These are representative sample records from Science.gov related to your search topic.
For comprehensive and current results, perform a real-time search at Science.gov.
1

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

NASA Astrophysics Data System (ADS)

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.

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

2005-08-01

2

X-ray absorption spectroscopic characterization of a cytochrome P450 compound II derivative  

PubMed Central

The cytochrome P450 enzyme CYP119, its compound II derivative, and its nitrosyl complex were studied by iron K-edge x-ray absorption spectroscopy. The compound II derivative was prepared by reaction of the resting enzyme with peroxynitrite and had a lifetime of ?10 s at 23°C. The CYP119 nitrosyl complex was prepared by reaction of the enzyme with nitrogen monoxide gas or with a nitrosyl donor and was stable at 23°C for hours. Samples of CYP119 and its derivatives were studied by x-ray absorption spectroscopy at temperatures below 140 (K) at the Advanced Photon Source of Argonne National Laboratory. The x-ray absorption near-edge structure spectra displayed shifts in edge and pre-edge energies consistent with increasing effective positive charge on iron in the series native CYP119 < CYP119 nitrosyl complex < CYP119 compound II derivative. Extended x-ray absorption fine structure spectra were simulated with good fits for k = 12 ??1 for native CYP119 and k = 13 ??1 for both the nitrosyl complex and the compound II derivative. The important structural features for the compound II derivative were an iron-oxygen bond length of 1.82 ? and an iron-sulfur bond length of 2.24 ?, both of which indicate an iron-oxygen single bond in a ferryl-hydroxide, FeIVOH, moiety. PMID:18174331

Newcomb, Martin; Halgrimson, James A.; Horner, John H.; Wasinger, Erik C.; Chen, Lin X.; Sligar, Stephen G.

2008-01-01

3

X-ray absorption spectroscopic studies of iron framework-substituted and exchanged zeolites: Characterization and quantification of incorporated iron species  

NASA Astrophysics Data System (ADS)

X-ray absorption spectroscopic (XAS) analysis methods were derived which allowed iron species within iron substituted and exchanged zeolites to be characterized, and the fractional contribution of each species to the zeolite iron population to be quantified. Framework (T-site occupant) and non-framework iron species simultaneously present within zeolites were differentiated. Non-framework iron was segregated further into phases respectively exhibiting and lacking long range order. The former was described as precipitate iron. Zeolitic precipitate iron was found to occur either as an ordered Goethite-type phase, or a disordered aggregate. Iron species lacking long range order were found to be approximated by hydrated ferric ions (Fe(Hsb2O)sb6sp{3+}). XAS methods allowed determination of the fractional contribution of each iron phase; framework, precipitate, and low long range order, to the zeolite. XAS analysis methods were applied to an iron framework-substituted LTL zeolite (Fe LTL2) and two ferric exchanged analogs of Fe LTL2 (Fesp{3+} exchanged Fe LTL2). Fesp{3+} exchanged Fe LTL2 zeolites differed according to ferric salt and acid exposure length. Fe LTL2 was found to contain 20% disordered aggregate precipitate iron, and 80% framework iron. Fesp{3+} exchanged Fe LTL2 zeolites contained three iron species; framework, precipitate, and low long range order. Exchange left Fe LTL2 precipitate type and quantity unchanged, while framework iron decreased. Elemental analysis indicated composition changes arose from framework iron removal by acid exposure. Iron lacking long range order served a charge-balancing function as increased levels correlated with decreased Ksp+/(Al + Fesbframework) ratios. XAS methods were additionally applied to six iron framework-substituted faujasites (Fe FAU) with Si/Al ratios consistent with zeolites X, Y, and ECR-32. Two iron substitution levels, low and high, were synthesized for each isotype. Iron within each faujasite partitioned into three phases; framework, precipitate, and low long range order. Disordered aggregate precipitate occurred in all samples excluding Fe Y (low Fe load) which contained Goethite-type precipitate. Fe FAU framework iron levels were considerably lower than those of framework-substituted LTL, suggesting destabilization of the FAU lattice toward iron T-site occupation. Framework iron fraction strongly correlated with zeolite Al/Fe ratio. Complete framework iron incorporation was predicted to occur in faujasites maintaining Al/Fe ? 26.

Stanfel, Christine Marie

4

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)

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.

Rock, M.

1981-01-01

5

Vibrational spectroscopic characterization of fluoroquinolones  

NASA Astrophysics Data System (ADS)

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

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

2005-05-01

6

Spectroscopic characterization of manganese minerals  

NASA Astrophysics Data System (ADS)

Manganese minerals ardenite, alleghanyite and leucopoenicite originated from Madhya Pradesh, India, Nagano prefecture Japan, Sussex Country and Parker Shaft Franklin, Sussex Country, New Jersey respectively are used in the present work. In these minerals manganese is the major constituent and iron if present is in traces only. An EPR study of on all of the above samples confirms the presence of Mn(II) with g around 2.0. Optical absorption spectrum of the mineral alleghanyite indicates that Mn(II) is present in two different octahedral sites and in leucophoenicite Mn(II) is also in octahedral geometry. Ardenite mineral gives only a few Mn(II) bands. NIR results of the minerals ardenite, leucophoenicite and alleghanyite are due to hydroxyl and silicate anions which confirming the formulae of the minerals.

Lakshmi Reddy, S.; Padma Suvarna, K.; Udayabhaska Reddy, G.; Endo, Tamio; Frost, R. L.

2014-01-01

7

Preparation and spectroscopic characterization of metal complexes of gliquidone  

NASA Astrophysics Data System (ADS)

Complexes of gliquidone with Mg(II), Ca(II), Cr(II), Mn(II), Fe(III), Co(II), Ni(II), Cu(II), Zn(II) and Cd(II) were obtained in methanolic solution to study the interaction of the drug with essential and trace elements present in human body or co administered during multivitamin therapy. These complexes were then characterized by spectroscopic techniques involving IR, 1H NMR, CHN elemental analysis, atomic absorption analysis and conductometric titrations. In most of the complexes, it is observed that the N-H stretch of sulfonamide and amide has disappeared.

Saeed Arayne, M.; Sultana, Najma; Zeeshan Mirza, Agha

2009-06-01

8

Characterization of clinohumite by selected spectroscopic methods.  

PubMed

Clinohumite, a humite group mineral, originated from Pamir Mountains, USSR, is used in the present work. Optical absorption, electron paramagnetic resonance (EPR), near infrared (NIR) and Mössbauer techniques are used in the characterization of the mineral sample. The optical absorption spectrum indicates that Fe(II) impurity is present in two sites with distorted octahedral structure. NIR results are attributed to water fundamentals. EPR studies on powder sample confirm the presence of Mn(II) in three different sites and also an iron impurity. Mössbauer studies confirm the presence of iron impurity in two different sites. PMID:16527527

Reddy, S Lakshmi; Reddy, N C Gangi; Reddy, G Siva; Reddy, B Jagannatha; Frost, Ray L

2006-11-01

9

Development of an infrared absorption spectroscope based on linear variable filters  

E-print Network

The objective of this thesis is to develop a low-cost infrared absorption spectroscope based on linear variable filter (LVF) technology for the automated detection of gases and vapors, and the semi-automated detection of liquids. This instrument...

Nogueira, Felipe Guimaraes

2009-05-15

10

Spectroscopic characterization of genetically modified flax fibers  

NASA Astrophysics Data System (ADS)

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 ?-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.

Dymi?ska, L.; G?gor, A.; Hanuza, J.; Kulma, A.; Preisner, M.; ?uk, M.; Szatkowski, M.; Szopa, J.

2014-09-01

11

Spectroscopic characterizations of organic/inorganic nanocomposites  

NASA Astrophysics Data System (ADS)

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

Govani, Jayesh R.

12

Photoelectron, nuclear gamma-ray and infrared absorption spectroscopic studies of neptunium in sodium silicate glass  

SciTech Connect

The valence state of neptunium ions in sodium silicate glasses prepared under reducing and oxidizing conditions has been investigated by the x-ray photoelectron, Moessbauer and optical absorption spectroscopic techniques. Results indicate that the Np ions are tetravalent in glasses prepared under reducing conditions and pentavalent in glasses prepared under oxidizing conditions.

Veal, B.W.; Carnall, W.T.; Dunlap, B.D.; Mitchell, A.W.; Lam, D.J.

1986-04-01

13

IR absorption spectroscopic study of mixed cobalt substituted lithium ferrites  

NASA Astrophysics Data System (ADS)

The IR spectra of Li0.5-(x/2)CoxFe2.5-(x/2)O4 ferrite samples (0?x?0.6) prepared by solution combustion method have been reported. The influence of Co substitution is verified. XRD studies confirm the spinel phase formation of ferrites. Lattice constant varies linearly from 8.31 Å (x=0) to 8.35 Å (x=0.6) with composition. Evidence of two absorption bands in the IR spectra (below 800 cm-1) reveals the characteristic feature of spinel ferrite. The IR spectra featured additional three absorption bands around 550, 670 and 705 cm-1 for the samples x=0.1 and x=0.6. Absence of bands splitting specifies that Fe ions do not exist in excess form. It is found that high frequency band (?1), due to tetrahedral (A) group, lies at around 600 cm-1 and low frequency band (?2), due to octahedral (B) group, around 450 cm-1. The positions of bands are found to be composition dependent. The IR bands due to tetrahedral complexes shift slightly towards high frequency side with composition upto x=0.4 where as that due to octahedral complexes shift towards lower frequency side with x. Based on the data of absorption bands, force constants (kt, ko) and bond lengths (RA, RB) were estimated. Compositional dependence of force constants is explained on the basis of cation-oxygen bond distances of respective sites and cation distribution.

Sawant, V. S.; Bagade, A. A.; Mohite, S. V.; Rajpure, K. Y.

2014-10-01

14

Synthesis and spectroscopic characterization of cannabinolic acid.  

PubMed

Cannabinoids, the main constituents of the cannabis plant, are being increasingly studied for their medicinal properties. Cannabinolic acid (CBNA; 1) was synthesized from tetrahydrocannabinolic acid (THCA; 2), a major constituent of the cannabis plant, by aromatization using selenium dioxide mixed with trimethylsilyl polyphosphate as catalyst in chloroform. Purification was achieved by centrifugal partition chromatography, and the final product had a purity of over 96% by GC analysis. Spectroscopic data on CBNA such as 1H-NMR and IR, and molar extinction coefficients, as well as chromatographic data are presented as useful references for further research on CBNA. The developed method allows production of CBNA on a preparative scale, making it available for further studies on its biological activities as well as use as a reference standard for analytical procedures. PMID:17354173

Bastola, Krishna Prasad; Hazekamp, Arno; Verpoorte, Robert

2007-03-01

15

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

ERIC Educational Resources Information Center

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…

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

2011-01-01

16

Synthesis, Spectroscopic Characterization, and Electro-Optical Properties of Noncentrosymmetric  

E-print Network

of noncentrosymmetric thin organic films for electro- optical devices.4-6 The electro-optical or Pockel's effect resultsSynthesis, Spectroscopic Characterization, and Electro-Optical Properties of Noncentrosymmetric, Wisconsin 53706 Ultrathin noncentrosymmetric nonlinear optical films based on zirconium phosphonate (ZP

17

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

NASA Astrophysics Data System (ADS)

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.

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

2011-03-01

18

Development of an Infrared Absorption Spectroscope Based on Linear Variable Filters  

Microsoft Academic Search

The objective of this research is to develop a low-cost infrared absorption spectroscope based on linear variable filter technology for the automated detection of concentrated gases and vapors, and the semiautomated detection of liquids. This instrument represents an alternative to electronic-nose devices based on cross-selective gas sensor arrays. Instead, the proposed instrument uses the concept of computational ldquopseudosensors,rdquo whereby spectral

Felipe G. Nogueira; Daniel Felps; Ricardo Gutierrez-Osuna

2007-01-01

19

Impedance spectroscopic characterization of solar cell  

NASA Astrophysics Data System (ADS)

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

Gautham, S.; Ramanathan, S.

2014-10-01

20

Synthesis and spectroscopic characterization of gold nanoparticles  

NASA Astrophysics Data System (ADS)

Photoluminescent nanoparticles of gold with size 3, 4, 6, and 9 nm are prepared by borohydride/citrate reduction in presence of polyethylene glycol (PEG)/tannic acid. The prepared nanomaterials are characterized by UV-vis spectroscopy and dynamic light scattering (DLS) technique. Intense photoluminescence (PL) is observed in nanoparticles prepared by fast reduction with borohydride in presence of PEG. A red shift of PL emission from 408 to 456 nm is observed for the change of size from 4 to 6 nm. Increase in PL intensity is observed for all the nanoparticles on the addition of KCl. Citrate reduced gold colloid which consists of large particles of size ˜35 nm with anisotropic shapes showing two plasmon peaks is also prepared. The anisotropy is confirmed by TEM measurement. SERS activity of this colloid is tested using glutamic acid as an adsorbate probe. Assignment of the observed bands is given.

Philip, Daizy

2008-11-01

21

Polarization-Modulated Infrared Reflection Absorption Spectroscopic Studies of a Hydrogen-Bonding Network at the Air-Water Interface  

E-print Network

Polarization-Modulated Infrared Reflection Absorption Spectroscopic Studies of a Hydrogen-Bonding, 33405 Talence, France ReceiVed: NoVember 11, 1998; In Final Form: February 2, 1999 The hydrogen-bonding absorption spectroscopy (PM-IRRAS). The molecular structure and orientation of the 1:1 hydrogen- bonding

Rusell, K.C.

22

Far Ultraviolet Spectroscopic Explorer Spectroscopy of Absorption and Emission Lines from the Narrow-Line Seyfert 1 Galaxy NGC 4051  

Microsoft Academic Search

We present three Far Ultraviolet Spectroscopic Explorer (FUSE) observations of the narrow-line Seyfert 1 galaxy NGC 4051. The most prominent features in the far-ultraviolet (FUV) spectrum are the O VI emission and absorption lines and the H I Lyman series absorption lines, which are detected up to the Lyman edge. We also identify weak emission from N III, C III,

Shai Kaspi; W. N. Brandt; M. J. Collinge; Martin Elvis; Christopher S. Reynolds

2004-01-01

23

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

PubMed Central

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 apo-enzyme. Crystals of apo-HpUreE and its Ni2+ and Zn2+ 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 (Ni) and 2.52 Å (Zn) 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 apo-protein 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 on solutions of Ni2+- and Zn2+-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 coordination number and geometry leading to metal selectivity. PMID:22010876

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

2012-01-01

24

Solvate Structures and Spectroscopic Characterization of LiTFSI Electrolytes.  

PubMed

A Raman spectroscopic evaluation of numerous crystalline solvates with lithium bis(trifluoromethanesulfonyl)imide (LiTFSI or LiN(SO2CF3)2) has been conducted over a wide temperature range. Four new crystalline solvate structures-(PHEN)3:LiTFSI, (2,9-DMPHEN)2:LiTFSI, (G3)1:LiTFSI and (2,6-DMPy)1/2:LiTFSI with phenanthroline, 2,9-dimethyl[1,10]phenanthroline, triglyme, and 2,6-dimethylpyridine, respectively-have been determined to aid in this study. The spectroscopic data have been correlated with varying modes of TFSI(-)···Li(+) cation coordination within the solvate structures to create an electrolyte characterization tool to facilitate the Raman band deconvolution assignments for the determination of ionic association interactions within electrolytes containing LiTFSI. It is found, however, that significant difficulties may be encountered when identifying the distributions of specific forms of TFSI(-) anion coordination present in liquid electrolyte mixtures due to the wide range of TFSI(-)···Li(+) cation interactions possible and the overlap of the corresponding spectroscopic data signatures. PMID:25345716

Seo, Daniel M; Boyle, Paul D; Sommer, Roger D; Daubert, James S; Borodin, Oleg; Henderson, Wesley A

2014-11-26

25

Spectroscope  

NSDL National Science Digital Library

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

Observatory, Mcdonald

2008-01-01

26

Spectroscopic characterization of femtosecond laser filament in argon gas  

SciTech Connect

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

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

2007-08-01

27

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

NASA Astrophysics Data System (ADS)

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.

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

2011-07-01

28

Spectroscope  

NSDL National Science Digital Library

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

Center, Oakland D.

2011-01-01

29

Spectroscopic measurements of a CO2 absorption line in an open vertical path using an airborne lidar  

NASA Astrophysics Data System (ADS)

We used an airborne pulsed integrated path differential absorption lidar to make spectroscopic measurements of the pressure-induced line broadening and line center shift of atmospheric carbon dioxide at the 1572.335 nm absorption line. We scanned the lidar wavelength over 13 GHz (110 pm) and measured the absorption lineshape at 30 discrete wavelengths in the vertical column between the aircraft and ground. A comparison of our measured absorption lineshape to calculations based on HIgh-resolution TRANsmission molecular absorption database shows excellent agreement with the peak optical depth accurate to within 0.3%. Additionally, we measure changes in the line center position to within 5.2 MHz of calculations and the absorption linewidth to within 0.6% of calculations. These measurements highlight the high precision of our technique, which can be applied to suitable absorption lines of any atmospheric gas.

Ramanathan, Anand; Mao, Jianping; Allan, Graham R.; Riris, Haris; Weaver, Clark J.; Hasselbrack, William E.; Browell, Edward V.; Abshire, James B.

2013-11-01

30

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

NASA Astrophysics Data System (ADS)

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

Coanga, Jean-Maurice

2013-04-01

31

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

NASA Astrophysics Data System (ADS)

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 ?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.

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

2010-02-01

32

X-ray absorption fine structure spectroscopic study of uranium nitrides  

Microsoft Academic Search

Uranium mononitride (UN), sesquinitride (U2N3) and dinitride (UN2) were characterized by extended X-Ray absorption fine structure spectroscopy. Analysis on UN indicate the presence of three uranium shells at distances of 3.46(3), 4.89(5) and 6.01(6) A and a nitrogen shell at a distance of 2.46(2) A . For U2N3, two absorbing uranium atoms at different crystallographic positions are present in the

Frederic Poineau; Charles B. Yeamans; Gary S. Cerefice; Alfred P Sattelberger; Ken R. Czerwinski

2012-01-01

33

BASE: Bayesian Astrometric and Spectroscopic Exoplanet Detection and Characterization Tool  

NASA Astrophysics Data System (ADS)

BASE is a novel program for the combined or separate Bayesian analysis of astrometric and radial-velocity measurements of potential exoplanet hosts and binary stars. The tool fulfills two major tasks of exoplanet science, namely the detection of exoplanets and the characterization of their orbits. BASE was developed to provide the possibility of an integrated Bayesian analysis of stellar astrometric and Doppler-spectroscopic measurements with respect to their binary or planetary companions' signals, correctly treating the astrometric measurement uncertainties and allowing to explore the whole parameter space without the need for informative prior constraints. The tool automatically diagnoses convergence of its Markov chain Monte Carlo (MCMC[2]) sampler to the posterior and regularly outputs status information. For orbit characterization, BASE delivers important results such as the probability densities and correlations of model parameters and derived quantities. BASE is a highly configurable command-line tool developed in Fortran 2008 and compiled with GFortran. Options can be used to control the program's behaviour and supply information such as the stellar mass or prior information. Any option can be supplied in a configuration file and/or on the command line.

Schulze-Hartung, Tim

2012-08-01

34

Spectroscopic characterization of collagen cross-links in bone  

NASA Technical Reports Server (NTRS)

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.

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

2001-01-01

35

Evaluation of laser absorption spectroscopic techniques for eddy covariance flux measurements of ammonia.  

PubMed

An intercomparison was made between eddy covariance flux measurements of ammonia by a quantum cascade laser absorption spectrometer (QCLAS) and a lead-salt tunable diode laser absorption spectrometer (TDLAS). The measurements took place in September 2004 and again in April 2005 over a managed grassland site in Southern Scotland, U.K. These were also compared with a flux estimate derived from an "Ammonia Measurement by ANnular Denuder with online Analysis" (AMANDA), using the aerodynamic gradient method (AGM). The concentration and flux measurements from the QCLAS correlated well with those of the TDLAS and the AGM systems when emissions were high, following slurry application to the field. Both the QCLAS and TDLAS, however, underestimated the flux when compared with the AMANDA system, by 64%. A flux loss of 41% due to chemical reaction of ammonia in the QCLAS (and 37% in the TDLAS) sample tube walls was identified and characterized using laboratory tests but did not fully accountforthis difference. Recognizing these uncertainties, the agreement between the systems was nevertheless very close (R2 = 0.95 between the QCLAS and the TDLAS; R2 = 0.84 between the QCLAS and the AMANDA) demonstrating the suitability of the laser absorption methods for quantifying the temporal dynamics of ammonia fluxes. PMID:18409634

Whitehead, James D; Twigg, Marsailidh; Famulari, Daniela; Nemitz, Eiko; Sutton, Mark A; Gallagher, Martin W; Fowler, David

2008-03-15

36

Synthesis, spectroscopic characterization and comparative DNA binding studies of Schiff base complexes derived from L-leucine and glyoxal.  

PubMed

The mononuclear Schiff base complexes of the type, [ML(CH(3)OH)(2)] [M = Co(II), Ni(II), Cu(II) and Zn(II)] have been synthesized by template condensation of L-leucine and glyoxal. The complexes have been characterized on the basis of the results of the elemental analysis, molar conductance, magnetic susceptibility measurements and spectroscopic studies viz, FT-IR, Mass, (1)H NMR and (13)C NMR spectra. The UV-vis and magnetic moment data revealed an octahedral geometry around Co(II), Ni(II) ion with distortion around Cu(II) ion complex confirmed by EPR data. The conductivity data show a non-electrolytic nature of the complexes. Absorption and fluorescence spectroscopic studies support that all the complexes exhibit a significant binding to calf thymus DNA. PMID:21807556

Shakir, Mohammad; Shahid, Nida; Sami, Naushaba; Azam, Mohammad; Khan, Asad U

2011-11-01

37

The gaseous extent of galaxies and the origin of Lyman-alpha absorption systems: A survey of galaxies in the fields of Hubble Space Telescope spectroscopic target QSOs  

Microsoft Academic Search

We present initial results of an imaging and spectroscopic survey of faint galaxies in fields of Hubble Space Telescope (HST) spectroscopic target QSOs. The primary objectives of the survey are (1) to determine the incidence, extent, and covering factor of extended gaseous envelopes of luminous galaxies and (2) to determine the fraction of Ly(alpha) absorption systems that arise in luminous

Kenneth M. Lanzetta; David V. Bowen; David Tytler; John K. Webb

1995-01-01

38

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

NASA Astrophysics Data System (ADS)

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.

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

2012-01-01

39

Far Ultraviolet Spectroscopic Explorer Spectroscopy of Absorption and Emission Lines from the Narrow-Line Seyfert 1 Galaxy NGC 4051  

E-print Network

We present three Far Ultraviolet Spectroscopic Explorer (FUSE) observations of the Narrow-Line Seyfert 1 galaxy NGC4051. The most prominent features in the far-ultraviolet (FUV) spectrum are the OVI emission and absorption lines and the HI Lyman series absorption lines which are detected up to the Lyman edge. We also identify weak emission from NIII, CIII, and HeII. The CIII line shows absorption while none is detected in the NIII and HeII lines. In HI and CIII we detect two main absorption systems at outflow velocities of -50+/-30 and -240+/-40 km/s, as well as a possible third one at ~ -450 km/s. These systems are consistent in velocity with the 10 absorption systems found previously in CIV, NV, and SiIV, though the individual systems are blended together in the FUV spectrum. We estimate column densities of the two main absorption systems and find that the HI column density is lower for systems with larger outflow velocity. We detect no flux or spectral variations of NGC4051 at FUV wavelengths during three ...

Kaspi, S; Collinge, M J; Elvis, M; Reynolds, C S; Kaspi, Shai; Elvis, Martin; Reynolds, Christopher S.

2004-01-01

40

Saturated absorption inside a Fabry-Perot resonator - Spectroscopic and metrological applications  

Microsoft Academic Search

A saturated absorption technique for spectroscopy and metrology based on the use of a Fabry-Perot resonator is presented and applications of the technique are reported. The method involves the placing of the absorption cell within a Fabry-Perot resonator, allowing a considerable increase in sensitivity if the reflection coefficient of the mirrors is close to 1. For saturated absorption spectroscopy of

P. Cerez; A. Brillet; C. Man-Pichot; J. Umezu

1980-01-01

41

X-ray diffraction and absorption spectroscopic studies of copper mixed ligand complexes with aminophenol as one of the ligands  

NASA Astrophysics Data System (ADS)

X-ray diffraction (XRD) and X-ray absorption spectroscopic (XAS) studies have been conducted on two copper complexes, i.e., copper macrocyclic complex of succinic acid and ortho aminophenol (complex-1) and copper macrocyclic complex of pthalic acid and ortho aminophenol (complex-2). The diffraction pattern of the complexes have been recorded using Rigaku RINT-2000 X-ray diffractometer equipped with rotating anode X-ray tube operated at 40 kV and 100 mA. The X-ray absorption spectra of the complexes have been recorded at the K-edge of copper on Cauchois type bent crystal spectrograph having radius 0.4 m employing a mica crystal, oriented to reflect from (100) planes, for dispersion. The X-ray absorption near edge structure (XANES) parameters, viz., chemical shift, energy position of the principal absorption maximum and edge-width have been determined and discussed. From the extended X-ray absorption fine structure (EXAFS) data, the bond lengths have been calculated using three methods, namely, Levy's method, Lytle, Sayers and Stern's (LSS) method and Fourier transformation method. The results obtained have been compared with each other and discussed.

Mishra, A.; Jain, Garima; Patil, H.

2012-05-01

42

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

NASA Astrophysics Data System (ADS)

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

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

43

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

SciTech Connect

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

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

2006-05-01

44

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

NASA Astrophysics Data System (ADS)

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.

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

45

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

PubMed Central

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

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

2014-01-01

46

New advances in the use of infrared absorption spectroscopy for the characterization of heterogeneous catalytic reactions.  

PubMed

Infrared absorption spectroscopy has proven to be one of the most powerful spectroscopic techniques available for the characterization of catalytic systems. Although the history of IR absorption spectroscopy in catalysis is long, the technique continues to provide key fundamental information about a variety of catalysts and catalytic reactions, and to also offer novel options for the acquisition of new information on both reaction mechanisms and the nature of the solids used as catalysts. In this review, an overview is provided of the main contributions that have been derived from IR absorption spectroscopy studies of catalytic systems, and a discussion is included on new trends and new potential directions of research involving IR in catalysis. We start by briefly describing the power of Fourier-transform IR (FTIR) instruments and the main experimental IR setups available, namely, transmission (TIR), diffuse reflectance (DRIFTS), attenuated total reflection (ATR-IR), and reflection-absorption (RAIRS), for advancing research in catalysis. We then discuss the different environments under which IR characterization of catalysts is carried out, including in situ and operando studies of typical catalytic processes in gas-phase, research with model catalysts in ultrahigh vacuum (UHV) and so-called high-pressure cell instruments, and work involving liquid/solid interfaces. A presentation of the type of information extracted from IR data follows in terms of the identification of adsorbed intermediates, the characterization of the surfaces of the catalysts themselves, the quantitation of IR intensities to extract surface coverages, and the use of probe molecules to identify and titrate specific catalytic sites. Finally, the different options for carrying out kinetic studies with temporal resolution such as rapid-scan FTIR, step-scan FTIR, and the use of tunable lasers or synchrotron sources, and to obtain spatially resolved spectra, by sample rastering or by 2D imaging, are introduced. PMID:24424375

Zaera, Francisco

2014-10-20

47

X-ray absorption fine structure spectroscopic study of uranium nitrides  

SciTech Connect

Uranium mononitride (UN), sesquinitride (U2N3) and dinitride (UN2) were characterized by extended X-Ray absorption fine structure spectroscopy. Analysis on UN indicate the presence of three uranium shells at distances of 3.46(3), 4.89(5) and 6.01(6) A and a nitrogen shell at a distance of 2.46(2) A . For U2N3, two absorbing uranium atoms at different crystallographic positions are present in the structure. One of the uranium atoms is surrounded by nitrogen atoms at 2.28(2) A and by uranium atoms at 3.66(4) and 3.95(4) A . The second type of uranium atom is surrounded by nitrogen atoms at 2.33(2) and 2.64(3) A and by uranium atoms at 3.66(4), 3.95(4) and 5.31(5) A . Results on UN2 indicate two uranium shells at 3.71(4) and 5.32(5) A and two nitrogen shells at 2.28(2).

Poineau, Frederic [University of Nevada, Las Vegas; Yeamans, Charles B. [University of California, Berkeley; Cerefice, Gary S. [University of Nevada, Las Vegas; Sattelberger, Alfred P [Argonne National Laboratory (ANL); Czerwinski, Ken R. [University of Nevada, Las Vegas

2012-01-01

48

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

Microsoft Academic Search

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

Le Qiu

2009-01-01

49

Spectroscopic characterization and detection of Ethyl Mercaptan in Orion  

E-print Network

New laboratory data of ethyl mercaptan, CH$_{3}$CH$_{2}$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$_3$CH$_2$SH towards Orion KL. 77 unblended or slightly blended lines plus no missing transitions in the range 80-280 GHz support this identification. A detection of methyl mercaptan, CH$_{3}$SH, in the spectral survey of Orion KL is reported as well. Our column density results indicate that methyl mercaptan is $\\simeq$ 5 times more abundant than ethyl mercaptan in the hot core of Orion KL.

Kolesniková, L; Cernicharo, J; Alonso, J L; Daly, A M; Gordon, B P; Shipman, S T

2014-01-01

50

Regular paper Spectroscopic characterization of the excitation energy transfer  

E-print Network

meneghiniana by conducting ultrafast transient absorption measurements. This light harvesting antenna has of a complex energy transfer network that also involves energy transfer from the unrelaxed or `hot spectral evolution in the Chl-a region of the spectrum. We have applied global and target analysis to model

van Stokkum, Ivo

51

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

E-print Network

) of traditional surface science techniques restrict the investigations of heterogeneous catalysis system under industrial working conditions (atmospheric pressures). Polarization Modulation Infrared Reflection-Absorption Spectroscopy (PM-IRAS) can be operated...

Cai, Yun

2010-01-14

52

Comprehensive Spectroscopic Characterization of Model Aromatic Substituents of Lignin  

NASA Astrophysics Data System (ADS)

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.

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

2012-06-01

53

Spectroscopic Characterization and Assignment of Reduction Potentials in the Tetraheme Cytochrome c554 from  

E-print Network

Spectroscopic Characterization and Assignment of Reduction Potentials in the Tetraheme Cytochrome c, Minnesota 55108 Received July 8, 2002 ; E-mail: hendrich@andrew.cmu.edu Abstract: The tetraheme cytochrome c in the biological oxidation of ammonia. The protein contains one 5-coordinate heme and three bis-His coordinated

Hendrich, Mike

54

Spectroscopic characterization of Stone-Wales defects in nanotubes Yoshiyuki Miyamoto,1  

E-print Network

Spectroscopic characterization of Stone-Wales defects in nanotubes Yoshiyuki Miyamoto,1 Angel Rubio to unambiguously identify the presence of Stone-Wales SW defects in carbon and boron nitride nanotubes. Based/heptagon pairs, called Stone-Wales SW defects3 --have been pro- posed to play a major role in the growth

55

Spectroscopic Characterization of Mixed Fe-Ni Oxide Electrocatalysts for the Oxygen Evolution Reaction in Alkaline  

E-print Network

with hydrogen evolution. The hydrogen evolution reaction is a relatively simple reaction that readily occursSpectroscopic Characterization of Mixed Fe-Ni Oxide Electrocatalysts for the Oxygen Evolution Information ABSTRACT: Mixed Fe-Ni oxide electrocatalysts for the oxygen evolution reaction in alkaline

Frenkel, Anatoly

56

Vibrational spectroscopic characterization of wild growing mushrooms and toadstools.  

PubMed

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 alpha- and beta-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. PMID:11789883

Mohacek-Grosev, V; Bozac, R; Puppels, G J

2001-12-01

57

Vibrational spectroscopic characterization of wild growing mushrooms and toadstools  

NASA Astrophysics Data System (ADS)

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

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

2001-12-01

58

Surface spectroscopic characterization of oxide thin films and bimetallic model catalysts  

E-print Network

(XPS), low energy electron diffraction (LEED), infrared reflection absorption spectroscopy (IRAS) and temperature programmed desorption (TPD) under ultra high vacuum (UHV) conditions. Of particular interest in this investigation was the characterization...

Wei, Tao

2009-05-15

59

IEEE SENSORS JOURNAL, VOL. 7, NO. 8, AUGUST 2007 1183 Development of an Infrared Absorption Spectroscope  

E-print Network

IEEE SENSORS JOURNAL, VOL. 7, NO. 8, AUGUST 2007 1183 Development of an Infrared Absorption clustering the response of an analytical instrument, i.e., retention time in a gas chromato- graph, Texas A&M University, College Station, TX 77840 USA (e-mail: fgn@tamu.edu; dlfelps@ tamu.edu; rgutier

Gutierrez-Osuna, Ricardo

60

Accurate Spectroscopic Characterization of Protonated Oxirane: A Potential Prebiotic Species in Titan's Atmosphere  

NASA Astrophysics Data System (ADS)

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.

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

2014-09-01

61

Spectroscopic characterization of ion-irradiated multi-layer graphenes  

NASA Astrophysics Data System (ADS)

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.

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

62

Synthesis and spectroscopic characterization of chiral biphenyl-cholesterol gels.  

PubMed

The synthesis of 4-(3-cholesteroxycarbonylpropyloxy)biphenyl (BO4-chol), 4-(7-cholesteroxycarbonylheptyloxy)biphenyl (BO8-chol), and 4,4'-bis(7-cholesteroxycarbonyl heptyloxy)biphenyl (BBO8-chol) is reported. These gelators form 1% and 2% (w/w) stable gels in n-octanol. The gels formed from single cholesterol gelators (BO4-chol and BO8-chol) exhibit lower phase transition temperatures (Tg) (62-65, 68-69 °C) than the gel obtained from the bischolesterol gelator BBO8-chol (96-98 °C). All three gelators form chiral gels in n-octanol as observed by induced circular dichroism (ICD) spectroscopy. The effect of two cholesterol moieties versus one cholesterol unit linked to a biphenyl molecule by a flexible chain, and the effect of the chain length on the gelation ability of these three novel gelators was investigated by circular dichroism (CD), absorption, and fluorescence spectroscopies. The gels obtained from BO4-chol and BO8-chol exhibit biphasic circular dichroism spectra with opposite chirality. The ICD spectra of both BO8-chol and BBO8-chol gels show a positive ICD band followed by a negative band at room temperature. However, while BO8-chol gel ICD absorptions decrease equally as temperature increases, BBO8-chol gel shows an inversion of the Cotton effect bands between 50 and 60 °C until completely disappearing above the phase transition temperature. SEM was used for the investigation of the morphology of the xerogels. On the basis of XRD data and molecular modeling, we propose packing modes for the formation of the organogelator aggregates. PMID:25350932

Geiger, H Cristina; Lamson, Melissa; Galka, Daniel J

2014-11-25

63

Raman spectroscopic characterization of some commercially available carbon black materials  

Microsoft Academic Search

Some commercially available carbon black materials were characterized by Raman spectroscopy. The Raman spectra were recorded between 1000 and 1800 cm?1, which corresponds to the spectral region that provides the most valuable data on the microstructure of carbons. A comparative study of the intensity, bandwidth and frequency shifts of the D and G bands, as well as the broad amorphous

T. Jawhari; A. Roid; J. Casado

1995-01-01

64

Spectroscopic Analysis of H I Absorption-Line Systems in 40 HIRES Quasars  

Microsoft Academic Search

We list and analyze H I absorption lines at redshifts 2 < z < 4 with column density 12 < log(N\\/cm-2) < 19 in 40 high-resolution (FWHM = 8.0 km s-1) quasar spectra obtained with the Keck HIRES. We deblend and fit all H I lines within 1000 km s-1 of 86 strong H I lines whose column densities are

Toru Misawa; David Tytler; Masanori Iye; David Kirkman; Nao Suzuki; Dan Lubin; Nobunari Kashikawa

2007-01-01

65

X-ray absorption spectroscopic studies of silicate glasses and minerals  

Microsoft Academic Search

Selected results of x-ray absorption spectroscopy (XAS) studies of amorphous silicates and minerals are presented in order to show their utility in providing short-and, in certain cases, medium-range structural and bonding information for cations and anions. EXAFS and XANES studies of amorphous silicates are reviewed with the objective of illustrating variations in structural environments of the various types of glass-forming

Georges Calas; Gordon E. Brown; Glenn A. Waychunas; Jacqueline Petiau

1987-01-01

66

Absorption and emission spectroscopic characterisation of the LOV2-His domain of phot from Chlamydomonas reinhardtii  

NASA Astrophysics Data System (ADS)

The absorption and emission behaviour of flavin mononucleotide (FMN) in the wild-type light, oxygen and voltage sensitive domain LOV2 of the photoreceptor phot from the green alga Chlamydomonas reinhardtii is studied. Actually a LOV2-His protein (LOV2 domain bound at N-terminal to 15 His aminoacids via a Gly aminoacid) expressed in an Escherichia coli strain is investigated. For fresh samples stored in the dark an initial fluorescence quantum yield of ?F = 0.12 ± 0.01 and an effective fluorescence lifetime of ?F = 2.4 ± 0.1 ns are determined. Blue-light photo-excitation generates an intermediate photoproduct (flavin-C(4a)-cysteinyl adduct with absorption peak at 390 nm) resulting in an intensity-dependent fluorescence quenching. In the aqueous solutions at pH 8 approximately 3.8% of the FMN molecules are not bound to the protein binding pocket, whereas 96.2% are non-covalently bound. Even at high-intensity light excitation at 428 nm a fraction of about 7% of the non-covalently bound FMN remains non-converted to an FMN-Cys adduct because of photo-induced back-relaxation of the adduct to non-covalently bound FMN. Two holo-LOV2-His conformations with different adduct recovery time constants are revealed by spectrally and temporally resolved fluorescence and absorption measurements: A fraction of about 48% forms FMN-Cys adducts with a fast recovery time constant of ?Ad,f = 19 ± 2 s in the dark, and the rest forms adducts with a slow recovery time constant of ?F,s = 5.5 ± 1 min. Prolonged blue light irradiation of the flavin-C(4a)-cysteinyl adducts reduces their ability to recover back in the dark to non-covalently bound FMN (photo-induced permanent adduct formation). Numerical simulations of the intensity-dependent absorption depletion reveals a quantum yield of intermediate photo-adduct formation of ?Ad = 0.9 ± 0.1. Simulation of the adduct absorption dynamics gives a quantum yield of photo-induced adduct back-relaxation of ?Ad,b = 0.15 ± 0.01 and a quantum yield of photo-induced permanent adduct formation of ?Ad,p = (2.6 ± 0.5) × 10 -4.

Holzer, W.; Penzkofer, A.; Hegemann, P.

2005-01-01

67

Spectroscopic characterization of Fe2+-doped II-VI ternary and quaternary mid-IR laser active powders  

NASA Astrophysics Data System (ADS)

We report on spectroscopic characterization of laser active powders based on iron doped II-VI ternary and quaternary semiconductors for mid-IR laser applications. Iron doped Cd1-x MnxTe, Cd1-x MnxS, Cd1-xMnxSe, Cd0.5Mn0.5S0.5Se0.5 , Cd1-xZnxTe compounds with x=0.5-0.25, were prepared by using thermo diffusion technique. The starting binary powders were mixed in the appropriate molar ratios, sealed in evacuated (10-3 Torr) quartz ampoules, and annealed at 800-1000oC for several days. Samples composition, integrity, and grain size were characterized by micro-Raman and Xray diffraction and revealed a variation of the crystal field parameters depending on powder composition. Fe2+ photoluminescence was characterized by spectral band position (normalized with respect to the detection platform spectral sensitivity) and lifetime at different temperatures, enabling calculation of the absorption and emission crosssections. Practical utility of the developed powders was demonstrated by a room temperature random lasing of iron doped Cd0.5Zn0.5Te powders over 5620-6020 nm spectral range pumped by a 2.94 ?m radiation of a Q-switched Er:YAG laser. In summary, the following has been accomplished: (1) It was demonstrated that laser active Fe2+ doped ternary and quaternary II-VI materials can be produced by simple annealing of the commercially available binary powders omitting expensive and complicated crystal growth processes; (2) It is possible to effectively shift PL of Fe2+ in II-VI host materials towards shorter or longer wavelength by varying composition, type and amount of the second cation in ternary II-VI materials; (3) Major spectroscopic characteristics of Fe2+ doped II-VI ternary and quaternary compounds were obtained and their practical utility for mid-IR lasing demonstrated.

Martinez, A.; Martyshkin, D. V.; Fedorov, V. V.; Mirov, S. B.

2014-02-01

68

NMR spectroscopic characterization of ?-cyclodextrin inclusion complex with vanillin  

NASA Astrophysics Data System (ADS)

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

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

2009-08-01

69

Resonance Raman spectroscopic characterization of compound III of lignin peroxidase  

SciTech Connect

Resonance Raman (RR) spectra of several compounds III of lignin peroxidase (LiP) have been measured at 90 K with Soret and visible excitation wavelengths. The samples include LiPIIIa (or oxyLiP) prepared by oxygenation of the ferrous enzyme, LiPIIIb generated by reaction of the native ferric enzyme with superoxide, LiPIIIc prepared from native LiP plus H{sub 2}O{sub 2} followed by removal of excess peroxide with catalase, and LiPIII made by addition of excess H{sub 2}O{sub 2} to the native enzyme. The RR spectra of these four products appear to be similar and, thus, indicate that the environments of these hexacoordinate, low-spin ferriheme species must also be very similar. Nonetheless, the Soret absorption band of LiPIII is red-shifted by 5 nm from the 414-nm maximum common to LiPIIIa, -b, and -c. Analysis of the iron-porphyrin vibrational frequencies indicates that the electronic structures for the various compounds III are consistent with an Fe{sup III}O{sub 2}{sup {center dot}-}formulation. The spectral changes observed between the oxygenated complex and the ferrous heme of lignin peroxidase are similar to those between oxymyoglobin and deoxymyoglobin. The contraction in the core sizes in compound III relative to the native peroxidase is analyzed and compared with that of other heme systems. The Fe-O{sub 2} stretching vibration of the oxygenated peroxidase is observed at 563 cm{sup {minus}1} and shifts of 538 cm{sup {minus}1} with {sup 18}O isotope. The Fe-histidine stretching vibration is observed at 245 cm{sup {minus}1} in ferrous peroxidase and appears to shift to 276 cm{sup {minus}1} in the oxygenated complex.

Mylrajan, M.; Valli, K.; Wariishi, Gold, M.H.; Loehr, T.M. (Oregon Graduate Institute of Science and Technology, Beaverton (USA))

1990-10-01

70

Raman spectroscopic instrumentation and plasmonic methods for material characterization  

NASA Astrophysics Data System (ADS)

The advent of nanotechnology has led to incredible growth in how we consume, make and approach advanced materials. By exploiting nanoscale material properties, unique control of optical, thermal, mechanical, and electrical characteristics becomes possible. This thesis describes the development of a novel localized surface plasmon resonant (LSPR) color sensitive photosensor, based on functionalization of gold nanoparticles onto tianium dioxide nanowires and sensing by a metal-semiconducting nanowire-metal photodiode structure. This LSPR photosensor has been integrated into a system that incorporates Raman spectroscopy, microfluidics, optical trapping, and sorting flow cytometry into a unique material characterization system called the microfluidic optical fiber trapping Raman sorting flow cytometer (MOFTRSFC). Raman spectroscopy is utilized as a powerful molecular characterization technique used to analyze biological, mineralogical and nanomaterial samples. To combat the inherently weak Raman signal, plasmonic methods have been applied to exploit surface enhanced Raman scattering (SERS) and localized surface plasmon resonance (LSPR), increasing Raman intensity by up to 5 orders of magnitude. The resultant MOFTRSFC system is a prototype instrument that can effectively trap, analyze, and sort micron-sized dielectric particles and biological cells. Raman spectroscopy has been presented in several modalities, including the development of a portable near-infrared Raman spectrometer and other emerging technologies.

Tanaka, Kazuki

71

Application of spectroscopic ellipsometry and Mueller ellipsometry to optical characterization.  

PubMed

This article provides a brief overview of both established and novel ellipsometry techniques, as well as their applications. Ellipsometry is an indirect optical technique, in that information about the physical properties of a sample is obtained through modeling analysis. Standard ellipsometry is typically used to characterize optically isotropic bulk and/or layered materials. More advanced techniques such as Mueller ellipsometry, also known as polarimetry in the literature, are necessary for the complete and accurate characterization of anisotropic and/or depolarizing samples that occur in many instances, both in research and in real-life activities. In this article, we cover three main subject areas: Basic theory of polarization, standard ellipsometry, and Mueller ellipsometry. The first section is devoted to a short, pedagogical introduction of the formalisms used to describe light polarization. The second section is devoted to standard ellipsometry. The focus is on the experimental aspects, including both pros and cons of commercially available instruments. The third section is devoted to recent advances in Mueller ellipsometry. Application examples are provided in the second and third sections to illustrate how each technique works. PMID:23317664

Garcia-Caurel, Enric; De Martino, Antonello; Gaston, Jean-Paul; Yan, Li

2013-01-01

72

Spectroscopic characterization of a novel electronic brachytherapy system.  

PubMed

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

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

2008-01-01

73

Spectroscopic ellipsometry characterization of electrochromic tungsten oxide and nickel oxide thin films made by sputter deposition  

Microsoft Academic Search

Electrochromic films of tungsten oxide and nickel oxide were made by reactive dc magnetron sputtering and were characterized by X-ray diffraction, Rutherford backscattering spectrometry, scanning electron microscopy, and atomic force microscopy. The optical properties were investigated in detail by spectroscopic ellipsometry and spectrophotometry, using a multiple-sample approach. The W-oxide film was modeled as a homogeneous isotropic layer, whereas the Ni-oxide

I. Valyukh; S. Green; H. Arwin; G. A. Niklasson; E. Wäckelgård; C. G. Granqvist

2010-01-01

74

X-ray absorption and emission spectroscopic investigation of Mn doped ZnO films  

NASA Astrophysics Data System (ADS)

The electronic structure of (Zn,Mn)O films with different Mn concentrations has been investigated by element-selective soft X-ray absorption and emission spectroscopy. The band gap narrowing of (Zn,Mn)O with increase of Mn concentration (<20% Mn) is attributed to the Mn doping and sp- d exchange interactions. According to analysis of the O K? and resonant Mn L2,3 X-ray emission spectra, the splitting of Mn 3 d subbands is related to Mn-derived states. It indicates that ferromagnetic coupling in (Zn,Mn)O can be taken into account to be carrier-induced. The presence of antiferromagnetism in the heavier Mn-doped films can be explained in terms of the existence of MnO secondary phases.

Jin, J.; Chang, G. S.; Zhou, Y. X.; Zhang, X. Y.; Boukhvalov, D. W.; Kurmaev, E. Z.; Moewes, A.

2011-10-01

75

Spectroscopic measurements and characterization of soft tissue phantoms  

NASA Astrophysics Data System (ADS)

Tissue phantoms are important tools to calibrate and validate light propagation effects, measurements and diagnostic test in real biological soft tissue. We produce low cost phantoms using standard commercial jelly, distillated water, glycerol and a 20% lipid emulsion (Oliclinomel N7-1000 ®) was used in place of the usual Intralipid®. In a previous work we designed a protocol to elaborate high purity phantoms which can be used over months. We produced three different types of phantoms regarding the lipid emulsion - glycerol - gelatin - water composition: Pure gelatin phantoms, lipid in glycerol, and lipid in gelatin phantoms were produced and different concentrations of the lipid emulsion were used to study optical propagation properties of diffusive mixtures. Besides, 1.09 ?m poly latex spheres in distilled water were used to produce reference phantoms. In order to use all the phantom sides, the phantoms were produced in disposable spectrometer cuvettes, designed for fluorescence studies. Measurements were performed using an OceanOptics 4000 channels spectrophotometer and integrating spheres. For the scattering measurements a homemade goniometer with a high resolution angular scale was used and the scattering detector was a linear array of optical fibers, with an angular collimator, connected to the spectrophotometer. White LED was used as light source, and the 6328.8 nm HeNe Laser was used for calibration. In this work we present characterization measurements for gelatin and microspheres phantoms using spectral reflectance, diffuse and direct spectral transmittance, and angle scattering measurements. The results of these measurements and their comparison are presented.

Solarte, Efrain; Ipus, Erick

2013-02-01

76

Synthesis and spectroscopic characterization of copper zinc aluminum nanoferrite particles.  

PubMed

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

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

2014-06-01

77

Synthesis and spectroscopic characterization of copper zinc aluminum nanoferrite particles  

NASA Astrophysics Data System (ADS)

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.

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

2014-06-01

78

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

E-print Network

those spectroscopic properties. Most blue copper proteins are similar to either plastocyanin or azurin, the best characterized of the blue copper proteins. All blue copper proteins contain a coordination site where Cu(II) is bound in a trigonal plane...

Daugherty, Roxanne Gail

2012-06-07

79

Synthesis, spectroscopic characterization, and reactivity of water-tolerant Eu3+-based precatalysts.  

PubMed

We report the synthesis, spectroscopic characterization, and reactivity of Eu(3+) in the presence of a new set of chiral ligands designed for the aqueous, enantioselective Mukaiyama aldol reaction. Luminescence and NMR measurements were used to characterize the coordination environments of the Eu(3+)-based precatalysts, and this data is compared with yields and stereoselectivities. In addition to structure-function relationships, we found that, in the presence of excess hexadentate ligands, Eu(3+) is coordinatively saturated, and subsequently, the reactivity of the precatalysts is reduced. These findings are helpful for the design of new ligands that bind Eu(3+) without saturating the Eu(3+) coordination sphere. PMID:24874180

Averill, Derek J; Allen, Matthew J

2014-06-16

80

Fe-complex of a tetraamido macrocyclic ligand: Spectroscopic characterization and catalytic oxidation studies  

Microsoft Academic Search

This work presents the spectroscopic characterization and reaction studies of a FeIII-complex (2) of a tetraamido macrocyclic ligand (1, 15,15-dimethyl-5,8,13,17-tetrahydro-5,8,13,17-tetraaza-dibenzo[a,g]cyclotridecene-6,7,14,16-tetraone). 2 was characterized primarily by means of EPR. In agreement with the magnetic moment (?eff=3.87 BM), EPR spectroscopy of 2 shows signals consistent with S=3\\/2 intermediate-spin ferric-iron. Besides EPR, mass spectrometry, UV\\/vis spectroscopy and cyclic voltammetry were used to further

Shane Z. Sullivan; Anindya Ghosh; Alexandru S. Biris; Sharon Pulla; Anna M. Brezden; Samulel L. Collom; Ross M. Woods; Pradip Munshi; Laura Schnackenberg; Brad S. Pierce; Ganesh K. Kannarpady

2010-01-01

81

Spectroscopic Analysis of H I Absorption Line Systems in 40 HIRES Quasars  

E-print Network

We list and analyze H I absorption lines at redshifts 2 15. Unlike most prior studies, we use not only Lya but also all visible higher Lyman series lines to improve the fitting accuracy. This reveals components near to higher column density systems that can not be seen in Lya. We list the Voigt profile fits to the 1339 H I components that we found. We examined physical properties of H I lines after separating them into several sub-samples according to their velocity separation from the quasars, their redshift, column density and the S/N ratio of the spectrum. We found two interesting trends for lines with 12 15. First, their column density distribution becomes steeper, meaning relatively fewer high column density lines, at z < 2.9. Second, their column density distribution also becomes steeper and their line width becomes broader by about 2-3 km/s when they are within 5,000 km/s of their quasar.

T. Misawa; D. Tytler; M. Iye; D. Kirkman; N. Suzuki; D. Lubin; N. Kashikawa

2007-06-29

82

Absorption  

NSDL National Science Digital Library

The process of absorption is a cellular process (microscopic). Absorption cells line the stomach and intestine walls and allow small nutrients (broken down from the food we eat) to pass through and into our blood. The process of absorption is much like a leaking balloon filled with water. The balloon is the stomach or intestine, the tiny holes are the absorption cells, and the water is nutrients leaving.

Katie Hale (CSUF;)

2002-09-26

83

Electron paramagnetic resonance, optical absorption and IR spectroscopic studies of the sulphate mineral apjohnite  

NASA Astrophysics Data System (ADS)

Apjohnite, a naturally occurring Mn-bearing pseudo-alum from Terlano, Bolzano, Italy, has been characterized by EPR, optical, IR and Raman spectroscopy. The optical spectrum exhibits a number of electronic bands around 400 nm due to Mn(II) ion in apjohnite. From EPR studies, the parameters derived, g = 2.0 and A = 8.82 mT, confirm MnO(H 2O) 5 distorted octahedra. The presence of iron impurity in the mineral is reflected by a broad band centered around 8400 cm -1 in the NIR spectrum. A complex band profile appears strongly both in IR and Raman spectra with four component bands around 1100 cm -1 due to the reduction of symmetry for sulphate ion in the mineral. A strong pair of IR bands at 1681 and 1619 cm -1 with variable intensity is a proof for the presence of water in two states in the structure of apjohnite.

Lakshmi Reddy, S.; Siva Reddy, G.; Wain, D. L.; Martens, W. N.; Jagannatha Reddy, B.; Frost, R. L.

2006-12-01

84

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

NASA Astrophysics Data System (ADS)

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.

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

85

Spectroscopic and electrochemical characterization of di- tert-butylated sterically hindered Schiff bases and their phenoxyl radicals  

NASA Astrophysics Data System (ADS)

A series of sterically hindered N-arylsalicylaldimines (SAs) previously prepared from substituted salicylaldehydes (X-Sal, where X = H, Cl, Br, NO 2, OH, OCH 3) and 2,6-di- t-butyl-1-hydroxyaniline (L xH) and 2,5-di- t-butylaniline (L x'H) were characterized by 1H and 13C NMR, UV-Vis and electrochemical methods. The electronic spectra (ES) (X = OH, OCH 3) in alcoholic solvents (MeOH, EtOH, PrOH, iso-PrOH) unlike other solvents exhibit a new absorption band in the region 630-675 nm ( ?=19-242 M -1 cm -1), which are not characteristic for other SA known in literature. The ESR studies of primary phenoxyl radicals generated from L xH by their oxidation with PbO 2 reveal that some of them with the time are converted to more stable secondary Coppinger's radical. The cyclic voltammograms of L xH and L x'H except NO 2-substituted ones in CH 3CN are similar and along with two or three irreversible anodic waves at the potentials ranging from 0.0 to +1.9 V versus Ag/AgCl, also display one or two irreversible reduction waves at potentials -0.6 to +0.5 V. A series of a new SA prepared from 3,5-di- t-butylsalicylaldehyde and mono-substituted anilines (X = H, o-, p-F, Cl, Br, OCH 3, p- t-butyl, 5,6-benzo) were characterized by analytical, spectroscopic (IR, UV-Vis, 1H and 13C NMR), and electrochemical techniques. The ES spectra of o-, p-Cl, p-Br, o-CH 3 and 5,6-benzo-substituted SA did not exhibit expected absorptions at 400-500 nm in alcoholic solutions.

Kasumov, V. T.; Medjidov, A. A.; Yayli, N.; Zeren, Y.

2004-11-01

86

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

SciTech Connect

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].

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

2009-05-22

87

Spectroscopic characterization of selected fullerene-organic chromophore Langmuir-Blodgett films  

NASA Astrophysics Data System (ADS)

Electronic absorption in polarized and unpolarized light and steady-state fluorescence emission and excitation spectra of zinc porphyrins, their dimers and dyads with a fullerene as well as perylene-derived molecular systems containing a fullerene were investigated. In particular, dyads of the fullerene covalently bonded to perylene- and porphyrin-derived dyes were comprehensively studied in chloroform solution and in a form of Langmuir-Blodgett layers on solid inorganic substrates. The spectroscopic examination of the samples allowed us to analysis charge redistribution after the chromophore-fullerene dyads formation - this effect was detected as changes of the band wavelengths and shape of the lines. The layer organization, in particular the dye molecule orientation, was estimated from. Usefulness of the investigated dyads in photovoltaic devices was signaled.

Lewandowska, Kornelia; Wróbel, Danuta; Graja, Andrzej

2012-08-01

88

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

SciTech Connect

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.

Arrington Jr., C. A.

2000-11-15

89

Mass spectroscopic characterization of yttrium-containing metallofullerene YC82 using resonant laser ablation  

SciTech Connect

In this paper, resonant laser ablation time-of-flight mass spectroscopy (RLA-TOF-MS) has been used to mass spectroscopic characterization of yttrium-containing fullerenes. Solvent soluble, yttrium-containing fullerenes are extracted from yttrium/carbon soot produced by the carbon-arc fullerene generation method. The RLA-TOF mass spectra indicate the presence of YC82. The metallofullerences YC60, YC70, Y2C82 and a series of Y2C2n are not observed by RLA-TOF-MS. This result is consistent with the ESR spectral result reported by Shinohara et al.

Wang Shiliang; Tian Jiahe; Dai Songtao; Chen Dieyan; Luo Chuping; Tan Haisong; Gan Liangbing; Huang Chunhui [Laser Single Atom Detection Laboratory, Department of Physics, Tsinghua University, Beijing 100084 (China); State Key Laboratory of Rare Earth Material Chemistry and Applications, Peking University, Beijing 100871 (China)

1995-04-01

90

Mass spectroscopic characterization of the GeSe:GeI4 vapor transport system  

NASA Technical Reports Server (NTRS)

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

Buchan, Nicholas I.; Rosenberger, Franz

1987-01-01

91

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

NASA Astrophysics Data System (ADS)

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.

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

92

Infrared spectroscopic characterization of human white matter, grey matter, and multiple sclerosis lesions  

NASA Astrophysics Data System (ADS)

FT-IR spectroscopy has been used to characterize white matter, grey matter, and multiple sclerosis (MS) plaques from human central nervous system (CNS) tissue. Discrimination among these three tissue types is possible due to variations in composition. Spectra of white matter exhibit strong lipid absorptions. In contrast, spectra of grey matter reveal a reduced lipid contribution and a significant absorption from water. MS plaques exhibit spectra indicative of lipid loss and, depending upon whether the plaques are chronic or acute, changes in the protein and/or water content.

Choo, Lin-P'ing; Jackson, Michael; Halliday, William C.; Mantsch, Henry H.

1994-01-01

93

Spectroscopic Characterization of the Water Oxidation Intermediates in the Blue Dimer Ru-Based Catalyst for Artificial Photosynthesis  

NASA Astrophysics Data System (ADS)

Utilization of sunlight requires solar capture, light-to-energy conversion and storage. One effective way to store energy is to convert it into chemical energy by fuel-forming reactions, such as water splitting into hydrogen and oxygen. Ruthenium complexes are among few molecular-defined catalysts capable of water splitting. Mechanistic insights about such catalysts can be acquired by spectroscopic analysis of short-lived intermediates of catalytic water oxidation. Use of techniques such as EPR and X-ray absorption spectroscopy (XAS) are used to determine electronic requirements of catalytic water oxidation. About 30 years ago Meyer and coworkers reported first ruthenium-based catalyst for water oxidation, the ``blue dimer''. We performed EPR studies and characterized structures and electronic configurations of intermediates of water oxidation by the ``blue dimer''. Intermediates were prepared chemically by oxidation of Ru-complexes with defined number of Ce (IV) equivalents and freeze-quenched at controlled times. Changes in oxidation state of Ru atom were detected by XANES at Ru K-edges. K-edges are sensitive to changes in Ru oxidation state for Blue Dimer [3,3]^4+, [3,4]^4+, [3,4]'^4+ and [4,5]^3+ allowing a clear assignment of Ru oxidation state in intermediates. EXAFS demonstrated structural changes.

Moonshiram, Dooshaye; Pushkar, Yulia; Jurss, Jonah; Concepcion, Javier; Meyer, Thomas; Zakharova, Taisiya; Alperovich, Igor

2012-02-01

94

Spectroscopic, orbital, and physical properties of the binary Feige 24 and detection of transient He II absorption in the system  

NASA Technical Reports Server (NTRS)

We have obtained new high-dispersion optical spectroscopy at Kitt Peak National Observatory (KPNO) and new International Ultraviolet Explorer (IUE) spectroscopy of the white dwarf+red dwarf binary system Feige 24. The optical range shows a composite DA+dM spectrum, together with H I Balmer and He I emission. The orbital phase dependence of the emission shows that it results from extreme ultraviolet (EUV) light reprocessing in the red dwarf upper atmosphere. The systems close enough and hot enough to show this reprocessing signature only recently emerged from common-envelope evolution. The ultraviolet spectrum exclusively emanates from the white dwarf and shows numerous heavy element absorption lines. We measured accurate radial velocities of the red dwarf component motion, traced by both optical absorption and emission lines, and new radial velocities of the white dwarf, traced by ultraviolet Fe V lines. Combining these measurements, we refined the orbital parameters presented by Vennes et al. (1991), and we confirmed that the white dwarf gravitational redshift is exceptionally small with 9 +/- 2 km/s. From this we deduced that the interior is either pure helium or carbon with a thick hydrogen layer, and we derived, for the combined interior compositions, a white dwarf mass and radius of M(sub WD) = 0.44-050 solar mass and R(sub WD) = 0.028-0.036 solar radius. We suggest that Feige 24 could be a typical case of close binary evolution leading to the formation of a low-mass helium white dwarf. The mass of the red dwarf and the inclination of the system naturally follow: M(sub dM) = 0.26-0.33 solar mass, i greater than or equal to 75 deg. High-dispersion H-alpha line profiles are asymmetrical, strongly enhanced toward the blue, suggesting a moving atmosphere possibly linked to a mass loss rate of 10(exp -10) solar mass/yr. The IUE spectra taken when the system is near inferior conjunction show strong He II 1640 A absorption. The profile is highly variable in width and intensity. Because it is correlated with the passage of the white dwarf at inferior conjunction, the absorption may occur in some foreground plasma emanated by the red dwarf and accumulating near a Lagrangian point or, alternatively, it may originate in an accretion spot on the white dwarf surface coaligned with the major orbital axis. Either way, the He II detection may imply substantial mass loss from the red dwarf with a corollary reclassification of Feige 24 as a mixed He/H DAO white dwarf resulting from accretion of secondary mass-loss material. Feige 24 is the prototype of a class of young, EUV-emitting, binary systems comprising a late main sequence secondary and a hot H-rich white dwarf; the class is characterized by optical and ultraviolet photospheric He II absorption, circumstellar C IV lambda (1550) absorption, and by the presence of EUV-induced, phase-dependent Balmer fluorescence. These young systems present the best opportunity to constrain theory of common-envelope evolution.

Vennes, Stephane; Thorstensen, John R.

1994-01-01

95

The gaseous extent of galaxies and the origin of Lyman-alpha absorption systems: A survey of galaxies in the fields of Hubble Space Telescope spectroscopic target QSOs  

NASA Technical Reports Server (NTRS)

We present initial results of an imaging and spectroscopic survey of faint galaxies in fields of Hubble Space Telescope (HST) spectroscopic target QSOs. The primary objectives of the survey are (1) to determine the incidence, extent, and covering factor of extended gaseous envelopes of luminous galaxies and (2) to determine the fraction of Ly(alpha) absorption systems that arise in luminous galaxies. The goal of the survey is to identify in each field under construction all objects with apparent r-band magnitudes satisfying r less than 21.5 within angular distances to the QSOs satisfying 0 less thyan 1.3'. The current observations cover six fields and are 37% complete to the goal ofthe survey. These observations identify 46 galaxies at redshifts spanning z = 0.0700-0.5526 and at impact parameters to the QSOs spanning rho = 16.6-346.9/h kpc. Of these galaxies, 11 are coincident in redshift with absorption systems and 21 do not give rise to absorption to within sensitive upper limits. Nine galaxies are coincident in redshift with 'Ly(alpha)-forest' absorption systems that show Ly(alpha) absorption but no corresponding metal-line absorption, and two galaxies are coincident in redshift with C IV absorption systems that show both Ly(alpha) and C IV absorption. Various lines of evidence demonstrate that the coincident galaxies are responsible for the corresponding absorption systems and are not present as the result of chance coincidence or merely spatial correlated with the absorption systems. The most important evidence is that there exists a statistical anti-correlation between Ly(aplha) rest-frame equivalent width and the impact parameter. Each of five galaxies with rho = 70-160/h kpc give rise to Ly(alpha) absorption, and just one of nine galaxies with rho greater than 70-160/h kpc gives rise to Ly(alpha) absorption. At least eight of 23 Ly(alpha) absorption systyems arise in galaxies. On the basis of these results we reach the following conclusions: (1) At z less than or approximately = 1 most luminosu galaxies are surrounded by extended gaseous envelopes of approximately = 160/h kpc radius and of roughly unit covering factor. This conclusion confirms previous speculation that normal luminosu galaxies possess extended gaseous halos or extended gaseous disks. (2) At z less than or approximately = 1 the fraction of Ly(aplha) absorption systems-including Ly(alpha)-forest absorption systems-that arise in luminous galaxies is at least 0.32 +/- 0.10 and may be as high as 0.60 +/- 0.19. This conclusion runs contrary to the longstanding belief that Ly(alpha)-forest absorption systems arise in intergalactic clouds.

Lanzetta, Kenneth M.; Bowen, David B.; Tytler, David; Webb, John K.

1995-01-01

96

The synthesis, structural, and spectroscopic characterization of uranium(IV) perrhenate complexes.  

PubMed

We report the synthesis, structural, and spectroscopic characterization of a series of uranium(IV)-perrhenato complexes. Three isostructural complexes with general formula [U(ReO4)4(L)4] (where L = tri-n-butylphosphine oxide/TBPO (2), triethyl phosphate/TEP (3), or tri-iso-butyl phosphate/TiBP (4)), have been synthesized, both through the photoreduction of ethanolic {UO2}2+ solutions and also via a novel U(IV) starting material, U(ReO4)4.5H2O (1). Compound 1 has also been used in the preparation of [U(ReO4)4(TPPO)3(CH3CN)].2CH3CN (5) and [U(ReO4)(DPPMO2)3(OH)][ReO4]2.2CH3CN (6), where TPPO represents triphenylphosphine oxide and DPPMO2 represents bis(diphenylphosphino)methane dioxide. All six complexes have been spectroscopically characterized using NMR, UV-vis-NIR, and IR techniques, with 2, 3, 5, and 6 also fully structurally characterized. The U atoms in compounds 2-6 all exhibit eight-coordinate geometry with up to four perrhenate groups in addition to three (DPPMO2 and TPPO) or four (TEP, TiBP, TBPO) coordinated organic ligands. In the case of compounds 5 and 6, the coordination of eight ligands to the U(IV) center is completed by the binding of a solvent molecule (CH3CN) and OH-, respectively. Solid-state physical analysis (elemental and thermogravimetric) and infrared spectroscopy are in agreement with the structural studies. The crystallographic data suggest that the strength of the U(IV)-O-donor ligand bonds decreases across the series R3PO > [ReO4]- > (RO)3PO. Solution-state IR and 31P NMR spectroscopy appear to be in agreement with these solid-state results. PMID:16212387

John, Gordon H; May, Iain; Sharrad, Clint A; Sutton, Andrew D; Collison, David; Helliwell, Madeleine; Sarsfield, Mark J

2005-10-17

97

Characterization of High Ge Content SiGe Heterostructures and Graded Alloy Layers Using Spectroscopic Ellipsometry  

NASA Technical Reports Server (NTRS)

Si(x)Ge(1-x)heterostructures on Si substrates have been widely studied due to the maturity of Si technology. However, work on Si(x)Ge)1-x) heterostructures on Ge substrates has not received much attention. A Si(x)Ge(1-x) layer on a Si substrate is under compressive strain while Si(x)Ge(1-x) on Ge is under tensile strain; thus the critical points will behave differently. In order to accurately characterize high Ge content Si(x)Ge(1-x) layers the energy shift algorithm used to calculate alloy compositions, has been modified. These results have been used along with variable angle spectroscopic ellipsometry (VASE) measurements to characterize Si(x)Ge(1-x)/Ge superlattices grown on Ge substrates. The results agree closely with high resolution x-ray diffraction measurements made on the same samples. The modified energy shift algorithm also allows the VASE analysis to be upgraded in order to characterize linearly graded layers. In this work VASE has been used to characterize graded Si(x)Ge(1-x) layers in terms of the total thickness, and the start and end alloy composition. Results are presented for a 1 micrometer Si(x)Ge(1-x) layer linearly graded in the range 0.5 less than or equal to x less than or equal to 1.0.

Heyd, A. R.; Alterovitz, S. A.; Croke, E. T.

1995-01-01

98

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

E-print Network

Direct characterization and removal of interfering absorption trends in two-layer turbid media Rolf confined to the lower layer of a two-layer turbid medium, as is desired in near-infrared spectroscopy (NIRS

Berger, Andrew J.

99

Chemical Characterization and Absorption of Phytochemicals From Mangifera indica L.  

E-print Network

It was hypothesized that ester-linked gallic acid glycosides could be absorbed and metabolized in vivo due to the instability of an ester-linked glycosides at neutral pH. To evaluate in vivo absorption of Mangifera Indica, L. var. Keitt...

Krenek, Kimberly Ann

2013-08-12

100

Synthesis, spectroscopic characterization, DNA interaction and antibacterial study of metal complexes of tetraazamacrocyclic Schiff base  

NASA Astrophysics Data System (ADS)

The template condensation reaction between benzil and 3,4-diaminotoulene resulted mononuclear 12-membered tetraimine macrocyclic complexes of the type, [MLCl2] [M = Co(II), Ni(II), Cu(II) and Zn(II)]. The synthesized complexes have been characterized on the basis of the results of elemental analysis, molar conductance, magnetic susceptibility measurements and spectroscopic studies viz. FT-IR, 1H and 13C NMR, FAB mass, UV-vis and EPR. An octahedral geometry has been envisaged for all these complexes, while a distorted octahedral geometry has been noticed for Cu(II) complex. Low conductivity data of all these complexes suggest their non-ionic nature. The interactive studies of these complexes with calf thymus DNA showed that the complexes are avid binders of calf thymus DNA. The in vitro antibacterial studies of these complexes screened against pathogenic bacteria proved them as growth inhibiting agents.

Shakir, Mohammad; Khanam, Sadiqa; Firdaus, Farha; Latif, Abdul; Aatif, Mohammad; Al-Resayes, Saud I.

101

Spectroscopic characterization of recently excavated archaeological potsherds from Tamilnadu, India with multi-analytical approach.  

PubMed

A combined analytical study of potsherds excavated from different archaeological sites of Tamilnadu (Kavalapatti, Nattapuraki and Thamaraikulam villages), India are analyzed by spectroscopic techniques such as FTIR, X-ray diffraction, thermogravimetric analysis (TGA) and Scanning Electron Microscope (SEM) coupled with Energy Dispersive Spectrometer (EDS). FTIR and XRD techniques have been attempted to characterize the mineralogical composition, firing temperature and firing conditions of the archaeological potsherds. Thermogravimetric analysis (TGA) is the complementary study to estimate the firing temperature from characteristic thermal reactions in potsherds under controlled firing in inert gas atmosphere. Further, Scanning Electron Microscopy (SEM) equipped and coupled with an Energy Dispersive Spectrometer (EDS) to analyze internal morphology and chemical composition of the potsherds was used. From the results of the above techniques, the firing temperatures of potsherds were found to be greater than 650°C. PMID:24929323

Raja Annamalai, G; Ravisankar, R; Rajalakshmi, A; Chandrasekaran, A; Rajan, K

2014-12-10

102

Spectroscopic characterization and reactivity studies of a mononuclear nonheme Mn(III)-hydroperoxo complex.  

PubMed

We report the first example of a mononuclear nonheme manganese(III)-hydroperoxo complex derived from protonation of an isolated manganese(III)-peroxo complex bearing an N-tetramethylated cyclam (TMC) ligand, [Mn(III)(TMC)(OOH)](2+). The Mn(III)-hydroperoxo intermediate is characterized with various spectroscopic methods as well as with density functional theory (DFT) calculations, showing the binding of a hydroperoxide ligand in an end-on fashion. The Mn(III)-hydroperoxo species is a competent oxidant in oxygen atom transfer (OAT) reactions, such as the oxidation of sulfides. The electrophilic character of the Mn(III)-hydroperoxo complex is demonstrated unambiguously in the sulfoxidation of para-substituted thioanisoles. PMID:25116698

So, Hee; Park, Young Jun; Cho, Kyung-Bin; Lee, Yong-Min; Seo, Mi Sook; Cho, Jaeheung; Sarangi, Ritimukta; Nam, Wonwoo

2014-09-01

103

Spectroscopic Character and Spatial Distribution of Hydroxyl and Water Absorption Features Measured on the Lunar Surface by the Moon Mineralogy Mapper Imaging Spectrometer on Chandrayaan-1  

NASA Astrophysics Data System (ADS)

The Moon Mineralogy Mapper imaging spectrometer on Chandrayaan-1 has a broad spectral range from 430 to 3000 nm. By design, the range was specified to extend to 3000 nm to allow for possible detection of trace volatile compounds that possess absorption bands near 3000 nm. Soon after acquisition and calibration of a large fraction of the lunar surface in early February 2009, absorption features in the 2700 to 3000 nm region were detected over unexpectedly large regional areas. This extraordinary discovery has withstood extensive re-analysis and falsification efforts. We have concluded these absorption features are fundamentally present in the M3 measurements and are indicators of extensive hydroxyl and water-bearing materials occurring on the surface of the Moon. Based on current analyses, these absorption features appear strongest at high latitudes, but also occur in association with several fresh feldspathic craters. Interestingly, the distribution of these absorption features are not directly correlated with existing neutron spectrometer hydrogen abundance data for the sunlight surface. This may indicate that the formation and retention of hydroxyl and water is an active process largely restricted to the upper most surface. We present the detailed spectroscopic character of these absorption features in the 2700 to 3000 nm spectral region, including selected examples through all levels of measurement processing from raw data to calibrated apparent surface reflectance. In summary we show the measured strength and latitudinal distribution of the absorptions as well as selected localized occurrences in association with fresh feldspathic craters. The presence of hydroxyl and water bearing material over extensive regions of the lunar surface provides a new and unexpected source of volatiles. Options for harvesting these elements directly from the regolith may provide an alternate supply of volatiles for long term human exploration objectives.

Green, R. O.; Pieters, C. M.; Goswami, J.; Clark, R. N.; Annadurai, M.; Boardman, J. W.; Buratti, B. J.; Combe, J.; Dyar, M. D.; Head, J. W.; Hibbitts, C.; Hicks, M.; Isaacson, P.; Klima, R. L.; Kramer, G. Y.; Kumar, S.; Livo, K. E.; Lundeen, S.; Malaret, E.; McCord, T. B.; Mustard, J. F.; Nettles, J. W.; Petro, N. E.; Runyon, C. J.; Staid, M.; Sunshine, J. M.; Taylor, L. A.; Tompkins, S.; Varanasi, P.

2009-12-01

104

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

PubMed

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

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

105

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

PubMed Central

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

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

2014-01-01

106

Spectroscopic characterization and modeling of quadrupolar charge-transfer dyes with bulky substituents.  

PubMed

Joint experimental and theoretical work is presented on two quadrupolar D-?-A-?-D chromophores characterized by the same bulky donor (D) group and two different central cores. The first chromophore, a newly synthesized species with a malononitrile-based acceptor (A) group, has a V-shaped structure that makes its absorption spectrum very broad, covering most of the visible region. The second chromophore has a squaraine-based core and therefore a linear structure, as also evinced from its absorption spectra. Both chromophores show an anomalous red shift of the absorption band upon increasing solvent polarity, a feature that is ascribed to the large, bulky structure of the molecules. For these molecules, the basic description of polar solvation in terms of a uniform reaction field fails. Indeed, a simple extension of the model to account for two independent reaction fields associated with the two molecular arms quantitatively reproduces the observed linear absorption and fluorescence as well as fluorescence anisotropy spectra, fully rationalizing their nontrivial dependence on solvent polarity. The model derived from the analysis of linear spectra is adopted to predict nonlinear spectra and specifically hyper-Rayleigh scattering and two-photon absorption spectra. In polar solvents, the V-shaped chromophore is predicted to have a large HRS response in a wide spectral region (approximately 600-1300 nm). Anomalously large and largely solvent-dependent HRS responses for the linear chromophores are ascribed to symmetry lowering induced by polar solvation and amplified in this bulky system by the presence of two reaction fields. PMID:22469003

Sissa, Cristina; Terenziani, Francesca; Painelli, Anna; Siram, Raja Bhaskar Kanth; Patil, Satish

2012-04-26

107

Spectroscopic characterization of the ground and low-lying electronic states of Ga2N via anion photoelectron spectroscopy  

E-print Network

Spectroscopic characterization of the ground and low-lying electronic states of Ga2N via anion 2005; accepted 30 November 2005; published online 8 February 2006 Anion photoelectron spectra of Ga2N to a transition between linear ground states of Ga2N- X 1 g + and Ga2N X 2 u + , yielding the electron affinity

Neumark, Daniel M.

108

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

PubMed

Two synthetic pathways were adopted to synthesize the target 2-oxo-1,4-disubstituted-1,2,5,6-tetrahydro-benzo[h]quinoline-3-carbonitriles. Structure of the synthesized compounds has been characterized based on FT-IR, (1)H NMR, (13)C NMR and elemental analyses. UV-Vis and fluorescence spectroscopy measurements provided that all compounds are good absorbent and fluorescent. Fluorescence polarity study demonstrated that these compounds were sensitive to the polarity of the microenvironment provided by different solvents. In addition, spectroscopic and physicochemical parameters, including singlet absorption, extinction coefficient, Stokes shift, oscillator strength and dipole moment were investigated in order to explore the analytical potential of synthesized compounds. PMID:24934972

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

2014-12-10

109

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

NASA Astrophysics Data System (ADS)

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

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

2014-12-01

110

Synthesis, isolation, spectroscopic and electrochemical characterization of some calcium-containing metallofullerenes  

Microsoft Academic Search

A few Ca-containing mono-metallofullerenes, i.e. Ca@C76, Ca@C88, Ca@C90 (I, II), were synthesized by an improved DC arc discharge method and isolated by a multi-stage HPLC method for the first time. These isomer-separated metallofullerenes were characterized by LD-TOF MS and UV–vis–NIR spectrometry. Their HOMO-LUMO band gaps and possible molecular geometries are discussed according to the absorption spectra in this report. In

Ya Zhang; Jianxun Xu; Ce Hao; Zujin Shi; Zhennan Gu

2006-01-01

111

Spectroscopic characterization of the SH2- and active site-directed peptide sequences of a bivalent Src kinase inhibitor.  

PubMed

The spectral properties of the SH2 and active site-directed sequences of the bivalent Src kinase inhibitor Ac-EELL(F5)Phe-(GABA)3-pYEEIE-amide (1) have been determined. Ac-pYEEIE-amide (2) and AcEELL(F5)Phe-amide (3), as well as the amino acids phosphotyrosine (pTyr) and pentafluorophenylalanine (F5)Phe, have been characterized by electronic absorption, fluorescence, and vibrational spectroscopy. Specific and unique marker bands that originate from the phosphate group of pTyr and the fluorinated aromatic ring of (F5)Phe have been identified, with the latter showing some solvent dependence. Peptide 2 was found to have excitation and emission wavelengths emanating from pTyr at 268 and 295 nm, respectively, whereas peptide 3 displayed excitation and emission peaks attributable to (F5)Phe at 274 and 315 nm, respectively. Fourier transform infrared (FT-IR) analysis of the amino acid pTyr identified distinct marker bands at approximately 930, 1090, and 1330 cm(-1) that could be attributed to the phosphate group. These markers were also observed in the IR spectrum of peptide 2. Likewise, peptide 3 displayed a characteristic C-F stretching mode at 961 cm(-1) due to the presence of (F5)Phe, including two C-F reporting ring modes at 1509 and 1527 cm(-1). Identifying and monitoring spectroscopic changes in these marker bands may afford a means to observe the molecular interactions that occur when peptides 1-3 bind to the Src kinase. PMID:19589214

Desamero, Ruel Z B; Kang, Jeonghee; Dol, Chrystel; Chinwong, Justina; Walters, Karim; Sivarajah, Thulashie; Profit, Adam A

2009-07-01

112

Characterization of Spectral Absorption Properties of Aerosols Using Satellite Observations  

NASA Technical Reports Server (NTRS)

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.

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

2012-01-01

113

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

SciTech Connect

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.

Ogino, Isao; Gates, Bruce C.; (UCD)

2010-01-12

114

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

NASA Astrophysics Data System (ADS)

Pullulan is a water-soluble, extracellular neutral polysaccharide with a linear flexible chain of ?-(1 ? 6)-linked maltotriose units, the structure of which is intermediate between pullulan and amylose structures because of the co-existence of both ?-(1 ? 6) and ?-(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 (?- 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 ?(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).

Miti?, Ž.; Nikoli?, G. S.; Caki?, M.; Premovi?, P.; Ili?, Lj.

2009-04-01

115

X-Ray Absorption Characterization of Diesel Exhaust Particulates  

SciTech Connect

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

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

1999-11-18

116

IR spectroscopic characterization of oh defects in jadeite from a vein occurrence  

NASA Astrophysics Data System (ADS)

The role of OH defects in pyroxenes is of considerable geological interest in view of characterizing the chemistry of nominally anhydrous mineral phases likely to be present in the Earth's mantle. Pyroxene may indeed be the main storage site for hydrogen in the Earth's upper mantle, revealing concentrations ranging from about 100 to 1300 wt.ppm H2O (Ingrin and Skogby, 2000). The jadeite sample of the present study originates from the locality of the Clear Creek area, New Idria district, California (Coleman, 1961). Small colorless cleavage fragments of near end-member jadeite single-crystals found within veins of "white jadeite" were separated and oriented. Under the microscope the strongly elongated crystal fragment, 500 x 200 x 150 70?m in size, proved in parts to be free from impurities and inclusions. The OH defect incorporation mode in vein jadeite must also be considered for pyroxenes formed in mantle regions. IR spectroscopy provides an extremely sensitive method for detecting trace hydrogen bonded to oxygen, thus forming structural OH defects. In the present case it was necessary to use an FTIR microscope providing suitable measuring spot sizes for the absorption measurements. Using polarized IR radiation, the pleochroic scheme of the OH absorption bands allows to impose defined constraints on the OH orientation. Polarized single-crystal spectra of the oriented jadeite crystal fragment were recorded from 4000 to 2000 cm-1. Jadeite is characterized by two small but broad absorption bands centered at 3618 and 3556 cm-1. Both bands show a distinct pleochroism in the (010) plane. The maximum of absorption is observed when the angle between the E vector of the polarized radiation and the c-axis, measured within the positive a- and c-axis, amounts to 70o. In contrast, only a weak pleochroism was observed in (100) with a slightly stronger absorption parallel to the b-axis. Some similarities exist with the pleochroic behavior of group II bands in diopside, which occur around 3535, 3460, and 3355 cm-1 (Ingrin and Skogby, 2000), suggesting a partial replacement of the O2 oxygen atoms by OH groups with an OH dipole orientation pointing to the vicinity of vacant M2 sites also in jadeite. Literature Coleman RG (1961) J Petrol 2, 209 Ingrin J, Skogby H (2000) Eur J Mineral 12, 543 Acknowledgements: This work was partly supported by the EU through the Human Potential Program under Grant HPRN-CT-2000-0056.

Andrut, M.; Beran, A.; Wildner, M.

2003-04-01

117

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

NASA Astrophysics Data System (ADS)

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.

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

2004-12-01

118

Characterization of SiGe/Ge heterostructures and graded layers using variable angle spectroscopic ellipsometry  

NASA Technical Reports Server (NTRS)

Variable angle spectroscopic ellipsometry (VASE) has been used to characterize Si(x)Ge(1-x)/Ge superlattices (SLs) grown on Ge substrates and thick Si(x)Ge(1-x)/Ge heterostructures grown on Si substrates. Our VASE analysis yielded the thicknesses and alloy compositions of all layers within the optical penetration depth of the surface. In addition, strain effects were observed in the VASE results for layers under both compressive and tensile strain. Results for the SL structures were found to be in close agreement with high resolution x-ray diffraction measurements made on the same samples. The VASE analysis has been upgraded to characterize linearly graded Si(x)Ge(1-x) buffer layers. The algorithm has been used to determine the total thickness of the buffer layer along with the start and end alloy composition by breaking the total thickness into many (typically more than 20) equal layers. Our ellipsometric results for 1 (mu)m buffer layers graded in the ranges 0.7 less than or = x less than or = 1.0, and 0.5 less than or = x less than or = 1.0 are presented, and compare favorably with the nominal values.

Croke, E. T.; Wang, K. L.; Heyd, A. R.; Alterovitz, S. A.; Lee, C. H.

1996-01-01

119

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

PubMed

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

Chakdar, N; Sakha, S; Pabbi, S

2014-01-01

120

UV-visible and infrared absorption spectroscopic studies of gamma irradiated tungsten-doped lithium phosphate glasses  

NASA Astrophysics Data System (ADS)

Ultraviolet-visible and infrared spectroscopic techniques were employed to investigate the undoped lithium phosphate glass and other samples of the same composition doped with varying WO3 contents. The same spectroscopic properties were remeasured after subjecting the samples to 3 and 6 Mrad doses of gamma irradiation on the measured properties. Such combined analytical techniques are expected to give information about the state of tungsten ions in such lithium phosphate glass and justify the effect of gamma irradiation. The work aims to deduce the radiation-induced defects generated through successive gamma irradiation by optical measurements. Also, the study is expected to realize through IR spectroscopy, the main structural building groups and the influence of tungsten ions within the structural vibrational groups of the studied glasses.

ElBatal, F. H.; Ouis, M. A.

2011-11-01

121

Comparison of spectroscopic flame temperature measurements: NaD line reversal, rotational and vibrational Raman, and OH absorption  

Microsoft Academic Search

Different spectroscopic methods are used for the measurement of flame temperature. This report compares measurement of temperature profiles for atmospheric premixed Hâ\\/Oâ\\/Nâ laminar flames using the methods of: (1) Raman scattering (Nâ, vibrational and rotational temperatures); (2) line reversal (D-line of Na, electronic temperature); and (3) line ratio (OH, rotational temperature). Two separate burner designs are considered. To obtain the

M. C. Drake; L. H. Grabner; J. W. Hastie

1979-01-01

122

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

NASA Astrophysics Data System (ADS)

Context. Broad absorption lines indicate gas outflows with velocities from thousands of km s-1 to about 0.2 the speed of light, which may be present in all quasars and may play a major role in the evolution of the host galaxy. The variability of absorption patterns can provide information on changes in the density and velocity distributions of the absorbing gas and its ionisation status. Aims: We want to accurately follow the evolution in time of the luminosity and both the broad and narrow C IV absorption features of an individual object, the quasar APM 08279+5255, and analyse the correlations among these quantities. Methods: We have collected 23 photometrical and spectro-photometrical observations at the 1.82 m Telescope of the Asiago Observatory since 2003, plus 5 other spectra from the literature. We analysed the evolution in time of the equivalent width of the broad absorption feature and two narrow absorption systems, the correlation among them and with the R band magnitude. We performed a structure function analysis of the equivalent width variations. Results: We present an unprecedented monitoring of a broad absorption line quasar based on 28 epochs during 14 years. The shape of broad absorption feature shows relative stability, while its equivalent width slowly declines until it sharply increases during 2011. At the same time, the R magnitude stays almost constant until it sharply increases during 2011. The equivalent width of the narrow absorption redwards of the systemic redshift only shows a decline. Conclusions: The broad absorption behaviour suggests changes in the ionisation status as the main cause of variability. We show for the first time a correlation of this variability with the R band flux. The different behaviour of the narrow absorption system might be due to recombination time delay. The structure function of the absorption variability has a slope comparable with typical optical variability of quasars. This is consistent with variations of the 200 Å ionising flux originating in the inner part of the accretion disk.

Trevese, D.; Saturni, F. G.; Vagnetti, F.; Perna, M.; Paris, D.; Turriziani, S.

2013-09-01

123

Synergic use of TOMS and AERONET observations for characterization of aerosol absorption  

NASA Astrophysics Data System (ADS)

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.

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

2003-04-01

124

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

NASA Astrophysics Data System (ADS)

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, ?=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.

Kyono, Atsushi

2010-11-01

125

Spectroscopic characterization of Au 3+ biosorption by waste biomass of Saccharomyces cerevisiae  

NASA Astrophysics Data System (ADS)

Some spectroscopic characteristics of Au 3+ biosorption by waste biomass of Saccharomyces cerevisiae have been reported in this paper. The effect of temperature on the correlation parameters of chemical kinetics and thermodynamics of the binding reaction was investigated by using AAS. XRD diffraction pattern of gold-loaded biomass revealed that the Au 3+ bound on the cell wall of the biomass had been reduced into gold particle. FTIR spectrophotometry on blank and gold-loaded biomass demonstrated that active groups such as the hydroxyl group of saccharides, and the carboxylate anion of amino-acid residues, from the peptidoglycan layer on the cell wall seem to be the sites for the Au 3+ binding, and the free aldehyde group of the hemiacetalic hydroxyl group from reducing sugars, i.e. the hydrolysates of the polysaccharides on the peptidoglycan layer, serving as the electron donor, in situ reduced the Au 3+ to Au 0. XPS and IR characterizations of the interaction between glucose and Au 3+ further supported that the reduction of Au 3+ to Au 0 can directly occur at the aldehyde group of the reducing sugars.

Lin, Zhongyu; Wu, Jianming; Xue, Ru; Yang, Yong

2005-02-01

126

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

PubMed

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

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

2010-03-01

127

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

NASA Technical Reports Server (NTRS)

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.

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

1993-01-01

128

Optical absorption and infrared spectroscopic analysis of ?-irradiated ZnO-BaO-B 2O 3 glasses  

NASA Astrophysics Data System (ADS)

A new series of borate glasses containing ZnO and BaO as network modifiers with compositions of xZnO-2 xBaO-(1 - 3 x)B 2O 3 ( x varying from 0.10 to 0.21 mol fraction) were prepared by conventional melt quenching. Optical and structural properties were determined before and after successive ?-ray irradiation at 2.5 kGy dose using, UV-vis and Fourier transform infrared spectroscopic techniques to elucidate the effect of ?-irradiation. The results are supported by additional density and molar volume studies.

Singh, D.; Thind, K. S.; Mudahar, G. S.; Bajwa, B. S.

2010-10-01

129

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

PubMed

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) (1)H and (13)C 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. PMID:25168237

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

2015-01-25

130

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

NASA Astrophysics Data System (ADS)

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

Templier, J.; Derenne, S.

2006-12-01

131

Thermal, optical and spectroscopic characterizations of borate laser Chavoutier M., Jubera V., Veber P., Velazquez M., Viraphong O., Hejtmanek J., Decourt R., Debray J., Menaert  

E-print Network

Thermal, optical and spectroscopic characterizations of borate laser crystals Chavoutier M., Jubera). Physical properties relevant to laser operation like mechanical hardness, thermal expansion and thermal. Introduction : The development of high average power lasers providing short pulses or continuous waves requires

Boyer, Edmond

132

X-ray absorption and X-ray photoelectron spectroscopic studies of air-oxidized chromium nitride thin films  

Microsoft Academic Search

The surface oxidation of CrN thin films prepared by the cathode are ion plating method was studied by X-ray absorption spectroscopy (XAS) and X-ray photoelectron spectroscopy (XPS) using soft X-rays from synchrotron radiation. The results indicate that molecular nitrogen is formed in the interstitial position of the chromium oxide matrix at the initial stage of oxidation. On further oxidation, at

F. Esaka; H. Shimada; M. Imamura; N. Matsubayashi; T. Sato; A. Nishijima; A. Kawana; H. Ichimura; T. Kikuchi; K. Furuya

1996-01-01

133

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

SciTech Connect

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.

Tan, G.O.

1993-06-01

134

Far ultraviolet polychromator for spectroscopic characterization of the tokamak divertor and plasma scrape-off layer  

SciTech Connect

The Plasma Spectroscopy Group of The Johns Hopkins University is developing diagnostics for spectroscopic characterization of the tokamak plasma scrape-off layer and divertor regions. A far ultraviolet polychromator has been designed for radiative divertor studies at the Alcator C-Mod and D-IIID tokamaks. Local measurements of resonant transitions of lithium- to boron-like ions of intrinsic or seeded low {ital Z} impurity elements will be performed along multiple chords around the {ital X} point. Planar diffraction gratings and stacked grids will be used for dispersion and angular collimation of radiation. Phosphor wavelength converters coupled to a photomultiplier tube by an optical fiber will be used as detectors. The design provides a wavelength resolution of {approx_equal}10 {Angstrom}, a spatial resolution of {le}2 cm, and an adequate photometric sensitivity. The in-vessel instrument, proposed for the Alcator C-Mod tokamak, will measure intensities of the lines at 1240 (N V), 765, 923 (N IV), and 990 {Angstrom} (N III). The port-mounted polychromator at DIII-D will be able to monitor intensities of 1550 (C IV), 977, 1176 (C III), and 1335 {Angstrom} (C II) lines. This, together with visible and bolometric diagnostics, should enable estimates of power losses, charge state distribution and local transport of the impurity ions in the divertor. A one-channel prototype of the C-Mod and D-IIID instruments is being built for the CDX-U spherical tokamak. Line-integrated brightnesses of the 2s{endash}2p transition at 1550 {Angstrom} will be measured and inverted to obtain C IV emissivity distribution. {copyright} {ital 1999 American Institute of Physics.}

Soukhanovskii, V.A.; Stutman, D.; May, M.J.; Finkenthal, M.; Moos, H.W. [Plasma Spectroscopy Group, Department of Physics and Astronomy, The Johns Hopkins University, Baltimore, Maryland 21218 (United States)] [Plasma Spectroscopy Group, Department of Physics and Astronomy, The Johns Hopkins University, Baltimore, Maryland 21218 (United States); Terry, J.L.; Goetz, J.A.; Lipschultz, B. [Plasma Science and Fusion Center, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139 (United States)] [Plasma Science and Fusion Center, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139 (United States)

1999-01-01

135

Chemical and spectroscopic characterization of some phosphate accessory minerals from pegmatites of the Sowie Góry Mts, SW Poland  

NASA Astrophysics Data System (ADS)

Aggregates of phosphate accessory minerals from the Micha?kowa pegmatite in the Sowie Góry Mts, Lower Silesia, southwestern Poland were studied by means of electron microprobe, IR and Raman spectroscopies. Samples of phosphate minerals were collected from the Micha?kowa type locality. Precise chemical analyses in microarea indicate that studied samples are not pure chemical phases, but lamellar intergrowths of various phosphate minerals. These aggregates consist mostly of sarcopside (Fe 2+,Mn 2+,Mg) 3(PO 4) 2 and graftonite (Fe 2+,Mn 2+,Ca) 3(PO 4) 2 with minor amounts of other phosphates. The aims of our study are detailed spectroscopic investigations of sarcopside and graftonite from the Micha?kowa site combined with precise chemical analyses. The authors provide a full spectroscopic characterization of these minerals in the ranges from 1400 to 400 cm -1 - IR investigations and from 1300 to 250 cm -1 - Raman investigations. Spectra of pure sarcopside, pure graftonite and mixture of these minerals are compiled. The results show that Raman microspectroscopy allows discerning sarcopside from graftonite in an easy, non-destructive and fast way. Micro-Raman method is proper to distinguish phases in solid solutions as it allows discerning end-members basing on shifted bands in a spectrum. Spectroscopic characterization is also useful in investigation of the presence of H 2O and OH molecules in structure of studied phosphates. Increased content of such molecules can confirm a higher level of phosphate alterations.

?odzi?ski, M.; Sitarz, M.

2009-04-01

136

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

SciTech Connect

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.

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

1996-06-01

137

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)

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 (?, ? and ?*). 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.

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

2014-01-01

138

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

NASA Astrophysics Data System (ADS)

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.

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

2008-09-01

139

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

SciTech Connect

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

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

1996-06-01

140

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

USGS Publications Warehouse

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.

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

1999-01-01

141

Preparation and characterization of silver nanoparticles on localized surface plasmon-enhanced optical absorption  

NASA Astrophysics Data System (ADS)

Self-assembly silver nanoparticles were successfully prepared on indium tin oxide coated glass substrates by means of a vacuum vapor evaporation method followed by thermal annealing. The nanoparticles were characterized using a field-emission scanning election microscopy with an energy dispersive X-ray analyzer and a UV-vis spectrometer. It was found that the particle morphology was drastically changed depending both on the evaporated silver mass thickness and the length of time of the thermal annealing. Some absorption peaks were observed in the UV-vis spectra and the peaks showed red-shift with the average particle size increase. These facts suggest that the absorption peaks may arise from the localized surface plasmon resonance. These controllable absorptions may be suitable for photon management in dye sensitized solar cells.

Mijanur Rahman, Md.; Hattori, Nampei; Nakagawa, Yuta; Lin, Xu; Yagai, Shiki; Sakai, Masatoshi; Kudo, Kazuhiro; Yamamoto, Kazunuki

2014-11-01

142

Calibration method for spectroscopic systems  

DOEpatents

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.

Sandison, David R. (Edgewood, NM)

1998-01-01

143

Calibration method for spectroscopic systems  

DOEpatents

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.

Sandison, D.R.

1998-11-17

144

Spectrum of excess partial molar absorptivity. Part II: a near infrared spectroscopic study of aqueous Na-halides.  

PubMed

Our earlier thermodynamic studies suggested that F(-) and Cl(-) form hydration shells with the hydration number 14 ± 2 and 2.3 ± 0.6, respectively, and leave the bulk H(2)O away from hydration shells unperturbed. Br(-) and I(-), on the other hand, form hydrogen bonds directly with the momentarily existing hydrogen bond network of H(2)O, and retard the degree of entropy-volume cross fluctuation inherent in liquid H(2)O. The effect of the latter is stronger for I(-) than Br(-). Here we seek additional information about this qualitative difference between Cl(-) and (Br(-) and I(-)) pair by near infrared (NIR) spectroscopy. We analyze the ?(2) + ?(3) band of H(2)O in the range 4600-5500 cm(-1) of aqueous solutions of NaCl, NaBr and NaI, by a new approach. From observed absorbance, we calculate excess molar absorptivity, ?(E), excess over the additive contributions of solute and solvent. ?(E) thus contains information about the effect of inter-molecular interactions in the ?(2) + ?(3) spectrum. The spectrum of ?(E) shows three bands; two negative ones at 5263 and 4873 cm(-1), and the positive band at 5123 cm(-1). We then define and calculate the excess partial molar absorptivity of each salt, ?(E)(salt). From the behaviour of ?(E)(salt) we suggest that the negative band at 5263 cm(-1) represents free H(2)O without much hydrogen bonding under the influence of local electric field of ions. Furthermore, from a sudden change in the x(salt) (mole fraction of salt) dependence of ?(E)(salt), we suggest that there is an ion-pairing in x(salt) > 0.032, 0.036, and 0.04 for NaCl, NaBr and NaI respectively. The positive band of ?(E) at 5123 cm(-1) is attributed to a modestly organized hydrogen bond network of H(2)O (or liquid-likeness), and the x(salt) dependence of ? indicated a qualitative difference in the effect of Cl(-) from those of Br(-) and I(-). Namely, the values of ?(E)(salt) stay constant for Cl(-) but those for Br(-) and I(-) decrease smoothly on increasing the salt mole fraction. The mole fraction dependence of ?(E)(salt) at the 4873 cm(-1) band, due to ice-likeness in H(2)O, shows a subtle difference between Cl(-) and (Br(-), I(-)) pair. PMID:22358251

Sebe, Fumie; Nishikawa, Keiko; Koga, Yoshikata

2012-04-01

145

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

NASA Astrophysics Data System (ADS)

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

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

2014-08-01

146

X-ray photoelectron and optical absorption spectroscopic studies on the dye chlorodiane blue, used as a carrier generation molecule in organic photoconductors  

SciTech Connect

The dye chlorodiane blue, used as a carrier generation molecule in organic photoconductors, is characterized via optical absorption and X-ray photoelectron spectroscopy, and the results are interpreted on the basis of ab initio quantum mechanical molecular models. These data indicate that chlorodiane blue exists as azo-enol and hydrazone-quinone chemical structures and it is the hydrazone-quinone form that provides the higher xerographic gain in electrophotographic applications. Optimized geometries, atomic charges, and molecular orbital plots and energies are reported for both the azo-enol and hydrazone-quinone forms of chlorodiane blue. The two structural forms of the dye are experimentally distinguishable via both optical absorption and X-ray photoelectron spectroscopy, and the wavelength and chemical shifts, respectively, are interpreted via the theoretical results. 29 refs., 9 figs., 4 tabs.

Pacansky, J.; Waltman, R.J. [IBM Almaden Research Center, San Jose, CA (United States)

1992-07-01

147

Lithium thiazolidine-4-carboxylate: synthesis, spectroscopic characterization and preliminary in vitro cytotoxic studies in human HeLa cells.  

PubMed

A new water-soluble lithium salt of thiazolidine-4-carboxylic acid was synthesized and characterized by chemical and spectroscopic techniques. Elemental and mass spectrometric (ESI-MS) analyses of the solid compound fit to the composition LiC(4)H(6)NSO(2). (1)H, (13)C nuclear magnetic resonance (NMR), [(1)H-(15)N] NMR and infrared (IR) analyses permitted to elucidate the structure of the compound. 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. PMID:18353709

Corbi, Pedro P; Andrade, Fabiana C; Massabni, Antonio C; Heinrich, Tassiele A; Souza, Pedro P C; Costa-Neto, Cláudio M

2008-12-01

148

Synthesis, conformational and spectroscopic characterization of monomeric styrene derivatives having pendant p-substituted benzylic ether groups.  

PubMed

Three derivatives of styrene monomer, 4-chlorophenyl-4-vinylbenzyl ether (I), 4-methoxyphenyl-4-vinylbenzyl ether (II) and 4-ethylphenyl-4-vinylbenzyl ether (III) were synthesized. The synthesized two novel compounds (I and III) and one with undefined structural features were identified by experimental spectroscopic techniques and density functional approach. The optimized geometrical structure, vibrational and electronic transitions along with chemical shifts of those compounds were presented in this study. The vibrational spectra of investigated compounds were recorded in solid state with FT-IR spectrometry in the range of 4000-400 cm(-1). The computational vibrational wavenumbers and also ground state equilibrium conformations were carried out by using density functional method with 6-311++G(d,p) basis set. Assignments of the fundamental vibrational modes were examined on the basis of the measured data and total energy distribution (TED) of the vibrational modes, calculated with scaled quantum mechanical (SQM) method. Isotropic chemical shift of hydrogen and carbon nuclei were investigated via observed (1)H and (13)C NMR spectra in deuterated DMSO solution and predicted data applied with gauge-invariant atomic orbitals (GIAOs) method. The UV absorption spectra of monomers were observed in the range of 200-800 nm in ethanol, and time dependent DFT method was used to obtain the electronic properties. A detailed description of spectroscopic behaviors of compound was given based on the comparison of experimental measurements and theoretical computations. PMID:23608133

Cinar, Mehmet; Ozcan, Levent; Karabacak, Mehmet; Erol, Ibrahim

2013-07-01

149

Synthesis, conformational and spectroscopic characterization of monomeric styrene derivatives having pendant p-substituted benzylic ether groups  

NASA Astrophysics Data System (ADS)

Three derivatives of styrene monomer, 4-chlorophenyl-4-vinylbenzyl ether (I), 4-methoxyphenyl-4-vinylbenzyl ether (II) and 4-ethylphenyl-4-vinylbenzyl ether (III) were synthesized. The synthesized two novel compounds (I and III) and one with undefined structural features were identified by experimental spectroscopic techniques and density functional approach. The optimized geometrical structure, vibrational and electronic transitions along with chemical shifts of those compounds were presented in this study. The vibrational spectra of investigated compounds were recorded in solid state with FT-IR spectrometry in the range of 4000-400 cm-1. The computational vibrational wavenumbers and also ground state equilibrium conformations were carried out by using density functional method with 6-311++G(d,p) basis set. Assignments of the fundamental vibrational modes were examined on the basis of the measured data and total energy distribution (TED) of the vibrational modes, calculated with scaled quantum mechanical (SQM) method. Isotropic chemical shift of hydrogen and carbon nuclei were investigated via observed 1H and 13C NMR spectra in deuterated DMSO solution and predicted data applied with gauge-invariant atomic orbitals (GIAOs) method. The UV absorption spectra of monomers were observed in the range of 200-800 nm in ethanol, and time dependent DFT method was used to obtain the electronic properties. A detailed description of spectroscopic behaviors of compound was given based on the comparison of experimental measurements and theoretical computations.

Cinar, Mehmet; Ozcan, Levent; Karabacak, Mehmet; Erol, Ibrahim

2013-07-01

150

Soft X-ray absorption spectroscopic studies with different probing depths: Effect of an electrolyte additive on electrode surfaces  

NASA Astrophysics Data System (ADS)

A solid electrolyte interphase (SEI) formed on a model LiCoO2 electrode was analyzed by the ultra-soft X-ray absorption spectroscopy (XAS). The data of Li K-, B K-, C K-, O K-, and Co L-edges spectra for the SEI film on the electrode were collected using three detection methods with different probing depths. The electrode was prepared by a pulsed laser deposition method. All the spectral data consistently indicated that the SEI film containing lithium carbonate was instantly formed just after the soak of the electrode into the electrolyte solution and that it decomposed during the repeated charge-discharge reactions. The decomposition of the SEI film seems to cause the deterioration in lithium ion battery cycle performance. By adding lithium bis(oxalate) borate (LiBOB) to the electrolyte the decomposition could be suppressed leading to longer cycle life. It was found that some of the Co ions at the electrode surface were reduced to Co(II) during the charge-discharge reactions and this reaction could also be suppressed by the addition of LiBOB.

Yogi, Chihiro; Takamatsu, Daiko; Yamanaka, Keisuke; Arai, Hajime; Uchimoto, Yoshiharu; Kojima, Kazuo; Watanabe, Iwao; Ohta, Toshiaki; Ogumi, Zenpachi

2014-02-01

151

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

SciTech Connect

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.

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

1999-01-15

152

X-ray absorption and X-ray photoelectron spectroscopic study of arsenic mobilization during mackinawite (FeS) oxidation.  

PubMed

In this study we investigated the speciation of the solid-phase As formed by reacting 2 x 10(-4) M As(III) with 1.0 g/L mackinawite and the potential for these sorbed species to be mobilized (released into the aqueous phase) upon exposure to atmospheric oxygen at pH 4.9, 7.1, and 9.1. Before oxygen exposure, X-ray absorption spectroscopy (XAS) and X-ray photoelectron spectroscopy (XPS) analyses indicated that As(III) was removed from the aqueous phase by forming As(0), AsS, and surface precipitates as thioarsenites at pH 4.9 and As(0) and thioarsenite surface precipitates at pH 7.1 and 9.1. When oxygen was introduced, XAS analysis indicated that As(0) and the surface precipitates were quickly transformed, whereas AsS was persistent. During intermediate oxygen exposure times, dissolved As increased at pH 4.9 and 7.1 due to the rapid oxidation of As(0) and the slow precipitation of iron (oxyhydr)oxides, the oxidation products of mackinawite. This indicates that oxidative mobilization is a potential pathway for arsenic contamination of water at acidic to neutral pH. The mobilized As was eventually resorbed by forming edge-sharing and double-corner-sharing surface complexes with iron (oxyhydr)oxides. PMID:20041638

Jeong, Hoon Y; Han, Young-Soo; Hayes, Kim F

2010-02-01

153

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

NASA Astrophysics Data System (ADS)

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.

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

2013-06-01

154

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

SciTech Connect

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.

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

2012-01-01

155

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

NASA Astrophysics Data System (ADS)

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

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

2011-11-01

156

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

SciTech Connect

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

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

2011-11-07

157

Nuclear magnetic resonance and optical absorption spectroscopic studies on paramagnetic praseodymium(III) complexes with ?-diketone and heterocyclic amines  

NASA Astrophysics Data System (ADS)

The optical absorption spectra of [Pr(acac) 3(H 2O) 2]·H 2O, [Pr(acac) 3phen·H 2O] and [Pr(acac) 3bpy] (where acac is the anion of acetylacetone, phen is 1,10-phenanthroline and bpy is 2,2'-bipyridyl) have been analyzed in the visible region in a series of non-aqueous solvents (methanol, ethanol, isopropanol, chloroform, acetonitrile and pyridine). The complexes display four non-hypersensitive 4f-4f transitions ( 3P 2, 3P 1 + 1I 6, 3P 0 and 1D 2) from the 3H 4 ground state. The band shape of the transitions shows remarkable changes upon dissolving in different solvents. Distinctively different band shapes have been observed for phen and bpy complexes. The phen is more effective in producing changes and the splitting of the bands is more pronounced in phen complex since it is a stronger ligand and leads to stronger Pr-N(phen) bond. The splitting of the bands is indicative of partaking of f-orbitals in bonding. The NMR signals of heterocyclic amines have been shifted to high fields while the resonances due to acetylacetone moiety have moved to low fields which is the consequence of change in geometry of the complexes upon coordination of the heterocyclic amines and reflects the importance of geometric factor (3 cos 2? - 1) in changing sign of the shift and to a good approximation the shifts arise predominantly from the dipolar mechanism. The phen complexes have narrower line width than bpy complexes. The line broadening in the case of bpy complexes is suggestive of exchange between inter-converting forms. The bpy possesses some degree of rotational freedom about C(6)-C(6') bond and the two pyridine rings undergo scissoring motion with respect to each other.

Ansari, A. A.; Ahmed, Zubair; Iftikhar, K.

2007-09-01

158

Spectroscopic and electrochemical characterization of the [NiFeSe] hydrogenase from Desulfovibrio vulgaris Miyazaki F: reversible redox behavior and interactions between electron transfer centers.  

PubMed

Characterizing a new hydrogenase: The newly isolated [NiFeSe] hydrogenase from Desulfovibrio vulgaris Miyazaki F displays catalytic properties distinct from other hydrogenase proteins. Here we apply site-specific spectroscopic and electrochemical techniques to characterize these unique features at the molecular level. PMID:24038675

Riethausen, Jana; Rüdiger, Olaf; Gärtner, Wolfgang; Lubitz, Wolfgang; Shafaat, Hannah S

2013-09-23

159

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)

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.

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

2012-11-01

160

Thermal and spectroscopic characterization of Mg(II) complexes of nitro-substituted benzoic acids  

Microsoft Academic Search

The Mg(II) complexes of the nitro-substituted benzoic acids have been investigated by thermal and spectroscopic methods. Thermogravimetry (TG), differential thermal analysis (DTA), differential scanning calorimetry (DSC), and other spectroscopic methods have been used to investigate the thermal behavior and structure of the compounds [Mg(H2O)6](4-nba)2·2H2O 1, [Mg(H2O)6](3-nba)2·2H2O 2, [Mg(H2O)6](2-nba)2·2H2O 3 (4-nba=para-nitrobenzoate; 3-nba=meta-nitrobenzoate; and 2-nba=ortho-nitrobenzoate). All the complexes are formulated as consisting

B. R. Srinivasan; Sarvesh C. Sawant

2003-01-01

161

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

Microsoft Academic Search

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

B. R. Strohmeier; D. M. Hercules

1094-01-01

162

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

SciTech Connect

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.

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

2014-01-01

163

Self-Assembling of Redox-Active Atrazine Poly(ethylenimine) Conjugates – Interfacial Electrochemical and Spectroscopic Characterization  

Microsoft Academic Search

Thin films of polymers tethered with both atrazine haptens and ferrocenyl (Fc) probes were formed on polycrystalline gold electrodes by taking advantage of the facile formation of self-assembled monolayers (SAMs) of thiolates. These films were characterized by polarization modulation Fourier transform infrared reflection - absorption spectrometry (PM-IRRAS), X-ray photoelectron spectroscopy (XPS) and cyclic voltammetry. The combination of these techniques gave

Zhaohui Chen; Michèle Salmain; Claire-Marie Pradier; Nathalie Fischer-Durand; Alain Pailleret; Fethi Bedioui; Sandrine Zannae

2006-01-01

164

Spectroscopic characterization of reaction centers of the (M)Y210W mutant of the photosynthetic bacterium Rhodobacter sphaeroides  

Microsoft Academic Search

The tyrosine-(M)210 of the reaction center of Rhodobacter sphaeroides 2.4.1 has been changed to a tryptophan using site-directed mutagenesis. The reaction center of this mutant has been characterized by low-temperature absorption and fluorescence spectroscopy, time-resolved sub-picosecond spectroscopy, and magnetic resonance spectroscopy. The charge separation process showed bi-exponential kinetics at room temperature, with a main time constant of 36 ps and

Susana Shochatl; Thomas Arlt; Christof Franckel; Peter Gastl; Paula I. van Noortl; Stephan C. M. Otte; Hans P. M. Schelvis; Stefan Schmidt; Erik Vijgenboom; Jacobien Vrieze; Wolfgang Zinth; Arnold J. Hoff

1994-01-01

165

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

PubMed

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

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

2010-08-01

166

The PtAl- and PtAl2- anions: Theoretical and photoelectron spectroscopic characterization  

NASA Astrophysics Data System (ADS)

We report a joint photoelectron spectroscopic and theoretical study of the PtAl- and PtAl2- anions. The ground state structures and electronic configurations of these species were identified to be C?v, 1?+ for PtAl-, and C2v, 2B1 for PtAl2-. 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.

Zhang, Xinxing; Ganteför, Gerd; Bowen, Kit H.; Alexandrova, Anastassia N.

2014-04-01

167

X-ray Absorption Spectroscopic and Theoretical Studies on (L)2[Cu2(S2)n]2+ Complexes: Disulfide Versus Disulfide(o1-) Bonding  

PubMed Central

Cu K-, L- and S K-edge X-ray absorption spectroscopic (XAS) data have been combined with density functional theory (DFT) calculations on [{(TMPA)Cu}2S2](ClO4)2 (1), [{Cu[HB(3,5-Pri2pz)3]}2(S2)] (2) and [{(TMEDA)Cu}2(S2)2](OTf)2 (3) to obtain a quantitative description of their ground state wavefunctions. The Cu L-edge intensities give 63% and 37% Cu d-character in the ground state of 1 and 2, respectively while the S K-pre-edge intensities reflect 20% and 48% S character in their ground states. These data indicate a more than two-fold increase in the total disulfide bonding character in 2 relative to 1. The increase in the number of Cu-S bonds in 2 (µ-?2:?2 S22? bridge) compared to 1 ((µ-?1:?1 S22? bridge), dominantly determines the large increase in covalency and Cu-disulfide bond strength in 2. Cu K- and L- and S K-pre-edge energy positions directly demonstrate the CuII/(S2?)2 nature of 3. The two disulfide(•1?)’s in 3 undergo strong bonding interactions which destabilize the resultant filled antibonding ?* orbitals of the (S2?)2 fragment relative to the Cu 3d levels. This leads to an inverted bonding scheme in 3 with dominantly ligand based holes in its ground state, consistent with its description as a dicopper(II)-bis-disulfide(•1?) complex. PMID:18076173

Sarangi, Ritimukta; York, John T.; Helton, Matthew E.; Fujisawa, Kiyoshi; Karlin, Kenneth D.; Tolman, William B.; Hodgson, Keith O.; Hedman, Britt; Solomon, Edward I.

2008-01-01

168

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

SciTech Connect

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.

N Ramaswamy; R Allen; S Mukerjee; Y

2011-12-31

169

Growth and spectroscopic characterization of Pb2+:CaF2 crystals  

NASA Astrophysics Data System (ADS)

CaF2 crystals doped with various concentrations of PbF2 (0.4, 0.5, 1 and 2 mol%) were grown in vacuum, in a shaped graphite furnace using the vertical Bridgman method. The optical absorption spectra reveal the four characteristic UV absorption bands (labeled A, B, C and D) of the Pb2+ ions. As the PbF2 concentration increases, the structure of the bands become clearly visible, that is characteristic for the ns 2 ions in various hosts. High intensity emission bands in the near UV spectral region have been observed. The dependence on the Pb2+ concentration of the optical absorption and emission of the Pb2+:CaF2 crystals were not reported before.

Nicoara, I.; Paraschiva, M.; Stef, M.; Stef, F.

2012-08-01

170

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

Microsoft Academic Search

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

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

2008-01-01

171

Spectroscopic effects resulting from interacting singlet and triplet excited states: vibronic structure involving the O-H stretching mode in d-d absorption bands of Ni(H2O)6(2+).  

PubMed

The ligand-field absorption spectrum of the Ni(H2O)6(2+) cation has been thoroughly measured and analyzed over the past sixty years, often on crystals with low symmetry at the metal site, and its absorption band maxima have been used as a benchmark for increasingly sophisticated electronic structure calculations over the last decades. We present variable-temperature absorption spectra measured on crystals with cubic Th symmetry at the site of the nickel(ii) cation. This high site symmetry is confirmed for CsNi(H2O)6PO4 by X-ray diffraction and allows for a direct comparison with ligand-field calculations in Th symmetry, at the basis of an analysis of the vibronic structure in the energy range of the lowest-energy spin-forbidden transition, the "red" or middle band of the spectrum. This spectroscopic region displays effects of strong interactions between singlet and triplet excited states, influencing intensities and vibronic structure. A particular feature that has not been analyzed in detail is a clearly discernible vibronic progression involving the O-H stretching mode on the high-energy side of the absorption band. A quantitative model is presented and applied in order to rationalize this unusual effect, originating from coupling between normal coordinates, to the best of our knowledge the first analysis of this distinct spectroscopic feature arising from interacting excited states. PMID:25311941

Dobe, Christopher; González, Emmanuel; Tregenna-Piggott, Philip L W; Reber, Christian

2014-11-12

172

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)

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.

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

2014-01-01

173

Studies related to Norway spruce galactoglucomannans: chemical synthesis, conformation analysis, NMR spectroscopic characterization, and molecular recognition of model compounds.  

PubMed

Galactoglucomannan (GGM) is a polysaccharide mainly consisting of mannose, glucose, and galactose. GGM is the most abundant hemicellulose in the Norway spruce (Picea abies), but is also found in the cell wall of flax seeds, tobacco plants, and kiwifruit. Although several applications for GGM polysaccharides have been developed in pulp and paper manufacturing and the food and medical industries, attempts to synthesize and study distinct fragments of this polysaccharide have not been reported previously. Herein, the synthesis of one of the core trisaccharide units of GGM together with a less-abundant tetrasaccharide fragment is described. In addition, detailed NMR spectroscopic characterization of the model compounds, comparison of the spectral data with natural GGM, investigation of the acetyl-group migration phenomena that takes place in the polysaccharide by using small model compounds, and a binding study between the tetrasaccharide model fragment and a galactose-binding protein (the toxin viscumin) are reported. PMID:23008171

Ekholm, Filip S; Ardá, Ana; Eklund, Patrik; André, Sabine; Gabius, Hans-Joachim; Jiménez-Barbero, Jesús; Leino, Reko

2012-11-01

174

Characterization of the SEI on a carbon film electrode by combinedEQCM and spectroscopic ellipsometry  

SciTech Connect

The electrochemical quartz crystal microbalance (EQCM) andcyclic voltammetry have been applied simultaneously to characterizeelectron-beam deposited carbon film electrodes in LiClO4 orLiPF6-containing mixed electrolytes of ethylene carbonate (EC) anddimethyl carbonate (DMC). The structure of the carbon electrode was foundto be amorphous/disordered using Raman spectroscopy. Cyclic voltammetryin LiClO4 / EC+DMC demonstrated features typical of Liintercalation/deintercalation into/from the disordered carbon electrode,and EQCM showed a corresponding mass increase/decrease. Contrary to thecase of LiClO4 / EC+DMC electrolyte, LiPF6/EC+DMC electrolyte showed noLi deintercalation out of the thin-film carbon electrode. Combined EQCMand spectroscopic ellipsometry data were compared, and the solidelectrolyte interphase density after the first cycle in LiClO4 /EC+DMCwas estimated to be 1.3 g/cm3.

evans@socrates.berkeley.edu

2002-01-01

175

Characterization of Arsenic Ultra-Shallow Junctions in Silicon Using Photocarrier Radiometry and Spectroscopic Ellipsometry  

NASA Astrophysics Data System (ADS)

Photocarrier radiometry (PCR) and spectroscopic ellipsometry (SE) techniques were employed to measure ultra-shallow junction (USJ) wafers. These USJ wafers were prepared by As+ ion implantation at energies of 0.5 keV to 5 keV, at a dose of 1 × 1015 As+/cm2 and spike annealing. The experimental data showed that the PCR signal versus implantation energy exhibits a monotonic behavior. The damaged layer of the as-implanted wafer and the recrystallization and activation of the post-annealed wafer were evaluated by SE in the spectral range from 0.27 ?m to 20 ?m. PCR and SE were shown to provide non-destructive metrology tools for process monitoring in USJ fabrication.

Huang, Qiuping; Li, Bincheng; Gao, Weidong

2012-11-01

176

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

NASA Astrophysics Data System (ADS)

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

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

2013-07-01

177

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

NASA Astrophysics Data System (ADS)

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.

Gupta, Lokesh Kumar

2012-11-01

178

Spectroscopic characterization of the oligomeric surface structures on polyamide materials formed during accelerated aging.  

PubMed

Crystalline surface species were observed at the surface of polyamide 12 materials upon accelerated aging. After detection of the depositions with scanning electron microscopy (SEM), the crystalline surface precipitations were analyzed with Fourier transform infrared (FT-IR) and Raman imaging microscopy. These surface species were supposed to be cyclic oligomers (dimer and trimer) of the PA12 monomer laurolactam, which are usually present in polyamide materials and tend to migrate to the surface when the material is subjected to accelerated aging. The evidence for the chemical identity of the crystalline surface structures to be mainly the cyclic dimer and trimer of laurolactam was given by melting-point identification and mass spectroscopic analysis of the methanol eluate of the surface. The Raman and FT-IR spectra of the mixture were extracted from the recorded images. PMID:21986073

Chernev, Boril S; Eder, Gabriele C

2011-10-01

179

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

NASA Astrophysics Data System (ADS)

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

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

2004-09-01

180

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

SciTech Connect

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.

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

2004-12-13

181

Cyclodextrins as carriers for kavalactones in aqueous media: spectroscopic characterization of (S)-7,8-dihydrokavain and beta-cyclodextrin inclusion complex.  

PubMed

Kavalactones represent the active constituents of kava-kava (Piper methysticum G. Forster), endowed with sedative and anaesthetic properties. Kavalactones are polar constituents, but poorly soluble in water with a low bioavailability. In this study, the formation of inclusion complexes of one of the most representative kavalactone isolated from kava-kava extract, (S)-7,8-dihydrokavain (DHK), with beta-cyclodextrin (beta-CyD) was investigated mainly by spectroscopic methods. NMR experiments were extensively used for the complete characterization of the complex and included (1)H NMR complexation shifts analysis, (1)H NMR diffusion measurements (DOSY), and ROESY experiments. In particular DOSY experiments demonstrated that in the presence of beta-CyD the translational diffusion of kavalactone is sizably slowed down (2.5x10(-10)m(2)/s) with respect to the free drug (4.4x10(-10)m(2)/s) according to the inclusion of DHK in the cavity of (beta-CyD). ROESY experiments confirmed the inclusion of DHK in the hydrophobic pocket of beta-CyD through the primary hydroxyl rim, being the most relevant interactions between the H3' of beta-CyD and the ortho protons on the phenyl ring of the DHK, and between H5' of beta-CyD and the meta/para protons of DHK phenyl ring. The inclusion of the phenyl ring of DHK, leaving the lactone moiety outside of CyD was also confirmed by the induced CD effects. The binary solution DHK/beta-CyD shows a 50% intensity increase of the negative band of the pi-pi* transitions of the phenyl ring with respect to the absorption observed with DHK alone. Molecular dynamics simulations results corroborated and further clarify observed spectroscopic data. It was found that the phenylethyl substituent at C6 has a preferential equatorial position in the free state, and an axial one in the complex, justifying the large downfield shift experienced by H6 of DHK upon binding. Finally the influence of beta-CyD on water solubility of DHK was investigated by phase-solubility studies. In the range 2-4mM of host, solubility of DHK was increased only two-fold, but being beta-CyD also a penetration enhancer, in vivo studies will be performed to clarify a possible role of the complex on the bioavailability of DHK. PMID:20185265

Pescitelli, G; Bilia, A R; Bergonzi, M C; Vincieri, F F; Di Bari, L

2010-08-01

182

Spectroscopic characterization of chromium (IV, V, VI) in Cr:Li2MSiO4 (M=Mg,Zn)  

NASA Astrophysics Data System (ADS)

To understand the exceptionally long fluorescence lifetime of CrIV in Li2MSiO4 (M=Mg,Zn), several spectroscopic investigations are performed on Cr:Li2MSiO4 (M=Mg,Zn) crystals. X-ray absorption near-edge structure investigations attest that chromium is localized in tetrahedral sites and that CrVI is the major species while CrIV is the minor one in both compounds. Electron paramagnetic resonance studies confirm the occurrence of CrV in elongated tetrahedral environment (dx2-y2 ground state), corresponding probably to the silicon site, and suggest the presence of several charge compensation schemes. Fluorescence and fluorescence dynamics of CrIV:Li2MSiO4 are reported. The very long CrIV excited state lifetime previously observed on powders samples is confirmed for the crystals (117 ?s at room temperature, 305 ?s at 30 K for Cr:Li2MgSiO4) and is explained by combined contributions to the emission from both 1E level and the lowest component of the 3T2 level, in thermal equilibrium. Contrary to the situation found in most CrIV activated compounds, the 1E level lies below the 3T2 one.

Jousseaume, C.; Vivien, D.; Kahn-Harari, A.; Derouet, J.; Ribot, F.; Villain, F.

2003-05-01

183

Characterization of gastrointestinal absorption of digoxin involving influx and efflux transporter in rats: application of mdr1a knockout (-/-) rats into absorption study of multiple transporter substrate.  

PubMed

Abstract 1.? This study was aimed to characterize gastrointestinal absorption of digoxin using wild-type (WT) and multidrug resistance protein 1a [mdr1a; P-glycoprotein (P-gp)] knockout (-/-) rats. 2.? In WT rats, the area under the plasma concentration-time curve (AUC) of oral digoxin increased after oral pretreatment with quinidine at 30?mg/kg compared with non-treatment, but the increasing ratio tended to decrease at a high dose of 100?mg/kg. In mdr1a (-/-) rats, however, quinidine pretreatment caused a dose-dependent decrease in the AUC. 3.? Quinidine pretreatment did not alter the hepatic availability of digoxin, indicating that the changes in the digoxin AUC were attributable to inhibition of the absorption process by quinidine; i.e. inhibition of influx by quinidine in mdr1a (-/-) rats and inhibition of efflux and influx by quinidine in WT rats. 4.? An in situ rat intestinal closed loop study using naringin implied that organic anion transporting peptide (Oatp) 1a5 may be a responsible transporter in the absorption of digoxin. 5.? These findings imply that the rat absorption behavior of digoxin is possibly governed by Oatp1a5-mediated influx and P-gp-mediated efflux. The mdr1a (-/-) rat is therefore a useful in vivo tool to investigate drug absorption associated with multiple transporters including P-gp. PMID:24839994

Suzuki, Motoya; Komura, Hiroshi; Yoshikawa, Tomonori; Enya, Seiji; Nagao, Akemi; Takubo, Hiroaki; Kogayu, Motohiro

2014-11-01

184

Spectroscopic characterization of oils yielded from Brazilian offshore basins: Potential applications of remote sensing  

Microsoft Academic Search

Spectroscopy is the basis to detect and characterize offshore hydrocarbon (HC) seeps through optical remote sensing. Diagnostic spectral features of HCs are linked to their chemical composition and fundamental molecular vibrations (SWIR-TIR features), as well as overtones and combinations of these vibrations (VNIR-SWIR). These features allow for the characterization of oil, oil on water and emulsified oil. This work shows

Talita Lammoglia; Carlos Roberto de Souza Filho

2011-01-01

185

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

NASA Astrophysics Data System (ADS)

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 ? <~ 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 lang?0.3rang ? 70% for absorbers of Wr (2796) >= 0.3 Å and lang?0.1rang ? 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.

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

2010-05-01

186

Spectroscopic characterization of the alkylated alpha-sarcin cytotoxin: analysis of the structural requirements for the protein-lipid bilayer hydrophobic interaction.  

PubMed

alpha-Sarcin is a ribosome-inactivating protein that translocates across lipid bilayers, these two abilities explaining its cytotoxic character. This protein is composed of a single polypeptide chain with two disulfide bridges. Reduction and carboxyamidomethylation of alpha-sarcin results in protein unfolding, based on the results of the spectroscopic characterization of the chemically modified protein. The absorption and fluorescence emission bands of the tryptophan residues of the modified protein appear blue- and red-shifted, respectively. Far-UV circular dichroism analysis reveals the presence of residual secondary structure (beta-strands and turns) in the alkylated protein. This retains its ability to interact with lipid bilayers. It promotes vesicle aggregation, lipid-mixing between bilayers and leakage of the intravesicular aqueous contents. The modified protein tends to abolish the phase transition of acid phospholipids as detected by differential scanning calorimetry and depolarization measurements of fluorescence-labelled vesicles. The protein gain access to vesicle-entrapped trypsin. The fluorescence emission of the tryptophan residues is blue-shifted upon interaction of the protein with the bilayers, and anthracene incorporated into the hydrophobic core of the membranes quenches the tryptophan fluorescence emission of the protein. The secondary structure of the alkylated protein interacting with lipid vesicles has been studied by infrared spectroscopy. An increase in the alpha-helix and turn contents and a concomitant decrease in the beta-structure content are observed upon interaction with the bilayers. The results obtained are discussed in terms of the structural requirements for the interaction of alpha-sarcin with lipid membranes. PMID:7548165

Gasset, M; Mancheño, J M; Lacadena, J; Martinez del Pozo, A; Oñaderra, M; Gavilanes, J G

1995-09-27

187

[FTIR spectroscopic characterization of chromium-induced changes in root cell wall of plants].  

PubMed

Due to its wide industrial use, chromium is considered a serious environmental pollutant. Contamination of soil and water by chromium (Cr) is of recent concern. Chromium mainly accumulates in root in plants, and the change in compounds of the root cell wall have a close relation with the Cr accumulation. Compared with the other identification methods, the identification of the Chinese traditional and herbal drugs using Fourier transform infrared spectrometer with OMNI collector is simple and convenient, fast and accurate. In the present paper, the spectra of cell wall of Cr-treated root and control of Eichhornia crassipes and Alternanthera philoxeroides were determined. Absorption peaks were identified to the corresponding functional groups and half-quantitative analysis was also used. The results showed that a significant shift of -OH absorption peaks can be seen when comparing the FTIR spectra of control and Cr-treated plants, and the absorbency of -OH and COO- groups went up in E. crassipes root cell wall while droped in A. philoxeroides root cell wall. It is suggested that -OH and COO groups were referred in binding Cr6+ in aqueous solutions, and this may be included in the mechanism of Cr accumulation in E. crassipes roots. Therefore, FTIR spectrometry could be widely used to monitor changes in chemical composition of plant parts under stresses and environmental restoration. PMID:18720803

Zhang, Xiao-Bin; Liu, Peng; Li, Dan-Ting; Xu, Gen-Di; Jiang, Min-Jiao

2008-05-01

188

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

PubMed

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

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

2008-09-01

189

Absorption in the Cosmic Web: Characterizing the Intergalactic Medium in Cosmological Filaments  

NASA Astrophysics Data System (ADS)

We propose to observe and characterize the IGM associated with cosmological filaments in a statistical manner up to redshift ~0.4. For this purpose, we have used a published cluster catalog (Hao et al. 2010) to identify massive nodes in the cosmic web. We used cluster-pairs separated by < 20 Mpc (transverse) and < 2000 km/s (along the LOS) to identify zones where filaments should reside with high probabilities. We have selected a single QSO whose sightline passess through a total of 9 independent cluster-pairs (8 of which having spectroscopic redshifts) at impact parameters <10 Mpc (7 of which at < 5 Mpc). We propose to observe the QSO with HST/COS using the G130M and G160M gratings to cover the full FUV spectral range at medium resolution (R~20000). We require observations at S/N>10 to ensure a full characterization of HI and OVI lines at column densities N~10^13 cm^-2. This setup will allow us to detect broad and shallow HI and OVI lines (if any) at the redshifts of these filaments, believed to trace portions of the warm-hot intergalactic medium (WHIM). Combining these new observations with those from our pilot study carried out in cycle 20 (ID 12958, PI Tejos), we aim to provide a firm detection of the WHIM in cosmological filaments, at the 95% confidence level. Our findings will test our understanding of galaxy formation and the role of AGN/supernova feedback by comparing them with state-of-the-art hydrodynamical simulations. We will also test the the hypothesis which states that the majority of OVI absorbers at low-z are confined within <300 kpc from galaxies (i.e. circumgalactic medium) thus not related to the WHIM (Prochaska et al. 2011; Tumlinson et al. 2011).

Tejos, Nicolas

2014-10-01

190

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

NASA Astrophysics Data System (ADS)

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.

Luo, Juhua; Xu, Yang; Gao, Duoduo

2014-11-01

191

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

PubMed

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

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

2015-01-25

192

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

PubMed

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, (1)H-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, (1)H-NMR, and IR suggested the transformation from free base porphyrin to indium(III) porphyrin. Besides, (13)C-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

Bajju, Gauri D; Ahmed, Altaf; Gupta, Deepmala; Kapahi, Ashu; Devi, Gita

2014-01-01

193

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

SciTech Connect

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.

Huang, Chun-Chao; Chang, Shu-Jui; Yang, Chao-Yao; Tseng, Yuan-Chieh [Department of Materials Science and Engineering, National Chiao Tung University, Hsinchu, Taiwan (China)] [Department of Materials Science and Engineering, National Chiao Tung University, Hsinchu, Taiwan (China); Chou, Hsiung [Department of Physics, National Sun Yat-sen University, Kaohsiung, Taiwan (China)] [Department of Physics, National Sun Yat-sen University, Kaohsiung, Taiwan (China)

2013-12-15

194

Spectroscopic and molecular characterization of the oligomeric antenna of the diatom Phaeodactylum tricornutum.  

PubMed

The photosynthetic antenna system of diatoms contains fucoxanthin chlorophyll a/c binding proteins (FCPs), which are membrane intrinsic proteins showing high homology to the light harvesting complexes (LHC) of higher plants. In the present study, we used a mild solubilization of P. tricornutum thylakoid membranes in combination with sucrose density gradient centrifugation or gelfiltration and obtained an oligomeric FCP complex (FCPo). The spectroscopic characteristics and pigment stoichiometries of the FCPo complex were comparable to FCP complexes that were isolated after solubilization with higher detergent per chlorophyll ratios. The excitation energy transfer between the FCP-bound pigments was more efficient in the oligomeric FCPo complexes, indicating that these complexes may represent the native form of the diatom antenna system in the thylakoid membrane. Determination of the molecular masses of the two different FCP fractions by gelfiltration revealed that the FCP complexes consisted of trimers, whereas the FCPo complexes were either composed of six monomers or two tightly associated trimers. In contrast to vascular plants, stable functional monomers could not be isolated in P. tricornutum. Both types of FCP complexes showed two protein bands in SDS-gels with apparent molecular masses of 18 and 19 kDa, respectively. Sequence analysis by MS/MS revealed that the 19 kDa protein corresponded to the fcpC and fcpD genes, whereas the 18 kDa band contained the protein of the fcpE gene. The presence of an oligomeric antenna in diatoms is in line with the oligomeric organization of antenna complexes in different photoautotrophic groups. PMID:17672483

Lepetit, Bernard; Volke, Daniela; Szabó, Milán; Hoffmann, Ralf; Garab, Gyözö; Wilhelm, Christian; Goss, Reimund

2007-08-28

195

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

NASA Astrophysics Data System (ADS)

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.

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

2014-09-01

196

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

PubMed

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

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

2014-09-14

197

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

NASA Astrophysics Data System (ADS)

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.

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

2011-12-01

198

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

PubMed

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 SiOSi bond angles and bond lengths. Moreover, deconvolution of the IR-active antisymmetric SiOSi 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. PMID:24992921

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

2014-12-10

199

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

Microsoft Academic Search

Raman, infrared and X-ray photoelectron spectroscopies were used to characterize the thick coating of reaction products on carbon and MnO2 coated carbon cathodes produced during discharge of Li-air cells. The results show that neither Li2O2 or Li2O are major components of the insoluble discharge products; instead the products are largely composed of fluorine, lithium, and carbon, with surprisingly little oxygen.

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

2011-01-01

200

Accurate Spectroscopic Characterization of Ethyl Mercaptan and Dimethyl Sulfide Isotopologues: A Route toward their Astrophysical Detection  

NASA Astrophysics Data System (ADS)

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.

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

2014-11-01

201

Spectroscopic Characterization of Intermediates in the Iron Catalyzed Activation of Alkanes  

SciTech Connect

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.

Edward M. Eyring

2007-05-28

202

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

SciTech Connect

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

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

2006-06-21

203

AN EMPIRICAL CHARACTERIZATION OF EXTENDED COOL GAS AROUND GALAXIES USING Mg II ABSORPTION FEATURES  

SciTech Connect

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 (z) = 0.24 in fields around 70 distant background QSOs (z{sub QSO} > 0.6), 71 of which are in an 'isolated' environment with no known companions and located at {rho} {approx_lt} 120 h {sup -1} kpc from the line of sight of a background QSO. The rest-frame absolute B-band magnitudes span a range from M{sub B} - 5log h = -16.4 to M{sub B} - 5log h = -21.4 and rest-frame B{sub AB} - R{sub AB} colors range from B{sub AB} - R{sub AB} {approx} 0 to B{sub AB} - R{sub AB} {approx} 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 W{sub r} (2796) = 0.1-2.34 A, and 24 do not give rise to Mg II absorption to sensitive upper limits. Our analysis shows that (1) W{sub r} (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{sub gas} = 75 x (L{sub B} /L{sub B{sub *}}){sup (0.35{+-}0.03)} h {sup -1} kpc; (3) there is little dependence between the observed absorber strength and galaxy intrinsic colors; and (4) within R{sub gas}, we find a mean covering fraction of ({kappa}{sub 0.3}) {approx} 70% for absorbers of W{sub r} (2796) {>=} 0.3 A and ({kappa}{sub 0.1}) {approx} 80% for absorbers of W{sub r} (2796) {>=} 0.1 A. 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 W{sub r} (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.

Chen, Hsiao-Wen; Helsby, Jennifer E.; Gauthier, Jean-Rene [Department of Astronomy and Astrophysics and Kavli Institute for Cosmological Physics, University of Chicago, Chicago, IL 60637 (United States); Shectman, Stephen A.; Thompson, Ian B. [The Observatories of Carnegie Institution for Science, 813 Santa Barbara St., Pasadena, CA 91101 (United States); Tinker, Jeremy L., E-mail: hchen@oddjob.uchicago.ed [Berkeley Center for Cosmological Physics, University of California-Berkeley, Berkeley, CA (United States)

2010-05-10

204

Spectroscopic characterization of chromite from the Moa-Baracoa Ophiolitic Massif, Cuba  

NASA Astrophysics Data System (ADS)

The Cuban chromites with a spinel structure, FeCr 2O 4 have been studied using optical absorption and EPR spectroscopy. The spectral features in the electronic spectra are used to map the octahedral and tetrahedral co-ordinated cations. Bands due Cr 3+ and Fe 3+ ions could be distinguished from UV-vis spectrum. Chromite spectrum shows two spin allowed bands at 17390 and 23810 cm -1 due to Cr 3+ in octahedral field and they are assigned to 4A 2g(F) ? 4T 2g(F) and 4A 2g(F) ? 4T 1g(F) transitions. This is in conformity with the broad resonance of Cr 3+ observed from EPR spectrum at g = 1.903 and a weak signal at g = 3.861 confirms Fe 3+ impurity in the mineral. Bands of Fe 3+ ion in the optical spectrum at 13700, 18870 and 28570 cm -1 are attributed to 6A 1g(S) ? 4T 1g(G), 6A 1g(S) ? 4T 2g(G) and 6A 1g(S) ? 4T 2g(P) transitions, respectively. Near-IR reflectance spectroscopy has been used effectively to show intense absorption bands caused by electronic spin allowed d -d transitions of Fe 2+ in tetrahedral symmetry, in the region 5000-4000 cm -1. The high frequency region (7500-6500 cm -1) is attributed to the overtones of hydroxyl stretching modes. Correlation between Raman spectral features and mineral chemistry are used to interpret the Raman data. The Raman spectrum of chromite shows three bands in the CrO stretching region at 730, 560 and 445 cm -1. The most intense peak at 730 cm -1 is identified as symmetric stretching vibrational mode, A 1g(? 1) and the other two minor peaks at 560 and 445 cm -1 are assigned to F 2g(? 4) and E g(? 2) modes, respectively. Cation substitution in chromite results various changes both in Raman and IR spectra. In the low-wavenumber region of Raman spectrum a significant band at 250 cm -1 with a component at 218 cm -1 is attributed F 2g(? 3) mode. The minor peaks at 195, 175, 160 cm -1 might be due to E g and F 2g symmetries. Broadening of the peak of A 1g mode and shifting of the peak to higher wavenumber observed as a result of increasing the proportion of Al 3+O 6. The presence of water in the mineral shows bands in the IR spectrum at 3550, 3425, 3295, 1630 and 1455 cm -1. The vibrational spectrum of chromite gives raise to four frequencies at 985, 770, 710 and 650 cm -1. The first two frequencies ? 1 and ? 2 are related to the lattice vibrations of octahedral groups. Due to the influence of tetrahedral bivalent cation, vibrational interactions occur between ? 3 and ? 4 and hence the low frequency bands, ? 3 and ? 4 correspond to complex vibrations involving both octahedral and tetrahedral cations simultaneously. Cr 3+ in Cuban natural chromites has highest CFSE (20,868 cm -1) when compared to other oxide minerals.

Reddy, B. Jagannadha; Frost, Ray L.

2005-06-01

205

UV spectroscopic characterization of an alkyl substituted Criegee intermediate CH3CHOO.  

PubMed

Ozonolysis of alkenes in the troposphere proceeds through a Criegee intermediate, or carbonyl oxide, which has only recently been detected in the gas phase. The present study focuses on the production of an alkyl-substituted Criegee intermediate, CH3CHOO, in a pulsed supersonic expansion, and then utilizes VUV photoionization at 118 nm and UV-induced depletion of the m?z = 60 signal to probe the B (1)A(') ? X (1)A(') transition. The UV-induced depletion approaches 100% near the peak of the profile at 320 nm, indicating rapid dynamics in the B state, and corresponds to a peak absorption cross section of ?5 × 10(-17) cm(2) molecule(-1). The electronic spectrum for CH3CHOO is similar to that reported recently for CH2OO, but shifted 15 nm to shorter wavelength, which will result in a longer tropospheric lifetime for CH3CHOO with respect to solar photolysis. Complementary electronic structure calculations (EOM-CCSD) are carried out for the B and X potentials of these Criegee intermediates along the O-O coordinate. An intramolecular interaction stabilizes the ground state of the syn-conformer of CH3CHOO relative to anti-CH3CHOO, and indicates that the syn-conformer will be the more abundant species in the expansion. The excited B electronic state of syn-CH3CHOO is also predicted to be destabilized relative to that for anti-CH3CHOO and CH2OO, in accord with the shift in the B-X transition observed experimentally. Hydroxyl radicals produced concurrently with the generation of the Criegee intermediates are detected by 1+1(') resonance enhanced multiphoton ionization. The OH yield observed with CH3CHOO is 4-fold larger than that from CH2OO, consistent with prior studies of OH generation from alkene ozonolysis. PMID:23822244

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

2013-06-28

206

UV spectroscopic characterization of an alkyl substituted Criegee intermediate CH3CHOO  

NASA Astrophysics Data System (ADS)

Ozonolysis of alkenes in the troposphere proceeds through a Criegee intermediate, or carbonyl oxide, which has only recently been detected in the gas phase. The present study focuses on the production of an alkyl-substituted Criegee intermediate, CH3CHOO, in a pulsed supersonic expansion, and then utilizes VUV photoionization at 118 nm and UV-induced depletion of the m/z = 60 signal to probe the B 1A' <-- X 1A' transition. The UV-induced depletion approaches 100% near the peak of the profile at 320 nm, indicating rapid dynamics in the B state, and corresponds to a peak absorption cross section of ~5 × 10-17 cm2 molecule-1. The electronic spectrum for CH3CHOO is similar to that reported recently for CH2OO, but shifted 15 nm to shorter wavelength, which will result in a longer tropospheric lifetime for CH3CHOO with respect to solar photolysis. Complementary electronic structure calculations (EOM-CCSD) are carried out for the B and X potentials of these Criegee intermediates along the O-O coordinate. An intramolecular interaction stabilizes the ground state of the syn-conformer of CH3CHOO relative to anti-CH3CHOO, and indicates that the syn-conformer will be the more abundant species in the expansion. The excited B electronic state of syn-CH3CHOO is also predicted to be destabilized relative to that for anti-CH3CHOO and CH2OO, in accord with the shift in the B-X transition observed experimentally. Hydroxyl radicals produced concurrently with the generation of the Criegee intermediates are detected by 1+1' resonance enhanced multiphoton ionization. The OH yield observed with CH3CHOO is 4-fold larger than that from CH2OO, consistent with prior studies of OH generation from alkene ozonolysis.

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

2013-06-01

207

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

PubMed

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

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

2014-08-01

208

Synthesis, spectroscopic, structural characterization, electrochemical and antimicrobial activity studies of the Schiff base ligand and its transition metal complexes  

NASA Astrophysics Data System (ADS)

In this study, the Schiff base ligand trans-N,N'-bis[(2,4-dichlorophenyl) methylidene] cyclohexane-1,2-diamine (L) and its copper(II), nickel(II) and palladium(II) transition metal complexes were prepared and characterized by the analytical and spectroscopic methods. The 1H( 13C) NMR spectra of the ligand and its diamagnetic complexes were recorded in DMSO-d 6 solvent and obtained data confirm that the nitrogen atoms of the imine groups coordinated to the metal ions. Electrochemical properties of the ligand and its metal complexes were investigated in the DMF solvent at the 100 and 250 mV s -1 scan rates. The ligand and metal complexes showed both reversible and irreversible processes at these scan rates. The single crystal of the ligand (L) was obtained from MeOH solution, and its crystal structure was determined by X-ray diffraction. The C-H⋯Cl hydrogen bonding interactions in the molecule were seen which increase the stability of the crystal structure. The antimicrobial activity studies of the ligand and its metal complexes were carried out by using the various bacteria and fungi.

Aslanta?, Mehmet; Kendi, Engin; Demir, Necmettin; ?abik, Ali E.; Tümer, Mehmet; Kertmen, Metin

2009-10-01

209

Spectroscopic and kinetic characterization of the light-dependent enzyme protochlorophyllide oxidoreductase (POR) using monovinyl and divinyl substrates.  

PubMed

The enzyme POR [Pchlide (protochlorophyllide) oxidoreductase] catalyses the reduction of Pchlide to chlorophyllide, which is a key step in the chlorophyll biosynthesis pathway. This light-dependent reaction has previously been studied in great detail but recent reports suggest that a mixture of MV (monovinyl) and DV (divinyl) Pchlides may have influenced some of these properties of the reaction. Low-temperature absorbance and fluorescence spectroscopy have revealed several spectral differences between MV and DV Pchlides, which were purified from a Rhodobacter capsulatus strain that was shown to contain a mixture of the two pigments. A thorough steady-state kinetic characterization using both Pchlide forms demonstrates that neither pigment appears to affect the kinetic properties of the enzyme. The reaction has also been monitored following illumination at low temperatures and was shown to consist of an initial photochemical step followed by four 'dark' steps for both pigments. However, minor differences were observed in the spectral properties of some of the intermediates, although the temperature dependency of each step was nearly identical for the two pigments. This work provides the first detailed kinetic and spectroscopic study of this unique enzyme using biologically important MV and DV substrate analogues. It also has significant implications for the DV reductase enzyme, which is responsible for converting DV pigments into their MV counterparts, and its position in the sequence of reactions that comprise the chlorophyll biosynthesis pathway. PMID:16274361

Heyes, Derren J; Kruk, Jerzy; Hunter, C Neil

2006-02-15

210

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

NASA Astrophysics Data System (ADS)

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.

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

1998-04-01

211

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

PubMed Central

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

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

2009-01-01

212

Spectroscopic and chromatographic characterization of triflusal delivery systems prepared by using supercritical impregnation technologies.  

PubMed

This study describes the development and evaluation of an analytical method for the characterization of triflusal (2-acetoxy-4-(trifluoromethyl) benzoic acid) dispersed in sustained delivery systems prepared using supercritical fluid impregnation technology. Characterization assays comprised the determination of the percentage of triflusal and its degradation product impregnated in polymeric supports and further monitoring of the releases of the two drug components over time in physiological conditions. Preliminary delivery profiles were monitored spectrophotometrically using a continuous-flow system. In this case, no selective wavelength for discriminating between triflusal and metabolite was found so that measurements at 225 nm provided overall profiles corresponding to the two compounds. For a more accurate study, a chromatographic method was developed for monitoring the evolution of the concentration of the two components independently. Triflusal and metabolite were separated in a C(18) column and 25 mM acetic acid/acetate (pH 5.0)+methanol (40/60v/v) mobile phase. Several triflusal-polymer samples were prepared under different experimental conditions and release features were evaluated. Excellent delivery systems were obtained with poly(methyl)methacrylate beads treated at 40 degrees C and 190 bar for 48 h using supercritical carbon dioxide as a solvent. These samples showed a constant sustained release of drug for several weeks. PMID:18093783

Argemí, Anna; López-Periago, Ana; Domingo, Concepción; Saurina, Javier

2008-02-13

213

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

NASA Astrophysics Data System (ADS)

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

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

2009-12-01

214

Doppler-shifted optical absorption characterization of plume-lateral expansion in laser ablation of a cerium target  

NASA Astrophysics Data System (ADS)

The temporal evolution of the ablation plume of cerium was investigated by absorption spectroscopy. Cerium oxide pellets were ablated in a helium atmosphere by second-harmonic radiation (532 nm) from a Nd:YAG laser at a fluence of 0.5 J/cm2. The lateral velocity (expansion velocity horizontal to the sample surface) of the plume was determined from the magnitude of the Doppler splitting of the absorption spectra measured close to the sample surface. The lateral velocities of neutral and singly ionized atoms were systematically investigated by varying several parameters, such as ambient gas pressure, ablation laser fluence, observation timing, and observation height. In addition, temporal profiles of the absorption signal were measured by detuning the probe laser frequency from the atomic resonant frequency in order to obtain the temporal variation of the velocity. On the basis of the drag force model, the slowing coefficients for atomic and ionic species in a helium atmosphere were evaluated along with lateral velocity in a vacuum. This study may help in understanding the plume dynamics effect on deposited film properties as well as optimizing experimental conditions for ablation-based spectroscopic analysis.

Miyabe, M.; Oba, M.; Iimura, H.; Akaoka, K.; Maruyama, Y.; Ohba, H.; Tampo, M.; Wakaida, I.

2012-12-01

215

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

NASA Astrophysics Data System (ADS)

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.

Shahabadi, Nahid; Heidari, Leila

2014-07-01

216

An in situ cell for characterization of solids by soft x-ray absorption Ian J. Drake  

E-print Network

the bulk or near-surface oxidation state of a solid is obtained from either x-ray photoelectronAn in situ cell for characterization of solids by soft x-ray absorption Ian J. Drake Department microchannels. The performance of the cell was tested by acquiring Cu L3-edge x-ray appearance near

Bell, Alexis T.

217

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

NASA Astrophysics Data System (ADS)

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

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

2012-04-01

218

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

PubMed

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

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

2013-03-15

219

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

SciTech Connect

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

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

2011-01-01

220

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

NASA Astrophysics Data System (ADS)

Some mixed sulfur donor ligand complexes of antimony(III) of the general formula [(R 2NCS 2)] 2SbS 2COR' where R = CH 3, C 2H 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 ( 1H and 13C), 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.

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

2011-10-01

221

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

NASA Astrophysics Data System (ADS)

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.

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

2013-03-01

222

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

PubMed

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

Duarte, Luís; Fausto, Rui; Reva, Igor

2014-08-28

223

Optical, laser spectroscopic, and electrical characterization of transion metal doped zinc selenide and zinc sulfide nano-and-microcrystals  

NASA Astrophysics Data System (ADS)

Middle-infrared lasers operating over a "molecular fingerprint" 2-15 mum spectral range are in great demand for a variety of applications. One of the best choices for lasing in the 2-5 mum spectral range is direct oscillation from divalent transition metal ions (TM2+: Cr 2+, Fe2+, Co2+)-doped wide bandgap II-VI semiconductor crystals. There are three major objectives in this dissertation: (1) Realize and study middle-infrared electroluminescence of n and p-type, Cr doped bulk ZnSe crystals. We have demonstrated a method of ZnSe crystals thermal-diffusion doping with donor (In, Zn, and Al) and acceptor (Cu, Ag, and N through CrN) impurities resulting in n and p-type conductivity of Cr:ZnSe. We are the first to our knowledge to obtain mid-IR electroluminescence in nominally p-type Cr:Ag:ZnSe, which could prove valuable for developing of novel mid-IR laser diodes. (2) En route to low dimensional gain material, develop simple method for making microscopic laser active Cr doped ZnSe, ZnS and CdSe powders, realize and study their laser spectroscopic characteristics. We have demonstrated a simple physical method of Cr2+:ZnSe, ZnS and CdSe powder fabrication with average sizes below ˜ 10mum and ˜1mum (eliminating stage of bulk crystal growth) and demonstrated first ever mid-IR random lasing on these powders under optical excitation. In addition, we have examine suspensions and polymer films impregnated with Cr:II-VI powders for random lasing in the mid-IR. The powder, suspension and polymer samples are fabricated and characterized through the measurement of photoluminescence (PL) spectra, PL kinetics, and lasing threshold energy. (3) En route to low dimensional gain material, develop method for making laser active Cr, Co, and Fe doped ZnSe and ZnS quantum dots (QD), realize and study their laser spectroscopic characteristics. We have demonstrated a novel method of TM doped II-VI QDs fabrication based on laser ablation in liquid and Ar environment. TM doped II-VI QDs demonstrated strong mid-IR luminescence. And we also demonstrated the first mid-IR (2-3 mum) random lasing at room temperature of Cr2+:ZnS QD powders. The results obtained in this work open a new pathway for development of low-cost optically and electrically pumped broadly tunable mid-IR laser sources. Keyword: Middle-Infrared lasers, Electroluminescence, Transition Metal ions, powder random lasers, nanocrystal lasers, Polymer film and Suspension.

Kim, Changsu

224

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

PubMed

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

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

2014-03-28

225

The Synthesis, Characterization, Spectroscopic Studies and Catalyst Properties of Some New Dinuclear Uranyl (VI) Metal Complexes Bearing Different vic?Dioxime Groups  

Microsoft Academic Search

The synthesis, characterization and spectroscopic studies of some new dinuclear uranyl (VI) metal complexes prepared from different vic?dioximes ligands and the uranyl acetate metal salt. The structure of these uranyl (VI) metal complexes have been determined as according to elemental analysis, H?NMR spectra, FT?IR spectra, UV?Vis spectra, magnetic susceptibility measurements, melting point and molar conductivity measurements. The metal to ligand

A. Kilic; E. Tas

2007-01-01

226

In-situ characterization of the amorphous to microcrystalline transition in hot wire CVD growth of Si:H using real time spectroscopic ellipsometry  

Microsoft Academic Search

We have used in-situ real-time spectroscopic ellipsometry (RTSE) to characterize the morphology and crystallinity of hot-wire CVD (HWCVD) Si:H films as a function of hydrogen dilution R=[H]\\/[H+SiH4], substrate temperature Ts, and film thickness db. Transitions from one mode of film growth to another are correlated with changes in the magnitude of the surface roughness during growth. The degree of crystallinity

D. H. Levi; B. P. Nelson; J. D. Perkins; H. R. Moutinho

2002-01-01

227

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

NASA Astrophysics Data System (ADS)

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 ?) 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.

Abd El-Wahab, Zeinab H.

2007-05-01

228

Spectroscopic characterization of the molybdenum cofactor of the sulfane dehydrogenase SoxCD from Paracoccus pantotrophus.  

PubMed

The bacterial sulfane dehydrogenase SoxCD is a distantly related member of the sulfite oxidase (SO) enzyme family that is proposed to oxidize protein-bound sulfide (sulfane) of SoxY as part of a multienzyme mechanism of thiosulfate metabolism. This study characterized the molybdenum cofactor of SoxCD1, comprising the catalytic molybdopterin subunit SoxC and the truncated c-type cytochrome subunit SoxD1. Electron paramagnetic resonance spectroscopy of the Mo(V) intermediate generated by dithionite reduction revealed low- and high-pH species with g and A((95,97)Mo) matrices nearly identical to those of SO, indicating a similar pentacoordinate active site in SoxCD1. However, no sulfite-induced reduction to Mo(V) was detected, nor could a strongly coupled (1)H signal or a phosphate-inhibited species be generated. This indicates that the outer coordination sphere controls substrate binding in SoxCD, permitting access only to protein-bound sulfur via the C-terminal tail of SoxY. PMID:21142117

Drew, Simon C; Reijerse, Eduard; Quentmeier, Armin; Rother, Dagmar; Friedrich, Cornelius G; Lubitz, Wolfgang

2011-01-17

229

Synthesis, characterization and spectroscopic investigation of Cr3+ doped wollastonite nanophosphor  

NASA Astrophysics Data System (ADS)

This work explores the preparation of nanocrystalline Cr3+ (1-5 mol%) doped CaSiO3 phosphors by solution combustion process and study of its photoluminescence (PL) behavior. The nanopowders are well characterized by powder X-ray diffraction (PXRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and Fourier transform infra-red (FTIR) spectroscopy. PXRD results confirm monoclinic phase upon calcination at 950 °C for 3 h. SEM micrographs indicates that the powder is highly porous and agglomerated. The TEM images show the powder to consist of spherical shaped particles of size ?30-60 nm. Upon 323 nm excitation, the emission profile of CaSiO3:Cr3+ exhibits a narrow red emission peak at 641 nm due to 2E ? 4A2 transition and broad band at 722 nm due to 4T2g ? 4A2g. It is observed that PL intensity increases with increase in Cr3+ concentration and highest PL intensity is observed for 3 mol% doped sample. The PL intensity decreases with further increase in Cr3+ doping. This decrease in PL intensity beyond 3 mol% is ascribed to concentration quenching. Racah parameters are calculated to describe the effects of electron-electron repulsion within the crystal lattice. The parameters show 21% reduction in the Racah parameter of free ion and the complex, indicating the moderate nephelauxetic effect in the lattice.

Madesh Kumar, M.; Nagabhushana, H.; Nagabhushana, B. M.; Suriyamurthy, N.; Sharma, S. C.; Shivakumara, C.; Hari Krishna, R.

2014-07-01

230

Chlorodifluoroacetyl cyanide, ClF2CC(O)CN: synthesis, structure, and spectroscopic characterization.  

PubMed

The novel molecule difluorochloroacetyl cyanide, ClF(2)CC(O)CN, has been characterized by IR (gas phase, Ar matrix), Raman (liquid), (19)F and (13)C NMR, and photoelectron (PES) spectroscopies; photoionization mass spectrometry (PIMS); and gas electron diffraction (GED). The conformational properties of ClF(2)CC(O)CN have been studied by joint application of vibrational spectroscopy, GED, and quantum chemical calculations. The existence of two conformers is detected in the gas and liquid phases, in which the C-Cl bond adopts gauche and syn orientations with respect to the C?O group. The computed enthalpy difference is in harmony with the experimental results of the gauche being more stable than the syn conformer by ?H° = 1.3 kcal mol(-1) (MP2/cc-pVTZ). The valence electronic properties and the possible ionization and dissociation processes of the title compound are studied using the PES and PIMS. The experimental first vertical ionization energy of 12.0 eV corresponds to the ejection of an electron of the oxygen lone pairs. Taking into account the properties and broad applications of acyl cyanides, ClF(2)CC(O)CN is a promising new precursor in preparative chemistry. PMID:21870792

Ramos, Luis A; Ulic, Sonia E; Romano, Rosana M; Tong, Shengrui; Ge, Maofa; Vishnevskiy, Yuri V; Berger, Raphael J; Mitzel, Norbert W; Beckers, Helmut; Willner, Helge; Della Védova, Carlos O

2011-10-01

231

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

NASA Astrophysics Data System (ADS)

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.

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

2011-10-01

232

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

PubMed

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

Ren, Fuzeng; Ding, Yonghui; Leng, Yang

2014-02-01

233

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

NASA Astrophysics Data System (ADS)

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

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

2011-01-01

234

Raman spectroscopic characterization of a synthetic, non-stoichiometric Cu-Ba uranyl phosphate.  

PubMed

Crystals of phases belonging to the autunite group (general formula X(2+)(UO2)2(X(5+)O4)2·nH2O), specifically the uranyl phosphates (X(5+)=P) metauranocircite (X(2+)=Ba(2+)), metatorbernite (X(2+)=Cu(2+)) and a barian metatorbenite phase (X(2+)=Cu(2+)/Ba(2+)), have been synthesized in a silica gel medium and characterized by Raman spectroscopy. The Raman spectra showed bands in the range 750-1100 cm(-1), which were attributed to the ?1 and ?3 (PO(4))(3-) and (UO(2))(2+) stretching vibrations. By using the wavenumbers of the most intense and well defined ?1 (UO(2))(2+) vibration, the U-O bonds lengths were calculated for the three uranyl phosphate minerals. The results are in good agreement with previous single crystal structure analysis data. Bands in the spectra from 350 to 700 cm(-1) were attributed to the (PO(4))(3-) bending modes. Moreover, in the range 70-350 cm(-1), two groups of bands could be defined. The first group, with vibrations at lower wavenumbers, was attributed to the lattice modes and the second group, from 150 to 350 cm(-1), was assigned to the ?2 (UO(2))(2+) bending mode. Finally, in the case of the barian metatorbernite, bands in the range 1500-3800 cm(-1) were assigned to the OH stretching and the ?2 bending vibrations of water molecules. In this phase, all the vibrations show bandshifts when compared to the vibrations in metatorbernite. These bandshifts can be related to transitional Cu-O and Ba-O bond lengths. PMID:23727673

Sánchez-Pastor, Nuria; Pinto, André J; Astilleros, José Manuel; Fernández-Díaz, Lurdes; Gonçalves, Mário A

2013-09-01

235

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

PubMed

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

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

2013-06-01

236

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

NASA Astrophysics Data System (ADS)

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

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

2012-12-01

237

Full elastic characterization of absorptive rubber using laser excited guided ultrasonic waves  

NASA Astrophysics Data System (ADS)

Because of the highly damping nature of rubber, it is difficult to characterize its dynamic elastic properties using classical methods. In this paper, an experimental approach employing laser excited guided acoustic waves is proposed to accurately determine the real and imaginary part of the longitudinal and shear elastic modulus of a rubber layer. From the spatiotemporal evolution of a propagating laser excited Lamb wave measured by a laser Doppler vibrometer, which is scanning along a line perpendicular to a line of excitation, the phase velocity dispersion curves in the wave number - frequency domain are obtained. The results are interpreted in the framework of a detailed semianalytical study, analyzing the influence of elastic damping on the Lamb dispersion curves. This analysis is exploited to adequately fit the experimental dispersion curves and thus extract information about the elastic moduli and absorption coefficients of the rubber plate. The results are validated by a pulse-echo measurement, and by guided wave propagation results with the rubber layer connected in a bi-layer plate configuration to non-damping plates.

Verstraeten, Bert; Xu, Xiadong; Martinez, Loïc; Glorieux, Christ

2012-05-01

238

Synthesis spectroscopic characterization antimicrobial activity cobalt(II) complexes acetone-N(4)-phenylsemicarbazone: crystal structure Co(HL)2(MeOH)2 (NO3)2 Transition Chem (2011) 36:417-424.  

EPA Pesticide Factsheets

Search instead for Synthesis spectroscopic characterization antimicrobial activity cobalt(II) complexes acetone-N(4)-phenylsemicarbazone: crystal structure Co(HL)2(MeOH)2 (NO3)2 Transition Chem (2011) 36:417-424. ?

239

Spectroscopic characterizations of a mixed surfactant mesophase and its application in materials synthesis  

NASA Astrophysics Data System (ADS)

A viscous lyotropic crystalline mesophase containing bis (2-ethylhexyl) sodium sulfosuccinate (AOT), alpha-phosphatidylcholine (lecithin), with comparable volume fractions of isooctane and water was characterized by Fourier-transform 31P and 1H nuclear magnetic resonance (NMR) spectroscopy. Shear alignment on the reverse hexagonal mesophase was reflected through both 31P NMR and 1H NMR spectra. A complicated 31P spectrum was observed as a result of superposition of chemical shifts according to the distribution of crystalline domains prior to shear. The initially disordered samples with polydomain structures became macroscopically aligned after Couette shear and the alignment retained for a long period of time. 31P NMR chemical shift anisotropy characteristics were used to elucidate orientation of the hexagonal phase. Interestingly, 1H NMR of the water, methyl and methylene groups exhibited spectral changes upon shear alignment closely corresponding with that of 31P NMR spectra. A reverse hexagonal to lamellar phase transition was manifested as an expanding of the expressed 31P NMR chemical shift anisotropy and an apparent reversal of the powder pattern with increasing water content and/or temperature. Correspondingly, 1H NMR spectra also experienced a spectral pattern transition as the water content or temperature was increased. These observations complement the findings of mesophase alignment obtained using small angle neutron scattering (SANS) and imply that 31P and 1H NMR spectroscopy can be used as probes to define microstructure and monitor orientation changes in this binary surfactant system. This is especially beneficial if these mesophases are used as templates for materials synthesis. The mesophase retains its alignment for extended periods allowing materials synthesis to be decoupled from the application of shear. Highly aligned string-like silica nanostructures were obtained through templated synthesis in the columnar hexagonal structure of the viscous lyotropic crystalline mesophase. A two-step procedure was used to first shear-align the surfactant mesophase, and then conduct synthesis under quiescent conditions in the mesophase. Polystyrene was post-grafted to the silica surface without disturbing its nanostring morphology. The coupling of materials synthesis in surfactant mesophases with processing techniques (e.g. extrusion) may result in functional materials, such as new catalyst support and membrane nanoarchitectures.

Liu, Limin

240

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

NASA Astrophysics Data System (ADS)

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

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

2014-11-01

241

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

SciTech Connect

Single crystals of Zn{sub 4}(OH){sub 2}[(UO{sub 2})(PO{sub 4}){sub 2}(OH){sub 2}(H{sub 2}O)] (UZnP), Cs[(UO{sub 2})(HPO{sub 4})NO{sub 3}] (UCsP), and In{sub 3}[(UO{sub 2}){sub 2}(PO{sub 4}){sub 4}OH(H{sub 2}O){sub 6}].2H{sub 2}O (UInP) were obtained from hydrothermal reactions and have been structurally and chemically characterized. UZnP crystallizes in space group Pbcn, a=8.8817(7), b=6.6109(5), c=19.569(1) A; UCsP crystallizes in P-1, a=7.015(2), b=7.441(1), c=9.393(2) A, {alpha}=72.974(2), {beta}=74.261(2), {gamma}=79.498(2); and UInP crystallizes in P-1, a=7.9856(5), b=9.159(1), c=9.2398(6) A {alpha}=101.289(1), {beta}=114.642(1), {gamma}=99.203(2). The U{sup 6+} cations are present as (UO{sub 2}){sup 2+} uranyl ions coordinated by five O atoms to give pentagonal bipyramids. The structural unit in UZnP is a finite cluster containing a uranyl pentagonal bipyramid that shares corners with two phosphate tetrahedra. The structural unit in UCsP is composed of uranyl pentagonal bipyramids with one chelating nitrate group that are linked into chains by three bridging hydrogen phosphate tetrahedra. In UInP, the structural unit contains pairs of edge-sharing uranyl pentagonal bipyramids with two chelating phosphate tetrahedra that are linked into chains through two bridging phosphate tetrahedra. Indium octahedra link these uranyl phosphate chains into a 3-dimensional framework. All three compounds exhibit unique structural units that deviate from the typical layered structures observed in uranyl phosphate solid-state chemistry. - Graphical abstract: Three new uranyl phosphates with unique structural units are reported. Black-Small-Square Highlights: Black-Right-Pointing-Pointer Three new uranyl phosphates have been synthesized hydrothermally. Black-Right-Pointing-Pointer Single crystal analyses reveal unique structural units. Black-Right-Pointing-Pointer The dimensionality of these compounds deviate from typical U{sup 6+} layered structures.

Wylie, Ernest M.; Dawes, Colleen M. [Department of Civil and Environmental Engineering and Earth Sciences, University of Notre Dame, Notre Dame, IN 46556 (United States)] [Department of Civil and Environmental Engineering and Earth Sciences, University of Notre Dame, Notre Dame, IN 46556 (United States); Burns, Peter C., E-mail: pburns@nd.edu [Department of Civil and Environmental Engineering and Earth Sciences, University of Notre Dame, Notre Dame, IN 46556 (United States); Department of Chemistry and Biochemistry, University of Notre Dame, Notre Dame, IN 46556 (United States)

2012-12-15

242

Structural, Spectroscopic, and Computational Characterization of the Azide Adduct of FeIII(2,6-diacetylpyridinebis(semioxamazide)), a Functional Analogue of Iron Superoxide Dismutase  

PubMed Central

We have prepared and thoroughly characterized, using X-ray crystallographic, spectroscopic, and computational methods, the diazide adduct of [FeIII(dapsox)(H2O)2]1+ [dapsox=2,6-diacetylpyridinebis(semioxamazide)] (1), alow-molecular weight, functional analogue of iron superoxide dismutase (FeSOD). The X-ray crystal structure of the dimeric form of 1, (Na[FeIII(dapsox)(N3)2] DMF)2 (2) shows two axially coordinated, symmetry inequivalent azides with differing Fe–N3 bond lengths and Fe–N–N2 bond angles. This inequivalence of the azide ligands likely reflects the presence of an inter-dimer H-bonding interaction between a dapsox NH group and the coordinated nitrogen of one of the two azide ligands. Resonance Raman (rR) data obtained for frozen aqueous solution and solid-state samples of 2 indicate that the azides remain inequivalent in solution, suggesting that one of the azide ligands of 1 engages in an intermolecular hydrogen bonding interaction with a water molecule. Density functional theory (DFT) and time-dependent DFT calculations have been used to study two different computational models of 1, one using coordinates taken from the X-ray crystal structure of 2, and the other generated via DFT geometry optimization. An evaluation of these models on the basis of electronic absorption, magnetic circular dichroism, and rR data indicates that the crystal structure based model provides a more accurate electronic structure description of 1, providing further support for the proposed intermolecular hydrogen bonding of 1 in the solid state and in solution. An analysis of the experimentally validated DFT results for this model reveals that the azides have both ?- and ?-bonding interactions with the FeIII center and that more negative charge is located on the Fe-bound, rather than on the terminal, nitrogen atom of each azide. These observations are reminiscent of the results previously reported for the azide adduct of FeSOD and provide clues regarding the origin the high catalytic activity of Fe-dapsox for superoxide disproportionation. PMID:23875582

Gutman, Craig T.; Guzei, Ilia A.; Brunold, Thomas C.

2013-01-01

243

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

SciTech Connect

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.

Willey, T; Willey, T

2004-03-24

244

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)

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.

Willey, Trevor Michael

245

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

PubMed

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

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

2014-11-21

246

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)

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

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

2014-12-01

247

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

In this study, isolation and characterization of trans-resveratrol (RES) as an antioxidant compound were carried out from VLE, VLG and VLS. Furthermore, antioxidant activities were evaluated by using six different methods. Finally, total phenolic, flavonoid, ascorbic acid, anthocyanin, lycopene, ?-carotene and vitamin E contents were carried out. In addition, the FT-IR, (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

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

2014-12-10

248

Characterization and intercomparison of aerosol absorption photometers: result of two intercomparison workshops  

NASA Astrophysics Data System (ADS)

Absorption photometers for real time application have been available since the 1980s, but the use of filter-based instruments to derive information on aerosol properties (absorption coefficient and black carbon, BC) is still a matter of debate. Several workshops have been conducted to investigate the performance of individual instruments over the intervening years. Two workshops with large sets of aerosol absorption photometers were conducted in 2005 and 2007. The data from these instruments were corrected using existing methods before further analysis. The inter-comparison shows a large variation between the responses to absorbing aerosol particles for different types of instruments. The unit to unit variability between instruments can be up to 30% for Particle Soot Absorption Photometers (PSAPs) and Aethalometers. Multi Angle Absorption Photometers (MAAPs) showed a variability of less than 5%. Reasons for the high variability were identified to be variations in sample flow and spot size. It was observed that different flow rates influence system performance with respect to response to absorption and instrumental noise. Measurements with non absorbing particles showed that the current corrections of a cross sensitivity to particle scattering are not sufficient. Remaining cross sensitivities were found to be a function of the total particle load on the filter. The large variation between the response to absorbing aerosol particles for different types of instruments indicates that current correction functions for absorption photometers are not adequate.

Müller, T.; Henzing, J. S.; de Leeuw, G.; Wiedensohler, A.; Alastuey, A.; Angelov, H.; Bizjak, M.; Collaud Coen, M.; Engström, J. E.; Gruening, C.; Hillamo, R.; Hoffer, A.; Imre, K.; Ivanow, P.; Jennings, G.; Sun, J. Y.; Kalivitis, N.; Karlsson, H.; Komppula, M.; Laj, P.; Li, S.-M.; Lunder, C.; Marinoni, A.; Martins Dos Santos, S.; Moerman, M.; Nowak, A.; Ogren, J. A.; Petzold, A.; Pichon, J. M.; Rodriquez, S.; Sharma, S.; Sheridan, P. J.; Teinilä, K.; Tuch, T.; Viana, M.; Virkkula, A.; Weingartner, E.; Wilhelm, R.; Wang, Y. Q.

2011-02-01

249

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

PubMed

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

Alpaslan, Gökhan; Macit, Mustafa

2014-01-01

250

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

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…

McClain, Robert L.; Wright, John C.

2014-01-01

251

Spectroscopic characterization of Sm3+ doped (Lu0.4Gd0.6)2SiO5 single crystals  

NASA Astrophysics Data System (ADS)

Results of spectroscopic investigations of single crystal with general formula (Lu0.4Gd0.55Sm0.05)2SiO5 are presented. Optical anisotropy of material is evidenced in polarized absorption as well as in emission spectra. Based on polarized absorption spectra calculations in framework of Judd-Ofelt fenemenological model was done. Intensity parameters ?t was evaluated to be ?2 = 1.26 (±0.46), ?4 = 4.68 (±0.36), ?6 = 2.32 (±0.16) [10-20 cm2]. Obtained value of radiative lifetime from Inokuti Hirayama model (1.80 ms) is close to calculated from Judd-Ofelt analysis (1.89 ms), what results in ca. 95% theoretical quantum efficiency. Strong absorption line located at 403 nm, could be utilized for efficient excitation of material by InGaN/GaN laser diodes. Intense emission line at 601 nm, with experimental branching ratio ? = 42.9%, gives high chance for obtaining laser action in four level operation scheme.

Strz?p, Adam; Lisiecki, Rados?aw; Solarz, Piotr; Ryba-Romanowski, Witold; Berkowski, Marek

2014-02-01

252

Characterization of shear-thickening fluid-filled foam systems for use in energy absorption devices  

E-print Network

The absorption of energy during impacts is ubiquitous in society. From our car seats to body armor, the ability to divert or dissipate unwanted energy is an aspect that has many engineering challenges. One approach to this ...

Ramirez, Jose G. (Jose Guadalupe), 1980-

2004-01-01

253

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

NASA Astrophysics Data System (ADS)

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

Hagvall, Kristoffer; Persson, Per; Karlsson, Torbjörn

2014-12-01

254

Spectroscopic evidence for and characterization of a trinuclear ferroxidase center in bacterial ferritin from Desulfovibrio vulgaris Hildenborough.  

PubMed

Ferritins are ubiquitous and can be found in practically all organisms that utilize Fe. They are composed of 24 subunits forming a hollow sphere with an inner cavity of ~80 Å in diameter. The main function of ferritin is to oxidize the cytotoxic Fe(2+) ions and store the oxidized Fe in the inner cavity. It has been established that the initial step of rapid oxidation of Fe(2+) (ferroxidation) by H-type ferritins, found in vertebrates, occurs at a diiron binding center, termed the ferroxidase center. In bacterial ferritins, however, X-ray crystallographic evidence and amino acid sequence analysis revealed a trinuclear Fe binding center comprising a binuclear Fe binding center (sites A and B), homologous to the ferroxidase center of H-type ferritin, and an adjacent mononuclear Fe binding site (site C). In an effort to obtain further evidence supporting the presence of a trinuclear Fe binding center in bacterial ferritins and to gain information on the states of the iron bound to the trinuclear center, bacterial ferritin from Desulfovibrio vulgaris (DvFtn) and its E130A variant was loaded with substoichiometric amounts of Fe(2+), and the products were characterized by Mössbauer and EPR spectroscopy. Four distinct Fe species were identified: a paramagnetic diferrous species, a diamagnetic diferrous species, a mixed valence Fe(2+)Fe(3+) species, and a mononuclear Fe(2+) species. The latter three species were detected in the wild-type DvFtn, while the paramagnetic diferrous species was detected in the E130A variant. These observations can be rationally explained by the presence of a trinuclear Fe binding center, and the four Fe species can be properly assigned to the three Fe binding sites. Further, our spectroscopic data suggest that (1) the fully occupied trinuclear center supports an all ferrous state, (2) sites B and C are bridged by a ?-OH group forming a diiron subcenter within the trinuclear center, and (3) this subcenter can afford both a mixed valence Fe(2+)Fe(3+) state and a diferrous state. Mechanistic insights provided by these new findings are discussed and a minimal mechanistic scheme involving O-O bond cleavage is proposed. PMID:22681596

Pereira, Alice S; Timóteo, Cristina G; Guilherme, Márcia; Folgosa, Filipe; Naik, Sunil G; Duarte, Américo G; Huynh, Boi Hanh; Tavares, Pedro

2012-07-01

255

Spectroscopic Evidence for and Characterization of a Trinuclear Ferroxidase Center in Bacterial Ferritin from Desulfovibrio vulgaris Hildenborough  

PubMed Central

Ferritins are ubiquitous and can be found in practically all organisms that utilize Fe. They are composed of 24 subunits forming a hollow sphere with an inner cavity of ~80 Å in diameter. The main function of ferritin is to oxidize the cytotoxic Fe2+ ions and store the oxidized Fe in the inner cavity. It has been established that the initial step of rapid oxidation of Fe2+ (ferroxidation) by H-type ferritins, found in vertebrates, occurs at a diiron binding center, termed ferroxidase center. In bacterial ferritins, however, X-ray crystallographic evidence and amino-acid sequence analysis revealed a trinuclear Fe binding center comprising a binuclear Fe binding center (sites A and B), homologous to the ferroxidase center of H-type ferritin, and an adjacent mononuclear Fe binding site (site C). In an effort to obtain further evidence supporting the presence of a trinuclear Fe binding center in bacterial ferritins and to gain information on the states of the iron bound to the trinuclear center, bacterial ferritin from Desulfovibrio vulgaris (DvFtn) and its E130A variant were loaded with sub-stoichiometric amounts of Fe2+ and products were characterized by Mössbauer and EPR spectroscopy. Four distinct Fe species were identified: a paramagnetic diferrous species, a diamagnetic diferrous species, a mixed valence Fe2+Fe3+ species and a mononuclear Fe2+ species. The latter three species were detected in the wild-type DvFtn, while the paramagnetic diferrous species was detected in the E130A variant. These observations can be rationally explained by the presence of a trinuclear Fe binding center, and the four Fe species can be properly assigned to the three Fe binding sites. Further, our spectroscopic data suggest that (1) the fully occupied trinuclear center supports an all ferrous state, (2) site B and C are bridged by a ?-OH group forming a diiron sub-center within the trinuclear center, and (3) this sub-center can afford both a mixed valence Fe2+Fe3+ state and a diferrous state. Mechanistic insights provided by these new findings are discussed and a minimal mechanistic scheme involving O-O bond cleavage is proposed. PMID:22681596

Pereira, Alice S.; Timoteo, Cristina G.; Guilherme, Marcia; Folgosa, Filipe; Naik, Sunil G.; Duarte, Americo G.; Huynh, Boi Hanh; Tavares, Pedro

2012-01-01

256

Thermophysics Characterization of Multiply Ionized Air Plasma Absorption of Laser Radiation  

NASA Technical Reports Server (NTRS)

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.

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

2002-01-01

257

A facial microwave-assisted synthesis, spectroscopic characterization and preliminary complexation studies of calix[4]pyrroles containing the hydroxamic-acid moiety  

Microsoft Academic Search

The synthesis, spectroscopic characterization and preliminary complexation properties of functionalized calix[4]pyrroles are\\u000a described. To date, two generalized preparative approaches have been pursued (i) modifying the basic pyrrole-plus-ketone synthesis\\u000a of calix[4]pyrrole by using microwave irradiation protocol, (ii) the basic meso-tetra(methyl) meso-tetra(p-nitrophenyl) calix[4]pyrrole skeleton was functionalized to give hydroxamic acids, especially in the meso-position of the macrocycles. The structures of novel calix[4]pyrrole

Vinod K. Jain; Hiren C. Mandalia; Eringathodi Suresh

2008-01-01

258

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)

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.

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

2013-06-01

259

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

PubMed

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

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

2007-11-01

260

FT-IR spectroscopic assessment of gas-phase absorption of atmospheric molecular species at low concentrations and their associated adsorption effects on various material surfaces  

NASA Astrophysics Data System (ADS)

Changes in the infrared absorbance observed at levels of concentration in the subparts per million (sub-ppm) of atmospherically significant molecular species, such as HCl, SO2, NO2 and NH3, has been quantified as a function of pressure and temperature for the surface reactions of these gases with various materials (e.g. copper, aluminum, stainless steel and teflon). A Nicolet Magna-IR 550 Fourier transform infrared (FT-IR) spectrometer operating in the 400-4000 cm-1 region and fitted with a 10-meter multipass absorption cell and a deuterated triglycine sulfate (DTGS) detector has been used for recording the spectra. Tubing materials chosen are typically associated with the hardware of measuring instruments used to collect atmospheric trace gas samples. The FT-IR spectrometer has been used to determine the concentration levels at the inlet and outlet tubing of the absorption cell. Small changes in the species concentration down to sub-ppm levels have also been recorded in the 650-4000 cm-1 region using a liquid nitrogen-cooled Mercury Cadmium Telluride (MCT-A) detector interfaced with the FT-IR spectrometer. The associated adsorption effects at the various gas-solid interfaces in the measuring apparatus, including the `sticking' effects on the walls of the absorption cell, have been quantified. Carefully monitored pressure and temperature conditions were utilized to provide a controlled environment, so as to quantify minute changes in the absorption of infrared radiation due to variations in the concentration of the gas samples brought about by different adsorption effects. Values for the absorption coefficients of the different gas phase molecular species in the infrared region of interest were derived from the absorbance measurements. The degree of adsorption for specific gassolid interfaces and the kinetic theory of the adsorption process (assuming a mono-layer) enabled the determination of the corresponding rate constants. It is envisioned that the accurate determination of the adsorption coverage parameters and the Langmuir rate constants for the various gas-material combinations will aid in the refinement of precise values for the associated residence time and activation energies and thereby lead to the development of a comprehensive adsorption isotherm model for gas-surface interactions.

Dowdye, Edward Henry, Jr.

2000-11-01

261

An X-ray absorption spectroscopic study on mixed conductive La0.6Sr0.4Co0.8Fe0.2O(3-?) cathodes. I. Electrical conductivity and electronic structure.  

PubMed

The electrical conduction mechanism of mixed conductive perovskite oxides, La(0.6)Sr(0.4)Co(0.8)Fe(0.2)O(3-?), for cathode materials of solid oxide fuel cells has been investigated from electronic structural changes during oxygen vacancy formation. La(0.6)Sr(0.4)Co(0.8)Fe(0.2)O(3-?) was annealed under various oxygen partial pressures p(O(2))s at 1073 K and quenched. Iodometric titration indicated that the oxygen nonstoichiometry of La(0.6)Sr(0.4)Co(0.8)Fe(0.2)O(3-?) depended on the annealing p(O(2)), with more oxygen vacancies introduced at lower than at higher p(O(2))s. X-Ray absorption spectroscopic measurements were performed at the O K-, Co L-, Fe L-, Co K-, and Fe K-edges. The valence states of the Co and Fe ions were investigated by the X-ray absorption near edge structure (XANES) at the Co and Fe L(III)-edges. While the Fe average valence was almost constant, the valence of the Co ions decreased with oxygen vacancy introduction. The O K-edge XANES spectra indicated that electrons were injected into the Co 3d/O 2p hybridization state with oxygen vacancy introduction. Both absorption edges at the Co and Fe K-edge XANES shifted towards lower energies with oxygen vacancy introduction. The shift at the Co K-edge resulted from the decrease in the Co average valence and that at the Fe K-edge appeared to be caused by changes in the coordination environment around the Fe ions. The total conductivity of La(0.6)Sr(0.4)Co(0.8)Fe(0.2)O(3-?) decreased with decreasing p(O(2)), due to a decreasing hole concentration. PMID:21850304

Orikasa, Yuki; Ina, Toshiaki; Nakao, Takayuki; Mineshige, Atsushi; Amezawa, Koji; Oishi, Masatsugu; Arai, Hajime; Ogumi, Zempachi; Uchimoto, Yoshiharu

2011-10-01

262

Characterization of the intestinal absorption of inorganic mercury in Caco-2 cells.  

PubMed

The main form of mercury exposure in the general population is through food. Intestinal absorption is therefore a key step in the penetration of mercury into the systemic circulation, and should be considered when evaluating exposure risk. Many studies have investigated the transport of mercury species in different cell lines, though the mechanisms underlying their intestinal absorption are not clear. This study evaluates the accumulation and transport of Hg(II), one of the mercury species ingested in food, using Caco-2 cells as intestinal epithelium model with the purpose of clarifying the mechanisms involved in its absorption. Hg(II) shows moderate absorption, and its transport fundamentally takes place via a carrier-mediated transcellular mechanism. The experiments indicate the participation of an energy-dependent transport mechanism. In addition, H(+)- and Na(+)-dependent transport is also observed. These data, together with those obtained from inhibition studies using specific substrates or inhibitors of different transporter families, suggest the participation of divalent cation and amino acid transporters, and even some organic anion transporters, in Hg(II) intestinal transport. An important cellular accumulation of up to 51% is observed - a situation which in view of the toxic nature of this species could affect intestinal mucosal function. This study contributes new information on the mechanisms of transport of Hg(II) at intestinal level, and which may be responsible for penetration of this mercurial form into the systemic circulation. PMID:25283090

Vázquez, M; Devesa, V; Vélez, D

2015-02-01

263

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

NASA Astrophysics Data System (ADS)

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

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

2004-07-01

264

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

NASA Astrophysics Data System (ADS)

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

Coughlin, Kathleen M.

265

Spectroscopic Observations  

NSDL National Science Digital Library

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

266

X-ray absorption spectroscopic studies of the dinuclear iron center in methane monooxygenase and the sulfure and chlorine centers in photographic materials  

SciTech Connect

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.

DeWitt, J.G.

1992-12-01

267

X-ray absorption spectroscopic studies of the dinuclear iron center in methane monooxygenase and the sulfure and chlorine centers in photographic materials  

SciTech Connect

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.

DeWitt, J.G.

1992-12-01

268

[CdSe/ZnSe quantum dots via a two-phase solution system process solubilization and spectroscopic characterization].  

PubMed

In the present work, the CdSe/ZnSe core/shell quantum dots (QDs) were successfully transferred from organic phase to water phase via a two-phase solution system process by surface coating with amphiphilic polymer. Surface coating with amphiphilic polymer is an effective method, which can form stable soluble QDs in water. However, the conventional polymer coating method is performed in homogeneous phase, and it easily induces the aggregation of the QDs attributing to the long chain of enlace of the polymer. It is thus necessary and meaningful to develop surface coating technique for getting monodisperse coating QDs with amphiphilic polymer. In comparison with previously reported coating method, the authors' experiment process is performed in two-phase solution system, and can effectively reduces the possibility of aggregation of the QDs. The resulting hydrophilic CdSe/ZnSe core/shell QDs have long-term stability in water, and high quantum yield. The polymer coating process was affirmed by various characterizations. Fourier transform infrared spectra suggest that the octylamine modified polymer was successfully coated on the surface of the CdSe/ZnSe QDs. The transmission electron microscopy suggests that the size and shape of the QDs showed no obvious change before and after the coating process. Dynamic light scattering results indicate that the hydrophilic QDs exhibit narrow hydrodynamic size distribution with the mean hydrodynamic diameters of about 19.7 nm. The luminescence properties of the QDs were investigated with photoluminescence spectra and ultraviolet-visible absorption spectra. This polymer coating process has less effect on luminescence capability. The quantum yield decreased from 43% to 30%. Further, in order to confirm that the polymer capped QDs is biocompatible, the QDs were used for specific detection of the human IgG with fluorescence mapping. The specific molecular recognition capacity of goat anti-human IgG-modified QDs confirms that the polymer coated QDs have compatible functional chemical groups for bioconjugation and are suitable for biological applications. PMID:20384140

Zhang, Qing-Bin; Song, Kai; Kong, Xiang-Gui; Zeng, Qing-Hui; Zhang, You-Lin; Sun, Ya-Juan; Liu, Xiao-Min

2010-02-01

269

X-ray absorption spectroscopic investigation of the spin-transition character in a series of single-site perturbed iron(II) complexes.  

PubMed

Select ferrous spin-transition complexes with the pentadentate ligand 2,6-bis(bis(2-pyridyl)methoxymethane)pyridine (PY5) were examined using variable-temperature solution solid-state magnetic susceptibility, crystallography, X-ray absorption spectroscopy (XAS), and UV/vis absorption spectroscopy. Altering the single exogeneous ligand, X, of [Fe(PY5)(X)]n)+ is sufficient to change the spin-state of the complexes. When X is the weak-field ligand Cl-, the resultant Fe complex is high-spin from 4 to 300 K, whereas the stronger-field ligand MeCN generates a low-spin complex over this temperature range. With intermediate-strength exogenous ligands (X = N3-, MeOH), the complexes undergo a spin-transition. [Fe(PY5)(N3)]+, as a crystalline solid, transitions gradually from a high-spin to a low-spin complex as the temperature is decreased, as evidenced by X-ray crystallography and solid-state magnetic susceptibility measurements. The spin-transition is also evident from changes in the pre-edge and EXAFS regions of the XAS Fe K-edge spectra on a ground crystalline sample. The spin-transition observed with [Fe(PY5)(MeOH)]2+ appears abrupt by solid-state magnetic susceptibility measurements, but gradual by XAS analysis, differences attributed to sample preparation. This research highlights the strengths of XAS in determining the electronic and geometric structure of such spin-transition complexes and underscores the importance of identical sample preparation in the investigation of these physical properties. PMID:15732962

Rudd, Deanne Jackson; Goldsmith, Christian R; Cole, Adam P; Stack, T Daniel P; Hodgson, Keith O; Hedman, Britt

2005-03-01

270

Laser induced fluorescence and absorption measurements for DUV optical thin film characterization  

NASA Astrophysics Data System (ADS)

Residual absorption in optical thin films due to impurities or defects causes thermal lens formation upon high power DUV laser irradiation. Furthermore, it may be one reason for functional degradation during prolonged laser irradiation. Pulsed ArF laser induced fluorescence (LIF) and direct absorption measurements (LID technique) are applied to investigate high reflecting coatings made from LaF3, MgF2 and AlF3 with respect to the influence of different raw materials and deposition temperatures. LIF measurements reveal emission bands that are partially attributed to certain impurities or defects which either origin from the raw material or the coating process. In addition, LIF measurements of single MgF2 and LaF3 layers are performed to investigate different raw material qualities and coating processes. The experimental results show the potential of both techniques for sensitive accompanying of coating process development.

Mühlig, Ch.; Triebel, W.; Kufert, S.; Bublitz, S.

2008-09-01

271

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

NASA Astrophysics Data System (ADS)

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

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

2011-12-01

272

An X-ray absorption spectroscopic study of the metal site preference in Al{sub 1-x}Ga{sub x}FeO{sub 3}  

SciTech Connect

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.}.

Walker, James D.S. [Department of Chemistry, University of Saskatchewan, Saskatoon, Saskatchewan, S7N 5C9 (Canada); Grosvenor, Andrew P., E-mail: andrew.grosvenor@usask.ca [Department of Chemistry, University of Saskatchewan, Saskatoon, Saskatchewan, S7N 5C9 (Canada)

2013-01-15

273

Constraining the N2O5 UV absorption cross section from spectroscopic trace gas measurements in the tropical mid-stratosphere  

NASA Astrophysics Data System (ADS)

The absorption cross section of N2O5, ?N2O5(?, T), which is known from laboratory measurements with the uncertainty of a factor of 2 (Table 4-2 in (Jet Propulsion Laboratory) JPL-2011; the spread in laboratory data, however, points to an uncertainty in the range of 25 to 30%, Sander et al., 2011), was investigated by balloon-borne observations of the relevant trace gases in the tropical mid-stratosphere. The method relies on the observation of the diurnal variation of NO2 by limb scanning DOAS (differential optical absorption spectroscopy) measurements (Weidner et al., 2005; Kritten et al., 2010), supported by detailed photochemical modelling of NOy (NOx(= NO + NO2) + NO3 + 2N2O5 + ClONO2 + HO2NO2 + BrONO2 + HNO3) photochemistry and a non-linear least square fitting of the model result to the NO2 observations. Simulations are initialised with O3 measured by direct sun observations, the NOy partitioning from MIPAS-B (Michelson Interferometer for Passive Atmospheric Sounding - Balloon-borne version) observations in similar air masses at night-time, and all other relevant species from simulations of the SLIMCAT (Single Layer Isentropic Model of Chemistry And Transport) chemical transport model (CTM). Best agreement between the simulated and observed diurnal increase of NO2 is found if the ?N2O5(?, T) is scaled by a factor of 1.6 ± 0.8 in the UV-C (200-260 nm) and by a factor of 0.9 ± 0.26 in the UV-B/A (260-350 nm), compared to current recommendations. As a consequence, at 30 km altitude, the N2O5 lifetime against photolysis becomes a factor of 0.77 shorter at solar zenith angle (SZA) of 30° than using the recommended ?N2O5(?, T), and stays more or less constant at SZAs of 60°. Our scaled N2O5 photolysis frequency slightly reduces the lifetime (0.2-0.6%) of ozone in the tropical mid- and upper stratosphere, but not to an extent to be important for global ozone.

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

274

Characterization of SEI layers on LiMn2O4 cathodes with in-situ spectroscopic ellipsometry  

SciTech Connect

In situ spectroscopic ellipsometry was employed to study the initial stage of SEI layer formation on thin-film LiMn{sub 2}O{sub 4} electrodes. It was found that the SEI layer formed immediately upon exposure of the electrode to EC/DMC (1:1 by vol) 1.0 M LiPF{sub 6} electrolyte. The SEI layer thickness then increased in proportion to a logarithmic function of elapsed time. In comparison, the SEI layer thickness on a cycled electrode increased in proportion to a linear function of the number of cycles.

Lei, Jinglei; Li, Lingjie; Kostecki, Robert; Muller, Rolf; McLarnon, Frank

2004-08-30

275

Spectroscopic characterization of SC-NTR: a subsidiary dye of allura red AC dye (FD&C red no. 40).  

PubMed

A major subsidiary dye in US certified Allura Red AC dye (FD&C Red No. 40) has been isolated by preparative high performance liquid chromatography. The paper chromatographic properties of the isolated dye indicate that it is the dye designated as SC-NTR in a previous paper (Marmion 1971). Spectroscopic analysis of the isolated dye is consistent with the disodium salt of 6-hydroxy-5-(2-methoxy-5-methyl-3-sulphophenylazo)-2-naphthalen esulphonic acid, which is an azo-coupling product between the meta-isomer of cresidine-p-sulphonic acid (CSA) and Schaeffer's salt (SS). PMID:8181638

Takeda, Y; Goda, Y; Noguchi, H; Yamada, T; Yoshihira, K; Takeda, M

1994-01-01

276

Distinguishing Förster Resonance Energy Transfer and solvent-mediated charge-transfer relaxation dynamics in a zinc(II) indicator: a femtosecond time-resolved transient absorption spectroscopic study.  

PubMed

A bifluorophoric molecule (1) capable of intramolecular Förster Resonance Energy Transfer (FRET) is reported. The emission intensity of the FRET acceptor in 1 depends on the molar absorptivity of the donor, which is a function of zinc(II) complexation. The FRET dynamics of [Zn(1)](ClO4)2 is characterized by femtosecond time-resolved transient absorption spectroscopy. The solvent-mediated relaxation of the charge-transfer (CT) state of the isolated donor and the FRET process of the donor–acceptor conjugate are on similar time scales (40–50 ps in CH3CN), but distinguishable by the opposite solvent polarity dependency. As the solvent polarity increases, the efficiency of Columbic-based FRET is reduced, whereas CT relaxation is accelerated. In addition to revealing a method to distinguish CT and FRET dynamics, this work provides a photophysical foundation for developing indicators based on the FRET strategy. PMID:24504046

Sreenath, Kesavapillai; Yi, Chongyue; Knappenberger, Kenneth L; Zhu, Lei

2014-03-21

277

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

NASA Astrophysics Data System (ADS)

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.

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

2013-11-01

278

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

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

Sharma, S P; Lahiri, S C

2008-06-01

279

X-ray Absorption Spectroscopic and Computational Investigation of a Possible S···S Interaction in the [Cu3S2]3+ Core  

PubMed Central

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 ?* 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

Sarangi, Ritimukta; Yang, Lei; Winikoff, Stuart G.; Gagliardi, Laura; Cramer, Christopher J.; Tolman, William B.; Solomon, Edward I.

2011-01-01

280

X-ray absorption spectroscopic and computational investigation of a possible S···S interaction in the [Cu3S2]3+ core.  

PubMed

The electronic structure of the [Cu(3)S(2)](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 [Cu(3)S(2)](3+) core is best described as having all copper centers close to but more oxidized than Cu(2+), while the charge on the S(2) fragment is between that of a sulfide (S(2-)) and a subsulfide (S(2)(3-)) species. The [Cu(3)S(2)](3+) core thus is different from a previously described, analogous [Cu(3)O(2)](3+) core, which has a localized [(Cu(3+)Cu(2+)Cu(2+))(O(2-))(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 ?* to the Cu and result in some bonding interaction between the two S atoms at ~2.69 Å in [Cu(3)S(2)](3+), stabilizing a delocalized S = 1 ground state. PMID:21923178

Sarangi, Ritimukta; Yang, Lei; Winikoff, Stuart G; Gagliardi, Laura; Cramer, Christopher J; Tolman, William B; Solomon, Edward I

2011-11-01

281

An X-ray absorption spectroscopic study of the metal site preference in Al1-xGaxFeO3  

NASA Astrophysics Data System (ADS)

Magnetoelectric materials have potential for being introduced into next generation technologies, especially memory devices. The AFeO3 (Pna21; 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, Al1-xGaxFeO3 was synthesized by the ceramic method and studied by X-ray absorption spectroscopy. Al L2,3-, 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 Al1-xGaxFeO3 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 AlFeO3 than in GaFeO3, implying more anti-site disorder is present in AlFeO3.

Walker, James D. S.; Grosvenor, Andrew P.

2013-01-01

282

In situ X-ray absorption spectroscopic investigation of the electrochemical conversion reactions of CuF{sub 2}-MoO{sub 3} nanocomposite  

SciTech Connect

We have used X-ray absorption spectroscopy at the Cu K-edge to investigate the electrochemical conversion reaction of 20 nm size 85 wt% CuF{sub 2}-15 wt% MoO{sub 3} nanocomposite under in situ conditions. The nanocomposite was prepared by high energy milling. Upon discharge, the lithiation reaction with the nanocomposite resulted in the formation of nanophase metallic Cu, which is consistent with the conversion of CuF{sub 2} into Cu and LiF. Based on XANES and Fourier transforms of EXAFS spectra, we show that the discharge process proceeded via the formation of highly dispersed Cu particles. Based on the coordination number of the first shell of Cu, the average size of the Cu particles was estimated to be in the 1-3 nm range in the fully discharged state. -- Graphical Abstract: Comparison of Fourier transform of in situ Cu K-edge EXAFS spectra for a fully discharged CuF{sub 2{center_dot}}MoO{sub 3} nanocomposite in a nonaqueous Li cell with that of a Cu foil. Quantitative analysis of the Fourier transforms confirmed that the discharge mechanism for the nanocomposite proceeds via the reaction CuF{sub 2}+2Li{yields}Cu+2LiF. The discharge product of Cu is in the form of highly dispersed nanoparticles. Display Omitted

Mansour, A.N., E-mail: Azzam.Mansour@navy.mi [Systems and Materials for Power and Protection Branch, Naval Surface Warfare Center, Carderock Division, 9500 MacArthur Boulevard, West Bethesda, MD 20817-5700 (United States); Badway, F. [Energy Storage Research Group, Department of Materials Science and Engineering, Rutgers, The State University of New Jersey, North Brunswick, NJ 08902 (United States); Yoon, W.-S. [School of Advanced Materials Eng., Kookmin University, 861-1 Jeongneung-dong, Seongbuk-gu, Seoul 136-702 (Korea, Republic of); Chung, K.Y. [Battery Research Center, Korea Institute of Science and Technology, Seoul 136-791 (Korea, Republic of); Amatucci, G.G. [Energy Storage Research Group, Department of Materials Science and Engineering, Rutgers, The State University of New Jersey, North Brunswick, NJ 08902 (United States)

2010-12-15

283

Bio-precipitation of uranium by two bacterial isolates recovered from extreme environments as estimated by potentiometric titration, TEM and X-ray absorption spectroscopic analyses.  

PubMed

This work describes the mechanisms of uranium biomineralization at acidic conditions by Bacillus sphaericus JG-7B and Sphingomonas sp. S15-S1 both recovered from extreme environments. The U-bacterial interaction experiments were performed at low pH values (2.0-4.5) where the uranium aqueous speciation is dominated by highly mobile uranyl ions. X-ray absorption spectroscopy (XAS) showed that the cells of the studied strains precipitated uranium at pH 3.0 and 4.5 as a uranium phosphate mineral phase belonging to the meta-autunite group. Transmission electron microscopic (TEM) analyses showed strain-specific localization of the uranium precipitates. In the case of B. sphaericus JG-7B, the U(VI) precipitate was bound to the cell wall. Whereas for Sphingomonas sp. S15-S1, the U(VI) precipitates were observed both on the cell surface and intracellularly. The observed U(VI) biomineralization was associated with the activity of indigenous acid phosphatase detected at these pH values in the absence of an organic phosphate substrate. The biomineralization of uranium was not observed at pH 2.0, and U(VI) formed complexes with organophosphate ligands from the cells. This study increases the number of bacterial strains that have been demonstrated to precipitate uranium phosphates at acidic conditions via the activity of acid phosphatase. PMID:22019055

Merroun, Mohamed L; Nedelkova, Marta; Ojeda, Jesus J; Reitz, Thomas; Fernández, Margarita López; Arias, José M; Romero-González, María; Selenska-Pobell, Sonja

2011-12-15

284

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)

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

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

2014-01-01

285

Spectroscopic characterization of the cured state of acetylene-terminated resin. Final report 1 Apr 1982-31 Mar 1983  

SciTech Connect

The acetylene-terminated resin, bis 4-(3-ethynylphenoxy)phenyl sulfone (AT) has been studied using Fourier transform infrared spectroscopy (FT-IR) and high resolution nuclear magnetic resonance spectroscopy of solids. Samples which were cured at different temperatures for various times were analyzed by FT-IR and the results interpreted using factor analysis. The analysis revealed that only two major components were involved in the curing mechanism, that is, only a single polymerization reaction occurred at low curing temperatures. The pure component spectra generated by the factor analysis procedure could be used to analyze the state of cure of the resin. The infrared spectrum of the polymer is consistent with a polydiene structure. The NMR results produced a similar structural result. The extent of cure of the AT resin as evidence by the disappearance of the acetylene carbon followed a similar path to the infrared results. Curve studies also focussed on the effect of high temperature post cures of the ATS resin. Structural changes were reflected by spectroscopic differences but the changes were small and precise assignments were not possible. Further model compound studies would allow a precise determination of the structural basis of these spectroscopic differences.

Koenig, J.L.

1983-08-01

286

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)

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.

Sanches, Ieda Del'Arco; Souza Filho, Carlos Roberto; Kokaly, Raymond Floyd

2014-11-01

287

An X-ray absorption spectroscopic study of the effect of bond covalency on the electronic structure of Gd2Ti(2-x)Sn(x)O7.  

PubMed

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

Aluri, Esther Rani; Grosvenor, Andrew P

2013-07-01

288

Absorption and fluorescence emission spectroscopic characters of size-expanded yDNA bases and effect of deoxyribose and base pairing.  

PubMed

We present an ab initio study of the optical absorption and emission spectra of size-expanded nucleic acid base analogues (yA, yT, yT-m, yG, yG-t2, and yC) obtained by benzo homologation (see Krueger, A. T.; Lu, H.; Lee, A. H. F.; Kool, E. T. Acc. Chem. Res. 2007, 40, 141 and references therein). Also examined were the effects of linking to deoxyribose and hydrogen bonding to their natural complementary bases (T, A, C, and G, respectively). The calculated excitation and emission energies are in good agreement with the measured data where experimental results are available. The geometries corresponding to the first excited singlet state of yA and yT are found to be quasi-planar, while those for yG and yC are nonplanar. In general, binding to deoxyribose will red shift the absorbance and fluorescence emission maxima of the y-bases. The ground-state geometries of the Watson-Crick analog base pairs (yAT, yTA, yGC, and yCG) are found to be planar, and the calculated interaction energies are very close to those of natural base pairs, indicating that the y-bases can pair with their natural complementary partners to generate stable base pairs. The base pairing has no significant effects on the fluorescence emission of yA, yC, and yT, but blue shifts the fluorescence emission of yG by 22 nm. PMID:19159339

Zhang, Laibin; Li, Huifang; Chen, Xiaohua; Cukier, Robert I; Bu, Yuxiang

2009-01-29

289

Constraining the N2O5 UV absorption cross-section from spectroscopic trace gas measurements in the tropical mid-stratosphere  

NASA Astrophysics Data System (ADS)

The absorption cross-section of N2O5, ?N2O5(?, T), which is known from laboratory measurements with the uncertainty of a factor of 2 (Table 4-2 in JPL-2011, Sander et al., 2011), was investigated by balloon-borne observations of the relevant trace gases in the tropical mid-stratosphere. The method relies on the observation of the diurnal variation of NO2 supported by detailed photochemical modelling of NOy (NOx(= NO + NO2) + NO3 + 2N2O5 + ClONO2 + HO2NO2 +BrONO2 + HNO3) photochemistry. Simulations are initialised with O3 measured by direct sun observations, the NOy partitioning from MIPAS-B (Michelson Interferometer for Passive Atmospheric Sounding-Balloon) observations in similar air masses at nighttime, and all other relevant species from simulations of the SLIMCAT chemical transport model (CTM). Best agreement between the simulated and observed diurnal increase of NO2 is found if the ?N2O5(?, T) is scaled by a factor of 1.6 ± 0.8 in the UV-C (200-260 nm) and by a factor of 0.9 ± 0.26 in the UV-B/A (260-350 nm), compared to current recommendations. In consequence, at 30 km altitude, the N2O5 lifetime against photolysis becomes a factor of 0.77 shorter at solar zenith angle (SZA) of 30° than using the recommended ?N2O5 (?, T), and stays more or less constant at SZAs of 60°. Our scaled N2O5 photolysis frequency slightly reduces the lifetime (0.2-0.6%) of ozone in the tropical mid- and upper stratosphere, but not to an extent to be important for global ozone.

Kritten, L.; Butz, A.; Chipperfield, M. P.; Dorf, M.; Dhomse, S.; Hossaini, R.; Oelhaf, H.; Prados-Roman, C.; Wetzel, G.; Pfeilsticker, K.

2014-02-01

290

Absorption spectra and photovoltaic characterization of chlorophyllins as sensitizers for dye-sensitized solar cells  

NASA Astrophysics Data System (ADS)

Dye-sensitized solar cells (DSSCs) based on Chlorine-e6 (Chl-e6), a Chlorophyll a derivative, and Chl-e6 containing Cu, have been investigated by carrying out incident photon to current efficiency (IPCE) and current-voltage (I-V) measurements. The effect of the metallic ion and the influence of the solvent polarity on the dye aggregation and their absorption bands have been analysed by performing electronic absorption measurements. The dependence of the photoelectrochemical parameters of these DSSCs on the electrolyte by the addition of pyrimidine and/or pyrrole has been discussed in details. For the first time I-V curves for a DSSC based on copper Chl-e6 dye have been shown and compared with Zn based chlorophyllin. Furthermore, the performance of a Cu-Chl-e6 based DSSC has been deeply improved by a progressive optimization of the TiO2 multilayer photoanode overcoming the best data reported in literature so far for this dye. It's worth to emphasize that, the analysis reported in this paper supplies very useful information which paves the way to further detailed studies turned to the employment of natural pigments as sensitizers for solar cells.

Calogero, Giuseppe; Citro, Ilaria; Crupi, Cristina; Di Marco, Gaetano

2014-11-01

291

Enhancement of oral bioavailability of tripterine through lipid nanospheres: preparation, characterization, and absorption evaluation.  

PubMed

Oral delivery of anticancer drugs remains challenging because of limited water-solubility and/or poor permeability. Here, we aimed to enhance the oral bioavailability of tripterine (TRI, a plant-derived anticancer compound) using lipid nanospheres (LNs) and to determine the mechanisms of oral absorption. TRI-loaded LNs (TRI-LNs) were prepared by rapid dispersion of an ethanol mixture of TRI, lecithin, sodium oleate, and soybean oil into water. The obtained LNs were 150 nm in size with a high value of entrapment efficiency (99.95%). TRI-LNs were fairly stable and the drug release was negligible (<0.2%) in simulated physiological fluid. The pharmacokinetic results showed that LNs significantly enhanced the oral bioavailability of TRI with a relative bioavailability of 224.88% (TRI suspensions was used as a reference). The mechanistic studies demonstrated that improved intestinal permeability and post-enterocyte lymphatic transport were mainly responsible for the enhanced oral absorption. Our findings suggested that LNs may be a viable oral carrier for poorly bioavailable drugs. PMID:24700417

Zhang, Xingwang; Zhang, Tianpeng; Zhou, Xiaotong; Liu, Hongming; Sun, Hua; Ma, Zhiguo; Wu, Baojian

2014-06-01

292

Spectroscopic characterization of co-precipitated arsenic- and iron-bearing sulfide phases at circum-neutral pH  

NASA Astrophysics Data System (ADS)

Precipitation of arsenic- and iron-sulfide phases from porewaters is an important mechanism for removing arsenic and other contaminant metals from solution, thus reducing their bioaccessibility and potential toxicity. Although sulfide phases form readily at low pH, the identity, crystallinity, and local structure of arsenic and iron co-precipitated phases that form at circum-neutral pH are less well known. In this study, co-precipitated As+Fe sulfide phases and end-member As-sulfides and Fe-sulfides were synthesized in batch experiments and in a gas-tight reaction vessel at 25°C. Reduced conditions were maintained by keeping a constant flow of a 95%N2 /5%H2 mixture gas. Fresh saturated solutions of 0.3 M Fe(II) or Fe(III), 0.3 M S2- and 0.2 M As(III) ions were mixed and pH was maintained at pH 4, 6 and 8 by small additions of concentrated HCl or NaOH. At different time intervals, aliquots were extracted from suspensions aged from hours to 1 month and analyzed for total iron, arsenic and sulfur (by ICP-OES and ICP-MS). The Fe-S-As precipitates were characterized by X-ray diffraction (XRD) and synchrotron X-ray absorption spectroscopy (XAS). X-ray diffraction and Fe k-edge EXAFS showed the precipitation of amorphous to poorly crystalline iron sulfide when Fe(II) was co-precipitated with sulfide (no arsenic) at pH 4, 6, and 8. The precipitate that formed in ~1-4 h was nanoparticle-sized and disordered mackinawite (FeS), which showed a characteristic broad, low-intensity Bragg peaks in the XRD patterns. After aging for ~7 d, XRD patterns showed a change to more crystalline mackinawite. In contrast, co-precipitation of As(III) with Fe(II) and sulfide resulted in x-ray amorphous (both synchrotron and laboratory XRD) precipitates for all pH and aging times (~4 h to 1 m). Arsenic and iron XANES and EXAFS spectra of precipitates at pH 4 showed a mixture of amorphous orpiment-type (As2S3) and mackinawite-type (FeS) phases. At pH 6 and 8, XANES showed As sulfide and a fraction of As(III) coordinated by oxygen, with a higher proportion of As(III)-O at pH 8 with arsenic EXAFS data showing two distinct coordination environments: oxygen atoms at 1.79 Å and sulfur atoms at 2.3, 3.2, and 3.5 Å, the latter consistent with the local structure of orpiment. When Fe(II) was co-precipitated with arsenic and sulfide, Fe EXAFS and XRD showed a mackinawite-type structure with evidence for formation of magnetite at pH 8. Arsenic EXAFS showed a mixture of arsenic sulfide and As(III)-O, with a higher proportion of As(III)-O at pH 8 than at pH 6. Also, analyses of the pH 6 and 8 supernatant solutions showed that ~95% of the iron, and 96-99% of arsenic and sulfur were precipitated with the highest arsenic uptake associated with the Fe(II) mixtures. Thus, at circum-neutral pH arsenic is effectively removed when combined with both iron and sulfide. A complicated mechanism of arsenic sequestration occurs through both rapid precipitation of amorphous arsenic sulfide phases and surface complexation. This differs from the precipitation dominated arsenic removal at low pH mixtures.

Illera, V.; Rivera, N. A.; O'Day, P. A.

2009-12-01

293

Study of a sample of faint Be stars in the exofield of CoRoT. I. Spectroscopic characterization  

NASA Astrophysics Data System (ADS)

Context. Be stars are probably the most rapid rotators among stars in the main sequence (MS) and, as such, are excellent candidates to study the incidence of the rotation on the characteristics of their non-radial pulsations, as well as on their internal structure. Pulsations are also thought to be possible mechanisms that help the mass ejection needed to build up the circumstellar disks of Be stars. Aims: The purpose of this paper is to identify a number of faint Be stars observed with the CoRoT satellite and to determine their fundamental parameters, which will enable us to study their pulsation properties as a function of the location in the HR diagram and to search for correlations with the light outbursts, which are possibly produced by discrete mass ejections. Methods: We identified those objects in the exofields of CoRoT presenting the Be phenomenon using H? surveys, as well as automated methods based on pulsation properties that we finally confirmed with FLAMES/GIRAFFE and X-shooter spectroscopic observations at VLT/ESO, and with near-IR photometry. The spectra were 1) corrected for the veiling effect, 2) treated with the GIRFIT code to determine apparent fundamental parameters, and 3) corrected with the FASTROT code for effects induced by the rapid rotation. Results: A list of 41 Be star candidates were found from photometric and spectroscopic criteria. The spectral coverage useful for determining the fundamental parameters was obtained for only about half of them. We then spectroscopically identified 21 Be stars, two probable Be stars, and two B stars contaminated by the Sh 2-284 nebulosity. A short description of the spectral characteristics of each star is given. The fundamental parameters and, in particular, the rotation frequency ?r (cycles per day) were all corrected for rotational effects at rotation rates ranging from ?/?c = 0.8 to 1.0. We have determined the positions of Be stars in the HR diagram and find two of them located beyond the MS phase. Conclusions: The well-determined fundamental parameters presented in this paper for a statistically reliable sample of Be stars will enable us in forthcoming papers to compare the properties of stars as pulsators either according to their location in different regions of the HR diagram or with those predicted from theory. Appendices are only available in electronic form at http://www.aanda.org

Semaan, T.; Hubert, A. M.; Zorec, J.; Martayan, C.; Frémat, Y.; Gutiérrez-Soto, J.; Fabregat, J.

2013-03-01

294

Reactivity-activity relationships of oral anti-diabetic vanadium complexes in gastrointestinal media: an X-ray absorption spectroscopic study.  

PubMed

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

Levina, Aviva; McLeod, Andrew I; Kremer, Lauren E; Aitken, Jade B; Glover, Christopher J; Johannessen, Bernt; Lay, Peter A

2014-10-01

295

Spectroscopic characterization of Co3O4 catalyst doped with CeO2 and PdO for methane catalytic combustion  

NASA Astrophysics Data System (ADS)

The study deals with the XPS, Raman and EDX characterization of a series of structured catalysts composed of cobalt oxides promoted by palladium and cerium oxides. The aim of the work was to relate the information gathered from spectroscopic analyses with the ones from kinetic tests of methane combustion to establish the basic structure-activity relationships for the catalysts studied. The most active catalyst was the cobalt oxide doped with little amount of palladium and wins a confrontation with pure palladium oxide catalyst which is commercially used in converters for methane. The analyses Raman and XPS analyses showed that this catalyst is composed of a cobalt spinel and palladium oxide. The quantitative approach to the composition of the catalysts by XPS and EDX methods revealed that the surface of palladium doped cobalt catalyst is enriched with palladium oxide which provides a great number of active centres for methane combustion indicated by kinetic parameters.

Jod?owski, P. J.; J?drzejczyk, R. J.; Rogulska, A.; Wach, A.; Ku?trowski, P.; Sitarz, M.; ?ojewski, T.; Ko?odziej, A.; ?ojewska, J.

2014-10-01

296

Synthesis, spectroscopic characterization, potentiometric studies, cytotoxic studies and molecular docking studies of DNA binding of transition metal complexes with 1,1-diaminopropane-Schiff base  

NASA Astrophysics Data System (ADS)

A new series of Schiff base transition metal complexes with N,N'-bis(2-hydroxybenzylidene)-1,1-diaminopropane (H2BHBDAP) have been prepared and characterized by elemental analysis, spectroscopic and magnetic measurements. Protonation constants of Schiff base and stability constants of their binary metal complexes have been determined potentiometrically in 50% DMSO-water media at 25 °C and ionic strength 0.10 M sodium perchlorate. Quantum chemical calculations were performed with semi-empirical method to find the optimum geometry of the ligand and its complexes. Additionally in silico, the Docking studies and the calculated pharmacokinetic parameters show promising futures for application of the ligand and complexes as high potency agents for DNA binding activity.

Alaghaz, Abdel-Nasser M. A.; El-Sayed, Badr A.; El-Henawy, Ahmed A.; Ammar, Reda A. A.

2013-03-01

297

The purple Codex Rossanensis: spectroscopic characterization and first evidence of the use of the elderberry lake in a 6th century manuscript  

E-print Network

The Codex Rossanensis is a 6th century Bizantine illuminated manuscript written on purple parchment and conserved at the Museo Diocesano in Rossano Calabro, Italy. It is one of the oldest surviving illuminated manuscripts of the New Testament. The challenge of the analysis of the Codex Rossanensis lies in the lack of analytical information on the pictorial media used in the Early Middle Ages. Even though old-medieval illuminated manuscripts have been deeply studied from the historical standpoint, they have been rarely described in their material composition. This paper presents the results obtained during the measurements campaign (June 2012 - November 2013). The spectroscopic analyses performed by Raman, micro-FTIR and XRF allowed for the complete characterization of the pictorial palette, the inks, the support and the material used in a previous restoration treatment. To the author knowledge the article shows the first experimental evidence of the usage of the elderberry lake in a 6th century illuminated ma...

Bicchieri, Marina

2014-01-01

298

A new pentanuclear cyano-bridged complex [{Fe II(tetraazamacrocycle)} 3{?-NC-Fe III(CN) 5} 2]: Synthesis, spectroscopic and magnetic characterization  

NASA Astrophysics Data System (ADS)

Hexacyanoferrate(III) reacts with [Fe II(meso)(CH 3CN) 2](ClO 4) 2·2CH 3CN (meso = 5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane) in acetonitrile/water mixture producing the title complex, where three [Fe(meso)] 2+ units are connected by two [Fe(CN) 6] 3- anions. Molecular modeling (MM +) shows a fairly linear molecule and Mössbauer data are consistent with two terminal pentacoordinated low spin iron(II)-meso units linked to one hexacoordinated low spin iron(II)-meso through two hexacoordinated low spin iron(III) units. Spectroscopic characterization showed a typical mixed-valence charge transfer band and the degree of electron coupling was calculated to be HAB = 678 cm -1. Magnetic properties exhibited an antiferromagnetic exchange interaction between the iron(III) ions with a coupling constant J = -44 cm -1.

Ishiruji, Fabiana H. O.; Evans, David J.; Benedito, Flávio L.; Nunes, Fábio S.

2008-10-01

299

Loss of anion transport without increased sodium absorption characterizes newborn porcine cystic fibrosis airway epithelia  

PubMed Central

SUMMARY Defective transepithelial electrolyte transport is thought to initiate cystic fibrosis (CF) lung disease. Yet, how loss of CFTR affects electrolyte transport remains uncertain. CFTR?/? pigs spontaneously develop lung disease resembling human CF. At birth, their airways exhibit a bacterial host defense defect, but are not inflamed. Therefore, we studied ion transport in newborn nasal and tracheal/bronchial epithelia in tissue, cultures, and in vivo. CFTR?/? epithelia showed markedly reduced Cl? and HCO3? transport. However, in contrast to a widely held view, lack of CFTR did not increase transepithelial Na+ or liquid absorption or reduce periciliary liquid depth. Like human CF, CFTR?/? pigs showed increased amiloride-sensitive voltage and current, but lack of apical Cl? conductance caused the change, not increased Na+ transport. These results indicate that CFTR provides the predominant transcellular pathway for Cl? and HCO3? in porcine airway epithelia, and reduced anion permeability may initiate CF airway disease. PMID:21145458

Chen, Jeng-Haur; Stoltz, David A.; Karp, Philip H.; Ernst, Sarah E.; Pezzulo, Alejandro A.; Moninger, Thomas O.; Rector, Michael V.; Reznikov, Leah R.; Launspach, Janice L.; Chaloner, Kathryn; Zabner, Joseph; Welsh, Michael J.

2011-01-01

300

Characterization of Metalloproteins by High-throughput X-ray Absorption Spectroscopy  

SciTech Connect

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.

W Shi; M Punta; J Bohon; J Sauder; R DMello; M Sullivan; J Toomey; D Abel; M Lippi; et al.

2011-12-31

301

Characterization and speciation of mercury-bearing mine wastes using X-ray absorption spectroscopy  

USGS Publications Warehouse

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.

Kim, C. S.; Brown, Jr. , G. E.; Rytuba, J. J.

2000-01-01

302

Characterization and speciation of mercury-bearing mine wastes using X-ray absorption spectroscopy.  

PubMed

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

Kim, C S; Brown, G E; Rytuba, J J

2000-10-16

303

Fabrication of calix[4]pyrrole nanofilms at the glassy carbon surface and their characterization by spectroscopic, optic and electrochemical methods  

Microsoft Academic Search

meso-Octamethylcalix[4]pyrrole (CP) and meso-heptaethylcalix[4]pyrrole-meso-4-aminophenyl (4APCP) modified glassy carbon (GC) electrodes were prepared by the electrochemical oxidation in acetonitrile solution. Binding of the calix[4]pyrroles with the glassy carbon surface was investigated that it is through the etheric linkage revealed from the reflection–absorption infrared spectroscopy (RAIRS). Surface films of CP and 4APCP were investigated by cyclic voltammetry (CV), ellipsometry, X-ray photoelectron spectroscopy,

Bilge Taner; Emine Özcan; Zafer Üstündag; Selda Keskin; Ali Osman Solak; Haslet Eksi

2010-01-01

304

Synthesis, Spectroscopic Characterization, X-Ray Structure, and DFT Calculations of Some New 1,4-Dihydro-2,6-Dimethyl-3,5 -Pyridinedicarboxamides  

PubMed Central

A series of novel 1,4-dihydro-2,6- dimethyl-3,5-pyridinedicarboxamides were synthesized and characterized by infrared absorption spectrum (IR), proton nuclear magnetic resonance (1H NMR), elemental analysis, ultraviolet spectrum (UV), and fluorescence techniques, together with X-ray single crystal diffraction. The results of density functional theory (DFT) and time-dependent density functional theory (TDDFT) calculations provided a reasonable explanation on the molecular structures, the molecular frontier orbital, and the spectra of electronic absorption and emission. The present work will be helpful to systematically understanding of the structures and the optical properties of 1,4-dihydropyridines for studying the structure-activity relationship and to develop new drugs and their analytical methods. PMID:24625887

Li, Yi; Liu, Yuan-Yuan; Chen, Xue-Jun; Xiong, Xiao-Hui; Li, Fang-Shi

2014-01-01

305

Synthesis, characterization and theoretical study of new hetarylazopyrazolone dyes and investigation of their absorption spectra  

NASA Astrophysics Data System (ADS)

A series of hetarylazopyrazolone dyes were synthesized by coupling 1-(2-benzothiazolyl)-3-methylpyrazol-5-one with six heterocylic amines prepared in nitrosyl sulphuric acid. The dyes were characterized by spectral methods and elemental analysis. The solvatochromic properties of the dyes were investigated in various solvents. Additionally, acid-base, concentration, temperature and substituent effects on the visible absorbtion spectra were also examined.

Aktan, Ebru; Ertan, Nermin; Uyar, Tahsin

2014-02-01

306

CD Spectroscope  

NSDL National Science Digital Library

In this activity, learners use an old CD to construct a spectroscope, a device that separates light into its component colors. Learners will hold it up to various light sources to examine how different light has different color strengths. Use this activity to introduce learners to the color spectrum and the tools scientists use to study it.

University, Colorado S.

2009-01-01

307

Spectroscopic characterization of polyethyleneglycol modified superoxide dismutase: sup 1 H NMR studies on its Cu sub 2 Co sub 2 derivative  

SciTech Connect

Spectroscopic methods have been employed in order to understand the molecular basis of the decrease in enzymatic activity of the antiinflammatory enzyme copper-zinc superoxide dismutase (SOD) following the covalent binding of polyethyleneglycol (PEG) chains to the protein amino-groups. The PEG modification is a general method recently proposed to improve the therapeutic index of enzymes. 1H NMR spectra on the cobalt substituted PEG-modified SOD, Cu2Co2-PEG-SOD, have been recorded. The signals are quite broad with respect to the unmodified enzyme. This has been interpreted on the basis of the effect of molecular weight on the linewidth. The analysis has shown that the histidine hydrogens involved in metal binding at the enzyme active site are the same in both native and PEG-modified SOD. Similarly, circular dichroism and absorption spectra indicate that the overall conformation of the metal clusters is not perturbed upon modification. On the other hand, azide titration shows that the affinity constant of N-3 for SOD is largely reduced upon PEG modification (K = 154 M-1 and 75 M-1 for the native and modified SOD, respectively). These results indicate that the decrease in enzymatic activity upon surface modification with PEG is not caused by a perturbation of the active site geometry, but to a decrease in the channeling of the O2- ion towards the enzyme active site.

Banci, L.; Bertini, I.; Caliceti, P.; Monsu Scolaro, L.; Schiavon, O.; Veronese, F.M. (Univ. of Florence (Italy))

1990-06-01

308

Spectroscopic ellipsometry characterization of amorphous and crystalline TiO2 thin films grown by atomic layer deposition at different temperatures  

NASA Astrophysics Data System (ADS)

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.

Saha, D.; Ajimsha, R. S.; Rajiv, K.; Mukherjee, C.; Gupta, M.; Misra, P.; Kukreja, L. M.

2014-10-01

309

Structural characterization of 1,1,3,3-tetramethylguanidinium chloride ionic liquid by reversible SO2 gas absorption.  

PubMed

A unique new ionic liquid-gas adduct solid state compound formed between 1,1,3,3-tetramethylguanidinium chloride ([tmgH]Cl) and sulfur dioxide has been characterized by X-ray diffraction and Raman spectroscopy. The structure contains SO2 molecules of near normal structure kept at their positions by Cl-S interactions. The crystals belong in the orthorhombic system, space group Pbcn, with unit cell dimensions of a = 15.6908(10) Å, b = 9.3865(6) Å, and c = 14.1494(9) Å, angles ? = ? = ? = 90°, and Z = 8 at 120 K. The [tmgH]Cl has a very high absorption capacity of nearly 3 mol of SO2 per mol of [tmgH]Cl at 1 bar of SO2 and at room temperature. However, part of the absorbed SO2 was liberated during the crystallization, probably because the crystal only accommodates one molecule of SO2 per [tmgH]Cl. The nature of the high absorption capacity of [tmgH]Cl as well as of the homologous compounds with bromide and iodide are discussed. Some of these salts may prove useful as reversible absorbents of SO2 in industrial flue gases. PMID:24088034

Berg, Rolf W; Harris, Pernille; Riisager, Anders; Fehrmann, Rasmus

2013-11-01

310

Gold Nanoclusters Entrapped in the alpha-Cages of Y Zeolites: Structural Characterization by X-ray Absorption Spectroscopy  

SciTech Connect

Au(CH{sub 3}){sub 2}(C{sub 5}H{sub 7}O{sub 2}) was used as a precursor to synthesize mononuclear gold complexes in faujasites, NaY zeolite, and dealuminated Y zeolite. Treatment of these supported complexes in flowing helium as the temperature was increased led to the gradual reduction of the gold and formation of gold nanoclusters in each zeolite, which were characterized by X-ray absorption spectroscopy. After treatment at the highest temperature, 573 K, the average diameters of the gold clusters were approximately 10 and 8 {angstrom} in NaY zeolite and dealuminated Y zeolite, respectively; these clusters are smaller than the diameters of the {alpha}-cages of the zeolite. The results indicate that the supported clusters were trapped within these cages and that the cages limited their sizes; in contrast, clusters formed similarly on the surfaces of metal oxides are significantly larger than those formed in the zeolites.

Fierro-Gonzalez,J.; Hao, Y.; Gates, B.

2007-01-01

311

Gold Nanoclusters Entrapped in the Alpha-Cages of Y-Zeolites: Structural Characterization By X-Ray Absorption Spectroscopy  

SciTech Connect

Au(CH{sub 3}){sub 2}(C{sub 5}H{sub 7}O{sub 2}) was used as a precursor to synthesize mononuclear gold complexes in faujasites, NaY zeolite, and dealuminated Y zeolite. Treatment of these supported complexes in flowing helium as the temperature was increased led to the gradual reduction of the gold and formation of gold nanoclusters in each zeolite, which were characterized by X-ray absorption spectroscopy. After treatment at the highest temperature, 573 K, the average diameters of the gold clusters were approximately 10 and 8 {angstrom} in NaY zeolite and dealuminated Y zeolite, respectively; these clusters are smaller than the diameters of the {alpha}-cages of the zeolite. The results indicate that the supported clusters were trapped within these cages and that the cages limited their sizes; in contrast, clusters formed similarly on the surfaces of metal oxides are significantly larger than those formed in the zeolites.

Fierro-Gonzalez, J.C.; Hao, Y.; Gates, B.C.

2009-06-03

312

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

NASA Astrophysics Data System (ADS)

Plutonium uranium mixed oxide (MOX) fuels are currently used in nuclear reactors. The actinides in these fuels need to be analyzed after irradiation for assessing their behaviour with regard to their environment and the coolant. In this work the study of the atomic structure and next-neighbour environment of Am in the (Pu,U)O2 lattice in an irradiated (60 MW d kg-1) MOX sample was performed employing micro-X-ray fluorescence (µ-XRF) and micro-X-ray absorption fine structure (µ-XAFS) spectroscopy. The chemical bonds, valences and stoichiometry of Am (˜0.66 wt%) are determined from the experimental data gained for the irradiated fuel material examined in its peripheral zone (rim) of the fuel. In the irradiated sample Am builds up as Am3+ species within an [AmO8]13- coordination environment (e.g. >90%) and no (<10%) Am(IV) or (V) can be detected in the rim zone. The occurrence of americium dioxide is avoided by the redox buffering activity of the uranium dioxide matrix.

Degueldre, Claude; Cozzo, Cedric; Martin, Matthias; Grolimund, Daniel; Mieszczynski, Cyprian

2013-06-01

313

Characterization of silver binding in cryptomelane by x-ray absorption spectroscopy  

SciTech Connect

Silver-manganese oxides are minerals that occur in the class of secondary ore bodies where silver is transported from its source and is subsequently trapped in a manganese oxide matrix. Silver-manganese oxide ores are present in parts of the western US, Mexico, South America, and Sumatra. The amount of silver in these ore bodies varies between a few parts per million (ppm) to thousands of ppm. However, these ores are not compatible with conventional metallurgical treatment for the extraction of silver. Using silver K-edge extended X-ray absorption fine structure (EXAFS) spectroscopy, two different samples of silver-containing manganese oxide were analyzed in the fluorescence mode. For the first sample, silver ions from solution were sorbed onto one synthetic manganese oxide phase, namely cryptomelane (K{sub x}Mn{sub 8}O{sub 16}, where 1 < x < 2). The second sample was a silver-manganese oxide from Colorado. From the EXAFS analysis, silver was found to occupy two different sites in the synthetic sample. The natural samples from Colorado also exhibited a very similar coordination distances as the synthetic samples. In the low temperature spectrum of the synthetic sample at 10 K, the Ag-O peak was found to be missing and the amplitude of the Ag-Ag peak was approximately three times larger than the corresponding room temperature sample.

Ravikumar, R. [Univ. of California, Berkeley, CA (United States). Dept. of Materials Science and Mineral Engineering; [Siemens Microelectronics Inc., Hopewell Junction, NY (United States); Fuerstenau, D.W. [Univ. of California, Berkeley, CA (United States). Dept. of Materials Science and Mineral Engineering; Waychunas, G.A. [Stanford Univ., CA (United States). Center for Materials Research; [Lawrence Berkeley National Lab., CA (United States). Earth Sciences Div.

1998-12-31

314

Single molecule spectroscopic characterization of a far-red fluorescent protein (HcRed) from the Anthozoa coral Heteractis crispa  

NASA Astrophysics Data System (ADS)

We report on the photophysical properties of a far-red intrinsic fluorescent protein by means of single molecule and ensemble spectroscopic methods. The green fluorescent protein (GFP) from Aequorea victoria is a popular fluorescent marker with genetically encoded fluorescence and which can be fused to any biological structure without affecting its function. GFP and its variants provide emission colors from blue to yellowish green. Red intrinsic fluorescent proteins from Anthozoa species represent a recent addition to the emission color palette provided by GFPs. Red intrinsic fluorescent markers are on high demand in protein-protein interaction studies based on fluorescence-resonance energy transfer or in multicolor tracking studies or in cellular investigations where autofluorescence possesses a problem. Here we address the photophysical properties of a far-red fluorescent protein (HcRed), a mutant engineered from a chromoprotein cloned from the sea anemone Heteractis crispa, by using a combination of ensemble and single molecule spectroscopic methods. We show evidence for the presence of HcRed protein as an oligomer and for incomplete maturation of its chromophore. Incomplete maturation results in the presence of an immature (yellow) species absorbing/fluorescing at 490/530-nm. This yellow chromophore is involved in a fast resonance-energy transfer with the mature (purple) chromophore. The mature chromophore of HcRed is found to adopt two conformations, a Transoriented form absorbing and 565-nm and non-fluorescent in solution and a Cis-oriented form absorbing at 590-nm and emitting at 645-nm. These two forms co-exist in solution in thermal equilibrium. Excitation-power dependence fluorescence correlation spectroscopy of HcRed shows evidence for singlet-triplet transitions in the microseconds time scale and for cis-trans isomerization occurring in a time scale of tens of microseconds. Single molecule fluorescence data recorded from immobilized HcRed proteins, all point to the presence of two classes of molecules: proteins with Cis and Trans-oriented chromophores. Immobilization of HcRed in water-filled pores of polyvinyl alcohol leads to a polymer matrix - protein barrel interaction which results in a 'freezing' of the chromophore in a stable conformation for which non-radiative deactivation pathways are either suppressed or reduced. As a result, proteins with both Cis- and Trans-oriented chromophores can be detected at the single molecule level. Polymer chain motion is suggested as a mediator for an eventual cis-trans isomerization of the chromophore in the case of single immobilized proteins.

Cotlet, Mircea; Habuchi, Satoshi; Whitier, Jennifer E.; Werner, James H.; De Schryver, Frans C.; Hofkens, Johan; Goodwin, Peter M.

2006-02-01

315

One-dimensional WO{sub 3} and its hydrate: One-step synthesis, structural and spectroscopic characterization  

SciTech Connect

We report on a one-step hydrothermal growth of one-dimensional (1D) WO{sub 3} nanostructures, using urea as 1D growth-directing agent and a precursor free of metals other than tungsten. By decreasing the pH of the starting solution, the size of the nanostructures was reduced significantly, this development being accompanied by the realization of phase pure hexagonal WO{sub 3} nanorods (elimination of monoclinic impurity phase) and a red shift in optical absorption edge. Surface analyses indicated the presence of reduced tungsten species in the WO{sub 3} nanostructures, which increased two-fold in a hydrated WO{sub 3} phase obtained with further decrease in pH. We suggest that oxygen vacancies are responsible for this defect state in WO{sub 3}, while protons are responsible or contribute significantly to the same in the hydrated phase. - Graphical abstract: The figure illustrates the role of pH in morphological and absorption edge evolution of WO{sub 3} (hydrate) as well as the variation in the concentration of defect electrons between anhydrous and hydrated WO{sub 3}. Highlights: Black-Right-Pointing-Pointer WO{sub 3} nanorods prepared in a one step procedure. Black-Right-Pointing-Pointer HCl (aq) enables phase pure WO{sub 3} nanorods. Black-Right-Pointing-Pointer HCl (aq) induces significant reduction in dimension of and red shift in absorption edge of nanorods. Black-Right-Pointing-Pointer W{sup 5+} detected in hydrothermal WO{sub 3} phase, the concentration of which increases in the hydrated phase. Black-Right-Pointing-Pointer W{sup 5+} from the two phases due to different positive defects.

Iwu, Kingsley O., E-mail: k.o.iwu@smn.uio.no [Department of Chemistry, University of Oslo, Centre for Materials Science and Nanotechnology, FERMiO, Gaustadalleen 21, NO-0349 Oslo (Norway); Galeckas, Augustinas, E-mail: augustinas.galeckas@fys.uio.no [Department of Physics, University of Oslo, Centre for Materials Science and Nanotechnology, P.O. Box 1048 Blindern, NO-0316 Oslo (Norway); Rauwel, Protima, E-mail: protima.singh@fys.uio.no [Centre for Materials Science and Nanotechnology, University of Oslo, P.O. Box 1126 Blindern, NO-0318 Oslo (Norway); Kuznetsov, Andrej Y., E-mail: andrej.kuznetsov@fys.uio.no [Department of Physics, University of Oslo, Centre for Materials Science and Nanotechnology, P.O. Box 1048 Blindern, NO-0316 Oslo (Norway); Norby, Truls, E-mail: truls.norby@kjemi.uio.no [Department of Chemistry, University of Oslo, Centre for Materials Science and Nanotechnology, FERMiO, Gaustadalleen 21, NO-0349 Oslo (Norway)

2012-01-15

316

Fourier Transform Infrared Spectroscopic characterization and optimization of Pb(II) biosorption by fish (Labeo rohita) scales.  

PubMed

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

Nadeem, Raziya; Ansari, Tariq Mahmood; Khalid, Ahmad Mukhtar

2008-08-15

317

Structural, Functional, and Spectroscopic Characterization of the Substrate Scope of the Novel Nitrating Cytochrome P450 TxtE.  

PubMed

A novel cytochrome P450 enzyme, TxtE, was recently shown to catalyze the direct aromatic nitration of L-tryptophan. This unique chemistry inspired us to ask whether TxtE could serve as a platform for engineering new nitration biocatalysts to replace current harsh synthetic methods. As a first step toward this goal, and to better understand the wild-type enzyme, we obtained high-resolution structures of TxtE in its substrate-free and substrate-bound forms. We also screened a library of substrate analogues for spectroscopic indicators of binding and for production of nitrated products. From these results, we found that the wild-type enzyme accepts moderate decoration of the indole ring, but the amino acid moiety is crucial for binding and correct positioning of the substrate and therefore less amenable to modification. A nitrogen atom is essential for catalysis, and a carbonyl must be present to recruit the ?B'1 helix of the protein to seal the binding pocket. PMID:25182183

Dodani, Sheel C; Cahn, Jackson K B; Heinisch, Tillmann; Brinkmann-Chen, Sabine; McIntosh, John A; Arnold, Frances H

2014-10-13

318

Structural characterization of C-S-H and C-A-S-H samples-Part II: Local environment investigated by spectroscopic analyses  

SciTech Connect

Spectroscopic studies ({sup 1}H, {sup 23}Na and {sup 27}Al MAS NMR and Raman spectroscopy) have been used to characterize three series of C-S-H samples (0.8Spectroscopic investigations indicate that the main part of the Al atoms is readily incorporated into the interlayer region of the C-S-H structure. Al atoms are mainly inserted as four-fold coordinated aluminates in the dreierketten silicate chain (either in bridging or paired tetrahedra) at low Ca/Si ratio. Four-fold aluminates are progressively replaced by six-fold coordinated aluminates located into the interlayer region of the C-S-H structure and bonded to silicate chains. Investigation of the hydrogen bonding in C-S-H indicates that the main part of the hydrogen bonds is intra-main layer, and thus explains the low stacking cohesion of the C-S-H structure leading to its nanometric crystal size and the OD character of the tobermorite like structures. - Graphical abstract: The insertion of aluminum atoms into the C-S-H structure has been investigated by spectroscopic analyses ({sup 27}Al and {sup 1}H MAS NMR and Raman). The previously determined structural continuity, when increasing the C/S ratio from the C-S-H(I) type to the C-S-H(II) type, has been confirmed even in the presence of aluminum.

Renaudin, Guillaume, E-mail: guillaume.renaudin@ensccf.f [Clermont-Universite, Ecole Nationale Superieure de Chimie de Clermont-Ferrand, LMI, BP 10448, F-63000 Clermont-Ferrand (France); CNRS, UMR 6002, F-63177 Aubiere Cedex (France); Russias, Julie [Commissariat a l'Energie Atomique, DEN, Marcoule, Waste Treatment and Conditioning Research Department, F-30207 Bagnols sur Ceze (France); Leroux, Fabrice [Clermont Universite, UBP, Laboratoire des Materiaux Inorganiques, F-63000 Clermont-Ferrand (France); CNRS, UMR 6002, F-63177 Aubiere Cedex (France); Cau-dit-Coumes, Celine; Frizon, Fabien [Commissariat a l'Energie Atomique, DEN, Marcoule, Waste Treatment and Conditioning Research Department, F-30207 Bagnols sur Ceze (France)

2009-12-15

319

Spectroscopic database  

NASA Technical Reports Server (NTRS)

Several aspects of quantitative atmospheric spectroscopy are considered, using a classification of the molecules according to the gas amounts in the stratosphere and upper troposphere, and reviews of quantitative atmospheric high-resolution spectroscopic measurements and field measurements systems are given. Laboratory spectroscopy and spectral analysis and prediction are presented with a summary of current laboratory spectroscopy capabilities. Spectroscopic data requirements for accurate derivation of atmospheric composition are discussed, where examples are given for space-based remote sensing experiments of the atmosphere: the ATMOS (Atmospheric Trace Molecule) and UARS (Upper Atmosphere Research Satellite) experiment. A review of the basic parameters involved in the data compilations; a summary of information on line parameter compilations already in existence; and a summary of current laboratory spectroscopy studies are used to assess the data base.

Husson, N.; Barbe, A.; Brown, L. R.; Carli, B.; Goldman, A.; Pickett, H. M.; Roche, A. E.; Rothman, L. S.; Smith, M. A. H.

1985-01-01

320

Structural characterization of C-S-H and C-A-S-H samples—Part II: Local environment investigated by spectroscopic analyses  

NASA Astrophysics Data System (ADS)

Spectroscopic studies ( 1H, 23Na and 27Al MAS NMR and Raman spectroscopy) have been used to characterize three series of C-S-H samples (0.8Spectroscopic investigations indicate that the main part of the Al atoms is readily incorporated into the interlayer region of the C-S-H structure. Al atoms are mainly inserted as four-fold coordinated aluminates in the dreierketten silicate chain (either in bridging or paired tetrahedra) at low Ca/Si ratio. Four-fold aluminates are progressively replaced by six-fold coordinated aluminates located into the interlayer region of the C-S-H structure and bonded to silicate chains. Investigation of the hydrogen bonding in C-S-H indicates that the main part of the hydrogen bonds is intra-main layer, and thus explains the low stacking cohesion of the C-S-H structure leading to its nanometric crystal size and the OD character of the tobermorite like structures.

Renaudin, Guillaume; Russias, Julie; Leroux, Fabrice; Cau-dit-Coumes, Céline; Frizon, Fabien

2009-12-01

321

Synthesis, isolation, and spectroscopic characterization of holmium-based mixed-metal nitride clusterfullerenes: HoxSc3-xN@C80 (x=1, 2).  

PubMed

The synthesis, isolation and spectroscopic characterization of holmium-based mixed metal nitride clusterfullerenes Ho(x) Sc(3-x) N@C(80) (x=1, 2) are reported. Two isomers of Ho(x) Sc(3-x) N@C(80) (x=1, 2) were synthesized by the reactive gas atmosphere method and isolated by multistep recycling HPLC. The isomeric structures of Ho(x) Sc(3-x) N@C(80) (x=1, 2) were characterized by laser-desorption time-of-flight (LD-TOF) mass spectrometry and UV/Vis/NIR, FTIR and Raman spectroscopy. A comparative study of M(x) Sc(3-x) N@C(80) (M=Gd, Dy, Lu, Ho) demonstrates the dependence of their electronic and vibrational properties on the encaged metal. Despite the distinct perturbation induced by 4f(10) electrons, we report the first paramagnetic (13) C?NMR study on Ho(x) Sc(3-x) N@C(80) (I; x=1, 2) and confirm I(h) -symmetric cage structure. A (45) Sc NMR study on HoSc(2) N@C(80) (I, II) revealed a temperature-dependent chemical shift in the temperature range of 268-308?K. PMID:22745152

Zhang, Yang; Popov, Alexey A; Schiemenz, Sandra; Dunsch, Lothar

2012-07-27

322

CHARACTERIZATION OF A SAMPLE OF INTERMEDIATE-TYPE AGNs. I. SPECTROSCOPIC PROPERTIES AND SERENDIPITOUS DISCOVERY OF NEW DUAL AGNs  

SciTech Connect

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.

Benitez, Erika; Cruz-Gonzalez, Irene; Martinez, Benoni; Jimenez-Bailon, Elena [Instituto de Astronomia, Universidad Nacional Autonoma de Mexico, Apdo. Postal 70-264, Mexico D.F. 04510 (Mexico)] [Instituto de Astronomia, Universidad Nacional Autonoma de Mexico, Apdo. Postal 70-264, Mexico D.F. 04510 (Mexico); Mendez-Abreu, Jairo; Lopez-Martin, Luis [Instituto de Astrofisica de Canarias, E-38200 La Laguna, Tenerife (Spain)] [Instituto de Astrofisica de Canarias, E-38200 La Laguna, Tenerife (Spain); Fuentes-Carrera, Isaura [Escuela Superior de Fisica y Matematicas, Instituto Politecnico Nacional (ESFM-IPN), U.P. Adolfo Lopez Mateos, Mexico D.F. 07730 (Mexico)] [Escuela Superior de Fisica y Matematicas, Instituto Politecnico Nacional (ESFM-IPN), U.P. Adolfo Lopez Mateos, Mexico D.F. 07730 (Mexico); Leon-Tavares, Jonathan [Aalto University Metsaehovi Radio Observatory, Metsaehovintie 114, FI-02540, Kylmaelae (Finland)] [Aalto University Metsaehovi Radio Observatory, Metsaehovintie 114, FI-02540, Kylmaelae (Finland); Chavushyan, Vahram H., E-mail: erika@astro.unam.mx [Instituto Nacional de Astrofisica, Optica y Electronica, Apdo. Postal 51-216, 72000 Puebla (Mexico)

2013-01-20

323

Portuguese tin-glazed earthenware from the 16th century: A spectroscopic characterization of pigments, glazes and pastes  

NASA Astrophysics Data System (ADS)

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.

Vieira Ferreira, L. F.; Ferreira Machado, I.; Ferraria, A. M.; Casimiro, T. M.; Colomban, Ph.

2013-11-01

324

UV-vis, IR and 1H NMR spectroscopic studies and characterization of ionic-pair crystal violet-oxytetracycline  

NASA Astrophysics Data System (ADS)

The present study shows the formation and characterization of the ionic-pair between the antibiotic oxytetracycline and the dye crystal violet in ammonia solution pH 9.0 ± 0.2 extracted into chloroform. The characterization was demonstrated using UV-vis spectrophotometry, 1H NMR, measurement of relaxation times T1 and IR spectroscopy, using a comparison between the signals of individual pure compounds with the signals with the mixture CV-OTC in different alkaline media. The formation of ionic-pair was also corroborated by new signals and chemical shifts. (2D) NMR spectroscopy experiments show that the interaction is electrostatic.

Orellana, Sandra; Soto, César; Toral, M. Inés

2010-01-01

325

Combined UHV/high-pressure catalysis setup for depth-resolved near-surface spectroscopic characterization and catalytic testing of model catalysts.  

PubMed

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

Mayr, Lukas; Rameshan, Raffael; Klötzer, Bernhard; Penner, Simon; Rameshan, Christoph

2014-05-01

326

Spectroscopic and Electrochemical Characterization of Benzoylglycine-Modified Glassy Carbon Electrode: Electrocatalytic Effect Towards Dioxygen Reduction in Aqueous Media  

Microsoft Academic Search

Present work aims to create a benzoylglycine (BG)-modified glassy carbon (GC) substrate exploiting the electroreduction of diazonium salts. Dopamine was used to confirm the attachment of benzoylglycine molecules onto the glassy carbon surface by observing the blockage of the electron transfer using cyclic voltammetry (CV). BG-modified GC surface (BG-GC) was also characterized by Raman spectroscopy and electrochemical impedance spectroscopy (EIS)

Aybüke A. ?sbir-Turan; Zafer Ustundag; Haslet Eksi; Remziye Guzel; Ali Osman Solak

2011-01-01

327

Microscopic and Spectroscopic Characterization of Calcified Microorganisms at the Nanometer-Scale in Experimental and Field Samples  

Microsoft Academic Search

Calcium phosphates and calcium carbonates are the most prevalent minerals involved in microbial fossilization. Structural characterization of both the organic and mineral components in such samples is, however, usually difficult at the appropriate spatial resolution, i.e., at the submicrometer scale. We have used a combination of Scanning Transmission X-ray microscopy (STXM), a synchrotron-based technique, and High-Resolution Transmission Electron Microscopy (HRTEM)

K. Benzerara; T. Yoon; N. Menguy; T. Tyliszczak; G. E. Brown

2004-01-01

328

Synthesis and spectroscopic characterization of trinuclear [Ru 3 O(O 2 CCH 3 ) 6 (pyrazine) 3 ] 0, + clusters  

Microsoft Academic Search

[Ru3O(O2CCH3)6(pyrazine)3]0, + clusters have been synthesized and characterized based on electronic, infrared and resonance Raman spectra. Selective enhancement of the pyrazine and Ru3O(O2CCH3)6 vibrational modes has been observed in the case of the reduced cluster using excitation wavelengths close to the metal-to-pyrazine and metal-metal charge transfer band in the visible region.

Henrique E. Toma; Cecilia Cipriano

1989-01-01

329

Reactions of Highly Uniform Zeolite H-Supported Rhodium Complexes: Transient Characterization by Infrared and X-ray Absorption Spectroscopies  

SciTech Connect

A zeolite H-{beta}-supported mononuclear rhodium diethene complex (Rh(C{sub 2}H{sub 4}){sub 2}{l_brace}O{sub 2}Al{r_brace}, where the braces indicate a part of the zeolite) was formed by the reaction of Rh(acac)({eta}{sub 2}-C{sub 2}H{sub 4}){sub 2} (acac = acetylacetonate, C{sub 5}H{sub 7}O{sub 2}{sup -}) with the zeolite. Transient characterization of the sample by X-ray absorption near edge structure (XANES) and infrared (IR) spectroscopies (combined with mass spectrometry of the effluent gas) while the sample was in contact with flowing CO indicates a simple stoichiometric conversion of the supported metal complex into another species, identified by the spectra as the zeolite-supported rhodium gem-dicarbonyl (Rh(CO){sub 2}{l_brace}O{sub 2}Al{r_brace}). The sharpness of the v{sub CO} bands in the IR spectrum indicates a high degree of uniformity of the supported rhodium gem-dicarbonyl, and isosbestic points in the XANES spectra as the transformation was occurring imply that the rhodium diethene complex was also highly uniform. Spectra similarly show that treatment of the supported rhodium gem-dicarbonyl with flowing C{sub 2}H{sub 4} resulted in another stoichiometrically simple transformation, giving a species suggested to be Rh(C{sub 2}H{sub 4})(CO){sub 2}{l_brace}O{sub 2}Al{r_brace}. The intermediate was ultimately transformed when the sample was purged with helium into another highly uniform supported species, inferred on the basis of IR spectra to be Rh(C{sub 2}H{sub 4})(CO){l_brace}O{sub 2}Al{r_brace}. Extended X-ray absorption fine structure spectra characterizing the supported rhodium diethene complex and the species formed from it show how the Rh-O bond distance at the Rh-support interface varied in response to the changes in the ligands bonded to the rhodium.

Ogino, I.; Gates, B

2010-01-01

330

Spectroscopic characterization of nitrosylheme in nitric oxide complexes of ferric and ferrous cytochrome c' from photosynthetic bacteria.  

PubMed

Reactions of ferric and ferrous cytochromes c' from four photosynthetic bacteria (Rhodobacter capsulatus ATCC 11166, Rhodopseudomonas palustris ATCC 17001, Rhodospirillum rubrum ATCC 11170, and Chromatium vinosum ATCC 17899) with nitric oxide have been investigated by electronic absorption and electron paramagnetic resonance spectroscopies. The heme iron(III) of these ferric cytochromes c' has been recently reported to be in a quantum mechanically admixed (S = 5/2, 3/2) state [Fujii, S., Yoshimura, T., Kamada, H., Yamaguchi, K., Suzuki, S., Shidara, S. and Takakuwa, S. (1995) Biochim. Biophys. Acta 1251, 161-169]. The affinity of ferric cytochromes c' for NO among these bacterial species (C. vinosum > Rps. palustris approximately Rb. capsulatus > R. rubrum) was apparently related to the S = 3/2 content in the or der. In the reaction of ferrous cytochrome c' with NO, six- and five-coordinated nitrosylhemes, which represent species with and without a ligand at the axial position trans to nitrosyl group, have been formed. The content of six-coordinated nitrosylheme in NO-ferrous cytochrome c' has been determined to be Rb. capsulatus approximately Rps. palustris > C. vinosum < R rubrum, suggesting that a stability of iron-to-histidine bond decreases with this order. The NO reactions of ferric and ferrous cytochromes c' from photosynthetic bacteria have been compared with those of cytochromes c' from denitrifying bacteria. PMID:8547347

Yoshimura, T; Fujii, S; Kamada, H; Yamaguchi, K; Suzuki, S; Shidara, S; Takakuwa, S

1996-01-01

331

Spectroscopic characterization of a multiband complex oxide: Insulating and conducting cement 12CaO·7Al2O3  

NASA Astrophysics Data System (ADS)

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. These measurements suggest the existence of a narrow conduction band between the main 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.

McLeod, J. A.; Buling, A.; Kurmaev, E. Z.; Sushko, P. V.; Neumann, M.; Finkelstein, L. D.; Kim, S.-W.; Hosono, H.; Moewes, A.

2012-01-01

332

Spectroscopic characterization of atmospheric pressure argon plasmas sustained with the Torche à Injection Axiale sur Guide d'Ondes  

NASA Astrophysics Data System (ADS)

An argon microwave (2.45 GHz) plasma produced by a microwave plasma torch known as "Torche à Injection Axiale sur Guide d'Ondes" (TIAGO) in air ambience at atmospheric pressure was experimentally characterized. The conditions for appropriate TIAGO torch operation in argon and flame morphology were researched under several experimental conditions of gas flow (0.15-5.00 L · min-1) rates and microwave input powers (100-1000 W). Gas temperature and electron density values were studied by means of optical emission spectroscopy. Besides, the processes inside the discharge and their interaction with the surrounding atmosphere were described according to the recorded spectra.

Rincón, R.; Muñoz, J.; Sáez, M.; Calzada, M. D.

2013-03-01

333

Synthesis, spectroscopic characterization and thermal studies of some rare earth metal complexes of unsymmetrical tetradentate Schiff base ligand  

Microsoft Academic Search

The solid complexes of La(III), Ce(III), Pr(III), Nd(III), Sm(III) and Gd(III) with 4-hydroxy-3-(1-{2-(2-hydroxy-benzylidene)-aminophenylimino}-thyl)-6-methy-pyran-2-one (H2L) derived from o-phenylenediamine, 3-acetyl-6-methyl-(2H)pyran,2,4(3H)-dione (dehydroacetic acid or DHA) and salicylic aldehyde have been synthesized and characterized by elemental analysis, conductometry, magnetic susceptibility, UV–visible, FTIR, 1H NMR spectra, X-ray diffraction, and thermal analysis and screened for antimicrobial activity. The FTIR spectral data suggest that the ligand behaves

V. A. Shelke; S. M. Jadhav; V. R. Patharkar; S. G. Shankarwar; A. S. Munde; T. K. Chondhekar

334

Synthesis and spectroscopic characterization of monometallic molybdenum (VI) complexes derived from bis(2-hydroxy-1-naphthaldehyde)succinoyldihydrazone  

NASA Astrophysics Data System (ADS)

Molybdenum complexes [(?2-O)2(MoO2)2(H4nsh)2]·2A·2C2H5OH (where A = O (1), py (2), 2-pic (3), 4-pic (4) and 5-pic (5)) have been synthesized in absolute ethanol from bis(2-hydroxy-1-naphthaldehyde)succinoyldihydrazone. The composition of the complexes has been deduced on the basis of the data obtained from elemental analyses and thermo-analytical data. All complexes are non-electrolyte in DMSO solution as evident from low value of molar conductance in the range 2.2-3.3 ?-1 cm2 mol-1. The complexes are diamagnetic and have molybdenum in +6 oxidation state. The dihydrazone coordinates to the molybdenum centre as a neutral bidentate ligand through two azomethine nitrogen atoms only. This is revealed by the downfield shift of ?(sbnd CHdbnd Nsbnd ) signals by 0.16-0.44 ppm as compared to that in the free dihydrazone. The carbon atoms closer to azomethine nitrogen atoms downfield shift confirming the coordination of azomethine nitrogen atoms. The ?(Cdbnd N) stretching vibrations also shift to lower frequency in the IR spectra of the complexes. Apart from the intra ligand bands, the complexes show a new absorption band in the region 421-423 nm attributed to charge-transfer transition from dihydrazone ligand to molybdenum centre. The dihydrazone is present in anti-cis conformation in all of the complexes. The complexes develop a new kind of intramolecular hydrogen bonding between naphtholic sbnd OH groups of coordinated dihydrazone.

Kumar, A.; Koch, A.; Borthakur, R.; Chakraborty, M.; De, A. K.; Phukan, A.; Bez, G.; Lal, R. A.

2014-04-01

335

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)

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.

Khan, Ishaat M.; Ahmad, Afaq; Kumar, Sarvendra

2013-03-01

336

Structural and spectroscopic characterization of 2-mesityl-1H-benzo[d]imidazol-3-ium chloride: A combined experimental and theoretical analysis  

NASA Astrophysics Data System (ADS)

The title molecular salt, 2-mesityl-1H-benzo[d]imidazol-3-ium chloride (C16H17N2+·Cl?), was synthesized unexpectedly from the reaction of N-[(1E)-mesitylmethylene]benzene-1,2-diamine and CoCl2·6H2O, and characterized by elemental analysis, 1H NMR and FT-IR spectroscopies, and single-crystal X-ray diffraction technique. In addition, quantum chemical calculations employing density functional theory (DFT) method with the 6-311++G(d,p) basis set were performed to study the molecular, spectroscopic and some electronic structure properties of the title compound, and the results were compared with the experimental findings. The computational result shows that the optimized geometry can well reproduce the crystal structural parameters. The intermolecular proton transfer process between the ionic (C16H17N2+·Cl?) and nonionic forms (C16H16N2·HCl) of the title salt is investigated and found to be almost barierless with an energy value of 0.20 kcal mol-1. The NLO properties of the compound are bigger than those of urea.

Özdemir, Nam?k

2012-06-01

337

Vibrational spectroscopic characterization of the phosphate mineral ludlamite (Fe,Mn,Mg)3(PO4)2?4H2O - A mineral found in lithium bearing pegmatites  

NASA Astrophysics Data System (ADS)

The objective of this work is to analyze ludlamite (Fe,Mn,Mg)3(PO4)2?4H2O 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 HOPO32- and PO43- units. Raman bands at 548, 564, 599 and 634 cm-1 are assigned to the ?4PO43- 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.

Frost, Ray L.; Xi, Yunfei; Scholz, Ricardo; Belotti, Fernanda M.

2013-02-01

338

Dissociative Binding of Carboxylic Acid Ligand on Nanoceria Surface in Aqueous Solution: A Joint in Situ Spectroscopic Characterization and First-Principles Study  

SciTech Connect

Carboxylic acid is a common ligand anchoring group to functionalize nanoparticle surfaces. Its binding structures and mechanisms as a function of the oxidation states of metal oxide nanoparticle surfaces are not well characterized experimentally. We present an in situ sum frequency generation vibrational spectroscopy (SFG-VS) study on the binding of deuterated acetic acid on ceria nanoparticles in the aqueous solution. In the SFG experiment, ceria nanoparticles were deposited on the flat surface of a CaF2 hemisphere in contact with acetic acid solutions. While the ceria nanoparticle deprotonated the acetic acid, the CaF2 surface could not. Thus, the binding of the deprotonated acetic acid on ceria can be selectively probed. SFG spectra revealed that the binding modes of the carboxylate group depend on the oxidation states of the ceria surfaces. SFG polarization analysis suggested that the bidentate chelating and bridging binding modes co-exist on the reduced ceria surfaces, while the oxidized ceria surfaces are dominated by the bidentate bridging mode. The direct spectroscopic evidence helps to clarify the binding structures and mechanisms on the ceria nanoparticles. Furthermore, the middle-infrared (IR) transparent CaF2 and its chemical inertness make CaF2 and similar substrate materials good candidates for direct SFG-VS measurement of nanoparticle surface reactions and binding chem-istry.

Lu, Zhou; Karakoti, Ajay S.; Velarde Ruiz Esparza, Luis A.; Wang, Weina; Yang, Ping; Thevuthasan, Suntharampillai; Wang, Hongfei

2013-11-21

339

Synthesis, spectroscopic characterization and reactivity studies of oxovanadium(IV) complexes with bulky N,N'-polymethylenebis(3,5- tBu 2salicylaldimine) ligands  

NASA Astrophysics Data System (ADS)

A series of new sterically hindered N,N'-polymethylenebis(3,5- tBu 2salicylaldimine) ligands (H 2L x) VO(IV) complexes, [VO{(2-O-3,5- tBu 2C 6H 2)CH dbnd N-R-N dbnd CH-(3,5- tBu 2-C 6H 2O-2)] ( X), where R = -(CH 2) 3- ( 3), -(CH 2) 4- ( 4), -(CH 2) 5- ( 5), -(CH 2) 6- ( 6) and -CH 2C(CH 3) 2CH 2- ( 7) and early reported -(CH 2) 2- ( 1) and -CH 2CH(CH 3)- ( 2), has been synthesized and characterized by spectroscopic (IR, UV/vis, 1H NMR, EPR), electrochemical and magnetic susceptibility measurements. Complexes 1- 7 are described a trigonal distorted pyramids. All seven compounds give nearly the same parallel hyperfine coupling constant ( Az) regardless that the geometry of VO(IV) changes from square pyramidal to trigonal distorted pyramids. Chemical oxidation of 1- 7 by one equiv Ce(IV) leads to the formation of stable [VO(V)L x] + complexes. Cyclic voltammograms of 2- 6 in DMSO along with a quasi-reversible VO(IV)/VO(V) redox couple also showed irreversible phenolate/phenoxyl responses. Each 1 and 7 shows only one reversible VO(IV) centered oxidation waves. Chemical oxidation of H 2L x forms the stable [H 2L x] + radical species.

Kasumov, Veli T.; Köksal, F.; Aslanoglu, M.; Yerli, Y.

2010-10-01

340

Thermal analysis and vibrational spectroscopic characterization of the boro silicate mineral datolite - CaBSiO4(OH)  

NASA Astrophysics Data System (ADS)

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.

Frost, Ray L.; Xi, Yunfei; Scholz, Ricardo; Lima, Rosa Malena Fernandes; Horta, Laura Frota Campos; Lopez, Andres

2013-11-01

341

Characterization of Ligand Effects on Water Activation in Triarylphosphoine-Stabilized Pt Nanoparticle Catalysts by X-ray Absorption Spectroscopy  

SciTech Connect

The synthesis, preparation, and electrochemical characterization of triphenylphosphine triphosphonate (TPPTP) stabilized Pt particles have been reported previously with the observation that the TPPTP ligands increase the specific activity of Pt for the oxygen reduction reaction (ORR). In this work the ORR activity of the Pt/TPPTP electrocatalyst is probed by analyzing water activation with Pt L3-edge X-ray absorption spectroscopy and the EXAFS and Delta XANES analysis techniques. The results are compared with that for similarly prepared Pt/C and Pt stabilized by an oxidized TPPTP ligand (Pt/ox-TPPTP). The Pt particles in the Pt/TPPTP catalyst at 0.54 V (RHE) are complexed via the P (i.e., Pt-P

Gatewood,D.; Schull, T.; Baturina, O.; Pietron, J.; Garsany, Y.; Swider-Lyons, K.; Ramaker, D.

2008-01-01

342

Synthesis, spectroscopic characterization and catalytic significance of Palladium(II) complexes derived from 1,1 bis(diphenylphosphinomethyl)ethane  

NASA Astrophysics Data System (ADS)

Two novel and neutral bidentate Palladium(II) complexes of the type, [PdX 2(dpme)] (X = Cl 1, OAc 2], have been synthesized from 1,1-bis(diphenylphosphinomethyl)ethene (dpme) ligand and characterized on the basis of elemental analyses, infrared, FAB-MS and 1H-, 13C-, and 31P-NMR spectroscopy. The structure of 1 has been ascertained by single crystal X-ray crystallography and shows cis configuration in a square planar structure while the structural behavior of the dpme ligand through the formation of these complexes has been monitored by 31P{ 1H} NMR and IR spectra. These Pd(II) complexes have shown a very significant catalytic role in Heck reaction giving high yield under mild condition.

Warad, Ismail; Azam, Mohammad; Karama, Usama; Al-Resayes, Saud; Aouissi, Ahmed; Hammouti, Belkheir

2011-09-01

343

Synthesis, spectroscopic characterization and X-ray structure of [1,2a]benzimidazol-2-yl amidine.  

PubMed

[1,2a]Benzimidazol-2-yl amidine was synthesized by adding cyclopentanamine to iminoester in ethanol. The structure of amidine 1 was characterized by IR, 1H NMR, 1H-1H NOESY, 13C NMR, DEPT, XHCOR spectra, thermogravimetric analysis (TGA), differential thermal analysis (DTA), differential scanning calorimetry thermograms (DSC), elementary analysis as well as by X-ray diffraction. The single crystals suitable for X-ray measurement were obtained by recrystallization at room temperature. The amidine group of a model was found to have Z configuration in the crystal. This compound crystallizes in a P2(1)/n monoclinic unit cell with parameters a=12.679(2) ?, b=8.468(3) ?, c=13.108(2) ?, ?=96.538(2)°, V=1398.2 ?3 and Z=4. PMID:21708483

Hajri, A; Smirani, W; Abderrahim, R

2011-09-01

344

Diorganotin(IV) complexes of biologically potent 4(3H)-quinazolinone derived Schiff bases: synthesis, spectroscopic characterization, DNA interaction studies and antimicrobial activity.  

PubMed

Four Schiff base ligands and their corresponding organotin(IV) complexes have been synthesized and characterized by elemental analyses, IR, (1)H NMR, MS and thermal studies. The Schiff bases are obtained by the condensation of 3-amino-2-methyl-4(3H)-quinazolinone with different substituted aldehydes. The elemental analysis data suggest the stoichiometry to be 1:1 ratio formation. Infrared spectral data agreed with the coordination to the central metal ion through imine nitrogen, lactam oxygen and deprotonated phenolic oxygen atoms. All the synthesized compounds have been evaluated for antimicrobial activity against selected species of microorganisms. In addition, DNA binding/cleavage capacity of the compounds was analyzed by absorption spectroscopy, viscosity measurements and gel electrophoresis methods. PMID:21741298

Prasad, Kollur Shiva; Kumar, Linganna Shiva; Chandan, Shivamallu; Jayalakshmi, Basvegowda; Revanasiddappa, Hosakere D

2011-10-15

345

Structural characterization of bismuth molybdates by x-ray absorption spectroscopy and powder neutron diffraction profile analysis  

Microsoft Academic Search

By use of synchrotron radiation, high-quality X-ray absorption data have been recorded for three bismuth molybdate phases with the general composition BiâOâ x nMoOâ, for n = 3 (..cap alpha..-phase) n = 2 (..beta..-phase), and n = 1 (..gamma..-phase). The results of these bismuth Lâ-edge and molybdenum K-edge X-ray absorption near edge structure (XANES) and extended X-ray absorption fine structure

Mark R. Antonio; Raymond G. Teller; D. R. Sandstorm; Meho Mehicic; James F. Brazdil

1988-01-01

346

Polyoxometalates Functionalized by Bisphosphonate Ligands: Synthesis, Structural, Magnetic and Spectroscopic Characterizations and Activity on Tumor Cell Lines  

PubMed Central

We report the synthesis and characterization of eight new Mo, W, or V-containing polyoxometalate (POM) bisphosphonate complexes with metal nuclearities ranging from 1 to 6. The compounds were synthesized in water by treating MoVI, WVI, VIV or VV precursors with biologically active bisphosphonates H2O3PCR(OH)PO3H2 (R = C3H6NH2, Ale; R = CH2S(CH3)2, Sul and R = C4H5N2, Zol, where Ale=alendronate, Sul=(2-Hydroxy-2,2-bis-phosphono-ethyl)-dimethyl-sulfonium and Zol=zoledronate.). Mo6(Sul)2 and Mo6(Zol)2 contain two trinuclear MoVI cores which can rotate around a central oxo group while Mo(Ale)2 and W(Ale)2 are mononuclear species. In V5(Ale)2 and V5(Zol)2 a central VIV ion is surrounded by two VV dimers bound to bisphosphonate ligands. V6(Ale)4 can be viewed as the condensation of one V5(Ale)2 with one additional VIV ion and two Ale ligands, while V3(Zol)3 is a triangular VIV POM. These new POM bisphosphonates complexes were all characterized by single-crystal X-ray diffraction. The stability of the Mo and W POMs was studied by 31P NMR spectroscopy and showed that all compounds except the mononuclear Mo(Ale)2 and W(Ale)2 were stable in solution. EPR measurements performed on the vanadium derivatives confirmed the oxidation state of the V ions and evidenced their stability in aqueous solution. Electrochemical studies on V5(Ale)2 and V5(Zol)2 showed reduction of VV to VIV and magnetic susceptibility investigations on V3(Zol)3 enabled a detailed analysis of the magnetic interactions. The presence of zoledronate or vanadium correlated with the most potent activity (IC50~1–5 ?M) against three human tumor cell lines. PMID:22725619

Moll, Hani El; Zhu, Wei; Oldfield, Eric; Albelo, L. Marleny Rodriguez; Mialane, Pierre; Marrot, Jerome; Vila, Neus; Mbomekalle, Israel Martyr; Riviere, Eric; Duboc, Carole; Dolbecq, Anne

2012-01-01

347

One pot synthesis of biologically active pregnane derivatives, their single crystal structures, spectroscopic characterization and theoretical calculations  

NASA Astrophysics Data System (ADS)

One pot allylic oxidation of 3?-acetoxypregna-5,16-diene-20-one (2) and nucleophilic addition at C-16 position of 3?-hydroxypregna-5,16-diene-20-one (3) yielded 3?-acetoxypregna-5,16-diene-7,20-dione (4) and 3?-hydroxy-16?-(5'-hydroxypentyloxy)-pregn-5-ene-20-one (5) respectively in high yield. A detailed theoretical study supported by X-ray analysis of compounds 4 and 5 has been carried out. Conformational analysis of compounds 4 and 5 was done with the help of crystal structure, which crystallize out in orthorhombic form having P212121 space group. Structural characterization of compounds 4 and 5 was done with the aid of 1H, 13C NMR, IR, UV, ESI-MS and ESI-HRMS. The molecular geometries and vibrational frequencies for compounds 4 and 5 in the ground state were calculated using the Density functional theory (DFT) with 6-31G(d,p) basis set and compared with experimental data. 1H and 13C nuclear magnetic resonance magnetic shifts of 4 and 5 were calculated using GIAO method and compared with the experimental data. UV-Vis spectra of both the compounds were recorded and electronic properties such as HOMO-LUMO energies were calculated by time dependent TD-DFT approach. The compounds were screened for their anti-hyperlipidemic and anti-oxidant activity.

Sethi, Arun; Bhatia, Akriti; Bhatia, Gitika; Shrivastava, Atul; Prakash, Rohit

2013-11-01

348

Raman and infrared spectroscopic characterization of beryllonite, a sodium and beryllium phosphate mineral - implications for mineral collectors  

NASA Astrophysics Data System (ADS)

The mineral beryllonite has been characterized by the combination of Raman spectroscopy and infrared spectroscopy. SEM-EDX was used for the chemical analysis of the mineral. The intense sharp Raman band at 1011 cm-1, was assigned to the phosphate symmetric stretching mode. Raman bands at 1046, 1053, 1068 and the low intensity bands at 1147, 1160 and 1175 cm-1 are attributed to the phosphate antisymmetric stretching vibrations. The number of bands in the antisymmetric stretching region supports the concept of symmetry reduction of the phosphate anion in the beryllonite structure. This concept is supported by the number of bands found in the out-of-plane bending region. Multiple bands are also found in the in-plane bending region with Raman bands at 399, 418, 431 and 466 cm-1. Strong Raman bands at 304 and 354 cm-1 are attributed to metal oxygen vibrations. Vibrational spectroscopy served to determine the molecular structure of the mineral. The pegmatitic phosphate minerals such as beryllonite are more readily studied by Raman spectroscopy than infrared spectroscopy.

Frost, Ray L.; Xi, Yunfei; Scholz, Ricardo; Belotti, Fernanda M.; Alberto Dias Menezes Filho, Luiz

2012-11-01

349

Spectroscopic characterization of dealuminated H-mordenites: The role of different aluminum species on the SCR of NO with methane  

SciTech Connect

In order to understand the role of different aluminum species in the selective catalytic reduction of nitrogen oxides with methane over H-mordenites, solids with varying Si/Al ratios (5.9-16.9) were prepared by acid leaching. They were thoroughly characterized before and after reaction. The distribution of Al was determined through {sup 27}Al MAS NMR. All the samples presented three signals, one at 54 ppm corresponding to lattice Al{sup IV}, another at 0 ppm associated with octahedrally coordinated Al, and a broad band, BB (ca 100 ppm wide), assigned to aluminum containing species. As the spinning rate increased up to 11.3 kHz, a decrease of the BB intensity and an increase of the Al{sup IV} signal took place, while the Al{sup VI} slightly increased. The best estimate of lattice aluminum was obtained from the Al{sup IV} peak intensity. Despite the high spinning rate employed, it was possible to observe only between 70-80% of the total Al present in the samples. The catalysts were also analyzed by XRD, FTIR, and {sup 129}Xe NMR of physisorbed Xenon. 48 refs., 13 figs., 6 tabs.

Lezcano, M.; Ribotta, A.; Miro, E. [Instituto de Investigaciones en Catalisis y Petroquimica, Sante Fe (Argentina)] [and others] [Instituto de Investigaciones en Catalisis y Petroquimica, Sante Fe (Argentina); and others

1997-06-01

350

Adsorption mechanisms of trivalent gold on iron- and aluminum-(oxy)hydroxides. Part 1: X-ray absorption and Raman scattering spectroscopic studies of Au(III) adsorbed on ferrihydrite, goethite, and boehmite  

NASA Astrophysics Data System (ADS)

Gold adsorption products on powdered ferrihydrite, goethite, and boehmite samples, prepared by reacting Au(III)-Cl solutions ([Au] = 4.2 × 10 -5-9.0 × 10 -3 M; [Cl] = 0.017-0.6 M) with these adsorbents at pH values of 4 to 9 and Au adsorption densities ranging from 0.046 to 1.53 ?mol/m 2 were characterized using Au-L III XAFS spectroscopy. The solutions (before and after uptake) were investigated by Raman scattering to determine speciation and by Inductively Coupled Plasma Atomic Emission Spectroscopy (ICP-AES) to determine solution composition. We present an analysis of several effects that are observed in the Au L III-edge XAFS spectra, including X-ray beam-induced photo-reduction, multi-electronic excitations, disorder effects, and multiple scattering, that would complicate interpretation of the spectra if not accounted for. A combination of methods (spectral deconvolution, principal component analysis, spectral inversion, and wavelet analysis) was used to identify and quantify these effects, to characterize the nature of mixed ligands around gold, and to distinguish between multiple-scattering features and features due to next-nearest neighbors in the XAFS spectra. Analysis of the Au-L III XAFS spectra showed that Au(III) is present as square-planar Au(III)(O,Cl) 4 complexes in the aqueous solutions and on the surfaces of the Al/Fe-(oxy)hydroxide adsorption samples with dominantly O ligands at pH > 6 and mixed O/Cl ligands at lower pH values. The EXAFS-derived Au-O and Au-Cl distances are 2.00(2) and 2.28(2) Å, respectively, and the magnitudes of the Debye-Waller factors and third cumulants from anharmonic analyses indicate very little thermal or positional disorder around Au(III) in the adsorption samples. Iron second neighbors are present around Au in the Au(III)/ferrihydrite and Au(III)/goethite adsorption samples, with Au-Fe distances of 3.1(1) and 3.3(1) Å. In boehmite, two sets of Au-Al distances were detected at 3.0(1) and 3.2(1) Å. A reverse Monte Carlo study of the XAFS spectroscopic data suggests the presence of a continuum of edge-shared AuO 4-FeO 6 distances, which cannot be described correctly by a classical model of these data in which only a mean distance (although severely under-estimated) is derived.

Berrodier, Ingrid; Farges, François; Benedetti, Marc; Winterer, Markus; Brown, Gordon E.; Deveughèle, Michel

2004-07-01

351

Preparation, spectroscopic and thermal characterization of new metal complexes of verlipride drug. In vitro biological activity studies  

NASA Astrophysics Data System (ADS)

Metal complexes of the general formula [M(VER)2Cl2(H2O)2]·yH2O and [Cr(VER)2Cl2(H2O)2]Cl·H2O (where VER = verlipride, M = Mn(II) (y = 2), Co(II) (y = 2), Ni(II) (y = 2), Cu(II) (y = 1) and Zn(II) (y = 0)) are prepared and characterized based on elemental analyses, IR, 1H NMR, magnetic moment, molar conductance, and thermal analyses (TG and DTA) techniques. From the elemental analyses data, the complexes are formed in 1:2 [Metal]:[VER] ratio. The molar conductance data reveal that all the metal chelates are non-electrolytes except Cr(III) complex, it is 1:1 electrolyte. IR spectra show that VER is coordinated to the metal ions in a neutral monodentate manner with O donor site of the carbonyl O atom. On the basis of spectral studies and magnetic moment measurements an octahedral geometry has been assigned for the complexes. The thermal behavior of these chelates is studied using thermogravimetric analysis technique. The results obtained show that the complexes lose hydrated water, HCl and coordinated water molecules followed immediately by decomposition of the ligand molecules in the successive unseparate steps. The VER drug, in comparison to its metal complexes is also screened for its biological activity against Gram positive bacterial (Staphylococcus aureus) and Gram negative bacteria (Escherichia coli) and fungi (Candida albicans and Aspergillus flavus) in vitro. The activity data show that most of the metal complexes have antibacterial activity like or higher than that of the parent VER drug against one or more species.

Soliman, M. H.; Mohamed, Gehad G.

2012-06-01

352

Structural and spectroscopic characterization of a series of potassium- and/or sodium-substituted ?-tricalcium phosphate.  

PubMed

In this paper, we report X-ray diffraction investigations as well as Raman and solid-state (31)P and (23)Na magic angle spinning nuclear magnetic resonance (NMR) characterization of three series of calcium orthophosphates. The general formulae of the studied compounds are Ca(10.5-x/2)M(x)(PO(4))(7), where M=K or Na and x=0, 0.25, 0.50, 0.75, 1.0; and Ca(10)K(x)Na(1-x)(PO(4))(7), where x=0, 0.25, 0.5, 0.75, 1.0. These calcium orthophosphates are found to be isostructural with ?-tricalcium phosphate (?-TCP, Ca(3)(PO(4))(2)) with the substitution of some calcium sites by potassium and/or sodium cations. The unit cell parameters vary continuously with the level of substitution, a characteristic of these solid solutions. The Raman spectra show the different vibrational bands of the phosphate groups PO(4), while the NMR chemical shifts are sensitive to the non-equivalent phosphorus and sodium ions present in these substituted samples. As both Raman and NMR spectroscopies are local probes, they offer tools to distinguish between these different phosphorus and phosphate groups, according to their structural site and local environment, especially the type of cation substituent. A convenient decomposition of the Raman and NMR spectra into Gaussian-Lorentzian components leads us to propose an assignment of the main observed bands of these substituted ?-TCPs. PMID:21185410

Quillard, S; Paris, M; Deniard, P; Gildenhaar, R; Berger, G; Obadia, L; Bouler, J-M

2011-04-01

353

Spectroscopic characterization and constitutional and rotational isomerism of ClC(O)SCN and ClC(O)NCS.  

PubMed

Chlorocarbonylthio- and isothiocyanate (ClC(O)SCN and ClC(O)NCS) have been isolated and characterized by IR (Ar matrix, gas), Raman (liquid), (13)C NMR and UV-visible spectroscopies. Vibrational and quantum chemical studies suggest the presence of the syn and anti conformers (SCN group with respect to the C?O bond) in the gas phase for both constitutional isomers. syn-ClC(O)SCN is preferred by ?H° (anti/syn) = 1.3(0.3) kcal mol(-1). The solid-state structure of ClC(O)SCN has been determined by single crystal X-ray diffraction analysis at low temperature. The crystalline solid consists exclusively of molecules in the syn conformation. On the other hand, the anti form is more stable for the ClC(O)NCS isomer. The structure of ClC(O)NCS and its conformational composition were determined by gas electron diffraction. An unusual low syn ? anti interconversion energy barrier of 0.98 (0.15) kcal mol(-1) was detected for ClC(O)NCS at cryogenic temperatures. The photochemistry of both constitutional isomers isolated in solid argon at 15 K was studied. Rearrangement of ClC(O)SCN to ClC(O)NCS was observed in the neat liquid and under UV-vis irradiation of ClC(O)SCN isolated in solid argon. Properties have been discussed in terms of the valence electronic structure, including the analysis of the He(I) photoelectron spectrum of ClC(O)SCN. PMID:23414067

Ramos, Luis A; Ulic, Sonia E; Romano, Rosana M; Erben, Mauricio F; Vishnevskiy, Yury V; Reuter, Christian G; Mitzel, Norbert W; Beckers, Helmut; Willner, Helge; Zeng, Xiaoqing; Bernhardt, Eduard; Ge, Maofa; Tong, ShengRui; Della Védova, Carlos O

2013-03-21

354

Efficient use of new laser crystals requires a full characteriza-tion of their absorption and fluorescence properties. For hexago-  

E-print Network

and form an orthonormal frame called the dielectric frame. For such crystals, measurements of absorptionEfficient use of new laser crystals requires a full characteriza- tion of their absorption and fluorescence properties. For hexago- nal, tetragonal, trigonal and orthorhombic crystals, these prop- erties

Canet, Léonie

355

Spectroscopic characterization of the 4-hydroxy catechol estrogen quinones-derived GSH and N-acetylated Cys conjugates.  

PubMed

Estrogens, including the natural hormones estrone (E(1)) and estradiol (E(2)), are thought to be involved in tumor induction. Specifically, catechol estrogen quinones (CEQs) derived from the catechol estrogens 4-hydroxyestrone (4-OHE(1)) and 4-hydroxyestradiol (4-OHE(2)) react with DNA and form DNA adducts (Cavalieri, E. L., et al. (1997) Proc. Natl Acad. Sci. U.S.A. 94, 10037). CEQs are also conjugated with GSH, a reaction that prevents damage to DNA, providing biomarkers of exposure to CEQs. Current detection limits for these analytes by HPLC with multichannel electrochemical detection are in the picomole range (Devanesan, P., et al. (2001) Carcinogenesis 22, 489). To improve the detection limit of CEQ-derived conjugates, spectrophotometric monitoring was investigated. Fluorescence and/or phosphorescence spectra of the 4-OHE(1), 4-OHE(2), Cys, N-acetylcysteine (NAcCys), 4-OHE(1)-2-SG, and 4-OHE(2)-2-SG conjugates and their decomposition products 4-OHE(1)-2-NAcCys and 4-OHE(2)-2-NAcCys were obtained at 300 and 77 K. It is shown that (i) 4-OHE(1)- and 4-OHE(2)-derived SG and NAcCys conjugates are weakly fluorescent at 300 K (with the emission maximum at 332 nm) but strongly phosphorescent at 77 K; (ii) Cys and NAcCys exhibit fluorescence and phosphorescence only at 77 K; and (iii) 4-OHE(1) and 4-OHE(2) are weakly fluorescent at 300 and 77 K and not phosphorescent. The phosphorescence spectra of SG and NAcCys conjugates are characterized by a weak origin band at approximately 383 nm and two intense vibronic bands at 407 and 425 nm. After they are cooled from 300 to 77 K, the total luminescence intensity of SG and NAcCys conjugates increases by a factor of approximately 150 predominantly due to phosphorescence enhancement. Theoretical calculations revealed, in agreement with the experimental data, that the lowest singlet (S(1)) and triplet (T(1)) states of 4-OHE(2)-2-NAcCys are of n,pi* and pi,pi* character, respectively, leading to a large intersystem crossing yield and strong phosphorescence. The limit of detection (LOD) for CEQ-derived conjugates, based on phosphorescence measurements, is in the low femtomole range. The concentration LOD is approximately 10(-9) M. Therefore, we propose that capillary electrophoresis interfaced with low temperature phosphorescence detection can be used to test for human exposure to CEQs by analyzing urine. PMID:12641430

Jankowiak, Ryszard; Markushin, Yuri; Cavalieri, Ercole L; Small, Gerald J

2003-03-01

356

Spectroscopic characterization and biological activity of dihydrazone transition metal complexes: crystal structure of 2,3-butanedione bis(isonicotinylhydrazone).  

PubMed

Metal complexes of the chloride, nitrate and acetate salts of Co(II), Ni(II) Cu(II), Zn(II), Cd(II) or Hg(II) with 2,3-butanedione bis(isonicotinylhydrazone) [BBINH] have been synthesized and structurally characterized. The crystal of BBINH was solved to crystallize as monoclinic system with space group of P121/c14. The formulae of the complexes were assigned based on the elemental analysis and mass spectra. The formation of BBINH complexes depend on the metal anion used. All complexes are nonelectrolytes except for the complexes 2, 3, 4 are (1:1) and 13 and 14 which are 1:2 electrolytes. BBINH behaves as a neutral tetradentate (N2O2) in the chloride complexes of Ni(II), Cu(II), Zn(II), Cd(II) and Hg(II). In [Co2(BBINH)(H2O)Cl3]Cl?H2O, BBINH has the same dentate but with the two Co(II) ions. In the acetate complexes, [Ni2(BBINH-2H)(H2O)2(OAc)2]?3H2O and [Cu2(BBINH-2H)(OAc)2]?5H2O, BBINH acts as a binegative tetradentate with the two metal ions. The ligand in the nitrate complexes acts as a neutral bidentate via the two hydrazone azomethine C=NHy; the nitrate ions are ionic in the Cd(II) and Zn(II) complexes and covalent in the Ni(II) complex. The data are supported by NMR ((1)H and (13)C) spectra. The magnetic moments and electronic spectra of all complexes provide tetrahedral, square planar and/or octahedral structure. The decomposition of the complexes revealed the outer and inner solvents as well as the remaining residue based on TGA. The complexes have variable activities against some bacteria and fungi. The ligand is inactive against all tested organisms. The activity of Cd(II) and Hg(II) may be related to the geometry of the complexes. PMID:25064505

El-Sayed, Ahmed E M; Al-Fulaij, O A; Elaasar, A A; El-Defrawy, M M; El-Asmy, A A

2015-01-25

357

Characterizing the Circumgalactic Medium of Nearby Galaxies with HST/COS and HST/STIS Absorption-line Spectroscopy  

NASA Astrophysics Data System (ADS)

The circumgalactic medium (CGM) of late-type galaxies is characterized using UV spectroscopy of 11 targeted QSO/galaxy pairs at z <= 0.02 with the Hubble Space Telescope Cosmic Origins Spectrograph (COS) and ~60 serendipitous absorber/galaxy pairs at z <= 0.2 with the Space Telescope Imaging Spectrograph. CGM warm cloud properties are derived, including volume filling factors of 3%-5%, cloud sizes of 0.1-30 kpc, masses of 10-108 M ?, and metallicities of ~0.1-1 Z ?. Almost all warm CGM clouds within 0.5 R vir are metal-bearing and many have velocities consistent with being bound, "galactic fountain" clouds. For galaxies with L >~ 0.1 L*, the total mass in these warm CGM clouds approaches 1010 M ?, ~10%-15% of the total baryons in massive spirals and comparable to the baryons in their parent galaxy disks. This leaves >~ 50% of massive spiral-galaxy baryons "missing." Dwarfs (<0.1 L*) have smaller area covering factors and warm CGM masses (<=5% baryon fraction), suggesting that many of their warm clouds escape. Constant warm cloud internal pressures as a function of impact parameter (P/k ~ 10 cm-3 K) support the inference that previous COS detections of broad, shallow O VI and Ly? absorptions are of an extensive (~400-600 kpc), hot (T ? 106 K), intra-cloud gas which is very massive (>=1011 M ?). While the warm CGM clouds cannot account for all the "missing baryons" in spirals, the hot intra-group gas can, and could account for ~20% of the cosmic baryon census at z ~ 0 if this hot gas is ubiquitous among spiral groups. Based on observations with the NASA/ESA Hubble Space Telescope, obtained at the Space Telescope Science Institute, which is operated by AURA, Inc., under NASA contract NAS 5-26555.

Stocke, John T.; Keeney, Brian A.; Danforth, Charles W.; Shull, J. Michael; Froning, Cynthia S.; Green, James C.; Penton, Steven V.; Savage, Blair D.

2013-02-01

358

Characterization of Ligand Effects on Water Activation in Triaryl Phospine Stabilized Pt Nanoparticle Catalysts by X-ray Absorption Spectroscopy  

SciTech Connect

The synthesis, preparation, and electrochemical characterization of triphenylphosphine triphosphonate (TPPTP) stabilized Pt particles have been reported previously with the observation that the TPPTP ligands increase the specific activity of Pt for the oxygen reduction reaction (ORR). In this work the ORR activity of the Pt/TPPTP electrocatalyst is probed by analyzing water activation with Pt L{sub 3}-edge X-ray absorption spectroscopy and the EXAFS and Delta XANES analysis techniques. The results are compared with that for similarly prepared Pt/C and Pt stabilized by an oxidized TPPTP ligand (Pt/ox-TPPTP). The Pt particles in the Pt/TPPTP catalyst at 0.54 V (RHE) are complexed via the P (i.e., Pt-P

Gatewood, D.; Schull, T; Baturina, O; Pietron, J; Garsany, Y; Swider-Lyons, K; Ramaker, D

2008-01-01

359

In situ x-ray absorption spectroscopic study of the Li[Ni[subscript 1/3]Co[subscript 1/3]Mn[subscript 1/3  

SciTech Connect

The layered LiNi{sub 1/3}Co{sub 1/3}Mn{sub 1/3}O{sub 2} 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 LiNi{sub 1/3}Co{sub 1/3}Mn{sub 1/3}O{sub 2} on a 25-{micro}m Al foil and had an area of 0.79 cm{sup 2}. 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 LiNi{sub 1/3}Co{sub 1/3}Mn{sub 1/3}O{sub 2} are Ni{sup 2+}, Co{sup 3+}, and Mn{sup 4+}, whereas during charging Ni{sup 2+} is oxidized to Ni{sup 4+} through an intermediate stage of Ni{sup 3+}, Co{sup 3+} is oxidized almost to Co{sup 4+} and, utilizing Faraday's calculation and XAS results, the Co was found to be at Co{sup 3.92+} at the end of the charge, while Mn was found to be electrochemically inactive and remains as Mn{sup 4+}. 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 LiNi{sub 1/3}Co{sub 1/3}Mn{sub 1/3}O{sub 2} cathode confirmed that the material retains its symmetry and good structural short-range order leading to superior cycling.

Deb, A.; Bergmann, U.; Cramer, S.P.; Cairns, E.J. (SSRL); (LBNL)

2010-07-13

360

A new microwave spectroscope  

E-print Network

A NEW MICROWAVE SPECTROSCOPE A Dissertation By Andrew E. Sail* June 1951 Approved as to style and content by Chairman of Com ttee A NEW MICROWAVE SPECTROSCOPE A Dissertation Submitted to the Faculty of the Agricultural and Mechanical.... THEORETICAL APPROACH TO THE DESIGNING OP A MICROWAVE SPECTROSCOPE .................... 7 III. DESIGN OF THE EXPERIMENTAL MICROWAVE SPECTROSCOPE .......................... 14 Microwave Source .............................. 17 Microwave Circuit...

Salis, Andrew E.

2013-10-04

361

Synthesis, spectroscopic characterization, electrochemical behavior and computational analysis of mixed diamine ligand gold(III) complexes: antiproliferative and in vitro cytotoxic evaluations against human cancer cell lines.  

PubMed

The gold(III) complexes of the type [(DACH)Au(en)]Cl3, 1,2-Diaminocyclohexane ethylenediamine gold(III) chloride [where 1,2-DACH = cis-, trans-1,2- and S,S-1,2diaminocyclohexane and en = ethylenediamine] have been synthesized and characterized using various analytical and spectroscopic techniques including elemental analysis, UV-Vis and FTIR spectra; and solution as well as solid-state NMR measurements. The solid-state (13)C NMR shows that 1,2-diaminocyclohexane (1,2-DACH) and ethylenediamine (en) are strongly bound to the gold(III) center via N donor atoms. The stability of the mixed diamine ligand gold(III) was determined by (1)H and (13)C NMR spectra. Their electrochemical behavior was studied by cyclic voltammetry. The structural details and relative stabilities of the four possible isomers of the complexes were also reported at the B3LYP/LANL2DZ level of theory. The coordination sphere of these complexes around gold(III) center adopts distorted square planar geometry. The computational study also demonstrates that trans- conformations is slightly more stable than the cis-conformations. The antiproliferative effects and cytotoxic properties of the mixed diamine ligand gold(III) complexes were evaluated in vitro on human gastric SGC7901 and prostate PC3 cancer cells using MTT assay. The antiproliferative study of the gold(III) complexes on PC3 and SGC7901 cells indicate that complex 1 is the most effective antiproliferative agent among mixed ligand based gold(III) complexes 1-3. The IC50 data reveal that the in vitro cytotoxicity of complexes 1 and 3 against SGC7901 cancer cells are fairly better than that of cisplatin. PMID:25034122

Al-Jaroudi, Said S; Monim-Ul-Mehboob, M; Altaf, Muhammad; Al-Saadi, Abdulaziz A; Wazeer, Mohammed I M; Altuwaijri, Saleh; Isab, Anvarhusein A

2014-12-01

362

Spectroscopic, steady-state kinetic, and mechanistic characterization of the radical SAM enzyme QueE, which catalyzes a complex cyclization reaction in the biosynthesis of 7-deazapurines  

PubMed Central

7-Carboxy-7-deazaguanine (CDG) synthase (QueE) catalyzes the complex heterocyclic radical-mediated conversion of 6-carboxy-5,6,7,8-tetrahydropterin (CPH4) to CDG in the third step of the biosynthetic pathway to all 7-deazapurines. Here we present a detailed characterization of QueE from Bacillus subtilis to delineate the mechanism of conversion of CPH4 to CDG. QueE is a member of the radical S-adenosyl-L-methionine (SAM) superfamily, all of which use a bound [4Fe-4S]+ cluster to catalyze the reductive cleavage of SAM cofactor to generate methionine and a 5?-deoxyadenosyl radical (5?-dAdo•), which initiates enzymatic transformations requiring H-atom abstraction. The UV-visible, EPR, and Mössbauer spectroscopic features of the homodimeric QueE point to the presence of a single [4Fe-4S] cluster per monomer. Steady-state kinetic experiments indicate a Km of 20 ± 7 ?M for CPH4 and kcat of 5.4 ± 1.2 min-1 for the overall transformation. The kinetically determined Kapp for SAM is 45 ± 1 ?M. QueE is also magnesium-dependent and exhibits a Kapp for the divalent metal ion of 0.21 ± 0.03 mM. The SAM cofactor supports multiple turnovers, indicating that it is regenerated at the end of each catalytic cycle. The mechanism of rearrangement of QueE was probed with CPH4 isotopologs containing deuterium at C-6 or the two prochiral positions at C-7. These studies implicate 5?-dAdo• as initiating the ring contraction reaction catalyzed by QueE by abstraction of the H-atom from C-6 of CPH4. PMID:23194065

McCarty, Reid M.; Krebs, Carsten; Bandarian, Vahe

2013-01-01

363

Heat loads from ICRF and LH wave absorption in the SOL: characterization on JET and implications for the ITER-Like Wall  

SciTech Connect

Heat loads from ICRF and LH wave absorption in the SOL are characterized on JET from the de-convolution of surface temperatures measured by infrared thermography. The spatial localization, quantitative estimates, parametric dependence and physical origin of the observed heat fluxes are documented. Implications of these observations are discussed for the operation of JET with an ITER-Like Wall, featuring Beryllium tiles with reduced power handling capability.

Colas, L.; Arnoux, G.; Goniche, M. [CEA, IRFM, F-13108 Saint-Paul-Lez-Durance (France); Jacquet, Ph.; Mayoral, M.-L.; Brix, M.; Fursdon, M.; Graham, M.; Mailloux, J.; Monakhov, I.; Noble, C.; Sirinelli, A.; Riccardo, V.; Vizvary, Z. [Euratom/CCFE Association, Culham Science Centre, Abingdon, OX14 3DB (United Kingdom); Bobkov, V. [Max-Planck-Institut fuer Plasmaphysik, EURATOM-Assoziation, Garching (Germany); Lerche, E.; Ongena, J. [Association EURATOM-Belgian State, ERM-KMS, Brussels (Belgium); Petrzilka, V. [Association EURATOM-IPP. CR, Za Slovankou 3, 182 21 Praha 8 (Czech Republic)

2011-12-23

364

Resolving Spectral Lines with a Periscope-Type DVD Spectroscope  

ERIC Educational Resources Information Center

A new type of DVD spectroscope, the periscope type, is described and the numerical analysis of the observed emission and absorption spectra is demonstrated. A small and thin mirror is put inside and an eighth part of a DVD is used as a grating. Using this improved DVD spectroscope, one can observe and photograph visible spectra more easily and…

Wakabayashi, Fumitaka

2008-01-01

365

Spectroscopic, thermal characterization and cytotoxic activity of bi-, tri- and tetra-nuclear Pd(II) and Pt(II) complexes with diSchiff base ligands  

NASA Astrophysics Data System (ADS)

In this paper; new di-, tri-, and tetra-nuclear Pd(II) and Pt(II) complexes of N,N?-bis(3,4-dihydroxybenzylidene)ethan-1,2-diamine (EDH4), N,N?-bis(3,4-dihydroxy-benzylidene)-benzene-1,2-diamine (PDH4) and N,N?-bis-(3,4-dihydroxybenzylidene)-4,5-dimethyl-1,2-diamine (MPDH4) ligands were synthesized by two different methods. The first method involve the synthesis of the three ligands from condensation reaction of 3,4-dihydroxybenzaldehyde (L?H2) with ethylenediamine (en), o-phenylenediamine (o-PD), or 4,5-dimethyl-1,2-phenylendiamine (DMPD) in a mole ratio of 2:1 followed by the reaction of the resulting Schiff bases ligands with Pd(II) or Pt(II) ions in the presence of 2,2?-dipyridyl (L) to form the di- and tri-nuclear metal complexes. The second method involve the condensation of the Pd complex LPd(II)L?, (L = 2,2?-dipyridyl, L? = 4-formylbenzene-1,2-bis(olate)) with en, o-PD, or DMPD in a mole ratio of 2:1, respectively, followed by reaction with PdCl2 to form di-, tri-, and tetra-nuclear palladium(II) complexes, respectively. Structures of ligands and metal complexes are characterized by physical properties, FT-IR spectra and nuclear magnetic resonance. The geometries of metal complexes are suggested according to elemental analysis, electronic absorption spectra, thermal analysis, atomic absorption, magnetic susceptibility and molar conductance. Cytotoxic activity against lung large cell carcinoma (H460), prostate carcinoma (DU145), breast adenocarcinoma (MCF-7), amelanotic melanoma (M-14), colon adenocarcinoma (HT-29), and chronic myelogenous leukemia (K562) is also reported.

Hegazy, Wael Hussein

2014-10-01

366

Genesis of a Cerium Oxide-Supported Gold Catalyst for CO Oxidation: Transformation of Mononuclear Gold Complexes into Clusters as Characterized by X-Ray Absorption Spectroscopy  

SciTech Connect

CeO{sub 2}-supported mononuclear gold species synthesized from Au(CH{sub 3}){sub 2}(acac) catalyzed CO oxidation at 353 K, with a turnover frequency of 6.5 x 10{sup -3} molecules of CO (Au atom s){sup -1} at CO and O{sub 2} partial pressures of 1.0 and 0.5 kPa, respectively. As the catalyst functioned in a flow reactor, the activity increased markedly so that within about 10 h the conversion of CO had increased from about 1% to almost 100%. Activated catalyst samples were characterized by X-ray absorption spectroscopy and found to incorporate clusters of gold, which increased in size, undergoing reduction, with increasing time of operation. The X-ray absorption near-edge structure spectrum of the catalyst used for the longest period was indistinguishable from that characterizing gold foil. Extended X-ray absorption fine structure data characterizing the catalyst after the longest period of operation indicated the presence of clusters of approximately 30 Au atoms each, on average. The evidence that the catalytic activity increased as the clusters grew is contrasted with earlier reports pointing to increasing activity of supported gold clusters as they were made smallerin a cluster size range largely exceeding ours.

Aguilar-Guerrero, V.; Lobo-Lapidus, R; Gates, B

2009-01-01

367

Synthesis, spectroscopic properties, and electropolymerization of azulene dyads.  

PubMed

Four azulene dyads have been synthesized and studied by spectroscopic and electrochemical methods. A triarylamine, a boron-dipyrromethene (BDP or BODIPY), a porphyrin, and an isoalloxazine moiety have been linked to an extended ? electron system at the 2-position of azulene, leading to the dyads 1-4, respectively. For the synthesis of 1-4, first 2-(4-ethynyl-phenyl)azulene (EPA) was prepared, which was further reacted with the halogenated chromophores by Pd-catalyzed cross-coupling reactions. The dyads 1-4 exhibit strong absorption bands in the visible range, which are dominated by the absorption spectra of the individual subchromophores. Fluorometric studies of 2-4 revealed that after excitation of the subchromophoric unit attached to the parent azulene moiety, quenching mainly through energy transfer to azulene is effective, whereas possible charge-transfer interactions play only a minor role. Potentiodynamic oxidation of the dyads 1-4 leads to the formation of polymer films, which are deposited at the electrode. The polymer film derived from 1 was further characterized by spectroelectrochemistry. During positive doping of poly-1, a strong absorption band appears at 13,200 cm(-1), which is typical for triarylamine radical cations. This band is overlapping with a broad absorption band in the low-energy region that might be caused by charge-transfer interactions within the polymer. PMID:21506604

Nöll, Gilbert; Daub, Jörg; Lutz, Michaela; Rurack, Knut

2011-06-17

368

Synthesis, spectroscopic characterization and biological activities of N4O2 Schiff base ligand and its metal complexes of Co(II), Ni(II), Cu(II) and Zn(II)  

NASA Astrophysics Data System (ADS)

The Schiff base ligand, bis(indoline-2-one)triethylenetetramine (L) obtained from condensation of triethylenetetramine and isatin was used to synthesize the complexes of type, [ML]Cl2 [M = Co(II), Ni(II), Cu(II) and Zn(II)]. L was characterized on the basis of the results of elemental analysis, FT-IR, 1H and 13C NMR, mass spectroscopic studies. The stoichiometry, bonding and stereochemistries of complexes were ascertained on the basis of results of elemental analysis, magnetic susceptibility values, molar conductance and various spectroscopic studies. EPR, UV-vis and magnetic moments revealed an octahedral geometry for complexes. L and its Cu(II) and Zn(II) complexes were screened for their antibacterial activity. Analgesic activity of Cu(II) and Zn(II) complexes was also tested in rats by tail flick method. Both complexes were found to possess good antibacterial and moderate analgesic activity.

Al-Resayes, Saud I.; Shakir, Mohammad; Abbasi, Ambreen; Amin, Kr. Mohammad Yusuf; Lateef, Abdul

369

Preparation, spectroscopic and thermal characterization of new charge-transfer complexes of ethidium bromide with ?-acceptors. In vitro biological activity studies  

NASA Astrophysics Data System (ADS)

Ethidium bromide (EtBr) is a strong DNA binder and has been widely used to probe DNA structure in drug-DNA and protein-DNA interaction. Four new charge-transfer (CT) complexes consisting of EtBr as donor and quinol (QL), picric acid (PA), tetracyanoquinodimethane (TCNQ) or dichlorodicyanobenzoquinone (DDQ) as acceptors, were synthesized and characterized by elemental analysis, electronic absorption, spectrophotometric titration, IR, Raman, 1H NMR and X-ray powder diffraction (XRD) techniques. The stoichiometry of these complexes was found to be 1:2 ratio and having the formula [(EtBr)(acceptor)]. The thermal stability of the synthesized CT complexes was investigated using thermogravimetric (TG) analyses, and the morphology and particle size of these complexes were obtained from scanning electron microscopy (SEM). The CT complexes were 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 aeuroginosa strains by using Tetracycline as standard and antifungal property against Aspergillus flavus and Candida albicans by using amphotericin B as standard. The results were compared with the standard drugs and significant conclusions were obtained. The results indicated that the [(EtBr)(QL)2] complex had exerted excellent inhibitory activity against the growth of the tested bacterial strains.

Eldaroti, Hala H.; Gadir, Suad A.; Refat, Moamen S.; Adam, Abdel Majid A.

2013-05-01

370

Water-related absorption in fibrous diamonds  

NASA Astrophysics Data System (ADS)

Cubic and coated diamonds from several localities (Brasil, Canada, Yakutia) were investigated using spectroscopic techniques. Special emphasis was put on investigation of water-related features of transmission Infra-red and Raman spectra. Presence of molecular water is inferred from broad absorption bands in IR at 3420 and 1640 cm-1. These bands were observed in many of the investigated samples. It is likely that molecular water is present in microinclusions in liquid state, since no clear indications of solid H_2O (ice VI-VII, Kagi et al., 2000) were found. Comparison of absorption by HOH and OH vibrations shows that diamonds can be separated into two principal groups: those containing liquid water (direct proportionality of OH and HOH absorption) and those with stronger absorption by OH group. Fraction of diamonds in every group depends on their provenance. There might be positive correlation between internal pressure in microinclusions (determined using quartz barometer, Navon et al., 1988) and affiliation with diamonds containing liquid water. In many cases absorption by HOH vibration is considerably lower than absorption by hydroxyl (OH) group. This may be explained if OH groups are partially present in mineral and/or melt inclusions. This hypothesis is supported by following fact: in diamonds with strong absorption by silicates and other minerals shape and position of the OH band differs from that in diamonds with low absorption by minerals. Moreover, in Raman spectra of individual inclusions sometimes the broad band at 3100 cm-1 is observed. This band is OH-related. In some samples water distribution is not homogeneous. Central part of the diamond usually contains more water than outer parts, but this is not a general rule for all the samples. Water absorption usually correlated with absorption of other components (carbonates, silicates and others). At that fibrous diamonds with relatively high content of silicates are characterized by molecular water. OH-enriched diamonds contain more carbonatitic material. This was supported by JSPS and grant of University of Russia (No. 09.01.054).

Zedgenizov, D. A.; Shiryaev, A. A.; Kagi, H.; Navon, O.

2003-04-01

371

Determining uranium speciation in Fernald soils by molecular spectroscopic methods. FY 1993 progress report  

SciTech Connect

This progress report describes new experimental results and interpretations for data collected from October 1, 1992, through September 30, 1993, as part of the Characterization Task of the Uranium in Soils Integrated Demonstration of the Office of Technology Development, Office of Environmental Restoration and Waste Management of the US Department of Energy. X-ray absorption, optical luminescence, and Raman vibrational spectroscopies were used to determine uranium speciation in contaminated soils from the US DOE`s former uranium production facility at Fernald, Ohio. These analyses were carried out both before and after application of one of the various decontamination technologies being developed within the Integrated Demonstration. This year the program focused on characterization of the uranium speciation remaining in the soils after decontamination treatment. X-ray absorption and optical luminescence spectroscopic data were collected for approximately 40 Fernald soil samples, which were treated by one or more of the decontamination technologies.

Allen, P.G.; Berg, J.M.; Crisholm-Brause, C.J.; Conradson, S.D.; Donohoe, R.J.; Morris, D.E.; Musgrave, J.A.; Tait, C.D.

1994-07-01

372

Characterization of Esterase and Alcohol Dehydrogenase Activity in Skin. Metabolism of Retinyl Palmitate to Retinol (Vitamin A) During Percutaneous Absorption  

Microsoft Academic Search

Retinyl palmitate, a widely used ingredient in cosmetic products, is promoted for its beneficial effects on the appearance of skin. Previous studies suggest that enzymes are available in skin to metabolize this ingredient during skin absorption. Esterase activity hydrolyzes retinyl palmitate to retinol (vitamin A), which is oxidized in many tissues to retinoic acid primarily by alcohol dehydrogenase. The activities

James Boehnlein; Adel Sakr; J. Leon Lichtin; Robert L. Bronaugh

1994-01-01

373

Spectroscopic Signature of a Ubiquitous Metal Binding Site in the Metallo-beta-lactamase Superfamily  

SciTech Connect

The metallo-{beta}-lactamase (M{beta}L) superfamily is a functionally diverse group of metalloproteins sharing a distinctive {alpha}{beta}/{alpha}{beta} fold and a characteristic metal binding motif. A large number of open reading frames identified in genomic sequencing efforts have been annotated as members of this superfamily through sequence comparisons. However, structural and functional studies performed on purified proteins are normally needed to unequivocally include a newly discovered protein in the M{beta}L superfamily. Here we report the spectroscopic characterization of recombinant YcbL, a gene product annotated as a member of the M{beta}L superfamily whose function in vivo remains unknown. By taking advantage of the structural features characterizing the M{beta}L superfamily metal binding motif, we performed spectroscopic studies on Zn(II)- and Co(II)-substituted YcbL to structurally interrogate the metal binding site. The dinuclear center in Co(II)-YcbL was shown to display characteristic electronic absorption features in the visible region, which were also observed in an engineered M{beta}L aimed at mimicking this metal site. Thus, the spectroscopic features reported herein can be employed as a signature to readily identify and characterize the presence of these ubiquitous metal binding sites.

V Campos-Bermudez; J Gonzalez; D Tierney; A Vila

2011-12-31

374

In-situ characterization of moisture absorption-desorption and hygroscopic swelling behavior of an underfill material  

Microsoft Academic Search

Mo isture absorption and hygroscopic swelling behavior of an underfill material were measured in-situ using the sorption TGA and the DMA-RH techniques, respectively. Results showed that moisture diffusion can be well described by Fick’s law when the relative humidity (RH) is 60% or less, and the diffusivity exhibits an Arrhenius temperature dependence with an activation energy of ~ 0.56 eV.

Yi He

2011-01-01

375

Mass absorption efficiency of elemental carbon (EC) in ambient aerosols: Characterization from high-altitude sites in India  

NASA Astrophysics Data System (ADS)

The mass absorption efficiency (MAE, ?abs) is an important parameter for the determination of atmospheric black carbon (BC) mass concentration by optical instruments. Recent studies suggest that ?abs is highly variable in space and time depending on the type of emission sources of carbonaceous aerosols and analytical methods employed. We have studied changes in ?abs of elemental carbon (EC) from two high-altitude sites in India; Mt Abu (coordinates; 1700 m asl): located in the Thar desert of western India (dominated by mineral dust) and Manora Peak (coordinates; 2200 m asl): located in the southern slopes of Himalaya (influenced by anthropogenic sources in the Indo-Gangetic Plain. Based on the data set collected during 2005-2006, we document large temporal variability in ?abs of EC (range: 3.6-13.7 m2g-1) at Mt Abu. The average ?abs (9.8±2.1 m2g-1) is similar to the most accepted value of 10 m2g-1 for ambient aerosols. Analytical data suggest that mineral dust contributes ~70% of the total suspended particulate (TSP) mass. Assuming it to be externally mixed with carbonaceous species and its absorption efficiency of 0.009 m2g-1, absorption due to mineral dust is no more than ~10% at Mt Abu. In contrast, long-term (2005-2008) average of 12.8±2.9 m2g-1 for ?abs (range: 6.1-19.1 m2g-1) is documented at Manora Peak. We suggest that relatively high ?abs of EC at Manora Peak is attributed to the internal mixing of carbonaceous aerosols and anthropogenic species (NO3- and SO4--) during transport from the Indo-Gangetic Plain. These results have implications to large seasonal variability in the aerosol absorption properties (due to change in the morphological feature of EC) and atmospheric radiative forcing on a regional scale.

Ram, K.; Sarin, M.

2012-12-01

376

Characterization of southern Taiwan red soils as a regenerable sorbent for sorption of hydrogen sulfide from coal gas with spectroscopic techniques  

Microsoft Academic Search

The purpose of this research is to use red soils as a high-temperature regenerable sorbent for sorption of hydrogen sulfide from coal gas and collocates with a series of spectroscopic apparatuses in order to investigate the structure changes after multiple sorption\\/regeneration processes. Results indicate that red soils could be reused after 10 multiple sorption\\/regeneration cycles and maintain approximately 80% sorption

T. H. Ko; H. Chu

2005-01-01

377

The HITRAN2012 molecular spectroscopic database  

NASA Astrophysics Data System (ADS)

This paper describes the status of the 2012 edition of the HITRAN molecular spectroscopic compilation. The new edition replaces the previous HITRAN edition of 2008 and its updates during the intervening years. The HITRAN molecular absorption compilation is comprised of six major components structured into folders that are freely accessible on the internet. These folders consist of the traditional line-by-line spectroscopic parameters required for high-resolution radiative-transfer codes, infrared absorption cross-sections for molecules not yet amenable to representation in a line-by-line form, ultraviolet spectroscopic parameters, aerosol indices of refraction, collision-induced absorption data, and general tables such as partition sums that apply globally to the data. The new HITRAN is greatly extended in terms of accuracy, spectral coverage, additional absorption phenomena, and validity. Molecules and isotopologues have been added that address the issues of atmospheres beyond the Earth. Also discussed is a new initiative that casts HITRAN into a relational database format that offers many advantages over the long-standing sequential text-based structure that has existed since the initial release of HITRAN in the early 1970s.

Rothman, L. S.; Gordon, I. E.; Babikov, Y.; Barbe, A.; Chris Benner, D.; Bernath, P. F.; Birk, M.; Bizzocchi, L.; Boudon, V.; Brown, L. R.; Campargue, A.; Chance, K.; Cohen, E. A.; Coudert, L. H.; Devi, V. M.; Drouin, B. J.; Fayt, A.; Flaud, J.-M.; Gamache, R. R.; Harrison, J. J.; Hartmann, J.-M.; Hill, C.; Hodges, J. T.; Jacquemart, D.; Jolly, A.; Lamouroux, J.; Le Roy, R. J.; Li, G.; Long, D. A.; Lyulin, O. M.; Mackie, C. J.; Massie, S. T.; Mikhailenko, S.; Müller, H. S. P.; Naumenko, O. V.; Nikitin, A. V.; Orphal, J.; Perevalov, V.; Perrin, A.; Polovtseva, E. R.; Richard, C.; Smith, M. A. H.; Starikova, E.; Sung, K.; Tashkun, S.; Tennyson, J.; Toon, G. C.; Tyuterev, Vl. G.; Wagner, G.

2013-11-01

378

In vivo 31P MR spectroscopic imaging of the human prostate at 7 T: safety and feasibility.  

PubMed

(31)P MR spectroscopic imaging of the human prostate provides information about phosphorylated metabolites that could be used for prostate cancer characterization. The sensitivity of a magnetic field strength of 7 T might enable 3D (31)P MR spectroscopic imaging with relevant spatial resolution in a clinically acceptable measurement time. To this end, a (31)P endorectal coil was developed and combined with an eight-channel (1)H body-array coil to relate metabolic information to anatomical location. An extensive safety validation was performed to evaluate the specific absorption rate, the radiofrequency field distribution, and the temperature distribution of both coils. This validation consisted of detailed Finite Integration Technique simulations, confirmed by MR thermometry and B?1+ measurements in a phantom and in vivo temperature measurements. The safety studies demonstrated that the presence of the (31)P endorectal coil had no influence on the specific absorption rate levels and temperature distribution of the external eight-channel (1)H array coil. To stay within a 10 g averaged local specific absorption rate of 10 W/kg, a maximum time-averaged input power of 33 W for the (1)H array coil was allowed. For transmitting with the (31)P endorectal coil, our safety limit of less than 1°C temperature increase in vivo during a 15-min MR spectroscopic imaging experiment was reached at a time-averaged input power of 1.9 W. With this power setting, a second in vivo measurement was performed on a healthy volunteer. Using adiabatic excitation, 3D (31)P MR spectroscopic imaging produced spectra from the entire prostate in 18 min with a spatial resolution of 4 cm(3). The spectral resolution enabled the separate detection of phosphocholine, phosphoethanolamine, inorganic phosphate, and other metabolites that could play an important role in the characterization of prostate cancer. PMID:22368094

Kobus, Thiele; Bitz, Andreas K; van Uden, Mark J; Lagemaat, Miriam W; Rothgang, Eva; Orzada, Stephan; Heerschap, Arend; Scheenen, Tom W J

2012-12-01

379

Infrared spectroscopic methods for the study of aerosol particles using White cell optics: Development and characterization of a new aerosol flow tube.  

PubMed

A description of a new aerosol flow tube apparatus for measurements in situ under atmospherically relevant conditions is presented here. The system consists of a laboratory-made nebulizer generation system and a flow tube with a White cell-based Fourier transform IR for the detection system. An assessment of the White cell coupled to the flow tube was carried out by an extensive set of experiments to ensure the alignment of the infrared beam and optimize the performance of this system. The detection limit for CO was established as (1.0+/-0.3) ppm and 16 passes was chosen as the optimum number of passes to be used in flow tube experiments. Infrared spectroscopy was used to characterize dry aerosol particles in the flow tube. Pure particles composed of ammonium sulfate or sodium chloride ranging between 0.8 and 2.1 mum for size diameter and (0.8-4.9)x10(6) particles/cm(3) for density number were generated by nebulization of aqueous solutions. Direct measurements of the aerosol particle size agree with size spectra retrieved from inversion of the extinction measurements using Mie calculations, where the difference residual value is in the order of 0.2%. The infrared detection limit for ammonium sulfate aerosol particles was determined as d(p)=0.9 mum and N=5x10(3) particles/cm(3) with sigma=1.1 by Mie calculation. Alternatively, Mie calculations were performed to determine the flexibility in varying the optical length when aerosol particles are sent by the injector. The very good agreement between the values retrieved for aerosol particles injected through the flow tube or through the injector clearly validates the estimation of the effective optical path length for the injector. To determine the flexibility in varying the reaction zone length, analysis of the extinction spectra as function of the position of the injector was carried out by monitoring the integrated area of different absorption modes of the ammonium sulfate. We conclude that the aerosol loss in the flow tube reactor is negligible and that the aerosol particles remain on-axis for the length of the flow tube. PMID:19123581

Nájera, Juan J; Fochesatto, Javier G; Last, Deborah J; Percival, Carl J; Horn, Andrew B

2008-12-01

380

Infrared spectroscopic methods for the study of aerosol particles using White cell optics: Development and characterization of a new aerosol flow tube  

NASA Astrophysics Data System (ADS)

A description of a new aerosol flow tube apparatus for measurements in situ under atmospherically relevant conditions is presented here. The system consists of a laboratory-made nebulizer generation system and a flow tube with a White cell-based Fourier transform IR for the detection system. An assessment of the White cell coupled to the flow tube was carried out by an extensive set of experiments to ensure the alignment of the infrared beam and optimize the performance of this system. The detection limit for CO was established as (1.0±0.3) ppm and 16 passes was chosen as the optimum number of passes to be used in flow tube experiments. Infrared spectroscopy was used to characterize dry aerosol particles in the flow tube. Pure particles composed of ammonium sulfate or sodium chloride ranging between 0.8 and 2.1 ?m for size diameter and (0.8-4.9)×106 particles/cm3 for density number were generated by nebulization of aqueous solutions. Direct measurements of the aerosol particle size agree with size spectra retrieved from inversion of the extinction measurements using Mie calculations, where the difference residual value is in the order of 0.2%. The infrared detection limit for ammonium sulfate aerosol particles was determined as dp=0.9 ?m and N =5×103 particles/cm3 with ? =1.1 by Mie calculation. Alternatively, Mie calculations were performed to determine the flexibility in varying the optical length when aerosol particles are sent by the injector. The very good agreement between the values retrieved for aerosol particles injected through the flow tube or through the injector clearly validates the estimation of the effective optical path length for the injector. To determine the flexibility in varying the reaction zone length, analysis of the extinction spectra as function of the position of the injector was carried out by monitoring the integrated area of different absorption modes of the ammonium sulfate. We conclude that the aerosol loss in the flow tube reactor is negligible and that the aerosol particles remain on-axis for the length of the flow tube.

Nájera, Juan J.; Fochesatto, Javier G.; Last, Deborah J.; Percival, Carl J.; Horn, Andrew B.

2008-12-01

381

Atmospheric and Spectroscopic Research in the Far Infrared  

NASA Technical Reports Server (NTRS)

The spectroscopic measurements of molecular parameters constitute one of the major areas of our research program. This part of our program has been conducted in close collaboration with Smithsonian Astrophysical Observatory (SAO) and National Institute of Standards and Technology (NIST). The references on HO2, OH, and O2 that appear on the publication list are examples of this type of work completed during the grant period. These pressure-broadening studies have provided the kind of improvements needed in the database for retrieving atmospheric profiles from far infrared limb sensing data. Authors summarized the laboratory spectroscopic studies conducted during the grant period. We attempted to measure the pressure broadening coefficients of the O2 lines in the 50 and 117/ cm regions. An accurate characterization of these lines using the IBEX detector system was needed to analyze the flight data. These are difficult lines to measure because they