dealuminated zeolite HY, Ru(acac)(C{sub 2}H{sub 4}){sup 2+} (acac = acetylacetonate, C{sub 5}H{sub 7}O{sup 2}{sup -}), was characterized in flow reactors by transient infrared (IR) spectroscopy and Ru K edge X-ray absorption spectroscopy. The combined results show how the supported complex was converted into a form that catalyzes ethene conversion to butene. The formation of these species resulted from the removal of acac ligands from the ruthenium (as shown by IR and extended X-ray absorption fine structure (EXAFS) spectra) and the simultaneous decrease in the symmetry of the ruthenium complex, with the ruthenium remaining mononuclear and its oxidation state remaining essentially unchanged (as shown by EXAFS and X-ray absorption near-edge structure spectra). The removal of anionic acac ligands from the ruthenium was evidently compensated by the bonding of other anionic ligands, such as hydride from H2 in the feed stream, to form species suggested to be Ru(H)(C{sub 2}H{sub 4}){sub 2}{sup +}, which is coordinatively unsaturated and inferred to react with ethene, leading to the observed formation of butene in a catalytic process.

  13. FTIR spectroscopic characterization of Cu(II) coordination compounds with exopolysaccharide pullulan and its derivatives

    NASA Astrophysics Data System (ADS)

    Mitić, Ž.; Nikolić, G. S.; Cakić, M.; Premović, P.; Ilić, Lj.

    2009-04-01

    Pullulan is a water-soluble, extracellular neutral polysaccharide with a linear flexible chain of α-(1 → 6)-linked maltotriose units, the structure of which is intermediate between pullulan and amylose structures because of the co-existence of both α-(1 → 6) and α-(1 → 4)-glycosidic linkages in single compounds. In alkali solutions Cu(II) ion forms complexes with reduced low-molar pullulan (RLMP). The metal content and the solution composition depends on pH. The complexing process begins in a weak alkali solution (pH > 7), and involves OH groups in C(2) and C(3) or C(6) pullulan monomer units (α- D-glucopyranose). Complexes of Cu(II) ion with reduced low-molar pullulan were synthesized in the water solutions, at the boiling temperature and at different pH values (7.512). Fourier-Transform Infrared (FTIR) spectroscopic data of synthesized complexes are rare in literature. FTIR spectroscopic characterization (FTIR, LNT-FTIR, ATR-FTIR, and FTIR microspectroscopy) of Cu(II) ion complexes with RLMP ( M w 6000 g mol -1) was carried out in this work. The similarities of the γ(C sbnd H) range in a part of FTIR spectra indicate that there is no difference in the conformation of the C 1 glucopyranose (Glc) unit in the RLMP and synthesized Cu(II) complexes. The complexing Cu(II) ion with RLMP in the dependence from the pH form different types of complex (pH 7-8: Cu(II)(Glc) 2(H 2O) 2, pH 8-10: Cu(II)(Glc) 2(H 2O)(OH), pH 10-12: Cu(II)(Glc) 2(OH) 2).

  14. Characterization of the oral absorption of several aminopenicillins: determination of intrinsic membrane absorption parameters in the rat intestine in situ

    NASA Technical Reports Server (NTRS)

    Sinko, P. J.; Amidon, G. L.

    1992-01-01

    The absorption mechanism of several penicillins was characterized using in situ single-pass intestinal perfusion in the rat. The intrinsic membrane parameters were determined using a modified boundary layer model (fitted value +/- S.E.): Jmax* = 11.78 +/- 1.88 mM, Km = 15.80 +/- 2.92 mM, Pm* = 0, Pc* = 0.75 +/- 0.04 for ampicillin; Jmax* = 0.044 +/- 0.018 mM, Km = 0.058 +/- 0.026 mM, Pm* = 0.558 +/- 0.051, Pc* = 0.757 +/- 0.088 for amoxicillin; and Jmax* = 16.30 +/- 3.40 mM, Km = 14.00 +/- 3.30 mM, Pm* = 0, Pc* = 1.14 +/- 0.05 for cyclacillin. All of the aminopenicillins studied demonstrated saturable absorption kinetics as indicated by their concentration-dependent wall permeabilities. Inhibition studies were performed to confirm the existence of a nonpassive absorption mechanism. The intrinsic wall permeability (Pw*) of 0.01 mM ampicillin was significantly lowered by 1 mM amoxicillin and the Pw* of 0.01 mM amoxicillin was reduced by 2 mM cephradine consistent with competitive inhibition.

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

    SciTech Connect

    Cortez, E.; Remsen, E; Chlanda, V.; Carrol, P.; Sneddon, L.

    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.}

  16. [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

  17. Solvate Structures and Computational/Spectroscopic Characterization of LiPF6 Electrolytes

    SciTech Connect

    Han, Sang D.; Yun, Sung-Hyun; Borodin, Oleg; Seo, D. M.; Sommer, Roger D.; Young, Victor G.; Henderson, Wesley A.

    2015-04-23

    Raman spectroscopy is a powerful method for identifying ion-ion interactions, but only if the vibrational band signature for the anion coordination modes can be accurately deciphered. The present study characterizes the PF6- anion P-F Raman symmetric stretching vibrational band for evaluating the PF6-...Li+ cation interactions within LiPF6 crystalline solvates to create a characterization tool for liquid electrolytes. To facilitate this, the crystal structures for two new solvates—(G3)1:LiPF6 and (DEC)2:LiPF6 with triglyme and diethyl carbonate, respectively—are reported. The information obtained from this analysis provides key guidance about the ionic association information which may be obtained from a Raman spectroscopic evaluation of electrolytes containing the LiPF6 salt and aprotic solvents. Of particular note is the overlap of the Raman bands for both solvent-separated ion pair (SSIP) and contact ion pair (CIP) coordination in which the PF6- anions are uncoordinated or coordinated to a single Li+ cation, respectively.

  18. Toward the characterization of biological toxins using field-based FT-IR spectroscopic instrumentation

    NASA Astrophysics Data System (ADS)

    Schiering, David W.; Walton, Robert B.; Brown, Christopher W.; Norman, Mark L.; Brewer, Joseph; Scott, James

    2004-12-01

    IR spectroscopy is a broadly applicable technique for the identification of covalent materials. Recent advances in instrumentation have made Fourier Transform infrared (FT-IR) spectroscopy available for field characterization of suspect materials. Presently, this instrumentation is broadly deployed and used for the identification of potential chemical hazards. This discussion concerns work towards expanding the analytical utility of field-based FT-IR spectrometry in the characterization of biological threats. Two classes of materials were studied: biologically produced chemical toxins which were non-peptide in nature and peptide toxin. The IR spectroscopic identification of aflatoxin-B1, trichothecene T2 mycotoxin, and strychnine was evaluated using the approach of spectral searching against large libraries of materials. For pure components, the IR method discriminated the above toxins at better than the 99% confidence level. The ability to identify non-peptide toxins in mixtures was also evaluated using a "spectral stripping" search approach. For the mixtures evaluated, this method was able to identify the mixture components from ca. 32K spectral library entries. Castor bean extract containing ricin was used as a representative peptide toxin. Due to similarity in protein spectra, a SIMCA pattern recognition methodology was evaluated for classifying peptide toxins. In addition to castor bean extract the method was validated using bovine serum albumin and myoglobin as simulants. The SIMCA approach was successful in correctly classifying these samples at the 95% confidence level.

  19. Chemical, spectroscopic characterization, DFT studies and antibacterial activities in vitro of a new gold(I) complex with rimantadine

    NASA Astrophysics Data System (ADS)

    Sucena, Suelen F.; Paiva, Raphael E. F.; Abbehausen, Camilla; Mattos, Ives B.; Lancellotti, Marcelo; Formiga, André L. B.; Corbi, Pedro P.

    2012-04-01

    A novel gold(I) complex with rimantadine (RTD) was obtained and structurally characterized by a set of chemical and spectroscopic analysis. 1H, 13C and 15N nuclear magnetic resonance (NMR) and infrared (IR) spectroscopic measurements suggest coordination of the ligand to Au(I) through the N atom of the ethanamine group. Theoretical (DFT) calculations confirmed the IR assignments and permit proposing an optimized geometry for the complex. The gold(I)-rimantadine complex (Au-RTD) is soluble in methanol, ethanol, dimethylsulfoxide, acetone and acetonitrile. The preliminary kinetic studies based on UV-vis spectroscopic measurements indicate the stability of the compound in solution. Antibacterial activities of the complex were evaluated by an antibiogram assay. The Au-RTD complex showed an effective in vitro antibacterial activity against the Pseudomonas aeruginosa, Escherichia coli (Gram-negative), and Staphylococcus aureus (Gram-positive) bacterial strains.

  20. Spectroscopic characterization of Er-doped KPb 2Cl 5 laser crystals

    NASA Astrophysics Data System (ADS)

    Jenkins, N. W.; Bowman, S. R.; O'Connor, S.; Searles, S. K.; Ganem, Joseph

    2003-06-01

    A discussion of the spectroscopic properties of the low-phonon energy laser host material potassium lead chloride, KPb 2Cl 5, doped with trivalent erbium is presented. In this paper we present room temperature spectroscopic measurements and subsequent analysis based on the Judd-Ofelt model. Additionally, Stark level energies of the Er 3+ ions in the crystal were determined from spectroscopic measurements performed at cryogenic temperatures.

  1. Spectroscopic networks

    NASA Astrophysics Data System (ADS)

    Csaszar, A. G.; Furtenbacher, T.

    2011-05-01

    Approaches related to graph theory are given which allow a better understanding of and yield routes for systematic enlargement and improvement of experimental spectroscopic line lists of molecules. The protocols are based on the fact that the information in line lists can be related to large-scale, weighted, undirected graphs, whereby the vertices are discrete energy levels, the edges are transitions, and the weights are transition intensities. The resulting graph is what one may call a spectroscopic network (SN). It is shown on the example of the HD16O isotopologue of the water molecule that both its measured and first-principles one-photon absorption SNs have a scale-free behavior with all of the usual consequences, including appearance of hubs, robustness, error tolerance, and the "small-world" property. The graph-theoretical view of molecular spectra offers several new ideas for improving the accuracy and robustness of the information systems containing high-resolution spectroscopic data.

  2. Raman Spectroscopic Characterization of the Feldspars: Implications for Surface Mineral Characterization in Planetary Exploration

    NASA Technical Reports Server (NTRS)

    Freeman, J. J.; Wang, Alian; Kuebler, K. E.; Haskin, L. A.

    2003-01-01

    The availability in the last decade of improved Raman instrumentation using small, stable, intense lasers, sensitive CCD array detectors, and advanced fast grating systems enabled us to develop the Mars Microbeam Raman Spectrometer (MMRS), a field-portable Raman spectrometer with precision and accuracy capable of identifying minerals and their different compositions. For example, we can determine Mg cation ratios in pyroxenes and olivines to +/-0.1 on the basis of Raman peak positions. Feldspar is another major mineral formed in igneous systems whose characterization is important for determining rock petrogenesis and alteration. From their Raman spectral pattern, feldspars can be readily distinguished from ortho- and chain-silicates and from other tecto-silicates such as quartz and zeolites. We show here how well Raman spectral analysis can distinguish among members within the feldspar group.

  3. 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.

  4. Optical Properties of CuInSe2 Bulk Material Characterized by a Fixed Polarizer-Rotating Analyzer Spectroscopic Ellipsometer

    NASA Astrophysics Data System (ADS)

    Hidalgo, M. L.; Lachab, M.; Zouaoui, A.; Alhamed, M.; Llinares, C.; Peyrade, J. P.; Galibert, J.

    1997-03-01

    In the present paper, we have investigated the optical properties of CuInSe2 single and polycrystals using a broad band fixed polarizer-rotating analyzer spectroscopic ellipsometer (RAE) in the spectral range 250 to 1700 nm. The wavelength dependence of CuInSe2 optical constants was studied assuming a two-phase system: the ambient medium and the sample. We have determined interband transition energies near and above the bandgap by a detailed analysis of the absorption spectrum and through the third joint-density-of-states (JDOS) derivative computation. Measurements were carried out on nearly-stoichiometric and In-rich CuInSe2 substrates.

  5. Spectroscopic and laser characterization of Yb,Tm:KLu(WO4)2 crystal

    NASA Astrophysics Data System (ADS)

    Loiko, P. A.; Serres, J. M.; Mateos, X.; Demesh, M. P.; Yasukevich, A. S.; Yumashev, K. V.; Petrov, V.; Griebner, U.; Aguiló, M.; Díaz, F.

    2016-01-01

    We report on a comprehensive spectroscopic and laser characterization of monoclinic Yb,Tm:KLu(WO4)2 crystals. Stimulated-emission cross-section spectra corresponding to the 3F4 → 3H6 transition of Tm3+ ions are determined. The radiative lifetime of the 3F4 state of Tm3+ ions is 0.82 ms. The maximum Yb3+ → Tm3+ energy transfer efficiency is 83.9% for 5 at.% Yb - 8 at.% Tm doping. The fractional heat loading for Yb,Tm:KLu(WO4)2 is 0.45 ± 0.05. Using a hemispherical cavity and 5 at.% Yb - 6 at.% Tm doped crystal, a maximum CW power of 227 mW is achieved at 1.983-2.011 μm with a maximum slope efficiency η = 14%. In the microchip laser set-up, the highest slope efficiency is 20% for a 5 at.% Yb- 8 at.% Tm doped crystal with a maximum output power of 201 mW at 1.99-2.007 μm. Operation of Yb,Tm:KLu(WO4)2 as a vibronic laser emitting at 2.081-2.093 μm is also demonstrated.

  6. Smooth and conductive DNA-templated Cu2O nanowires: growth morphology, spectroscopic and electrical characterization

    NASA Astrophysics Data System (ADS)

    Hassanien, Reda; Farha Al-Said, Said A.; Šiller, Lidija; Little, Ross; Wright, Nicholas G.; Houlton, Andrew; Horrocks, Benjamin R.

    2012-02-01

    DNA strands have been used as templates for the self-assembly of smooth and conductive cuprous oxide (Cu2O) nanowires of diameter 12-23 nm and whose length is determined by the template (16 μm for λ-DNA). A combination of spectroscopic, diffraction and probe microscopy techniques showed that these nanowires comprise single crystallites of Cu2O bound to the DNA molecules which fused together over time in a process analogous to Ostwald ripening, but driven by the free energy of interaction with the template as well as the surface tension. Electrical characterization of the nanowires by a non-contact method, scanned conductance microscopy and by contact mode conductive AFM showed the wires are electrically conductive. The conductivity estimated from the AFM cross section and the zero-bias conductance in conductive AFM experiments was 2.2-3.3 S cm-1. These Cu2O nanowires are amongst the thinnest reported and show evidence of strong quantum confinement in electronic spectra.

  7. Smooth and conductive DNA-templated Cu₂O nanowires: growth morphology, spectroscopic and electrical characterization.

    PubMed

    Hassanien, Reda; Al-Said, Said A Farha; Siller, Lidija; Little, Ross; Wright, Nicholas G; Houlton, Andrew; Horrocks, Benjamin R

    2012-02-24

    DNA strands have been used as templates for the self-assembly of smooth and conductive cuprous oxide (Cu₂O) nanowires of diameter 12-23 nm and whose length is determined by the template (16 μm for λ-DNA). A combination of spectroscopic, diffraction and probe microscopy techniques showed that these nanowires comprise single crystallites of Cu₂O bound to the DNA molecules which fused together over time in a process analogous to Ostwald ripening, but driven by the free energy of interaction with the template as well as the surface tension. Electrical characterization of the nanowires by a non-contact method, scanned conductance microscopy and by contact mode conductive AFM showed the wires are electrically conductive. The conductivity estimated from the AFM cross section and the zero-bias conductance in conductive AFM experiments was 2.2-3.3 S cm⁻¹. These Cu₂O nanowires are amongst the thinnest reported and show evidence of strong quantum confinement in electronic spectra. PMID:22261265

  8. Growth and Raman spectroscopic characterization of As 4S 4 (II) single crystals

    NASA Astrophysics Data System (ADS)

    Kyono, Atsushi

    2010-11-01

    As described by Kutoglu (1976 [16]), single crystals of As 4S 4 (II) phase have been grown using a new two-step synthesis that drastically increases the reproducibility that is attainable in synthetic experiments. First, through photo-induced phase transformation, pararealgar powder is prepared as a precursor instead of AsS melt. Then it is dissolved and recrystallized from CS 2 solvent. Results show that single crystals of the As 4S 4 (II) phase were obtained reproducibly through the dissolution-recrystallization process. Single crystals of As 4S 4 (II) obtained using this method were translucent and showed a uniform yellow-orange color. The crystal exhibits a platelet-like shape as a thin film with well-developed faces (0 1 0) and (0 1¯ 0). The grown crystals are as large as 0.50×0.50×0.01 mm. They were characterized using powder and single crystal X-ray diffraction techniques to confirm the phase identification and the lattice parameters. The As 4S 4 (II) phase crystallizes in monoclinic system with cell parameters a=11.202(4) Å, b=9.954(4) Å, c=7.142(4) Å, β=92.81(4)°, V=795.4(6) Å 3, which shows good agreement with the former value. Raman spectroscopic studies elucidated the behavior of the substance and the relation among phases of tetra-arsenic tetrasulfide.

  9. Characterization of organic matter from composting of different residues by physicochemical and spectroscopic methods.

    PubMed

    Fialho, Lucimar Lopes; Lopes da Silva, Wilson Tadeu; Milori, Débora M B P; Simões, Marcelo Luiz; Martin-Neto, Ladislau

    2010-03-01

    Chemical and spectroscopic methods were used to characterize organic matter transformations during the composting process. Four different residue mixtures were studied: P1--garden trimmings (GT) only, P2 - GT plus fresh cattle manure, P3--GT plus orange pomace and P4--GT plus filter cake. The thermophilic phase was not reached in P1 compost, but the P2, P3 and P4 composts showed all three typical process phases. The thermophilic phase and CEC/C ratio stabilized after 90 days, while C/N ratio and the ash content stabilized after 60 days. The increasing E(4)/E(6) ratio indicated oxidation reactions occurring during the process in the material from P2, P3 and P4. The (13)C NMR and FTIR results suggested extraction of both pectin and lignin in the HA-like fraction. The CEC/C ratio, temperature and E(4)/E(6) ratio showed that within 90 days P2, P3 and P4 composts were humified. However, material from P1 did not show characteristics of humified compost. From these data, it is apparent that C/N ratio and ash content are not reliable methods for monitoring the composting process. PMID:19954966

  10. 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.

  11. Characterization of Photon-Counting Detector Responsivity for Non-Linear Two-Photon Absorption Process

    NASA Technical Reports Server (NTRS)

    Sburlan, S. E.; Farr, W. H.

    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 singlephoton absorption for wavelengths slightly above the bandgap wavelength of silicon (approx. 1100 microns). One application for this low efficiency sub-band absorption is in deep space optical communication systems where it is desirable to track a 1030 nm uplink beacon on the same flight terminal detector array that monitors a 1550 nm downlink signal for pointingcontrol. The currently observed absorption at 1550 nm provides 60-70 dB of isolation compared to the response at 1064 nm, which is desirable to avoid saturation of the detector by scattered light from the downlink laser.

  12. A Multiscale Vibrational Spectroscopic Approach for Identification and Biochemical Characterization of Pollen

    PubMed Central

    Bağcıoğlu, Murat; Zimmermann, Boris; Kohler, Achim

    2015-01-01

    Background Analysis of pollen grains reveals valuable information on biology, ecology, forensics, climate change, insect migration, food sources and aeroallergens. Vibrational (infrared and Raman) spectroscopies offer chemical characterization of pollen via identifiable spectral features without any sample pretreatment. We have compared the level of chemical information that can be obtained by different multiscale vibrational spectroscopic techniques. Methodology Pollen from 15 different species of Pinales (conifers) were measured by seven infrared and Raman methodologies. In order to obtain infrared spectra, both reflectance and transmission measurements were performed on ground and intact pollen grains (bulk measurements), in addition, infrared spectra were obtained by microspectroscopy of multigrain and single pollen grain measurements. For Raman microspectroscopy measurements, spectra were obtained from the same pollen grains by focusing two different substructures of pollen grain. The spectral data from the seven methodologies were integrated into one data model by the Consensus Principal Component Analysis, in order to obtain the relations between the molecular signatures traced by different techniques. Results The vibrational spectroscopy enabled biochemical characterization of pollen and detection of phylogenetic variation. The spectral differences were clearly connected to specific chemical constituents, such as lipids, carbohydrates, carotenoids and sporopollenins. The extensive differences between pollen of Cedrus and the rest of Pinaceae family were unambiguously connected with molecular composition of sporopollenins in pollen grain wall, while pollen of Picea has apparently higher concentration of carotenoids than the rest of the family. It is shown that vibrational methodologies have great potential for systematic collection of data on ecosystems and that the obtained phylogenetic variation can be well explained by the biochemical composition of pollen. Out of the seven tested methodologies, the best taxonomical differentiation of pollen was obtained by infrared measurements on bulk samples, as well as by Raman microspectroscopy measurements of the corpus region of the pollen grain. Raman microspectroscopy measurements indicate that measurement area, as well as the depth of focus, can have crucial influence on the obtained data. PMID:26376486

  13. Characterizing the Structure of Lipodisq Nanoparticles for Membrane Protein Spectroscopic Studies

    PubMed Central

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

    2014-01-01

    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. 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

  14. 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

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

    NASA Astrophysics Data System (ADS)

    ?ahin, Musa; zdemir, Nam?k; Bal-Demirci, Tlay; lkseven, Bahri; Diner, 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.

  16. New spectroscopic tools and techniques for characterizing M dwarfs and discovering their planets in the near-infrared

    NASA Astrophysics Data System (ADS)

    Terrien, Ryan C.

    M dwarfs are the least massive and most common stars in the Galaxy. Due to their prevalence and long lifetimes, these diminutive stars play an outsize role in several fields of astronomical study. In particular, it is now known that they commonly host planetary systems, and may be the most common hosts of Earth-size, rocky planets in the habitable zone. A comprehensive understanding of M dwarfs is crucial for understanding the origins and conditions of their planetary systems, including their potential habitability. Such an understanding depends on methods for precisely and accurately measuring their properties. These tools have broader applicability as well, underlying the use of M dwarfs as fossils of Galactic evolution, and helping to constrain the structures and interiors of these stars. The measurement of the fundamental parameters of M dwarfs is encumbered by their spectral complexity. Unlike stars of spectral type F, G, or K that are similar to our G type Sun, whose spectra are dominated by continuum emission and atomic features, the cool atmospheres of M dwarfs are dominated by complex molecular absorption. Another challenge for studies of M dwarfs is that these stars are optically faint, emitting much of their radiation in the near-infrared (NIR). The availability and performance of NIR spectrographs have lagged behind those of optical spectrographs due to the challenges of producing low-noise, high-sensitivity NIR detector arrays, which have only recently become available. This thesis discusses two related lines of work that address these challenges, motivated by the development of the Habitable Zone Planet Finder (HPF), a NIR radial velocity (RV) spectrograph under development at Penn State that will search for and confirm planets around nearby M dwarfs. This work includes the development and application of new NIR spectroscopic techniques for characterizing M dwarfs, and the development and optimization of new NIR instrumentation for HPF. The first line of work is centered on a large NIR spectroscopic survey of nearby M dwarfs, undertaken to characterize potential targets for HPF. This survey, and new techniques for measuring M dwarf metallicity, are the subject of Chapter 2. These data will provide crucial information to assess planetary composition, and the stellar metallicities will help us understand the process of planet formation around M dwarfs. These techniques have also enabled strong tests of low-mass stellar models in the benchmark eclipsing binary system CM Draconis, and have helped identify potential directions for improvement in the models, as presented in Chapter 3. The development of new spectroscopic indices for measuring M dwarf luminosity, radius, and potentially alpha-element abundance is discussed in Chapter 4. Finally, Chapter 5 presents a synthesis of these M dwarf characterization techniques and radial velocity (RV) measurements from the SDSS-III APOGEE spectrograph, which we applied to confirm and characterize the first M dwarfs in the nearby Coma Berenices cluster. The second line of work relates to the optimization of HPF. By targeting M dwarfs, HPF will take advantage of the large signal induced by an Earth-mass planet orbiting an M dwarf compared to the same planet orbiting an FGK star. Chapter 6 discusses a number of design trades and parameter optimizations undertaken in order to ensure the best sensitivity to Earth-mass planets. These subtopics include the optimization of the HPF resolution, bandpass, operating temperature, and vacuum phase holographic cross-disperser, as well as prediction of anticipated HPF performance, and the development of an HPF software simulator tool. In carrying out NIR detector tests for HPF, we have also tested an optical filter that selectively blocks long-wavelength thermal background radiation. This type of contamination is a perennial source of noise for NIR instruments, and typically forces these instruments to operate fully cryogenically. The complexity and cost of this approach may be avoided: for instruments operating in the H-band or bluer, the thermal background can be optically filtered, freeing the instrument to operate at warmer temperatures. Chapter 7 details our characterization and application of an interference filter that effectively blocks thermal background when used with a 1.7mum-cutoff HAWAII-2RG NIR detector array. By effectively filtering the thermal background with a single coated optic, this filter offers the potential for simple, cost-effective, warm-pupil NIR astronomical instruments, which can take advantage of the increasing availability of low-noise, high-efficiency NIR detectors.

  17. Norharmane rhenium(I) polypyridyl complexes: synthesis, structural and spectroscopic characterization.

    PubMed

    Maisuls, Iván; Wolcan, Ezequiel; Piro, Oscar E; Etcheverría, Gustavo A; Petroselli, Gabriela; Erra-Ballsels, Rosa; Cabrerizo, Franco M; Ruiz, Gustavo T

    2015-10-21

    Two novel Re(i) complexes with the general formula fac-[Re(CO)3(L)(nHo)]CF3SO3, where L = 2,2'-bipyridine (bpy) or 1,10 phenanthroline (phen) and nHo (9H-pyrido[3,4-b]indole; norharmane) have been synthesized. The Re(i)-nHo complexes were characterized by structural X-ray diffraction, (1)H and (13)C NMR, UV-vis absorption and FT-IR spectroscopy, and by a combination of two mass spectrometry techniques, namely ESI-MS and UV-MALDI-MS. All characterizations showed that nHo is coordinated to the metal atom by the pyridine nitrogen of the molecule. X-ray structural analysis revealed that the crystal lattices for both complexes are further stabilized by a strong >N-HO bond between the pyrrole NH group of the pyridoindole ligand and one oxygen atom of the trifluoromethanesulfonate counter-ion. Ground state geometry optimization by DFT calculations showed that in fluid solution the nHo ligand may rotate freely. The nature of the electronic transitions of Re(CO)3(bpy)(nHo)(+) were established by TD-DFT calculations. The set of the most important electronic transitions present in this complex are comprised of π→π* electronic transitions centered on bpy and nHo moieties, LLCTnHo→COs, MLLCTRe(CO)3→bpy and LLCTnHo→bpy transitions. Additionally, TD-DFT calculations predict the existence of another two intense MLLCTRe(CO)3→nHo electronic transitions. Calculated UV-vis absorption spectra are in good agreement with the corresponding experimental data for the bpy-containing complex. PMID:26365709

  18. 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.

  19. 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.

  20. 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.

  1. Speciation of water soluble iron in size segregated airborne particulate matter using LED based liquid waveguide with a novel dispersive absorption spectroscopic measurement technique.

    PubMed

    Chan, K L; Jiang, S Y N; Ning, Z

    2016-03-31

    In this study, we present the development and evaluation of a dispersive absorption spectroscopic technique for trace level soluble ferrous detection. The technique makes use of the broadband absorption spectra of the ferrous-ferrozine complex with a novel spectral fitting algorithm to determine soluble ferrous concentrations in samples and achieves much improved measurement precision compared to conventional methods. The developed method was evaluated by both model simulations and experimental investigations. The results demonstrated the robustness of the method against the spectral fluctuation, wavelength drift and electronic noise, while achieving excellent linearity (R(2) > 0.999) and low detection limit (0.06 μg L(-1)) for soluble ferrous detection. The developed method was also used for the speciation of soluble iron in size segregated atmospheric aerosols. The measurement was carried out during Spring and Summer in typical urban environment in Hong Kong. The measured total iron concentrations are in good agreement compared to conventional Inductively Coupled Plasma - Optical Emission Spectroscopy (ICP-OES) measurements. Investigation on ambient particulate matter samples shows the size dependent characteristic of iron speciation in the atmosphere with a more active role of fine particles in transforming between ferrous and ferric. The method demonstrated in this study provides a cost and time effective approach for the speciation of iron in ambient aerosols. PMID:26965332

  2. Spectroscopic characterization and energy transfer process in cobalt and cobalt-iron co-doped ZnSe/ZnS crystals

    NASA Astrophysics Data System (ADS)

    Peppers, J.; Martyshkin, D. V.; Fedorov, V. V.; Mirov, S. B.

    2014-02-01

    Cobalt doped II-VI wide band semiconductors (e.g. ZnSe, ZnS, CdSe) are promising media for infrared (IR) laser applications. They could be utilized as effective passive Q-switches for cavities of Alexandrite as well as Nd and Er lasers operating over 0.7-0.8, 1.3-1.6, and ~2.8 μm spectral ranges. We report spectroscopic characterization of Co:ZnSe and Co:ZnS crystals. Absorption cross-sections were measured for 4A2(F) → 4T1(P), 4A2(F) → 4T1(F), and 4A2(F) → 4T2(F) transitions with maximum absorption at 768(726), 1615(1500), 2690(2740) nm for ZnSe(ZnS) crystals, respectively. The calculated absorption cross-sections of the above transitions were estimated to be 64(56)×1019, 7.5(7.8)×1019, and 0.52(0.49)×1019 cm2 for ZnSe(ZnS) crystal hosts. In addition to the above applications the cobalt ions could be utilized for excitation of Fe2+ ions via resonance energy transfer process. Tunable room temperature lasing of Fe 2+ doped binary and ternary chalcogenides has been successfully demonstrated over 3.5-6 μm spectral range. However, II-VI lasers based on Fe2+ active ions don't feature convenient commercially available pump sources (e.g. some Fe doped crystal hosts require pump wavelengths longer than 3 μm). Therefore, the process of energy transfer from Co2+ to Fe2+ ions could enable utilization of commercially available visible and near-infrared pump sources. We report a spectroscopic characterization of iron-cobalt co-doped ZnS and ZnSe crystals over 14-300K temperature range. Mid-IR laser oscillation at 3.9 μm(3.6 μm) via energy transfer in the Co:Fe:ZnSe (Co:Fe:ZnS) co-doped crystals was demonstrated under cobalt excitation at 4A2(F) → 4T1(P) (~0.7μm) and 4A2(F) → 4T1(F) (~1.56 μm) transitions.

  3. Spectroscopic characterization and density functional studies of (Z)-1-[(2-methoxy-5-(trifluoromethyl)phenylamino)methylene]naphthalene-2(1H)-one

    NASA Astrophysics Data System (ADS)

    Alpaslan, Yelda Bingöl; Gökce, Halil; Alpaslan, Gökhan; Macit, Mustafa

    2015-10-01

    In the current work, the Schiff base compound (Z)-1-[(2-Methoxy-5-(trifluoromethyl)phenylamino)methylene]naphthalene-2(1H)-one (I) has been characterized by using 13C NMR, 1H NMR, FT-IR and UV-vis spectroscopic techniques. Molecular geometry of the compound I in the ground state, vibrational frequencies, electronic absorption spectra and gauge including atomic orbital (GIAO) 1H and 13C NMR chemical shift values have been calculated by using the density functional method (DFT) with 6-311++G(d,p) basis set and compared with the experimental data. The optimized geometric parameters obtained by using DFT (B3LYP/6-311++G(d,p)) show good agreement with the experimental data. The vibrational frequencies were determined based on the recorded FT-IR spectra in the range of 4000-400 cm-1 for solid state. Using the TD-DFT method, electronic absorption spectra of the compound I have been predicted and good agreement is determined with the experimental ones. In addition, molecular electrostatic potential (MEP), frontier molecular orbital analysis (HOMO-LUMO), non-linear optical (NLO) properties, NBO analysis and NBO atomic charges of the compound I were investigated using same theoretical calculations.

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

    SciTech Connect

    Lezama-pacheco, Juan S; Conradson, Steven D; Clark, David L

    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.

  5. Characterization of ion-assisted induced absorption in A-Si thin-films used for multivariate optical computing

    NASA Astrophysics Data System (ADS)

    Nayak, Aditya B.; Price, James M.; Dai, Bin; Perkins, David; Chen, Ding Ding; Jones, Christopher M.

    2015-06-01

    Multivariate optical computing (MOC), an optical sensing technique for analog calculation, allows direct and robust measurement of chemical and physical properties of complex fluid samples in high-pressure/high-temperature (HP/HT) downhole environments. The core of this MOC technology is the integrated computational element (ICE), an optical element with a wavelength-dependent transmission spectrum designed to allow the detector to respond sensitively and specifically to the analytes of interest. A key differentiator of this technology is it uses all of the information present in the broadband optical spectrum to determine the proportion of the analyte present in a complex fluid mixture. The detection methodology is photometric in nature; therefore, this technology does not require a spectrometer to measure and record a spectrum or a computer to perform calculations on the recorded optical spectrum. The integrated computational element is a thin-film optical element with a specific optical response function designed for each analyte. The optical response function is achieved by fabricating alternating layers of high-index (a-Si) and low-index (SiO2) thin films onto a transparent substrate (BK7 glass) using traditional thin-film manufacturing processes (e.g., ion-assisted e-beam vacuum deposition). A proprietary software and process are used to control the thickness and material properties, including the optical constants of the materials during deposition to achieve the desired optical response function. The ion-assisted deposition is useful for controlling the densification of the film, stoichiometry, and material optical constants as well as to achieve high deposition growth rates and moisture-stable films. However, the ion-source can induce undesirable absorption in the film; and subsequently, modify the optical constants of the material during the ramp-up and stabilization period of the e-gun and ion-source, respectively. This paper characterizes the unwanted absorption in the a-Si thin-film using advanced thin-film metrology methods, including spectroscopic ellipsometry and Fourier transform infrared (FTIR) spectroscopy. The resulting analysis identifies a fundamental mechanism contributing to this absorption and a method for minimizing and accounting for the unwanted absorption in the thin-film such that the exact optical response function can be achieved.

  6. Porphyrins with exocyclic rings. 16. Synthesis and spectroscopic characterization of fluoranthoporphyrins, a new class of highly conjugated porphyrin chromophores.

    PubMed

    Lash, T D; Werner, T M; Thompson, M L; Manley, J M

    2001-05-01

    Porphyrins with fused aromatic rings are under detailed investigation due to their unique spectroscopic properties. To gain more insights into the effects due to ring annealation on the porphyrin chromophore, a series of fluoranthoporphyrins have been synthesized. Reaction of 3-nitrofluoranthene with isocyanoacetate esters in the presence of a phosphazene base afforded good yields of the fluorantho[2,3-c]pyrrole esters 8. Cleavage of the ester moiety with KOH in ethylene glycol afforded the parent heterocycle 9, and this condensed with 2 equiv of acetoxymethylpyrroles 10 in refluxing acetic acid-2-propanol to afford tripyrranes 11. Following cleavage of the tert-butyl ester protective groups with TFA, "3 + 1" condensation with pyrrole dialdehyde 12 gave the fluoranthoporphyrins 13 in good overall yields. In addition, reaction of tripyrrane 11 with acenaphthopyrrole dialdehyde 16 gave the mixed acenaphthofluoranthoporphyrin 17 in excellent yields. A difluoranthoporphyrin 18 was also prepared via a "2 + 2" MacDonald condensation. Reaction of fluoranthopyrrole 8a with dimethoxymethane in the presence of p-toluenesulfonic acid gave the symmetrical dipyrrylmethane 19, and following ester saponification, this was condensed with a dipyrrylmethane dialdehyde to afford the adj-difluoranthoporphyrin 18. The UV--vis spectra for these fluoranthoporphyrins gave a series of three broadened absorptions in the Soret band region, although the Q-bands were little effected by ring fusion. The nickel(II), copper(II), and zinc chelates were more unusual, showing strong absorptions near 600 nm. Difluoranthoporphyrin 18 showed many of the same spectroscopic features, although the presence of two ring fusions gave rise to an increase in the spectroscopic shifts. The mixed system 17 gave spectra that showed larger red shifts due to the acenaphthylene unit combined with the features due to the fluoranthene rings. This work further demonstrates the utility of aromatic ring fusion in altering the properties of porphyrinoid systems. PMID:11325282

  7. Melanin from the nitrogen-fixing bacterium Azotobacter chroococcum: a spectroscopic characterization.

    PubMed

    Banerjee, Aulie; Supakar, Subhrangshu; Banerjee, Raja

    2014-01-01

    Melanins, the ubiquitous hetero-polymer pigments found widely dispersed among various life forms, are usually dark brown/black in colour. Although melanins have variety of biological functions, including protection against ultraviolet radiation of sunlight and are used in medicine, cosmetics, extraction of melanin from the animal and plant kingdoms is not an easy task. Using complementary physicochemical techniques (i.e. MALDI-TOF, FTIR absorption and cross-polarization magic angle spinning solid-state (13)C NMR), we report here the characterization of melanins extracted from the nitrogen-fixing non-virulent bacterium Azotobacter chroococcum, a safe viable source. Moreover, considering dihydroxyindole moiety as the main constituent, an effort is made to propose the putative molecular structure of the melanin hetero-polymer extracted from the bacterium. Characterization of the melanin obtained from Azotobacter chroococcum would provide an inspiration in extending research activities on these hetero-polymers and their use as protective agent against UV radiation. PMID:24416247

  8. Absorption spectroscopy characterization measurements of a laser-produced Na atomic beam

    SciTech Connect

    Ching, C.H.; Bailey, J.E.; Lake, P.W.; Filuk, A.B.; Adams, R.G.; McKenney, J.

    1996-06-01

    This work describes a pulsed Na atomic beam source developed for spectroscopic diagnosis of a high-power ion diode on the Particle Beam Fusion Accelerator II. The goal is to produce a {approximately} 10{sup 12}-cm{sup {minus}3}-density Na atomic beam that can be injected into the diode acceleration gap to measure electric and magnetic fields from the Stark and Zeeman effects through laser-induced-fluorescence or absorption spectroscopy. A {approximately} 10 ns fwhm, 1.06 {micro}m, 0.6 J/cm{sup 2} laser incident through a glass slide heats a Na-bearing thin film, creating a plasma that generates a sodium vapor plume. A {approximately} 1 {micro}sec fwhm dye laser beam tuned to 5,890 {angstrom} is used for absorption measurement of the Na I resonant doublet by viewing parallel to the film surface. The dye laser light is coupled through a fiber to a spectrograph with a time-integrated CCD camera. A two-dimensional mapping of the Na vapor density is obtained through absorption measurements at different spatial locations. Time-of-flight and Doppler broadening of the absorption with {approximately} 0.1 {angstrom} spectral resolution indicate that the Na neutral vapor temperature is about 0.5 to 2 eV. Laser-induced-fluorescence from {approximately} 1 {times} 10{sup 12}-cm{sup {minus}3} Na I 3s-3p lines observed with a streaked spectrograph provides a signal level sufficient for {approximately} 0.06 {angstrom} wavelength shift measurements in a mock-up of an ion diode experiment.

  9. Spectroscopic Characterization of Dust-Fall Samples Collected from Greater Cairo, Egypt.

    PubMed

    Shaltout, Abdallah A; Allam, Mousa A; Mostafa, Nasser Y; Heiba, Zein K

    2016-04-01

    This work aimed to characterize dust-fall samples collected from street's trees in Greater Cairo (GC), Egypt, and its surroundings by different spectroscopic techniques, namely; X-ray diffraction (XRD), attenuated total-reflection Fourier transform infrared (ATR-FTIR), particle-size analyzer, and scanning electron microscopy (SEM) combined with energy dispersive X-ray measurements. Samples were collected from 19 different locations inside and outside of GC. Quantitative phase analysis of the dust-fall samples was performed using the Rietveld method. Results showed that the most frequently observed phases in the dust-fall samples were calcite (CaCO3), dolomite (CaMg(CO3)2), gypsum (CaSO4·2H2O), and quartz (SiO2) with average concentrations of 39 ± 16, 8 ± 7, 22 ± 13, and 33 ± 14 wt%, respectively. The occurrence of these constituents referred to a combination of different anthropogenic and natural sources. The ATR-FTIR results are in good agreements with XRD data of the different observed phases. Based on the SEM and particle-size measurements, quantitative determination of the particle-size distribution was described. It was found that not only the large-sized particles are deposited but also the small-sized ones (PM10 and PM2.5). In addition, the particle size of the collected dust-fall samples varied from 0.1 to 200 µm with an average particle size of 17.36 µm; however, the particle size ranged from 2.5 to 40 µm predominated in all of the dust-fall samples. PMID:26710766

  10. 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.

  11. Spectroscopic and DFT study of solvent effects on the electronic absorption spectra of sulfamethoxazole in neat and binary solvent mixtures.

    PubMed

    Almandoz, M C; Sancho, M I; Blanco, S E

    2014-01-24

    The solvatochromic behavior of sulfamethoxazole (SMX) was investigated using UV-vis spectroscopy and DFT methods in neat and binary solvent mixtures. The spectral shifts of this solute were correlated with the Kamlet and Taft parameters (α, β and π(*)). Multiple lineal regression analysis indicates that both specific hydrogen-bond interaction and non specific dipolar interaction play an important role in the position of the absorption maxima in neat solvents. The simulated absorption spectra using TD-DFT methods were in good agreement with the experimental ones. Binary mixtures consist of cyclohexane (Cy)-ethanol (EtOH), acetonitrile (ACN)-dimethylsulfoxide (DMSO), ACN-dimethylformamide (DMF), and aqueous mixtures containing as co-solvents DMSO, ACN, EtOH and MeOH. Index of preferential solvation was calculated as a function of solvent composition and non-ideal characteristics are observed in all binary mixtures. In ACN-DMSO and ACN-DMF mixtures, the results show that the solvents with higher polarity and hydrogen bond donor ability interact preferentially with the solute. In binary mixtures containing water, the SMX molecules are solvated by the organic co-solvent (DMSO or EtOH) over the whole composition range. Synergistic effect is observed in the case of ACN-H2O and MeOH-H2O, indicating that at certain concentrations solvents interact to form association complexes, which should be more polar than the individual solvents of the mixture. PMID:24044989

  12. Spectroscopic and DFT study of solvent effects on the electronic absorption spectra of sulfamethoxazole in neat and binary solvent mixtures

    NASA Astrophysics Data System (ADS)

    Almandoz, M. C.; Sancho, M. I.; Blanco, S. E.

    2014-01-01

    The solvatochromic behavior of sulfamethoxazole (SMX) was investigated using UV-vis spectroscopy and DFT methods in neat and binary solvent mixtures. The spectral shifts of this solute were correlated with the Kamlet and Taft parameters (α, β and π*). Multiple lineal regression analysis indicates that both specific hydrogen-bond interaction and non specific dipolar interaction play an important role in the position of the absorption maxima in neat solvents. The simulated absorption spectra using TD-DFT methods were in good agreement with the experimental ones. Binary mixtures consist of cyclohexane (Cy)-ethanol (EtOH), acetonitrile (ACN)-dimethylsulfoxide (DMSO), ACN-dimethylformamide (DMF), and aqueous mixtures containing as co-solvents DMSO, ACN, EtOH and MeOH. Index of preferential solvation was calculated as a function of solvent composition and non-ideal characteristics are observed in all binary mixtures. In ACN-DMSO and ACN-DMF mixtures, the results show that the solvents with higher polarity and hydrogen bond donor ability interact preferentially with the solute. In binary mixtures containing water, the SMX molecules are solvated by the organic co-solvent (DMSO or EtOH) over the whole composition range. Synergistic effect is observed in the case of ACN-H2O and MeOH-H2O, indicating that at certain concentrations solvents interact to form association complexes, which should be more polar than the individual solvents of the mixture.

  13. PROBING THE FERMI BUBBLES IN ULTRAVIOLET ABSORPTION: A SPECTROSCOPIC SIGNATURE OF THE MILKY WAY'S BICONICAL NUCLEAR OUTFLOW

    SciTech Connect

    Fox, Andrew J.; Bordoloi, Rongmon; Hernandez, Svea; Tumlinson, Jason; Savage, Blair D.; Wakker, Bart P.; Lockman, Felix J.; Bland-Hawthorn, Joss; Kim, Tae-Sun; Benjamin, Robert A.

    2015-01-20

    Giant lobes of plasma extend ≈55° above and below the Galactic center, glowing in emission from gamma rays (the Fermi Bubbles) to microwaves and polarized radio waves. We use ultraviolet absorption-line spectra from the Hubble Space Telescope to constrain the velocity of the outflowing gas within these regions, targeting the quasar PDS 456 (ℓ, b = 10.°4, +11.°2). This sightline passes through a clear biconical structure seen in hard X-ray and gamma-ray emission near the base of the northern Fermi Bubble. We report two high-velocity metal absorption components, at v {sub LSR} = –235 and +250 km s{sup –1}, which cannot be explained by co-rotating gas in the Galactic disk or halo. Their velocities are suggestive of an origin on the front and back side of an expanding biconical outflow emanating from the Galactic center. We develop simple kinematic biconical outflow models that can explain the observed profiles with an outflow velocity of ≳900 km s{sup –1} and a full opening angle of ≈110° (matching the X-ray bicone). This indicates Galactic center activity over the last ≈2.5-4.0 Myr, in line with age estimates of the Fermi Bubbles. The observations illustrate the use of UV spectroscopy to probe the properties of swept-up gas venting into the Fermi Bubbles.

  14. Absorption and fluorescence spectroscopic characterisation of the circadian blue-light photoreceptor cryptochrome from Drosophila melanogaster (dCry)

    NASA Astrophysics Data System (ADS)

    Shirdel, J.; Zirak, P.; Penzkofer, A.; Breitkreuz, H.; Wolf, E.

    2008-09-01

    The absorption and fluorescence behaviour of the circadian blue-light photoreceptor cryptochrome from Drosophila melanogaster (dCry) in a pH 8 aqueous buffer solution is studied. The flavin adenine dinucleotide (FAD) cofactor of dCry is identified to be present in its oxidized form (FAD ox), and the 5,10-methenyltetrahydrofolate (MTHF) cofactor is found to be hydrolyzed and oxidized to 10-formyldihydrofolate (10-FDHF). The absorption and the fluorescence behaviour of dCry is investigated in the dark-adapted (receptor) state, the light-adapted (signalling) state, and under long-time violet light exposure. Photo-excitation of FAD ox in dCry causes a reductive electron transfer to the formation of anionic FAD semiquinone (FAD rad - ), and photo-excitation of the generated FAD rad - causes an oxidative electron transfer to the back formation of FAD ox. In light adapted dCry a photo-induced equilibrium between FAD ox and FAD rad - exists. The photo-cycle dynamics of signalling state formation and recovery is discussed. Quantum yields of photo-induced signalling state formation of about 0.2 and of photo-induced back-conversion of about 0.2 are determined. A recovery of FAD rad - to FAD ox in the dark with a time constant of 1.6 min at room temperature is found.

  15. 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.

  16. 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.

  17. Size separation method for absorption characterization in brown carbon: Application to an aged biomass burning sample

    NASA Astrophysics Data System (ADS)

    Di Lorenzo, Robert A.; Young, Cora J.

    2016-01-01

    The majority of brown carbon (BrC) in atmospheric aerosols is derived from biomass burning (BB) and is primarily composed of extremely low volatility organic carbons. We use two chromatographic methods to compare the contribution of large and small light-absorbing BrC components in aged BB aerosols with UV-vis absorbance detection: (1) size exclusion chromatography (SEC) and (2) reverse phase high-performance liquid chromatography. We observe no evidence of small molecule absorbers. Most BrC absorption arises from large molecular weight components (>1000 amu). This suggests that although small molecules may contribute to BrC absorption near the BB source, analyses of aerosol extracts should use methods selective to large molecular weight compounds because these species may be responsible for long-term BrC absorption. Further characterization with electrospray ionization mass spectrometry (MS) coupled to SEC demonstrates an underestimation of the molecular size determined through MS as compared to SEC.

  18. Ellipsometric analysis and optical absorption characterization of gallium phosphide nanoparticulate thin film

    NASA Astrophysics Data System (ADS)

    Zhang, Qi-Xian; Wei, Wen-Sheng; Ruan, Fang-Ping

    2011-04-01

    Gallium phosphide (GaP) nanoparticulate thin films were easily fabricated by colloidal suspension deposition via GaP nanoparticles dispersed in N,N-dimethylformamide. The microstructure of the film was performed by x-ray diffraction, high resolution transmission electron microscopy and field emission scanning electron microscopy. The film was further investigated by spectroscopic ellipsometry. After the model GaP+void|SiO2 was built and an effective medium approximation was adopted, the values of the refractive index n and the extinction coefficient k were calculated for the energy range of 0.75 eV-4.0 eV using the dispersion formula in DeltaPsi2 software. The absorption coefficient of the film was calculated from its k and its energy gaps were further estimated according to the Tauc equation, which were further verified by its fluorescence spectrum measurement. The structure and optical absorption properties of the nanoparticulate films are promising for their potential applications in hybrid solar cells.

  19. Preparation, spectroscopic characterization and energy transfer investigation of iron-chromium diffusion co-doped ZnSe for mid-IR laser applications

    NASA Astrophysics Data System (ADS)

    Wang, XiangYong; Chen, Zhe; Zhang, Lianhan; Jiang, Benxue; Xu, Min; Hong, Jiaqi; Wang, Yaqi; Zhang, Peixiong; Zhang, Long; Hang, Yin

    2016-04-01

    The spectroscopic characterization and energy transfer mechanism of iron-chromium co-doped ZnSe polycrystalline (Cr,Fe:ZnSe) were reported with dimension of 15 mm × 15 mm × 2 mm obtained by controlled post-growth thermal diffusion method. The infrared absorption is characterized by a strong broad-band centered at 1770 nm which can be attributed to the only spin-allowed transition 5T2 → 5E within the 3d4 shell of Cr2+ ions. Photoluminescence spectrum shows a relatively strong broad emission band centered at 4.1 μm with a width of 0.8 μm (FWHM) under 1770 nm excitation at room temperature and reveals effective Cr2+ → Fe2+ energy transfer process. Room temperature photoluminescence decay about 8 μs was measured. All the results indicate that Cr,Fe:ZnSe could achieve laser operation at 3.7-4.5 μm via Cr2+ → Fe2+ energy transfer using a more convenient laser pump source in the near IR region.

  20. Electrochemical, Spectroscopic, and Density Functional Theory Characterization of Redox Activity in Nickel-Substituted Azurin: A Model for Acetyl-CoA Synthase.

    PubMed

    Manesis, Anastasia C; Shafaat, Hannah S

    2015-08-17

    Nickel-containing enzymes are key players in global hydrogen, carbon dioxide, and methane cycles. Many of these enzymes rely on Ni(I) oxidation states in critical catalytic intermediates. However, due to the highly reactive nature of these species, their isolation within metalloenzymes has often proved elusive. In this report, we describe and characterize a model biological Ni(I) species that has been generated within the electron transfer protein, azurin. Replacement of the native copper cofactor with nickel is shown to preserve the redox activity of the protein. The Ni(II/I) couple is observed at -590 mV versus NHE, with an interfacial electron transfer rate of 70 s(-1). Chemical reduction of Ni(II)Az generates a stable species with strong absorption features at 350 nm and a highly anisotropic, axial EPR signal with principal g-values of 2.56 and 2.10. Density functional theory calculations provide insight into the electronic and geometric structure of the Ni(I) species, suggesting a trigonal planar coordination environment. The predicted spectroscopic features of this low-coordinate nickel site are in good agreement with the experimental data. Molecular orbital analysis suggests potential for both metal-centered and ligand-centered reactivity, highlighting the covalency of the metal-thiolate bond. Characterization of a stable Ni(I) species within a model protein has implications for understanding the mechanisms of complex enzymes, including acetyl coenzyme A synthase, and developing scaffolds for unique reactivity. PMID:26234790

  1. SPECTROSCOPIC AND ELECTROCHEMICAL CHARACTERIZATION OF IRON(II) AND 2,4-DINITROTOLUENE

    PubMed Central

    Brown, Kristopher; Doo, Hyungie; Makamba, Honest; Seo, Seong S.

    2016-01-01

    The objective of this work was the development of reliable methods to determine 2,4-dinitrotoluene, a precursor to explosives. A complex between Fe(II) ion and 2,4-dinitrotoluene was formed in solution and characterized by ultraviolet-visible absorption spectroscopy using Job’s plots and attenuated total reflection-Fourier transform infrared spectroscopy. Surface modification of glassy carbon electrodes were performed with iron nanoparticles via electrochemical reduction of iron(II). The modified electrode was employed for the determination of 2,4-dinitrotoluene. Scanning electron micrographs showed that the iron nanoparticles were incorporated on the surface of glassy carbon electrode. The electrochemical determination of 2,4-dinitrotoluene was performed by cyclic voltammetry using the modified electrode. The iron modified electrode produced larger reduction currents than the unmodified electrode for the same concentration of 2,4-dinitrotoluene. Concentrations of 2,4-dinitrotoluene as low as 10 parts per billion were determined using the modified electrode.

  2. Spectroscopic and structural characterization of reduced technetium species in acetate media

    SciTech Connect

    Mausolf, Edward; Poineau, Frederic; Droessler, Janelle; Czerwinski, Kenneth R.

    2011-11-17

    The reduction of ammonium pertechnetate by sodium borohydride in 0.1 M NaOH/glacial acetic acid has been studied. The reduction products (solids and solutions) have been characterized by UV-Visible spectroscopy, Scanning Electron Microscopy/Energy-dispersive X-ray emission spectroscopy (SEM/EDS), and X-ray absorption fine structure (XAFS) spectroscopy. UV-Visible spectra of the solution, after reduction, exhibit bands at 350 and 500 nm that have been attributed to the formation of polymeric Tc(IV) species. SEM/EDS on the solid (X-ray amorphous) indicates the absence of metallic Tc and the presence of oxygen. EXAFS measurements further indicate that the precipitate exhibits a [Tc({mu}-O){sub 2}Tc] core structure. XANES is consistent with the formation of Tc(III) and/or Tc(IV). Results infer that reduction of aqueous Tc(VII) by borohydride in the presence of acetic acid does not produce metallic Tc, but a mixture of various oxidation states of Tc near Tc(III) and Tc(IV).

  3. Different speciation for bromine in brown and red algae, revealed by in vivo X-ray absorption spectroscopic studies.

    PubMed

    Küpper, Frithjof C; Leblanc, Catherine; Meyer-Klaucke, Wolfram; Potin, Philippe; Feiters, Martin C

    2014-08-01

    Members of various algal lineages are known to be strong producers of atmospherically relevant halogen emissions, that is a consequence of their capability to store and metabolize halogens. This study uses a noninvasive, synchrotron-based technique, X-ray absorption spectroscopy, for addressing in vivo bromine speciation in the brown algae Ectocarpus siliculosus, Ascophyllum nodosum, and Fucus serratus, the red algae Gracilaria dura, G. gracilis, Chondrus crispus, Osmundea pinnatifida, Asparagopsis armata, Polysiphonia elongata, and Corallina officinalis, the diatom Thalassiosira rotula, the dinoflagellate Lingulodinium polyedrum and a natural phytoplankton sample. The results highlight a diversity of fundamentally different bromine storage modes: while most of the stramenopile representatives and the dinoflagellate store mostly bromide, there is evidence for Br incorporated in nonaromatic hydrocarbons in Thalassiosira. Red algae operate various organic bromine stores - including a possible precursor (by the haloform reaction) for bromoform in Asparagopsis and aromatically bound Br in Polysiphonia and Corallina. Large fractions of the bromine in the red algae G. dura and C. crispus and the brown alga F. serratus are present as Br(-) defects in solid KCl, similar to what was reported earlier for Laminaria parts. These results are discussed according to different defensive strategies that are used within algal taxa to cope with biotic or abiotic stresses. PMID:26988449

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

    SciTech Connect

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

    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. 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 λmax 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 μg 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.

  6. Synthesis and spectroscopic characterization of super-stable rhenium(V)porphyrins

    NASA Astrophysics Data System (ADS)

    Bichan, N. G.; Tyulyaeva, E. Yu.; Khodov, I. A.; Lomova, T. N.

    2014-03-01

    The preparation of rhenium(V) porphyrin complexes {μ-oxo-bis[(oxo)(5,10,15,20-tetraphenyl-21H,23H-porphinato)rhenium(V)] [OReTPP]2O (1), (oxo)(phenoxo)(2,3,7,8,12,13,17,18-octaethyl-5-monophenyl-21H,23H-porphinato)rhenium(V) ORe(PhO)MPOEP (2), (cloro)(oxo)(2,3,7,8,12,13,17,18-octaethyl-5,15-diphenyl-21H,23H-porphinato)rhenium(V) ORe(Cl)5,15DPOEP (4), and (oxo)(phenoxo)(2,3,7,8,12,13,17,18-octaethyl-21H,23H-porphinato)rhenium(V) ORe(PhO)OEP (5)} by the interaction of H2ReCl6 with corresponding porphyrin in boiling phenol is described. (Cloro)(oxo)(2,3,7,8,12,13,17,18-octaethyl-5-monophenyl-21H,23H-porphinato)rhenium(V) ORe(Cl)MPOEP (3) and (oxo)(chloro)(2,3,7,8,12,13,17,18-octaethyl-21H,23H-porphinato)rhenium(V) ORe(Cl)OEP (6) have been prepared by the reaction of axial-ligand substitution from (2) and (5), respectively. Compounds (2-4) were newly synthesized. Characterization of the compounds (1-6) reported herein was made mainly by UV-Visible, IR, 1Н NMR, 1H1H 2D COSY, 1H1H 2D DOSY, 1H1H 2D ROESY, 1H1H 2D TOCSY spectroscopic techniques and elemental analysis. The stability of the complexes in solutions when exposed to strong acids at the presence of atmospheric oxygen has been estimated. Compounds (2-4) and (6) show them super-stable since they do not undergo dissociation along MN bonds in concentrated H2SO4 under heating up to 363 K. Compounds (3) and (4) undergo one-electron oxidation to form stable π-cation radicals ORe(HSO)P under these conditions. The products of the reaction between all studied porphyrins and concentrated H2SO4 were isolated in CHCl3 by reprecipitation onto ice and proved to be rhenium(V) complexes ORe(HSO4)P.

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

    PubMed

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

    2015-06-15

    A single crystal of 3,4-dihydroxybenzylidene isonicotinylhydrazone, HBINH, has been grown and solved by X-ray crystallography. The VO(2+), Zr(4+), Co(2+), Ni(2+), Cu(2+), Zn(2+), Cd(2+), Hg(2+) and Pd(2+) 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 (OCNH) 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 VO(2+) 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. PMID:25791887

  8. 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.

  9. Characterizing trace metal impurities in optical waveguide materials using x-ray absorption

    SciTech Connect

    Citrin, P.H.; Northrup, P.A.; Atkins, R.M.; Niu, L.; Marcus, M.A.; Jacobson, D.C.; Glodis, P.F.

    1998-12-31

    X-ray absorption measurements are described for identifying metal impurities in silica preforms, the rod-like starting materials from which hair-like optical fibers are drawn. The results demonstrate the effectiveness of this approach as a non-destructive, quantitative, element-selective, position-sensitive, and chemical-state-specific means for characterizing transition metals in the concentration regime of parts per billion.

  10. 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.

  11. 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 σ2 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 σ2 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

  12. Calibration method for spectroscopic systems

    DOEpatents

    Sandison, D.R.

    1998-11-17

    Calibration spots of optically-characterized material placed in the field of view of a spectroscopic system allow calibration of the spectroscopic system. Response from the calibration spots is measured and used to calibrate for varying spectroscopic system operating parameters. The accurate calibration achieved allows quantitative spectroscopic analysis of responses taken at different times, different excitation conditions, and of different targets. 3 figs.

  13. Calibration method for spectroscopic systems

    DOEpatents

    Sandison, David R.

    1998-01-01

    Calibration spots of optically-characterized material placed in the field of view of a spectroscopic system allow calibration of the spectroscopic system. Response from the calibration spots is measured and used to calibrate for varying spectroscopic system operating parameters. The accurate calibration achieved allows quantitative spectroscopic analysis of responses taken at different times, different excitation conditions, and of different targets.

  14. Mineralogical characterization of Los Escullos (Cabo de Gata) using spectroscopic techniques

    NASA Astrophysics Data System (ADS)

    Rull, F.; Klingelhöfer, G.; Venegas, G.; Medina, J.; Martínez-Frías, J.

    2012-09-01

    In this work a detailed mineral spectroscopic analysis has been performed in the area of Los Escullos, wich is of the great astrobiological interest. Spectra were taken in-situ using portable Raman, LIBS and Mössbauer instruments and complementary data were also obtained at the laboratory using XRD and IR.

  15. Spectroscopic characterization of dissolved organic matter derived from different biochars and their polycylic aromatic hydrocarbons (PAHs) binding affinity.

    PubMed

    Tang, Jianfeng; Li, Xinhu; Luo, Yan; Li, Gang; Khan, Sardar

    2016-06-01

    In recent years, biochar has received a great attention due to its high application in different sectors of environment. The feasibility of biochar applications is depended on its physical and chemical properties and biochar-derived dissolved organic matter (DOM) characteristics. This study was conducted to investigate the spectroscopic characteristics of biochar-derived DOM and its binding capacity of hydrophobic organic chemicals (HOCs). DOM solutions were isolated from five different biochars prepared through pyrolysis and analyzed for dissolved organic carbon (DOC) contents. The optical analysis with UV-visible absorption and excitation-emission matrix (EEM) fluorescence spectroscopes and DOC water distribution coefficient (KDOC) were calculated in the presence of PAHs and DOM. The DOC contents and the estimated aromaticity (SUVA254) were different for selected biochars. The DOM derived from soybean straw biochar (SBBC) showed the highest DOC contents followed by rice straw biochar (RSBC). The SBBC and RSBC peak position in the fluorescence excitation/emission matrix at longer wavelength corresponded to the peak position of other three biochars indicating that SBBC and RSBC had relatively higher degree of humification. This was well correlated with the observed KDOC values, suggesting that the KDOC value(')s dominant factor was the degree of biochar-derived DOM humification. The results of this study indicate that the optical analysis may provide valuable information regarding the characteristics of biochar-derived DOM and its application as environmental amendments for minimization of toxic organic compounds. PMID:26994600

  16. Vibrational spectroscopic methods to characterize the bionanoparticles originating from newly developed self-forming synthetic PEGylated lipids (QuSomes)

    NASA Astrophysics Data System (ADS)

    Bista, Rajan K.; Bruch, Reinhard F.; Covington, Aaron M.

    2011-03-01

    Vibrational spectroscopy has been used to elucidate the temperature dependence of structural and conformational changes in lipids and liposomes. In this work, the thermal properties of lipid-based nanovesicles originating from a newly developed self-forming synthetic PEGylated lipids has been investigated by variable-temperature Fourier-transform infrared (FTIR) absorption and Raman spectroscopic methods. Thermally-induced changes in infrared and Raman spectra of these artificial lipid based nanovesicles composed of 1,2-dimyristoyl-rac-glycerol-3-dodecaethylene glycol (GDM-12) and 1,2-distearoyl-rac-glycerol-3-triicosaethylene glycol (GDS-23) were acquired by using a thin layered FTIR spectrometer in conjunction with a unique custom built temperature-controlled demountable liquid cell and variable-temperature controlled Raman microscope, respectively. The lipids under consideration have long hydrophobic acyl chains and contain various units of hydrophilic polyethylene glycol headgroups. In contrast to conventional phospholipids, this new kind of lipid is forming liposomes or nanovesicles spontaneously upon hydration, without supplying external activation energy. We have found that the thermal stability of such PEGylated lipids and nanovesicles differs greatly depending upon the acyl chain-lengths as well as associated head group units. However, the thermal behavior observed from both spectroscopic vibrational techniques are in good agreement.

  17. Spectroscopic Characterization and Reactivity of Triplet and Quintet Iron(IV) Oxo Complexes in the Gas Phase

    PubMed Central

    Andris, Erik; Jašík, Juraj; Gómez, Laura

    2016-01-01

    Abstract Closely structurally related triplet and quintet iron(IV) oxo complexes with a tetradentate aminopyridine ligand were generated in the gas phase, spectroscopically characterized, and their reactivities in hydrogen‐transfer and oxygen‐transfer reactions were compared. The spin states were unambiguously assigned based on helium tagging infrared photodissociation (IRPD) spectra of the mass‐selected iron complexes. It is shown that the stretching vibrations of the nitrate counterion can be used as a spectral marker of the central iron spin state. PMID:26878833

  18. 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.

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

    PubMed

    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 (1)H 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. PMID:22100733

  20. Spectroscopic Characterization and Reactivity of Triplet and Quintet Iron(IV) Oxo Complexes in the Gas Phase.

    PubMed

    Andris, Erik; Jašík, Juraj; Gómez, Laura; Costas, Miquel; Roithová, Jana

    2016-03-01

    Closely structurally related triplet and quintet iron(IV) oxo complexes with a tetradentate aminopyridine ligand were generated in the gas phase, spectroscopically characterized, and their reactivities in hydrogen-transfer and oxygen-transfer reactions were compared. The spin states were unambiguously assigned based on helium tagging infrared photodissociation (IRPD) spectra of the mass-selected iron complexes. It is shown that the stretching vibrations of the nitrate counterion can be used as a spectral marker of the central iron spin state. PMID:26878833

  1. Purification and spectroscopic characterization of photosystem II reaction center complexes isolated with or without Triton X-100.

    PubMed

    Eijckelhoff, C; van Roon, H; Groot, M L; van Grondelle, R; Dekker, J P

    1996-10-01

    The pigment composition of the isolated photosystem II reaction center complex in its most stable and pure form currently is a matter of considerable debate. In this contribution, we present a new method based on a combination of gel filtration chromatography and diode array detection to analyze the composition of photosystem II reaction center preparations. We show that the method is very sensitive for the detection of contaminants such as the core antenna protein CP47, pigment-free and denatured reaction center proteins, and unbound chlorophyll and pheophytin molecules. We also present a method by which the photosystem II reaction center complex is highly purified without using Triton X-100, and we show that in this preparation the contamination with CP47 is less than 0.1%. The results strongly indicate that the photosystem II reaction center complex in its most stable and pure form binds six chlorophyll a, two pheophytin a, and two beta-carotene molecules and that the main effect of Triton X-100 is the extraction of beta-carotene from the complex. Analysis of 4 K absorption and emission spectra indicates that the spectroscopic properties of this preparation are similar to those obtained by a short Triton X-100 treatment. In contrast, preparations obtained by long Triton X-100 treatment show decreased absorption of the shoulder at 684 nm in the 4 K absorption spectrum and an increased number of pigments that trap excitation energy at very low temperatures. We conclude that the 684 nm shoulder in the 4 K absorption spectrum should at least in part be attributed to the primary electron donor of photosystem II. PMID:8841130

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

    SciTech Connect

    Wang, Hsiu-Wen; Bishop, David

    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.

  3. 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.

  4. 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.

  5. Spectroscopic ellipsometry characterization of microwave CVD grown silicon nanoparticles embedded in a silicon nitride matrix

    NASA Astrophysics Data System (ADS)

    Keita, A.-S.; Naciri, A. En; Delachat, F.; Carrada, M.; Ferblantier, G.; Slaoui, A.

    2009-11-01

    Plasma Enhanced Vapour Deposition (PECVD) is used to elaborate silicon nanoparticles (np-Si) embedded in silicon nitride (Si3N4) layers. The samples have been produced for various NH3 flows. The np-Si dielectric function (DF) have been determined by spectroscopic ellipsometry (SE) in the wavelength range from 210 nm to 880 nm. Thanks to ellipsometric modeling it has been possible to study the np-Si physical properties.

  6. Synthesis, spectroscopic characterization and quantum chemical computational studies of (S)-N-benzyl-1-phenyl-5-(pyridin-2-yl)-pent-4-yn-2-amine

    NASA Astrophysics Data System (ADS)

    Kose, Etem; Atac, Ahmet; Karabacak, Mehmet; Karaca, Caglar; Eskici, Mustafa; Karanfil, Abdullah

    2012-11-01

    The synthesis and characterization of a novel compound (S)-N-benzyl-1-phenyl-5-(pyridin-2-yl)-pent-4-yn-2-amine (abbreviated as BPPPYA) was presented in this study. The spectroscopic properties of the compound were investigated by FT-IR, NMR and UV spectroscopy experimentally and theoretically. The molecular geometry and vibrational frequencies of the BPPPYA in the ground state were calculated by using density functional theory (DFT) B3LYP method invoking 6-311++G(d,p) basis set. The geometry of the BPPPYA was fully optimized, vibrational spectra were calculated and fundamental vibrations were assigned on the basis of the total energy distribution (TED) of the vibrational modes, calculated with scaled quantum mechanics (SQM) method and PQS program. The results of the energy and oscillator strength calculated by time-dependent density functional theory (TD-DFT) and CIS approach complement with the experimental findings. Total and partial density of state (TDOS and PDOS) and also overlap population density of state (COOP or OPDOS) diagrams analysis were presented. The theoretical NMR chemical shifts (1H and 13C) complement with experimentally measured ones. The dipole moment, linear polarizability and first hyperpolarizability values were also computed. The linear polarizabilities and first hyper polarizabilities of the studied molecule indicate that the compound is a good candidate of nonlinear optical materials. The calculated vibrational wavenumbers, absorption wavelengths and chemical shifts showed the best agreement with the experimental results.

  7. Unusual ionospheric absorption characterizing energetic electron precipitation into the South Atlantic Magnetic Anomaly

    NASA Astrophysics Data System (ADS)

    Nishino, M.; Makita, K.; Yumoto, K.; Rodrigues, F. S.; Schuch, N. J.; Abdu, M. A.

    2002-09-01

    An imaging riometer (IRIS) was installed newly in the southern area of Brazil in order to investigate precipitation of energetic electrons into the South Atlantic Magnetic Anomaly (SAMA). An unusual ionospheric absorption event was observed in the nighttime (~20 h LT) near the maximum depression (Dst ~ -164 nT) and the following positive excursion during the strong geomagnetic storm on September 22-23, 1999. The unusual absorption that has short time-duration of 30-40 min shows two characteristic features: One feature is a sheet structure of the absorption appearing at the high-latitude part of the IRIS field-of-view, showing an eastward drift from the western to the eastern parts and subsequent retreat to the western part. Another feature is a meridionally elongated structure with a narrow longitudinal width (100-150 km) appearing from the zenith to the low-latitude part of the IRIS field-of-view, enhanced simultaneously with the sheet absorption, and is subsequently changed to a localized structure. These features likely characterize precipitation of energetic electrons into the SAMA ionosphere, associated with substorm occurrences during the strong geomagnetic storm. From the eastward drift (~250 m/s) of the sheet absorption, precipitating electrons are estimated to be ~20 keV energies, assuming plasmaspheric electric fields of 1.8 mV/m. However, no ionospheric effect due to the precipitating electrons was definitely detected by the ionosonde measurements at Cachoeira Paulista, separated eastward by about 1000 km from the IRIS station.

  8. Electrochemical Kinetics and X-ray Absorption Spectroscopic Investigations of Oxygen Reduction on Chalcogen-Modified Ruthenium Catalysts in Alkaline Media

    SciTech Connect

    N Ramaswamy; R Allen; S Mukerjee; Y

    2011-12-31

    The oxygen reduction reaction (ORR) in alkaline media has been investigated on chalcogen-modified ruthenium nanoparticles (Ru/C, Se/Ru/C, Se/RuMo/C, S/Ru/C, S/RuMo/C) synthesized in-house via aqueous routes. In acidic medium, it is well known that modification by a chalcogen prevents the oxidation of the underlying transition-metal (Ru) surface, thereby promoting direct molecular O{sub 2} adsorption on the Ru metal. On an unmodified Ru catalyst in alkaline media, the surface oxides on Ru mediate the 2e{sup -} reduction of molecular O{sub 2} to a stable peroxide anion (HO{sub 2}{sup -}) intermediate via an outer-sphere electron-transfer mechanism. This increases the activity of HO{sub 2}{sup -} near the electrode surface and decreases the overpotential for ORR by effectively carrying out the reduction of HO{sub 2}{sup -} to OH{sup -} at the oxide-free ruthenium metal site. An increase in ORR activity of Ru is observed by modification with a chalcogen; however, the increase is not as significant as observed in acidic media. Ternary additives, such as Mo, were found to significantly improve the stability of the chalcogen-modified catalysts. Detailed investigations of the ORR activity of this class of catalyst have been carried out in alkaline media along with comparisons to acidic media wherever necessary. A combination of electrochemical and X-ray absorption spectroscopic (EXAFS, XANES, {Delta}{mu}) studies has been performed in order to understand the structure/property relationships of these catalysts within the context of ORR in alkaline electrolytes.

  9. The WO3/WS2 nanostructures: Preparation, characterization and optical absorption properties

    NASA Astrophysics Data System (ADS)

    Cao, Shixiu; Zhao, Cong; Han, Tao; Peng, Lingling

    2016-07-01

    The WO3/WS2 nanostructures were successfully prepared using a two-step hydrothermal/gas phase method. The physical properties of the nanostructures were characterized using XRD, SEM, TEM, UV-visible spectroscopy. The WO3/WS2 nanostructures obtained were coexistence of WO3 and WS2 in the same particle. The WO3/WS2 nanostructures contained a wide and intensive absorption in the UV-visible light region of 245-750 nm, which showed that the WO3/WS2 nanostructures may have a potential application as an UV-visible photocatalyst.

  10. Ghanaian cocoa bean fermentation characterized by spectroscopic and chromatographic methods and chemometrics.

    PubMed

    Aculey, Patrick C; Snitkjaer, Pia; Owusu, Margaret; Bassompiere, Marc; Takrama, Jemmy; Nørgaard, Lars; Petersen, Mikael A; Nielsen, Dennis S

    2010-08-01

    Export of cocoa beans is of great economic importance in Ghana and several other tropical countries. Raw cocoa has an astringent, unpleasant taste, and flavor, and has to be fermented, dried, and roasted to obtain the characteristic cocoa flavor and taste. In an attempt to obtain a deeper understanding of the changes in the cocoa beans during fermentation and investigate the possibility of future development of objective methods for assessing the degree of fermentation, a novel combination of methods including cut test, colorimetry, fluorescence spectroscopy, NIR spectroscopy, and GC-MS evaluated by chemometric methods was used to examine cocoa beans sampled at different durations of fermentation and samples representing fully fermented and dried beans from all cocoa growing regions of Ghana. Using colorimetry it was found that samples moved towards higher a* and b* values as fermentation progressed. Furthermore, the degree of fermentation could, in general, be well described by the spectroscopic methods used. In addition, it was possible to link analysis of volatile compounds with predictions of fermentation time. Fermented and dried cocoa beans from the Volta and the Western regions clustered separately in the score plots based on colorimetric, fluorescence, NIR, and GC-MS indicating regional differences in the composition of Ghanaian cocoa beans. The study demonstrates the potential of colorimetry and spectroscopic methods as valuable tools for determining the fermentation degree of cocoa beans. Using GC-MS it was possible to demonstrate the formation of several important aroma compounds such 2-phenylethyl acetate, propionic acid, and acetoin and the breakdown of others like diacetyl during fermentation. Practical Application: The present study demonstrates the potential of using colorimetry and spectroscopic methods as objective methods for determining cocoa bean quality along the processing chain. Development of objective methods for determining cocoa bean quality will be of great importance for quality insurance within the fields of cocoa processing and raw material control in chocolate producing companies. PMID:20722952

  11. Multiparametric Characterization of Grade 2 Glioma Subtypes Using Magnetic Resonance Spectroscopic, Perfusion, and Diffusion Imaging1

    PubMed Central

    Bian, Wei; Khayal, Inas S; Lupo, Janine M; McGue, Colleen; Vandenberg, Scott; Lamborn, Kathleen R; Chang, Susan M; Cha, Soonmee; Nelson, Sarah J

    2009-01-01

    BACKGROUND AND PURPOSE: The purpose of this study was to derive quantitative parameters from magnetic resonance (MR) spectroscopic, perfusion, and diffusion imaging of grade 2 gliomas according to the World Health Organization and to investigate how these multiple imaging modalities can contribute to evaluating their histologic subtypes and spatial characteristics. MATERIALS AND METHODS: MR spectroscopic, perfusion, and diffusion images from 56 patients with newly diagnosed grade 2 glioma (24 oligodendrogliomas, 18 astrocytomas, and 14 oligoastrocytomas) were retrospectively studied. Metabolite intensities, relative cerebral blood volume (rCBV), and apparent diffusion coefficient (ADC) were statistically evaluated. RESULTS: The 75th percentile rCBV and median ADC were significantly different between oligodendrogliomas and astrocytomas (P < .0001) and between oligodendrogliomas and oligoastrocytomas (P < .001). Logistic regression analysis identified both 75th percentile rCBV and median ADC as significant variables in the differentiation of oligodendrogliomas from astrocytomas and oligoastrocytomas. Group differences in metabolite intensities were not significant, but there was a much larger variation in the volumes and maximum values of metabolic abnormalities for patients with oligodendroglioma compared with the other tumor subtypes. CONCLUSIONS: Perfusion and diffusion imaging provide quantitative MR parameters that can help to differentiate grade 2 oligodendrogliomas from grade 2 astrocytomas and oligoastrocytomas. The large variations in the magnitude and spatial extent of the metabolic lesions between patients and the fact that their values are not correlated with the other imaging parameters indicate that MR spectroscopic imaging may provide complementary information that is helpful in targeting therapy, evaluating residual disease, and assessing response to therapy. PMID:19956389

  12. Spectroscopic characterization of micro- and nanoparticle suspensions with size dynamics in plasmas

    NASA Astrophysics Data System (ADS)

    Mitic, S.; Pustylnik, M. Y.; Kova?evi?, E.; Berndt, J.; Boufendi, L.; Morfill, G. E.

    2012-08-01

    Mitic et al (2011 Opt. Lett. 36 3699) proposed a spectroscopic method of the in situ measurement of the size and optical properties of spherical micro- and nanoparticles with monotonically variable size. The method requires three optical channels: one for the illumination of a particle suspension by white light and two for the measurements of the spectra of scattered light. This allows one to determine the optical properties of the particles in a wide spectral range. In this work an extended description of the experimental setup and data analysis technique are given. Performance of the method is illustrated on particle suspensions in plasmas, exhibiting increase and decrease of particle size.

  13. Spectroscopic characterization of genetically modified flax fibres enhanced with poly-3-hydroxybutyric acid

    NASA Astrophysics Data System (ADS)

    Wróbel-Kwiatkowska, Magdalena; Szopa, Jan; Dymińska, Lucyna; Mączka, Mirosław; Hanuza, Jerzy

    2009-02-01

    Genetically modified flax fibres, derived from transgenic flax with expression of three bacterial genes necessary for synthesis of poly-3-hydroxybutyric acid (PHB), have been analysed. These transgenic flaxes, enhanced with different amount of the PHB, have been studied by FT-IR spectroscopy. The integral intensities of the IR bands have been used for estimation of the chemical content of the normal and transgenic flaxes as well as the differences between the natural and genetically modified flax fibres. The spectroscopic data were compared to those obtained from chemical analysis of flax fibres.

  14. 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.

  15. Cyanide/isocyanide abundances in the interstellar medium - I. Theoretical spectroscopic characterization

    NASA Astrophysics Data System (ADS)

    Senent, M. L.; Dumouchel, F.; Lique, F.

    2012-02-01

    Modelling molecular abundances in the interstellar medium requires accurate molecular data. In this work, structural and spectroscopic properties of a series of metal cyanides/isocyanide species containing Na, Mg, Al and Si are calculated and compared using highly correlated ab initio calculations. The metal substitution effect on molecular properties is discussed. Isomerization pathways and transitions states are detailed. NaCN shows three isomeric structures, one T shaped and two linear forms, whereas the remaining compounds display two linear minimum energy geometries. For the first time, NaCN secondary minima are described. Second-order perturbation theory spectroscopic parameters are determined from an anharmonic RCCSD(T)/aug-cc-pV5Z force field. Very accurate rotational constants are calculated using a complete basis set and taking into account vibrational effects and the structure variation with core electron correlation. For l-SiCN and l-SiNC, spin-orbit parameters are also provided. Present theoretical results are compared with available experimental data attaining a good agreement.

  16. Biochemical, Mechanistic, and Spectroscopic Characterization of Metallo-β-lactamase VIM-2

    PubMed Central

    2015-01-01

    This study examines metal binding to metallo-β-lactamase VIM-2, demonstrating the first successful preparation of a Co(II)-substituted VIM-2 analogue. Spectroscopic studies of the half- and fully metal loaded enzymes show that both Zn(II) and Co(II) bind cooperatively, where the major species present, regardless of stoichiometry, are apo- and di-Zn (or di-Co) enzymes. We determined the di-Zn VIM-2 structure to a resolution of 1.55 Å, and this structure supports results from spectroscopic studies. Kinetics, both steady-state and pre-steady-state, show that VIM-2 utilizes a mechanism that proceeds through a very short-lived anionic intermediate when chromacef is used as the substrate. Comparison with other B1 enzymes shows that those that bind Zn(II) cooperatively are better poised to protonate the intermediate on its formation, compared to those that bind Zn(II) non-cooperatively, which uniformly build up substantial amounts of the intermediate. PMID:25356958

  17. Biochemical and spectroscopic characterization of the blue-green photoreceptor in Halobacterium halobium

    SciTech Connect

    Scherrer, P.; McGinnis, K.; Bogomolni, R.A.

    1987-01-01

    Spectroscopic evidence indicates the presence of a second sensory receptor sR-II in Halobacterium halobium, which causes a repellent response to blue-green light. Reactions with hydroxylamine and NaCNBH/sub 3/ and reconstitution of the bleached pigment with retinal show that it is very similar to the other retinylidene pigments bacteriorhodopsin, halorhodopsin, and especially the earlier-discovered phototaxis receptor, sensory rhodopsin, renamed sR-I587. The second sensory receptor, sR-II480, has an absorbance maximum at 480 nm and undergoes a cyclic photoreaction with a half-time of approximately 200 msec. Its predominant photocycle intermediate absorbs maximally near 360 nm. The receptor can be detected spectroscopically in the presence of sR-I587 and quantitated through its transient response to 450-nm excitation. It is selectively bleached by low hydroxylamine concentrations that are insufficient to bleach sR-I587 significantly. Its photochemical and phototactic activities can be restored by addition of retinal. The mobility of the receptor, on NaDodSO4/polyacrylamide gels, was similar or identical to that of sR-I587 and slightly faster than bacteriorhodopsin, yielding an apparent molecular mass of 23-24 kDa.

  18. Biochemical, Mechanistic, and Spectroscopic Characterization of Metallo-β-lactamase VIM-2

    SciTech Connect

    Aitha, Mahesh; Marts, Amy R.; Bergstrom, Alex; Møller, Abraham Jon; Moritz, Lindsay; Turner, Lucien; Nix, Jay C.; Bonomo, Robert A.; Page, Richard C.; Tierney, David L.; Crowder, Michael W.

    2014-11-25

    Our study examines metal binding to metallo-β-lactamase VIM-2, demonstrating the first successful preparation of a Co(II)-substituted VIM-2 analogue. Spectroscopic studies of the half- and fully metal loaded enzymes show that both Zn(II) and Co(II) bind cooperatively, where the major species present, regardless of stoichiometry, are apo- and di-Zn (or di-Co) enzymes. We also determined the di-Zn VIM-2 structure to a resolution of 1.55 Å, and this structure supports results from spectroscopic studies. Kinetics, both steady-state and pre-steady-state, show that VIM-2 utilizes a mechanism that proceeds through a very short-lived anionic intermediate when chromacef is used as the substrate. Comparison with other B1 enzymes shows that those that bind Zn(II) cooperatively are better poised to protonate the intermediate on its formation, compared to those that bind Zn(II) non-cooperatively, which uniformly build up substantial amounts of the intermediate.

  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.

    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. Characterization of fine resolution field spectrometers using solar Fraunhofer lines and atmospheric absorption features.

    PubMed

    Meroni, Michele; Busetto, Lorenzo; Guanter, Luis; Cogliati, Sergio; Crosta, Giovanni Franco; Migliavacca, Mirco; Panigada, Cinzia; Rossini, Micol; Colombo, Roberto

    2010-05-20

    The accurate spectral characterization of high-resolution spectrometers is required for correctly computing, interpreting, and comparing radiance and reflectance spectra acquired at different times or by different instruments. In this paper, we describe an algorithm for the spectral characterization of field spectrometer data using sharp atmospheric or solar absorption features present in the measured data. The algorithm retrieves systematic shifts in channel position and actual full width at half-maximum (FWHM) of the instrument by comparing data acquired during standard field spectroscopy measurement operations with a reference irradiance spectrum modeled with the MODTRAN4 radiative transfer code. Measurements from four different field spectrometers with spectral resolutions ranging from 0.05 to 3.5nm are processed and the results validated against laboratory calibration. An accurate retrieval of channel position and FWHM has been achieved, with an average error smaller than the instrument spectral sampling interval. PMID:20490248

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

    NASA Astrophysics Data System (ADS)

    Piz, A. Montaner; Tan, J. L.; Agramunt, J.; Algora, A.; Guadilla, V.; Marn, E.; Rice, S.; Rubio, B.

    2013-06-01

    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.

  2. Spectroscopic characterization of cysteine and methionine using density functional theory method

    NASA Astrophysics Data System (ADS)

    Naganathappa, Mahadevappa; Chaudhari, Ajay

    2015-05-01

    The present study reports theoretical infrared and electronic absorption spectra of neutral cysteine and methionine molecules in gas phase, their ions and in water ice. We also report infrared and electronic absorption spectra of nitrogen-substituted (in place of sulfur atom) cysteine and methionine. The geometrical parameters, dipole moments, rotational and centrifugal distortional constants for these molecules are reported at B3LYP/6-311++g(d,p) level of theory. A large change in vibrational and electronic absorption spectra has been observed upon ionization of cysteine and methionine. Calculated vibrational frequencies are compared with the available experimental frequencies for the neutral cysteine and methionine in gas phase. An influence of water ice on vibrational frequencies of neutral cysteine and methionine is studied using integral equation formalism polarizable continuum model (IEFPCM) at the same level of theory. Time Dependent Density Functional Theory (TDDFT) approach has been adapted to calculate the electronic absorption spectra of these molecules. The intense lines are suggested in order to detect these molecules in space.

  3. Dehydration experiments on natural omphacites: qualitative and quantitative characterization by various spectroscopic methods

    NASA Astrophysics Data System (ADS)

    Koch-Müller, M.; Abs-Wurmbach, I.; Rhede, D.; Kahlenberg, V.; Matsyuk, S.

    2007-11-01

    A series of natural omphacites from a wide range of P, T occurrences were investigated by electron microprobe (EMP), infrared (IR)-, Mössbauer (MS)- and optical spectroscopy in the UV/VIS spectral range (UV/VIS), secondary ion mass spectrometry (SIMS) and single crystal structure refinement by X-ray diffraction (XRD) to study the influence of hydrogen loss on valence state and site occupancies of iron. In accordance with literature data we found Fe2+ at M1 as well as at M2, and in a first approach assigned Fe3+ to M1, as indicated by MS and XRD results. Hydrogen content of three of our omphacite samples were measured by SIMS. In combination with IR spectroscopy we determined an absorption coefficient: ɛ i,tot = 65,000 ± 3,000 lmolH2O -1 cm-2. Using this new ɛ i,tot value, we obtained water concentrations ranging from 60 to 700 ppm H2O (by weight). Hydrogen loss was simulated by stepwise heating the most water rich samples in air up to 800°C. After heat treatment the samples were analyzed again by IR, MS, UV/VIS, and XRD. Depending on the type of the OH defect, the grade of dehydration with increasing temperature is significantly different. In samples relatively poor in Fe3+ (<0.1 Fe3+ pfu), hydrogen associated with vacancies at M2 (OH bands around 3,450 cm-1) starts to leave the structure at about 550°C and is completely gone at 780°C. Hydrogen associated with Al3+ at the tetrahedral site (OH bands around 3,525 cm-1, Koch-Müller et al., Am Mineral, 89:921-931, 2004) remains completely unaffected by heat treatment up to 700°C. But all hydrogen vanished at about 775°C. However, this is different for a more Fe3+-rich sample (0.2 Fe3+ pfu). Its IR spectrum is characterized by a very intense OH band at 3,515 cm-1 plus shoulder at 3,450 cm-1. We assign this intense high-energy band to vibrations of an OH dipole associated with Fe3+ at M1 and a vacancy either at M1 or M2. OH release during heating is positively correlated with decrease in Fe2+ and combined with increase in Fe3+. That dehydration is correlated with oxidation of Fe2+ is indirectly confirmed by annealing of one sample in a gas mixing furnace at 700°C under reducing conditions keeping almost constant OH- content and giving no indication of Fe2+-oxidation. Obtained data indicate that in samples with a relatively high concentration of Fe2+ at M2 and low-water concentrations, i.e., at a ratio of Fe2+ M2/H > 10 dehydration occurs by iron oxidation of Fe2+ exclusively at the M2 site following the reaction: {left[ {{text{Fe}}^{{{text{2 + [ M2]}}}}{text{OH}}^{ - } } right]} = {left[ {{text{Fe}}^{{{text{3 + [ M2]}}}} {text{O}}^{{{text{2}} - }} } right]} + {text{1/2}}{text{H}}_{{text{2}}} \\uparrow . In samples having relatively low concentration of Fe2+ at M2 but high-water concentrations, i.e., ratio of Fe2+ M2/H < 5.0 dehydration occurs through oxidation of Fe2+ at M1.

  4. In situ x-ray absorption spectroscopic study of the Li[Ni1/3Co1/3Mn1/3]O2 cathode material

    NASA Astrophysics Data System (ADS)

    Deb, Aniruddha; Bergmann, Uwe; Cramer, Stephen P.; Cairns, Elton J.

    2005-06-01

    The layered LiNi1/3Co1/3Mn1/3O2 system has recently drawn considerable interest for use as a cathode material for rechargeable lithium batteries. In order to investigate the charge-compensation mechanism and structural perturbations occurring in the system during cycling, in situ x-ray absorption spectroscopy (XAS) measurements were performed utilizing a novel electrochemical in situ cell specifically designed for long term x-ray experiments. The cell was cycled at a moderate rate through a typical Li-ion battery operating voltage range (2.9-4.7 V). The electrode contained 2.025 mg of LiNi1/3Co1/3Mn1/3O2 on a 25-μm Al foil and had an area of 0.79cm2. The x-ray absorption spectroscopy (XAS) measurements were performed at the Ni, Co, and the Mn edges at different states of charge (SOC) during cycling, revealing details about the response of the cathode to Li insertion and extraction processes. Changes of bond distance and coordination number of Ni, Co, and Mn absorbers as a function of the state of charge of the material were obtained from the extended x-ray-absorption fine structure (EXAFS) region of the spectra. The x-ray absorption near-edge structure (XANES) region was studied in order to characterize the oxidation states of the 3d transition metals during cycling (Li extraction/insertion). We found that oxidation states of transition metals in LiNi1/3Co1/3Mn1/3O2 are Ni2+, Co3+, and Mn4+, whereas during charging Ni2+ is oxidized to Ni4+ through an intermediate stage of Ni3+,Co3+ is oxidized almost to Co4+ and, utilizing Faraday's calculation and XAS results, the Co was found to be at Co3.92+ at the end of the charge, while Mn was found to be electrochemically inactive and remains as Mn4+. The EXAFS data that were collected continuously during cycling revealed details about the response of the cathode to Li insertion and extraction. These measurements on the LiNi1/3Co1/3Mn1/3O2 cathode confirmed that the material retains its symmetry and good structural short-range order leading to superior cycling.

  5. An Empirical Characterization of Extended Cool Gas Around Galaxies Using Mg II Absorption Features

    NASA Astrophysics Data System (ADS)

    Chen, Hsiao-Wen; Helsby, Jennifer E.; Gauthier, Jean-René; Shectman, Stephen A.; Thompson, Ian B.; Tinker, Jeremy L.

    2010-05-01

    We report results from a survey of Mg II absorbers in the spectra of background quasi-stellar objects (QSOs) that are within close angular distances to a foreground galaxy at z < 0.5, using the Magellan Echellette Spectrograph. We have established a spectroscopic sample of 94 galaxies at a median redshift of langzrang = 0.24 in fields around 70 distant background QSOs (z QSO > 0.6), 71 of which are in an "isolated" environment with no known companions and located at ρ <~ 120 h -1 kpc from the line of sight of a background QSO. The rest-frame absolute B-band magnitudes span a range from MB - 5log h = -16.4 to MB - 5log h = -21.4 and rest-frame BAB - RAB colors range from BAB - RAB ≈ 0 to BAB - RAB ≈ 1.5. Of these "isolated" galaxies, we find that 47 have corresponding Mg II absorbers in the spectra of background QSOs and rest-frame absorption equivalent width Wr (2796) = 0.1-2.34 Å, and 24 do not give rise to Mg II absorption to sensitive upper limits. Our analysis shows that (1) Wr (2796) declines with increasing distance from "isolated" galaxies but shows no clear trend in "group" environments; (2) more luminous galaxies possess more extended Mg II absorbing halos with the gaseous radius scaled by B-band luminosity according to R gas = 75 × (LB /L B * )(0.35 ± 0.03) h -1 kpc; (3) there is little dependence between the observed absorber strength and galaxy intrinsic colors; and (4) within R gas, we find a mean covering fraction of langκ0.3rang ≈ 70% for absorbers of Wr (2796) >= 0.3 Å and langκ0.1rang ≈ 80% for absorbers of Wr (2796) >= 0.1 Å. The results confirm that extended Mg II absorbing halos are a common and generic feature around ordinary galaxies and that the gaseous radius is a fixed fraction of the dark matter halo radius. The lack of correlation between Wr (2796) strength and galaxy colors suggests a lack of physical connection between the origin of extended Mg II halos and recent star formation history of the galaxies. Finally, we discuss the total gas mass in galactic halos as traced by Mg II absorbers. We also compare our results with previous studies. This paper includes data gathered with the 6.5 m Magellan Telescopes located at Las Campanas Observatory, Chile.

  6. SEM, EDX, Infrared and Raman spectroscopic characterization of the silicate mineral yuksporite

    NASA Astrophysics Data System (ADS)

    Frost, Ray L.; López, Andrés; Scholz, Ricardo; Theiss, Frederick L.; Romano, Antônio Wilson

    2015-02-01

    The mineral yuksporite (K,Ba)NaCa2(Si,Ti)4O11(F,OH)ṡH2O has been studied using the combination of SEM with EDX and vibrational spectroscopic techniques of Raman and infrared spectroscopy. Scanning electron microscopy shows a single pure phase with cleavage fragment up to 1.0 mm. Chemical analysis gave Si, Al, K, Na and Ti as the as major elements with small amounts of Mn, Ca, Fe and REE. Raman bands are observed at 808, 871, 930, 954, 980 and 1087 cm-1 and are typical bands for a natural zeolite. Intense Raman bands are observed at 514, 643 and 668 cm-1. A very sharp band is observed at 3668 cm-1 and is attributed to the OH stretching vibration of OH units associated with Si and Ti. Raman bands resolved at 3298, 3460, 3562 and 3628 cm-1 are assigned to water stretching vibrations.

  7. Study of Characterization of Pure and Malachite Green Doped Samples Using Spectroscopic Studies

    NASA Astrophysics Data System (ADS)

    Mishra, Jyoti; Mishra, Pankaj K.; Khare, P. K.

    2011-07-01

    This paper describes the results of SEM, EDX, UV-vis and TSDC study of malachite green doped PVK thermelectrets. TSDC study has been carried out in the temperature range 300 °C to 1500 °C with four different polarizing fields. One peak was observed at 110±10 °C which shifts toward high temperature with the increase in polarizing field. The activation energy found by initial rise method are 0.27±0.02 eV for pure and 0.40±0.03 eV for malachite green doped PVK thermoelectrets. Spectroscopic study concluded that impregnation of malachite green in polymer matrix forms charge transfer complexes.

  8. Ab initio spectroscopic characterization of borane, BH, in its X1?+ electronic state.

    PubMed

    Koput, Jacek

    2015-11-15

    The accurate potential energy and electric dipole moment functions of borane, BH, in its X1?+ electronic state have been determined from ab initio calculations using the multireference averaged coupled-pair functional method in conjunction with the correlation-consistent core-valence basis sets up to septuple-zeta quality. The higher-order electron correlation, scalar relativistic, adiabatic, and nonadiabatic effects were discussed. Vibration-rotation energy levels of the (11)BH, (11)BD, (10)BH, and (10)BD isotopologues were predicted to near "spectroscopic" accuracy. For the main isotopologue (11)BH, the adiabatic dissociation energy D0 and the effective equilibrium internuclear distance r(e) were predicted to be 28,469??10 cm(-1) and 1.23214??0.0001 , respectively. PMID:26444679

  9. SEM, EDX, infrared and Raman spectroscopic characterization of the silicate mineral yuksporite.

    PubMed

    Frost, Ray L; López, Andrés; Scholz, Ricardo; Theiss, Frederick L; Romano, Antônio Wilson

    2015-02-25

    The mineral yuksporite (K,Ba)NaCa2(Si,Ti)4O11(F,OH)⋅H2O has been studied using the combination of SEM with EDX and vibrational spectroscopic techniques of Raman and infrared spectroscopy. Scanning electron microscopy shows a single pure phase with cleavage fragment up to 1.0 mm. Chemical analysis gave Si, Al, K, Na and Ti as the as major elements with small amounts of Mn, Ca, Fe and REE. Raman bands are observed at 808, 871, 930, 954, 980 and 1087 cm(-1) and are typical bands for a natural zeolite. Intense Raman bands are observed at 514, 643 and 668 cm(-1). A very sharp band is observed at 3668 cm(-1) and is attributed to the OH stretching vibration of OH units associated with Si and Ti. Raman bands resolved at 3298, 3460, 3562 and 3628 cm(-1) are assigned to water stretching vibrations. PMID:25240833

  10. Spectroscopic characterization of a radio-frequency argon plasma jet discharge in ambient air

    NASA Astrophysics Data System (ADS)

    Cullen, P. J.; Milosavljević, V.

    2015-06-01

    This study includes a detailed experimental investigation of the spatial and temporal spectroscopic emission of an argon plasma jet discharge. The study is carried out in ambient air and quenching by inflowing air species is considered. The optical emission spectroscopy of neutral atomic spectral lines and molecular bands, over a range of plasma process parameters, is investigated. Wavelength-resolved argon optical emission profiles are used to monitor the electron energy distribution function and the density of argon metastable atoms. The experimental data indicates that the argon flow rate, in a confined open-air plasma discharge, limits the impact of molecular oxygen in the creation of oxygen radicals. The absolute calibrated emission spectra facilitate the possibility of standardization of the so-called plasma dose.

  11. 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.

  12. Synthesis, spectroscopic characterization and structural investigations of new adduct compound of carbazole with picric acid: DNA binding and antimicrobial studies

    NASA Astrophysics Data System (ADS)

    Saravanabhavan, Munusamy; Sathya, Krishnan; Puranik, Vedavati G.; Sekar, Marimuthu

    2014-01-01

    Carbazole picrate (CP), a new organic compound has been synthesized, characterized by various analytical and spectroscopic technique such as FT-IR, UV-Vis, 1H and 13C NMR spectroscopy. An orthorhombic geometry was proposed based on single crystal XRD study. The thermal stability of the crystal was studied by using thermo-gravimetric and differential thermal analyses and found that it was stable up to 170 °C. Further, the newly synthesized title compound was tested for its in vitro antibacterial and antifungal activity against various bacterial and fungal species. Also, the compound was tested for its binding activity with Calf thymus (CT) DNA and the results show a considerable interaction between CP and CT-DNA.

  13. 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).

  14. Synthesis and spectroscopic characterization of water-soluble fluorescent ag nanoclusters.

    PubMed

    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

  15. 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.

    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.

  16. Effect of steric hindrance on carbon dioxide absorption into new amine solutions: thermodynamic and spectroscopic verification through solubility and NMR analysis.

    PubMed

    Park, Jung-Yeon; Yoon, Sang Jun; Lee, Huen

    2003-04-15

    Acid gas absorption technology is of great importance in these days for the prevention of global warming and the resulting worldwide climate change. More efficient process design and development for the removal of acid gases has become important, together with the development of new absorbents as one of urgent areas of research in addressing global-warming problems. In the present work, aqueous solutions of 2-amino-2-hydroxymethyl-1,3-propanediol (AHPD), a sterically hindered amine, has been examined as a potential CO2 absorbent and compared with the most commonly used absorbent, monoethanolamine (MEA) solution, through equilibrium solubility measurements and 13C NMR spectroscopic analyses. The solubilities of CO2 in aqueous 10 mass % AHPD solutions were higher than those in aqueous 10 mass % MEA solutions above 4 kPa at 298.15 K, but below 4 kPa, the solubility behavior appeared to be the opposite. The solubility difference between these two solutions increased with the CO2 partial pressures above the crossover pressure. Equilibrated CO2-MEA-H2O and CO2-AHPD-H2O solutions at various CO2 partal pressures ranging from 0.01 to 3000 kPa were analyzed by 13C NMR spectroscopy to provide a more microscopic understanding of the reaction mechanisms in the two solutions. In the CO2-amine-H2O solutions, amine reacted with CO2 to form mainly the protonated amine (AMH+), bicarbonate ion (HCO3-), and carbamate anion (AMCO2-), where the quantitative ratio of bicarbonate ion to carbamate anion strongly influenced the CO2 loading in the amine solutions. A profusion of bicarbonate ions, but a very small amount of carbamate anions, was identified in the CO2-AHPD-H2O solution, whereas a considerable amount of carbamate anions was formed in the CO2-MEA-H2O solution. AHPD contains more hydroxyl groups than nonhindered MEA, and hence, the chemical shifts in its 13C NMR spectra were strongly influenced by the solution pH values. In contrast, MEA appeared to be insensitive to pH. The strong interrelations among CO2 solubility, CO2 partial pressure, bulkiness of the amine structure, and pH identified through the present experimental investigations can provide basic guidelines for finding new potential organic absorbents, including specifically designed amine chemicals. PMID:12731852

  17. FTIR spectroscopic, thermal and XRD characterization of hydroxyapatite from new natural sources

    NASA Astrophysics Data System (ADS)

    Shaltout, Abdallah A.; Allam, Moussa A.; Moharram, Mohamed A.

    2011-12-01

    The inorganic constituents of 5 different plants (leaves and stalks) were investigated by using Fourier transformer infrared spectroscopy (FTIR), X-ray diffraction (XRD) and thermal analysis including thermal gravimetric analysis (TGA), derivative thermogravimetry (DTG) and differential scanning calorimetry (DSC). These plants are Catha edulis (Khat), basil, mint, green tea and trifolium. The absorption bands of carbonate ions CO 32- was exhibited at 1446 cm -1, and the phosphate ions PO 43- was assigned at 1105 and 1035 cm -1. At high temperatures (600, 700 and 600 °C) further absorption bands of the phosphate ions PO 43- was assigned at the frequencies 572, 617, 962, 1043 and 1110 cm -1 and the vibrational absorption band of the carbonate ions CO 32- was assigned at 871, 1416 and 1461 cm -1. X-ray diffraction and thermal analysis confirm the obtained results of FITR. Results showed that the main inorganic constituents of C. edulis and basil leaves are hydroxyapatite whereas the hydroxyapatite content in the other plant samples is less than that in case of C. edulis and basil plant leaves.

  18. A Complete Spectroscopic Characterization of SO and its Isotopologues up to the Terahertz Domain

    NASA Astrophysics Data System (ADS)

    Martin-Drumel, M. A.; Hindle, F.; Mouret, G.; Cuisset, A.; Cernicharo, J.

    2015-02-01

    In order to obtain accurate terahertz center frequencies for SO and its isotopologues, we have studied the absorption spectrum of SO, 34SO, and 33SO up to 2.5 THz using continuous-wave terahertz photomixing based on a frequency comb providing an accuracy down to 10 kHz. Sulfur monoxide was produced in a radio frequency discharge of air in a cell containing pure sulfur. Together with the strong absorption signal of the main isotopologue, transitions of 34SO (34S: 4.21%) and 33SO (33S: 0.75%) were observed in natural abundance. The newly observed transitions constitute an extension of the observed rotational quantum numbers of the molecule toward higher N values, allowing an improvement of the molecular parameters for the three species. An isotopically invariant fit has been performed based on pure rotational and ro-vibrational transitions of all SO isotopologues, enabling their accurate line position prediction at higher frequencies. Thanks to this new set of parameters, it is now possible to predict with very high accuracy the frequencies of the ro-vibrational lines. This should enable the research of SO in the mid-IR using ground-based IR telescopes, space-based telescope archives (Infrared Space Observatory, Spitzer), and future space missions such as the James Webb Space Telescope. This set of parameters is particularly well adapted for the detection of SO lines in O-rich evolved stars or in molecular clouds in absorption against bright IR sources.

  19. 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

  20. Characterizing the dissolution profiles of supersaturable salts, cocrystals, and solvates to enhance in vivo oral absorption.

    PubMed

    Hisada, Nozomi; Takano, Ryusuke; Takata, Noriyuki; Shiraki, Koji; Ueto, Takamitsu; Tanida, Satoshi; Kataoka, Makoto; Yamashita, Shinji

    2016-06-01

    The purposes of this study were to elucidate the type-specific characteristics of salt, cocrystal, and solvate formulations upon dissolution and precipitation, and to clarify their effect on enhancing oral absorption. Several types of solid formulations (dantrolene sodium salt [DAN-NA], pioglitazone hydrochloride salt [PIO-HCL], megestrol acetate saccharin cocrystal [MEG-SA], and an in-house compound ZR ethanolate [ZR-ETH]) that induce supersaturation of BCS class II drugs were compared to their crystalline free forms. An in vitro miniscale dissolution test in biorelevant media was used to characterize their dissolution profiles and residue forms. Both salts (DAN-NA and PIO-HCL) rapidly reached the maximum concentration within 5min, whereas the cocrystal (MEG-SA) did so slowly. After the maximum concentration had been reached, the dissolved concentrations of DAN-NA, PIO-HCL, and MEG-SA decreased, but that of ZR-ETH did not. Time-dependent XRPD analysis revealed that the initial solid state of each salt dissolved within 5min, whereas the cocrystal remained for more than 10min, and the solvate remained for 4h. It also revealed that PIO-HCL and MEG-SA precipitated to the stable free form, while DAN-NA precipitated to the metastable form, which maintains a higher concentration than the stable free form continuously. In vivo absorption in beagle dogs was also examined. The plasma AUC of DAN-NA, MEG-SA, and ZR-ETH was respectively 1.5-, 2.1-, and 11-fold more than each free form. On the other hand, the absorption of PIO-HCL was not enhanced compared with its free form. The results in the present study clarified that not only the precipitation rate and the form of precipitation but also the retention of the initial solid state in the absorption process contribute to enhancing the in vivo absorption of Class II drugs from solid formulations such as salts, solvates, and cocrystals. PMID:27060622

  1. Characterization of Si (sub X)Ge (sub 1-x)/Si Heterostructures for Device Applications Using Spectroscopic Ellipsometry

    NASA Technical Reports Server (NTRS)

    Sieg, R. M.; Alterovitz, S. A.; Croke, E. T.; Harrell, M. J.; Tanner, M.; Wang, K. L.; Mena, R. A.; Young, P. G.

    1993-01-01

    Spectroscopic ellipsometry (SE) characterization of several complex Si (sub X)Ge (sub 1-x)/Si heterostructures prepared for device fabrication, including structures for heterojunction bipolar transistors (HBT), p-type and n-type heterostructure modulation doped field effect transistors, has been performed. We have shown that SE can simultaneously determine all active layer thicknesses, Si (sub X)Ge (sub 1-x) compositions, and the oxide overlayer thickness, with only a general knowledge of the structure topology needed a priori. The characterization of HBT material included the SE analysis of a Si (sub X)Ge (sub 1-x) layer deeply buried (600 nanometers) under the silicon emitter and cap layers. In the SE analysis of n-type heterostructures, we examined for the first time a silicon layer under tensile strain. We found that an excellent fit can be obtained using optical constants of unstrained silicon to represent the strained silicon conduction layer. We also used SE to measure lateral sample homogeneity, providing quantitative identification of the inhomogeneous layer. Surface overlayers resulting from prior sample processing were also detected and measured quantitatively. These results should allow SE to be used extensively as a non-destructive means of characterizing Si (sub X)Ge (sub 1-x)/Si heterostructures prior to device fabrication and testing.

  2. The spectroscopic characterization of newly developed emissive materials and the effects of environment on their photophysical properties

    NASA Astrophysics Data System (ADS)

    McNamara, Louis Edward, III

    The development of new materials capable of efficient charge transfer and energy storage has become increasingly important in many areas of modern chemical research. This is especially true for the development of emissive optoelectronic devices and in the field of solar to electric energy conversion. The characterization of the photophysical properties of new molecular systems for these applications has become critical in the design and development of these materials. Many molecular building blocks have been developed and understanding the properties of these molecules at a fundamental level is essential for their successful implementation and future engineering. This dissertation focuses on the characterization of some of these newly-developed molecular systems. The spectroscopic studies focus on the characterization of newly-developed molecules based on perylene and indolizine derivatives for solar to electric energy conversion, thienopyrazine derivatives for near infrared (NIR) emissive applications, an SCS pincer complex for blue emissive materials and a fluorescent probe for medical applications. The effects of noncovalent interactions are also investigated on these systems and a benchmark biological molecule trimethylamine N-oxide (TMAO).

  3. Characterization of personal RF electromagnetic field exposure and actual absorption for the general public.

    PubMed

    Joseph, W; Vermeeren, G; Verloock, L; Heredia, Mauricio Masache; Martens, Luc

    2008-09-01

    In this paper, personal electromagnetic field exposure of the general public due to 12 different radiofrequency sources is characterized. Twenty-eight different realistic exposure scenarios based upon time, environment, activity, and location have been defined and a relevant number of measurements were performed with a personal exposure meter. Indoor exposure in office environments can be higher than outdoor exposure: 95th percentiles of field values due to WiFi ranged from 0.36 to 0.58 V m(-1), and for DECT values of 0.33 V m(-1) were measured. The downlink signals of GSM and DCS caused the highest outdoor exposures up to 0.52 V m(-1). The highest total field exposure occurred for mobile scenarios (inside a train or bus) from uplink signals of GSM and DCS (e.g., mobile phones) due to changing environmental conditions, handovers, and higher required transmitted signals from mobile phones due to penetration through windows while moving. A method to relate the exposure to the actual whole-body absorption in the human body is proposed. An application is shown where the actual absorption in a human body model due to a GSM downlink signal is determined. Fiftieth, 95th, and 99 th percentiles of the whole-body specific absorption rate (SAR) due to this GSM signal of 0.58 microW kg(-1), 2.08 microW kg(-1), and 5.01 microW kg(-1) are obtained for a 95th percentile of 0.26 V m(-1). A practical usable function is proposed for the relation between the whole-body SAR and the electric fields. The methodology of this paper enables epidemiological studies to make an analysis in combination with both electric field and actual whole-body SAR values and to compare exposure with basic restrictions. PMID:18695413

  4. Spectroscopic modeling and characterization of a laser-ablated lithium-silver plasma plume

    NASA Astrophysics Data System (ADS)

    Sherrill, Manolo Edgar

    In this dissertation, the modeling and spectroscopic analysis of optical line emission recorded during the laser ablation of plasma plumes from a solid Li-Ag alloy target is discussed. The spectral model considers the effects of multi-element collisional-radiative atomic kinetics, detailed Stark-broadened line profiles, and radiation transport. To compute the atomic data of neutrals and low-charge ions a semi-empirical procedure was implemented in a Hartree-Fock atomic structure code, that produces a set of wavefunctions consistent with measured energy levels. This procedure is critical to obtain spectroscopic quality atomic data for a transition element like silver. A large database of atomic cross sections and rates was computed to input the atomic kinetics calculations. Detailed line shapes were calculated for the Li and Ag line transitions observed in the experimental spectra taking into account the effects of natural, Doppler, Stark and resonance broadening. The radiation transport equation was solved to calculate the transport of the lines through the plasma and the emitted line intensity distribution. The final synthetic spectra self-consistently includes the Li and Ag line emissions. The temperature and density sensitivity of these spectra is discussed for the case of uniform and non-uniform plasmas. The spectral model was implemented in a versatile and efficient parallel processing code, and applied to the analysis of data recorded in laser ablation experiments performed at Sandia National Laboratories. First, raw data images recorded with a gated, space-resolving spectrograph were corrected for instrument efficiency, and the wavelength and space axes calibrated. Then, a collection of time- and space-resolved spectra lineouts was extracted for analysis. The results of the analysis indicate that early in time and close to the target's surface a dense plasma is formed with electron temperatures in the 1 eV to 2 eV range, and electron densities in the 1 x 1017 cm -3 to 1 x 1018 cm-3. The impact of plasma non-uniformities and opacity on the formation of the spectra close to the surface is discussed. Late in time and away from the surface the spectra are characteristic of a plasma undergoing a time-dependent (i.e. non-steady-state) recombination driven by thermal cooling and fast expansion. These results are important for testing hydrodynamic models of laser ablation and understanding the dynamics of plasma plumes.

  5. A COMPLETE SPECTROSCOPIC CHARACTERIZATION OF SO AND ITS ISOTOPOLOGUES UP TO THE TERAHERTZ DOMAIN

    SciTech Connect

    Martin-Drumel, M. A.; Hindle, F.; Mouret, G.; Cuisset, A.; Cernicharo, J.

    2015-02-01

    In order to obtain accurate terahertz center frequencies for SO and its isotopologues, we have studied the absorption spectrum of SO, {sup 34}SO, and {sup 33}SO up to 2.5 THz using continuous-wave terahertz photomixing based on a frequency comb providing an accuracy down to 10 kHz. Sulfur monoxide was produced in a radio frequency discharge of air in a cell containing pure sulfur. Together with the strong absorption signal of the main isotopologue, transitions of {sup 34}SO ({sup 34}S: 4.21%) and {sup 33}SO ({sup 33}S: 0.75%) were observed in natural abundance. The newly observed transitions constitute an extension of the observed rotational quantum numbers of the molecule toward higher N values, allowing an improvement of the molecular parameters for the three species. An isotopically invariant fit has been performed based on pure rotational and ro-vibrational transitions of all SO isotopologues, enabling their accurate line position prediction at higher frequencies. Thanks to this new set of parameters, it is now possible to predict with very high accuracy the frequencies of the ro-vibrational lines. This should enable the research of SO in the mid-IR using ground-based IR telescopes, space-based telescope archives (Infrared Space Observatory, Spitzer), and future space missions such as the James Webb Space Telescope. This set of parameters is particularly well adapted for the detection of SO lines in O-rich evolved stars or in molecular clouds in absorption against bright IR sources.

  6. Synthesis, characterization and microwave absorption properties of polyaniline/Sm-doped strontium ferrite nanocomposite

    NASA Astrophysics Data System (ADS)

    Luo, Juhua; Xu, Yang; Gao, Duoduo

    2014-11-01

    Sm-doped strontium ferrite nanopowders (SrSm0.3Fe11.7O19) and their composites of polyaniline (PANI)/SrSm0.3Fe11.7O19 with 10 wt% and 20 wt% ferrite were prepared by a sol-gel method and an in-situ polymerization process, respectively. The structure, magnetic properties and microwave absorption properties of the samples were characterized by means of X-ray diffraction (XRD), Fourier transform infrared spectra (FT-IR), transmission electron microscope (TEM), vibrating sample magnetometer (VSM) and vector network analyzer, respectively. The particle size of SrSm0.3Fe11.7O19 was about 35 nm by using XRD. The ferrite successfully packed by PANI. PANI/SrSm0.3Fe11.7O19 possessed the best absorption property with the optimum matching thickness of 3 mm in the frequency of 2-18 GHz. The value of the maximum reflection loss (RL) were -26.0 dB at 14.2 GHz with the 6.5 GHz bandwidth and -24.0 dB at 13.8 GHz with the 7.9 GHz bandwidth for the samples with 10 wt% and 20 wt% ferrite, respectively.

  7. Silica-coated iron nanocubes: preparation, characterization and application in microwave absorption.

    PubMed

    Ni, Xiaomin; Zheng, Zhong; Hu, Xiang; Xiao, Xiukun

    2010-01-01

    Novel cubic nanocapsules consisting of metallic iron core and amorphous silica shell were fabricated through a simple chemical reduction route followed by a Stöber process. Thus-prepared Fe@SiO(2) nanocubes were characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), X-ray photoelectron spectrometer (XPS), Fourier transform infrared spectrometer (FTIR), thermogravimetry-differential thermal analysis (TG-DTA), vibrating sample magnetometer (VSM) and scalar network analysis (SNA). Comparing with that of pure iron counterparts, silica-coated iron nanocubes exhibited improved magnetic properties, oxidation resistance and microwave absorption performance. A reflection loss (RL) exceeding -12 dB was obtained in the frequency range of 8-14 GHz for an absorber thickness of 2 mm, with an optimal RL of -18.2 dB at 9 GHz. Mechanism of the improved microwave absorption properties of the Fe@SiO(2) composite was discussed based on their magnetic properties and electromagnetic theory. PMID:19833348

  8. The role of terahertz polariton absorption in the characterization of crystalline iron sulfate hydrates.

    PubMed

    Ruggiero, Michael T; Bardon, Tiphaine; Strlič, Matija; Taday, Philip F; Korter, Timothy M

    2015-04-14

    Iron sulfate compounds have been used extensively to produce iron gall ink, a widely used writing ink in the western world from the 12th-20th centuries. Iron gall ink is well known to corrode writing supports, so detection of iron species is important for the preservation of historical artwork and documents. Iron(ii) sulfate readily changes hydration states and oxidizes in ambient conditions, forming compounds that contribute to this deterioration. In this study, five forms of iron sulfate are characterized by terahertz spectroscopy and solid-state density functional theory (DFT). The results have revealed that the room temperature spectra of FeSO4·7H2O and FeSO4·4H2O are remarkably similar, differing by only a single absorption feature. The identifying terahertz spectra provide an unambiguous metric to determine the relative concentrations of the most common hydrates FeSO4·7H2O and FeSO4·4H2O in a mixed sample. Complete spectral assignments of these species were accomplished by quantum mechanical simulations, with the exception being a single anomalous feature at approximately 40 cm(-1) in the heptahydrate. This peak is believed to be due to polariton absorption, brought about by the particular coordination structure of FeSO4·7H2O that results in a greater charge separation relative to the other iron sulfate crystals. PMID:25760695

  9. Physicochemical characterization of five glyburide powders: a BCS based approach to predict oral absorption.

    PubMed

    Wei, Hai; Dalton, Chad; Di Maso, Marie; Kanfer, Isadore; Lbenberg, Raimar

    2008-08-01

    The purpose of this study was to investigate the suitability of physicochemical parameters of Active Pharmaceutical Ingredients (APIs) as input functions for the Advanced Compartmental Absorption and Transit Model (ACAT) to predict the oral absorption of drug products. Five different glyburide APIs were characterized using X-ray powder diffraction (XRPD), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), Raman spectroscopy, particle size and particle size distribution, specific surface area and true density measurements, as well as dissociation constant (pKa), partition coefficient (log P) and distribution coefficient (log D). The computer simulations were performed using GastroPlus. The results of XPRD, DSC and Raman spectroscopy indicated that no significant differences in crystal form were present in the five APIs. However, significant differences in particle size and particle size distribution were observed. A basic in vitro/in vivo relationship between the APIs' particle size and clinically observed plasma time profiles was established. The study demonstrates that in silico methods can assist the formulation scientist to set meaningful API specifications. Computer simulations could shorten the drug development process since appropriate bioawaivers, based on data from simulation studies, may be justified. PMID:18374555

  10. Predicting X-ray absorption spectra of semiconducting polymers for electronic structure and morphology characterization

    NASA Astrophysics Data System (ADS)

    Su, Gregory; Patel, Shrayesh; Pemmaraju, C. Das; Kramer, Edward; Prendergast, David; Chabinyc, Michael

    2015-03-01

    Core-level X-ray absorption spectroscopy (XAS) reveals important information on the electronic structure of materials and plays a key role in morphology characterization. Semiconducting polymers are the active component in many organic electronics. Their electronic properties are critically linked to device performance, and a proper understanding of semiconducting polymer XAS is crucial. Techniques such as resonant X-ray scattering rely on core-level transitions to gain materials contrast and probe orientational order. However, it is difficult to identify these transitions based on experiments alone, and complementary simulations are required. We show that first-principles calculations can capture the essential features of experimental XAS of semiconducting polymers, and provide insight into which molecular model, such as oligomers or periodic boundary conditions, are best suited for XAS calculations. Simulated XAS can reveal contributions from individual atoms and be used to visualize molecular orbitals. This allows for improved characterization of molecular orientation and scattering analysis. These predictions lay the groundwork for understanding how chemical makeup is linked to electronic structure, and to properly utilize experiments to characterize semiconducting polymers.

  11. High sensitivity spectroscopic and thermal characterization of cooling efficiency for optical refrigeration materials

    NASA Astrophysics Data System (ADS)

    Melgaard, Seth D.; Seletskiy, Denis V.; Di Lieto, Alberto; Tonelli, Mauro; Sheik-Bahae, Mansoor

    2012-03-01

    Since recent demonstration of cryogenic optical refrigeration, a need for reliable characterization tools of cooling performance of different materials is in high demand. We present our experimental apparatus that allows for temperature and wavelength dependent characterization of the materials' cooling efficiency and is based on highly sensitive spectral differencing technique or two-band differential spectral metrology (2B-DSM). First characterization of a 5% w.t. ytterbium-doped YLF crystal showed quantitative agreement with the current laser cooling model, as well as measured a minimum achievable temperature (MAT) at 110 K. Other materials and ion concentrations are also investigated and reported here.

  12. Structural, spectroscopic, and electrochemical characterization of boron-doped diamond films from different provenances

    SciTech Connect

    Li, L.F.; Totir, D.A.; Vinokur, N.; Miller, B.; Chottiner, G.; Evans, E.A.; Angus, J.C.; Scherson, D.A.

    1998-05-01

    Morphological, spectroscopic, and electrochemical aspects of boron-doped diamond (BDD) films grown on silicon surfaces originating from three different laboratories have been examined by atomic force microscopy (AF), Raman scattering, Auger electron spectroscopy, and cyclic voltammetry in polyethylene oxide LiClO{sub 4} electrolytes in ultrahigh vacuum. All specimens displayed AFM images characteristic of diamond and Raman spectra consistent with a wide range of boron concentrations (10{sup 19} to 10{sup 21} B atom/cm{sup 3}), with no evidence for the presence of gross graphitic impurities. The cyclic voltammetry of two of the specimens (denoted as GV2 and CWRU), however, showed features at potentials positive to lithium bulk deposition attributed to lithium-ion intercalation/deintercalation phenomena in non-diamond carbon present as a surface impurity, perhaps at the grain boundaries. This finding is consistent with earlier results for a specimen of type GV2 in aqueous electrolytes for which rates of heterogeneous electron transfer for certain redox couples were found higher than those for nominally clean BDD surfaces.

  13. Minerals from Macedonia XXIII. Spectroscopic and structural characterization of schorl and beryl cyclosilicates.

    PubMed

    Makreski, Petre; Jovanovski, Gligor

    2009-08-01

    IR and Raman spectroscopy study on two collected cyclosilicate species: schorl (from tourmaline group), Na(Fe,Mg)(3)Al(6)(BO(3))(3)Si(6)O(18)(OH,F)(4) and beryl (Be,Mg,Fe)(3)Al(2)Si(6)O(18) were carried out. Although beryl is nominally anhydrous mineral, vibrational results strongly indicate that H(2)O molecules exist in the structural channels. The number of vibrational bands and their frequencies revealed the presence of H(2)O type II, in which C(2) symmetry axis of the water molecule is parallel to the structural channel (and to the c-axis of beryl). On the other hand, it was found that observed bands in the IR and Raman OH stretching region of the other tourmaline varieties appear as a result of the cation combinations involving dominant presence of Mg and Fe cations in the Y structural sites. The strong indication derived from the vibrational spectroscopic results that the studied mineral represents a schorl variety, coincide very well with the results obtained by powder X-ray diffraction and X-ray microprobe analysis. Both minerals show IR spectral similarities in the region below 1500 cm(-1), whereas the resemblance between the Raman spectra (1500-100 cm(-1)) is less expressed confirming that these spectra are more sensitive to compositional changes and to structural disorder. The identification of both minerals was additionally supported by studying the powder X-ray diffraction diagrams. PMID:18722809

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

    NASA Astrophysics Data System (ADS)

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

    2015-04-01

    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 λmax 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 13C and 1H NMR chemical shifts of Carbamazepine.

  15. Synthesis and spectroscopic characterization of solution processable highly ordered polythiophene-carbon nanotube nanohybrid structures

    NASA Astrophysics Data System (ADS)

    Schuettfort, T.; Snaith, H. J.; Nish, A.; Nicholas, R. J.

    2010-01-01

    We report on the synthesis and spectroscopic study of a novel highly ordered nanohybrid structure consisting of a single-walled carbon nanotube (SWNT) coated with highly crystalline regio-regular poly(3-hexylthiophene) (rrP3HT) and discuss the applicability of the nanohybrids in organic photovoltaics. The use of a solvent extraction technique allows the nanohybrids to be produced with a high yield and high purity. We find evidence that the crystallinity of rrP3HT is enhanced in the presence of SWNTs, which introduces a reduced optical band gap and increased carrier mobility in the polymer. Study of the photoluminescence excitation spectra of the SWNTs reveals an efficient energy transfer of excitons created on the rrP3HT to the SWNTs. This energy transfer is expected to limit our ability to use the nanohybrids as a charge separating interface and can therefore explain the low efficiency of P3HT-SWNT solar cells produced to date. In addition, careful consideration of the energy transfer is necessary when attempting to improve state of the art polymer-fullerene photovoltaic devices with SWNTs in order to make use of their high charge carrier mobilities and increased rrP3HT crystallinity.

  16. Synthesis and spectroscopic characterization of solution processable highly ordered polythiophene-carbon nanotube nanohybrid structures.

    PubMed

    Schuettfort, T; Snaith, H J; Nish, A; Nicholas, R J

    2010-01-15

    We report on the synthesis and spectroscopic study of a novel highly ordered nanohybrid structure consisting of a single-walled carbon nanotube (SWNT) coated with highly crystalline regio-regular poly(3-hexylthiophene) (rrP3HT) and discuss the applicability of the nanohybrids in organic photovoltaics. The use of a solvent extraction technique allows the nanohybrids to be produced with a high yield and high purity. We find evidence that the crystallinity of rrP3HT is enhanced in the presence of SWNTs, which introduces a reduced optical band gap and increased carrier mobility in the polymer. Study of the photoluminescence excitation spectra of the SWNTs reveals an efficient energy transfer of excitons created on the rrP3HT to the SWNTs. This energy transfer is expected to limit our ability to use the nanohybrids as a charge separating interface and can therefore explain the low efficiency of P3HT-SWNT solar cells produced to date. In addition, careful consideration of the energy transfer is necessary when attempting to improve state of the art polymer-fullerene photovoltaic devices with SWNTs in order to make use of their high charge carrier mobilities and increased rrP3HT crystallinity. PMID:19955610

  17. Synthesis, spectroscopic characterization and electrochemical studies of Girard's T chromone complexes

    NASA Astrophysics Data System (ADS)

    Al-Saeedi, Sameerah I.; Alaghaz, Abdel-Nasser M. A.; Ammar, Reda A.

    2016-05-01

    Complexes of cobalt(II), nickel(II), copper(II) and zinc(II) of general composition [M(L)2] have been. The elemental analyses, molar conductance, spectral, magnetic moment and thermal measurements studies of the compounds led to the conclusion that the ligand acts as a tridentate manner (OON). The molar conductance of the metal complexes in fresh solution of DMSO lies in the range of 8.10-10.18 Ω-1 cm2 mol-1 indicating their non-electrolytic behavior. On the basis of analytical and spectroscopic techniques, octahedral geometry of the complexes was proposed. The ligand field parameters were calculated for Co(II), Ni(II) and Cu(II) complexes and their values were found in the range reported for a octahedral structure. The data show that the complexes have composition of ML2 type. The activation of thermodynamic parameters are calculated using different equations. The octahedral geometry of the complexes is confirmed using DFT method from DMOL3 calculations and ligand field parameters. The cyclic voltammograms of the Cu(II)/Co(II)/Ni(II) complexes investigated in DMSO solution exhibit metal centered electroactivity in the potential range -1.5 to +1.5 V. The electrochemical data obtained for Cu(II) complexes explains the change of structural arrangement of the ligand around Cu(II) ions.

  18. Spectroscopic and Chromatographic Characterization of Wastewater Organic Matter from a Biological Treatment Plant

    PubMed Central

    Park, Min-Hye; Lee, Tae-Hwan; Lee, Bo-Mi; Hur, Jin; Park, Dae-Hee

    2010-01-01

    Spectroscopic and chromatographic changes in dissolved organic matter (DOM) characteristics of influent and treated sewage were investigated for a wastewater treatment plant (WWTP) with a biological advanced process. Refractory DOM (R-DOM) was defined as the dissolved organic carbon concentrations of the samples after 28-day incubation for this study. Specific UV absorbance (SUVA), hydrophobicity, synchronous fluorescence spectra and molecular weight (MW) distributions were selected as DOM characteristics. The percent distribution of R-DOM for the effluent was much higher than that of the influent, indicating that biodegradable DOM was selectively removed during the process. Comparison of the influent versus the effluent sewage revealed that SUVA, fulvic-like fluorescence (FLF), humic-like fluorescence (HLF), the apparent MW values were enhanced during the treatment. This suggests that more aromatic and humic-like compounds were enriched during the biological process. No significant difference in the DOM characteristics was observed between the original effluent (i.e., prior to the incubation) and the influent sewage after the incubation. This result suggests that the major changes in wastewater DOM characteristics occurring during the biological advanced process were similar to those for simple microbial incubation. PMID:22315538

  19. Characterization of the binding of nevadensin to bovine serum albumin by optical spectroscopic technique

    NASA Astrophysics Data System (ADS)

    Yu, Zhaolian; Li, Daojin; Ji, Baoming; Chen, Jianjun

    2008-10-01

    Binding of nevadensin to bovine serum albumin (BSA) has been studied in detail at 298 and 310 K using spectrophotometric technique. The intrinsic fluorescence of BSA was strongly quenched by the addition of nevadensin and spectroscopic observations are mainly rationalized in terms of a static quenching process at lower concentration of nevadensin ( Cdrug/ CBSA < 1) and a combined quenching process at higher concentration of nevadensin ( Cdrug/ CBSA > 1). The binding parameters for the reaction at a pH above (7.40) or below (3.40) the isoelectric point have been calculated according to the double logarithm regression curve. The thermodynamic parameters Δ H0, Δ G0, Δ S0 at different temperatures and binding mechanism of nevadensin to BSA at pH 7.40 and 3.40 were evaluated. The binding ability of nevadensin to BSA at pH 7.40 was stronger than that at pH 3.40. Steady fluorescence, synchronous fluorescence and circular dichroism (CD) were applied to investigate protein conformation. A value of 2.15 nm for the average distance r between nevadensin (acceptor) and tryptophan residues (Trp) of BSA (donor) was derived from the fluorescence resonance energy transfer. Moreover, influence of pH on the interaction nevadensin with BSA was investigated.

  20. NIR-FT-Raman spectroscopic analytical characterization of the fruits, seeds, and phytotherapeutic oils from rosehips.

    PubMed

    da Silva, Carlos Eduardo; Vandenabeele, Peter; Edwards, Howell G M; de Oliveira, Luiz Fernando Cappa

    2008-12-01

    In this study nondestructive Raman spectroscopic analysis of rosehips has been conducted by laser excitation at 1064 nm, with the objective of direct measurement of different parts of the fruit, including the inside and outside of the seeds, while preserving the integrity of the more representative chemicals. Carotenoid substances are responsible for the major Raman features in the spectra of the fruit parts; analysis of the nu(1) mode (1520 cm(-1)) strongly indicates the presence of a C(9) carotene, and analysis of the main characteristic carotene band set (C=C, C-C, and C-CH(3) stretching modes at 1520, 1157, and 1007 cm(-1), respectively) suggests the presence of beta-carotene as the main constituent. Raman spectra of the seed parts show the presence of unsaturated fatty acids, which are predominant inside the seed; these spectra also reveal the fatty products content comprises cis isomers. Analysis of the CH-stretching region bands and comparison with those in the spectra obtained from linoleic acid and commercial rosehip oil indicate that the relative band intensity of the CH-stretching mode is strongly affected by the chemical environment of the fatty acid esters present in both parts (inside and outside) of rosehips seeds. PMID:18931992

  1. Some polyhydroxy azo azomethine derivatives of salicylaldehyde: Synthesis, characterization, spectroscopic, molecular structure and antimicrobial activity studies

    NASA Astrophysics Data System (ADS)

    Odabaşoğlu, Mustafa; Albayrak, Çiğdem; Özkanca, Reşit; Aykan, Fatma Zehra; Lonecke, Peter

    2007-09-01

    Some new substituted polyhydroxy azo-azomethine compounds were prepared by reaction of tris(hydroxymethyl)aminomethane with ( E)-2-hydroxy-5-(phenyldiazenyl) benzaldehyde and its substituted derivatives. The structures of azo and azo-azomethine compounds were determined by IR, UV-vis, 1H NMR and 13C NMR spectroscopic techniques, and/or X-ray diffraction studies. According to IR spectra, all azo-azomethine compounds adopt keto form in solid state. UV-vis analysis has shown the presence of keto-enol tautomerism in solution for all azo-azomethine compounds, except that for nitro substituted derivative, enol form is dominantly favored in solution. At the same time, above mentioned derivative compounds were studied in vitro for their antimicrobial properties. Among the phenylazosalicylaldehyde series compound tested, 4-phenylazosalicylaldehyde, 4-(3-chlorophenylazo)salicylaldehyde, 4-(2-chlorophenylazo)salicylaldehyde, 4-(4-fluorophenylazo)salicylaldehyde, 4-(3-chlorophenylazo)salicylaldehyde and 4-(4-ethylphenylazo)salicylaldehyde showed a weak antimicrobial activity only against gram positive bacteria. On the contrary, phenylazosalicylaldehyde series compounds were reacted tris(hydroxmethyl)aminomethane, that exhibited a strong antimicrobial activity against gram positive bacteria, yeast and mould. Moreover, while the 2-{[1,3-dihydroxy-2-(hydroxymethyl)propan-2-ylimino]methyl}phenol did not show an inhibition on tested microorganism, the addition of phenyldiazine groups to 2-{[1,3-dihydroxy-2-(hydroxymethyl)propan-2-ylimino]methyl}phenol resulted in a strong increases in antimicrobial activity.

  2. Surface layer in composites containing 4- n-octyl-4'-cyanobiphenyl. FTIR spectroscopic characterization

    NASA Astrophysics Data System (ADS)

    Frunza, L.; Kosslick, H.; Bentrup, U.; Pitsch, I.; Fricke, R.; Frunza, S.; Schönhals, A.

    2003-06-01

    Composites containing 4- n-octyl-4'-cyanobiphenyl (8CB) either confined to nanopores of molecular sieves with very large pores or coating silica nanoparticles of aerosil type at high silica-to-8CB ratios are investigated by IR spectroscopy. Band shape analysis was performed in wavenumber regions in which the peaks due to CN stretching, CH stretching and CH out-of-plane vibrations appear. Some of molecules confined to molecular sieves show spectroscopic features characteristic to a bulk-like 8CB matter located in the centre of the pores or in the inter-grain space. Other features of the IR spectra are due to 8CB molecules located in the surface layer, mostly forming hydrogen bonds between their CN groups and surface OH groups. Another part of the 8CB molecules in the surface layer may also interact by π electrons of the aromatic rings. Hydrogen bonding is less hindered for the molecules of the surface layers onto aerosil particles than inside pores of the molecular sieves. Comparison is also made with the case of composites based on molecular sieves with small pores.

  3. 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.

  4. Instrument for x-ray absorption spectroscopy with in situ electrical control characterizations

    SciTech Connect

    Huang, Chun-Chao; Chang, Shu-Jui; Yang, Chao-Yao; Tseng, Yuan-Chieh; Chou, Hsiung

    2013-12-15

    We report a synchrotron-based setup capable of performing x-ray absorption spectroscopy and x-ray magnetic circular dichroism with simultaneous electrical control characterizations. The setup can enable research concerning electrical transport, element- and orbital-selective magnetization with an in situ fashion. It is a unique approach to the real-time change of spin-polarized electronic state of a material/device exhibiting magneto-electric responses. The performance of the setup was tested by probing the spin-polarized states of cobalt and oxygen of Zn{sub 1-x}Co{sub x}O dilute magnetic semiconductor under applied voltages, both at low (?20 K) and room temperatures, and signal variations upon the change of applied voltage were clearly detected.

  5. In situ characterization of few-cycle laser pulses in transient absorption spectroscopy.

    PubMed

    Blättermann, Alexander; Ott, Christian; Kaldun, Andreas; Ding, Thomas; Stooß, Veit; Laux, Martin; Rebholz, Marc; Pfeifer, Thomas

    2015-08-01

    Attosecond transient absorption spectroscopy has thus far been lacking the capability to simultaneously characterize the intense laser pulses at work within a time-resolved quantum-dynamics experiment. However, precise knowledge of these pulses is key to extracting quantitative information in strong-field highly nonlinear light-matter interactions. Here, we introduce and experimentally demonstrate an ultrafast metrology tool based on the time-delay-dependent phase shift imprinted on a strong-field-driven resonance. Since we analyze the signature of the laser pulse interacting with the absorbing spectroscopy target, the laser pulse duration and intensity are determined in situ. As we also show, this approach allows for the quantification of time-dependent bound-state dynamics in one and the same experiment. In the future, such experimental data will facilitate more precise tests of strong-field dynamics theories. PMID:26258333

  6. Applied quantum chemistry: Spectroscopic detection and characterization of the F{sub 2}BS and Cl{sub 2}BS free radicals in the gas phase

    SciTech Connect

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

    2015-03-28

    In this and previous work [D. J. Clouthier, J. Chem. Phys. 141, 244309 (2014)], the spectroscopic signatures of the X{sub 2}BY (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 F{sub 2}BS and Cl{sub 2}BS free radicals have been identified and characterized. The radicals were prepared in a free jet expansion by subjecting precursor mixtures of BF{sub 3} or BCl{sub 3} and CS{sub 2} vapor to an electric discharge at the exit of a pulsed molecular beam valve. The B{sup ~2}A{sub 1}–X{sup ~} {sup 2}B{sub 2} laser-induced fluorescence spectra were found within 150 cm{sup −1} of their theoretically predicted positions with vibronic structure consistent with our Franck-Condon simulations. The B{sup ~2}A{sub 1} state emits down to the ground state and to the low-lying A{sup ~2}B{sub 1} 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{sup ~}–X{sup ~} band system of Cl{sub 2}BS is evident, as signaled by the activity in the b{sub 2} modes in the spectrum. Symmetry arguments indicate that this component gains intensity due to a vibronic interaction of the B{sup ~2}A{sub 1} state with a nearby electronic state of {sup 2}B{sub 2} symmetry.

  7. 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 B̃(2)A1-X̃(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 B̃(2)A1 state emits down to the ground state and to the low-lying Ã(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 B̃-X̃ 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 B̃(2)A1 state with a nearby electronic state of (2)B2 symmetry. PMID:25833573

  8. Comparative in vitro characterization of moxidectin and doramectin percutaneous absorption through bovine skin.

    PubMed

    Sallovitz, J M; Nejamkin, P; Lifschitz, A L; Virkel, G L; Imperiale, F A; Lanusse, C E

    2012-04-01

    Topical formulations have achieved worldwide acceptance in veterinary medicine because their administration is an easy, less labor-intensive and nonstressing form. Any chemical compound that comes in contact with the skin has the potential to be locally and/or systemically absorbed. However, many factors related to the features of animal skin, composition of the topical formulation and to the drug itself can determine marked differences in the percutaneous absorption process. The aim of the current work was to characterize the pattern of in vitro percutaneous absorption for moxidectin (MXD) and doramectin (DRM), two of the most worldwide used topical macrocyclic lactone antiparasitic compounds in cattle. The work included the development of a simple and inexpensive in vitro assay useful to predict in vivo drug percutaneous absorption in cattle. Both drugs were administered as the commercial formulations intended for their topical administration to cattle. The in vitro studies were carried out using modified Franz-type vertical diffusion cells. Cattle skin slices of 500 ?m thickness were prepared using a dermatome to separate the stratum corneum and upper epidermis from dermis and subcutaneous tissue. The receptor medium was sampled up to 72 h postadministration and drug concentrations were measured by HPLC. The parameters used to estimate the comparative in vitro skin permeation showed marked differences between DRM and MXD. A 5.29-fold longer lag time (T(lag)) was observed for DRM. Similarly, the flux (J) (2.93-fold) and the permeation coefficients (K(p) ) (2.95-fold) in cattle skin were significantly higher (P < 0.05) for DRM compared to those obtained for MXD. Additionally, the data obtained from the in vitro permeation studies was correlated with the plasma concentrations of both compounds achieved in vivo in cattle treated with the same topical formulations. Correlation coefficients between percentage of drug permeated in vitro vs. percentage of drug absorbed in vivo (up to 48 h post-treatment) were 0.856-0.887 (MXD) and 0.976-0.990 (DRM). However, the highest in vitro-in vivo correlations for both molecules were observed up to 24 h post-treatment A rapid screening method for testing different topical formulations can be achieved with the simple in vitro cattle skin permeation technique described here, which has been successfully adapted to test the comparative percutaneous absorption of MXD and DRM. PMID:21521238

  9. Synthesis, spectroscopic characterization, crystallographic studies and antibacterial assays of new copper(II) complexes with sulfathiazole and nimesulide

    NASA Astrophysics Data System (ADS)

    Nunes, Julia Helena Bormio; de Paiva, Raphael Enoque Ferraz; Cuin, Alexandre; da Costa Ferreira, Ana Maria; Lustri, Wilton Rogério; Corbi, Pedro Paulo

    2016-05-01

    New ternary copper(II) complexes of sulfathiazole (SFT, C9H8N3O2S2) or nimesulide (NMS, C13H11N2O5S) and 2,2‧-bipyridine (bipy) were synthesized, and characterized by chemical and spectroscopic techniques. Elemental analyses indicated a 2:1:1 sulfonamide/copper/bipy composition for both complexes. Mass spectrometric measurements permitted identifying the molecular ions [Cu(SFT)2(bipy)+H]+ and [Cu(NMS)2(bipy)+H]+ at m/z 728 and 835, respectively, confirming the proposed compositions. Crystal structure of the [Cu(SFT)2(bipy)] complex was solved by powder X-ray diffraction analysis (PXRD), attesting that the Cu(II) ion is hexacoordinated in a distorted octahedral geometry. Each SFT molecule coordinates to the metal ion by the nitrogen atoms of the SO2-N group and of the heterocyclic ring. The coordination sphere is completed by a bipyridine. Electronic paramagnetic resonance (EPR) studies were carried out for the [Cu(NMS)2(bipy)] complex, indicating a tetragonal environment around the metal ion. It was suggested that NMS coordinates to Cu(II) by the nitrogen and oxygen atoms of the SO2-N group, which was confirmed by infrared spectroscopic studies. Biological studies showed the antibacterial activity of both Cu-SFT and Cu-NMS complexes, with the minimum inhibitory concentration (MIC) values ranging from 0.10 to 0.84 mmol L-1 against Gram-negative bacteria for [Cu(SFT)2(bipy)], and from 1.50 to 3.00 mmol L-1 against Gram-positive and -negative bacteria for [Cu(NMS)2(bipy)].

  10. Theoretical Spectroscopic Characterization at Low Temperatures of Dimethyl Sulfoxide: The Role of Anharmonicity.

    PubMed

    Senent, M L; Dalbouha, S; Cuisset, A; Sadovskii, D

    2015-09-17

    The structural and spectroscopic parameters of dimethyl sulfoxide (DMSO) are predicted from CCSD(T)-F12 calculations that can help to resolve the outstanding problem of the rovibrational spectroscopy. DMSO is a near oblate top that presents a trigonal pyramidal geometry. Rotational parameters are determined at the equilibrium and in selected vibrational states. For the ground state, the rotational constants were calculated to be A0 = 7031.7237 MHz, B0 = 6920.1221 MHz, and C0 = 4223.3389 MHz, at few megahertz from the previous experimental measurements. Ab initio calculations allow us to assert that DMSO rotational constants are strongly dependent on anharmonic effects. Asymmetry increases with the vibrational energy. Harmonic frequencies, torsional parameters, and a two-dimensional potential energy surface (2D-PES) focused to describe the internal rotation of the two methyl groups are determined at the CCSD(T)-F12 level of theory. For the medium and small amplitude motions, anharmonic effects are estimated with MP2 theory getting an excellent agreement with experimental data for the ν11 and ν23 fundamentals. Torsional energies and transitions are computed variationally form the 2D-PES that denotes strong interactions between both internal tops. The vibrationally corrected V3 torsional barrier is evaluated to be 965.32 cm(-1). The torsional splitting of the ground vibrational state has been estimated to be lower than 0.01 cm(-1). Although the ν13 torsional fundamental is found at 229.837 cm(-1) in good agreement with previous assessment, there is not accord for the low intense transition ν24. A new assignment predicting ν24 to lie between 190 and 195 cm(-1) is proposed. PMID:26317485

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

    SciTech Connect

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

    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.

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

    PubMed

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

    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 CH3-S-CHO (MSCHO) and O-methyl thioformate CH3-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-CH3-S-CHO represents the most stable structure lying 4372.2 cm(-1) below cis-CH3-O-CHS. The energy difference between the cis and trans forms is drastically lower for MSCHO (1134 cm(-1)) than for MOCHS (1963.6 cm(-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 V3(cis) are determined to be 139.7 cm(-1) (CH3-S-CHO) and 670.4 cm(-1) (CH3-O-CHS). The A/E splitting of ground torsional state has been estimated to be 0.438 cm(-1) for CH3-S-CHO and negligible for CH3-O-CHS. PMID:25217912

  13. Characterization of the Interaction between Eupatorin and Bovine Serum Albumin by Spectroscopic and Molecular Modeling Methods

    PubMed Central

    Xu, Hongliang; Yao, Nannan; Xu, Haoran; Wang, Tianshi; Li, Guiying; Li, Zhengqiang

    2013-01-01

    This study investigated the interaction between eupatorin and bovine serum albumin (BSA) using ultraviolet-visible (UV-vis) absorption, fluorescence, synchronous fluorescence, circular dichroism (CD) spectroscopies, and molecular modeling at pH 7.4. Results of UV-vis and fluorescence spectroscopies illustrated that BSA fluorescence was quenched by eupatorin via a static quenching mechanism. Thermodynamic parameters revealed that hydrophobic and electrostatic interactions played major roles in the interaction. Moreover, the efficiency of energy transfer, and the distance between BSA and acceptor eupatorin, were calculated. The effects of eupatorin on the BSA conformation were analyzed using UV-vis, CD, and synchronous fluorescence. Finally, the binding of eupatorin to BSA was modeled using the molecular docking method. PMID:23839090

  14. 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.

  15. 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

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

    NASA Astrophysics Data System (ADS)

    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 β-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 (1H NMR, 13C 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 β-ketiminate hafnium(IV) chloride complexes (4a-d). Sublimation enthalpies (ΔHsub) were calculated from thermogravimetric analysis (TGA) data, which show that, the dependence of ΔHsub on the molecular weight (4a-c) and inductive effects from chlorine (4d).

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

    NASA Astrophysics Data System (ADS)

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

    2015-01-01

    The vanadyl(IV) adenine complex; [VO(Adn)2]ṡSO4; 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.

  18. 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

  19. Hafnium(IV) chloride complexes with chelating β-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 β-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 β-ketiminate hafnium(IV) chloride complexes (4a-d). Sublimation enthalpies (ΔHsub) were calculated from thermogravimetric analysis (TGA) data, which show that, the dependence of ΔHsub on the molecular weight (4a-c) and inductive effects from chlorine (4d). PMID:25897715

  20. Infrared absorption spectroscopic and DFT calculation studies on the adsorption structures of nitromethane on the single crystals of Cu and Ag

    NASA Astrophysics Data System (ADS)

    Itoh, K.; Iwa, A.; Uriu, Y.; Kadokura, K.

    2008-07-01

    The adsorption structures of nitromethane on Ag(1 1 0), Ag(1 1 1), Cu(1 1 0) and Cu(1 1 1) at 80 K were studied by using infrared reflection absorption spectroscopy (IRAS) and non-local density functional theory (DFT) calculation performed on nitromethane/Cu(1 1 0) and nitromethane/Cu(1 1 1) cluster models. Upon increasing exposure levels, the adsorbate on each substrate exhibits discrete spectral changes, characterizing sub-monolayer and/or monolayer, amorphous and multilayer (crystalline) states. The DFT calculation successively simulated the IRA spectra of nitromethane on the copper substrates, suggesting that nitromethane adsorbs on Cu(1 1 0) through an on-top coordination with one of the oxygen atom of the NO 2 group to the Cu atom and that nitromethane adsorbs on Cu(1 1 1) through a bridging coordination of the oxygen atom. In both states nitromethane takes an eclipsed form with the molecular plane perpendicular to the substrates surface and the hydrogen atom pointing to the surface in the molecular plane plays an important role in stabilizing the adsorption states in addition to the coordination interaction.

  1. Spectroscopic and Electrical Characterization of FeSO4.7H2O Doped Poly (o-toluidine)

    NASA Astrophysics Data System (ADS)

    Kumar, Anand; Ali, Vazid; Kumar, Sushil; Husain, M.

    2011-12-01

    Poly (o-toluidine) has received much attention because of its electronic, thermoelectric, environmental stability and diversified utilization. Various dopants and solvents for control of physical and chemical properties of poly (o-toluidine) has been examined. In the present work, poly (o-toluidine) has been synthesized by chemical oxidative polymerization in acidic medium using o-toluidine monomer. The Poly (o-toluidine) so obtained has been doped with transition metal salt FeSO4.7H2O with different concentration such as 2, 6 and 10% (w/w). In order to investigate the influence of dopant on the properties of poly (o-toluidine), the prepared samples have been characterized by UV-visible spectroscopy, FTIR and I-V characterization. Samples for UV-visible spectroscopy were prepared by dissolving a small amount of doped poly (o-toluidine) in tetrahydrofuran in quartz cuvvets. The absorption spectra of the samples were recorded in wavelength range 200-800 nm using UV-visible spectrophotometer. UV-visible study revealed that optical parameters such as absorption coefficient and band gap changed considerably with concentration. Samples for FTIR spectroscopy were prepared as pellets by pressing a mixture of doped poly (o-toluidine) and potassium bromide. FTIR spectra were recorded in wavenumber range 400-4000 cm-1 on FTIR spectrophotometer. It has been observed that dc conductivity of the samples, measured at room temperature (300 K), increases with increase in doping concentration.

  2. 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).

  3. Complementary characterization of Ti-Si-C films by x-ray diffraction and absorption

    NASA Astrophysics Data System (ADS)

    Lawniczak-Jablonska, K.; Klepka, M. T.; Dynowska, E.; Wolska, A.; Borysiewicz, M. A.; Piotrowska, A.

    2013-12-01

    Advanced electronic devices based on III-N semiconductors, particularly these operated at the high power and high frequency or corrosive atmosphere, need elaboration of new technology for contacts metallization which are thermally and chemically stable. Performed studies aimed at the development of materials for applications in the improved metallization. Due to the unique combination of the metallic electro-thermal conductivity and ceramic resistance to oxidation and thermal stability, the MAX phases were chosen as the materials potentially applicable to this task. Particular interest lies in the MAX phases based on the Ti, Si and C or N atoms, especially on the Ti3SiC2 phase. The paper focuses on a comprehensive characterization of films grown by means of high-temperature magnetron Ti, Si and C co-sputtering. The complementary characterization by X-ray diffraction (XRD) and X-ray absorption spectroscopy (XAS) is presented. XRD studies pointed out the presence of several phases in the investigated samples, therefore XAS as an atomic sensitive probe was applied to examine the average atomic order around Ti atoms as a function of the technological parameters and to point towards proper procedures to achieve the appropriate stoichiometry around Ti atoms and finally the Ti3SiC2 phase.

  4. Spectroscopic Characterization of Structural Changes in Membrane Scaffold Proteins Entrapped within Mesoporous Silica Gel Monoliths.

    PubMed

    Zeno, Wade F; Hilt, Silvia; Risbud, Subhash H; Voss, John C; Longo, Marjorie L

    2015-04-29

    The changes in the orientation and conformation of three different membrane scaffold proteins (MSPs) upon entrapment in sol-gel-derived mesoporous silica monoliths were investigated. MSPs were examined in either a lipid-free or a lipid-bound conformation, where the proteins were associated with lipids to form nanolipoprotein particles (NLPs). NLPs are water-soluble, disk-shaped patches of a lipid bilayer that have amphiphilic MSPs shielding the hydrophobic lipid tails. The NLPs in this work had an average thickness of 5 nm and diameters of 9.2, 9.7, and 14.8 nm. We have previously demonstrated that NLPs are more suitable lipid-based structures for silica gel entrapment than liposomes because of their size compatibility with the mesoporous network (2-50 nm) and minimally altered structure after encapsulation. Here we further elaborate on that work by using a variety of spectroscopic techniques to elucidate whether or not different MSPs maintain their protein-lipid interactions after encapsulation. Fluorescence spectroscopy and quenching of the tryptophan residues with acrylamide, 5-DOXYL-stearic acid, and 16-DOXYL-stearic acid were used to determine the MSP orientation. We also utilized fluorescence anisotropy of tryptophans to measure the relative size of the NLPs and MSP aggregates after entrapment. Finally, circular dichroism spectroscopy was used to examine the secondary structure of the MSPs. Our results showed that, after entrapment, all of the lipid-bound MSPs maintained orientations that were minimally changed and indicative of association with lipids in NLPs. The tryptophan residues appeared to remain buried within the hydrophobic core of the lipid tails in the NLPs and appropriately spaced from the bilayer center. Also, after entrapment, lipid-bound MSPs maintained a high degree of α-helical content, a secondary structure associated with protein-lipid interactions. These findings demonstrate that NLPs are capable of serving as viable hosts for functional integral membrane proteins in the synthesis of sol-gel-derived bioinorganic hybrid nanomaterials. PMID:25849085

  5. Spectroscopic Characterization of Intermediates in the Iron Catalyzed Activation of Alkanes

    SciTech Connect

    Edward M. Eyring

    2007-05-28

    The present report begins with a brief survey of recent hypervalent iron chemistry and mentions two previously reported ferrate papers funded by the DOE/BES grant. The focus is then shifted to the seven publications acknowledging support of the grant that have not been reported since the last Progress Report, DOE/ER/14340-9, was prepared. These papers deal with: (a) the successful use of an ATR element in a stopped-flow infrared spectrometer, (b) the rationalization of a depolarization of a LiClO4 solution in polyethylene oxide high polymer, (c) an analysis of several coupled ultrasonic relaxations observed in solutions of pentoses undergoing isomerization, (d) the combination of ultrasonic absorption and Raman scattering measurements to elucidate zinc thiocyanate solutions in water, (e) the use of NMR to determine stability constants when LiClO4:12-crown-4 is dissolved in acetonitrile and in methanol, (f) the possible existence of triple ions in low permittivity solutions, and (g) the properties of a high surface area ceria aerogel. Collectively, these papers illustrate advantages of bringing several modern experimental techniques to bear on complex chemical systems.

  6. 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-σ 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-σ 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.

  7. Cell-free synthesis, functional refolding, and spectroscopic characterization of bacteriorhodopsin, an integral membrane protein.

    PubMed

    Sonar, S; Patel, N; Fischer, W; Rothschild, K J

    1993-12-21

    Bacteriorhodopsin (bR) is an integral membrane protein which functions as a light-driven proton pump in Halobacterium halobium (also known as Halobacterium salinarium). The cell-free synthesis of bR in quantities sufficient for FTIR and NMR spectroscopy and the ability to selectively isotope label bR using aminoacylated suppressor tRNAs would provide a powerful approach for studying the role of specific amino acid residues. However, no integral membrane protein has yet been expressed in a cell-free system in quantities sufficient for such biophysical studies. We report the cell-free synthesis of bacterioopsin, its purification, its refolding in polar lipids from H. halobium, and its regeneration with all-trans-retinal to yield bacteriorhodopsin in a form functionally similar to bR in purple membrane. Importantly, the yields obtained from in vitro and in vivo expression are comparable. Functionality of the cell-free expressed bR is established using static and time-resolved absorption spectroscopy and FTIR difference spectroscopy. PMID:8268152

  8. Infrared and Raman spectroscopic characterization of some organic substituted hybrid silicas

    NASA Astrophysics Data System (ADS)

    Capeletti, Larissa B.; Baibich, Ione M.; Butler, Ian S.; dos Santos, João H. Z.

    2014-12-01

    Nine hybrid silicas bearing the organic substituent groups methyl, octyl, octadecyl, vinyl, phenyl, mercaptopropyl, isocyanatopropyl, chloropropyl and glycidoxypropyl were synthesized by an acid-catalyzed, hydrolytic sol-gel process. The resulting solid materials were characterized by their absorbance and attenuated total reflection (ATR) IR and Raman spectra. The latter technique proved to be particularly useful in the identification of the organic moieties in the hybrid silicas. The effect of the presence of the organic groups on the silica networks was also investigated - there were increases observed in both the Sisbnd Osbnd Si bond angles and bond lengths. Moreover, deconvolution of the IR-active antisymmetric Sisbnd Osbnd Si stretching bands permitted detection of the four- and six-membered siloxane rings present in the silicas. There proved to be a greater number of four-membered rings on the surfaces of the particles. Both IR and Raman spectroscopy proved to be invaluable in the characterization of these hybrid materials.

  9. Spectroscopic Characterization of a Monomeric, Cyclopentadienyl-Based Rhenium(V) Dioxo Complex.

    PubMed

    Raju, Suresh; Jastrzebski, Johann T B H; Lutz, Martin; Witteman, Léon; Dethlefsen, Johannes R; Fristrup, Peter; Moret, Marc-Etienne; Gebbink, Robertus J M Klein

    2015-11-16

    Mononuclear, coordinatively unsaturated rhenium(V) dioxo species of the type XReO2 (X = Me, substituted cyclopentadienyl) have long been postulated as intermediates in rhenium-catalyzed deoxydehydration, but their characterization was precluded because of aggregation into dimeric or oligomeric structures. Using the bulky 1,2,4-tri-tert-butylcyclopentadienyl (Cp(ttt)) ligand, the rhenium(V) dioxo species (Cp(ttt))ReO2 could now be observed, in equilibrium with the dimeric form [(Cp(ttt))Re(O)μ-O]2, and characterized by NMR, IR, and UV-vis spectroscopies, as well as electrospray ionization mass spectrometry. (Cp(ttt))ReO2 is shown to be the primary product of reduction of the rhenium(VII) complex (Cp(ttt))ReO3 with PPh3 and demonstrated to react with ethylene glycol significantly faster than its dimeric counterpart, supporting its role as an intermediate in rhenium-catalyzed deoxydehydration reactions. PMID:26517008

  10. Accurate spectroscopic characterization of ethyl mercaptan and dimethyl sulfide isotopologues: a route toward their astrophysical detection

    SciTech Connect

    Puzzarini, C.; Senent, M. L.; Domínguez-Gómez, R.; Carvajal, M.; Hochlaf, M.; Al-Mogren, M. Mogren E-mail: senent@iem.cfmac.csic.es E-mail: miguel.carvajal@dfa.uhu.es E-mail: mmogren@ksu.edu.sa

    2014-11-20

    Using state-of-the-art computational methodologies, we predict a set of reliable rotational and torsional parameters for ethyl mercaptan and dimethyl sulfide monosubstituted isotopologues. This includes rotational, quartic, and sextic centrifugal-distortion constants, torsional levels, and torsional splittings. The accuracy of the present data was assessed from a comparison to the available experimental data. Generally, our computed parameters should help in the characterization and the identification of these organo-sulfur molecules in laboratory settings and in the interstellar medium.

  11. X-ray absorption spectroscopic study of new high-Tc superconducting intercalation compound of (HgX2)0.5Bi2Sr2CaCu2Oy(X=Br,I)

    NASA Astrophysics Data System (ADS)

    Choy, Jin-Ho; Park, Nam-Gyu; Hwang, Seong-Ju; Hwang, Sung-Ho; Kim, Dong-Hoon

    1996-06-01

    We have systematically performed x-ray absorption spectroscopic (XAS) studies on the new mercuric halide intercalated superconductors, (HgX2)0.5Bi2Sr2CaCu2Oy with X equals Br and I, in order to investigate the electronic and crystal structure of these compounds. The present Hg LIII-edge EXAFS results indicate that the mercury is coordinated with two bromide or iodide ligands with bond length of 2.46 angstrom for the HgBr2-intercalate and 2.65 angstrom for the HgI2-one. This is the first example of linear molecular salt of HgX2 stabilized in the solid lattice. According to the I LI- and Br K-edge x-ray absorption near edge structure (XANES) spectroscopic studies, a small amount of electron transfer from the intercalant HgX2 to the host lattice could be observed upon intercalation, resulting in the negatively charged state of (HgX2)(delta -). The Cu K-edge EXAFS analysis reveals that the bond distance of Cu-Oaxial is slightly shortened upon intercalation, reflecting the oxidation of (Cu-O) layer, which is well consistent with the I LI- and Br K-edge XANES results.

  12. 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.

  13. Fe(II) uptake on natural montmorillonites. I. Macroscopic and spectroscopic characterization.

    PubMed

    Soltermann, Daniela; Marques Fernandes, Maria; Baeyens, Bart; Dähn, Rainer; Joshi, Prachi A; Scheinost, Andreas C; Gorski, Christopher A

    2014-01-01

    Iron is an important redox-active element that is ubiquitous in both engineered and natural environments. In this study, the retention mechanism of Fe(II) on clay minerals was investigated using macroscopic sorption experiments combined with Mössbauer and extended X-ray absorption fine structure (EXAFS) spectroscopy. Sorption edges and isotherms were measured under anoxic conditions on natural Fe-bearing montmorillonites (STx, SWy, and SWa) having different structural Fe contents ranging from 0.5 to 15.4 wt % and different initial Fe redox states. Batch experiments indicated that, in the case of low Fe-bearing (STx) and dithionite-reduced clays, the Fe(II) uptake follows the sorption behavior of other divalent transition metals, whereas Fe(II) sorption increased by up to 2 orders of magnitude on the unreduced, Fe(III)-rich montmorillonites (SWy and SWa). Mössbauer spectroscopy analysis revealed that nearly all the sorbed Fe(II) was oxidized to surface-bound Fe(III) and secondary Fe(III) precipitates were formed on the Fe(III)-rich montmorillonite, while sorbed Fe is predominantly present as Fe(II) on Fe-low and dithionite-reduced clays. The results provide compelling evidence that Fe(II) uptake characteristics on clay minerals are strongly correlated to the redox properties of the structural Fe(III). The improved understanding of the interfacial redox interactions between sorbed Fe(II) and clay minerals gained in this study is essential for future studies developing Fe(II) sorption models on natural montmorillonites. PMID:24930689

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

    SciTech Connect

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

    2015-02-21

    The low temperature spectra of the detectable species methyl hydroperoxide (CH{sub 3}OOH) and three sulfur analogs, the two isomers of methanesulfenic acid (CH{sub 3}SOH and CH{sub 3}OSH) and the methyl hydrogen disulfide (CH{sub 3}SSH), 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.

  15. Spectrophotometric and Raman spectroscopic characterization of ALD grown TiO II thin films

    NASA Astrophysics Data System (ADS)

    Aarik, Jaan; Kasikov, Aarne; Niilisk, Ahti

    2007-02-01

    Properties of titanium dioxide thin films grown by atomic layer deposition from TiCl 4 and H IIO on SiO II substrates were characterized using Raman spectroscopy and spectrophotometry methods. Raman spectroscopy revealed transformation of the film structure from amorphous to anatase, to anatase/rutile mixture and then back to anatase with the increase of deposition temperature from 100 to 680 °C. Variations in the growth rate, refractive index and extinction index accompanied these structural changes. Analysis of the transmission curves demonstrated that differently from amorphous films, the crystalline films were optically inhomogeneous in the growth direction.

  16. 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 π2 + π2 + σ2 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

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

    NASA Astrophysics Data System (ADS)

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

    2015-02-01

    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.

  18. Synthesis, spectroscopic characterization, biological screenings, DNA binding study and POM analyses of transition metal carboxylates

    NASA Astrophysics Data System (ADS)

    Uddin, Noor; Sirajuddin, Muhammad; Uddin, Nizam; Tariq, Muhammad; Ullah, Hameed; Ali, Saqib; Tirmizi, Syed Ahmed; Khan, Abdur Rehman

    2015-04-01

    This article contains the synthesis of a novel carboxylic acid derivative, its transition metal complexes and evaluation of biological applications. Six carboxylate complexes of transition metals, Zn(II) and Hg(II), have been successfully synthesized and characterized by FT-IR and NMR (1H, 13C). The ligand, HL, (4-[(2,6-Diethylphenyl)amino]-4-oxobutanoic acid) was also characterized by single crystal X-ray analysis. The complexation occurs via oxygen atoms of the carboxylate moiety. FT-IR date show the bidentate nature of the carboxylate moiety of the ligand as the Δν value in all complexes is less than that of the free ligand. The ligand and its complexes were screened for antifungal and antileishmanial activities. The results showed that the ligand and its complexes are active with few exceptions. UV-visible spectroscopy and viscometry results reveal that the ligand and its complexes interact with the DNA via intercalative mode of interaction. A new and efficient strategy to identify the pharmacophores and anti-pharmacophores sites in carboxylate derivatives for the antibacterial/antifungal activity using Petra, Osiris and Molinspiration (POM) analyses was also carried out.

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

    NASA Astrophysics Data System (ADS)

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

    2009-07-01

    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 all the metal chelates are non-electrolytes. IR spectra show that HL is coordinated to the metal ions in a uninegatively tridentate manner with NNO donor sites of the azomethine N, amino N and deprotonated caroxylic-O. From the magnetic and solid reflectance spectra, it is found that the geometrical structures of these complexes are octahedral. The thermal behaviour of these chelates shows that the hydrated complexes losses water molecules of hydration in the first step followed immediately by decomposition of the anions and ligand molecules in the subsequent steps. The activation thermodynamic parameters, such as, E*, ΔH*, ΔS* and ΔG* are calculated from the DrTG curves using Coats-Redfern method. The synthesized ligands, in comparison to their metal complexes also were screened for their antibacterial activity against bacterial species, Escherichia Coli, Pseudomonas aeruginosa, Staphylococcus Pyogones and Fungi (Candida). The activity data show that the metal complexes to be more potent/antibacterial than the parent Shciff base ligand against one or more bacterial species.

  20. Solvate Structures and Computational/Spectroscopic Characterization of LiBF4 Electrolytes

    SciTech Connect

    Seo, D. M.; Boyle, Paul D.; Allen, Joshua L.; Han, Sang D.; Jonsson, Erlendur; Johansson, Patrik; Henderson, Wesley A.

    2014-07-21

    Crystal structures have been determined for both LiBF4 and HBF4 solvates—(acetonitrile)2:LiBF4, (ethylene glycol diethyl ether)1:LiBF4, (diethylene glycol diethyl ether)1:LiBF4, (tetrahydrofuran)1:LiBF4, (methyl methoxyacetate)1:LiBF4, (suc-cinonitrile)1:LiBF4, (N,N,N',N",N"-pentamethyldiethylenetriamine)1:HBF4, (N,N,N',N'-tetramethylethylenediamine)3/2:HBF4 and (phenanthroline)2:HBF4. These, as well as other known LiBF4 solvate structures, have been characterized by Raman vibrational spectroscopy to unambiguously assign the anion Raman band positions to specific forms of BF4-...Li+ cation coordination. In addition, complementary DFT calculations of BF4-...Li+ cation complexes have provided additional insight into the challenges associated with accurately interpreting the anion interactions from experimental Raman spectra. This information provides a crucial tool for the characterization of the ionic association interactions within electrolytes.

  1. Synthesis, spectroscopic characterization, biological screenings, DNA binding study and POM analyses of transition metal carboxylates.

    PubMed

    Uddin, Noor; Sirajuddin, Muhammad; Uddin, Nizam; Tariq, Muhammad; Ullah, Hameed; Ali, Saqib; Tirmizi, Syed Ahmed; Khan, Abdur Rehman

    2015-04-01

    This article contains the synthesis of a novel carboxylic acid derivative, its transition metal complexes and evaluation of biological applications. Six carboxylate complexes of transition metals, Zn(II) and Hg(II), have been successfully synthesized and characterized by FT-IR and NMR (1H, 13C). The ligand, HL, (4-[(2,6-Diethylphenyl)amino]-4-oxobutanoic acid) was also characterized by single crystal X-ray analysis. The complexation occurs via oxygen atoms of the carboxylate moiety. FT-IR date show the bidentate nature of the carboxylate moiety of the ligand as the ?? value in all complexes is less than that of the free ligand. The ligand and its complexes were screened for antifungal and antileishmanial activities. The results showed that the ligand and its complexes are active with few exceptions. UV-visible spectroscopy and viscometry results reveal that the ligand and its complexes interact with the DNA via intercalative mode of interaction. A new and efficient strategy to identify the pharmacophores and anti-pharmacophores sites in carboxylate derivatives for the antibacterial/antifungal activity using Petra, Osiris and Molinspiration (POM) analyses was also carried out. PMID:25646895

  2. Gas-Phase Spectroscopic Signatures of Carboxylate-Li(+) Contact Ion Pairs: New Benchmarks For Characterizing Ion Pairing in Solution.

    PubMed

    Habka, Sana; Brenner, Valérie; Mons, Michel; Gloaguen, Eric

    2016-04-01

    The coexistence of several types of ion pairs in solution together with their elusive nature hampers their experimental characterization, which relies in practice on theoretical models resorting to numerous approximations. In this context, a series of isolated contact ion pairs between a lithium cation and phenyl-tagged carboxylate anions of various lengths (Ph-(CH2)n-COO(-), n = 1-3) has been investigated in a conformer-selective manner by IR and UV laser spectroscopy, in conjunction with quantum chemistry calculations. The typical gas-phase IR signature of the bidentate structure formed between the carboxylate moiety and Li(+) has thus been obtained in the CO2(-) stretch region. In addition to the cation-anion interaction, a cation-π interaction occurs simultaneously in the largest system investigated (n = 3). The resulting distorted ion pair structure has been evidenced from both the IR signature of the CO2(-) stretches and the unique vibrationally resolved UV spectroscopy of a phenyl ring interacting with a cation. Such specific spectroscopic signatures of contact ion pairs provide experimental benchmarks, alternative to theoretical predictions, that can assist the assignment of vibrational spectra in solution. PMID:26978595

  3. Optical spectroscopic approach as a rapid tool to characterize the interactions of retinoids with human nuclear receptors

    NASA Astrophysics Data System (ADS)

    Morjani, Hamid; Sockalingum, Ganesh D.; Beljebbar, Abdelilah; Manfait, Michel

    1998-04-01

    Retinoids are potent molecules that can affect a variety of fundamental biological processes including cell differentiation and proliferation and apoptosis. These molecules elicit their biological effects by activating a family of nuclear receptors which act as ligand-inducible transcription factors belonging to the steroid/thyroid receptor superfamily. Retinoic acid receptors form heterodimers in which response to ligand binding, both partners contribute to transactivation and/or DNA binding in vivo. Surface-enhanced Raman scattering (SERS), Fourier transform-SERS (FT-SERS), fluorescence and circular dichroism are proposed to rapidly give information on the interaction of the different RARs and RXRs with their specific ligands at physiological concentrations. FT-SERS data reveal a significant attenuation in intensity of the bands originating from the retinoic polyenic chain upon complexation. The spectrum is dominantly of the (Beta) - ionone ring. Fluorescence measurements supported the hydrophobic character of the ligand binding pocket and the circular dichroic data indicate that the protein helices extend upon ligand binding. These novel spectroscopic information are fully consistent with published x-ray crystallographic results and suggest that these techniques may be valuable additional tools to characterize the interactions of agonists and antagonists with residues of the ligand binding pocket retinoid receptor homo- and hetero-dimers.

  4. Overexpression, Isolation, and Spectroscopic Characterization of the Bidirectional [NiFe] Hydrogenase from Synechocystis sp. PCC 6803*

    PubMed Central

    Germer, Frauke; Zebger, Ingo; Saggu, Miguel; Lendzian, Friedhelm; Schulz, Rüdiger; Appel, Jens

    2009-01-01

    The bidirectional [NiFe] hydrogenase of the cyanobacterium Synechocystis sp. PCC 6803 was purified to apparent homogeneity by a single affinity chromatography step using a Synechocystis mutant with a Strep-tag II fused to the C terminus of HoxF. To increase the yield of purified enzyme and to test its overexpression capacity in Synechocystis the psbAII promoter was inserted upstream of the hoxE gene. In addition, the accessory genes (hypF, C, D, E, A, and B) from Nostoc sp. PCC 7120 were expressed under control of the psbAII promoter. The respective strains show higher hydrogenase activities compared with the wild type. For the first time a Fourier transform infrared (FTIR) spectroscopic characterization of a [NiFe] hydrogenase from an oxygenic phototroph is presented, revealing that two cyanides and one carbon monoxide coordinate the iron of the active site. At least four different redox states of the active site were detected during the reversible activation/inactivation. Although these states appear similar to those observed in standard [NiFe] hydrogenases, no paramagnetic nickel state could be detected in the fully oxidized and reduced forms. Electron paramagnetic resonance spectroscopy confirms the presence of several iron-sulfur clusters after reductive activation. One [4Fe4S]+ and at least one [2Fe2S]+ cluster could be identified. Catalytic amounts of NADH or NADPH are sufficient to activate the reaction of this enzyme with hydrogen. PMID:19801638

  5. Synthesis, spectroscopic characterization and antibacterial activity of antimony(III) bis(dialkyldithiocarbamato)alkyldithiocarbonates.

    PubMed

    Chauhan, H P S; Bakshi, Abhilasha; Bhatiya, Sumit

    2011-10-15

    Some mixed sulfur donor ligand complexes of antimony(III) of the general formula [(R(2)NCS(2))](2)SbS(2)COR' where R = CH(3), C(2)H(5) and R' = Me, Et, Pr(n), Pr(i), Bu(n) and Bu(i) have been synthesized by the reaction of antimony(III) bis(dialkyldithiocarbamate) chloride with potassium organodithiocarbonate in an equimolar ratio by stirring at room temperature in benzene/CS(2) mixture. These complexes have been characterized by physicochemical [elemental analysis, melting points and molecular weight determinations] and spectral [UV, IR, Far-IR, NMR ((1)H and (13)C), FAB(+) mass and powder X-ray diffraction] studies. Free ligands and synthesized complexes have also been screened against different bacterial strains and results obtained made it desirable to delineate a comparison between free ligands, standard drug used and synthesized complexes. PMID:21764366

  6. Cloning and characterization of Enterobacter sakazakii pigment genes and in situ spectroscopic analysis of the pigment.

    PubMed

    Lehner, Angelika; Grimm, Maya; Rattei, Thomas; Ruepp, Andreas; Frishman, Dmitrij; Manzardo, Giuseppe G G; Stephan, Roger

    2006-12-01

    Enterobacter sakazakii is considered an opportunistic foodborne pathogen that is characterized by formation of yellow-pigmented colonies. Because of the lack of basic knowledge about Enterobacter sakazakii genetics, the BAC approach and the heterologous expression of the pigment in Escherichia coli were used to elucidate the molecular structure of the genes responsible for pigment production in Enterobacter sakazakii strain ES5. Sequencing and annotation of a 33.025 bp fragment revealed seven ORFs that could be assigned to the carotenoid biosynthesis pathway. The gene cluster had the organization crtE-idi-XYIBZ, with the crtE-idi-XYIB genes putatively transcribed as an operon and the crtZ gene transcribed in the opposite orientation. The carotenogenic nature of the pigment of Enterobacter sakazakii wt was ascertained by in situ analysis using visible microspectroscopy and resonance Raman microspectroscopy. PMID:17069626

  7. 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.

  8. NMR spectroscopic characterization of β-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 β-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 β-cyclodextrin has been obtained at 298 K by fitting the experimental chemical shifts differences, Δδobs = δfree - δobs 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.

  9. Raman spectroscopic characterization of the core-rim structure in reaction bonded boron carbide ceramics

    SciTech Connect

    Jannotti, Phillip; Subhash, Ghatu; Zheng, James Q.; Halls, Virginia; Karandikar, Prashant G.; Salamone, S.; Aghajanian, Michael K.

    2015-01-26

    Raman spectroscopy was used to characterize the microstructure of reaction bonded boron carbide ceramics. Compositional and structural gradation in the silicon-doped boron carbide phase (rim), which develops around the parent boron carbide region (core) due to the reaction between silicon and boron carbide, was evaluated using changes in Raman peak position and intensity. Peak shifting and intensity variation from the core to the rim region was attributed to changes in the boron carbide crystal structure based on experimental Raman observations and ab initio calculations reported in literature. The results were consistent with compositional analysis determined by energy dispersive spectroscopy. The Raman analysis revealed the substitution of silicon atoms first into the linear 3-atom chain, and then into icosahedral units of the boron carbide structure. Thus, micro-Raman spectroscopy provided a non-destructive means of identifying the preferential positions of Si atoms in the boron carbide lattice.

  10. Infrared spectroscopic characterization of [2]rotaxane molecular switch tunnel junction devices.

    PubMed

    DeIonno, Erica; Tseng, Hsian-Rong; Harvey, Desmond D; Stoddart, J Fraser; Heath, James R

    2006-04-20

    Langmuir-Blodgett monolayers of a bistable [2]rotaxane were prepared at packing densities of 118, 73, and 54 A(2)/molecule. The monolayers were both characterized via infrared spectroscopy before and after evaporation of a 2 nm film of titanium and incorporated into molecular switch tunnel junction devices. The study suggests that the evaporation process primarily affects portions of the molecule exposed to the metal atom source. Thus, in tightly packed monolayers (73 and 54 A(2)/molecule), only the portions of the [2]rotaxane that are present at the molecule/air interface are clearly affected, leaving key functionality necessary for switching intact. Monolayers transferred at a lower pressure (118 A(2)/molecule) exhibit nonspecific damage and poor switching behavior following Ti deposition. These results indicate that tightly packed monolayers and sacrificial functionality displayed at the molecule/air interface are important design principles for molecular electronic devices. PMID:16610848

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

    PubMed

    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. PMID:25617979

  12. 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

  13. Structural and spectroscopic characterization of prepared Ag2S nanoparticles with a novel sulfuring agent

    NASA Astrophysics Data System (ADS)

    Shakouri-Arani, Maryam; Salavati-Niasari, Masoud

    2014-12-01

    Ag2S nanoparticles were prepared by a solvothermal process via reaction of Ag(NO3) and a new sulfuring agent from class of thio Schiff-base (2-(benzylidene amino) benzenethiol (C13H11NS)) in presence of various solvents. Spectra such as X-ray diffraction (XRD), transmission electron microscopy (TEM), selected area electron diffraction (SEAD), ultraviolet-visible (UV-Vis) spectroscopy, thermo gravimetric-differential thermal analysis (TG-DTA), and Fourier transform Infrared (FT-IR) employed to characterize the synthesized products. Results of this paper indicate that shape and size of the silver sulfide can be controlled by means of setting certain reaction parameters such as the reaction temperature, presence of surfactant, and type of solvent. Silver sulfide nanoparticles with different morphology and size successfully prepared. In addition, the growth mechanisms of the Ag2S nanoparticles discussed preliminarily.

  14. Synthesis and spectroscopic characterization of gold nanobipyramids prepared by a chemical reduction method

    NASA Astrophysics Data System (ADS)

    Thanh Ngo, Vo Ke; Phat Huynh, Trong; Giang Nguyen, Dang; Phuong Uyen Nguyen, Hoang; Lam, Quang Vinh; Dat Huynh, Thanh

    2015-12-01

    Gold nanobipyramids (NBPs) have attracted much attention because they have potential for applications in smart sensing devices, such as medical diagnostic equippments. This is due to the fact that they show more advantageous plasmonic properties than other gold nanostructures. We describe a chemical reduction method for synthesizing NBPs using conventional heating with ascorbic acid reduction and cetyltrimethylamonium bromide (CTAB) + AgNO3 as capping agents. The product was characterized by ultraviolet-visible spectroscopy (UV-vis), Fourier transmission infrared spectroscopy (FTIR), transmission electron microscopy (TEM), x-ray powder diffraction (XRD). The results showed that gold nanoparticles were formed with bipyramid shape (tip-to-tip distance of 88.4 ± 9.4 nm and base length of 29.9 ± 3.2 nm) and face-centered-cubic crystalline structure. Optimum parameters for preparation of NBPs are also found.

  15. Raman Spectroscopic Characterization of Packaged L. pneumophila Strains Expelled by T. thermophila.

    PubMed

    Kusi?, Dragana; Ramoji, Anuradha; Neugebauer, Ute; Rsch, Petra; Popp, Jrgen

    2016-03-01

    The intracellular lifestyle of L. pneumophila within protozoa is considered to be a fundamental process that supports its survival in nature. However, after ingesting the cells of L. pneumophila, some protozoa expel them as compressed live cells in the form of small rounded pellets. The pellets of tightly packaged viable but not culturable forms (VBNCFs) as well as highly infectious mature intracellular forms (MIFs) of L. pneumophila are considered as infectious particles most likely capable to cause human infection. Since L. pneumophila cells are hardly culturable from these pellets, detection methods for packaged live L.pneumophila forms remaining in water should be cultivation free. Hence, we demonstrate the potential of Raman microspectroscopy to directly sort pellets containing L. pneumophila cells, expelled by T.thermophila, and to characterize them on the basis of their Raman spectra. PMID:26853973

  16. Spectroscopic and morphological characterization of inflow cannulas of left ventricular assist devices.

    PubMed

    Pappalardo, Federico; Cristaldi, Domenico A; Fragalà, Ignazio L; Millesi, Salvatrice; De Bonis, Michele; Gulino, Antonino

    2015-01-01

    Despite the consistent clinical data on the positive effects of left ventricular assist devices (LVADs) in the treatment of refractory heart failure, unfortunately these devices yet show some limitations such as the risk of stroke, infection, and device malfunction. The complex interplay between blood and the foreign material has a major role in the occurrence of these complications and biocompatibility of the inflow cannula would be pivotal in these terms. In this study, we carried out an in-depth physicochemical characterization of two commercially available LVADs by means of field emission gun scanning electron microscopy, energy dispersive X-ray, and X-ray photoelectron spectra. Our results show that, despite both pumps share the same physicochemical concepts, major differences can be identified in the surface nature, morphology, and chemical composition of their inflow cannulas. PMID:25396275

  17. Raman spectroscopic characterization of the core-rim structure in reaction bonded boron carbide ceramics

    NASA Astrophysics Data System (ADS)

    Jannotti, Phillip; Subhash, Ghatu; Zheng, James Q.; Halls, Virginia; Karandikar, Prashant G.; Salamone, S.; Aghajanian, Michael K.

    2015-01-01

    Raman spectroscopy was used to characterize the microstructure of reaction bonded boron carbide ceramics. Compositional and structural gradation in the silicon-doped boron carbide phase (rim), which develops around the parent boron carbide region (core) due to the reaction between silicon and boron carbide, was evaluated using changes in Raman peak position and intensity. Peak shifting and intensity variation from the core to the rim region was attributed to changes in the boron carbide crystal structure based on experimental Raman observations and ab initio calculations reported in literature. The results were consistent with compositional analysis determined by energy dispersive spectroscopy. The Raman analysis revealed the substitution of silicon atoms first into the linear 3-atom chain, and then into icosahedral units of the boron carbide structure. Thus, micro-Raman spectroscopy provided a non-destructive means of identifying the preferential positions of Si atoms in the boron carbide lattice.

  18. 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.

  19. 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.

  20. Meso-Scale Modeling to Characterize Moisture Absorption of 3D Woven Composite

    NASA Astrophysics Data System (ADS)

    Yuan, Yuan; Zhou, Chu-wei

    2016-03-01

    For polymer-matrix composites, moisture is expected to degrade their mechanical properties due to matrix plasticization and moisture introduced micro-scale defects. In this study, the moisture absorptions of bulk epoxy, unidirectional composite (UD) and 3D woven composite (3D WC) were tested. Two-stage features have been observed for all these three materials. Moisture properties for UD and 3D WC were found not in simple direct proportion to their matrix volume fractions. The moisture approach of UD was modeled including the effect of fiber/matrix interphase which promotes the moisture uptake. Then, meso-scale FE model for 3D WC was established to characterize the inhomogeneous moisture diffusion. The moisture properties of resin-rich region and fiber bundle in 3D WC were determined from water uptake experiments of bulk epoxy and UD, respectively. Through homogenizing moisture properties of surface and interior weave structures, a simplified theoretical sandwich moisture diffusion approach was established. The moisture weight gains of 3D WC predicted by both meso-scale FE model and simplified sandwich approach were well agreed with the experimental data.

  1. 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

  2. CSP Spectroscopic Classification of AT 2016adj in NGC 5128 (Centaurus A)

    NASA Astrophysics Data System (ADS)

    Stritzinger, M.; Hsiao, E. Y.; Morrell, N.; Phillips, M. M.; Contreras, C.; Castellón, S.; Clocchiatti, A.

    2016-02-01

    We report spectroscopic classification of AT 2016adj (cf. ATEL #8651) based on a visual-wavelength spectrum obtained on Feb. 9.2 UT with the 2.5-m du Pont Telescope (+ WFCCD) at LCO. The spectrum exhibits prevalent Na-I D absorption at the redshift of NGC 5128 characterized by an equivalent width of 0.44-nm.

  3. Infrared spectroscopic characterization of the interaction of cationic lipids with plasmid DNA.

    PubMed

    Choosakoonkriang, S; Wiethoff, C M; Anchordoquy, T J; Koe, G S; Smith, J G; Middaugh, C R

    2001-03-16

    Fourier transform infrared spectroscopy was used to characterize the interaction of the cationic lipids 1,2-dioleoyl-3-trimethylammonium-propane and dioctadecyldimethylammonium bromide with plasmid DNA. The effect of incorporating the neutral colipids cholesterol and dioleoylphosphatidylethanolamine on this interaction was also examined. Additionally, dynamic and phase analysis light scattering were used to monitor the size and zeta potential of the resulting complexes under conditions similar to the Fourier transform infrared measurements. Results suggest that upon interaction of cationic lipids with DNA, the DNA remains in the B form. Distinct changes in the frequency of several infrared bands arising from the DNA bases, however, suggest perturbation of their hydration upon interaction with cationic lipids. A direct interaction of the lipid ammonium headgroup with and dehydration of the DNA phosphate is observed when DNA is complexed with these lipids. Changes in the apolar regions of the lipid bilayer are minimal, whereas the interfacial regions of the membrane show changes in hydration or molecular packing. Incorporation of helper lipids into the cationic membranes results in increased conformational disorder of the apolar region and further dehydration of the interfacial region. Changes in the hydration of the DNA bases were also observed as the molar ratio of helper lipid in the membranes was increased. PMID:11118456

  4. Synthesis, spectroscopic and computational characterization of the tautomerism of pyrazoline derivatives from chalcones

    NASA Astrophysics Data System (ADS)

    Miguel, Fbio Balbino; Dantas, Juliana Arantes; Amorim, Stefany; Andrade, Gustavo F. S.; Costa, Luiz Antnio Sodr; Couri, Mara Rubia Costa

    2016-01-01

    In the present study a series of novel pyrazolines derivatives has been synthesized, and their structures assigned on the basis of FT-Raman, 1H and 13C NMR spectral data and computational DFT calculations. A joint computational study using B3LYP/6-311G(2d,2p) density functional theory and FT-Raman investigation on the tautomerism of 3-(4-substituted-phenyl)-4,5-dihydro-5-(4-substituted-phenyl)pyrazole-1-carbothioamide and 3-(4-substituted-phenyl)-4,5-dihydro-5-(4-substituted-phenyl)pyrazole-1-carboxamide are presented. The structures were characterized as a minimum in the potential energy surface using DFT. The calculated Raman and NMR spectra were of such remarkable agreement to the experimental results that the equilibrium between tautomeric forms has been discussed in detail. Our study suggests the existence of tautomers, the carboxamide/carbothioamide group may tautomerize, in the solid state or in solution. Thermodynamic data calculated suggests that the R(Cdbnd S)NH2 and R(Cdbnd O)NH2 species are more stable than the R(Cdbnd NH)SH and R(Cdbnd NH)OH species. Additionally, results found for the 1H NMR shifting, pointed out to which structure is present.

  5. Spectroscopic, Structural, and Computational Characterization of Three Bispidinone Derivatives, as Ligands for Enantioselective Metal Catalyzed Reactions.

    PubMed

    Castellano, Carlo; Sacchetti, Alessandro; Meneghetti, Fiorella

    2016-04-01

    Three chiral derivatives of the alkaloid sparteine (bispidines), characterized by the 3,7-diazabicyclo[3.3.1]nonane moiety, were designed as efficient ligands in a number of enantioselective reactions due to their metal coordination properties. A full evaluation of the 3D properties of the compounds was carried out, as the geometrical features of the bicyclic framework are strictly related to the efficiency of the ligands in the asymmetric catalysis. The selected molecules have different molecular complexity for investigating the effects of different chiral groups on the bicycle conformation. We report here a thorough analysis of their molecular arrangement, by NMR spectroscopy, single crystal X-ray crystallography, and computational techniques, which put in evidence their conformational preferences and the parameters needed for the design of more efficient ligands in asymmetric synthetic routes. The results confirmed the high molecular flexibility of the compounds, and indicated how to achieve a control of the chair-chair/boat-chair conformational ratio, by adjusting the relative size of the substituents on the piperidine nitrogens. Chirality 28:332-339, 2016. © 2016 Wiley Periodicals, Inc. PMID:26899470

  6. 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.

  7. 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

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

    PubMed

    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 (1)H, (13)C and (93)Nb NMR, UV-Vis, and FT-IR spectroscopies, and single-crystal X-ray diffraction. The molecular structures of the niobium complexes, [Nb4(μ-O)4(μ-OEt)2(ONC10H8)2(OEt)8] (I) and [Nb4(μ-O)4(μ-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 (93)Nb NMR spectra of complexes. PMID:25756687

  9. 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(μ-O)4(μ-OEt)2(ONC10H8)2(OEt)8] (I) and [Nb4(μ-O)4(μ-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.

  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. Combined Raman spectroscopic and electrical characterization of the conductive channel in pentacene based OFETs

    NASA Astrophysics Data System (ADS)

    Paez S., Beynor A.; Thurzo, Ilja; Salvan, Georgeta; Scholz, Reinhard; Zahn, Dietrich R. T.; von Seggern, H.

    2005-08-01

    During the deposition of Pentacene on a Si-SiO2 gate structure with Au bottom contacts for source and drain, the film growth was monitored with simultaneous in situ macro Raman spectroscopy and drain current measurements of the OFET device. The deposition of the active layer was carried out under UHV conditions at a growth rate of 0.65 Å/min. The purpose of the in situ characterization was to determine the minimum nominal thickness of the Pentacene layer required for efficient charge transport through the OFET circuit. At a thickness around 1.5 nm nominal coverage, the first percolation paths through the first organic monolayer develop, resulting in a sharp rise of the drain current. Up to a nominal film thickness of 30 nm, a subsequent slower increase of the drain current can be observed, revealing that the percolation of the first monolayer continues on a slower pace up to rather thick organic layers. These in situ measurements were complemented by ex situ isothermal deep level transient spectroscopy (charge QTS).

  12. Spectroscopic characterization and molecular modeling of novel palladium(II) complexes with carbazates and hydrazides

    NASA Astrophysics Data System (ADS)

    Sousa, L. M.; Corbi, P. P.; Formiga, A. L. B.; Lancellotti, Marcelo; Marzano, I. M.; Pereira-Maia, E. C.; Von Poelhsitz, G.; Guerra, W.

    2015-10-01

    Palladium(II) complexes of the type trans-[Pd(L)2Cl2], where L = 4-methoxybenzylcarbazate (4-MC), benzyl carbazate (BC), 4-fluorophenoxyacetic acid hydrazide (4-FH), 3-methoxybenzoic acid hydrazide (3-MH), ethyl carbazate (EC) and tert-butyl carbazate (TC) were synthesized by the slow addition of the ligand to K2PdCl4 previously dissolved in water or ethanol. These complexes were characterized by elemental analyses, conductivity measurements, TG/DTA, FT-IR, mass spectrometric and NMR spectroscopy (solution and solid-state). All coordination compounds exhibit a square planar coordination geometry in which the palladium(II) ion coordinates to two nitrogen atoms and two chlorine atoms. The structures of the palladium(II) complexes were optimized and theoretical data show that the trans isomer is more stable, in accordance with the experimental data. Preliminary in vitro tests of some these new palladium complexes in a chronic myelogenous leukemia cell line (k562 cells) are also reported.

  13. Spectroscopic characterization of zinc oxide nanorods synthesized by solid-state reaction.

    PubMed

    Prasad, Virendra; D'Souza, Charlene; Yadav, Deepti; Shaikh, A J; Vigneshwaran, Nadanathangam

    2006-09-01

    Well-crystallized zinc oxide nanorods have been fabricated by single step solid-state reaction using zinc acetate and sodium hydroxide, at room temperature. The sodium lauryl sulfate (SLS) stabilized zinc oxide nanorods were characterized by using X-ray diffraction, Fourier transform infrared spectroscopy, transmission electron microscopy and photoluminescence spectroscopy. The X-ray diffraction revealed the wurtzite structure of zinc oxide. The size estimation by XRD and TEM confirmed that the ZnO nanorods are made of single crystals. The growth of zinc oxide crystals into rod shape was found to be closely related to its hexagonal nature. The mass ratio of SLS:ZnO in the nanorods was found to be 1:10 based on the thermogravimetric analysis. Blue shift of photoluminescence emission was noticed in the ZnO nanorods when compared to that of ZnO bulk. FT-IR analysis confirmed the binding of SLS with ZnO nanorods. Apart from ease of preparation, this method has the advantage of eco-friendliness since the solvent and other harmful chemicals were eliminated in the synthesis protocol. PMID:16458053

  14. Synthesis, spectroscopic and computational characterization of the tautomerism of pyrazoline derivatives from chalcones.

    PubMed

    Miguel, Fábio Balbino; Dantas, Juliana Arantes; Amorim, Stefany; Andrade, Gustavo F S; Costa, Luiz Antônio Sodré; Couri, Mara Rubia Costa

    2016-01-01

    In the present study a series of novel pyrazolines derivatives has been synthesized, and their structures assigned on the basis of FT-Raman, (1)H and (13)C NMR spectral data and computational DFT calculations. A joint computational study using B3LYP/6-311G(2d,2p) density functional theory and FT-Raman investigation on the tautomerism of 3-(4-substituted-phenyl)-4,5-dihydro-5-(4-substituted-phenyl)pyrazole-1-carbothioamide and 3-(4-substituted-phenyl)-4,5-dihydro-5-(4-substituted-phenyl)pyrazole-1-carboxamide are presented. The structures were characterized as a minimum in the potential energy surface using DFT. The calculated Raman and NMR spectra were of such remarkable agreement to the experimental results that the equilibrium between tautomeric forms has been discussed in detail. Our study suggests the existence of tautomers, the carboxamide/carbothioamide group may tautomerize, in the solid state or in solution. Thermodynamic data calculated suggests that the R(CS)NH2 and R(CO)NH2 species are more stable than the R(CNH)SH and R(CNH)OH species. Additionally, results found for the (1)H NMR shifting, pointed out to which structure is present. PMID:26232575

  15. Mononuclear metal complexes of organic carboxylic acid derivatives: Synthesis, spectroscopic characterization, thermal investigation and antimicrobial activity

    NASA Astrophysics Data System (ADS)

    Abd El-Wahab, Zeinab H.

    2007-05-01

    Two Schiff base ligands bearing organic acid moiety, vis., N-(2-thienylmethylidene)-2-amino-4-chlorobenzoic acid (HL 1) and N-(2-hydroxybenzylidene)-2-amino-4-chlorobenzoic acid (H 2L 2) have been synthesized by the interaction of 2-thiophenecarboxaldehyde and 2-hydroxybenzaldehyde with 2-amino-4-chlorobenzoic acid. Co(II), Ni(II), Cu(II) and Zn(II) complexes of these ligands have been prepared. They are characterized on the basis of analytical data, molar conductance, IR, 1H NMR, UV-vis, mass spectra, magnetic measurements, thermal analysis and X-ray powder diffraction technique. The molar conductance data reveal that these complexes are non-electrolytes. The ligands are coordinated to the metal ions in a terdentate manner with ONO/ONS donor sites of the carbonyl oxygen, azomethine nitrogen and phenolic oxygen or thiophenic sulphur. An octahedral structure is proposed for the prepared metal complexes and some ligand field parameters ( Dq, B and β) in addition to CFSE were calculated. The thermal stability of the metal complexes is evaluated. The Schiff base ligands and their metal complexes have been tested against four species of bacteria as well as four species of fungi and the results have been compared with some known antibiotics.

  16. Raman, infrared and near-infrared spectroscopic characterization of the herderite-hydroxylherderite mineral series

    NASA Astrophysics Data System (ADS)

    Frost, Ray L.; Scholz, Ricardo; López, Andrés; Xi, Yunfei; Queiroz, Camila de Siqueira; Belotti, Fernanda M.; Filho, Mauro Cândido

    2014-01-01

    Natural single-crystal specimens of the herderite-hydroxylherderite series from Brazil, with general formula CaBePO4(F,OH), were investigated by electron microprobe, Raman, infrared and near-infrared spectroscopies. The minerals occur as secondary products in granitic pegmatites. Herderite and hydroxylherderite minerals show extensive solid solution formation. The Raman spectra of hydroxylherderite are characterized by bands at around 985 and 998 cm-1, assigned to ν1 symmetric stretching mode of the HOPO33- and PO43- units. Raman bands at around 1085, 1128 and 1138 cm-1 are attributed to both the HOP and PO antisymmetric stretching vibrations. The set of Raman bands observed at 563, 568, 577, 598, 616 and 633 cm-1 are assigned to the ν4 out of plane bending modes of the PO4 and H2PO4 units. The OH Raman stretching vibrations of hydroxylherderite were observed ranging from 3626 cm-1 to 3609 cm-1. The infrared stretching vibrations of hydroxylherderites were observed between 3606 cm-1 and 3599 cm-1. By using a Libowitzky type function, hydrogen bond distances based upon the OH stretching bands were calculated. Characteristic NIR bands at around 6961 and 7054 cm-1 were assigned to the first overtone of the fundamental, whilst NIR bands at 10,194 and 10,329 cm-1 are assigned to the second overtone of the fundamental OH stretching vibration. Insight into the structure of the herderite-hydroxylherderite series is assessed by vibrational spectroscopy.

  17. Syntheses, crystal structure, spectroscopic characterization and antifungal activity of new N-R-sulfonyldithiocarbimate metal complexes.

    PubMed

    Alves, Leandro C; Rubinger, Mayura M M; Lindemann, Renata H; Perpétuo, Genivaldo J; Janczak, Jan; Miranda, Liany D L; Zambolim, Laércio; Oliveira, Marcelo R L

    2009-07-01

    Five new compounds with the general formula of (Bu(4)N)(2)[M(RSO(2)NCS(2))(2)], where Bu(4)N=tetrabutylammonium cation, (M=Ni, R=4-FC(6)H(4)) (1), (M=Zn, R=4-FC(6)H(4), 4-ClC(6)H(4), 4-BrC(6)H(4), 4-IC(6)H(4)), (2), (3), (4) and (5), respectively, were obtained by the reaction of the appropriate potassium N-R-sulfonyldithiocarbimate (RSO(2)N=CS(2)K(2)) with nickel(II) chloride hexahydrate or zinc(II) acetate dihydrate in metanol:water 1:1. The elemental analyses and the IR data are consistent with the formation of the expected bis(dithiocarbimato)metal(II) complexes. The (1)H and (13)C NMR spectra showed the signals for the tetrabutylammonium cation and the dithiocarbimate moieties. The compounds 1, 2 and 5 were also characterized by X-ray diffraction techniques. The nickel(II) is coordinated by two N-4-fluorophenylsulphonyldithiocarbimato(2-) ligands forming a planar coordination. The zinc(II) exhibits distorted tetrahedral configuration in compounds 2 and 5 due to the chelation effect of two sulfur atoms of the N-R-sulfonyldithiocarbimate ligands. The antifungal activities of the compounds were tested in vitro against Colletotrichum gloeosporioides, an important fungus that causes the plant disease known as anthracnose in fruit trees. All the complexes were active. PMID:19505726

  18. Spectroscopic Characterizations of Molecularly-Linked Gold Nanoparticle Assemblies Upon Thermal Treatment

    SciTech Connect

    Luo, Jin; Maye, Mathew M.; Han, Li; Kariuki, Nancy N.; Jones, V W.; Lin, Yuehe; Engelhard, Mark H.; Zhong, Chuan-Jian

    2004-05-11

    Nanostructured gold catalysts have attracted increasing interest since the pioneer work of Haruta which demonstrated unusually high catalytic activities for CO oxidation when the nanoparticles were made less than {approx}10 nm diameter in size and supported on oxides. It is possible to use core-shell gold nanoparticles to construct the catalyst and activate the catalytic activity by applying a thermal-treatment process. The understanding of how the core-shell surface components reconstitute in such a catalytic activation process will have important implications in expanding this approach to the design and fabrication of nanostructured catalysts. We report herein the results of a study of decanethiolate-capped gold nanoparticles of 2-nm and 5-nm core sizes assembled on planar substrates using 1,9-nonanedithiol (NDT) and 11-mercaptoundecanoic acid (MUA) as molecular linkers were studied as a model system. XPS and IR are employed to detect the identity of surface species and to analyze the elemental composition or oxidation states of the nanomaterials, from which we derive structural information about the surface reconstitution of the core-shell nanostructured catalysts. Electrochemical methods are used to characterize the electrocatalytic activities.

  19. Raman, infrared and near-infrared spectroscopic characterization of the herderite-hydroxylherderite mineral series.

    PubMed

    Frost, Ray L; Scholz, Ricardo; López, Andrés; Xi, Yunfei; Queiroz, Camila de Siqueira; Belotti, Fernanda M; Cândido Filho, Mauro

    2014-01-24

    Natural single-crystal specimens of the herderite-hydroxylherderite series from Brazil, with general formula CaBePO4(F,OH), were investigated by electron microprobe, Raman, infrared and near-infrared spectroscopies. The minerals occur as secondary products in granitic pegmatites. Herderite and hydroxylherderite minerals show extensive solid solution formation. The Raman spectra of hydroxylherderite are characterized by bands at around 985 and 998 cm(-1), assigned to ν1 symmetric stretching mode of the HOPO3(3-) and PO4(3-) units. Raman bands at around 1085, 1128 and 1138 cm(-1) are attributed to both the HOP and PO antisymmetric stretching vibrations. The set of Raman bands observed at 563, 568, 577, 598, 616 and 633 cm(-1) are assigned to the ν4 out of plane bending modes of the PO4 and H2PO4 units. The OH Raman stretching vibrations of hydroxylherderite were observed ranging from 3626 cm(-1) to 3609 cm(-1). The infrared stretching vibrations of hydroxylherderites were observed between 3606 cm(-1) and 3599 cm(-1). By using a Libowitzky type function, hydrogen bond distances based upon the OH stretching bands were calculated. Characteristic NIR bands at around 6961 and 7054 cm(-1) were assigned to the first overtone of the fundamental, whilst NIR bands at 10,194 and 10,329 cm(-1) are assigned to the second overtone of the fundamental OH stretching vibration. Insight into the structure of the herderite-hydroxylherderite series is assessed by vibrational spectroscopy. PMID:24076459

  20. Characterization of tablet film coatings using a laser-induced breakdown spectroscopic technique.

    PubMed

    Madamba, M Cecilia; Mullett, Wayne M; Debnath, Smita; Kwong, Elizabeth

    2007-01-01

    Laser-induced breakdown spectroscopy (LIBS) was evaluated as an early phase process analytical technology (PAT) tool for the rapid characterization of pharmaceutical tablet coatings. Measurement of coating thickness, uniformity, and photodegradation-predictive potential of the technique were evaluated. Model formulation tablets were coated with varying amounts (2%-4% wt/wt) of red and yellow Opadry II, and a pulsed laser was used to sample at multiple sites across the tablet face. LIBS was able to successfully detect the emissions of Fe and Ti in the coated samples, and a proportional increase in signal with coating thickness was observed. Batch-to-batch variability in the coating procedure was also easily monitored by LIBS. The coating thickness was non-uniform across the tablet surface with higher thickness at the edges, likely due to the concave shape of the tablet. Film coating levels and color of the film had been subjected to photostability studies according to the International Conference on Harmonisation (ICH) guideline to determine effectiveness of the film coats. LIBS measurements of coating thickness provided a good correlation (R (2) > 0.99) to photodegradation as measured by high-performance liquid chromatography (HPLC). Last, the concentration of Fe in the coating was varied and monitored by LIBS. Increasing photostability was observed with increasing levels of ferric oxide, providing a new understanding of the photoprotection mechanism in the coated formulation. Determination of levels of ferric oxide and coating thickness by LIBS demonstrated its utility as a good PAT tool for the determination of photoprotection of the drug, thereby enabling facile optimization of the coating process. PMID:18181524

  1. Osmium NAMI-A analogues: synthesis, structural and spectroscopic characterization, and antiproliferative properties.

    PubMed

    Cebrin-Losantos, Berta; Krokhin, Artem A; Stepanenko, Iryna N; Eichinger, Rene; Jakupec, Michael A; Arion, Vladimir B; Keppler, Bernhard K

    2007-06-11

    The osmium(III) complex [(DMSO)2H][trans-OsIIICl4(DMSO)2] (1) has been prepared via stepwise reduction of OsO4 in concentrated HCl using N2H(4).2HCl and SnCl(2).2H2O in DMSO. 1 reacts with a number of azole ligands, namely, indazole (Hind), pyrazole (Hpz), benzimidazole (Hbzim), imidazole (Him), and 1H-1,2,4-triazole (Htrz), in organic solvents, affording novel complexes (H2ind)[OsIIICl4(Hind)(DMSO)] (2), (H2pz)[OsIIICl4(Hpz)(DMSO)] (3), (H2bzim)[OsIIICl4(Hbzim)(DMSO)] (4), (H2im)[OsIIICl4(Him)(DMSO)] (6), and (H2trz)[OsIIICl4(Htrz)(DMSO)] (7), which are close analogues of the antimetastatic complex NAMI-A. Metathesis reaction of 4 with benzyltriphenylphosphonium chloride in methanol led to the formation of (Ph3PCH2Ph)[OsIIICl4(Hbzim)(DMSO)] (5). The complexes were characterized by IR, UV-vis, ESI mass spectrometry, 1H NMR spectroscopy, cyclic voltammetry, and X-ray crystallography. In contrast to NAMI-A, 2-4, 6, and 7 are kinetically stable in aqueous solution and resistant to hydrolysis. Surprisingly, they show reasonable antiproliferative activity in vitro in two human cell lines, HT-29 (colon carcinoma) and SK-BR-3 (mammary carcinoma), when compared with analogous ruthenium compounds. Structure-activity relationships and the potential of the prepared complexes for further development are discussed. PMID:17497853

  2. Structural and spectroscopic characterization of ettringite mineral -combined DFT and experimental study

    NASA Astrophysics Data System (ADS)

    Scholtzová, Eva; Kucková, Lenka; Kožíšek, Jozef; Tunega, Daniel

    2015-11-01

    The structure of the ettringite mineral was studied by means of FTIR spectroscopy and single crystal X-ray diffraction method. The experimental study was combined with the first principle calculations based on density functional theory (DFT) method. Predicted structural parameters (unit cell vectors and positions of heavy atoms) are in a very good agreement with the experimental data. Moreover, calculations also enabled to refine the positions of the hydrogen atoms not determined precisely by the single crystal X-ray measurement. The detailed analysis of the hydrogen bonds in the ettringite structure was performed and several groups of the hydrogen bonds were classified. It was found that the water molecules from the coordination sphere of Ca2+ cations act as proton donors in moderate O-H···O hydrogen bonds with SO 32- anions. Further, multiple O-H···O hydrogen bonds were identified among water molecules themselves. In addition, also hydroxyl groups from the [Al(OH)6]3- octahedral units are involved in the weak O-H···O hydrogen bonding with the water molecules. The calculated vibrational spectrum showed all typical features observed in the experimental FTIR spectrum. Moreover, performing the analysis of the calculated spectrum, all vibrational modes were distinguished and assigned. Such a complete analysis of the measured IR and/or Raman spectra is not fully possible, specifically for the region below 1500 cm-1, which is characterized by a complex curve with many overlapped bands. A comparison of the vibrational spectra of ettringite and thaumasite (mineral structurally similar to ettringite) revealed the origin of the most important differences between them.

  3. Synthesis, spectroscopic characterization, and conformational properties of trichloromethanesulfenyl acetate, CCl3SOC(O)CH3.

    PubMed

    Reina, Marlene Cuaquira; Boese, Roland; Ge, Maofa; Ulic, Sonia E; Beckers, Helmut; Willner, Helge; Della Vdova, Carlos O

    2008-08-28

    Trichloromethanesulfenyl acetate, CCl 3SOC(O)CH 3, belongs to the family of sulfenic esters. This molecule has been characterized by vibrational spectroscopy. The conformational and geometrical properties of this species have been determined by IR and Raman spectroscopy, X-ray diffraction, and quantum chemical calculations. Geometry optimizations of the most stable forms were performed with ab initio (HF, MP2) and density functional theory (B3LYP) methods. According to our data, this compound results in a gauche-syn conformer with C 1 symmetry (gauche orientation around the S-O bond and syn orientation of the CO double bond with respect to the S-O single bond) for the most stable geometry, and trans-syn conformer with C s symmetry (trans orientation around the S-O bond and syn orientation of the CO double bond with respect to the S-O single bond) for the second stable conformer (1.1 and 0.53 kcal/mol higher in energy than the most stable C 1 form according to the matrix FTIR spectroscopy and MP2/6-31G* level of the theory, respectively). The crystalline solid (monoclinic, P2 1/ n, a = 8.0152(17) A, b = 5.7922(13) A, c = 17.429(4) A, alpha = gamma = 90 degrees , beta = 100.341(3) degrees ) consists exclusively of the main form. The geometrical parameters (X-ray diffraction) are d C-Cl = 1.767(19) A, d C-S = 1.797(2) A, d S-O = 1.663(14) A, d CO = 1.189(2) A, d O-C = 1.389(3) A, d C-C = 1.483(3) A, angles Cl-C-Cl = 110.3(11) degrees , Cl-C-S = 111.8(12) degrees , C-S-O = 97.4(8) degrees , S-O-C = 116.7(11) degrees , O-CO = 122.8(19) degrees , OC-C = 127.1(2) degrees , and the main torsion angles are delta(CSOC) = 105.9(15) degrees and delta(SOC(O)) = 7.6(3) degrees . The geometrical data calculated with B3LYP/6-31G++(3df,3pd), B3LYP/6-311G++(3df,3pd), B3LYP/aug-cc-pVTZ, and MP2/6-31G* are in good agreement with diffraction data. PMID:18671379

  4. Characterization of butyrate-dependent electroneutral Na-Cl absorption in the rat distal colon.

    TOXLINE Toxicology Bibliographic Information

    Binder HJ; Mehta P

    1990-12-01

    Recent studies have established that mucosal butyrate stimulates electroneutral sodium-chloride (Na-Cl) absorption in the distal colon of the rat and a model in which Na-hydrogen (H) and Cl-butyrate exchanges are coupled has been proposed as the mechanism of butyrate-dependent electroneutral Na-Cl absorption. These studies were designed to examine butyrate-dependent electroneutral Na-Cl absorption in experimental conditions in which HCO3-dependent electroneutral Na-Cl absorption is inhibited: in Na-depleted (aldosterone-treated) animals and in the presence of increased mucosal cyclic adenosine monophosphate (AMP). Butyrate-dependent electroneutral Na-Cl absorption was markedly reduced in Na-depleted rats. In contrast, the inhibition of both net Na and net Cl absorption by 5 mM serosal theophylline was significantly less in butyrate-containing, HCO3-free Ringer solution than in butyrate-free- HCO3-containing Ringer solution. These studies indicate that cyclic AMP does not inhibit butyrate-dependent electroneutral Na-Cl absorption and we propose that the mechanism of cyclic AMP inhibition of HCO3-dependent electroneutral Na-Cl absorption may be a result of its inhibition of Cl-HCO3, not Na-H exchange.

  5. Characterization of butyrate-dependent electroneutral Na-Cl absorption in the rat distal colon.

    PubMed

    Binder, H J; Mehta, P

    1990-12-01

    Recent studies have established that mucosal butyrate stimulates electroneutral sodium-chloride (Na-Cl) absorption in the distal colon of the rat and a model in which Na-hydrogen (H) and Cl-butyrate exchanges are coupled has been proposed as the mechanism of butyrate-dependent electroneutral Na-Cl absorption. These studies were designed to examine butyrate-dependent electroneutral Na-Cl absorption in experimental conditions in which HCO3-dependent electroneutral Na-Cl absorption is inhibited: in Na-depleted (aldosterone-treated) animals and in the presence of increased mucosal cyclic adenosine monophosphate (AMP). Butyrate-dependent electroneutral Na-Cl absorption was markedly reduced in Na-depleted rats. In contrast, the inhibition of both net Na and net Cl absorption by 5 mM serosal theophylline was significantly less in butyrate-containing, HCO3-free Ringer solution than in butyrate-free- HCO3-containing Ringer solution. These studies indicate that cyclic AMP does not inhibit butyrate-dependent electroneutral Na-Cl absorption and we propose that the mechanism of cyclic AMP inhibition of HCO3-dependent electroneutral Na-Cl absorption may be a result of its inhibition of Cl-HCO3, not Na-H exchange. PMID:2080102

  6. Aminophenyl double decker silsesquioxanes: Spectroscopic elucidation, physical and thermal characterization, and their applications

    NASA Astrophysics Data System (ADS)

    Schoen, Beth Whitney

    The incorporation of cage-like silsesquioxanes (SQ) to form polymers has demonstrated property enhancements in areas such as: thermal and mechanical characteristics, flame retardance, dielectric properties, and oxidative resistance. However, with most hybrid polymers investigated, the attached SQs are pendant with respect to the polymer backbone. A recently developed class of these nano-structured, cage-like silsesquioxanes, formally known as double decker silsesquioxanes (DDSQ), offers the opportunity to form hybrid polymers with SQ cages as a part of the polymer backbone. However, during the capping reaction, these functionalized DDSQs generate cis and trans isomers with respect to the 3D Si-O core. Therefore, it is logical to characterize properties, which will allow for optimization of capping reaction parameters, particularly if one isomer is favored over the other. Moreover, these characteristics are also relevant when reacting or incorporating these isomers, or mixtures thereof, with other molecules to form novel materials. In this dissertation, three aminophenyl DDSQs were synthesized. More specifically, two meta- aminophenyl DDSQs, which were differentiated according to the moiety attached to the D-Si (methyl or cyclohexyl), and one para-aminophenyl DDSQ with a methyl moiety were used. Chemical, physical, and thermal characteristics were evaluated for individual isomers as well as binary mixtures of different cis/trans ratios. The 1H NMR spectra of the cis and trans isomers of these DDSQ had not previously been assigned to a degree that allowed for quantification, which was necessary for these studies. Thus, 1H-29Si HMBC correlations were applied to facilitate 1H spectral assignments and also to confirm previous 29Si assignments. Using 1H NMR not only saves time and material over 29Si NMR, but also provides a more accurate quantification, thus allowing for the ratio of cis and trans isomers present in each compound to be determined. Solubility behavior was investigated for the individual isomers, such that separation techniques could be developed. It was found that cis isomers were 33 times more soluble than trans isomers for para-aminophenyl (R = methyl), and 22 times more soluble for the analogous meta-aminophenyl in a solution of THF and hexanes. For a more sterically hindered meta-aminophenyl (R = cyclohexyl), cis isomers were only 3.5 times more soluble, and the overall solubility was also the lowest. Phase diagrams representing solid-liquid melt equilibria of the binary cis/trans mixtures were developed. Single crystal x-ray diffraction data of isolated isomers helped to interpret the phase behavior. Both compounds with a methyl moiety exhibited eutectic phase diagrams. Their trans isomers were higher melting and exhibited larger packing density. Changing from para- to meta-aminophenyl shifted the solid-liquid equilibrium further from ideal, with decreased activity coefficients. Cyclohexyl DDSQ exhibited an isomorphic phase diagram (a complete solid-solution), attributed to cyclohexyl being more similar in size to the phenyl moieties. A specific application that was chosen for these DDSQ was high performance thermosetting oligoimides. They displayed advantages over their organic counterparts in areas such as the liquid to solid transition and viscosity, which improves the processing window. Additionally, they increased the overall degree of cross-linking leading to improved oxidative stability at elevated temperatures.

  7. 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.

  8. Synthesis and microwave absorption characterization of SiO2 coated Fe3O4-MWCNT composites.

    PubMed

    Hekmatara, Hoda; Seifi, Majid; Forooraghi, Keyvan; Mirzaee, Sharareh

    2014-11-21

    This study investigated the microwave absorption properties of core-shell composites containing; iron oxide decorated carbon nanotubes (CNTs) and silica (SiO2@Fe3O4-MWCNTs) with various thicknesses of silica shells (7, 20 and 50 nm). Transmission electron microscopy (TEM) and X-ray diffraction results confirmed the formation of these core-shell structures. Microwave absorption characterization of the samples at the ranging band under consideration (the X-band) showed increased absorption and shifting of the peaks to lower frequencies compared to the uncoated sample (Fe3O4-MWCNTs). The minimum reflection loss decreased with increasing SiO2 thickness. The minimum reflection loss of the composite with an optimized thickness of the silica shell (7 nm) exceeded -41 dB at 8.7-9 GHz. PMID:25288483

  9. 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.

  10. Characterization of functionalized self-assembled monolayers and surface-attached interlocking molecules using near-edge X-ray absorption fine structure spectroscopy

    NASA Astrophysics Data System (ADS)

    Willey, Trevor Michael

    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.

  11. Magnetic Resonance Spectroscopic Imaging of Tumor Metabolic Markers for Cancer Diagnosis, Metabolic Phenotyping, and Characterization of Tumor Microenvironment

    PubMed Central

    He, Qiuhong; Xu, Ray Z.; Shkarin, Pavel; Pizzorno, Giuseppe; Lee-French, Carol H.; Rothman, Douglas L.; Shungu, Dikoma C.; Shim, Hyunsuk

    2004-01-01

    Cancer cells display heterogeneous genetic characteristics, depending on the tumor dynamic microenvironment. Abnormal tumor vasculature and poor tissue oxygenation generate a fraction of hypoxic tumor cells that have selective advantages in metastasis and invasion and often resist chemo- and radiation therapies. The genetic alterations acquired by tumors modify their biochemical pathways, which results in abnormal tumor metabolism. An elevation in glycolysis known as the “Warburg effect” and changes in lipid synthesis and oxidation occur. Magnetic resonance spectroscopy (MRS) has been used to study tumor metabolism in preclinical animal models and in clinical research on human breast, brain, and prostate cancers. This technique can identify specific genetic and metabolic changes that occur in malignant tumors. Therefore, the metabolic markers, detectable by MRS, not only provide information on biochemical changes but also define different metabolic tumor phenotypes. When combined with the contrast-enhanced Magnetic Resonance Imaging (MRI), which has a high sensitivity for cancer diagnosis, in vivo magnetic resonance spectroscopic imaging (MRSI) improves the diagnostic specificity of malignant human cancers and is becoming an important clinical tool for cancer management and care. This article reviews the MRSI techniques as molecular imaging methods to detect and quantify metabolic changes in various tumor tissue types, especially in extracranial tumor tissues that contain high concentrations of fat. MRI/MRSI methods have been used to characterize tumor microenvironments in terms of blood volume and vessel permeability. Measurements of tissue oxygenation and glycolytic rates by MRS also are described to illustrate the capability of the MR technology in probing molecular information non-invasively in tumor tissues and its important potential for studying molecular mechanisms of human cancers in physiological conditions. PMID:15096706

  12. Structures and spectroscopic characterization of calcium chloride-nicotinamide, -isonicotinamide, -picolinamide and praseodymium bromide-nicotinamide complexes

    NASA Astrophysics Data System (ADS)

    Xue, Junhui; Jiang, Ye; Li, Weihong; Yang, Limin; Xu, Yizhuang; Zhao, Guozhong; Zhang, Gaohui; Bu, Xiaoxia; Liu, Kexin; Chen, Jia'er; Wu, Jinguang

    2015-02-01

    The coordination structures formed by calcium complexes with nicotinamide (na), isonicotinamide (ina) and picolinamide (pa) and praseodymium bromide-na are reported. The structures of CaCl2·(C6H6N2O)2·2H2O (Ca-na), CaCl2·(C6H6N2O)2·4H2O (Ca-ina), CaCl2·(C6H6N2O)2·5H2O (Ca-pa) and PrBr3·(C6H6N2O)2·6H2O (PrBr-na) in the solid state have been characterized by X-ray single crystal diffraction, FTIR, FIR, THz and Raman spectroscopies. Carbonyl oxygen of nicotinamide is coordinated to Ca2+, but it is O-monodentate (carbonyl oxygen) and N,O-bidentate ligand (pyridyl nitrogen and carbonyl oxygen) for Pr3+ to form a chain structure in PrBr-na. For isonicotinamide, only carbonyl oxygen atom is coordinated to Ca2+. Pyridyl nitrogen and carbonyl oxygen of picolinamide are coordinated to Ca2+ to form a five-membered ring structure. The crystal structure and spectroscopic results indicate the differences of the coordination of Ca and Pr ions, the changes of hydrogen bonds and conformation of the ligands induced by complexation. Unlike transition metal ions, Sr2+ or lanthanide ions, Ca2+ is inclined to coordinate to carbonyl oxygen atoms of the ligands.

  13. Structures and spectroscopic characterization of calcium chloride-nicotinamide, -isonicotinamide, -picolinamide and praseodymium bromide-nicotinamide complexes.

    PubMed

    Xue, Junhui; Jiang, Ye; Li, Weihong; Yang, Limin; Xu, Yizhuang; Zhao, Guozhong; Zhang, Gaohui; Bu, Xiaoxia; Liu, Kexin; Chen, Jia'er; Wu, Jinguang

    2015-02-25

    The coordination structures formed by calcium complexes with nicotinamide (na), isonicotinamide (ina) and picolinamide (pa) and praseodymium bromide-na are reported. The structures of CaCl2·(C6H6N2O)2·2H2O (Ca-na), CaCl2·(C6H6N2O)2·4H2O (Ca-ina), CaCl2·(C6H6N2O)2·5H2O (Ca-pa) and PrBr3·(C6H6N2O)2·6H2O (PrBr-na) in the solid state have been characterized by X-ray single crystal diffraction, FTIR, FIR, THz and Raman spectroscopies. Carbonyl oxygen of nicotinamide is coordinated to Ca(2+), but it is O-monodentate (carbonyl oxygen) and N,O-bidentate ligand (pyridyl nitrogen and carbonyl oxygen) for Pr(3+) to form a chain structure in PrBr-na. For isonicotinamide, only carbonyl oxygen atom is coordinated to Ca(2+). Pyridyl nitrogen and carbonyl oxygen of picolinamide are coordinated to Ca(2+) to form a five-membered ring structure. The crystal structure and spectroscopic results indicate the differences of the coordination of Ca and Pr ions, the changes of hydrogen bonds and conformation of the ligands induced by complexation. Unlike transition metal ions, Sr(2+) or lanthanide ions, Ca(2+) is inclined to coordinate to carbonyl oxygen atoms of the ligands. PMID:25280333

  14. Synthesis, spectroscopic characterization and antimicrobial activity of binuclear metal complexes of a new asymmetrical Schiff base ligand: DNA binding affinity of copper(II) complexes.

    PubMed

    Shebl, Magdy

    2014-01-01

    The 1:1 condensation of o-acetoacetylphenol and 1,2-diaminopropane under condition of high dilution gives the mono-condensed Schiff base, (E)-3-(1-aminopropan-2-ylimino)-1-(2-hydroxyphenyl)butan-1-one. The mono-condensed Schiff base has been used for further condensation with isatin to obtain the new asymmetrical dicompartmental Schiff base ligand, (E)-3-(2-((E)-4-(2-hydroxyphenyl)-4-oxobutan-2-ylideneamino) propylimino)indolin-2-one (H3L) with a N2O3 donor set. Reactions of the ligand with metal salts give a series of new binuclear complexes. The ligand and its metal complexes were characterized by elemental analyses, IR, (1)H and (13)C NMR, electronic, ESR and mass spectra, conductivity and magnetic susceptibility measurements as well as thermal analyses. The analytical and spectroscopic tools showed that the complexes can be formulated as: [(HL)(VO)2(SO4)(H2O)]·4H2O, [(HL)Fe2Cl4(H2O)3]·EtOH, [(HL)Fe2(ox)Cl2(H2O)3]·2H2O, [(L)M2(OAc)(H2O)m]·nH2O; M=Co, Ni or Cu, m=4, 0 and n=2, 3, [(HL)Cu2Cl]Cl·6H2O and [(L)(UO2)2(OAc)(H2O)3]·6H2O. The metal complexes exhibited octahedral geometrical arrangements except copper complexes that exhibited tetrahedral geometries and uranyl complex in which the metal ion is octa-coordinated. The Schiff base and its metal complexes were evaluated for antimicrobial activity against Gram positive bacteria (Staphylococcus aureus), Gram negative bacteria (Escherichia coli) and fungi (Candida albicans and Aspergillus flavus). The ligand and some of its complexes were found to be biologically active. The DNA-binding properties of the copper complexes (6 and 7) have been investigated by electronic absorption, fluorescence and viscosity measurements. The results obtained indicate that these complexes bind to DNA via an intercalation binding mode with an intrinsic binding constant, Kb of 1.34×10(4) and 2.5×10(4) M(-1), respectively. PMID:23988527

  15. Synthesis, spectroscopic characterization and antimicrobial activity of binuclear metal complexes of a new asymmetrical Schiff base ligand: DNA binding affinity of copper(II) complexes

    NASA Astrophysics Data System (ADS)

    Shebl, Magdy

    2014-01-01

    The 1:1 condensation of o-acetoacetylphenol and 1,2-diaminopropane under condition of high dilution gives the mono-condensed Schiff base, (E)-3-(1-aminopropan-2-ylimino)-1-(2-hydroxyphenyl)butan-1-one. The mono-condensed Schiff base has been used for further condensation with isatin to obtain the new asymmetrical dicompartmental Schiff base ligand, (E)-3-(2-((E)-4-(2-hydroxyphenyl)-4-oxobutan-2-ylideneamino) propylimino)indolin-2-one (H3L) with a N2O3 donor set. Reactions of the ligand with metal salts give a series of new binuclear complexes. The ligand and its metal complexes were characterized by elemental analyses, IR, 1H and 13C NMR, electronic, ESR and mass spectra, conductivity and magnetic susceptibility measurements as well as thermal analyses. The analytical and spectroscopic tools showed that the complexes can be formulated as: [(HL)(VO)2(SO4)(H2O)]·4H2O, [(HL)Fe2Cl4(H2O)3]·EtOH, [(HL)Fe2(ox)Cl2(H2O)3]·2H2O, [(L)M2(OAc)(H2O)m]·nH2O; M = Co, Ni or Cu, m = 4, 0 and n = 2, 3, [(HL)Cu2Cl]Cl·6H2O and [(L)(UO2)2(OAc)(H2O)3]·6H2O. The metal complexes exhibited octahedral geometrical arrangements except copper complexes that exhibited tetrahedral geometries and uranyl complex in which the metal ion is octa-coordinated. The Schiff base and its metal complexes were evaluated for antimicrobial activity against Gram positive bacteria (Staphylococcus aureus), Gram negative bacteria (Escherichia coli) and fungi (Candida albicans and Aspergillus flavus). The ligand and some of its complexes were found to be biologically active. The DNA-binding properties of the copper complexes (6 and 7) have been investigated by electronic absorption, fluorescence and viscosity measurements. The results obtained indicate that these complexes bind to DNA via an intercalation binding mode with an intrinsic binding constant, Kb of 1.34 × 104 and 2.5 × 104 M-1, respectively.

  16. Generation, characterization and spectroscopic use of ultrashort pulses fully tunable from the deep UV to the MIR

    NASA Astrophysics Data System (ADS)

    Riedle, Eberhard

    2011-03-01

    The impressive work of Ian Walmsley has brought us invaluable new possibilities for the full characterization of ultrashort pulses. Spectroscopy of physical, chemical and biological relevance does, however, need pulses far from the 800 nm Ti:sapphire wavelength used for testing SPIDER and its advanced versions. Fortunately, optical parametric amplification (OPA) allows for easy generation of fully tunable pulses. I will review our efforts, highlighting noncollinear OPA, i.e. NOPA, for visible pulses shorter than 10 fs, mixing into the UV down to below 200 nm at 20 fs duration and novel hybrid schemes to efficiently reach the middle IR. I will show that these schemes can be used equally well from kHz to MHz repetition rates. The tunable ultrafast pulses in turn also demand improvements in characterization. The UV range led us to use difference frequency generation instead of the sum frequency mixing employed in the original SPIDER. The lack of proper beam splitters and auto-referencing led us to the use of two auxiliary pulses and the avoidance of any additional chirp added to the test pulse. We termed this zero-additional-phase SPIDER, i.e. ZAP-SPIDER. Lately, with increased use of UV pulses, we came to the conclusion, that the ubiquitous two-photon-absorption can well serve as nonlinearity, at least in UV autocorrelation measurement. How do we use this for full characterization? Hopefully, Ian will tell us! Since the proof is known to be in the eating, I will demonstrate the success of our technical efforts with examples taken from ultrafast molecular dynamics. Highly pronounced vibronic wavepackets in the product of ultrafast excited state proton transfer and the very primary processes leading to homolytic and heterolytic bond cleavage will serve as easy to comprehend illustrations.

  17. Accurate Spectroscopic Characterization of Oxirane: A Valuable Route to its Identification in Titan's Atmosphere and the Assignment of Unidentified Infrared Bands

    NASA Astrophysics Data System (ADS)

    Puzzarini, Cristina; Biczysko, Malgorzata; Bloino, Julien; Barone, Vincenzo

    2014-04-01

    In an effort to provide an accurate spectroscopic characterization of oxirane, state-of-the-art computational methods and approaches have been employed to determine highly accurate fundamental vibrational frequencies and rotational parameters. Available experimental data were used to assess the reliability of our computations, and an accuracy on average of 10 cm-1 for fundamental transitions as well as overtones and combination bands has been pointed out. Moving to rotational spectroscopy, relative discrepancies of 0.1%, 2%-3%, and 3%-4% were observed for rotational, quartic, and sextic centrifugal-distortion constants, respectively. We are therefore confident that the highly accurate spectroscopic data provided herein can be useful for identification of oxirane in Titan's atmosphere and the assignment of unidentified infrared bands. Since oxirane was already observed in the interstellar medium and some astronomical objects are characterized by very high D/H ratios, we also considered the accurate determination of the spectroscopic parameters for the mono-deuterated species, oxirane-d1. For the latter, an empirical scaling procedure allowed us to improve our computed data and to provide predictions for rotational transitions with a relative accuracy of about 0.02% (i.e., an uncertainty of about 40 MHz for a transition lying at 200 GHz).

  18. ACCURATE SPECTROSCOPIC CHARACTERIZATION OF OXIRANE: A VALUABLE ROUTE TO ITS IDENTIFICATION IN TITAN’S ATMOSPHERE AND THE ASSIGNMENT OF UNIDENTIFIED INFRARED BANDS

    PubMed Central

    Puzzarini, Cristina; Biczysko, Malgorzata; Bloino, Julien; Barone, Vincenzo

    2015-01-01

    In an effort to provide an accurate spectroscopic characterization of oxirane, state-of-the-art computational methods and approaches have been employed to determine highly accurate fundamental vibrational frequencies and rotational parameters. Available experimental data were used to assess the reliability of our computations, and an accuracy on average of 10 cm−1 for fundamental transitions as well as overtones and combination bands has been pointed out. Moving to rotational spectroscopy, relative discrepancies of 0.1%, 2%–3%, and 3%–4% were observed for rotational, quartic, and sextic centrifugal-distortion constants, respectively. We are therefore confident that the highly accurate spectroscopic data provided herein can be useful for identification of oxirane in Titan’s atmosphere and the assignment of unidentified infrared bands. Since oxirane was already observed in the interstellar medium and some astronomical objects are characterized by very high D/H ratios, we also considered the accurate determination of the spectroscopic parameters for the mono-deuterated species, oxirane-d1. For the latter, an empirical scaling procedure allowed us to improve our computed data and to provide predictions for rotational transitions with a relative accuracy of about 0.02% (i.e., an uncertainty of about 40 MHz for a transition lying at 200 GHz). PMID:26543240

  19. Accurate spectroscopic characterization of oxirane: A valuable route to its identification in Titan's atmosphere and the assignment of unidentified infrared bands

    SciTech Connect

    Puzzarini, Cristina; Biczysko, Malgorzata; Bloino, Julien; Barone, Vincenzo

    2014-04-20

    In an effort to provide an accurate spectroscopic characterization of oxirane, state-of-the-art computational methods and approaches have been employed to determine highly accurate fundamental vibrational frequencies and rotational parameters. Available experimental data were used to assess the reliability of our computations, and an accuracy on average of 10 cm{sup –1} for fundamental transitions as well as overtones and combination bands has been pointed out. Moving to rotational spectroscopy, relative discrepancies of 0.1%, 2%-3%, and 3%-4% were observed for rotational, quartic, and sextic centrifugal-distortion constants, respectively. We are therefore confident that the highly accurate spectroscopic data provided herein can be useful for identification of oxirane in Titan's atmosphere and the assignment of unidentified infrared bands. Since oxirane was already observed in the interstellar medium and some astronomical objects are characterized by very high D/H ratios, we also considered the accurate determination of the spectroscopic parameters for the mono-deuterated species, oxirane-d1. For the latter, an empirical scaling procedure allowed us to improve our computed data and to provide predictions for rotational transitions with a relative accuracy of about 0.02% (i.e., an uncertainty of about 40 MHz for a transition lying at 200 GHz).

  20. Description of the Role of Shot Noise in Spectroscopic Absorption and Emission Measurements with Photodiode and Photomultiplier Tube Detectors: Information for an Instrumental Analysis Course

    ERIC Educational Resources Information Center

    McClain, Robert L.; Wright, John C.

    2014-01-01

    A description of shot noise and the role it plays in absorption and emission measurements using photodiode and photomultiplier tube detection systems is presented. This description includes derivations of useful forms of the shot noise equation based on Poisson counting statistics. This approach can deepen student understanding of a fundamental

  1. Description of the Role of Shot Noise in Spectroscopic Absorption and Emission Measurements with Photodiode and Photomultiplier Tube Detectors: Information for an Instrumental Analysis Course

    ERIC Educational Resources Information Center

    McClain, Robert L.; Wright, John C.

    2014-01-01

    A description of shot noise and the role it plays in absorption and emission measurements using photodiode and photomultiplier tube detection systems is presented. This description includes derivations of useful forms of the shot noise equation based on Poisson counting statistics. This approach can deepen student understanding of a fundamental…

  2. 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, β-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.

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

    PubMed

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

    2014-12-10

    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, β-carotene and vitamin E contents were carried out. In addition, the FT-IR, (13)C and (1)H 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. PMID:24967544

  4. Thermophysics Characterization of Multiply Ionized Air Plasma Absorption of Laser Radiation

    NASA Technical Reports Server (NTRS)

    Wang, Ten-See; Rhodes, Robert; Turner, Jim (Technical Monitor)

    2002-01-01

    The impact of multiple ionization of air plasma on the inverse Bremsstrahlung absorption of laser radiation is investigated for air breathing laser propulsion. Thermochemical properties of multiply ionized air plasma species are computed for temperatures up to 200,000 deg K, using hydrogenic approximation of the electronic partition function; And those for neutral air molecules are also updated for temperatures up to 50,000 deg K, using available literature data. Three formulas for absorption are calculated and a general formula is recommended for multiple ionization absorption calculation. The plasma composition required for absorption calculation is obtained by increasing the degree of ionization sequentially, up to quadruple ionization, with a series of thermal equilibrium computations. The calculated second ionization absorption coefficient agrees reasonably well with that of available data. The importance of multiple ionization modeling is demonstrated with the finding that area under the quadruple ionization curve of absorption is found to be twice that of single ionization. The effort of this work is beneficial to the computational plasma aerodynamics modeling of laser lightcraft performance.

  5. Microthermometric and Raman spectroscopic detection limits of CO{sub 2} in fluid inclusions and the Raman spectroscopic characterization of CO{sub 2}

    SciTech Connect

    Rosso, K.M.; Bodnar, R.J.

    1995-10-01

    In many geologic environments, dominantly aqueous solutions contain low concentrations of CO{sub 2}. At ambient temperature, the typical phase assemblage in fluid inclusions which trap these solutions, consists of a CO{sub 2}-rich vapor (where P{sub CO{sub 2}} {approx} P {sub internal}) and an aqueous phase containing dissolved salts and CO{sub 2}. In this study, the CO{sub 2} detection limits (DLs) using microthermometry and Raman spectroscopy are established in terms of P{sub CO{sub 2}} using synthetic H{sub 2}O-CO{sub 2} inclusions of known compositions. The purpose of the microthermometric experiments was to identify the diagnostic CO{sub 2} phase changes and determine the quantity of CO{sub 2} necessary to result in observable solid CO{sub 2} melting event in liquid-rich aqueous inclusions requires P{sub CO{sub 2}} {ge} 45 bars at 25{degrees}C. The Raman spectroscopic detection limits were investigated using a multichannel Raman spectrometer. The CO{sub 2} DLs were obtained by determining signal-to-noise ratios for both the upper and lower v{sub 1}-2v{sub 2} bands as a function of CO{sub 2} pressure (5-60 bars) over a range of integration times and incident laser power. The resulting CO{sub 2} DLs are on the order of 1 bar for the instrument used. The band splitting of the v{sub 1}-2v{sub 2} diad as a function of CO{sub 2} pressure, converted to CO{sub 2} density, was measured up to 500 bars at ambient temperature. The results are given in terms of the frequency separation between upper and lower bands and are compared to results are given in terms of the frequency separation between the upper and lower bands and are compared to results of previous studies. An analysis of the estimated errors indicates that the technique can be used to determine CO{sub 2} densities in fluid inclusions containing a homogeneous, free CO{sub 2} phase to a precision of approximately {+-}0.02 g/cm{sup 3}. 44 refs., 16 figs.

  6. Characterization and Processing of Organic Nonlinear Optical Materials using Ellipsometric, Waveguiding, and Absorption Spectroscopy Techniques

    NASA Astrophysics Data System (ADS)

    Olbricht, Benjamin C.

    The first focus of this work is to describe methods for characterizing organic electro-optic materials. Teng-Man Ellipsometry and Attenuated Total Internal Reflection are reviewed. Experimental techniques for these instruments are described and the calculation of an electro-optic activity is derived. The two techniques are compared; it has been found that in Situ Teng-Man ellipsometry is useful to determine poling conditions but not for reliably evaluating electro-optic activity. Attenuated Total Internal Reflection is found to provide very reliable and precise measurements of electro-optic activity and linear optical constants. As a reference, many materials systems have been evaluated and their electro-optic activities are recorded herein. Methods for fabricating devices for test by Teng-Man ellipsometry and Attenuated Total Internal Reflection are presented. A process for inducing Pockel's response via contact-geometry electric field poling is also described, along with modifications to the simple slab dielectric device to enhance the efficacy of poling. An additional method for enhancing the efficiency of poling is presented. This technique relies on the photoisomerization of azobenzene dyes under 532nm radiation to reduce the dimensionality accessible to chromophores doped into the azobenzene matrix. This effect is known as "Laser Assisted Poling" and is shown to increase poling efficiency by more than two fold. The second purpose of this work is to present an experimental technique to measure the order parameter = 3cos 2q -12 . This method is known as Variable-Angle Polarization-Referenced Absorption Spectroscopy (VAPRAS). The experimental apparatus used for VAPRAS introduces small alterations to a UV/Vis Spectrophotometer and an order parameter is derived by exclusively using classical models for transmittance. VAPRAS provides an effective refractive index for the electro-optic material film which is used to calculate the order of absorbers in the film. The results of the VAPRAS method are compared with rigorous (Jones Matrix) simulations of absorbance and Monte Carlo simulations of poling. Both comparisons conclude that the order is low, ≈ 0.05, and their agreement with theory is within experimental error. Theoretical simulations of poling are employed to relate the results of VAPRAS to a noncentrosymmetric order parameter . Finally, a solid-state first molecular hyperpolarizability is calculated from these values, measurements of electro-optic activity, linear optical constants and other secondary properties of the electro-optic material.

  7. Crystal structure, spectroscopic characterization and density functional studies of (E)-1-((3-methoxyphenylimino)methyl)naphthalen-2-ol.

    PubMed

    Alpaslan, Gökhan; Macit, Mustafa

    2014-01-01

    The Schiff base compound (E)-1-((3-methoxyphenylimino)methyl)naphthalen-2-ol was synthesized from the reaction of 2-hydroxy-1-naphthaldehyde with 3-methoxyaniline. The structural properties of the compound has been characterized by using FT-IR, UV-vis and X-ray single-crystal methods. According to X-ray diffraction result, the title compound exists in the phenol-imine tautomeric form. The molecular geometry, vibrational frequencies 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, and compared with the experimental data. The obtained results show that the optimized molecular geometry is well reproduce the crystal structure. The theoretical vibrational frequencies are in good agreement with the experimental values. The calculations of electronic absorption spectra of tautomeric forms of the compound were performed by using TD-DFT calculations both in the gas phase and ethanol solvent. To investigate the tautomeric stability, optimization calculations at the B3LYP/6-311++G(d,p) level were performed for the phenol-imine and keto-amine forms of the compound. According to calculated results, the OH form is more stable than NH form. In addition, molecular electrostatic potential (MEP), frontier molecular orbital analysis (HOMO-LUMO), thermodynamic and, non-linear optical (NLO) properties of the compound were investigated using same theoretical calculations. PMID:24280299

  8. Synthesis, spectroscopic characterization and DFT calculations of N-Methyl-2-(2ʹ-hydroxyphenyl)benzimidazole derivatives

    NASA Astrophysics Data System (ADS)

    Saral, Hasan; Özdamar, Özgür; Uçar, İbrahim; Bekdemir, Yunus; Aygün, Muhittin

    2016-01-01

    1-Methyl-2-(2ʹ-hydroxyphenyl)benzimidazole (1) and 1-Methyl-2-(2ʹ-hydroxy-4ʹ-methylphenyl)benzimidazole (2) compounds have been synthesized and characterized by XRD, IE-MS, FT-IR, UV-Vis and 1H, 13C NMR techniques. The crystal structure of both compounds is stabilized with very strong O-H … N hydrogen-bond and π-π interactions. In the compound 1, an infinite chain structure with a trans-zigzag type was formed along the crystallographic [101] direction. Quantum mechanical calculations of energies, geometries, vibrational wavenumbers, NMR and electronic transitions were carried out by DFT using B3LYP functional combined with 6.31G(d,p) basis set. Calculated bond lengths, bond angles and dihedral angles were only slightly different from the experimental ones. The vibrational study was interpreted by means of potential energy distribution (PED). The electronic absorption spectra of the both compounds were predicted by using the time-dependent DFT methods and good agreement was found between the computational and the experimental values. The chemical shifts (1H and 13C NMR) and isotropic shielding values were calculated by using the gauge-invariant atomic orbital (GIAO) method. The analyses of HOMO and LUMO have been used to explain the charge transfer within the molecule.

  9. X-Ray Absorption And EPR Spectroscopic Studies of the Biotransformations of Chromium(Vi) in Mammalian Cells. Is Chromodulin An Artifact of Isolation Methods?

    SciTech Connect

    Levina, A.; Harris, H.H.; Lay, P.A.; /Sydney U.

    2007-07-10

    Very different biological activities are usually ascribed to Cr(VI) (a toxin and carcinogen) and Cr(III) (an antidiabetic agent), although recent evidence suggests that both these types of actions are likely to arise from cellular uptake of varying concentrations of Cr(VI). The first systematic study of XANES spectra of Cr(III) complexes formed in Cr(VI)-treated mammalian cells (A549, HepG2, V79, and C2C12 cell lines), and in subcellular fractions of A549 cells, has been performed using a library of XANES spectra of model Cr(III) complexes. The results of multiple linear regression analyses of XANES spectra, in combination with multiple-scattering fits of XAFS spectra, indicate that Cr(III) formed in Cr(VI)-treated cells is most likely to bind to carboxylato, amine, and imidazole residues of amino acids, and to a lesser extent to hydroxo or aqua ligands. A combination of XANES and EPR spectroscopic data for Cr(VI)-treated cells indicates that the main component of Cr(III) formed in such cells is bound to high-molecular-mass ligands (>30 kDa, probably proteins), but significant redistribution of Cr(III) occurs during the cell lysis, which leads to the formation of a low-molecular-mass (<30 kDa) Cr(III)-containing fraction. The spectroscopic (XANES, XAFS, and EPR) properties of this fraction were strikingly similar to those of the purported natural Cr(III)-containing factor, chromodulin, that was reported to be isolated from the reaction of Cr(VI) with liver. These data support the hypothesis that a chromodulin-like species, which is formed from such a reaction, is an artifact of the reported isolation procedure.

  10. 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.

  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 μg 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 μg 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 μg 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 μg 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. Ultra-violet and visible absorption characterization of explosives by differential reflectometry

    NASA Astrophysics Data System (ADS)

    Dubroca, Thierry; Moyant, Kyle; Hummel, Rolf E.

    2013-03-01

    This study presents some optical properties of TNT (2,4,6-trinitrotoluene), RDX, HMX and tetryl, specifically their absorption spectra as a function of concentration in various solvents in the ultraviolet and visible portion of the electromagnetic spectrum. We utilize a standoff explosives detection method, called differential reflectometry (DR). TNT was diluted in six different solvents (acetone, acetonitrile, ethanol, ethyl acetate, methanol, and toluene), which allowed for a direct comparison of absorption features over a wide range of concentrations. A line-shape analysis was adopted with great accuracy (R2 > 0.99) to model the absorption features of TNT in differential reflectivity spectra. We observed a blue shift in the pertinent absorption band with decreasing TNT concentration for all solvents. Moreover, using this technique, it was found that for all utilized solvents the concentration of TNT as well as of RDX, HMX, and tetryl, measured as a function of the transition wavelength of the ultra-violet absorption edge in differential reflectivity spectra shows three distinct regions. A model is presented to explain this behavior which is based on intermolecular hydrogen bonding of explosives molecules with themselves (or lack thereof) at different concentrations. Other intermolecular forces such as dipole-dipole interactions, London dispersion forces and ?-stacking contribute to slight variations in the resulting spectra, which were determined to be rather insignificant in comparison to hydrogen bonding. The results are aimed towards a better understanding of the DR spectra of explosives energetic materials.

  13. Free electron concentration dependent sub-bandgap optical absorption characterization of bulk GaN crystals

    NASA Astrophysics Data System (ADS)

    Pimputkar, S.; Suihkonen, S.; Imade, M.; Mori, Y.; Speck, J. S.; Nakamura, S.

    2015-12-01

    Optical transmission measurements were performed on high quality bulk gallium nitride (GaN) crystals grown by sodium flux, hydride vapor phase epitaxy, and the ammonothermal method with varying free electron concentrations ranging from 4×1016 cm-3 to 9×1018 cm-3. The quality of the crystals was analyzed by x-ray diffraction, threading dislocation density determination, impurity concentrations, and Hall mobility measurements. The sub-bandgap absorption coefficient and index of refraction was determined based on illumination wavelengths ranging from 360 nm to 800 nm. Phonon-assisted free carrier absorption was determined to be the dominant absorption mechanism above approximately 0.1 cm-1. The absorption coefficient at 450 nm varied linearly from 0.1 cm-1 to 5 cm-1 for free electron concentrations ranging from 1×1017 cm-3 to 9×1018 cm-3. The ammonothermal GaN samples exhibited a strong defect related onset of absorption above 2.9 eV which can be explained by the presence of appreciable hydrogenated gallium vacancies having defect states close to the valance band within the electric bandgap of GaN. The presence of hydrogenated gallium vacancies was experimentally confirmed by Fourier transform infrared absorbance measurements and double hydrogenated gallium vacancy defect are speculated to be prominent in ammonothermal GaN.

  14. Ultra-violet and visible absorption characterization of explosives by differential reflectometry.

    PubMed

    Dubroca, Thierry; Moyant, Kyle; Hummel, Rolf E

    2013-03-15

    This study presents some optical properties of TNT (2,4,6-trinitrotoluene), RDX, HMX and tetryl, specifically their absorption spectra as a function of concentration in various solvents in the ultraviolet and visible portion of the electromagnetic spectrum. We utilize a standoff explosives detection method, called differential reflectometry (DR). TNT was diluted in six different solvents (acetone, acetonitrile, ethanol, ethyl acetate, methanol, and toluene), which allowed for a direct comparison of absorption features over a wide range of concentrations. A line-shape analysis was adopted with great accuracy (R(2)>0.99) to model the absorption features of TNT in differential reflectivity spectra. We observed a blue shift in the pertinent absorption band with decreasing TNT concentration for all solvents. Moreover, using this technique, it was found that for all utilized solvents the concentration of TNT as well as of RDX, HMX, and tetryl, measured as a function of the transition wavelength of the ultra-violet absorption edge in differential reflectivity spectra shows three distinct regions. A model is presented to explain this behavior which is based on intermolecular hydrogen bonding of explosives molecules with themselves (or lack thereof) at different concentrations. Other intermolecular forces such as dipole-dipole interactions, London dispersion forces and π-stacking contribute to slight variations in the resulting spectra, which were determined to be rather insignificant in comparison to hydrogen bonding. The results are aimed towards a better understanding of the DR spectra of explosives energetic materials. PMID:23299022

  15. 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 ℓ = 0 to ℓ = 3 (36 individual modes). Results: Precise estimates of the atmospheric parameters (Teff, [M/H], log g) and of the ν sin i of HD 49385 are obtained. The seismic analysis of the star leads to a clear identification of the modes for degrees ℓ = 0,1,2. Around the maximum of the signal (ν ≃ 1013 μHz), some peaks are found significant and compatible with the expected characteristics of ℓ = 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.

  16. Synthesis, characterization and microwave absorption properties of dendrite-like Fe3O4 embedded within amorphous sugar carbon matrix

    NASA Astrophysics Data System (ADS)

    Wu, Hao; Wang, Liuding; Wu, Hongjing

    2014-01-01

    Magnetite dendrites/sugar carbon (MDs/SC) nanocomposites, embedding MDs within amorphous SC matrix, were prepared by simple carbonization-reduction method using α-Fe2O3 dendrites (HDs) as precursor of MDs and sucrose as SC source, while still maintain the dendritic shape of the precursor. The morphology, composition, structure and static magnetic properties of the as-prepared MDs/SC nanocomposites were characterized by various techniques thoroughly. Particularly, the electromagnetic and microwave absorption properties of the MDs/SC and MDs paraffin composites (40 wt.%) were compared over 2-14 GHz. The results show that the microwave absorption performance of MDs/SC samples is comparable or even superior to that of MDs case. The absorption band with reflection loss (RL) below -20 dB for one of the MDs/SC samples can cover the whole X-band (8-12 GHz) with thickness of 1.8-2.4 mm when the content of MDs in the MDs/SC nanocomposite is 25.8 wt.%, and the minimum RL can reach -49.9 dB at 12.1 GHz when the layer thickness is only 1.9 mm. The excellent microwave absorption properties of the MDs/SC paraffin composites are attributed to the proper match between the complex permittivity and permeability, and the unique fractal structures of MDs.

  17. Chemical and spectroscopic characterizations, ESI-QTOF mass spectrometric measurements and DFT studies of new complexes of palladium(II) with tryptamine and mefenamic acid

    NASA Astrophysics Data System (ADS)

    Carvalho, Marcos A.; Arruda, Eduardo G. R.; Profirio, Daniel M.; Gomes, Alexandre F.; Gozzo, Fábio C.; Formiga, André L. B.; Corbi, Pedro P.

    2015-11-01

    New palladium(II) complexes with tryptamine (Pd-tra) and mefenamic acid (Pd-mef) were prepared and characterized by chemical and spectroscopic methods. Elemental, ESI-QTOF mass spectrometric and thermogravimetric analyses of the compounds confirm the composition [PdCl2(tra)2] for Pd-tra and [Pd(mef)2(bipy)] for Pd-mef. Infrared data indicate the coordination of tryptamine to Pd(II) by the nitrogen atom of the amino group, while for mefenamic acid coordination occurs by the oxygen atom of carboxylate group in a monodentate form. The 1H, 13C and {15N,1H} NMR spectroscopic data confirm the nitrogen coordination of the NH2 group of trypatmine to Pd(II) in the Pd-tra complex and also the oxygen coordination of the carboxylate group of mefenamic acid to Pd(II) in the Pd-mef complex. Density functional theory (DFT) studies were applied to determine the difference in energy between the geometric isomers (cis/trans) of Pd-tra and to optimize the structure of the Pd-mef complex. Raman spectroscopic measurements reinforce the nitrogen coordination of tryptamine to Pd(II) in the Pd-tra complex and confirms the presence of the cis-[PdCl2(tra)2] isomer in the solid state. The complexes are insoluble in water.

  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. Spectroscopic characterization of iron ores formed in different geological environments using FTIR, XPS, Mössbauer spectroscopy and thermoanalyses

    NASA Astrophysics Data System (ADS)

    Salama, Walid; El Aref, Mourtada; Gaupp, Reinhard

    2015-02-01

    Application of thermoanalyses, FTIR, XPS and Mössbauer spectroscopic methods can differentiate between iron ores formed in different geological environments. Two types of iron ore are formed in shallow marine environments in the Bahariya Depression, Egypt, yellowish brown ooidal ironstones (type 1) and black mud and fossiliferous ironstones (type 2). Both types were subjected to subaerial weathering, producing a dark brown lateritic (pedogenic) iron ore (type 3). Microscopic investigation indicates goethite is the main mineral in types 1 and 3, while hematite is the main mineral in type 2 and also occurs in type 3. Thermoanalyses indicated the dehydroxylation endothermic peak of goethite of type 1 occurs between 329 and 345 °C, while in type 3 occurs between 284 and 330 °C. This variation can be attributed to the nanocrystalline nature of the pedogenic goethite. The presence of an exothermic peak at 754 °C in type 3 is probably attributed to goethite-hematite phase transformation. FTIR spectroscopy indicated that goethite of type 1 is characterized by the presence of the δ-OH band between 799 and 802 cm-1, the γ-OH between 898 and 904 cm-1 and the bulk hydroxyl stretch between 3124 and 3133 cm-1. Goethite of type 3 is characterized by the absence of the bulk hydroxyl stretch band and the δ-OH and γ-OH are shifted to higher Wavenumbers that can attributed to a relative Al-for Fe-substitution. Hematite is identified by two IR bands; the first is between 464 and 475 cm-1 and at the second is between 540 and 557 cm-1. Quartz is identified in all iron ore types, nitrates are identified in types 1 and 2, but absent in type 3 and Kaolinite is identified in type 2. The Mössbauer spectrum of type 1 is fitted with one magnetic sextet corresponding to goethite with an isomer shift (IS) = 0.374 mm s-1, a quadruple splitting (QS) = -0.27 mm s-1 and a hyperfine magnetic field (BHF) = ∼37. The Mössbauer spectrum of type 2 is fitted with one magnetic sextet corresponding to hematite with IS = 0.363 mm s-1, QS = -0.23 mm s-1 and BHF = ∼50. The Mössbauer spectrum of type 3 is best fitted with a single doublet corresponding to ferrihydrite and one sextet corresponding to hematite. The XPS survey scans and the high resolution of the Fe 2p3/2 can differentiate between the yellowish-brown and green ooidal laminae of type 1. The XPS survey scans indicate the presence of Fe, O, C, N, Na, Cl, Ca and Si in all laminae, while S, Zn, Ti and P are only restricted to the green laminae. The high resolution of the Fe 2p3/2 indicates that Fe is linked to OH- ligand in the yellowish-brown laminae that correspond to goethite, while Fe is linked to SO42- ligand in the green laminae. The XPS survey scans of types 2 and 3 indicate that Fe is linked to O2- ligand that corresponds to hematite.

  20. Effect of characterization of porous metal fiber media on sound absorption coefficient

    NASA Astrophysics Data System (ADS)

    Wang, J. Z.; Ao, Q. B.; Tang, H. P.; Bao, T. F.

    2015-03-01

    Porous metal fiber media (PMFM) is a kind of advanced structural and functional material, and it has attracted a wide spread attention owing to excellent sound absorption performance. The sound absorption property of PMFM is mainly influenced by the fiber diameter, the average pore size and thickness of PMFM. In the paper, three stainless steel fibers with the diameters (?) of 8, 12 and 20 ?m were used to make PMFM with the average pore sizes of 10, 20, 30 and 40 ?m and the thicknesses of 1, 2 and 3 mm by air-laid and sintering processes. The sound absorption coefficients of PMFM were tested in impedance tube using two-microphone transfer-function method according to ISO 10534-2 and ASTM E1050-98 international standards at room temperature. The results show that when the frequency ranges from 50 Hz to 6,400 Hz in material with the average pore size of 20 ?m and the thickness of 3 mm and the fiber diameter of ?8 ?m, the average sound absorption coefficient is the highest.

  1. Synthesis, characterization and femtosecond nonlinear saturable absorption behavior of copper phthalocyanine nanocrystals doped-PMMA polymer thin films

    NASA Astrophysics Data System (ADS)

    Zongo, S.; Dhlamini, M. S.; Neethling, P. H.; Yao, A.; Maaza, M.; Sahraoui, B.

    2015-12-01

    In this work, we report the femtosecond nonlinear saturable absorption response of synthesized copper phthalocyanine nanocrystals (CPc-NCs)-doped PMMA polymer thin films. The samples were initially characterized by X-ray diffraction (XRD), Fourier transform infrared (FT-IR), UV-Vis and scanning electron microscopy (SEM) techniques. The crystalline phase and morphological analysis revealed nanocrystals of monoclinic structure with an average crystallite size between 31.38 nm and 42.5 nm. The femtosecond Z-scan study at 800 nm central wavelength indicated a saturable absorption behavior of which the mechanism is closely related to the surface plasmon resonance (SPR) of the particles. This nonlinear effect could potentially make the CPc-NCs useful in nonlinear optical devices.

  2. 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.

  3. Structure of the dinuclear active site of urease. X-ray absorption spectroscopic study of native and 2-mercaptoethanol-inhibited bacterial and plant enzymes

    SciTech Connect

    Wang, Shengke; Scott, R.A. ); Lee, M.H.; Hausinger, R.P. ); Clark, P.A.; Wilcox, D.E. )

    1994-04-13

    The structures of the dinuclear Ni(II) active sites of urease from jack bean and Klebsiella aerogenes are compared with and without the addition of the inhibitor 2-mercaptoethanol (2-ME). No significant differences are observed by nickel K-edge X-ray absorption spectroscopy between the plant and bacterial enzymes. The Ni X-ray absorption edge spectra display an 8332-eV 1s[yields]3d peak intensity similar to that observed for five-coordinate Ni(II) compounds[sup 1] for both native and 2-ME-bound derivatives. Curve-fitting of Ni EXAFS data indicates that the average Ni(II) coordination environment in native urease can be described as Ni(imidazole)[sub x](N,O)[sub 5[minus]x], with x = 2 or 3. Addition of 2-ME results in replacement of one of the non-imidazole (N,O) ligands with (S,Cl) (most likely the thiolate sulfur of 2-ME) and results in the appearance of a new peak in the Fourier transforms that can only be fit with a Ni[center dot][center dot][center dot]Ni scattering component at a Ni-Ni distance of [approximately]3.26 [angstrom]. A structure for this 2-ME-bound dinuclear site is proposed to contain the two Ni(II) ions bridged by the thiolate sulfur of 2-ME.

  4. 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

  5. Characterization of selenium in UO2 spent nuclear fuel by micro X-ray absorption spectroscopy and its thermodynamic stability.

    PubMed

    Curti, E; Puranen, A; Grolimund, D; Jädernas, D; Sheptyakov, D; Mesbah, A

    2015-10-01

    Direct disposal of spent nuclear fuel (SNF) in deep geological formations is the preferred option for the final storage of nuclear waste in many countries. In order to assess to which extent radionuclides could be released to the environment, it is of great importance to understand how they are chemically bound in the waste matrix. This is particularly important for long-lived radionuclides such as (79)Se, (129)I, (14)C or (36)Cl, which form poorly sorbing anionic species in water and therefore migrate without significant retardation through argillaceous repository materials and host rocks. We present here X-ray absorption spectroscopic data providing evidence that in the investigated SNF samples selenium is directly bound to U atoms as Se(-II) (selenide) ion, probably replacing oxygen in the cubic UO2 lattice. This result is corroborated by a simple thermodynamic analysis, showing that selenide is the stable form of Se under reactor operation conditions. Because selenide is almost insoluble in water, our data indirectly explain the unexpectedly low release of Se in short-term aqueous leaching experiments, compared to iodine or cesium. These results have a direct impact on safety analyses for potential nuclear waste repository sites, as they justify assuming a small fractional release of selenium in performance assessment calculations. PMID:26365814

  6. VizieR Online Data Catalog: Absorption in multiphase circumgalactic medium (Liang+, 2014)

    NASA Astrophysics Data System (ADS)

    Liang, C. J.; Chen, H.-W.

    2015-05-01

    We have assembled a large sample (ngal~300) of spectroscop identified galaxies that occur at small projected distances <~500kpc from the sightline of a background UV bright QSO. This galaxy sample is ideal for characterizing extended gaseous haloes around galaxies based on the absorption features imprinted in the spectra of the background QSOs. (3 data files).

  7. A multi-epoch spectroscopic study of the BAL quasar APM 08279+5255. II. Emission- and absorption-line variability time lags

    NASA Astrophysics Data System (ADS)

    Saturni, F. G.; Trevese, D.; Vagnetti, F.; Perna, M.; Dadina, M.

    2016-03-01

    Context. The study of high-redshift bright quasars is crucial to gather information about the history of galaxy assembly and evolution. Variability analyses can provide useful data on the physics of quasar processes and their relation with the host galaxy. Aims: In this study, we aim to measure the black hole mass of the bright lensed BAL QSO APM 08279+5255 at z = 3.911 through reverberation mapping, and to update and extend the monitoring of its C IV absorption line variability. Methods: We perform the first reverberation mapping of the Si IV and C IV emission lines for a high-luminosity quasar at high redshift with the use of 138 R-band photometric data and 30 spectra available over 16 years of observations. We also cross-correlate the C IV absorption equivalent width variations with the continuum light curve to estimate the recombination time lags of the various absorbers and infer the physical conditions of the ionised gas. Results: We find a reverberation-mapping time lag of ~900 rest-frame days for both Si IV and C IV emission lines. This is consistent with an extension of the BLR size-to-luminosity relation for active galactic nuclei up to a luminosity of ~1048 erg s-1, and implies a black hole mass of 1010 M⊙. Additionally, we measure a recombination time lag of ~160 days in the rest frame for the C IV narrow absorption system, which implies an electron density of the absorbing gas of ~2.5 × 104 cm-3. Conclusions: The measured black hole mass of APM 08279+5255 indicates that the quasar resides in an under-massive host-galaxy bulge with Mbulge ~ 7.5MBH, and that the lens magnification is lower than ~8. Finally, the inferred electron density of the narrow-line absorber implies a distance of the order of 10 kpc of the absorbing gas from the quasar, placing it within the host galaxy.

  8. Characterization of external quantum efficiency and absorption efficiency in GaAs/ InGaP double heterostructures for laser cooling applications

    NASA Astrophysics Data System (ADS)

    Wang, Chengao; Hasselbeck, Michael P.; Li, Chia-Yeh; Sheik-Bahae, Mansoor

    2010-02-01

    The state of current research in laser cooling of semiconductors is reviewed. Emphasis is placed on the characterization of external quantum efficiency and absorption efficiency in GaAs/InGaP double heterostuctures. New experimental results will be presented that characterize device operation as a function of laser excitation power and temperature. Optimum carrier density is obtained independently and used as a screening tool for sample quality. The crucial importance of parasitic background absorption is discussed.

  9. Self-assembled and Langmuir—Blodgett stearic acid monolayers on silver: a comparative reflection—absorption Fourier transform infrared spectroscopic study

    NASA Astrophysics Data System (ADS)

    Jung Ahn, Sang; Hee Son, Dong; Kim, Kwan

    1994-08-01

    Self-assembled (SA) and Langmuir—Blodgett (LB) monolayers of stearic acid on the surface of silver have been investigated by reflection—absorption Fourier transform infrared spectroscopy. Stearic acid was adsorbed onto silver as the carboxylate with its two oxygen atoms bound symmetrically to the surface. Although both the SA and the LB monolayers consisted of fully extended trans zigzag carbon chains, a closer examination indicated that the SA monolayers should possess a more ordered crystalline structure than the LB monolayers. The infrared spectral data dictated that the extent of methyl group exposure at the air—film interface was greater in the SA monolayers than in the LB monolayers, in agreement with the contact angle measurement. From a theoretical analysis, the alkyl chains in the two monolayers seemed to be tilted away from the surface by less than 5°, but in opposite directions.

  10. 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.

  11. 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.

  12. 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 TiO2 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.

  13. X-Ray Absorption Fine Structure Spectroscopic Studies of Octakis(DMSO)Lanthanoid(III) Complexes in Solution And in the Solid Iodides

    SciTech Connect

    Persson, I.; Risberg, E.Damian; D'Angelo, P.; Panfilis, S.De; Sandstrom, M.; Abbasi, A.

    2009-06-04

    Octakis(DMSO)lanthanoid(III) iodides (DMSO = dimethylsulfoxide), [Ln(OS(CH{sub 3}){sub 2}){sub 8}]I{sub 3}, of most lanthanoid(III) ions in the series from La to Lu have been studied in the solid state and in DMSO solution by extended X-ray absorption fine structure (EXAFS) spectroscopy. L{sub 3}-edge and also some K-edge spectra were recorded, which provided mean Ln-O bond distances for the octakis(DMSO)lanthanoid(III) complexes. The agreement with the average of the Ln-O bond distances obtained in a separate study by X-ray crystallography was quite satisfactory. The crystalline octakis(DMSO)lanthanoid(III) iodide salts have a fairly broad distribution of Ln-O bond distances, ca. 0.1 {angstrom}, with a few disordered DMSO ligands. Their EXAFS spectra are in excellent agreement with those obtained for the solvated lanthanoid(III) ions in DMSO solution, both of which show slightly asymmetric distributions of the Ln-O bond distances. Hence, all lanthanoid(III) ions are present as octakis(DMSO)lanthanoid(III) complexes in DMSO solution, with the mean Ln-O distances centered at 2.50 (La), 2.45 (Pr), 2.43 (Nd), 2.41 (Sm), 2.40 (Eu), 2.39 (Gd), 2.37 (Tb), 2.36 (Dy), 2.34 (Ho), 2.33 (Er), 2.31 (Tm), and 2.29 {angstrom} (Lu). This decrease in the Ln-O bond distances is larger than expected from the previously established ionic radii for octa-coordination. This indicates increasing polarization of the Ln{sup III}-O(DMSO) bonds with increasing atomic number. However, the S(1s) electron transition energies in the sulfur K-edge X-ray absorption near-edge structure (XANES) spectra, probing the unoccupied molecular orbitals of lowest energy of the DMSO ligands for the [Ln(OS(CH{sub 3}){sub 2}){sub 8}]{sup 3+} complexes, change only insignificantly from Ln = La to Lu. This indicates that there is no appreciable change in the ?-contribution to the S-O bond, probably due to a corresponding increase in the contribution from the sulfur lone pair to the bonding.

  14. 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.; Grosvenor, Andrew P.

    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.}.

  15. 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, σN2O5(λ, 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 σN2O5(λ, 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 σN2O5(λ, 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.

  16. Infrared reflection absorption spectroscopic study on the adsorption structures of ethylene on Ag(110) and atomic oxygen pre-covered Ag(110) surfaces

    NASA Astrophysics Data System (ADS)

    Akita, Masato; Osaka, Naoki; Hiramoto, Shuji; Itoh, Koichi

    1999-06-01

    Infrared reflection absorption spectra in the CH 2 out-of-plane wagging (ω(CH 2)) vibration region were measured for ethylene (C 2H 4) adsorbed on Ag(110) as well as on the oxygen-induced p( n×1) reconstructed surfaces of Ag(110) ( n=2, 3, 4 and 6) at 80 K. C 2H 4 on Ag(110) gives a main peak at 955 cm -1, while on p(2×1)O-Ag(110) it exhibits a broad features of at least four components (997, 984, 970 and 954 cm -1) at saturation coverage. C 2H 4 on p( n×1)O-Ag(110) ( n=6, 4, 3) gives rise to a 972-976 cm -1 band at low exposures, shifting to 966-970 cm -1 at saturation coverage. The spectral changes are interpreted by assuming a pair of adsorption sites on both sides of the added Ag-O rows of the reconstructed surfaces.

  17. X-ray Absorption Spectroscopic and Computational Investigation of a Possible S···S Interaction in the [Cu3S2]3+ Core

    PubMed Central

    Sarangi, Ritimukta; Yang, Lei; Winikoff, Stuart G.; Gagliardi, Laura; Cramer, Christopher J.; Tolman, William B.; Solomon, Edward I.

    2011-01-01

    The electronic structure of the [Cu3S2]3+ core of [(LCu)3(S)2]3+ (L = N,N,N′,N′-tetramethyl-2R,3R-cyclohexanediamine) is investigated using a combination of Cu and S K-edge X-ray absorption spectroscopy and calculations at the density functional and multireference second-order perturbation levels of theory. The results show that the [Cu3S2]3+ core is best described as having all copper centers close to, but more oxidized than, Cu2+, while the charge on the S2 fragment is between that of a sulfide (S2−) and a subsulfide (S23−) species. The [Cu3S2]3+ core thus is different from a previously described, analogous [Cu3O2]3+ core, which has a localized [(Cu3+Cu2+Cu2+)(O2−)2]3+ electronic structure. The difference in electronic structure between the two analogues is attributed to increased covalent overlap between the Cu 3d and S 3p orbitals and the increased radial distribution function of the S 3p orbital (relative to O 2p). These features result in donation of electron density from the S-S σ* to the Cu and result in some bonding interaction between the two S atoms at ~ 2.69 Å in [Cu3S2]3+, stabilizing a delocalized S=1 ground state. PMID:21923178

  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

    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 ɛ value of the complex with ethylenediamine. The vertical electron affinity ( EA) of TNT was calculated using the method suggested by Mulliken.

  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.

    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

  20. 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.

  1. Synthesis, Characterization, and Microwave Absorption Properties of Reduced Graphene Oxide/Strontium Ferrite/Polyaniline Nanocomposites.

    PubMed

    Luo, Juhua; Shen, Pan; Yao, Wei; Jiang, Cuifeng; Xu, Jianguang

    2016-12-01

    Strontium ferrite nanoparticles were prepared by a coprecipitation method, and reduced graphene oxide/strontium ferrite/polyaniline (R-GO/SF/PANI) ternary nanocomposites were prepared by in situ polymerization method. The morphology, structure, and magnetic properties of the ternary nanocomposites were investigated by X-ray powder diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), TEM, Raman, and VSM. The microwave-absorbing properties of the composites were measured by a vector network analyzer. The XRD patterns show the single phase of strontium hexaferrite without other intermediate phases. TEM photographs reveal that strontium ferrite nanoparticles are uniformly dispersed on the surfaces of R-GO sheets. The R-GO/SF/PANI nanocomposite exhibited the best absorption property with the optimum matching thickness of 1.5 mm in the frequency of 2-18 GHz. The value of the maximum RL was -45.00 dB at 16.08 GHz with the 5.48-GHz bandwidth. The excellent absorption properties of R-GO/SF/PANI nanocomposites indicated their great potential as microwave-absorbing materials. PMID:26969594

  2. Particle extinction measured at ambient conditions with differential optical absorption spectroscopy. 1. System setup and characterization

    NASA Astrophysics Data System (ADS)

    Müller, Thomas; Müller, Detlef; Dubois, René

    2005-03-01

    We describe an instrument for measuring the particle extinction coefficient at ambient conditions in the spectral range from 270 to 1000 nm. It is based on a differential optical absorption spectroscopy (DOAS) system, which was originally used for measuring trace-gas concentrations of atmospheric absorbers in the ultraviolet-visible wavelength range. One obtains the particle extinction spectrum by measuring the total atmospheric extinction and subtracting trace-gas absorption and Rayleigh scattering. The instrument consists of two nested Newton-type telescopes, which are simultaneously used for emitting and detecting light, and two arrays of retroreflectors at the ends of the two light paths. The design of this new instrument solves crucial problems usually encountered in the design of such instruments. The telescope is actively repositioned during the measurement cycle. Particle extinction is simultaneously measured at several wavelengths by the use of two grating spectrometers. Optical turbulence causes lateral movement of the spot of light in the receiver telescope. Monitoring of the return signals with a diode permits correction for this effect. Phase-sensitive detection efficiently suppresses background signals from the atmosphere as well as from the instrument itself. The performance of the instrument was tested during a measurement period of 3 months from January to March 2000. The instrument ran without significant interruption during that period. A mean accuracy of 0.032 km^-1 was found for the extinction coefficient for an 11-day period in March.

  3. Linear and nonlinear optical absorption characterization of natural laccaic acid dye

    NASA Astrophysics Data System (ADS)

    Zongo, S.; Dhlamini, M. S.; Kerasidou, A. P.; Beukes, P.; Sahraoui, B.; Maaza, M.

    2015-09-01

    We report on the optical performances of laccaic acid dye in solution at different concentrations and dye-poly(methyl methacrylate) composite thin films. The linear spectral characteristics including optical constants, i.e. refractive index ( n) and extinction coefficient ( k), were carried out in a comprehensive way through absorbance, fluorescence and ellipsometric studies. The nonlinear optical parameters such as nonlinear absorption coefficient β eff (or β 2), the imaginary third-order susceptibility (Im[ χ (3)]) and the imaginary part of second-order hyperpolarizability ( γ) of the samples were evaluated using the open-aperture Z-scan technique with a laser pulse duration of 10 ns at 532 nm wavelength. The corresponding numerical values of these parameters were of 10-10, 10-11 and 10-32 order, respectively. Two-photon absorption was revealed to be the main driving physical mechanism in the nonlinear response. This suggests that laccaic acid dye can be a potential candidate for NLO materials application.

  4. Synthesis, Characterization, and Microwave Absorption Properties of Reduced Graphene Oxide/Strontium Ferrite/Polyaniline Nanocomposites

    NASA Astrophysics Data System (ADS)

    Luo, Juhua; Shen, Pan; Yao, Wei; Jiang, Cuifeng; Xu, Jianguang

    2016-03-01

    Strontium ferrite nanoparticles were prepared by a coprecipitation method, and reduced graphene oxide/strontium ferrite/polyaniline (R-GO/SF/PANI) ternary nanocomposites were prepared by in situ polymerization method. The morphology, structure, and magnetic properties of the ternary nanocomposites were investigated by X-ray powder diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), TEM, Raman, and VSM. The microwave-absorbing properties of the composites were measured by a vector network analyzer. The XRD patterns show the single phase of strontium hexaferrite without other intermediate phases. TEM photographs reveal that strontium ferrite nanoparticles are uniformly dispersed on the surfaces of R-GO sheets. The R-GO/SF/PANI nanocomposite exhibited the best absorption property with the optimum matching thickness of 1.5 mm in the frequency of 2-18 GHz. The value of the maximum RL was -45.00 dB at 16.08 GHz with the 5.48-GHz bandwidth. The excellent absorption properties of R-GO/SF/PANI nanocomposites indicated their great potential as microwave-absorbing materials.

  5. Characterization of infrared and near-infrared absorptions of free alcoholic OH groups in hydrocarbon.

    PubMed

    Iwamoto, Reikichi; Matsuda, Toshihiko

    2004-08-01

    We have demonstrated that the near-infrared and infrared absorptions in the 8000-3200 cm(-1) region of an OH group of 2-nonanol, 1-nonanol, etc., in n-heptane are excellently separated by subtraction without any serious interference down to very low concentrations at which OH groups are completely free. The separated sharp absorptions are assigned to the fundamental, combination, and overtone bands that are concerned with the OH stretching of free OH. Two components of a sharp overtone band around 7100 cm(-1), which are observed for primary and secondary alcohols, are assigned to coexisting internal rotational isomers of an OH group around the O-C bond. The frequencies of the OH stretching fundamental and overtone bands that are assigned to internal rotational positions are consistent for all the investigated alcohols, including methanol and tertiary butanol. Comparison of the separated spectrum of 2-nonanol in n-heptane with that in 1-chlorooctane or in carbon tetrachloride makes it clear that hydrocarbon is an inert solvent that does not disturb the intrinsic nature of an alcohol OH group. There actually exists a constant anharmonicity shift of 169-175 cm(-1) between the double frequency (2nu(OH)o) of the observed fundamental and the observed overtone frequency ([2nu(OH)]o) for free OH of various alcohols in n-heptane. PMID:18070393

  6. Facile preparation and characterization of modified magnetic silica nanocomposite particles for oil absorption

    NASA Astrophysics Data System (ADS)

    Yu, Liuhua; Hao, Gazi; Liang, Qianqian; Zhou, Shuai; Zhang, Ning; Jiang, Wei

    2015-12-01

    In this study, a novel environmental-friendly and superhydrophobic oil absorbent was fabricated by modifying magnetic silica nanocomposites. It was demonstrated that the modified rough magnetic silica nanocomposite particles possessed a number of superior features such as superhydrophobicity, superoleophilicity, and high oil-water separation efficiency etc. Moreover, the as-obtained material could be used as excellent absorbents for high density oils such as toluene and many organic liquids including viscous oils e.g. lubricating oil. The lubricating oil intake capacity for the nanocomposites was 7.15 times of its own weight. Importantly, the oil-absorption process of the nanocomposites was selective, fast and efficient when they were used in the purification of oil-contaminated water. Notably, the oil-absorbed nanocomposites could be renewed after suitable absolute ethanol washing and natural drying. In addition, the renewed nanocomposites still remained high oil-absorption capacity after the 20th cycle. These inspiring results show that the oil-absorbent material has good prospects for selection removal of oils and organic solvents on water surface. It is believed that the present work may have provided a novel and facile way for preparing environmental-friendly materials with ideal properties.

  7. Large-scale synthesis, characterization and microwave absorption properties of carbon nanotubes of different helicities

    SciTech Connect

    Qi Xiaosi; Yang Yi; Zhong Wei; Deng Yu; Au Chaktong; Du Youwei

    2009-10-15

    Carbon nanotubes of high helicity (H-HCNTs, Sample A) have been synthesized in large-scale by pyrolysis of acetylene at 450 deg. C over Fe nanoparticles derived from coprecipitation/hydrogen reduction method. With controlled introduction of hydrogen during acetylene pyrolysis, CNTs of low helicity (L-HCNTs, Sample B) and worm-like CNTs (Sample C) were obtained in large quantities. The yields of the CNTs products are high, especially that of H-HCNTs (ca. 7474%). The complex permittivity and permeability of Composites A, B, and C that contain Samples A, B and C (30 wt%) were measured in the 2-18 GHz frequency range. Good absorption of electromagnetic wave (reflection loss<-20 dB) was observed in the 7.18-10.68 and 7.5-10.7 GHz range over Composites B and C (2.0-3.0 mm thickness), respectively. Thus, through the suggested route, CNTs can be produced easily and selectively in large quantities. The lightweight materials can be utilized for microwave absorption. - Graphical abstract: FESEM image of Sample B and reflection loss versus frequency of Composite B (containing 30 wt% of Sample B) in the range of 2-18 GHz.

  8. Spectroscopic analysis of small organic molecules: A comprehensive near-edge x-ray-absorption fine-structure study of C{sub 6}-ring-containing molecules

    SciTech Connect

    Kolczewski, C.; Puettner, R.; Martins, M.; Schlachter, A.S.; Snell, G.; Sant'Anna, M.M.; Hermann, K.; Kaindl, G.

    2006-01-21

    We report high-resolution C 1s near-edge x-ray-absorption fine-structure (NEXAFS) spectra of the C{sub 6}-ring-containing molecules benzene (C{sub 6}H{sub 6}), 1,3- and 1,4-cyclohexadiene (C{sub 6}H{sub 8}), cyclohexene (C{sub 6}H{sub 10}), cyclohexane (C{sub 6}H{sub 12}), styrene (C{sub 8}H{sub 8}), and ethylbenzene (C{sub 8}H{sub 10}) which allow us to examine the gradual development of delocalization of the corresponding {pi} electron systems. Due to the high experimental resolution, vibrational progressions can be partly resolved in the spectra. The experimental spectra are compared with theoretical NEXAFS spectra obtained from density-functional theory calculations where electronic final-state relaxation is accounted for. The comparison yields very good agreement between theoretical spectra and experimental results. In all cases, the spectra can be described by excitations to {pi}*- and {sigma}*-type final-state orbitals with valence character, while final-state orbitals of Rydberg character make only minor contributions. The lowest C 1s{yields}1{pi}* excitation energy is found to agree in the (experimental and theoretical) spectra of all molecules except for 1,3-cyclohexadiene (C{sub 6}H{sub 8}) where an energy smaller by about 0.6 eV is obtained. The theoretical analysis can explain this result by different binding properties of this molecule compared to the others.

  9. 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.

  10. An X-ray absorption spectroscopic study of the effect of bond covalency on the electronic structure of Gd2Ti(2-x)Sn(x)O7.

    PubMed

    Aluri, Esther Rani; Grosvenor, Andrew P

    2013-07-01

    The titanate and stannate pyrochlore-type oxides have been investigated because of their potential applications in different fields. Pyrochlore-type oxides exhibit a wide variety of properties such as fast ionic conduction, resistance to radiation induced structural damage, and ferro- and antiferro-magnetism. These properties mainly depend on the metal-oxygen bonding interactions and electronic structure of the materials, both of which can change with composition. The Gd2Ti(2-x)Sn(x)O7 (0 ≤ x ≤ 2) system was synthesized by the ceramic method and investigated by X-ray absorption near edge spectroscopy (XANES), which allows for the examination of the effect of substitution on bonding and the electronic structure of materials. Examination of metal K- and L3-edge XANES spectra from the Gd2Ti(2-x)Sn(x)O7 system allowed for the elucidation of how the metal-oxygen bond covalency effects the electronic structure of these materials with increasing Sn content. The ionic character of the Ti-O and Gd-O bonds increases while the Sn-O bond becomes more covalent as x increases in the formula, and resulted in changes in energy and/or line shape of the spectra. This study shows that the bonding interactions between metal and oxygen vary strongly with composition, which may affect the fast ionic conduction and resistance to radiation induced structural damage that has been previously reported for these materials. It was also observed in this study that the intensity of the intersite-hybrid peaks found in the pre-edge region of the Ti K-edge XANES spectra resulting from excitations of 1s electrons into next-nearest neighbour Ti 3d states decreased significantly with increasing Sn incorporation. PMID:23681175

  11. X-ray absorption and photoelectron spectroscopic study of the association of As(III) with nanoparticulate FeS and FeS-coated sand.

    PubMed

    Han, Young-Soo; Jeong, Hoon Y; Demond, Avery H; Hayes, Kim F

    2011-11-01

    Iron sulfide (FeS) has been demonstrated to have a high removal capacity for arsenic (As) in reducing environments. However, FeS may be present as a coating, rather than in nanoparticulate form, in both natural and engineered systems. Frequently, the removal capacity of coatings may be different than that of nanoparticulates in batch systems. To assess the differences in removal mechanisms between nanoparticulate FeS and FeS present as a coating, the solid phase products from the reaction of As(III) with FeS-coated sand and with suspensions of nanoparticulate (NP) FeS were determined using x-ray absorption spectroscopy and x-ray photoelectron spectroscopy. In reaction with NP FeS at pH 5, As(III) was reduced to As(II) to form realgar (AsS), while at pH 9, As(III) adsorbed as an As(III) thioarsenite species. In contrast, in the FeS-coated sand system, As(III) formed the solid phase orpiment (As(2)S(3)) at pH 5, but adsorbed as an As(III) arsenite species at pH 9. These different solid reaction products are attributed to differences in FeS concentration and the resultant redox (pe) differences in the FeS-coated sand system versus suspensions of NP FeS. These results point to the importance of accounting for differences in concentration and redox when making inferences for coatings based on batch suspension studies. PMID:21911241

  12. Spectroscopic Low Coherence Interferometry

    NASA Astrophysics Data System (ADS)

    Bosschaart, Nienke; van Leeuwen, T. G.; Aalders, Maurice C.; Hermann, Boris; Drexler, Wolfgang; Faber, Dirk J.

    Low-coherence interferometry (LCI) allows high-resolution volumetric imaging of tissue morphology and provides localized optical properties that can be related to the physiological status of tissue. This chapter discusses the combination of spatial and spectroscopic information by means of spectroscopic OCT (sOCT) and low-coherence spectroscopy (LCS). We describe the theory behind these modalities for the assessment of spatially resolved optical absorption and (back)scattering coefficient spectra. These spectra can be used for the highly localized quantification of chromophore concentrations and assessment of tissue organization on (sub)cellular scales. This leads to a wealth of potential clinical applications, ranging from neonatology for the determination of billibrubin concentrations, to oncology for the optical assessment of the aggressiveness of a cancerous lesion.

  13. Infrared reflection absorption spectroscopic studies on the adsorption structures of dimethyl sulfide and methyl ethyl sulfide on Ag(1 1 0) and Cu(1 1 0)

    NASA Astrophysics Data System (ADS)

    Kasahara, T.; Shinohara, H.; Oshima, Y.; Kadokura, K.; Uriu, Y.; Ohe, C.; Itoh, K.

    2004-06-01

    Infrared reflection absorption (IRA) spectra were measured for dimethyl sulfide (CH 3SCH 3, DMS) and methyl ethyl sulfide (CH 3SCH 2CH 3, MES) with increasing exposure to metal substrates, Ag(1 1 0) and Cu(1 1 0), at 80 K. The spectral simulations performed by using the DFT calculation at the B3LYP/6-311++G** level indicated that (i) DMS adsorbs on the substrates with the CSC plane appreciably tilted from the surface normal, the tilt angle being about 80° for the adsorbate on Ag(1 1 0) and about 60° for the adsorbate on Cu(1 1 0), (ii) MES on Ag(1 1 0) at a submonolayer coverage state takes on the trans form with the molecular plane tilted from the surface normal by about 60°, and (iii) MES on Cu(1 1 0) takes the gauche form with the CSC plane almost perpendicular to the surface. The tilting of DMS is contrasted to dimethyl ether (DME) adsorbs on Ag(1 1 0) and Cu(1 1 0), where the molecular plane is perpendicular to the substrate surfaces [J. Phys. Chem. B 106 (2002) 3469]. The adsorption structures of DMS and DME are mainly determined by the coordination of the sulfur and oxygen atoms, the sulfur atom tending to coordinate to the Ag and Cu atoms through one of the 3p lone pairs (atop coordination) and the oxygen atom to the metal atoms through both of the 2p lone pairs (bridging coordination). It has been known that methyl ethyl ether (MEE) on Ag(1 1 0) takes on the trans form with the molecular plane tilted by about 45° and MEE on Cu(1 1 0) the gauche form with the COC plane almost perpendicular to the surface [J. Phys. Chem. B 107 (2003) 5008]. These results suggest that an attractive van der Waals interaction between the ethyl group of the adsorbates and the substrate surfaces play an important role in addition to the coordination of the sulfur and oxygen atoms in determining the rotational isomerism and orientation of MES and MEE on Ag(1 1 0) and Cu(1 1 0).

  14. Morphological and spectroscopic investigation of the behavior of permanent iridium modifier deposited on pyrolytic graphite coated and zirconium treated platforms in electrothermal atomic absorption spectrometry

    NASA Astrophysics Data System (ADS)

    Slaveykova, Vera I.; Lampugnani, Leonardo; Tsalev, Dimiter L.; Sabbatini, L.

    1997-12-01

    In order to better characterise a permanent modifier based on iridium deposited on zirconium or tungsten treated platforms of transversely heated graphite atomizer, and to gain additional information about its chemical behavior directed to an eventual further optimization, a series of experiments were carried out, both by surface techniques such as scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS or ESCA) and X-ray fluorescence (XRF) and by electrothermal atomic absorption spectrometry on the iridium release from unmodified and various other modified pyrolytic graphite platforms. Special attention was paid to the influence of the amount of iridium, zirconium carbide coating of the platform surface and the presence of citric acid on the iridium vaporization during pyrolysis and atomization. The processes of iridium losses during pyrolysis and atomization and peak maximum alignment depend on the amount of the iridium deposited on the pyrolytic graphite coated platforms in the presence of nitric acid. A fractional order of release which suggests an atom vaporization from the surface or edges of the iridium islands was estimated. In the presence of citric acid, mass independence and zero order of the atom release were found. The zirconium treatment of the platform results in change of the spatial distribution of iridium and hence its vaporization. Vaporization temperatures as high as 2100°C, and first order of the process of atom generation were obtained. While it was possible to study the iridium atomization from uncoated and zirconium coated surfaces, evidencing a different order for the release process, the same was not possible for the tungsten coated platforms due to an 'overstabilization' that brought the iridium atomization temperature out of the working range of the instrument used. The different chemical behavior of tungsten and zirconium was also confirmed by XPS investigations. With tungsten, evidence of both WC and WO bonding was found, while zirconium on the contrary shows only ZrO bonding and no evidence of carbide bonding. The SEM revealed a highly dispersed distribution of spot-like features whose smallest average diameter was of the order of 0.1 μm. The XRF asserted the confinement of iridium in these features and a strict association with zirconium in the case of zirconium treated surfaces. It is worth mentioning that such structure was preserved also after 400 thermal cycles simulating an atomization step at 1900°C despite a quite evident deterioration of the graphite surface, thus confirming the excellent durability of this modifier.

  15. Reactivity-activity relationships of oral anti-diabetic vanadium complexes in gastrointestinal media: an X-ray absorption spectroscopic study.

    PubMed

    Levina, Aviva; McLeod, Andrew I; Kremer, Lauren E; Aitken, Jade B; Glover, Christopher J; Johannessen, Bernt; Lay, Peter A

    2014-10-01

    The reactions of oral V(V/IV) anti-diabetic drugs within the gastrointestinal environment (particularly in the presence of food) are a crucial factor that affects their biological activities, but to date these have been poorly understood. In order to build up reactivity-activity relationships, the first detailed study of the reactivities of typical V-based anti-diabetics, Na3V(V)O4 (A), [V(IV)O(OH2)5](SO4) (B), [V(IV)O(ma)2] (C, ma = maltolato(-)) and (NH4)[V(V)(O)2(dipic)] (D, dipic = pyridine-2,5-dicarboxylato(2-)) with simulated gastrointestinal (GI) media in the presence or absence of food components has been performed by the use of XANES (X-ray absorption near edge structure) spectroscopy. Changes in speciation under conditions that simulate interactions in the GI tract have been discerned using correlations of XANES parameters that were based on a library of model V(V), V(IV), and V(III) complexes for preliminary assessment of the oxidation states and coordination numbers. More detailed speciation analyses were performed using multiple linear regression fits of XANES from the model complexes to XANES obtained from the reaction products from interactions with the GI media. Compounds B and D were relatively stable in the gastric environment (pH ∼ 2) in the absence of food, while C was mostly dissociated, and A was converted to [V10O28](6-). Sequential gastric and intestinal digestion in the absence of food converted A, B and D to poorly absorbed tetrahedral vanadates, while C formed five- or six-coordinate V(V) species where the maltolato ligands were likely to be partially retained. XANES obtained from gastric digestion of A-D in the presence of typical food components converged to that of a mixture of V(IV)-aqua, V(IV)-amino acid and V(III)-aqua complexes. Subsequent intestinal digestion led predominantly to V(IV) complexes that were assigned as citrato or complexes with 2-hydroxyacidato donor groups from other organic compounds, including certain carbohydrates. The absence of strong reductants (such as ascorbate) in the food increased the V(V) component in gastrointestinal digestion products. These results can be used to predict the oral bioavailability of various types of V(V/IV) anti-diabetics, and the effects of taking such drugs with food. PMID:25100248

  16. 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

  17. Characterization of the dominating bulk recombination in bulk-heterojunction blends using photoinduced absorption

    NASA Astrophysics Data System (ADS)

    Sandén, S.; Wilson, N. M.; Sandberg, O. J.; Ã-sterbacka, R.

    2016-05-01

    In this work we show how to clarify the dominating bulk recombination in organic solar cells by using photoinduced absorption. We show how to use the intensity and frequency dependence of the in-phase and quadrature signals to obtain the effective reaction order. For trap-assisted recombination, we can show using a multiple trapping and retrapping model with an exponential tail-state distribution that a temperature dependent reaction order is obtained which allows for determination of the characteristic energy of the exponential distribution of trap-states. In the model system pBTTT:PC60BM, we show that trap-assisted recombination is the dominating bulk recombination in 1:1 blends with a characteristic energy of the exponential trap distribution E c h = 44 ± 5 meV. The 1:4 blend, on the other hand, shows temperature independent behavior in good agreement with a dominating 2D Langevin bulk recombination.

  18. 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.

  19. 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 μg/ml insulin, 10 ng/ml epidermal growth factor, 100 U/ml penicillin, 100 μg/ml streptomycin, 50 μg/ml gentamycin and 2.5 μg/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

  20. Characterization of Metalloproteins by High-throughput X-ray Absorption Spectroscopy

    SciTech Connect

    W Shi; M Punta; J Bohon; J Sauder; R DMello; M Sullivan; J Toomey; D Abel; M Lippi; et al.

    2011-12-31

    High-throughput X-ray absorption spectroscopy was used to measure transition metal content based on quantitative detection of X-ray fluorescence signals for 3879 purified proteins from several hundred different protein families generated by the New York SGX Research Center for Structural Genomics. Approximately 9% of the proteins analyzed showed the presence of transition metal atoms (Zn, Cu, Ni, Co, Fe, or Mn) in stoichiometric amounts. The method is highly automated and highly reliable based on comparison of the results to crystal structure data derived from the same protein set. To leverage the experimental metalloprotein annotations, we used a sequence-based de novo prediction method, MetalDetector, to identify Cys and His residues that bind to transition metals for the redundancy reduced subset of 2411 sequences sharing <70% sequence identity and having at least one His or Cys. As the HT-XAS identifies metal type and protein binding, while the bioinformatics analysis identifies metal-binding residues, the results were combined to identify putative metal-binding sites in the proteins and their associated families. We explored the combination of this data with homology models to generate detailed structure models of metal-binding sites for representative proteins. Finally, we used extended X-ray absorption fine structure data from two of the purified Zn metalloproteins to validate predicted metalloprotein binding site structures. This combination of experimental and bioinformatics approaches provides comprehensive active site analysis on the genome scale for metalloproteins as a class, revealing new insights into metalloprotein structure and function.

  1. Characterization of metalloproteins by high-throughput X-ray absorption spectroscopy.

    PubMed

    Shi, Wuxian; Punta, Marco; Bohon, Jen; Sauder, J Michael; D'Mello, Rhijuta; Sullivan, Mike; Toomey, John; Abel, Don; Lippi, Marco; Passerini, Andrea; Frasconi, Paolo; Burley, Stephen K; Rost, Burkhard; Chance, Mark R

    2011-06-01

    High-throughput X-ray absorption spectroscopy was used to measure transition metal content based on quantitative detection of X-ray fluorescence signals for 3879 purified proteins from several hundred different protein families generated by the New York SGX Research Center for Structural Genomics. Approximately 9% of the proteins analyzed showed the presence of transition metal atoms (Zn, Cu, Ni, Co, Fe, or Mn) in stoichiometric amounts. The method is highly automated and highly reliable based on comparison of the results to crystal structure data derived from the same protein set. To leverage the experimental metalloprotein annotations, we used a sequence-based de novo prediction method, MetalDetector, to identify Cys and His residues that bind to transition metals for the redundancy reduced subset of 2411 sequences sharing <70% sequence identity and having at least one His or Cys. As the HT-XAS identifies metal type and protein binding, while the bioinformatics analysis identifies metal- binding residues, the results were combined to identify putative metal-binding sites in the proteins and their associated families. We explored the combination of this data with homology models to generate detailed structure models of metal-binding sites for representative proteins. Finally, we used extended X-ray absorption fine structure data from two of the purified Zn metalloproteins to validate predicted metalloprotein binding site structures. This combination of experimental and bioinformatics approaches provides comprehensive active site analysis on the genome scale for metalloproteins as a class, revealing new insights into metalloprotein structure and function. PMID:21482623

  2. Characterization and speciation of mercury-bearing mine wastes using X-ray absorption spectroscopy.

    PubMed

    Kim, C S; Brown, G E; Rytuba, J J

    2000-10-16

    Mining of mercury deposits located in the California Coast Range has resulted in the release of mercury to the local environment and water supplies. The solubility, transport, and potential bioavailability of mercury are controlled by its chemical speciation, which can be directly determined for samples with total mercury concentrations greater than 100 mg kg(-1) (ppm) using X-ray absorption spectroscopy (XAS). This technique has the additional benefits of being non-destructive to the sample, element-specific, relatively sensitive at low concentrations, and requiring minimal sample preparation. In this study, Hg L(III)-edge extended X-ray absorption fine structure (EXAFS) spectra were collected for several mercury mine tailings (calcines) in the California Coast Range. Total mercury concentrations of samples analyzed ranged from 230 to 1060 ppm. Speciation data (mercury phases present and relative abundances) were obtained by comparing the spectra from heterogeneous, roasted (calcined) mine tailings samples with a spectral database of mercury minerals and sorbed mercury complexes. Speciation analyses were also conducted on known mixtures of pure mercury minerals in order to assess the quantitative accuracy of the technique. While some calcine samples were found to consist exclusively of mercuric sulfide, others contain additional, more soluble mercury phases, indicating a greater potential for the release of mercury into solution. Also, a correlation was observed between samples from hot-spring mercury deposits, in which chloride levels are elevated, and the presence of mercury-chloride species as detected by the speciation analysis. The speciation results demonstrate the ability of XAS to identify multiple mercury phases in a heterogeneous sample, with a quantitative accuracy of +/-25% for the mercury-containing phases considered. Use of this technique, in conjunction with standard microanalytical techniques such as X-ray diffraction and electron probe microanalysis, is beneficial in the prioritization and remediation of mercury-contaminated mine sites. PMID:11036987

  3. Characterization of metalloproteins by high-throughput X-ray absorption spectroscopy

    PubMed Central

    Shi, Wuxian; Punta, Marco; Bohon, Jen; Sauder, J. Michael; D'Mello, Rhijuta; Sullivan, Mike; Toomey, John; Abel, Don; Lippi, Marco; Passerini, Andrea; Frasconi, Paolo; Burley, Stephen K.; Rost, Burkhard; Chance, Mark R.

    2011-01-01

    High-throughput X-ray absorption spectroscopy was used to measure transition metal content based on quantitative detection of X-ray fluorescence signals for 3879 purified proteins from several hundred different protein families generated by the New York SGX Research Center for Structural Genomics. Approximately 9% of the proteins analyzed showed the presence of transition metal atoms (Zn, Cu, Ni, Co, Fe, or Mn) in stoichiometric amounts. The method is highly automated and highly reliable based on comparison of the results to crystal structure data derived from the same protein set. To leverage the experimental metalloprotein annotations, we used a sequence-based de novo prediction method, MetalDetector, to identify Cys and His residues that bind to transition metals for the redundancy reduced subset of 2411 sequences sharing <70% sequence identity and having at least one His or Cys. As the HT-XAS identifies metal type and protein binding, while the bioinformatics analysis identifies metal- binding residues, the results were combined to identify putative metal-binding sites in the proteins and their associated families. We explored the combination of this data with homology models to generate detailed structure models of metal-binding sites for representative proteins. Finally, we used extended X-ray absorption fine structure data from two of the purified Zn metalloproteins to validate predicted metalloprotein binding site structures. This combination of experimental and bioinformatics approaches provides comprehensive active site analysis on the genome scale for metalloproteins as a class, revealing new insights into metalloprotein structure and function. PMID:21482623

  4. Characterization and speciation of mercury-bearing mine wastes using X-ray absorption spectroscopy

    USGS Publications Warehouse

    Kim, C.S.; Brown, Gordon E., Jr.; Rytuba, J.J.

    2000-01-01

    Mining of mercury deposits located in the California Coast Range has resulted in the release of mercury to the local environment and water supplies. The solubility, transport, and potential bioavailability of mercury are controlled by its chemical speciation, which can be directly determined for samples with total mercury concentrations greater than 100 mg kg-1 (ppm) using X-ray absorption spectroscopy (XAS). This technique has the additional benefits of being non-destructive to the sample, element-specific, relatively sensitive at low concentrations, and requiring minimal sample preparation. In this study, Hg L(III)-edge extended X-ray absorption fine structure (EXAFS) spectra were collected for several mercury mine tailings (calcines) in the California Coast Range. Total mercury concentrations of samples analyzed ranged from 230 to 1060 ppm. Speciation data (mercury phases present and relative abundances) were obtained by comparing the spectra from heterogeneous, roasted (calcined) mine tailings samples with a spectral database of mercury minerals and sorbed mercury complexes. Speciation analyses were also conducted on known mixtures of pure mercury minerals in order to assess the quantitative accuracy of the technique. While some calcine samples were found to consist exclusively of mercuric sulfide, others contain additional, more soluble mercury phases, indicating a greater potential for the release of mercury into solution. Also, a correlation was observed between samples from hot-spring mercury deposits, in which chloride levels are elevated, and the presence of mercury-chloride species as detected by the speciation analysis. The speciation results demonstrate the ability of XAS to identify multiple mercury phases in a heterogeneous sample, with a quantitative accuracy of ??25% for the mercury-containing phases considered. Use of this technique, in conjunction with standard microanalytical techniques such as X-ray diffraction and electron probe microanalysis, is beneficial in the prioritization and remediation of mercury-contaminated mine sites. (C) 2000 Elsevier Science B.V.

  5. Development of Cellular Absorptive Tracers (CATs) for a Quantitative Characterization of the Complexity of Nanoscale Biological Systems

    NASA Astrophysics Data System (ADS)

    Choi, J.; Saripalli, P.; Meldrum, D.; Lee, S.

    2005-12-01

    A new method is proposed in this study, which is entitled Cellular Absorptive Tracers (CATs; PNNL Invention Disclosure; Saripalli, P. 2001), to characterize the extent, location, and morphology of cell mass in microelectromechanical systems (MEMS), by preferentially absorbing into the living or lysed cells or adsorbing at the cell surfaces. The CATs were used to demonstrate their utility to quantitatively characterize the biomass, its location, and morphology in MEMS. A series of experiments had conducted, using different number/types of cells and morphologic distributions (e.g., concentrated vs. disperse) within the microenvironmental chamber. The experiments were conducted such that, simultaneously with CATs characterization, a number of metabolic parameters (such as oxygen, CO2, glucose, pH, methanol, formate and small molecule metabolites, etc.) also were measured by fluorescence microscopy (Lidstrom and Meldrum, Nature, 2003). Results of partition and transport experiments show that adsorption of a CAT molecule into the cellular mass results in its retardation during flow, which is a good measure of the biomass quantity and distribution. The molecules chosen were used to demonstrate their utility to quantitatively characterize the biomass, its location and morphology in MEMS. The results yield first-of-their-kind data sets relating metabolic parameters to location, heterogeneity, and morphology of cells. The data were used to obtain quantitative information needed for the characterization of biomass in MEMS, and to develop the theory relating the cellular phenomena of interest to cellular heterogeneity and morphology. The proposed research contributes a new set of tools for a rapid, noninvasive characterization of nano-scale biological systems.

  6. 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 μM.

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

    PubMed

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

    2014-01-24

    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 μM. PMID:24084484

  8. Synthesis, spectroscopic characterization, DFT studies, and antibacterial and antitumor activities of a novel water soluble Pd(II) complex with L-alliin

    NASA Astrophysics Data System (ADS)

    Abbehausen, Camilla; Sucena, Suelen F.; Lancellotti, Marcelo; Heinrich, Tassiele A.; Abrão, Emiliana P.; Costa-Neto, Claudio M.; Formiga, André L. B.; Corbi, Pedro P.

    2013-03-01

    A new water soluble Pd(II) complex with L-alliin (S-allyl-L-cysteine sulfoxide) was obtained and characterized by a set of chemical and spectroscopic measurements. Elemental and mass spectrometric data are consistent with the formula [Pd(C6H10NO3S)2]. The 1H and 13C nuclear magnetic resonance (NMR) data, [1H-15N] two dimensional (2D) NMR and infrared spectroscopic measurements indicate coordination of the ligand to Pd(II) through N and O atoms. DFT studies showed that the trans isomer is the most stable and preferred geometry for the complex. The complex is soluble in water and dimethylsulfoxide. An antibiogram assay revealed that the complex possess antibacterial activity against Escherichia coli, Pseudomonas aeruginosa and Staphylococcus aureus bacterial strains in the range 125-500 μg mL-1. Antitumor assays revealed that the complex presents cytotoxic activity over HeLa cells with an estimated IC50 of 20 μmol L-1.

  9. Synthesis and characterizations of ultra-small ZnS and Zn(1-x)Fe(x)S quantum dots in aqueous media and spectroscopic study of their interactions with bovine serum albumin.

    PubMed

    Khani, Omid; Rajabi, Hamid Reza; Yousefi, Mohammad Hasan; Khosravi, Ali Azam; Jannesari, Mohammad; Shamsipur, Mojtaba

    2011-07-01

    This work reports a new experimental methodology for the synthesis of ultra small zinc sulfide and iron doped zinc sulfide quantum dots in aqueous media. The nanoparticles were obtained using a simple procedure based on the precipitation of ZnS in aqueous solution in the presence of 2-mercaptoethanol as a capping agent, at room temperature. The effect of Fe(3+) ion concentration as dopant on the optical properties of ZnS was studied. The size of quantum dots was determined to be about 1nm, using scanning tunneling microscopy. The synthesized nanoparticles were characterized by X-ray diffraction, UV-Vis absorption and photoluminescence emission spectroscopies. The presence and amount of iron impurity in the structure of Zn((1-x))Fe(x)S nanocrystals were confirmed by atomic absorption spectrometry. A blue shift in band-gap of ZnS was observed upon increasing incorporation of Fe(3+) ion in the iron doped zinc sulfide quantum dots. The photoluminescence investigations showed that, in the case of iron doped ZnS nanoparticles, the emission band of pure ZnS nanoparticles at 427nm shifts to 442nm with appearance of a new sharp emission band around 532nm. The X-ray diffraction analysis indicated that the iron doped nanoparticles are crystalline, with cubic zinc blend structure, having particle diameters of 1.7±022nm. Finally, the interaction of the synthesized nanoparticles with bovine serum albumin was investigated at pH 7.2. The UV-Vis absorption and fluorescence spectroscopic methods were applied to compare the optical properties of pure and iron doped ZnS quantum dots upon interaction with BSA. It was proved that, in both cases, the fluorescence quenching of BSA by the quantum dots is mainly a result of the formation of QDs-BSA complex in solution. In the steady-state fluorescence studies, the interaction parameters including binding constants (K(a)), number of binding sites (n), quenching constants ( [Formula: see text] ), and bimolecular quenching rate constants (k(q)) were determined at three different temperatures and the results were then used to evaluate the corresponding thermodynamic parameters ΔH, ΔS and ΔG. PMID:21482179

  10. Multiple angle of incidence, spectroscopic, plasmon-enhanced, internal reflection ellipsometry for the characterization of solid-liquid interface processes

    NASA Astrophysics Data System (ADS)

    Petrik, P.; Agocs, E.; Kalas, B.; Kozma, P.; Fodor, B.; Nador, J.; Major, C.; Fried, M.

    2015-05-01

    A semi-cylindrical lens in Kretschmann geometry combined with a flow cell was designed for a commercial rotating compensator ellipsometer to perform internal reflection spectroscopic ellipsometry measurements, while allowing the use of multiple angles of incidence. A thin glass slide covered with a gold film was mounted between the half-cylindrical lens and a small-volume flow cell ensuring an improved sensitivity for protein adsorption experiments. The performance of the system was investigated depending on the angle of incidence, wavelength range and thickness of the gold films for surface plasmon resonance enhanced ellipsometric measurements, and a sensitivity increase was revealed compared to ellipsometric measurements with standard flow cells, depending on the measurement parameters and configuration. The sensitivity increase was demonstrated for fibrinogen adsorption.

  11. 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: ana@chem.ucla.edu; Alexandrova, Anastassia N. E-mail: ana@chem.ucla.edu

    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}Σ{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.

  12. 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, Jiří

    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.

  13. Flow field-flow fractionation with off-line electrothermal atomic absorption spectrometry for size characterization of silver nanoparticles.

    PubMed

    Songsilawat, Kanchana; Shiowatana, Juwadee; Siripinyanond, Atitaya

    2011-07-01

    Flow field-flow fractionation (Fl-FFF) with off-line electrothermal atomic absorption spectrometry (ETAAS) detection was developed and employed for particle size characterization of Ag NPs stabilized by citrate, pectin, and alginate. Citrate stabilized-Ag NPs were prepared from sodium borohydride reduction of silver nitrate. Sodium citrate was used as the capping agent to stabilize Ag NPs and prevent the aggregation process. Pectin stabilized- and alginate stabilized-Ag NPs were prepared from ascorbic acid reduction of silver nitrate. Pectin and alginate were used as the capping agent for pectin stabilized- and alginate stabilized-Ag NPs, respectively. Three types of Ag NPs were characterized by using FlFFF, zeta potentiometer, and TEM technique. The mean particle sizes of Ag NPs as characterized by FlFFF were 9 nm, 19 nm, and 45 nm for citrate stabilized-, pectin stabilized-, and alginate stabilized-Ag NPs, respectively, in deionized water. Further, FlFFF with ETAAS detection was employed to observe the aggregation of Ag NPs of various types in environmental water in the absence and presence of humic acid. Citrate stabilized-Ag NPs underwent aggregation more rapid than the pectin stabilized- and alginate stabilized-Ag NPs as the latter two types were sterically stabilized. Further, humic acid could prolong the stability of Ag NPs in the environment. PMID:21236433

  14. 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.

  15. X-ray Absorption Spectroscopy Characterization of a Li/S Cell

    DOE PAGESBeta

    Ye, Yifan; Kawase, Ayako; Song, Min-Kyu; Feng, Bingmei; Liu, Yi-Sheng; Marcus, Matthew A.; Feng, Jun; Cairns, Elton J.; Guo, Jinghua; Zhu, Junfa

    2016-01-11

    The X-ray absorption spectroscopy technique has been applied to study different stages of the lithium/sulfur (Li/S) cell life cycle. We investigated how speciation of S in Li/S cathodes changes upon the introduction of CTAB (cetyltrimethylammonium bromide, CH3(CH2)15N+(CH3)3Br₋) and with charge/discharge cycling. The introduction of CTAB changes the synthesis reaction pathway dramatically due to the interaction of CTAB with the terminal S atoms of the polysulfide ions in the Na2Sx solution. For the cycled Li/S cell, the loss of electrochemically active sulfur and the accumulation of a compact blocking insulating layer of unexpected sulfur reaction products on the cathode surface duringmore » the charge/discharge processes make the capacity decay. Lastly, a modified coin cell and a vacuum-compatible three-electrode electro-chemical cell have been introduced for further in-situ/in-operando studies.« less

  16. 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.

  17. 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

  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. Fourier transform infrared absorption spectroscopy characterization of gaseous atmospheric pressure plasmas with 2 mm spatial resolution

    SciTech Connect

    Laroche, G.; Vallade, J.; Bazinette, R.; Hernandez, E.; Hernandez, G.; Massines, F.; Nijnatten, P. van

    2012-10-15

    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 Multiplication-Sign 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 Degree-Sign 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.

  20. Electronic transport characterization of silicon wafers by combination of modulated free carrier absorption and photocarrier radiometry

    NASA Astrophysics Data System (ADS)

    Huang, Qiuping; Li, Bincheng

    2011-01-01

    A combined modulated free carrier absorption (MFCA) and photocarrier radiometry (PCR) technique is developed to determine simultaneously the electronic transport properties (carrier diffusion coefficient, carrier lifetime, and front surface recombination velocity) of silicon wafers. Comparative computer simulations are carried out to investigate how the experimental measurement errors affect the simultaneous determination of the electronic transport parameters by introducing random or systematic errors into the simulated MFCA and PCR data and statistically analyzing the fitted results, by means of separate MFCA and PCR, as well as the combined MFCA and PCR through fitting the experimental dependences of signal amplitudes and phases to the corresponding theoretical models via a multiparameter fitting procedure, respectively. The simulation results show that with the combined MFCA and PCR the effect of experimental errors on the simultaneous determination of the transport parameters is significantly reduced and therefore the accuracy of the fitted results is greatly improved. Experiments with two c-Si wafers with the three methods were performed and the results were compared. The experimental results showed that the combined MFCA and PCR provided the most accurate fitted transport parameters, in agreement with the simulation results.

  1. Monitoring and characterization of compost obtained from household waste and pine sawdust in a facultative reactor by conventional and spectroscopic analyses.

    PubMed

    de Campos, Sandro Xavier; Resseti, Rolan Roney; Zittel, Rosimara

    2014-12-01

    This study proposes a new facultative reactor configuration for the treatment of organic household waste and pine sawdust. The process was monitored and the compost characterized by conventional (temperature, moisture, pH, ash content and ratio C/N) conjugated with spectroscopic analyses (ultraviolet (UV)/visible (Vis) and infrared (IR)) and germination index. The spectroscopy results revealed enrichment of carbon-carbon unsaturation structures and a degradation of the aliphatic structures. The results showed that stability of the final product was reached after 90 days and that the compost obtained presents substantial richness of stabilized organic matter and an absence of toxicity, so it may be considered as an organic fertilizer. Finally, this study led to the conclusion that the reactor proposed can be a promising technology for the management of organic household waste and sawdust. PMID:25106532

  2. Characterization of selective binding of alkali cations with carboxylate by x-ray absorption spectroscopy of liquid microjets

    PubMed Central

    Uejio, Janel S.; Schwartz, Craig P.; Duffin, Andrew M.; Drisdell, Walter S.; Cohen, Ronald C.; Saykally, Richard J.

    2008-01-01

    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. PMID:18463292

  3. 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.

  4. 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 μm. 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. pK(a) (7.49 ± 0.01), log P (5.10 ± 0.02) and intrinsic solubility (S0) (1.75 μg/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 T(max), C(max), AUC(0-t) and absolute bioavailability were 1.60 ± 0.81 h, 0.78 ± 0.47 μg/ml, 3.77 ± 1.85 μg·h/ml and 52.30 ± 19.39%, respectively. The preformulation characterization provides valuable information for further development of oral administration of JFD. PMID:24694186

  5. Characterization of two quinone radicals in the NADH:ubiquinone oxidoreductase from Escherichia coli by a combined fluorescence spectroscopic and electrochemical approach.

    PubMed

    Hielscher, Ruth; Yegres, Michelle; Voicescu, Mariana; Gnandt, Emmanuel; Friedrich, Thorsten; Hellwig, Petra

    2013-12-17

    The NADH:ubiquinone oxidoreductase (complex I) couples the transfer of electrons from NADH to ubiquinone with the translocation of protons across the membrane. It was proposed that the electron transfer involves quinoid groups localized at the end of the electron transfer chain. To identify these groups, fluorescence excitation and emission spectra of Escherichia coli complex I and its fragments, namely, the NADH dehydrogenase fragment containing the flavin mononucleotide and six iron-sulfur (Fe-S) clusters, and the quinone reductase fragment containing three Fe-S clusters were measured. Signals sensitive to reduction by either NADH or dithionite were detected within the complex and the quinone reductase fragment and attributed to the redox transition of protonated ubiquinone radicals. A fluorescence spectroscopic electrochemical redox titration revealed midpoint potentials of -37 and- 235 mV (vs the standard hydrogen electrode) for the redox transitions of the quinone radicals in complex I at pH 6 with an absorption around 325 nm and a fluorescence emission at 460/475 nm. The role of these cofactor(s) for electron transfer is discussed. PMID:24279322

  6. Spectroscopic ellipsometry characterization of amorphous and crystalline TiO2 thin films grown by atomic layer deposition at different temperatures

    NASA Astrophysics Data System (ADS)

    Saha, D.; Ajimsha, R. S.; Rajiv, K.; Mukherjee, C.; Gupta, M.; Misra, P.; Kukreja, L. M.

    2014-10-01

    TiO2 thin films of widely different structural and morphological characteristics were grown on Si (1 0 0) substrates using Atomic Layer Deposition (ALD) by varying the substrate temperature (Ts) in a wide range (50 °C ≤ Ts ≤ 400 °C). Spectroscopic ellipsometry (SE) measurements were carried out to investigate the effect of growth temperature on the optical properties of the films. Measured SE data were analyzed by considering double layer optical model for the sample together with the single oscillator Tauc-Lorentz dispersion relation. Surface roughness was taken into consideration due to the columnar growths of grains in crystalline films. The refractive index was found to be increased from amorphous (Ts ≤ 150 °C) to the nanocrystalline films (2500 < Ts ≤ 400 °C). The pronounced surface roughening for the large-grained anatase film obtained at the amorphous to crystalline phase transformation temperature of 200 °C, impeded SE measurement. The dispersions of refractive indices below the interband absorption edge were found to be strongly correlated with the single oscillator Wemple-DiDomenico (WD) model. The increase in dispersion energy parameter in WD model from disordered amorphous to the more ordered nanocrystalline films was found to be associated with the increase in the film density and coordination number.

  7. Quest for Environmentally-Benign Ligands for Actinide Separations: Thermodynamic, Spectroscopic, and Structural Characterization of U(VI) Complexes with Oxa-Diamide and Related Ligands

    SciTech Connect

    Advanced Light Source; Tian, Guoxin; Rao, Linfeng; Teat, Simon J.; Liu, Guokui

    2009-01-05

    Complexation of U(VI) with N,N,N{prime},N{prime}-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 ODA, TMOGA and DMOGA form tridentate U(VI) complexes, with three oxygen atoms (the amide, ether and/or carboxylate oxygen) coordinating to the linear UO{sub 2}{sup 2+} cation via the equatorial plane. The stability constants, enthalpy and entropy of complexation all decrease in the order ODA > DMOGA > TMOGA, showing that the complexation is entropy driven and the substitution of a carboxylate group with an amide group reduces the strength of complexation with U(VI) due to the decrease in the entropy of complexation. The trend in the thermodynamic stability of the complexes correlates very well with the structural and spectroscopic data obtained by single crystal XRD, FT-IR and laser-induced luminescence spectroscopy.

  8. Subzero-temperature stabilization and spectroscopic characterization of homogeneous oxyferrous complexes of the cytochrome P450 BM3 (CYP102) oxygenase domain and holoenzyme

    SciTech Connect

    Perera, Roshan; Sono, Masanori; Raner, Gregory M.; Dawson, John H. . E-mail: dawson@sc.edu

    2005-12-09

    We describe herein for the first time the formation and spectroscopic characterization of homogeneous oxyferrous complexes of the cytochrome P450 BM3 (CYP102) holoenzyme and heme domain (BMP) at -55 {sup o}C using a 70/30 (v/v) glycerol/buffer cryosolvent. The choice of buffer is a crucial factor with Tris [tris(hydroxymethyl)aminomethane] buffer being significantly more effective than phosphate. The oxyferrous complexes have been characterized with magnetic circular dichroism spectroscopy and the resulting spectra compared to those of the more well-characterized oxyferrous cytochrome P450-CAM. The formation of a stable substrate-bound oxyferrous CYP BM3 holoenzyme, despite the fact that it has the necessary reducing equivalents for turnover, indicates that electron transfer from the flavin domain to the oxyferrous center is very slow at this temperature. The ability to prepare stable homogeneous oxyferrous derivatives of both BMP and the CYP BM3 holoenzyme will enable these species to be used as starting materials for mechanistic investigation of dioxygen activation.

  9. X-ray Absorption and Emission Spectroscopic Studies of [L2Fe2S2](n) Model Complexes: Implications for the Experimental Evaluation of Redox States in Iron-Sulfur Clusters.

    PubMed

    Kowalska, Joanna K; Hahn, Anselm W; Albers, Antonia; Schiewer, Christine E; Bjornsson, Ragnar; Lima, Frederico A; Meyer, Franc; DeBeer, Serena

    2016-05-01

    Herein, a systematic study of [L2Fe2S2](n) model complexes (where L = bis(benzimidazolato) and n = 2-, 3-, 4-) has been carried out using iron and sulfur K-edge X-ray absorption (XAS) and iron Kβ and valence-to-core X-ray emission spectroscopies (XES). These data are used as a test set to evaluate the relative strengths and weaknesses of X-ray core level spectroscopies in assessing redox changes in iron-sulfur clusters. The results are correlated to density functional theory (DFT) calculations of the spectra in order to further support the quantitative information that can be extracted from the experimental data. It is demonstrated that due to canceling effects of covalency and spin state, the information that can be extracted from Fe Kβ XES mainlines is limited. However, a careful analysis of the Fe K-edge XAS data shows that localized valence vs delocalized valence species may be differentiated on the basis of the pre-edge and K-edge energies. These findings are then applied to existing literature Fe K-edge XAS data on the iron protein, P-cluster, and FeMoco sites of nitrogenase. The ability to assess the extent of delocalization in the iron protein vs the P-cluster is highlighted. In addition, possible charge states for FeMoco on the basis of Fe K-edge XAS data are discussed. This study provides an important reference for future X-ray spectroscopic studies of iron-sulfur clusters. PMID:27097289

  10. 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.

  11. Binary iron-chromium oxide as negative electrode for lithium-ion micro-batteries - spectroscopic and microscopic characterization

    NASA Astrophysics Data System (ADS)

    Tian, Bingbing; Światowska, Jolanta; Maurice, Vincent; Zanna, Sandrine; Seyeux, Antoine; Marcus, Philippe

    2015-10-01

    (Fe,Cr)-binary oxide thin film electrodes were prepared as negative electrode material for lithium-ion micro-batteries by thermal growth on a stainless steel (AISI 410, FeCr12.5) current collector. The mechanisms of lithiation/delithiation were investigated by means of electrochemical (CV, galvanostatic cycling), spectroscopic (XPS, ToF-SIMS) and microscopic (SEM, AFM) analytical techniques. The as-prepared (Fe, Cr)-binary oxide electrodes exhibit a good cycling performance except the first discharge/charge cycle where a high irreversible capacity is observed due to formation of a solid electrolyte interphase (SEI) layer. The influence of substituting an oxidized iron by an oxidized chromium (CrxFe2-xO3 phase) was evaluated. The data show that the inferior electrochemical conversion activity of substituted oxidized chromium results in hindering lithium transport in the bulk thin film electrode. It was observed that the irreversible morphology modifications together with SEI evolution are critical to capacity degradation while retaining good coulombic efficiency.

  12. 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.

  13. Site-directed mutagenesis and spectroscopic characterization of human ferrochelatase: identification of residues coordinating the [2Fe-2S] cluster.

    PubMed

    Crouse, B R; Sellers, V M; Finnegan, M G; Dailey, H A; Johnson, M K

    1996-12-17

    The five cysteines closest to the carboxyl terminus of human ferrochelatase have been individually mutated to serine, histidine, or aspartate residues in an attempt to identify the protein ligands to the [2Fe-2S] cluster. Mutations of cysteines at positions 403, 406, and 411 (C403D, C403H, C406D, C406H, C406S, C411H, and C411S mutants) all resulted in inactive enzyme that failed to assemble the [2Fe-2S] cluster as judged by whole-cell EPR studies. In contrast, mutation of the cysteines at positions 360 and 395 to serines (C360S and C395S mutants) did not affect the enzymatic activity, and the resulting enzyme assembled a [2Fe-2S] cluster that was spectroscopically indistinguishable from the wild-type enzyme. The results indicate that three of the conserved cysteines in the 30-residue C-terminal extension of mammalian ferrochelatase are involved in ligating the [2Fe-2S] cluster. Resonance Raman and variable-temperature magnetic circular dichroism studies of heme-free preparations of human ferrochelatase are reported, and the spectra are best interpreted in terms of one non-cysteinyl, oxygenic ligand for the [2Fe-2S] cluster. Such anomalous coordination could account for the cluster lability compared to similar clusters with complete cysteinyl ligation and hence may be intrinsic to the proposed regulatory role for this cluster in mammalian ferrochelatases. PMID:8973195

  14. Fourier Transform Infrared Spectroscopic characterization and optimization of Pb(II) biosorption by fish (Labeo rohita) scales.

    PubMed

    Nadeem, Raziya; Ansari, Tariq Mahmood; Khalid, Ahmad Mukhtar

    2008-08-15

    The present study reports the use of locally available fish (Labeo rohita) scales for Pb(II) removal from aqueous solutions under different experimental conditions. Maximum Pb(II) adsorption (196.8 mg g(-1)) occurred at pH 3.5. Pb(II) sorption was found to be pH, dose, initial metal concentration, contact time and shaking speed dependent while particle size and temperature independent. Experimental data of Pb(II) biosorption onto fish scales fitted well to Freundlich isotherm model in comparison to the model of Langmuir. The fast adsorption process in first 30 min followed by subsequent slow adsorption rate was suitably described by pseudo-second order model. In addition, this study was designed to evaluate the effect of physical and chemical pretreatments on surface properties of fish scales by the application of Fourier Transform Infrared (FTIR) Spectroscopic analysis. Physical pretreatments resulted in partial degradation of some functional groups. Alkaline pretreatments of fish scales did not have any significant influence on the nature of functional groups responsible for Pb(II) uptake, while acidic pretreatments resulted in degeneration of the most of functional groups on biosorbent cell wall. FTIR analysis confirmed the involvement of amino, carboxylic, phosphate and carbonyl groups in Pb(II) biosorption by fish scales. PMID:18242826

  15. Time- and space-resolved spectroscopic characterization of a laser carbon plasma plume in an argon background

    NASA Astrophysics Data System (ADS)

    Ruiz, H. M.; Guzmán, F.; Favre, M.; Bhuyan, H.; Chuaqui, H.; Wyndham, E. S.

    2012-06-01

    We present time- and space-resolved spectroscopic observations of a laser-produced carbon plasma, in an argon background. An Nd : YAG laser pulse, 370 mJ, 3.5 ns, at 1.06 µm, with a fluence of 6.9 J cm-2, is used to produce a plasma from a solid graphite target in a 0.5 to 415 mTorr argon background. The spectral emission in the visible is recorded with 15 ns time resolution. We use 20 ns time resolution plasma imaging, filtered at characteristic carbon species emission wavelengths, to study the dynamics of the expanding plasma. The carbon plasma emission is found to evolve from the characteristic of single ionized carbon, to a more complex one, where C2 and C3 molecular bands dominate. Several plasma fronts, with either ionic or molecular composition, are seen to detach from the laser target plasma. The temporal and spatial features of the molecular carbon species evolution are found to be dependent on the actual argon background pressure.

  16. Complex of manganese (II) with curcumin: Spectroscopic characterization, DFT study, model-based analysis and antiradical activity

    NASA Astrophysics Data System (ADS)

    Gorgannezhad, Lena; Dehghan, Gholamreza; Ebrahimipour, S. Yousef; Naseri, Abdolhossein; Nazhad Dolatabadi, Jafar Ezzati

    2016-04-01

    The complex formation between curcumin (Cur) and Manganese (II) chloride tetrahydrate (MnCl2.4H2O) was studied by UV-Vis and IR spectroscopy. Spectroscopic data suggest that Cur can chelate Manganese cations. A simple multi-wavelength model-based method was used to define stability constant for complexation reaction regardless of the spectra overlapping of components. Also, pure spectra and concentration profiles of all components were extracted using this method. Density functional theory (DFT) was also used to view insight into complexation mechanism. Antioxidant activity of Cur and Cur-Mn(II) complex was evaluated using 1,1-diphenyl-2-picrylhydrazyl (DPPH) scavenging method. Bond dissociation energy (BDE), the highest occupied molecular orbital (HOMO), lowest unoccupied molecular orbital (LUMO) and Molecular electrostatic potential (MEP) of Cur and the complex also were calculated at PW91/TZ2P level of theory using ADF 2009.01 package. The experimental results show that Cur has a higher DPPH radical scavenging activity than Cur-Mn(II). This observation is theoretically justified by means of lower BDE and higher HOMO and LUMO energy values of Cur ligand as compared with those of Cur-Mn(II) complex.

  17. [Vermicomposting of different organic materials and three-dimensional excitation emission matrix fluorescence spectroscopic characterization of their dissolved organic matter].

    PubMed

    Yang, Wei; Wang, Dong-sheng; Liu, Man-qiang; Hu, Feng; Li, Hui-xin; Huang, Zhong-yang; Chang, Yi-jun; Jiao, Jia-guo

    2015-10-01

    In this experiment, different proportions of the cattle manure, tea-leaf, herb and mushroom residues, were used as food for earthworm (Eisenia fetida) to study the growth of the earth-worm. Then the characteristics and transformation of nutrient content and three-dimensional excitation emission matrix fluorescence (3DEEM) of dissolved organic matter (DOM) during vermistabilization were investigated by means of chemical and spectroscopic methods. The result showed that the mixture of different ratios of cattle manure with herb residue, and cattle manure with tea-leaf were conducive to the growth of earthworm, while the materials compounded with mushroom residue inhibited the growth of earthworm. With the increasing time of verimcomposting, the pH in vermicompost tended to be circumneutral and weakly acidic, and there were increases in electrical conductivity, and the contents of total nitrogen, total phosphorus, available nitrogen, and available phosphorus, while the total potassium and available potassium increased first and then decreased, and the organic matter content decreased. 3DEEM and fluorescence regional integration results indicated that, the fluorescence of protein-like fluorescence peaks declined significantly, while the intensity of humic-like fluorescence peak increased significantly in DOM. Vermicomposting process might change the compositions of DOM with elevated concentrations of humic acid and fulvic acid in the organics. In all, this study suggested the suitability of 3DEEM for monitoring the organics transformation and assessing the maturity in the vermicomposting. PMID:26995929

  18. Characterization of Copper(II) Interactions with Sinefungin, a Nucleoside Antibiotic: Combined Potentiometric, Spectroscopic and DFT Studies

    PubMed Central

    Jaworska, Maria; Lodowski, Piotr; Mucha, Ariel; Szczepanik, Wojciech; Valensin, Gianni; Cappannelli, Massimo; Je?owska-Bojczuk, Ma?gorzata

    2007-01-01

    Interactions between sinefungin and copper(II) ions were investigated. Stoichiometry and stability constants of the metal-free system and two mononuclear complexes present in solution were determined on the basis of potentiometric data analysis. The results were compared to the Cu(II)-ornithine system due to structural similarities between both molecules. Combined spectroscopic and theoretical studies allowed for determination of coordination pattern for the Cu(II)-sinefungin complexes. At acidic pH, copper is bound in glycine-like coordination mode, identical with that of ornithine. This involves ?-amino group and the carboxyl oxygen. At higher pH, a bis-complex is formed by two sinefungin molecules. The second ligand binds in equatorial position displacing two water molecules, what results in the stable {2N,2O} coordination. Both axial positions are supposed to be occupied by N1 nitrogen donors of adenine moiety, what is confirmed by DFT calculations. They interact indirectly with copper(II) through water molecules as the result of dominant syn conformation of purine. PMID:18273386

  19. 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

  20. Characterization of automotive paint clear coats by ultraviolet absorption microspectrophotometry with subsequent chemometric analysis.

    PubMed

    Liszewski, Elisa A; Lewis, Simon W; Siegel, Jay A; Goodpaster, John V

    2010-10-01

    Clear coats have been a staple in automobile paints for almost thirty years and are of forensic interest when comparing transferred and native paints. However, the ultraviolet (UV) absorbers in these paint layers are not typically characterized using UV microspectrophotometry, nor are the results studied using multivariate statistical methods. In this study, measurements were carried out by UV microspectrophotometry on 71 samples from American and Australian automobiles, with subsequent chemometric analysis of the absorbance spectra. Sample preparation proved to be vital in obtaining accurate absorbance spectra and a method involving peeling the clear coat layer and not using a mounting medium was preferred. Agglomerative hierarchical clustering indicated three main groups of spectra, corresponding to spectra with one, two, and three maxima. Principal components analysis confirmed this clustering and the factor loadings indicated that a substantial proportion of the variance in the data set originated from specific spectral regions (230-265 nm, 275-285 nm, and 300-370 nm). The three classes were well differentiated using discriminant analysis, where the cross-validation accuracy was 91.6% and the external validation accuracy was 81.1%. However, results showed no correlation between the make, model, and year of the automobiles. PMID:20925981

  1. Spectroscopic characterization of enzymatic flax retting: Factor analysis of FT-IR and FT-Raman data

    NASA Astrophysics Data System (ADS)

    Archibald, D. D.; Henrikssen, G.; Akin, D. E.; Barton, F. E.

    1998-06-01

    Flax retting is a chemical, microbial or enzymatic process which releases the bast fibers from the stem matrix so they can be suitable for mechanical processing before spinning into linen yarn. This study aims to determine the vibrational spectral features and sampling methods which can be used to evaluate the retting process. Flax stems were retted on a small scale using an enzyme mixture known to yield good retted flax. Processed stems were harvested at various time points in the process and the retting was evaluated by conventional methods including weight loss, color difference and Fried's test, a visual ranking of how the stems disintegrate in hot water. Spectroscopic measurements were performed on either whole stems or powders of the fibers that were mechanically extracted from the stems. Selected regions of spectra were baseline and amplitude corrected using a variant of the multiplicative signal correction method. Principal component regression and partial least-squares regression with full cross-validation were used to determine the spectral features and rate of spectral transformation by regressing the spectra against the retting time in hours. FT-Raman of fiber powders and FT-IR reflectance of whole stems were the simplest and most precise methods for monitoring the retting transformation. Raman tracks the retting by measuring the decrease in aromatic signal and subtle changes in the C-H stretching vibrations. The IR method uses complex spectral features in the fingerprint and carbonyl region, many of which are due to polysaccharide components. Both spectral techniques monitor the retting process with greater precision than the reference method.

  2. CHARACTERIZATION OF A SAMPLE OF INTERMEDIATE-TYPE AGNs. I. SPECTROSCOPIC PROPERTIES AND SERENDIPITOUS DISCOVERY OF NEW DUAL AGNs

    SciTech Connect

    Benitez, Erika; Cruz-Gonzalez, Irene; Martinez, Benoni; Jimenez-Bailon, Elena; Mendez-Abreu, Jairo; Lopez-Martin, Luis; Fuentes-Carrera, Isaura; Leon-Tavares, Jonathan; Chavushyan, Vahram H.

    2013-01-20

    A sample of 10 nearby intermediate-type active galactic nuclei (AGNs) drawn from the Sloan Digital Sky Survey is presented. The aim of this work is to provide estimations of the black hole (BH) mass for the sample galaxies from the dynamics of the broad-line region. For this purpose, a detailed spectroscopic analysis of the objects was done. Using Baldwin-Phillips-Terlevich diagnostic diagrams, we have carefully classified the objects as true intermediate-type AGNs and found that 80%{sup +7.2%} {sub -17.3%} are composite AGNs. The BH mass estimated for the sample is within 6.54 {+-} 0.16 < log M {sub BH} < 7.81 {+-} 0.14. Profile analysis shows that five objects (J120655.63+501737.1, J121607.08+504930.0, J141238.14+391836.5, J143031.18+524225.8, and J162952.88+242638.3) have narrow double-peaked emission lines in both the red (H{alpha}, [N II] {lambda}{lambda}6548,6583 and [S II] {lambda}{lambda}6716, 6731) and the blue (H{beta} and [O III] {lambda}{lambda}4959, 5007) regions of the spectra, with velocity differences ({Delta}V) between the double peaks within 114 km s{sup -1} < {Delta}V < 256 km s{sup -1}. Two of them, J121607.08+504930.0 and J141238.14+391836.5, are candidates for dual AGNs since their double-peaked emission lines are dominated by AGN activity. In searches of dual AGNs, type 1, type II, and intermediate-type AGNs should be carefully separated, due to the high serendipitous number of narrow double-peaked sources (50% {+-} 14.4%) found in our sample.

  3. Characterization by spectroscopic, kinetic and equilibrium methods of the interaction between recombinant human cystatin A (stefin A) and cysteine proteinases.

    PubMed Central

    Pol, E; Olsson, S L; Estrada, S; Prasthofer, T W; Björk, I

    1995-01-01

    The near-UV spectroscopic changes induced by the binding of recombinant human cystatin A to papain were appreciably different from those induced by cystatin C, reflecting mainly interactions involving the single tryptophan of cystatin C, Trp-106. Cystatin A bound tightly and rapidly to papain and cathepsin L, with dissociation equilibrium constants of approximately 10(-11)-10(-13) M and association rate constants of 3 x 10(6)-5 x 10(6) M-1.s-1. These affinities are at least 50-100-fold higher than previously reported values. The kinetics of binding to papain were consistent with a simple reversible bimolecular reaction mechanism, indicating that cystatin A, like chicken cystatin and cystatin C, binds to papain with no appreciable conformational adaptation of either reacting protein. Cystatin A bound more weakly to actinidin and cathepsins B, C and H, with dissociation equilibrium constants of 10(-8)-10(-9) M. The weaker binding to cathepsin B was largely due to a considerably reduced association rate constant (approximately 4 x 10(4) M-1.s-1), consistent with the 'occluding loop' of cathepsin B markedly restricting the access of cystatin A to the active site. The lower affinities for actinidin and cathepsins C and H were due partly to lower association rate constants (2 x 10(5)-6 x 10(5) M-1.s-1) but primarily to higher dissociation rate constants. The mode of binding of cystatin A to inactivated papains indicated that there is appreciably less space around the active-site cysteine of papain in the complex with cystatin A than in the complexes with chicken cystatin and cystatin C. An N-terminally truncated form of cystatin A, lacking the first six residues, had considerably lower affinity for papain than the full-length inhibitor, consistent with an intact N-terminal region being of importance for proteinase binding. PMID:7575465

  4. Spectroscopic and wet chemical characterization of solid waste organic matter of different age in landfill sites, southern Germany.

    PubMed

    Bumler, Rupert; Kgel-Knabner, Ingrid

    2008-01-01

    Landfill sites are potential sources of hazardous emissions by degradation and transformation processes of waste organic matter. Its chemical composition and microbial degradability are key factors for risk management, after-care, and estimation of potential emissions. The aim of the study is to provide information about composition and extent of transformation of waste organic matter in four landfill sites in Bavaria, Southern Germany by means of (13)C NMR spectroscopy, acid-hydrolyzable carbohydrates, chloroform-methanol extractable lipids, acid-hydrolyzable proteins, and lignin compounds after CuO oxidation. Ten samples of about 20 to 25 yr, 15 to 20 yr, and 5 to 10 yr of deposition each were taken at 2 m depth intervals by grab drilling till 10-m depth. Increasing temperatures from about 15 degrees C at 2-m depth to >40 degrees C at 10-m depth are found at some of the sites, representing optimum conditions for mesophile methane bacteria. Moisture contents of 160 to 310 g kg(-1) (oven dry), however, provide limiting conditions for anaerobic biodecay. Spectroscopic and chemical variables generally indicate a low extent of biodegradation and transformation at all sites despite a considerable heterogeneity of the samples. Independent of the time and depth of deposition more than 50% of the carbohydrate fraction of the waste organic matter provide a high potential for methane emissions and on-site energy production. There was no significant accumulation of long-chain organic and aromatic compounds, and of lignin degradation products even after more than 25 yr of rotting indicating higher extent of decomposition or stabilization of the waste organic matter. Installation of seepage water cleaning and recirculation systems are recommended to increase suboptimal moisture contents with respect to microbial methanogenesis, energy production, and long-term stabilization of municipal solid waste. PMID:18178887

  5. 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.

  6. Spectroscopic and Thermogravimetric Characterization of Pb(II) Dinonyldithiophosphate: Removal of Pb(II) from Aqueous Solution

    NASA Astrophysics Data System (ADS)

    Gümgüm, H. B.; Biricik, N.

    2015-07-01

    Dinonyldithiophosphoric acid (DNDTPA) was prepared by adding phosphorus pentasulfide to nonyl alcohol. The lead dinonyl dithiophosphate complex Pb(DNDTP) 2 was prepared by mixing a solution of lead(II) with a solution of DNDTPA in ethanol at room temperature. The recovered Pb(DNDTP) 2 was crystallized in ethanol, and fi ne colorless needles were obtained. The complex was characterised by elemental analysis and IR, UV-vis and atomic absorption spectroscopy. The thermal behavior of Pb(DNDTP) 2 was investigated by thermogravimetric analysis under a nitrogen atmosphere. Removal of Pb(II) from aqueous media by DNDTPA solutions was investigated. The optimum conditions for extraction, such as the organic solvent, pH of the aqueous phase, time of equilibration, concentration, and effect of anions, were investigated. It was found that DNDTPA is an effective substance for removing Pb(II) from aqueous solution.

  7. Synthesis, crystal structure, spectroscopic characterization and nonlinear optical properties of manganese (II) complex of picolinate: A combined experimental and computational study

    NASA Astrophysics Data System (ADS)

    Tamer, Ömer; Avcı, Davut; Atalay, Yusuf; Çoşut, Bünyemin; Zorlu, Yunus; Erkovan, Mustafa; Yerli, Yusuf

    2016-02-01

    A novel manganese (II) complex with picolinic acid (pyridine 2-carboxylic acid, Hpic), namely, [Mn(pic)2(H2O)2] was prepared and its crystal structure was fully characterized by using single crystal X-ray diffraction. Picolinate (pic) ligands were coordinated to the central manganese(II) ion as bidentate N,O-donors through the nitrogen atoms of pyridine rings and the oxygen atoms of carboxylate groups forming five-membered chelate rings. The spectroscopic characterization of Mn(II) complex was performed by the applications of FT-IR, Raman, UV-vis and EPR techniques. In order to support these studies, density functional theory (DFT) calculations were carried out by using B3LYP level. IR and Raman spectra were simulated at B3LYP level, and obtained results indicated that DFT calculations generally give compatible results to the experimental ones. The electronic structure of the Mn(II) complex was predicted using time dependent DFT (TD-DFT) method with polarizable continuum model (PCM). Molecular stability, hyperconjugative interactions, intramolecular charge transfer (ICT) and bond strength were investigated by applying natural bond orbital (NBO) analysis. Nonlinear optical properties of Mn(II) complex were investigated by the determining of molecular polarizability (α) and hyperpolarizability (β) parameters.

  8. Fingerprints of polycyclic aromatic hydrocarbons (PAHs) in infrared absorption spectroscopy.

    PubMed

    Tommasini, Matteo; Lucotti, Andrea; Alfè, Michela; Ciajolo, Anna; Zerbi, Giuseppe

    2016-01-01

    We have analyzed a set of 51 PAHs whose structures have been hypothesized from mass spectrometry data collected on samples extracted from carbon particles of combustion origin. We have obtained relationships between infrared absorption signals in the fingerprint region (mid-IR) and the chemical structures of PAHs, thus proving the potential of IR spectroscopy for the characterization of the molecular structure of aromatic combustion products. The results obtained here for the spectroscopic characterization of PAHs can be also of interest in Materials Science and Astrophysics. PMID:26208268

  9. Fingerprints of polycyclic aromatic hydrocarbons (PAHs) in infrared absorption spectroscopy

    NASA Astrophysics Data System (ADS)

    Tommasini, Matteo; Lucotti, Andrea; Alfè, Michela; Ciajolo, Anna; Zerbi, Giuseppe

    2016-01-01

    We have analyzed a set of 51 PAHs whose structures have been hypothesized from mass spectrometry data collected on samples extracted from carbon particles of combustion origin. We have obtained relationships between infrared absorption signals in the fingerprint region (mid-IR) and the chemical structures of PAHs, thus proving the potential of IR spectroscopy for the characterization of the molecular structure of aromatic combustion products. The results obtained here for the spectroscopic characterization of PAHs can be also of interest in Materials Science and Astrophysics.

  10. Macroscopic and spectroscopic characterization of selenate, selenite, and chromate adsorption at the solid-water interface of gamma-Al(2)O(3).

    PubMed

    Elzinga, Evert J; Tang, Yuanzhi; McDonald, Jason; DeSisto, Stephanie; Reeder, Richard J

    2009-12-15

    The interaction of selenate, selenite, and chromate with the hydrated surface of gamma-Al(2)O(3) was studied using a combination of macroscopic pH edge data, electrophoretic mobility measurements, and X-ray absorption spectroscopic analyses. The pH edge data show generally increased oxyanion adsorption with decreasing pH, and indicate ionic strength-(in)dependent adsorption of chromate and selenate across the pH range 4-9, and ionic strength-(in)dependent adsorption of selenite in this pH range. The adsorption of chromate peaks at pH 5.0, whereas for selenate and selenite no pH adsorption maxima are observed. Electrophoretic mobility measurements show that all three oxyanions decrease the zeta potential of gamma-Al(2)O(3) upon adsorption; however, only selenite decreased the pH(PZC) of the gamma-Al(2)O(3) sorbent. EXAFS data indicate that selenite ions are coordinated in a bridging bidentate fashion to surface AlO(6) octahedra, whereas no second-neighbor Al scattering was observed for adsorbed selenate ions. Combined, the results presented here show that pH is a major factor in determining the extent of adsorption of selenate, selenite, and chromate on hydrated gamma-Al(2)O(3). The results point to substantial differences between these anions as to the mode of adsorption at the hydrated gamma-Al(2)O(3) surface, with selenate adsorbing as nonprotonated outer-sphere complexes, chromate forming a mixture of monoprotonated and nonprotonated outer-sphere adsorption complexes, and selenite coordinating as inner-sphere surface complexes in bridging configuration. PMID:19796769

  11. Portuguese tin-glazed earthenware from the 17th century. Part 2: A spectroscopic characterization of pigments, glazes and pastes of the three main production centers.

    PubMed

    Vieira Ferreira, L F; Ferreira, D P; Conceição, D S; Santos, L F; Pereira, M F C; Casimiro, T M; Ferreira Machado, I

    2015-10-01

    Sherds representative of the three Portuguese faience production centers of the 17th century - Lisbon, Coimbra and Vila Nova were studied with the use of mostly non-invasive spectroscopies, namely: ground state diffuse reflectance absorption (GSDR), micro-Raman, Fourier-transform infrared (FT-IR) and proton induced X-ray (PIXE) or X-ray fluorescence emission (XRF). X-ray diffraction (XRD) experiments were also performed. The obtained results evidence a clear similarity in the pastes of the pottery produced Vila Nova and some of the ceramic pastes from Lisbon, in accordance with documental sources that described the use of Lisbon clays by Vila Nova potters, at least since mid 17th century. Quartz and Gehlenite are the main components of the Lisbon's pastes, but differences between the ceramic pastes were detected pointing out to the use of several clay sources. The spectroscopic trend exhibited Coimbra's pottery is remarkably different, Quartz and Diopside being the major components of these pastes, enabling one to well define a pattern for these ceramic bodies. The blue pigment from the Lisbon samples is a cobalt oxide that exists in the silicate glassy matrix, which enables the formation of detectable cobalt silicate microcrystals in most productions of the second half of the 17th century. No micro-Raman cobalt blue signature could be detected in the Vila Nova and Coimbra blue glazes. This is in accordance with the lower kiln temperatures in these two production centers and with Co(2+) ions dispersed in the silicate matrix. In all cases the white glaze is obtained with the use of tin oxide. Hausmannite was detected as the manganese oxide mineral used to produce the purple glaze (wine color "vinoso") in Lisbon. PMID:25965511

  12. Spectroscopic detection

    DOEpatents

    Woskov, Paul P.; Hadidi, Kamal

    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.

  13. Spectroscopic studies of coumarin in micelles.

    PubMed

    Marques, A D; Marques, G S

    1994-02-01

    Steady-state and time-resolved emission spectroscopic techniques have been employed to characterize the coumarin species and identify which species is solubilized in the hydrocarbon core micelles of triton X-100 (neutral), hexadecyltrimethyl ammonium bromide (cationic) and dodecyl lithium sulfate (anionic) solutions under physiological conditions at 77 K. The emission and absorption spectra for the following species of coumarin-monomer, hydrogenbonded complex, molecular aggregation and strong hydrophobic aggregates-were recorded in methylcyclohexane (MCH), ethanol, buffers and aqueous solutions. The fluorescence and phosphorescence emissions of monomer in MCH at 77 K are assigned as resulting from 1(pi, pi*)1 and 3(pi, pi*)1 states, respectively, originated from the ethylenic bond and carbonyl of the pyrone ring. Molecular orbital calculations using the Hydrogenic Atoms in Molecule, version 3, method were carried out to help interpretation of the spectroscopic results. The photophysical properties from each species are used to probe which species penetrates in the hydrophobic region of micelles. It was found that a fifth species of coumarin assigned as the "action species" is solubilized into the interior of micelles. These observations could lend some insight into the mechanism of transporting coumarins across the membrane. PMID:8165234

  14. Spectroscopic Characterization of a Multiband Complex Oxide: Insulating and Conducting Cement 12CaO·7Al₂O₃

    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·7Al₂O₃ (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.

  15. Luminescence and advanced mass spectroscopic characterization of sodium zinc orthophosphate phosphor for low-cost light-emitting diodes.

    PubMed

    Mishra, Savvi; Swati, G; Rajesh, B; Tyagi, Kriti; Gahtori, Bhasker; Sivaiah, B; Vijayan, N; Dalai, M K; Dhar, A; Auluck, S; Jayasimhadri, M; Haranath, D

    2016-03-01

    A new rare-earth-free NaZnPO4 :Mn(2+) (NZP:Mn) phosphor powder has been developed by our group and investigated meticulously for the first time using secondary ion mass spectroscopy and chemical imaging techniques. The studies confirmed the effective incorporation of Mn(2+) into the host lattice, resulting in an enhancement of photoluminescence intensity. Phase purity has been verified and structure parameters have been determined successfully by Rietveld refinement studies. The NZP:Mn phosphor powder exhibits strong absorption bands in the ultraviolet and visible (300-470 nm) regions with a significant broad yellow-green (~543 nm) emission due to the characteristic spin forbidden d-d transition ((4) T1 →(6) A1 ) of Mn(2+) ions, indicating weak crystal field strength at the zinc-replaced manganese site. The decay constants are a few milliseconds, which is a pre-requisite for applications in many display devices. The results obtained suggest that this new phosphor powder will find many interesting applications in semiconductor physics, as cost-effective light-emitting diodes (LEDs), as solar cells and in photo-physics. Copyright © 2015 John Wiley & Sons, Ltd. PMID:26198805

  16. Combined UHV/high-pressure catalysis setup for depth-resolved near-surface spectroscopic characterization and catalytic testing of model catalysts.

    PubMed

    Mayr, Lukas; Rameshan, Raffael; Klötzer, Bernhard; Penner, Simon; Rameshan, Christoph

    2014-05-01

    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. PMID:24880412

  17. Combined UHV/high-pressure catalysis setup for depth-resolved near-surface spectroscopic characterization and catalytic testing of model catalysts

    NASA Astrophysics Data System (ADS)

    Mayr, Lukas; Rameshan, Raffael; Klötzer, Bernhard; Penner, Simon; Rameshan, Christoph

    2014-05-01

    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.

  18. 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; Rameshan, Raffael; Department of Inorganic Chemistry, Fritz Haber Institute of the Max Planck Society, Faradayweg 4-6, 14195 Berlin ; Rameshan, Christoph; Institute of Materials Chemistry, Vienna University of Technology, Getreidemarkt 9/BC/01, 1060 Vienna

    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.

  19. Characterization of Ag/Pt core-shell nanoparticles by UV-vis absorption, resonance light-scattering techniques.

    PubMed

    Chen, Langxing; Zhao, Wenfeng; Jiao, Yufen; He, Xiwen; Wang, Jing; Zhang, Yukui

    2007-11-01

    The water-soluble Ag/Pt core-shell nanoparticles were prepared by deposition Pt over Ag colloidal seeds with the seed-growth method using K2PtCl4 with trisodium citrate as reduced agent. The Ag:Pt ratio is varied from 9:1 to 1:3 for synthesizing Pt shell layer of different thickness. A remarkable shift and broadening of Ag surface plasmon band around 410 nm was observed. The contrast of TEM images of Ag/Pt colloids has been obtained. Various techniques, such as transmission electron microscopy (TEM), UV-vis absorption and resonance light-scattering spectroscopy were used to characterize nanoparticles. The data of TEM, UV-vis and resonance light-scattering spectrum all confirm formation of Ag/Pt core-shell nanoparticles. Resonance light-scattering and emission spectrum show the Ag and Ag/Pt core-shell nanoparticles have a nonlinear light-scattering characteristic. PMID:17329151

  20. Spectroscopic features of cytochrome P450 reaction intermediates.

    PubMed

    Luthra, Abhinav; Denisov, Ilia G; Sligar, Stephen G

    2011-03-01

    Cytochromes P450 constitute a broad class of heme monooxygenase enzymes with more than 11,500 isozymes which have been identified in organisms from all biological kingdoms [1]. These enzymes are responsible for catalyzing dozens chemical oxidative transformations such as hydroxylation, epoxidation, N-demethylation, etc., with very broad range of substrates [2,3]. Historically these enzymes received their name from 'pigment 450' due to the unusual position of the Soret band in UV-vis absorption spectra of the reduced CO-saturated state [4,5]. Despite detailed biochemical characterization of many isozymes, as well as later discoveries of other 'P450-like heme enzymes' such as nitric oxide synthase and chloroperoxidase, the phenomenological term 'cytochrome P450' is still commonly used as indicating an essential spectroscopic feature of the functionally active protein which is now known to be due to the presence of a thiolate ligand to the heme iron [6]. Heme proteins with an imidazole ligand such as myoglobin and hemoglobin as well as an inactive form of P450 are characterized by Soret maxima at 420nm [7]. This historical perspective highlights the importance of spectroscopic methods for biochemical studies in general, and especially for heme enzymes, where the presence of the heme iron and porphyrin macrocycle provides rich variety of specific spectroscopic markers available for monitoring chemical transformations and transitions between active intermediates of catalytic cycle. PMID:21167809

  1. Spectroscopic features of cytochrome P450 reaction intermediates

    PubMed Central

    Luthra, Abhinav; Denisov, Ilia G.; Sligar, Stephen G.

    2010-01-01

    Preface Cytochromes P450 constitute a broad class of heme monooxygenase enzymes with more than 11,500 isozymes which have been identified in organisms from all biological kingdoms [1]. These enzymes are responsible for catalyzing dozens chemical oxidative transformations such as hydroxylation, epoxidation, N-demethylation, etc., with very broad range of substrates [2-3]. Historically these enzymes received their name from pigment 450 due to the unusual position of the Soret band in UV-Vis absorption spectra of the reduced CO-saturated state [4-5]. Despite detailed biochemical characterization of many isozymes, as well as later discoveries of other P450-like heme enzymes such as nitric oxide synthase and chloroperoxidase, the phenomenological term cytochrome P450 is still commonly used as indicating an essential spectroscopic feature of the functionally active protein which is now known to be due to the presence of a thiolate ligand to the heme iron [6]. Heme proteins with an imidazole ligand such as myoglobin and hemoglobin as well as an inactive form of P450 are characterized by Soret maxima at 420 nm [7]. This historical perspective highlights the importance of spectroscopic methods for biochemical studies in general, and especially for heme enzymes, where the presence of the heme iron and porphyrin macrocycle provides rich variety of specific spectroscopic markers available for monitoring chemical transformations and transitions between active intermediates of catalytic cycle. PMID:21167809

  2. Thermal analysis and vibrational spectroscopic characterization of the boro silicate mineral datolite - CaBSiO4(OH)

    NASA Astrophysics Data System (ADS)

    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 1077 cm-1 assigned to the symmetric stretching modes of BO and SiO tetrahedra. A very intense Raman band is observed at 3498 cm-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 782 cm-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.

  3. Modern spectroscopic technique in the characterization of biosensitive macrocyclic Schiff base ligand and its complexes: Inhibitory activity against plantpathogenic fungi

    NASA Astrophysics Data System (ADS)

    Tyagi, Monika; Chandra, Sulekh; Akhtar, Jameel; Chand, Dinesh

    2014-01-01

    Complexes of the type [M(L)Cl2], where M = Co(II), Ni(II) and Cu(II) have been synthesized with a macrocyclic Schiff base ligand (1,4,5,7,10,11,12,15-octaaza,5,11,16,18-tetraphenyl, 3,4,12,13-tetramethyl cyclo-octadecane) derived from Schiff base (obtained by the condensation of 4-aminoantipyrine and dibenzoyl methane) and ethylenediamine. The ligand was characterized on the basis of elemental analysis, IR, 1H NMR, EI Mass and molecular modeling studies while the complexes were characterized by elemental analysis, molar conductance measurements, magnetic susceptibility measurements, IR, electronic and EPR spectral studies. All the complexes are non-electrolyte in nature. The covalency factor (β) and coefficient factor (α) suggest the covalent nature of the complexes. The ligand and its metal complexes have shown antifungal activity with their LD50 values determined by probit analysis against two economically important fungal plant pathogens i.e. Macrophomina phaseolina and Fusarium solani.

  4. Characterization of a 7Fe ferredoxin isolated from the marine denitrifier Pseudomonas nautica strain 617: spectroscopic and electrochemical studies.

    PubMed

    Macedo, A L; Besson, S; Moreno, C; Fauque, G; Moura, J J; Moura, I

    1996-12-13

    A 7Fe ferredoxin, isolated from the marine denitrifier Pseudomonas nautica strain 617, was characterized. The NH2-terminal sequence analysis, performed until residue number 56, shows a high similarity with the 7Fe ferredoxins isolated from Azotobacter vinelandii, Pseudomonas putida, and Pseudomonas stutzeri. EPR and NMR spectroscopies identify the presence of both [3Fe-4S] and [4Fe-4S] clusters, with cysteinyl coordination. The electrochemical studies on [Fe-S] clusters show that a fast diffusion-dominated electron transfer, promoted by Mg(II), takes place between the ferredoxin and the glassy carbon electrode. Square wave voltammetry studies gave access to the electrosynthesis of a 4Fe center formed within the [3Fe-4S] core. The [3Fe-4S] cluster exhibited two reduction potentials at -175 and -680 +/- 10 mV and the [4Fe-4S] cluster was characterized by an unusually low reduction potential of -715 +/- 10 mV, at pH 7.6 PMID:8954931

  5. 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

  6. Synthesis, spectroscopic characterization and structural investigations of a new charge transfer complex of 2,6-diaminopyridine with 3,5-dinitrobenzoic acid: DNA binding and antimicrobial studies

    NASA Astrophysics Data System (ADS)

    Khan, Ishaat M.; Ahmad, Afaq; Kumar, Sarvendra

    2013-03-01

    A new charge transfer (CT) complex [(DAPH)+(DNB)-] consisting of 2,6-diaminopyridine (DAP) as donor and 3,5-dinitrobenzoic acid (DNB-H) as acceptor, was synthesized and characterized by FTIR, 1H and 13C NMR, ESI mass spectroscopic and X-ray crystallographic techniques. The hydrogen bonding (N+-H⋯O-) plays an important role to consolidate the cation and anion together. CT complex shows a considerable interaction with Calf thymus DNA. The CT complex was also tested for its antibacterial activity against two Gram-positive bacteria Staphylococcus aureus and Bacillus subtilis and two Gram-negative bacteria Escherichia coli and Pseudomonas aeruginosa strains by using Tetracycline as standard, and antifungal property against Aspergillus niger, Candida albicans, and Penicillium sp. by using Nystatin as standard. The results were compared with standard drugs and significant conclusions were obtained. A polymeric net work through H-bonding interactions between neighboring moieties was observed. This has been attributed to the formation of 1:1 type CT complex.

  7. Vibrational spectroscopic characterization of the phosphate mineral ludlamite (Fe,Mn,Mg)₃(PO₄)₂⋅4H₂O - a mineral found in lithium bearing pegmatites.

    PubMed

    Frost, Ray L; Xi, Yunfei; Scholz, Ricardo; Belotti, Fernanda M

    2013-02-15

    The objective of this work is to analyze ludlamite (Fe,Mn,Mg)(3)(PO(4))(2)⋅4H(2)O from Boa Vista mine, Galiléia, Brazil and to assess the molecular structure of the mineral. The phosphate mineral ludlamite has been characterized by EMP-WDS, Raman and infrared spectroscopic measurements. The mineral is shown to be a ferrous phosphate with some minor substitution of Mg and Mn. Raman bands at 917 and 950 cm(-1) are assigned to the symmetric stretching mode of HOPO(3)(2-) and PO(4)(3-) units. Raman bands at 548, 564, 599 and 634 cm(-1) are assigned to the ν(4)PO(4)(3-) bending modes. Raman bands at 2605, 2730, 2896 and 3190 cm(-1) and infrared bands at 2623, 2838, 3136 and 3185 cm(-1) are attributed to water stretching vibrations. By using a Libowitzky empirical function, hydrogen bond distances are calculated from the OH stretching wavenumbers. Strong hydrogen bonds in the structure of ludlamite are observed as determined by their hydrogen bond distances. The application of infrared and Raman spectroscopy to the study of ludlamite enables the molecular structure of the pegmatite mineral ludlamite to be assessed. PMID:23257342

  8. Characterization of the 6-methyl isoxanthopterin (6-MI) base analog dimer, a spectroscopic probe for monitoring guanine base conformations at specific sites in nucleic acids

    PubMed Central

    Datta, Kausiki; Johnson, Neil P.; Villani, Giuseppe; Marcus, Andrew H.; von Hippel, Peter H.

    2012-01-01

    We here characterize local conformations of site-specifically placed pairs of guanine (G) residues in RNA and DNA, using 6-methyl isoxanthopterin (6-MI) as a conformational probe. 6-MI is a base analog of G and spectroscopic signals obtained from pairs of adjacent 6-MI residues reflect base–base interactions that are sensitive to the sequence context, local DNA conformation and solvent environment of the probe bases. CD signals show strong exciton coupling between stacked 6-MI bases in double-stranded (ds) DNA; this coupling is reduced in single-stranded (ss) DNA sequences. Solvent interactions reduce the fluorescence of the dimer probe more efficiently in ssDNA than dsDNA, while self-quenching between 6-MI bases is enhanced in dsDNA. 6-MI dimer probes closely resemble adjacent GG residues, in that these probes have minimal effects on the stability of dsDNA and on interactions with solvent additive betaine. They also serve as effective template bases, although further polymerase-dependent extension of DNA primers past 6-MI template bases is significantly inhibited. These probes are also used to monitor DNA ‘breathing’ at model replication forks. The 6-MI dimer probe can serve in many contexts as a useful tool to investigate GG conformations at specific sites within the nucleic acid frameworks of functioning macromolecular machines in solution. PMID:22009678

  9. Characterization of the 6-methyl isoxanthopterin (6-MI) base analog dimer, a spectroscopic probe for monitoring guanine base conformations at specific sites in nucleic acids.

    PubMed

    Datta, Kausiki; Johnson, Neil P; Villani, Giuseppe; Marcus, Andrew H; von Hippel, Peter H

    2012-02-01

    We here characterize local conformations of site-specifically placed pairs of guanine (G) residues in RNA and DNA, using 6-methyl isoxanthopterin (6-MI) as a conformational probe. 6-MI is a base analog of G and spectroscopic signals obtained from pairs of adjacent 6-MI residues reflect base-base interactions that are sensitive to the sequence context, local DNA conformation and solvent environment of the probe bases. CD signals show strong exciton coupling between stacked 6-MI bases in double-stranded (ds) DNA; this coupling is reduced in single-stranded (ss) DNA sequences. Solvent interactions reduce the fluorescence of the dimer probe more efficiently in ssDNA than dsDNA, while self-quenching between 6-MI bases is enhanced in dsDNA. 6-MI dimer probes closely resemble adjacent GG residues, in that these probes have minimal effects on the stability of dsDNA and on interactions with solvent additive betaine. They also serve as effective template bases, although further polymerase-dependent extension of DNA primers past 6-MI template bases is significantly inhibited. These probes are also used to monitor DNA 'breathing' at model replication forks. The 6-MI dimer probe can serve in many contexts as a useful tool to investigate GG conformations at specific sites within the nucleic acid frameworks of functioning macromolecular machines in solution. PMID:22009678

  10. Dissociative Binding of Carboxylic Acid Ligand on Nanoceria Surf