In situ temperature measurement of. alpha. -mercuric iodide by reflection spectroscopy

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

Nason, D.; Burger, A.

1991-12-30

Crystal face temperatures of single crystals of {alpha}-HgI{sub 2} growing in transparent ampules by physical vapor transport have been measured, {ital in} {ital situ}, by a novel, noncontact method which may be called reflectance spectroscopy thermometry. The method is based on the temperature dependence of the energy of the free-exciton peak as detected with a low-energy reflected beam. As presently configured, the accuracy is {plus minus}1.5 {degree}C for a slowly varying surface temperature. The method has potential for noncontact temperature measurement in some systems for which pyrometry is unsatisfactory.

Wisconsin H-Alpha Mapper | UW-Madison Astronomy

Science.gov Websites

Department of Astronomy Wisconsin H-Alpha Mapper Overview Description About WHAM Fabry-Perot Spectroscopy National Science Foundation Astronomy and... 02.20.2012 | Continue Reading » WHAM featured at Natural Astronomy Galactic Structure GALFA GLIMPSE GLIMPSE360 WHAM Extragalactic Astronomy & Cosmology Local

Synthesis of methyl 2-O- and 3-O-alpha-D-talopyranosyl-alpha-D-mannopyranoside.

PubMed

Rana, S S; Matta, K L

1986-09-01

Methyl 3,4,6-tri-O-benzyl-2-O-[6-O-(tert-butyldiphenylsilyl)-alpha-D- mannopyranosyl]-alpha-D-mannopyranoside (2) was synthesized by treatment of methyl 3,4,6-tri-O-benzyl-2-O-alpha-D-mannopyranosyl-alpha-D-mannopyranoside with tert-butylchlorodiphenylsilane in the presence of imidazole. Isopropylidenation, followed by oxidation with pyridinium chlorochromate, and stereoselective reduction with sodium borohydride, converted 2 into methyl 3,4,6-tri-O-benzyl-2-O-[6-O-(tert-butyldiphenylsilyl)-2,3-O-isopro pylidene- alpha-D-talopyranosyl]-alpha-D-mannopyranoside (5). Treatment of 5 with a molar solution of tetrabutylammonium fluoride in dry oxolane produced a diol which, on O-de-isopropylidenation followed by catalytic hydrogenolysis, afforded the disaccharide glycoside methyl 2-O-alpha-D-talopyranosyl-alpha-D-mannopyranoside. Synthesis of methyl 3-O-alpha-D-talopyranosyl-alpha-D-mannopyranoside was accomplished by a similar reaction-sequence. The structures of the final disaccharides, and of various other intermediates, were established by 1H- and 13C-n.m.r. spectroscopy.

New Binding Mode to TNF-Alpha Revealed by Ubiquitin-Based Artificial Binding Protein

PubMed Central

Hoffmann, Andreas; Kovermann, Michael; Lilie, Hauke; Fiedler, Markus; Balbach, Jochen; Rudolph, Rainer; Pfeifer, Sven

2012-01-01

A variety of approaches have been employed to generate binding proteins from non-antibody scaffolds. Utilizing a beta-sheet of the human ubiquitin for paratope creation we obtained binding proteins against tumor necrosis factor (TNF)-alpha. The bioactive form of this validated pharmacological target protein is a non-covalently linked homo-trimer. This structural feature leads to the observation of a certain heterogeneity concerning the binding mode of TNF-alpha binding molecules, for instance in terms of monomer/trimer specificity. We analyzed a ubiquitin-based TNF-alpha binder, selected by ribosome display, with a particular focus on its mode of interaction. Using enzyme-linked immunosorbent assays, specific binding to TNF-alpha with nanomolar affinity was observed. In isothermal titration calorimetry we obtained comparable results regarding the affinity and detected an exothermic reaction with one ubiquitin-derived binding molecule binding one TNF-alpha trimer. Using NMR spectroscopy and other analytical methods the 1∶3 stoichiometry could be confirmed. Detailed binding analysis showed that the interaction is affected by the detergent Tween-20. Previously, this phenomenon was reported only for one other type of alternative scaffold-derived binding proteins – designed ankyrin repeat proteins – without further investigation. As demonstrated by size exclusion chromatography and NMR spectroscopy, the presence of the detergent increases the association rate significantly. Since the special architecture of TNF-alpha is known to be modulated by detergents, the access to the recognized epitope is indicated to be restricted by conformational transitions within the target protein. Our results suggest that the ubiquitin-derived binding protein targets a new epitope on TNF-alpha, which differs from the epitopes recognized by TNF-alpha neutralizing antibodies. PMID:22363609

Structural Characteristics of the Alpha-Synuclein Oligomers Stabilized By the Flavonoid Baicalein

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

Hong, D.-P.; Fink, A.L.; Uversky, V.N.

The flavonoid baicalein inhibits fibrillation of alpha-synuclein, which is a major component of Lewy bodies in Parkinson's disease. It has been known that baicalein induces the formation of alpha-synuclein oligomers and consequently prevents their fibrillation. In order to evaluate the structural properties of baicalein-stabilized oligomers, we purified oligomer species by HPLC and examined their stability and structure by CD, Fourier transform infrared spectroscopy, size exclusion chromatography HPLC, small-angle X-ray scattering, and atomic force microscopy. Baicalein-stabilized oligomers are beta-sheet-enriched according to CD and Fourier transform infrared spectroscopy analyses. They did not form fibrils even after very prolonged incubation. From small-angle X-raymore » scattering data and atomic force microscopy images, the oligomers were characterized as quite compact globular species. Oligomers were extremely stable, with a GdmCl C(m)=3.3 M. This high stability explains the previously observed inhibition properties of baicalein against alpha-synuclein fibrillation. These baicalein-stabilized oligomers, added to the solution of aggregating alpha-synuclein, were able to noticeably inhibit its fibrillation. After prolonged coincubation, short fibrils were formed, suggesting an effective interaction of oligomers with monomeric alpha-synuclein. Membrane permeability tests suggested that the baicalein-stabilized oligomers had a mild effect on the integrity of the membrane surface. This effect was rather similar to that of the monomeric protein, suggesting that targeted stabilization of certain alpha-synuclein oligomers might offer a potential strategy for the development of novel Parkinson's disease therapies.« less

A consumer`s guide to lattice QCD results

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

DeGrand, T.

1994-12-01

The author presents an overview of recent lattice QCD results on hadron spectroscopy and matrix elements. Case studies include light quark spectroscopy, the determination of {alpha}{sub s} from heavy quark spectroscopy, the D-meson decay constant, a calculation of the Isgur-Wise function, and some examples of the (lack of) effect of sea quarks on matrix elements. The review is intended for the nonexpert.

Regioselectivity in Organic Synthesis: Preparation of the Bromohydrin of [alpha]-Methylstyrene

ERIC Educational Resources Information Center

Andersh, Brad; Kilby, Kathryn N.; Turnis, Meghan E.; Murphy, Drew L.

2008-01-01

In the described experiment, the regiochemical outcome of the addition of "HOBr" to [alpha]-methylstyrene is investigated. Although both "classic" qualitative analysis and instrumental techniques are described, the emphasis of this experiment is on the utilization [to the thirteenth power]C and DEPT-135 NMR spectroscopy to determine the…

PG 0308 + 096 and PG 1026 + 002 - Two new short period binary stars resulting from common-envelope evolution

NASA Technical Reports Server (NTRS)

Saffer, Rex A.; Wade, Richard A.; Liebert, James; Green, Richard F.; Sion, Edward M.; Bechtold, J.; Foss, Diana; Kidder, K.

1993-01-01

Ultraviolet spectroscopy, optical spectroscopy, and spectrophotometry have been used to study the excess UV stars PG 0308 + 096 and PG 1026 + 002. Both objects are short-period binary systems, each containing a DA white dwarf star and a dM star. Orbital periods of approximately 0.284 day for PG 0308 + 096, and aproximately 0.597 day for PG 1026, have been found by spectroscopic analysis of the H-alpha emission line. Ly-alpha and Balmer line profile fitting were used to estimate the mass of white dwarf stars; mass estimates for the dM stars are based on their spectral types. The orbital inclinations are derived from these masses, the periods, and amplitudes of the H-alpha radial velocity curves. The equivalent width of the H-alpha emission line, in each binary system, varies with the orbital phase in such a manner as to imply that it arises, in large part at least, from the hemisphere of the M star that faces the white dwarf star.

Structural determination of the acidic exopolysaccharide produced by a Pseudomonas sp. strain 1.15.

PubMed

Cescutti, P; Toffanin, R; Pollesello, P; Sutherland, I W

1999-01-31

Pseudomonas strain 1.15 was isolated from a freshwater biofilm and shown to produce considerable amounts of an acidic polysaccharide which was investigated by methylation analysis, NMR spectroscopy and ionspray mass spectrometry (ISMS). The polysaccharide was depolymerised by a bacteriophage-associated endoglucosidase and by autohydrolysis, and the resulting oligosaccharides were investigated by NMR spectroscopy and mass spectrometry. The resulting data showed that the parent repeating unit of the 1.15 exopolysaccharide (EPS) is a branched hexasaccharide. The main chain is constituted of the trisaccharide -->4)-alpha-L-Fucp-(1-->4)-alpha-L-Fucp-(1-->3)-beta-D-Glcp- (1--> and the side chain alpha-D-Galp-(1-->4)-beta-D-GlcAp-(1-->3)-alpha-D-Galp-(1-->is linked to O-3 of the first Fuc residue. The terminal non-reducing Gal carries a 1-carboxyethylidene acetal in the R configuration at the positions 4 and 6. Of the four different O-acetyl groups present in non-stoichiometric amounts, two were established to be on O-2 of the 3-linked Gal and on O-2 of the 4-linked Fuc.

Compact oleic acid in HAMLET.

PubMed

Fast, Jonas; Mossberg, Ann-Kristin; Nilsson, Hanna; Svanborg, Catharina; Akke, Mikael; Linse, Sara

2005-11-07

HAMLET (human alpha-lactalbumin made lethal to tumor cells) is a complex between alpha-lactalbumin and oleic acid that induces apoptosis in tumor cells, but not in healthy cells. Heteronuclear nuclear magnetic resonance (NMR) spectroscopy was used to determine the structure of 13C-oleic acid in HAMLET, and to study the 15N-labeled protein. Nuclear Overhauser enhancement spectroscopy shows that the two ends of the fatty acid are in close proximity and close to the double bond, indicating that the oleic acid is bound to HAMLET in a compact conformation. The data further show that HAMLET is a partly unfolded/molten globule-like complex under physiological conditions.

Glycosides from Bougainvillea glabra.

PubMed

Simon, András; Tóth, Gábor; Duddeck, Helmut; Soliman, Hesham S M; Mahmoud, Ibrahim I; Samir, Hanan

2006-01-01

Three glycosides were isolated from Bougainvillea glabra and their structures were determined by extensive use of 1D and 2D NMR spectroscopy ((1)H and (13)C). First compound was identical to momordin IIc (quinoside D) [beta-D-glucopyranosyl 3-O-[beta-D-xylopyranosyl-(1 --> 3)-O-(beta-D-glucopyranosyluronic acid)] oleanolate], second compound was quercetin 3-O-alpha-L-(rhamnopyranosyl)(1 --> 6)-[alpha-L-rhamnopy-ranosyl(1 --> 2)]-beta-D-galactopyranoside and third compound was its derivative quercetin 3-O-alpha-L-(4-caffeoylrhamnopyranosyl)(1 --> 6)-[alpha-L-rhamnopyranosyl (1 --> 2)]-beta-D-galactopyranoside, a new natural product.

Structural features of the exocellular polysaccharides of Mycobacterium tuberculosis.

PubMed Central

Lemassu, A; Daffé, M

1994-01-01

The cell envelope which surrounds pathogenic mycobacteria is postulated to be a defence barrier against phagocytic cells and its outermost constituents have a tendency to accumulate in the culture medium. The present work demonstrates that the exocellular material of Mycobacterium tuberculosis contains large amounts of polysaccharides with only traces, if any at all, of lipids. Three types of polysaccharides were purified by anion-exchange and gel-filtration chromatography; all were found to be neutral compounds devoid of acyl substituents. They consisted of D-glucan, D-arabino-D-mannan and D-mannan, which were eluted from gel-filtration columns in positions corresponding to molecular masses of 123, 13 and 4 kDa respectively. Their predominant structural features were determined by the characterization of the per-O-methyl derivatives of enzymic, acetolysis and Smith-degradation products and by 1H- and 13C-n.m.r. spectroscopy of the purified polysaccharides, using mono- and two-dimensional homonuclear chemical-shift correlated spectroscopy and two-dimensional heteronuclear (1H/13C) spectroscopy. The glucan which represented up to 90% of the polysaccharides was composed of repeating units of five or six-->4-alpha-D-Glcp-1--> residues and a -->4-alpha-D-Glcp substituted at position 6 with an alpha-D-Glcp, indicating a glycogen-like highly branched structure not related to the so-called polysaccharide-II previously identified in tuberculin. The arabinomannan consisted of a mannan segment composed of a -->6-alpha-D-Man-1--> core substituted at some positions 2 with an alpha-D-Manp. The arabinan termini of the arabinomannan were found to be extensively capped with mannosyl residues. The possibility that these polysaccharides contribute to the persistence of the tubercle bacillus in the macrophage by molecular mimicry is discussed. PMID:8297342

Structural features of the exocellular polysaccharides of Mycobacterium tuberculosis.

PubMed

Lemassu, A; Daffé, M

1994-01-15

The cell envelope which surrounds pathogenic mycobacteria is postulated to be a defence barrier against phagocytic cells and its outermost constituents have a tendency to accumulate in the culture medium. The present work demonstrates that the exocellular material of Mycobacterium tuberculosis contains large amounts of polysaccharides with only traces, if any at all, of lipids. Three types of polysaccharides were purified by anion-exchange and gel-filtration chromatography; all were found to be neutral compounds devoid of acyl substituents. They consisted of D-glucan, D-arabino-D-mannan and D-mannan, which were eluted from gel-filtration columns in positions corresponding to molecular masses of 123, 13 and 4 kDa respectively. Their predominant structural features were determined by the characterization of the per-O-methyl derivatives of enzymic, acetolysis and Smith-degradation products and by 1H- and 13C-n.m.r. spectroscopy of the purified polysaccharides, using mono- and two-dimensional homonuclear chemical-shift correlated spectroscopy and two-dimensional heteronuclear (1H/13C) spectroscopy. The glucan which represented up to 90% of the polysaccharides was composed of repeating units of five or six-->4-alpha-D-Glcp-1--> residues and a -->4-alpha-D-Glcp substituted at position 6 with an alpha-D-Glcp, indicating a glycogen-like highly branched structure not related to the so-called polysaccharide-II previously identified in tuberculin. The arabinomannan consisted of a mannan segment composed of a -->6-alpha-D-Man-1--> core substituted at some positions 2 with an alpha-D-Manp. The arabinan termini of the arabinomannan were found to be extensively capped with mannosyl residues. The possibility that these polysaccharides contribute to the persistence of the tubercle bacillus in the macrophage by molecular mimicry is discussed.

Resistance of alpha-crystallin quaternary structure to UV irradiation.

PubMed

Krivandin, A V; Muranov, K O; Yakovlev, F Yu; Poliansky, N B; Wasserman, L A; Ostrovsky, M A

2009-06-01

The damaging effect of UV radiation (lambda > 260 nm) on bovine alpha-crystallin in solution was studied by small-angle X-ray scattering, gel permeation chromatography, electrophoresis, absorption and fluorescence spectroscopy, and differential scanning calorimetry. The results obtained show that damage to even a large number of subunits within an alpha-crystallin oligomer does not cause significant rearrangement of its quaternary structure, aggregation of oligomers, or the loss of their solubility. Due to the high resistance of its quaternary structure, alpha-crystallin is able to prevent aggregation of destabilized proteins (especially of gamma- and beta-crystallins) and so to maintain lens transparency throughout the life of an animal (the chaperone-like function of alpha-crystallin).

Zinc oxide nanoparticles as novel alpha-amylase inhibitors

NASA Astrophysics Data System (ADS)

Dhobale, Sandip; Thite, Trupti; Laware, S. L.; Rode, C. V.; Koppikar, Soumya J.; Ghanekar, Ruchika-Kaul; Kale, S. N.

2008-11-01

Amylase inhibitors, also known as starch blockers, contain substances that prevent dietary starches from being absorbed by the body via inhibiting breakdown of complex sugars to simpler ones. In this sense, these materials are projected as having potential applications in diabetes control. In this context, we report on zinc oxide nanoparticles as possible alpha-amylase inhibitors. Zinc oxide nanoparticles have been synthesized using soft-chemistry approach and 1-thioglycerol was used as a surfactant to yield polycrystalline nanoparticles of size ˜18 nm, stabilized in wurtzite structure. Conjugation study and structural characterization have been done using x-ray diffraction technique, Fourier transform infrared spectroscopy, UV-visible spectroscopy, and transmission electron microscopy. Cytotoxicity studies on human fibrosarcoma (HT-1080) and skin carcinoma (A-431) cell lines as well as mouse primary fibroblast cells demonstrate that up to a dose of 20 μg/ml, ZnO nanoparticles are nontoxic to the cells. We report for the first time the alpha-amylase inhibitory activity of ZnO nanoparticles wherein an optimum dose of 20 μg/ml was sufficient to exhibit 49% glucose inhibition at neutral pH and 35 °C temperature. This inhibitory activity was similar to that obtained with acarbose (a standard alpha-amylase inhibitor), thereby projecting ZnO nanoparticles as novel alpha-amylase inhibitors.

TCAD simulation for alpha-particle spectroscopy using SIC Schottky diode.

PubMed

Das, Achintya; Duttagupta, Siddhartha P

2015-12-01

There is a growing requirement of alpha spectroscopy in the fields context of environmental radioactive contamination, nuclear waste management, site decommissioning and decontamination. Although silicon-based alpha-particle detection technology is mature, high leakage current, low displacement threshold and radiation hardness limits the operation of the detector in harsh environments. Silicon carbide (SiC) is considered to be excellent material for radiation detection application due to its high band gap, high displacement threshold and high thermal conductivity. In this report, an alpha-particle-induced electron-hole pair generation model for a reverse-biased n-type SiC Schottky diode has been proposed and verified using technology computer aided design (TCAD) simulations. First, the forward-biased I-V characteristics were studied to determine the diode ideality factor and compared with published experimental data. The ideality factor was found to be in the range of 1.4-1.7 for a corresponding temperature range of 300-500 K. Next, the energy-dependent, alpha-particle-induced EHP generation model parameters were optimised using transport of ions in matter (TRIM) simulation. Finally, the transient pulses generated due to alpha-particle bombardment were analysed for (1) different diode temperatures (300-500 K), (2) different incident alpha-particle energies (1-5 MeV), (3) different reverse bias voltages of the 4H-SiC-based Schottky diode (-50 to -250 V) and (4) different angles of incidence of the alpha particle (0°-70°).The above model can be extended to other (wide band-gap semiconductor) device technologies useful for radiation-sensing application. © The Author 2015. Published by Oxford University Press. All rights reserved. For Permissions, please email: journals.permissions@oup.com.

The Ly(alpha) Line Profiles of Ultraluminous Infrared Galaxies: Fast Winds and Lyman Continuum Leakage

NASA Technical Reports Server (NTRS)

Martin, Crystal L.; Dijkstra, Mark; Henry, Alaina L.; Soto, Kurt T.; Danforth, Charles W.; Wong, Joseph

2015-01-01

We present new Hubble Space Telescope Cosmic Origins Spectrograph far-ultraviolet (far-UV) spectroscopy and Keck Echellete optical spectroscopy of 11 ultraluminous infrared galaxies (ULIRGs), a rare population of local galaxies experiencing massive gas inflows, extreme starbursts, and prominent outflows. We detect Ly(alpha) emission from eight ULIRGs and the companion to IRAS09583+4714. In contrast to the P Cygni profiles often seen in galaxy spectra, the Ly(alpha) profiles exhibit prominent, blueshifted emission out to Doppler shifts exceeding -1000 km/s in three H II-dominated and two AGN-dominated ULIRGs. To better understand the role of resonance scattering in shaping the Ly(alpha) line profiles, we directly compare them to non-resonant emission lines in optical spectra. We find that the line wings are already present in the intrinsic nebular spectra, and scattering merely enhances the wings relative to the line core. The Ly(alpha) attenuation (as measured in the COS aperture) ranges from that of the far-UV continuum to over 100 times more. A simple radiative transfer model suggests the Ly(alpha) photons escape through cavities which have low column densities of neutral hydrogen and become optically thin to the Lyman continuum in the most advanced mergers. We show that the properties of the highly blueshifted line wings on the Ly(alpha) and optical emission-line profiles are consistent with emission from clumps of gas condensing out of a fast, hot wind. The luminosity of the Ly(alpha) emission increases nonlinearly with the ULIRG bolometric luminosity and represents about 0.1-1% of the radiative cooling from the hot winds in the H II-dominated ULIRGs.

The role of alpha-, 3(10)-, and pi-helix in helix-->coil transitions.

PubMed

Armen, Roger; Alonso, Darwin O V; Daggett, Valerie

2003-06-01

The conformational equilibrium between 3(10)- and alpha-helical structure has been studied via high-resolution NMR spectroscopy by Millhauser and coworkers using the MW peptide Ac-AMAAKAWAAKA AAARA-NH2. Their 750-MHz nuclear Overhauser effect spectroscopy (NOESY) spectra were interpreted to reflect appreciable populations of 3(10)-helix throughout the peptide, with the greatest contribution at the N and C termini. The presence of simultaneous alphaN(i,i + 2) and alphaN(i,i + 4) NOE cross-peaks was proposed to represent conformational averaging between 3(10)- and alpha-helical structures. In this study, we describe 25-nsec molecular dynamics simulations of the MW peptide at 298 K, using both an 8 A and a 10 A force-shifted nonbonded cutoff. The ensemble averages of both simulations are in reasonable agreement with the experimental helical content from circular dichroism (CD), the (3)J(HNalpha) coupling constants, and the 57 observed NOEs. Analysis of the structures from both simulations revealed very little formation of contiguous i --> i + 3 hydrogen bonds (3(10)-helix); however, there was a large population of bifurcated i --> i + 3 and i --> i + 4 alpha-helical hydrogen bonds. In addition, both simulations contained considerable populations of pi-helix (i --> i + 5 hydrogen bonds). Individual turns formed over residues 1-9, which we predict contribute to the intensities of the experimentally observed alphaN(i,i + 2) NOEs. Here we show how sampling of both folded and unfolded structures can provide a structural framework for deconvolution of the conformational contributions to experimental ensemble averages.

Communication: nanosecond folding dynamics of an alpha helix: time-dependent 2D-IR cross peaks observed using polarization-sensitive dispersed pump-probe spectroscopy.

PubMed

Panman, Matthijs R; van Dijk, Chris N; Meuzelaar, Heleen; Woutersen, S

2015-01-28

We present a simple method to measure the dynamics of cross peaks in time-resolved two-dimensional vibrational spectroscopy. By combining suitably weighted dispersed pump-probe spectra, we eliminate the diagonal contribution to the 2D-IR response, so that the dispersed pump-probe signal contains the projection of only the cross peaks onto one of the axes of the 2D-IR spectrum. We apply the method to investigate the folding dynamics of an alpha-helical peptide in a temperature-jump experiment and find characteristic folding and unfolding time constants of 260 ± 30 and 580 ± 70 ns at 298 K.

Solution structure of {alpha}-conotoxin PIA, a novel antagonist of {alpha}6 subunit containing nicotinic acetylcholine receptors

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

Chi, Seung-Wook; Lee, Si-Hyung; Kim, Do-Hyoung

2005-12-30

{alpha}-Conotoxin PIA is a novel nicotinic acetylcholine receptor (nAChR) antagonist isolated from Conus purpurascens that targets nAChR subtypes containing {alpha}6 and {alpha}3 subunits. {alpha}-conotoxin PIA displays 75-fold higher affinity for rat {alpha}6/{alpha}3{beta}2{beta}3 nAChRs than for rat {alpha}3{beta}2 nAChRs. We have determined the three-dimensional structure of {alpha}-conotoxin PIA by nuclear magnetic resonance spectroscopy. The {alpha}-conotoxin PIA has an '{omega}-shaped' overall topology as other {alpha}4/7 subfamily conotoxins. Yet, unlike other neuronally targeted {alpha}4/7-conotoxins, its N-terminal tail Arg{sup 1}-Asp{sup 2}-Pro{sup 3} protrudes out of its main molecular body because Asp{sup 2}-Pro{sup 3}-Cys{sup 4}-Cys{sup 5} forms a stable type I {beta}-turn. In addition, amore » kink introduced by Pro{sup 15} in the second loop of this toxin provides a distinct steric and electrostatic environment from those in {alpha}-conotoxins MII and GIC. By comparing the structure of {alpha}-conotoxin PIA with other functionally related {alpha}-conotoxins we suggest structural features in {alpha}-conotoxin PIA that may be associated with its unique receptor recognition profile.« less

Synthesis of methyl 2-O-alpha-D-mannopyranosyl-alpha-D-talopyranoside and methyl 2-O-alpha-D-talopyranosyl-alpha-D-talopyranoside.

PubMed

Jain, R K; Dubey, R; Abbas, S A; Matta, K L

1987-03-15

Treatment of methyl 3-O-benzyl-2-O-(2,3,4,6-tetra-O-acetyl-alpha-D-mannopyranosyl)-alpha-D- mannopyranoside (1) with tert-butyldiphenylsilyl chloride in N,N-dimethylformamide afforded methyl 3-O-benzyl-6-O-tert-butyldiphenylsilyl-2-O-(2,3,4,6-tetra-O-acetyl -alpha-D- mannopyranosyl)-alpha-D-mannopyranoside (2). Oxidation of 2 with pyridinium chlorochromate, followed by reduction of the carbonyl group, and subsequent O-deacetylation afforded methyl 3-O-benzyl-6-O-tert-butyldiphenylsilyl-2-O-alpha-D-mannopyranosyl- alpha-D- talopyranoside (5). Cleavage of the tert-butyldiphenylsilyl group of 5 with tetrabutylammonium fluoride in oxolane, followed by hydrogenolysis, gave methyl 2-O-alpha-D-mannopyranosyl-alpha-D-talopyranoside (7). O-Deacetylation of 1 gave methyl 3-O-benzyl-2-O-alpha-D-mannopyranosyl-alpha-D-mannopyranoside (8). Treatment of 8 with tert-butyldiphenylsilyl chloride afforded a 6,6'-disilyl derivative, which was converted into a 2',3'-O-isopropylidene derivative, and then further oxidized with pyridinium chlorochromate. The resulting diketone was reduced and removal of the protecting groups gave methyl 2-O-alpha-D-talopyranosyl-alpha-D-talopyranoside (15). The structures of both 7 and 15 were established by 13C-n.m.r. spectroscopy.

Design and performance of an ionisation chamber for the measurement of low alpha-activities

NASA Astrophysics Data System (ADS)

Hartmann, A.; Hutsch, J.; Krüger, F.; Sobiella, M.; Wilsenach, H.; Zuber, K.

2016-04-01

A new ionisation chamber for alpha-spectroscopy has been built from radio-pure materials for the purpose of investigating long lived alpha-decays. The measurement makes use of pulse shape analysis to discriminate between signal and background events. The design and performance of the chamber is described in this paper. A background rate of (10.9 ± 0.6) counts per day in the energy region of 1-9 MeV was achieved with a run period of 30.8 days. The background is dominantly produced by radon daughters.

First Results from Faint Infrared Grism Survey (Figs): First Simultaneous Detection of Ly Alpha Emission and Lyman Break From a Galaxy at Z =7.51

NASA Technical Reports Server (NTRS)

Tilvi, V.; Pirzkal, N.; Malhotra, S.; Finkelstein, S. L.; Rhoads, J. E.; Windhorst, R.; Grogin, N. A.; Koekemoer, A.; Zakamska, N. L.; Ryan, R.;

Structural Characterization of the Putative Cholinergic Binding Region alpha(179-201) of the Nicotinic Acetylcholine Receptor. Part 1. Review and Experimental Design.

DTIC Science & Technology

1993-04-01

SUBJCT TERMS .. 15. NUMBER OF PAGES Nicotinic acetylcholine receptor FTIR 21 Vibrational spectroscopy Cholinergic 16. PRICE COOE Resonance raman 17...Wilson et al 1955). FMR spectroscopy measures the absorbance of infra-red rad iation, where as Raman spectroscopy measures inelastic scattering of...frequency is domrunated by that chromophore, then Raman scattering involving vibrations localized in that chromophore will be sharply enhanced(Cantor and

MAPPING THE CLUMPY STRUCTURES WITHIN SUBMILLIMETER GALAXIES USING LASER-GUIDE STAR ADAPTIVE OPTICS SPECTROSCOPY

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

Menendez-Delmestre, Karin; Goncalves, Thiago S.; Blain, Andrew W.

2013-04-20

We present the first integral-field spectroscopic observations of high-redshift submillimeter-selected galaxies (SMGs) using Laser-Guide Star Adaptive Optics. We target H{alpha} emission of three SMGs at redshifts z {approx} 1.4-2.4 with the OH-Suppressing Infrared Imaging Spectrograph on Keck. The spatially resolved spectroscopy of these galaxies reveals unresolved broad-H{alpha} line regions (FWHM >1000 km s{sup -1}) likely associated with an active galactic nucleus (AGN) and regions of diffuse star formation traced by narrow-line H{alpha} emission (FWHM {approx}< 500 km s{sup -1}) dominated by multiple H{alpha}-bright stellar clumps, each contributing 1%-30% of the total clump-integrated H{alpha} emission. We find that these SMGs hostmore » high star formation rate surface densities, similar to local extreme sources, such as circumnuclear starbursts and luminous infrared galaxies. However, in contrast to these local environments, SMGs appear to be undergoing such intense activity on significantly larger spatial scales as revealed by extended H{alpha} emission over 4-16 kpc. H{alpha} kinematics show no evidence of ordered global motion as would be found in a disk, but rather large velocity offsets ({approx}few Multiplication-Sign 100 km s{sup -1}) between the distinct stellar clumps. Together with the asymmetric distribution of the stellar clumps around the AGN in these objects, it is unlikely that we are unveiling a clumpy disk structure as has been suggested in other high-redshift populations of star-forming galaxies. The SMG clumps in this sample may correspond to remnants of originally independent gas-rich systems that are in the process of merging, hence triggering the ultraluminous SMG phase.« less

Effect of alpha-particle irradiation on the electrical properties of n-type Ge

NASA Astrophysics Data System (ADS)

Roro, K. T.; Janse van Rensburg, P. J.; Auret, F. D.; Coelho, S.

2009-12-01

Deep-level transient spectroscopy was used to investigate the effect of alpha particle irradiation on the electrical properties of n-type Ge. The samples were irradiated with alpha particles at room temperature using an americium-241 (Am-241) radionuclide source. The main defects introduced were found to be electron traps with energy levels at EC-0.38, EC-0.21, EC-0.20, EC-0.15, and EC-0.10 eV, respectively. The main defects in alpha particle irradiation are similar to those introduced by MeV electron irradiation, where the main defect is the E-center. A quadratic increase in concentration as a function of dose is observed.

Identification of triterpenes from milkweed (Asclepias syriaca).

PubMed

Háznagy-Radnai, Erzsébet; Wéber, Edit; Czigle, Szilvia; Máthé, Imre

2012-09-01

The chloroform extract of Asclepias syriaca stem were investigated. Three triterpenes were isolated by TLC, VLC, and preparative chromatography, and their structures established by one and two-dimensional NMR spectroscopy. Lupenyl acetate has been isolated for the first time from A. syriaca; this is thefirst representative of a triterpene bearing a lupane skeleton in this species. In addition, alpha-amyrin acetate and alpha-amyrin butyrate were isolated.

Raman structural studies of the nickel electrode

NASA Technical Reports Server (NTRS)

Cornilsen, Bahne C.

1994-01-01

The objectives of this investigation have been to define the structures of charged active mass, discharged active mass, and related precursor materials (alpha-phases), with the purpose of better understanding the chemical and electrochemical reactions, including failure mechanisms and cobalt incorporation, so that the nickel electrode may be improved. Although our primary tool has been Raman spectroscopy, the structural conclusions drawn from the Raman data have been supported and augmented by three other analysis methods: infrared spectroscopy, powder X-ray Diffraction (XRD), and x-ray absorption spectroscopy (in particular EXAFS, Extended X-ray Absorption Fine Structure spectroscopy).

Stability of HAMLET--a kinetically trapped alpha-lactalbumin oleic acid complex.

PubMed

Fast, Jonas; Mossberg, Ann-Kristin; Svanborg, Catharina; Linse, Sara

2005-02-01

The stability toward thermal and urea denaturation was measured for HAMLET (human alpha-lactalbumin made lethal to tumor cells) and alpha-lactalbumin, using circular dichroism and fluorescence spectroscopy as well as differential scanning calorimetry. Under all conditions examined, HAMLET appears to have the same or lower stability than alpha-lactalbumin. The largest difference is seen for thermal denaturation of the calcium free (apo) forms, where the temperature at the transition midpoint is 15 degrees C lower for apo HAMLET than for apo alpha-lactalbumin. The difference becomes progressively smaller as the calcium concentration increases. Denaturation of HAMLET was found to be irreversible. Samples of HAMLET that have been renatured after denaturation have lost the specific biological activity toward tumor cells. Three lines of evidence indicate that HAMLET is a kinetic trap: (1) It has lower stability than alpha-lactalbumin, although it is a complex of alpha-lactalbumin and oleic acid; (2) its denaturation is irreversible and HAMLET is lost after denaturation; (3) formation of HAMLET requires a specific conversion protocol.

Dimerization of A-[alpha]-[SiNb3W9O40]7- by pH-controlled formation of individual Nb−µ-O−Nb linkages

Treesearch

Gyu-Shik Kim; Huadong Zeng; Wade A. Neiwert; Jennifer J. Cowan; Donald VanDerveer; Craig L. Hill; Ira A. Weinstock

2003-01-01

The reversible, stepwise formation of individual Nb−µ-O−Nb linkages during acid condensation of 2 equiv of A-[alpha]-[SiNb3W9O40]7- (1) to the tri-µ-oxo-bridged structure A-[alpha]-[Si2Nb6W18O77]8- (4) is demonstrated by a combination of X-ray crystallography and variable-pD solution 183W and 29Si NMR spectroscopy. Addition of DCl to a pD 8.4...

Multipoint attachment to a support protects enzyme from inactivation by organic solvents: alpha-Chymotrypsin in aqueous solutions of alcohols and diols.

PubMed

Mozhaev, V V; Sergeeva, M V; Belova, A B; Khmelnitsky, Y L

1990-03-25

Inactivation of alpha-chymotrypsin in aqueous solutions of alcohols and diols proceeds both reversibly and irreversibly. Reversible loss of the specific enzyme activity results from conformational changes (unfolding) of the enzyme detected by fluorescence spectroscopy. Multipoint covalent attachment to the matrix of polyacryl-amide gel by copolymerization method stabilizes alpha-chymotrypsin from denaturation by alcohols, the stabilizing effect increasing with the number of bonds between the protein and the support. Immobilization protects the enzyme also from irreversible inactivation by organic solvents resulting from bimolecular aggregation and autolysis.

Laser-induced breakdown spectroscopy for in-cylinder equivalence ratio measurements in laser-ignited natural gas engines.

PubMed

Joshi, Sachin; Olsen, Daniel B; Dumitrescu, Cosmin; Puzinauskas, Paulius V; Yalin, Azer P

2009-05-01

In this contribution we present the first demonstration of simultaneous use of laser sparks for engine ignition and laser-induced breakdown spectroscopy (LIBS) measurements of in-cylinder equivalence ratios. A 1064 nm neodynium yttrium aluminum garnet (Nd:YAG) laser beam is used with an optical spark plug to ignite a single cylinder natural gas engine. The optical emission from the combustion initiating laser spark is collected through the optical spark plug and cycle-by-cycle spectra are analyzed for H(alpha)(656 nm), O(777 nm), and N(742 nm, 744 nm, and 746 nm) neutral atomic lines. The line area ratios of H(alpha)/O(777), H(alpha)/N(746), and H(alpha)/N(tot) (where N(tot) is the sum of areas of the aforementioned N lines) are correlated with equivalence ratios measured by a wide band universal exhaust gas oxygen (UEGO) sensor. Experiments are performed for input laser energy levels of 21 mJ and 26 mJ, compression ratios of 9 and 11, and equivalence ratios between 0.6 and 0.95. The results show a linear correlation (R(2) > 0.99) of line intensity ratio with equivalence ratio, thereby suggesting an engine diagnostic method for cylinder resolved equivalence ratio measurements.

Transformation of alpha-tocopherol (vitamin E) and related chromanol model compounds into their phenoxonium ions by chemical oxidation with the nitrosonium cation.

PubMed

Lee, Stephen B; Lin, Ching Yeh; Gill, Peter M W; Webster, Richard D

2005-12-09

[reaction: see text] Alpha-tocopherol (alpha-TOH), the main oil component making up vitamin E, and its nonnatural solid 6-hydroxy-2,2,5,7,8-pentamethylchroman and 6-hydroxy-2,5,7,8-tetramethylchroman-2-carboxylic acid structurally related analogues were oxidized quantitatively with 2 mol equiv of NO+ SbF6(-) in CH3CN at 233 K to form phenoxonium cations (alpha-TO+ SbF6(-)) in a chemically reversible two-electron/one-proton process. Solution-phase infrared spectroscopy, 1H and 13C NMR spectroscopy, and corresponding theoretical calculations of the spectroscopic data using density-based and wave-function-based models support the identity of the remarkably stable phenoxonium cations. The presence of an oxygen atom in the para position to the hydroxyl group and the chromanol ring structure appear to be important factors in stabilization of the phenoxonium ions, which raises the interesting possibility that the cations play a crucial role in the mode of action of vitamin E in biological systems. Although the phenoxonium cations are reactive toward nucleophiles such as water, they may be moderately stable in the hydrophobic (lipophilic) environment where vitamin E is known to occur naturally.

An {alpha}-cluster model for {sub {Lambda}}{sup 9}Be spectroscopy

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

Filikhin, I. N., E-mail: ifilikhin@nccu.edu; Suslov, V. M.; Vlahovic, B.

An {alpha}-cluster model is applied to study low-lying spectrum of the {sub {Lambda}}{sup 9}Be hypernucleus. The three-body {alpha}{alpha}{Lambda} problem is numerically solved by the Faddeev equations in configuration space using phenomenological pair potentials. We found a set of the potentials that reproduces experimental data for the ground state (1/2{sup +}) binding energy and excitation energy of the 5/2{sup +} and 3/2{sup +} states, simultaneously. This set includes the Ali-Bodmer potential of the version 'e' for {alpha}{alpha} and modified Tang-Herndon potential for {alpha}{Lambda} interactions. The spin-orbit {alpha}{Lambda} interaction is given by modified Scheerbaum potential. Low-lying energy levels are evaluated applying amore » variant of the analytical continuation method in the coupling constant. It is shown that the spectral properties of {sub {Lambda}}{sup 9}Be can be classified as an analog of {sup 9}Be spectrum with the exception of several 'genuine hypernuclear states'. This agrees qualitatively with previous studies. The results are compared with experimental data and new interpretation of the spectral structure is discussed.« less

Poly-alpha,beta-(N-(2-hydroxyethyl)-L-aspartamide)-g-poly(1,3trimethylene carbonate) amphiphilic graft co-polymer as a potential drug carrier.

PubMed

Peng, Tao; Su, Jing; Cheng, Si-Xue; Zhuo, Ren-Xi

2006-01-01

A biodegradable amphiphilic graft polymer was successfully synthesized by grafting hydrophobic poly(1,3-trimethylene carbonate) (PTMC) sequences onto a hydrophilic poly-alpha,beta-(N-(2-hydroxyethyl)-L-aspartamide) (PHEA) backbone. The graft polymer, PHEA-g-PTMC, was synthesized by ring-opening polymerization initiated by the macroinitiator PHEA bearing hydroxyl groups without adding any catalyst. The graft polymer was characterized by Fourier transform infrared spectroscopy, 1H-nuclear magnetic resonance spectroscopy, combined size-exclusion chromatography and multiangle laser light scattering analysis. Two drugs with distinct water solubility, prednisone acetate and tegafur, were encapsulated in the PHEA-g-PTMC nanoparticles. The in vitro release of two drugs from PHEA-g-PTMC nanoparticle drug-delivery systems was investigated.

Growth and Characterization of alpha-PbO for Room Temperature Radiation Detection

NASA Astrophysics Data System (ADS)

Ford, Erin Leigh

A global trading structure and high throughput of shipping containers into ports around the world increases the chance of nuclear terrorism via cargo containers. Harmless radioactive sources confuse and impede detection of the materials that pose a real threat, making spectroscopy difficult and requiring detectors with high resolution. The current methods that are used to check containers in ports have security flaws, and only 5% of all shipping containers are checked. The development of semiconductor gamma-ray detectors is one of the protocols being advanced to alleviate this risk because they can function at room temperature and they are cost effective, easily produced, and have high resolution. This dissertation has addressed the current lack of "perfect" room temperature detector materials by investigating alpha-PbO, a novel material in this field. This includes the development of a growth process for alpha-PbO thin films, as well as its structural and performance characterization as a detector material. Because we intend alpha-PbO to be a photoconductive detector, it should have certain properties. A photoconductive detector consists of a highly resistive material with a voltage bias across it. It absorbs incident gamma-rays, creating electron-hole pairs that provide a signal. To function well, it must have a high atomic number and a high density in order to absorb high-energy photons via the photoelectric effect. It should also have a large resistivity and a wide band gap to avoid large leakage currents at room temperature. Finally, it must have good charge carrier transport properties and detector resolution in order to be able to determine the characteristic energy peaks of the radiation-emitting source. We chose alpha-PbO because it has a very high Z and a very high density and a band gap in the correct range. It also has a rich history of use as a photoconductor that reaches back to the 1950s. Numerous methods have been used to grow thin films of alpha-PbO. However, rarely are those films single phase or highly oriented. Pulsed laser deposition provides a method to grow epitaxial thin films of alpha-PbO. The structure of the grown films was characterized using X-ray diffraction 2θ-o scans, rocking curves, and reciprocal space mapping. Feedback from a parameterized study of the structural characterization enabled optimization of the growth process to improve the quality of the thin films. The methods used for the optical measurement of alpha-PbO films included absorption spectroscopy and ellipsometry. Determination of the spectral absorption coefficient was achieved by transmission spectroscopy and reflection spectroscopy via a PerkinElmer Lambda 950 UV-Vis spectrophotometer. Study of the electronic and transport properties of alpha-PbO is important in order to understand how the material will behave as a radiation detector. Spectral photoconductivity was measured to ensure that alpha-PbO's response to light was large enough for it to be a useful detector material and to confirm the band gap measurements. In the field of detector materials, the mutau-product is commonly used as a figure of merit because it enables a measurement of the trapping length of the charge carriers within the detector. Many's equation, which is a derivation of the photocurrent with respect to the applied voltage across a wide band gap semiconductor, is one of the methods used to determine the mutau-product. The photocurrent voltage measurements were obtained from the 0.5 V to 80 V range. This data was difficult to fit with Many's equation over that whole range. Higher voltages displayed deviation from ideal behavior due to the contact effects, but at the lower voltages the data were unaffected. Fits to the lower voltage range, from 0.5 V to 10 V, yielded mutau = 6.8 x 10-4 cm2/V. Room temperature photoconductors will ultimately be used to detect gamma-rays; however, thin films do not have enough stopping power to absorb the total energy of a gamma-ray. Therefore, we study the alpha-PbO detector response to radiation in the form of alpha particles because they are large, charged, and relatively easy to stop. SRIM calculation estimated that alpha particles have a range of up to 16 mum in alpha-PbO. The initial long-duration film growth yielded films that were ˜ 8 mum thick. Therefore, a full energy peak from alpha particles was not seen in alpha-PbO. We did see a shoulder protruding out of the noise peak due to the charge carriers that were created before the alpha particles escaped the detector volume. (Abstract shortened by UMI.)

Investigation of crystalline morphology in poly (ether ether ketone) using dielectric relaxation spectroscopy

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

Kalika, D.S.; Krishnaswamy, R.K.

1993-12-31

The relaxation behavior of poly (ether ether ketone) [PEEK] has been investigated using dielectric relaxation spectroscopy; the glass-rubber ({alpha}) relaxation and a sub-glass ({beta}) relaxation were examined for the amorphous material and both cold-crystallized and melt-crystallized specimens. Analysis of the data using the Cole-Cole modification of the Debye equation allowed determination of the dielectric relaxation strength and relaxation broadening parameter for both transitions as a function of material crystallization history. The crystallized specimens displayed a positive offset in isochronal loss temperature for both the {alpha} and {beta} relaxations, with the {alpha} relaxation broadened significantly. The measured dipolar response was interpretedmore » using a three-phase morphological model encompassing a crystalline phase, a mobile amorphous phase, and a rigid amorphous phase. Determination of phase fractions based on dipolar mobilization across the glass-rubber relaxation revealed a finite rigid amorphous phase fraction for both the cold-crystallized specimens which was relatively insensitive to thermal history and degree of crystallinity (W{sub RAP}40.20).« less

Spatiotemporal image correlation spectroscopy (STICS) theory, verification, and application to protein velocity mapping in living CHO cells.

PubMed

Hebert, Benedict; Costantino, Santiago; Wiseman, Paul W

2005-05-01

We introduce a new extension of image correlation spectroscopy (ICS) and image cross-correlation spectroscopy (ICCS) that relies on complete analysis of both the temporal and spatial correlation lags for intensity fluctuations from a laser-scanning microscopy image series. This new approach allows measurement of both diffusion coefficients and velocity vectors (magnitude and direction) for fluorescently labeled membrane proteins in living cells through monitoring of the time evolution of the full space-time correlation function. By using filtering in Fourier space to remove frequencies associated with immobile components, we are able to measure the protein transport even in the presence of a large fraction (>90%) of immobile species. We present the background theory, computer simulations, and analysis of measurements on fluorescent microspheres to demonstrate proof of principle, capabilities, and limitations of the method. We demonstrate mapping of flow vectors for mixed samples containing fluorescent microspheres with different emission wavelengths using space time image cross-correlation. We also present results from two-photon laser-scanning microscopy studies of alpha-actinin/enhanced green fluorescent protein fusion constructs at the basal membrane of living CHO cells. Using space-time image correlation spectroscopy (STICS), we are able to measure protein fluxes with magnitudes of mum/min from retracting lamellar regions and protrusions for adherent cells. We also demonstrate the measurement of correlated directed flows (magnitudes of mum/min) and diffusion of interacting alpha5 integrin/enhanced cyan fluorescent protein and alpha-actinin/enhanced yellow fluorescent protein within living CHO cells. The STICS method permits us to generate complete transport maps of proteins within subregions of the basal membrane even if the protein concentration is too high to perform single particle tracking measurements.

Characterization of a Dopaminergic Stimulatory Factor Derived From Monoclonal Cell Lines of Striatal Origin

DTIC Science & Technology

2005-12-01

purification scheme that appears most advantageous. The purest product obtained will be subjected to NMR analysis by Josh Kurutz and mass spectroscopy by...Phosphoenolpyruvate carboxykinase 2 Phosphomevalonate kinase Protein phosphatase 1A, magnesium dependent, alpha isoform Uridine- cytidine kinase 1-like 1...more purified preparation should permit structural analysis of the molecules responsible for the activity using mass spectroscopy and nuclear

Effects of packaging environments on free radicals in gamma-irradiated UHMWPE resin powder blend with vitamin E.

PubMed

Ridley, M D; Jahan, M S

2009-03-15

Ultra-high molecular weight polyethylene (UHMWPE) powder (GUR 1020) was blended with high concentration (20%) of vitamin E (alpha-Tocopherol (alpha-T)) for direct detection of alpha-T radicals in presence of PE radicals. Samples were gamma-irradiated in sealed packages filled with N(2), or in open air. Free radicals were measured in open air environment for 71 days using electron spin resonance (ESR) technique. When irradiated in air, both alpha-T and alpha-T-resin produced identical ESR signals characteristics of tochopheroxyl radicals (alpha-T-O(*)), suggesting that PE radicals are quenched by alpha-T. There was no indication of growth of oxygen-induced radicals (OIR) either. However, when alpha-T-resin was irradiated in N(2), presence of both PE and alpha-T radicals were evident in the ESR spectra. And, OIR were produced by the same samples when they were subsequently exposed to air (for 71 days). Oxidation data recorded 85 days after postirradiation aging in air using Fourier transform infra-red (FTIR) spectroscopy, however, did not show any measurable difference between samples irradiated in N(2) and air.

A Ly{alpha} GALAXY AT REDSHIFT z = 6.944 IN THE COSMOS FIELD

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

Rhoads, James E.; Hibon, Pascale; Malhotra, Sangeeta

2012-06-20

Ly{alpha} emitting galaxies can be used to study cosmological reionization, because a neutral intergalactic medium (IGM) scatters Ly{alpha} photons into diffuse halos whose surface brightness falls below typical survey detection limits. Here, we present the Ly{alpha} emitting galaxy LAE J095950.99+021219.1, identified at redshift z = 6.944 in the COSMOS field using narrowband imaging and follow-up spectroscopy with the IMACS instrument on the Magellan I Baade telescope. With a single object spectroscopically confirmed so far, our survey remains consistent with a wide range of IGM neutral fraction at z Almost-Equal-To 7, but further observations are planned and will help clarify themore » situation. Meantime, the object we present here is only the third Ly{alpha}-selected galaxy to be spectroscopically confirmed at z {approx}> 7, and is {approx}2-3 times fainter than the previously confirmed z Almost-Equal-To 7 Ly{alpha} galaxies.« less

Occurrence of a unique sialyl tetrasaccharide in colostrum of a bottlenose dolphin (Tursiops truncatus).

PubMed

Uemura, Yusuke; Asakuma, Sadaki; Nakamura, Tadashi; Arai, Ikichi; Taki, Michihiro; Urashima, Tadasu

2005-10-10

Crude oligosaccharides were recovered from bottlenose dolphin (Tursiops truncatus) colostrum after chloroform/methanol extraction of lipids and protein precipitation, and purified using gel filtration, anion exchange chromatography and high performance liquid chromatography (HPLC). Their chemical structures characterized by NMR spectroscopy were as follows: GalNAc(beta1-4)[Neu5Ac(alpha2-3)]Gal(beta1-4)Glc, Neu5Ac(alpha2-3)Gal(beta1-4)Glc, Neu5Ac(alpha2-6)Gal(beta1-4)Glc and Gal(alpha1-4)Gal(beta1-4)Glc. The monosialyltetrasaccharide and neutral trisaccharide have not previously been found as free forms in any natural sources including milk or colostrum, although these structures have been found in the carbohydrate units of glycosphingolipids GM2 and Gb3.

Effects of a high-pressure treatment on the wheat alpha-amylase inhibitor and its relationship to elimination of allergenicity

NASA Astrophysics Data System (ADS)

Yamamoto, S.; Takanohashi, K.; Hara, T.; Odani, S.; Suzuki, A.; Nishiumi, T.

2010-03-01

In this study, the effects of high-pressure treatment on structure and allergeincity of alpha amylase inhibitor (a-AI) were investigated. The pressure-induced structural changes of α-AI were estimated by fluorescence spectra and by fourth derivative UV-spectroscopy for probed tyrosine residues and by circular dichroism (CD) spectroscopy. The changes in the tertiary structure detected by fluorescence spectra and by fourth derivative UV-spectroscopy under high pressure were indicated at over 300 MPa. Measurements of CD spectroscopy suggested that the effects of a high-pressure treatment on changes in the secondary structure of α-AI were little. From our results, pressure-induced changes of the α-AI structure were not apparent. On the other hands, the IgE-specific binding activities of pressurized α-AI to sera from allergic patients against wheat, which is estimated by observations of dot-blotting, were decreased by high-pressure treatment. It is known that the pressure-induced elimination of allergenicity is related to the tertiary structural changes of allergen molecules. This study are suspected that the epitopes of α-AI do not contain tyrosine residues, and thus the decrease of IgE-specific binding activities is probably caused by the tertiary structural changes of these parts of α-AI.

Geometrical behavior of hydrogen bonding patterns in the alpha-dodecyl-omega-hydroxy-tris(oxyethylene)-water system monitored by near infrared spectroscopy.

PubMed

Ohno, Keiichi; Takao, Hiroshi; Katsumoto, Yukiteru

2006-03-01

Changes in the geometry of hydrogen bonding patterns in the alpha-dodecyl-omega-hydroxy-tris(oxyethylene) (C(12)E(3))-water system have been investigated by near infrared (NIR) spectroscopy. In the 5,300-4,600 cm(-1) region, the characteristic bands for C(12)E(3) and water can be separately investigated, since the combination bands of the OH stretching and its COH bending of alcohols are observed at 5,000-4,650 cm(-1), whereas the combination bands of the OH stretching and its HOH bending of water, at 5,300-5,000 cm(-1). The NIR result has revealed that the addition of water to C(12)E(3) promotes the formation of the OHcdots, three dots, centeredOHcdots, three dots, centeredO hydrogen bonds.

Ages of M Dwarf Stars from their Alpha Enhancement

NASA Astrophysics Data System (ADS)

Muirhead, Philip Steven; Veyette, Mark

2018-01-01

M dwarf stars dominate stellar populations, and recent results from NASA's Kepler Mission suggest rocky planets are abundant around M dwarf stars. With so many planets orbiting M dwarfs, exoplanet scientists can now turn to questions about their history and evolution. Unfortunately, measuring fundamental properties of M dwarfs is challenging for a variety of reasons. I will discuss the importance of near-infrared spectroscopy in this effort. With high-resolution near-infrared spectroscopy covering Y to K band, we can measure detailed fundamental properties of low-mass stars. With new techniques to measure stellar alpha and iron abundances, we can begin to measure the most challenging fundamental property of M dwarfs: their age. These efforts are even more exciting in the coming years, when the TESS spacecraft is expected to discover five times as many planets orbiting low-mass stars as Kepler.

Light-induced yellowing of selectively 13C-enriched dehydrogenation polymers (DHPs). Part 1, Side-chain 13C-enriched DHP ([alpha], [beta], and [gamma]-13C)

Treesearch

Jim Parkas; Magnus Paulsson; Terashima Noritsugu; Ulla Westermark; Sally Ralph

2004-01-01

Light-induced yellowing has been studied using side-chain ([alpha], [beta], and [gamma]) 13C-enriched DHP (dehydrogenation polymer) and quantitative solution state 13C NMR spectroscopy. The DHP was formed from 13C-enriched coniferin using an enzymatic system consisting of [beta]-glucosidase, glucose oxidase, and peroxidase in a pH 6 buffer solution. The DHP was applied...

A sulfated alpha-L-fucan from sea cucumber.

PubMed

Ribeiro, A C; Vieira, R P; Mourão, P A; Mulloy, B

1994-03-04

A purified sulfated alpha-L-fucan from the sea cucumber body wall was studied, before and after almost complete desulfation, using methylation analysis and NMR spectroscopy. NMR analysis indicates that 2,4-di-O-sulfo-L-fucopyranose and unsubstituted fucopyranose are present in equal proportions, and that 2-O-sulfo-L-fucopyranose is present in twice that proportion. There is some NMR evidence that a regular repeating sequence of four residues comprises most or all of the polysaccharide chain.

Large-area imager of hydrogen leaks in fuel cells using laser-induced breakdown spectroscopy.

PubMed

Hori, M; Hayano, R S; Fukuta, M; Koyama, T; Nobusue, H; Tanaka, J

2009-10-01

We constructed a simple device, which utilized laser-induced breakdown spectroscopy to image H2 gas leaking from the surfaces of hydrogen fuel cells to ambient air. Nanosecond laser pulses of wavelength lambda=532 nm emitted from a neodymium-doped yttrium aluminum garnet laser were first compressed to a pulse length Deltat<1 ns using a stimulated Brillouin backscattering cell. Relay-imaging optics then focused this beam onto the H(2) leak and initiated the breakdown plasma. The Balmer-alpha (H-alpha) emission that emerged from this was collected with a 2-m-long macrolens assembly with a 90-mm-diameter image area, which covered a solid angle of approximately 1 x 10(-3)pi steradians seen from the plasma. The H-alpha light was isolated by two 100-mm-diameter interference filters with a 2 nm bandpass, and imaged by a thermoelectrically cooled charge-coupled device camera. By scanning the position of the laser focus, the spatial distribution of H2 gas over a 90-mm-diameter area was photographed with a spatial resolution of < or = 5 mm. Photoionization of the water vapor in the air caused a strong H-alpha background. By using pure N2 as a buffer gas, H2 leaks with rates of <1 cc/min were imaged. We also studied the possibilities of detecting He, Ne, or Xe gas leaks.

The relationship between structural stability and electrochemical performance of multi-element doped alpha nickel hydroxide

NASA Astrophysics Data System (ADS)

Miao, Chengcheng; Zhu, Yanjuan; Huang, Liangguo; Zhao, Tengqi

2015-01-01

The multi-element doped alpha nickel hydroxide has been prepared by supersonic co-precipitation method. Three kinds of samples A, B and C are prepared by chemically coprecipitating Ni/Al, Ni/Al/Mn and Ni/Al/Mn/Yb, respectively. Inductively coupled plasma atomic emission spectroscopy (ICP-AES), Particle size distribution (PSD) measurement, X-ray diffraction (XRD), scanning electron microscope (SEM) and Fourier transform infrared spectroscopy (FT-IR) are used to characterize the physical properties of the synthesized α-Ni(OH)2 samples, such as chemical composition, morphology, structural stability of the crystal. The results show that all samples are nano-sized materials and the interlayer spacing becomes larger and the structural stability becomes better with the increase of doped elements and doped ratio. The prepared alpha nickel hydroxide samples are added into micro-sized beta nickel hydroxide to form biphase electrode materials for Ni-MH battery. The electrochemical characterization of the biphase electrodes, including cyclic voltammetry (CV) and charge/discharge test, are also performed. The results demonstrate that the biphase electrode with sample C exhibits better electrochemical reversibility and cyclic stability, higher charge efficient and discharge potential, larger proton diffusion coefficient (5.81 × 10-12 cm2 s-1) and discharge capacity (309.0 mAh g-1). Hence, it indicates that all doped elements can produce the synergic effect and further improve the electrochemical properties of the alpha nickel hydroxide.

Synthetic mucin fragments: synthesis of O-sulfo and O-methyl derivatives of allyl O-(beta-D-galactopyranosyl)-(1-->3)-2-acetamido-2-deoxy-alpha-D- galactopyranoside as potential compounds for sulfotransferases.

PubMed

Jain, R K; Piskorz, C F; Matta, K L

1995-10-02

Allyl 2-acetamido-4,6-O-(4-methoxybenzylidene)-2-deoxy-alpha-D-galact opy ranoside (1) was condensed with either 2,3,4,6-tetra-O-acetyl-alpha-D-galactopyranosyl bromide (2) or 2,3,4-tri-O-benzoyl-6-O-bromoacetyl-alpha-D-galactopyranosyl bromide (14) in the presence of mercuric cyanide. Selective substitution with methyl, sulfo or both at desired positions, followed by the removal of protecting groups, afforded allyl O-(beta-D-galactopyranosyl)-(1-->3)-2-acetamido-2-deoxy-6-O-methyl-alpha -D- galactopyranoside (5), allyl O-(6-O-sulfo-beta-D-galactopyranosyl sodium salt)-(1-->3)-2-acetamido-2-deoxy-6- O-methyl-alpha-D-galactopyranoside (10), allyl O-(beta-D-galactopyranosyl)-(1-->3)-2-acetamido-2-deoxy-6-O-sulfo-alpha- D- galactopyranoside sodium salt (13), allyl O-(6-O-sulfo-beta-D-galactopyranosyl sodium salt)-(1-->3)-2-acetamido-2-deoxy- alpha-D-galactopyranoside (17) and allyl O-(3-O-sulfo-beta-D-galactopyranosyl sodium salt)-(1-->3)-2-acetamido-2-deoxy- alpha-D-galactopyranoside (22). The structures of compounds 5, 10, 13, 17 and 22 were established by 13C NMR and FAB mass spectroscopy.

Emulsion Polymerization of Butyl Acrylate: Spin Trapping and EPR Study

NASA Technical Reports Server (NTRS)

Kim, S.; Westmoreland, D.

1994-01-01

The propagating radical in the emulsion polymerization reaction of butyl acrylate was detected by Electron Paramagnetic Resonance spectroscopy using two spin trapping agents, 2-methyl-2nitrosopropane and alpha -N-tert-butylnitrone.

Electron exchange between r-keggin tungstoaluminates and a well-defined cluster-anion probe for studies in electron transfer

Treesearch

Yurii V. Geletii; Craig L. Hill; Alan J. Bailey; Kenneth I. Hardcastle; Rajai H. Atalla; Ira A. Weinstock

2005-01-01

Fully oxidized [alpha]-AlIIIW12O405-(1ox), and one-electron-reduced [alpha]-AlIIIW12O406-(1red), are well-behaved (stable and free of ion pairing) over a wide range of pH and ionic-strength values at room temperature in water. Having established this, 27Al NMR spectroscopy is used to measure rates of electron exchange between 1ox (27Al NMR: 72.2 ppm relative to Al(H2O)...

A study of various synthetic routes to produce a halogen-labeled traction fluid

NASA Technical Reports Server (NTRS)

Jones, W. R., Jr.; Zimmer, H.

1978-01-01

Several synthetic routes were studied for the synthesis of the compound 1, 1, 3-trimethyl-1, 3-dicyclohexyl-2 chloropropane. This halogen-labeled fluid would be of use in the study of high traction lubricants under elastohydrodynamic lubrication conditions using infrared emission spectroscopy. The synthetic routes included: dimerization of alpha-methylstyrene, methanol addition to alpha-methylstyrene, a Wittig reaction, and an organometallic approach. Because of steric hindrance and competing reactions, none of these routes were successful.

Comparison of Cf-252 thin-film sources prepared by evaporation or self-transfer

DOE PAGES

Algutifan, Noor J.; Sherman, Steven R.; Alexander, Charles W.

2014-11-29

Californium-252 (Z = 98) is valued as a potent neutron source due to its spontaneous fission decay path. Thin film sources containing Cf-252 were prepared by two techniques: evaporation and self-transfer. The sources were analyzed by alpha and gamma spectroscopy. Results indicate that self-transfer sources exhibit less alpha energy straggling and energy loss than evaporative sources. Fission fragments may also self-transfer, and sources made by self-transfer may need some decay time to reach radioactive equilibrium.

Early stages of the oxidation of metal surfaces. [photoelectron spectroscopy of zinc oxide

NASA Technical Reports Server (NTRS)

Gatos, H. C.; Johnson, K. H.

1978-01-01

Photoemission cross sections were calculated for the ZnO4(-6) cluster using the self consistent-chi alpha- scattered wave theory to display the main features of the ultraviolet and X-ray photoemission data from ZnO. A solid model is suggested for an absolute photoemission intensity comparison resulting in chi alpha intensities which are roughly 70% of the experimental values. Together with the experimental data, the calculations allow a complete determination of the electronic structure of a ZnO surface.

Thermodynamic confinement and alpha-helix persistence length in poly(gamma-benzyl-L-glutamate)-b-poly(dimethyl siloxane)-b-poly(gamma-benzyl-L-glutamate) triblock copolymers.

PubMed

Papadopoulos, P; Floudas, G; Schnell, I; Lieberwirth, I; Nguyen, T Q; Klok, H-A

2006-02-01

The structure and the associated dynamics of a series of poly(gamma-benzyl-L-glutamate)-b-poly(dimethyl siloxane)-b-poly(gamma-benzyl-L-glutamate) (PBLG-b-PDMS-b-PBLG) triblock copolymers were investigated using small- and wide-angle X-ray scattering, NMR, transmission electron microscopy, and dielectric spectroscopy, respectively. The structural analysis revealed phase separation in the case of the longer blocks with defected alpha-helical segments embedded within the block copolymer nanodomains. The alpha-helical persistence length was found to depend on the degree of segregation; thermodynamic confinement and chain stretching results in the partial annihilation of helical defects.

Interaction of anti-cancer drug-cisplatin with major proteinase inhibitor-alpha-2-macroglobulin: Biophysical and thermodynamic analysis.

PubMed

Zia, Mohammad Khalid; Siddiqui, Tooba; Ali, Syed Saqib; Ahsan, Haseeb; Khan, Fahim Halim

2018-05-09

Alpha-2-macroglobulin is a multifunctional, highly abundant, plasma protein which reacts with a wide variety of molecules and drugs including cisplatin. Cisplatin is commonly used anticancer drug widely used for treatment of testicular, bladder, ovarian, head and neck, lung and cervical cancers. This study is designed to examine the interaction of cisplatin with human alpha-2-macroglobulin through various biophysical techniques and drug binding through molecular modeling. Cisplatin alters the function of alpha-2-macroglobulin and the thiolesters are most likely the reactive sites for cisplatin. Our result suggests that cisplatin decreases the antiproteolytic potential and causes structural and functional change in human alpha-2-macroglobulin as evident by absorption and fluorescence spectroscopy. Change in secondary structure of alpha-2-macroglobulin was confirmed by CD and FTIR. Thermodynamics parameters such as entropy (ΔS), enthalpy (ΔH) and Gibb's free energy changes (ΔG) along with number of binding sites (N) of alpha-2-macroglobulin-cisplatin binding in solutions were determined by isothermal titration calorimetry (ITC). It was found that binding of cisplatin with alpha-2-macroglobulin was exothermic in nature. The interaction of drug with alpha-2-macroglobulin in the plasma could lead to structural alterations in the conformational status of alpha-2-macroglobulin resulting in its functional inactivation. Copyright © 2018 Elsevier B.V. All rights reserved.

The damaging effect of UV-C irradiation on lens alpha-crystallin.

PubMed

Fujii, Noriko; Uchida, Hiroki; Saito, Takeshi

2004-11-02

To evaluate the effect of UV-C irradiation on the structural properties of alpha-crystallin and its chaperone activity. alpha- and betaL-crystallins were isolated from bovine lenses using gel chromatography. The purified alpha-crystallin was subjected to UV-C irradiation (254 nm; 1, 2, 5, 10, 20, 50 J/cm2). We measured the tryptophan fluorescence, circular dichroism (CD) spectroscopy in the far UV, and the chaperone activity of both irradiated and non-irradiated alpha-crystallin. The tryptophan fluorescence of alpha-crystallin decreased, whereas the N-formylkynurenine fluorescence increased markedly with increasing doses of UV-C irradiation. Both the oxidation of Met1 and the racemization of Asp151 of alphaA-crystallin increased at a dose of 1-2 J/cm2 and then gradually decreased. The CD spectrum showed that the secondary structure of alpha-crystallin altered with increasing radiation dose, and almost all of the beta-sheet structure was lost at doses above 50 J/cm2. The chaperone activity of alpha-crystallin irradiated with doses under 5 J/cm2 remained intact. However, it was reduced to only 40% after irradiation at 10 J/cm2. Our study suggests that photo-oxidation of tryptophan residues in alpha-crystallin may be one of the events that affects the three-dimensional packing array and chaperone activity of this lens protein.

Reusable magnetic nanobiocatalyst for synthesis of silver and gold nanoparticles.

PubMed

Mazumder, Jahirul Ahmed; Ahmad, Razi; Sardar, Meryam

2016-12-01

In the present work, we describe a simple procedure for the biosynthesis of nanosilver and gold by the reduction of silver nitrate and auric chloride respectively using a nanobiocatalyst. The nanobiocatalyst was prepared by covalent coupling of alpha amylase on (3-aminopropyl)triethoxysilane (APTES) modified iron oxide magnetic nanoparticles. The nanobiocatalyst retains 77% of its activity as compared to free alpha amylase. The nanobiocatalyst can be used up to three consecutive cycles for the synthesis of nano silver and gold. The biosynthesized nanoparticles after each cycle were characterized by UV-vis spectrophotometer, Dynamic Light Spectroscopy (DLS), Transmission Electron Microscope (TEM), X-ray powder diffraction (XRD), and Fourier transform infrared spectroscopy (FTIR). Silver and gold nanoparticles of same morphology and dimensions were formed in each cycle. The procedure for synthesis of nanoparticles using an immobilized enzyme is eco-friendly and can be used repeatedly. Copyright © 2016 Elsevier B.V. All rights reserved.

Structural relaxation in the hydrogen-bonding liquids N-methylacetamide and water studied by optical Kerr effect spectroscopy.

PubMed

Turton, David A; Wynne, Klaas

2008-04-21

Structural relaxation in the peptide model N-methylacetamide (NMA) is studied experimentally by ultrafast optical Kerr effect spectroscopy over the normal-liquid temperature range and compared to the relaxation measured in water at room temperature. It is seen that in both hydrogen-bonding liquids, beta relaxation is present, and in each case, it is found that this can be described by the Cole-Cole function. For NMA in this temperature range, the alpha and beta relaxations are each found to have an Arrhenius temperature dependence with indistinguishable activation energies. It is known that the variations on the Debye function, including the Cole-Cole function, are unphysical, and we introduce two general modifications: One allows for the initial rise of the function, determined by the librational frequencies, and the second allows the function to be terminated in the alpha relaxation.

Spatially Resolved Emission of a z~3 Damped Lyman Alpha Galaxy with Keck/OSIRIS IFU

NASA Astrophysics Data System (ADS)

Christenson, Holly; Jorgenson, Regina

2017-01-01

The damped Lyman alpha (DLA) class of galaxies contains most of the neutral hydrogen gas over cosmic time. Few DLAs have been detected directly, which limits our knowledge of fundamental properties like size and mass. We present Keck/OSIRIS infrared integral field spectroscopy (IFU) observations of a DLA that was first detected in absorption toward a background quasar. Our observations use the Keck Laser Guide Star Adaptive Optics system to reduce the point-spread function of the quasar, making it possible to spatially resolve the DLA emission. We map this emission in O[III] 5007 Å. At redshift z~3, this DLA represents one of the highest redshift DLAs mapped with IFU spectroscopy. We present measurements of the star formation rate, metallicity, and gas mass of the galaxy.This project was supported in part by the NSF REU grant AST-1358980 and by the Nantucket Maria Mitchell Association.

Spectroscopy of an unusual emission line M star

NASA Technical Reports Server (NTRS)

Schneider, Donald P.; Greenstein, Jesse L.; Schmidt, Maarten; Gunn, James E.

1991-01-01

Moderate-resolution spectroscopy of an unusual late-type faint emission-line star, PC 0025 + 0047, is reported. A very strong (greater than 250 A equivalent width) an H-alpha emission line was detected by the present automated line search algorithm. The spectrum was found to have two unresolved emission lines (H-alpha and H-beta) near zero velocity, superposed on the absorption spectrum of a very red M dwarf which has strong K I, and relatively weak bands of TiO. From the weakness of the subordinate lines of Na I (8192 A) and other spectral features, it is inferred that it is definitely a cooler, and probably fainter, analog of LHS 2924. The strength of the emission lines indicates that PC 0025 + 0447 is very young and may be a fading predecessor brown drawf at an estimated M(bol) approaching 14m at a distance of about 60 pc.

Atypical binding of the Swa2p UBA domain to ubiquitin.

PubMed

Matta-Camacho, Edna; Kozlov, Guennadi; Trempe, Jean-François; Gehring, Kalle

2009-02-20

Swa2p is an auxilin-like yeast protein that is involved in vesicular transport and required for uncoating of clathrin-coated vesicles. Swa2p contains a ubiquitin-associated (UBA) domain, which is present in a variety of proteins involved in ubiquitin (Ub)-mediated processes. We have determined a structural model of the Swa2p UBA domain in complex with Ub using NMR spectroscopy and molecular docking. Ub recognition occurs predominantly through an atypical interaction in which UBA helix alpha1 and the N-terminal part of helix alpha2 bind to Ub. Mutation of Ala148, a key residue in helix alpha1, to polar residues greatly reduced the affinity of the UBA domain for Ub and revealed a second low-affinity Ub-binding site located on the surface formed by helices alpha1 and alpha3. Surface plasmon resonance showed that the Swa2p UBA domain binds K48- and K63-linked di-Ub in a non-linkage-specific manner. These results reveal convergent evolution of a Ub-binding site on helix alpha1 of UBA domains involved in membrane protein trafficking.

Periplasmic expression of human interferon-alpha 2c in Escherichia coli results in a correctly folded molecule.

PubMed Central

Voss, T; Falkner, E; Ahorn, H; Krystek, E; Maurer-Fogy, I; Bodo, G; Hauptmann, R

1994-01-01

Human interferon-alpha 2c (IFN-alpha 2c) was produced in Escherichia coli under the control of the alkaline phosphatase promoter using a periplasmic expression system. Compared with other leader sequences, the heat-stable enterotoxin II leader of E. coli (STII) resulted in the highest rate of correct processing as judged by Western-blot analysis. The fermentation was designed as a batch-fed process in order to obtain a high yield of biomass. The processing rate of IFN-alpha 2c could be increased from 25% to more than 50% by shifting the fermentation pH from 7.0 to 6.7. IFN-alpha 2c extracted from the periplasm was purified by a new four-step chromatographic procedure. Whereas cytoplasmically produced IFN-alpha 2c does not have its full native structure, IFN-alpha 2c extracted from the periplasm was found to be correctly folded, as shown by c.d. spectroscopy. Peptide-map analysis in combination with m.s. revealed the correct formation of disulphide bridges. N-terminal sequence analysis showed complete removal of the leader sequence, creating the authentic N-terminus starting with cysteine. Images Figure 3 Figure 4 Figure 6 PMID:8141788

XPS studies of UO 2 oxidation by alpha radiolysis of water at 100°C

NASA Astrophysics Data System (ADS)

Sunder, S.; Boyer, G. D.; Miller, N. H.

1990-12-01

The effect of alpha radiolysis of water on the oxidation and dissolution of UO 2 was studied at 100°C as a function of alpha-field strength and water chemistry using X-ray photoelectron spectroscopy. In N 2-purged solutions the oxidation of UO 2 increases with the strength of the alpha flux; an alpha flux greater than or equal to that from a 250-μ Ci americium-241 source leads to oxidation of UO 2 beyond the UO 2.33 (U 3O 7) stage, and an alpha flux equal to that from a 5-μ Ci source does not result in UO 2 oxidation beyond the UO 2.33 stage. The presence of dissolved H 2 in water, at a concentration ≥ 1.6 × 10 -4moldm-3, reduces the oxidation and dissolution of UO 2 due to alpha radiolysis at temperatures ≥ 100° C. It is concluded that the radiolysis of groundwater at ~ 100°C, due to the alpha flux associated with used CANDU fuel, is unlikely to make a significant contribution to its oxidative dissolution in the geological disposal vault planned in the Canadian Nuclear Fuel Waste Management Program. CANada Deuterium Uranium. Registered trademark.

Quantification of transuranic elements by time interval correlation spectroscopy of the detected neutrons

PubMed

Baeten; Bruggeman; Paepen; Carchon

2000-03-01

The non-destructive quantification of transuranic elements in nuclear waste management or in safeguards verifications is commonly performed by passive neutron assay techniques. To minimise the number of unknown sample-dependent parameters, Neutron Multiplicity Counting (NMC) is applied. We developed a new NMC-technique, called Time Interval Correlation Spectroscopy (TICS), which is based on the measurement of Rossi-alpha time interval distributions. Compared to other NMC-techniques, TICS offers several advantages.

Fraction of free-base nicotine in fresh smoke particulate matter from the Eclipse "cigarette" by 1H NMR spectroscopy.

PubMed

Pankow, James F; Barsanti, Kelley C; Peyton, David H

2003-01-01

Solution 1H NMR (proton-NMR) spectroscopy was used to measure the distribution of nicotine between its free-base and protonated forms at 20 degrees C in (a) water; (b) glycerin/water mixtures; and (c) puff-averaged "smoke" particulate matter (PM) produced by the Eclipse cigarette, a so-called "harm reduction" cigarette manufactured by R. J. Reynolds (RJR) Tobacco Co. Smoke PM from the Eclipse contains glycerin, water, nicotine, and numerous other components. Smoke PM from the Eclipse yielded a signal for the three N-methyl protons on nicotine at a chemical shift of delta (ppm) = 2.79 relative to a trimethylsilane standard. With alpha fb = fraction of the total liquid nicotine in free-base form, and alpha a = fraction in the acidic, monoprotonated NicH+ form, then alpha a + alpha fb approximately 1. (The diprotonated form of nicotine was assumed negligible.) When the three types of solutions were adjusted so that alpha a approximately 1, the N-methyl protons yielded delta a = 2.82 (Eclipse smoke PM); 2.79 (35% water/65% glycerin); and 2.74 (water). When the solutions were adjusted so that alpha fb approximately 1, the N-methyl protons yielded delta fb = 2.16 (Eclipse smoke PM); 2.13 (35% water/65% glycerin); and 2.10 (water). In all of the solutions, the rate of proton exchange between NicH+ and Nic was fast relative to the 1H-NMR chemical shift difference in hertz. Each solution containing both NicH+ and Nic thus yielded a single N-methyl peak at a delta given by delta = alpha a delta a + alpha fb delta fb so that delta varied linearly between delta a and delta fb. Since alpha fb = (delta a-delta)/(delta a-delta fb), then delta = 2.79 for the unadjusted Eclipse smoke PM indicates alpha fb approximately 0.04. The effective pH of the Eclipse smoke PM at 20 degrees C may then be calculated as pHeff = 8.06 + log[alpha fb/(1-alpha fb)] = 6.69, where 8.06 is the pKa of NicH+ in water at 20 degrees C. The measurements obtained for the puff-averaged Eclipse smoke PM pertain to the chemistry of the smoke PM as it might be initially inhaled at 20 degrees C. Upon inhalation, the volatilization of nicotine and other acid/base active compounds (as well as a warming toward a body temperature of 37 degrees C) will alter the pHeff value of the smoke PM during the time that it resides and ages in the respiratory tract.

Precision measurements on trapped antihydrogen in the ALPHA experiment

NASA Astrophysics Data System (ADS)

Eriksson, S.

2018-03-01

Both the 1S-2S transition and the ground state hyperfine spectrum have been observed in trapped antihydrogen. The former constitutes the first observation of resonant interaction of light with an anti-atom, and the latter is the first detailed measurement of a spectral feature in antihydrogen. Owing to the narrow intrinsic linewidth of the 1S-2S transition and use of two-photon laser excitation, the transition energy can be precisely determined in both hydrogen and antihydrogen, allowing a direct comparison as a test of fundamental symmetry. The result is consistent with CPT invariance at a relative precision of around 2×10-10. This constitutes the most precise measurement of a property of antihydrogen. The hyperfine spectrum of antihydrogen is determined to a relative uncertainty of 4×10-4. The excited state and the hyperfine spectroscopy techniques currently both show sensitivity at the few 100 kHz level on the absolute scale. Here, the most recent work of the ALPHA collaboration on precision spectroscopy of antihydrogen is presented together with an outlook on improving the precision of measurements involving lasers and microwave radiation. Prospects of measuring the Lamb shift and determining the antiproton charge radius in trapped antihydrogen in the ALPHA apparatus are presented. Future perspectives of precision measurements of trapped antihydrogen in the ALPHA apparatus when the ELENA facility becomes available to experiments at CERN are discussed. This article is part of the Theo Murphy meeting issue `Antiproton physics in the ELENA era'.

Titration of Alanine Monitored by NMR Spectroscopy: A Biochemistry Laboratory Experiment

ERIC Educational Resources Information Center

Waller, Francis J.; And Others

1977-01-01

The experiment described here involves simultaneous monitoring of pH and NMR chemical shifts during an aqueous titration of alpha- and beta-alanine. This experiment is designed for use in an undergraduate biochemistry course. (MR)

Diagnostic Suite for HyperV Coaxial Plasma Gun Development for the PLX- α Project

NASA Astrophysics Data System (ADS)

Case, Andrew; Brockington, Sam; Witherspoon, F. Douglas

2015-11-01

We present the diagnostic suite to be used during development of the coaxial guns HyperV will deliver to LANL in support of the ARPA-E Accelerating Low-Cost Plasma Heating And Assembly (ALPHA) program. For plasma jet diagnostics this includes fast photodiodes for velocimetry, a ballistic pendulum for measuring total plasmoid momentum, interferometry for line integrated plasma density, deflectometry for line integrated perpendicular density gradient measurements, and spectroscopy, both time resolved high resolution spectroscopy using a novel detector developed by HyperV and time integrated survey spectroscopy, for measurements of velocity and temperature as well as impurities. In addition, we plan to use fast pressure probes for stagnation pressure, a Faraday cup for density, fast imaging for plume geometry and time integrated imaging for overall light emission. A novel low resolution long record length camera developed by HyperV will also be used for plume diagnostics. For diagnostics of gun operation, we will use Rogowski coils to measure current, voltage dividers for voltages, B-dot probes for magnetic field, and time resolved fast photodiodes to measure plasmoid velocity inside the accelerator. This work supported by the ARPA-E ALPHA program.

Evidence for cross-linking in tomato cutin using HR-MAS NMR spectroscopy.

PubMed

Deshmukh, Ashish P; Simpson, André J; Hatcher, Patrick G

2003-11-01

Cutin is a polyester biopolymer component of plant leaf and fruit cuticles, most often associated with waxes and cuticular polysaccharides, and sometimes with another aliphatic biopolymer called cutan. Insolubility of these cuticular biopolymers has made it difficult to apply traditional analytical techniques for structure determination, because most techniques providing molecular level details require solubility. By using the relatively new technique of one and two-dimensional high-resolution magic angle spinning (HR-MAS) NMR spectroscopy, with added information from solid-state 13C NMR spectroscopy, detailed through-bond connectivities and assignments are made for cutin from Lycopersicon esculentum (tomato) fruit. Based on the data obtained, tomato cutin is found to be predominantly an aliphatic polyester with some olefinic and aromatic moieties, consistent with previous studies that employed various degradative approaches. Aside from esters, there are free primary and secondary alcohol groups, as well as free fatty acids. A significant finding is the presence of alpha-branched fatty acids/esters. Mid-chain hydroxyls appear to be generally unesterified, but esters of mid-chain hydroxyls have been identified. The alpha-branched fatty acids/esters and esters of mid-chain hydroxyls could point towards cross-linking.

Characterization and optimization of the HyperV PLX- α coaxial-gun plasma jet

NASA Astrophysics Data System (ADS)

Case, Andrew; Brockington, Sam; Cruz, Edward; Witherspoon, F. Douglas

2017-10-01

We present results from characterizing and optimizing performance of the contoured gap coaxial plasma guns under development for the ARPA-E Accelerating Low-Cost Plasma Heating And Assembly (ALPHA) program. Plasma jet diagnostics include fast photodiodes for velocimetry and interferometry for line integrated density. Additionally we present results from spectroscopy, both time resolved high resolution spectroscopy using a novel detector and time integrated survey spectroscopy, for measurements of velocity and temperature as well as impurities. Fast imaging gives plume geometry and time integrated imaging gives overall light emission. Results from a novel long record length camera developed by HyperV will also be presented. Experimental results are compared to the desired target parameters for the plasma jets. The target values for the plasmoid are velocity of 50 km/s, mass of 3.5 mg, and length of 10 cm. The best results so far from the exploration of parameter space for gun operation are: 4 mg at >50 km/s, with a length of 10 cm. Peak axial density 34 cm downstream from the muzzle is 2 ×1016 cm-3. This work supported by the ARPA-E ALPHA Program under contract DE-AR0000566.

Substitution of histidine-137 by glutamine abolishes the catalytic activity of the ribosome-inactivating protein alpha-sarcin.

PubMed Central

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

1995-01-01

The alpha-sarcin cytotoxin is an extracellular fungal protein that inhibits protein biosynthesis by specifically cleaving one phosphodiester bond of the 28 S rRNA. The His137 residue of alpha-sarcin is suggested to be involved in the catalytic activity of this protein, based on the observed sequence similarity with some fungal ribonucleases. Replacement of this residue by Gln (H137Q mutant variant of alpha-sarcin) abolishes the ribonuclease activity of the protein. This has been demonstrated for an homogeneous preparation of the H137Q alpha-sarcin by measuring its effect against both intact rabbit ribosomes and the homopolymer poly(A). The conformation of H137Q alpha-sarcin is highly similar to that of the wild-type protein, which has been analysed by CD and fluorescence spectroscopy. Both H137Q and wild-type alpha-sarcin exhibit identical CD spectra in the peptide-bond region, indicating that no changes at the level of the secondary structure are produced upon mutation. Only minor differences are observed in both near-UV CD and fluorescence emission spectra in comparison to those of the wild-type protein. Moreover, H137Q alpha-sarcin interacts with phospholipid vesicles, promoting the same effects as the native cytotoxin. Therefore, we propose that His137 is part of the ribonucleolytic active site of the cytotoxin alpha-sarcin. Images Figure 4 PMID:7626023

Structural characterization of novel L-galactose-containing oligosaccharide subunits of jojoba seed xyloglucans.

PubMed

Hantus, S; Pauly, M; Darvill, A G; Albersheim, P; York, W S

1997-10-28

Jojoba seed xyloglucan was shown to be a convenient source of biologically active xyloglucan oligosaccharides that contain both L- and D-galactosyl residues [E. Zablackis et al., Science, 272 (1996) 1808-1810]. Oligosaccharides were isolated by liquid chromatography of the mixture of oligosaccharides generated by treating jojoba seed xyloglucan with a beta-(1-->4)-endoglucanase. The purified oligosaccharides were reduced with NaBH4, converting them to oligoglycosyl alditol derivatives that were structurally characterized by a combination of mass spectrometry and 2-dimensional NMR spectroscopy. This analysis established that jojoba xyloglucan oligosaccharides contain the novel side-chain [alpha-L-Gal p-(1-->2)-beta-D-Galp-(1-->2)-alpha-D-Xyl p-(1-->6)-], which is structurally homologous to the fucose-containing side-chain [alpha-L-Fucp-(1-->2)-beta-D-Galp-(1-->2)-alpha-D-Xyl p-(1-->6)-] found in other biologically active xyloglucan oligosaccharides.

Laser-produced lithium plasma as a narrow-band extended ultraviolet radiation source for photoelectron spectroscopy.

PubMed

Schriever, G; Mager, S; Naweed, A; Engel, A; Bergmann, K; Lebert, R

1998-03-01

Extended ultraviolet (EUV) emission characteristics of a laser-produced lithium plasma are determined with regard to the requirements of x-ray photoelectron spectroscopy. The main features of interest are spectral distribution, photon flux, bandwidth, source size, and emission duration. Laser-produced lithium plasmas are characterized as emitters of intense narrow-band EUV radiation. It can be estimated that the lithium Lyman-alpha line emission in combination with an ellipsoidal silicon/molybdenum multilayer mirror is a suitable EUV source for an x-ray photoelectron spectroscopy microscope with a 50-meV energy resolution and a 10-mum lateral resolution.

Synthesis and conformational studies of carrabiose and its 4'-sulphate and 2,4'-disulphate.

PubMed

Parra, E; Caro, H N; Jiménez-Barbero, J; Martín-Lomas, M; Bernabé, M

1990-12-15

Methyl alpha-carrabioside (13), and its 4-sulphate (19) and 2,4-disulphate (20) have been synthesised via glycosylation of methyl 3,6-anhydro-2-O-benzyl-alpha-D-galactopyranoside with 2,3,6-tri-O-acetyl-4-O-benzyl-beta-D-galactopyranosyl bromide and subsequent partial or complete debenzylation, sulphation, and deprotection of the resulting disaccharide derivatives. Conformational studies have been carried out on 13, 19, and 20 on the basis of 1D and 2D 1H-n.m.r. spectroscopy and molecular mechanics calculations.

Measurement of myocardial free radical production during exercise using EPR spectroscopy.

PubMed

Traverse, Jay H; Nesmelov, Yuri E; Crampton, Melanie; Lindstrom, Paul; Thomas, David D; Bache, Robert J

2006-06-01

Exercise is associated with an increase in oxygen flux through the mitochondrial electron transport chain that has recently been demonstrated to increase the production of reactive oxygen species (ROS) in skeletal muscle. This study examined whether exercise also causes free radical production in the heart. We measured ROS production in seven chronically instrumented dogs during rest and treadmill exercise (6.4 km/h at 10 degrees grade; and heart rate, 204 +/- 3 beats/min) using electron paramagnetic resonance spectroscopy in conjunction with the spin trap alpha-phenyl-tert-butylnitrone (PBN) (0.14 mol/l) in blood collected from the aorta and coronary sinus (CS). To improve signal detection, the free radical adducts were deoxygenated over a nitrogen stream for 15 min and extracted with toluene. The hyperfine splitting constants of the radicals were alpha(N) = 13.7 G and alpha(H) = 1.0 G, consistent with an alkoxyl or carbon-centered radical. Resting aortic and CS PBN adduct concentrations were 6.7 and 6.3 x 10(8) arbitrary units (P = not significant). Both aortic and CS adduct concentrations increased during exercise, but there was no significant difference between the aortic and CS concentrations. Thus, in contrast to skeletal muscle, submaximal treadmill exercise did not result in detectable free radical production by the heart.

Characterization of beryllium-boron-bearing materials by Parallel Electron Energy-Loss Spectroscopy (PEELS)

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

Garvie, L.A.J.; Buseck, P.R.; Rez, P.

The stoichiometry of a set of commercial and laboratory-synthesized Be-B-bearing materials was determined by parallel electron energy-loss spectroscopy (PEELS). The Be and B K edges are well separated in energy, allowing easy determination of the elemental ratios. PEELS analyses of materials with reported compositions of {open_quotes}Be{sub 2}B{close_quotes} and {open_quotes}Be{sub 2}B{sub 3}{close_quotes} provided stoichiometries near Be{sub 2.8}B and Be{sub 4}B{sub 5}, respectively. We confirmed an earlier report of Be{sub 0.6({+-}0.1)} B{sub 5.9({+-}0.7)}C, a material with the {alpha}-rhombohedral B structure. We also synthesized and characterized Be{sub 0.5({+-}0.1)}B{sub 4.9({+-}0.3)}N, a new ternary material with the {alpha}-rhombohedral B structure with refined hexagonal cell parametersmore » of a{sub h} = 5.487(5) {alpha} and c{sub h} = 12.486(14) {angstrom}. By comparison of the features at the core-loss edges of Be{sub 0.5({+-}0.1)} B{sub 4.9({+-}0.3)}N, we conclude the most N forms N{sub 2} pairs between the icosahedra and Be substitutes for B within the icosahedra.« less

A THz Spectroscopy System Based on Coherent Radiation from Ultrashort Electron Bunches

NASA Astrophysics Data System (ADS)

Saisut, J.; Rimjaem, S.; Thongbai, C.

2018-05-01

A spectroscopy system will be discussed for coherent THz transition radiation emitted from short electron bunches, which are generated from a system consisting of an RF gun with a thermionic cathode, an alpha-magnet as a magnetic bunch compressor, and a linear accelerator for post-acceleration. The THz radiation is generated as backward transition radiation when electron bunches pass through an aluminum foil. The emitted THz transition radiation, which is coherent at wavelengths equal to and longer than the electron bunch length, is coupled to a Michelson interferometer. The performance of the spectroscopy system employing a Michelson interferometer is discussed. The radiation power spectra under different conditions are presented. As an example, the optical constant of a silicon wafer can be obtained using the dispersive Fourier transform spectroscopy (DFTS) technique.

Conformation of glycomimetics in the free and protein-bound state: structural and binding features of the C-glycosyl analogue of the core trisaccharide alpha-D-Man-(1 --> 3)-[alpha-D-Man-(1 --> 6)]-D-Man.

PubMed

Mikkelsen, Lise Munch; Hernáiz, María José; Martín-Pastor, M; Skrydstrup, Troels; Jiménez-Barbero, Jesús

2002-12-18

The conformational properties of the C-glycosyl analogue of the core trisaccharide alpha-D-Man-(1 --> 3)-[alpha-D-Man-(1 --> 6)]-D-Man in solution have been carefully analyzed by a combination of NMR spectroscopy and time-averaged restrained molecular dynamics. It has been found that both the alpha-1,3- and the alpha-1,6-glycosidic linkages show a major conformational averaging. Unusual Phi ca. 60 degrees orientations for both Phi torsion angles are found. Moreover, a major conformational distinction between the natural compound and the glycomimetic affects to the behavior of the omega(16) torsion angle around the alpha-1 --> 6-linkage. Despite this increased flexibility, the C-glycosyl analogue is recognized by three mannose binding lectins, as shown by NMR (line broadening, TR-NOE, and STD) and surface plasmon resonance (SPR) methods. Moreover, a process of conformational selection takes place, so that these lectins probably bind the glycomimetic similarly to the way they recognize the natural analogue. Depending upon the architecture and extension of the binding site of the lectin, loss or gain of binding affinity with respect to the natural analogue is found.

Microwave-assisted synthesis and humidity sensing of nanostructured {alpha}-Fe{sub 2}O{sub 3}

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

Deshmukh, Rupali G.; Badadhe, Satish S.; Mulla, Imtiaz S.

2009-05-06

Nanocrystalline {alpha}-Fe{sub 2}O{sub 3} has been prepared on a large-scale by a facile microwave-assisted hydrothermal route from a solution of Fe(NO{sub 3}){sub 3}.9H{sub 2}O and pentaerythritol. A systematic study of the morphology, crystallinity and oxidation state of Fe using different characterization techniques, such as transmission electron microscopy, X-ray diffraction, and X-ray photoelectron spectroscopy was performed. It reveals that nanostructured {alpha}-Fe{sub 2}O{sub 3} comprises bundles of nanorods with a rhombohedral crystalline structure. The individual nanorod has 8-10 nm diameter and {approx}50 nm length. The as-prepared nanostructured {alpha}-Fe{sub 2}O{sub 3} (sensor) gives selective response towards humidity. The sensor shows high sensitivity, fastmore » linear response to change in the humidity with almost 100% reproducibility. The sensor works at room temperature and rejuvenates without heat treatment. The as-prepared nanostructured {alpha}-Fe{sub 2}O{sub 3} appears to be a promising humidity sensing material with the potential for commercialization.« less

[Safety and structural analysis of polymers produced in manufacturing process of alpha-lipoic acid].

PubMed

Shimoda, Hiroshi; Tanaka, Junji; Seki, Azusa; Honda, Haruya; Akaogi, Seiichiro; Komatsubara, Hirobumi; Suzuki, Nobuo; Kameyama, Mayumi; Tamura, Satoru; Murakami, Nobutoshi

2007-10-01

Alpha-Lipoic acid has recently been permitted for use in foodstuffs and is contained in tablets and capsules. Although alpha-lipoic acid is synthesized from adipic acid, the safety of polymers produced during the purification and drying processes has been an issue of concern. Hence, we examined the safety profiles of thermally denatured polymer (LAP-A) and ethanol-denatured polymer (LAP-B) produced in the manufacturing process of alpha-lipoic acid. Furthermore, we conducted structural analysis of these polymers by 1H-NMR and FAB-MS spectroscopy. In a consecutive ingestion test, male and female mice ingested diet containing 0.1 and 0.2% LAP-A and -B for 4 weeks. Blood uric acid, potassium and lactate dehydrogenase (LDH) tended to increase without dose-dependency. Relative liver weights were also increased. However, male dogs that were orally administered LAP-B (500 mg/kg) once did not show any abnormalities in blood parameters or general condition. These findings indicate that alpha-lipoic acid polymers are not acutely toxic; however, chronic ingestion of these polymers may affect liver and kidney functions.

Surface characterization of hydrogen charged and uncharged alpha-2 and gamma titanium aluminide alloys using AES and REELS

NASA Technical Reports Server (NTRS)

Shanabarger, M. R.

1990-01-01

The surfaces of selected uncharged and hydrogen charged alpha-2 and gamma titanium aluminide alloys with Nb additions were characterized by Auger electron (AES) and reflected electron energy loss (REELS) spectroscopy. The alloy surfaces were cleaned before analysis at room temperature by ion sputtering. The low energy (500 eV) ion sputtering process preferentially sputtered the surface concentration. The surface concentrations were determined by comparing AES data from the alloys with corresponding data from elemental references. No differences were observed in the Ti or Nb Auger spectra for the uncharged and hydrogen charged alloys, even though the alpha-2 alloy had 33.4 atomic percent dissolved hydrogen. Also, no differences were observed in the AES spectra when hydrogen was adsorbed from the gas phase. Bulk plasmon energy shifts were observed in all alloys. The energy shifts were induced either by dissolved hydrogen (alpha-2 alloy) or hydrogen adsorbed from the gas phase (alpha-2 and gamma alloys). The adsorption induced plasmon energy shifts were greatest for the gamma alloy and cp-Ti metal.

Precision measurements on trapped antihydrogen in the ALPHA experiment.

PubMed

Eriksson, S

2018-03-28

Both the 1S-2S transition and the ground state hyperfine spectrum have been observed in trapped antihydrogen. The former constitutes the first observation of resonant interaction of light with an anti-atom, and the latter is the first detailed measurement of a spectral feature in antihydrogen. Owing to the narrow intrinsic linewidth of the 1S-2S transition and use of two-photon laser excitation, the transition energy can be precisely determined in both hydrogen and antihydrogen, allowing a direct comparison as a test of fundamental symmetry. The result is consistent with CPT invariance at a relative precision of around 2×10 -10 This constitutes the most precise measurement of a property of antihydrogen. The hyperfine spectrum of antihydrogen is determined to a relative uncertainty of 4×10 -4 The excited state and the hyperfine spectroscopy techniques currently both show sensitivity at the few 100 kHz level on the absolute scale. Here, the most recent work of the ALPHA collaboration on precision spectroscopy of antihydrogen is presented together with an outlook on improving the precision of measurements involving lasers and microwave radiation. Prospects of measuring the Lamb shift and determining the antiproton charge radius in trapped antihydrogen in the ALPHA apparatus are presented. Future perspectives of precision measurements of trapped antihydrogen in the ALPHA apparatus when the ELENA facility becomes available to experiments at CERN are discussed.This article is part of the Theo Murphy meeting issue 'Antiproton physics in the ELENA era'. © 2018 The Author(s).

Induced secondary structure and polymorphism in an intrinsically disordered structural linker of the CNS: solid-state NMR and FTIR spectroscopy of myelin basic protein bound to actin.

PubMed

Ahmed, Mumdooh A M; Bamm, Vladimir V; Shi, Lichi; Steiner-Mosonyi, Marta; Dawson, John F; Brown, Leonid; Harauz, George; Ladizhansky, Vladimir

2009-01-01

The 18.5 kDa isoform of myelin basic protein (MBP) is a peripheral membrane protein that maintains the structural integrity of the myelin sheath of the central nervous system by conjoining the cytoplasmic leaflets of oligodendrocytes and by linking the myelin membrane to the underlying cytoskeleton whose assembly it strongly promotes. It is a multifunctional, intrinsically disordered protein that behaves primarily as a structural stabilizer, but with elements of a transient or induced secondary structure that represent binding sites for calmodulin or SH3-domain-containing proteins, inter alia. In this study we used solid-state NMR (SSNMR) and Fourier transform infrared (FTIR) spectroscopy to study the conformation of 18.5 kDa MBP in association with actin microfilaments and bundles. FTIR spectroscopy of fully (13)C,(15)N-labeled MBP complexed with unlabeled F-actin showed induced folding of both protein partners, viz., some increase in beta-sheet content in actin, and increases in both alpha-helix and beta-sheet content in MBP, albeit with considerable extended structure remaining. Solid-state NMR spectroscopy revealed that MBP in MBP-actin assemblies is structurally heterogeneous but gains ordered secondary structure elements (both alpha-helical and beta-sheet), particularly in the terminal fragments and in a central immunodominant epitope. The overall conformational polymorphism of MBP is consistent with its in vivo roles as both a linker (membranes and cytoskeleton) and a putative signaling hub.

Structural analyses of polymorphic transitions of sn-1, 3-distearoyl-2-oleoylglycerol (SOS) and sn-1, 3-dioleoyl-2-stearoylglycerol (OSO): assessment on steric hindrance of unsaturated and saturated acyl chain interactions.

PubMed

Yano, J; Sato, K; Kaneko, F; Small, D M; Kodali, D R

1999-01-01

Polymorphic transformations in two saturated-unsaturated mixed acid triacylglycerols, SOS (sn -1,3-distearoyl-2-oleoylglycerol) and OSO (sn -1,3-dioleoyl-2-stearoylglycerol), have been studied by FT-IR spectroscopy using deuterated specimens in which stearoyl chains are fully deuterated. A reversible phase transition between sub alpha and alpha and a series of irreversible transitions (alpha-->gamma-->beta'-->beta (beta2, beta1) for SOS and alpha-->beta'-->beta for OSO) were studied with an emphasis on the conformational ordering process of stearoyl and oleoyl chains. The alpha-->sub alpha reversible transition was due to the orientational change of stearoyl chains in the lateral directions from the hexagonal subcell to a perpendicularly packed one. As the first stage of the series of irreversible transitions from alpha to beta, the conformational ordering of saturated chains took place in the alpha-->gamma transition of SOS and in the alpha-->beta' transition of OSO; one stearoyl chain in SOS and OSO takes the all-trans conformation and the second stearoyl chain in SOS takes the bent conformation like those observed in the most stable beta-type. As the final stage, the ordering of unsaturated chains occurred in the beta'-->beta transition both for SOS and OSO. A conversion in the layered structure from bilayer to trilayer was also accompanied by the conformational ordering in the alpha-->gamma transition of SOS and in the beta'-->beta transition of OSO.

Shock wave-induced phase transition in RDX single crystals.

PubMed

Patterson, James E; Dreger, Zbigniew A; Gupta, Yogendra M

2007-09-20

The real-time, molecular-level response of oriented single crystals of hexahydro-1,3,5-trinitro-s-triazine (RDX) to shock compression was examined using Raman spectroscopy. Single crystals of [111], [210], or [100] orientation were shocked under stepwise loading to peak stresses from 3.0 to 5.5 GPa. Two types of measurements were performed: (i) high-resolution Raman spectroscopy to probe the material at peak stress and (ii) time-resolved Raman spectroscopy to monitor the evolution of molecular changes as the shock wave reverberated through the material. The frequency shift of the CH stretching modes under shock loading appeared to be similar for all three crystal orientations below 3.5 GPa. Significant spectral changes were observed in crystals shocked above 4.5 GPa. These changes were similar to those observed in static pressure measurements, indicating the occurrence of the alpha-gamma phase transition in shocked RDX crystals. No apparent orientation dependence in the molecular response of RDX to shock compression up to 5.5 GPa was observed. The phase transition had an incubation time of approximately 100 ns when RDX was shocked to 5.5 GPa peak stress. The observation of the alpha-gamma phase transition under shock wave loading is briefly discussed in connection with the onset of chemical decomposition in shocked RDX.

A procedural manual for measurement of uranium and thorium isotopes utilizing the USGS-Stanford Finnegan Mat 262

USGS Publications Warehouse

Shamp, Donald D.

2001-01-01

Over the past several decades investigators have extensively examined the 238U-234U- 230Th systematics of a variety of geologic materials using alpha spectroscopy. Analytical uncertainty for 230Th by alpha spectroscopy has been limited to about 2% (2σ). The advantage of thermal ionization mass spectroscopy (TIMS), introduced by Edwards and co-workers in the late 1980’s is the increased detectability of these isotopes by a factor of ~200, and decreases in the uncertainty for 230Th to about 5‰ (2σ) error. This report is a procedural manual for using the USGS-Stanford Finnegan-Mat 262 TIMS to collect and isolate Uranium and Thorium isotopic ratio data. Chemical separation of Uranium and Thorium from the sample media is accomplished using acid dissolution and then processed using anion exchange resins. The Finnegan-Mat262 Thermal Ionization Mass Spectrometer (TIMS) utilizes a surface ionization technique in which nitrates of Uranium and Thorium are placed on a source filament. Upon heating, positive ion emission occurs. The ions are then accelerated and focused into a beam which passes through a curved magnetic field dispersing the ions by mass. Faraday cups and/or an ion counter capture the ions and allow for quantitative analysis of the various isotopes.

Development of optical monitor of alpha radiations based on CR-39.

PubMed

Joshirao, Pranav M; Shin, Jae Won; Vyas, Chirag K; Kulkarni, Atul D; Kim, Hojoong; Kim, Taesung; Hong, Seung-Woo; Manchanda, Vijay K

2013-11-01

Fukushima accident has highlighted the need to intensify efforts to develop sensitive detectors to monitor the release of alpha emitting radionuclides in the environment caused by the meltdown of the discharged spent fuel. Conventionally, proportional counting, scintillation counting and alpha spectrometry are employed to assay the alpha emitting radionuclides but these techniques are difficult to be configured for online operations. Solid State Nuclear Track Detectors (SSNTDs) offer an alternative off line sensitive technique to measure alpha emitters as well as fissile radionuclides at ultra-trace level in the environment. Recently, our group has reported the first ever attempt to use reflectance based fiber optic sensor (FOS) to quantify the alpha radiations emitted from (232)Th. In the present work, an effort has been made to develop an online FOS to monitor alpha radiations emitted from (241)Am source employing CR-39 as detector. Here, we report the optical response of CR-39 (on exposure to alpha radiations) employing techniques such as Atomic Force Microscopy (AFM) and Reflectance Spectroscopy. In the present work GEANT4 simulation of transport of alpha particles in the detector has also been carried out. Simulation includes validation test wherein the projected ranges of alpha particles in the air, polystyrene and CR-39 were calculated and were found to agree with the literature values. An attempt has been further made to compute the fluence as a function of the incidence angle and incidence energy of alphas. There was an excellent correlation in experimentally observed track density with the simulated fluence. The present work offers a novel approach to design an online CR-39 based fiber optic sensor (CRFOS) to measure the release of nanogram quantity of (241)Am in the environment. © 2013 Elsevier Ltd. All rights reserved.

Hard-sphere-like dynamics in highly concentrated alpha-crystallin suspensions

DOE PAGES

Vodnala, Preeti; Karunaratne, Nuwan; Lurio, Laurence; ...

2018-02-02

The dynamics of concentrated suspensions of the eye-lens protein alpha crystallin have been measured using x-ray photon correlation spectroscopy. Measurements were made at wave vectors corresponding to the first peak in the hard-sphere structure factor and volume fractions close to the critical volume fraction for the glass transition. Langevin dynamics simulations were also performed in parallel to the experiments. The intermediate scattering function f(q,τ) could be fit using a stretched exponential decay for both experiments and numerical simulations. The measured relaxation times show good agreement with simulations for polydisperse hard-sphere colloids.

Hard-sphere-like dynamics in highly concentrated alpha-crystallin suspensions

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

Vodnala, Preeti; Karunaratne, Nuwan; Lurio, Laurence

The dynamics of concentrated suspensions of the eye-lens protein alpha crystallin have been measured using x-ray photon correlation spectroscopy. Measurements were made at wave vectors corresponding to the first peak in the hard-sphere structure factor and volume fractions close to the critical volume fraction for the glass transition. Langevin dynamics simulations were also performed in parallel to the experiments. The intermediate scattering function f(q,τ) could be fit using a stretched exponential decay for both experiments and numerical simulations. The measured relaxation times show good agreement with simulations for polydisperse hard-sphere colloids.

The Influence of Gas Composition in Dielectric Barrier Discharges on the Broadening of the Hydrogen H{alpha} Transition

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

Janus, H. W.

The distribution of hydrogen atoms responsible for emission of the Balmer H{alpha} line in the region of the dielectric barrier discharges in the helium and hydrogen as well as in the argon and hydrogen mixtures, in the direction perpendicular to the electrode surfaces, has bee determined by the optical emission spectroscopy accounting for the polarization of the emitted light. The procedure of fitting the measured line profiles accounting for the Stark effect has been used for determination of the distribution of the electric field in the discharge region.

Hard-sphere-like dynamics in highly concentrated alpha-crystallin suspensions

NASA Astrophysics Data System (ADS)

Vodnala, Preeti; Karunaratne, Nuwan; Lurio, Laurence; Thurston, George M.; Vega, Michael; Gaillard, Elizabeth; Narayanan, Suresh; Sandy, Alec; Zhang, Qingteng; Dufresne, Eric M.; Foffi, Giuseppe; Grybos, Pawel; Kmon, Piotr; Maj, Piotr; Szczygiel, Robert

2018-02-01

The dynamics of concentrated suspensions of the eye-lens protein alpha crystallin have been measured using x-ray photon correlation spectroscopy. Measurements were made at wave vectors corresponding to the first peak in the hard-sphere structure factor and volume fractions close to the critical volume fraction for the glass transition. Langevin dynamics simulations were also performed in parallel to the experiments. The intermediate scattering function f (q ,τ ) could be fit using a stretched exponential decay for both experiments and numerical simulations. The measured relaxation times show good agreement with simulations for polydisperse hard-sphere colloids.

Cold molecule spectroscopy for constraining the evolution of the fine structure constant.

PubMed

Hudson, Eric R; Lewandowski, H J; Sawyer, Brian C; Ye, Jun

2006-04-14

We report precise measurements of ground-state, Lambda-doublet microwave transitions in the hydroxyl radical molecule (OH). Utilizing slow, cold molecules produced by a Stark decelerator we have improved over the precision of the previous best measurement 25-fold for the F'=2-->F=2 transition, yielding (1 667 358 996 +/- 4)Hz, and by tenfold for the F'=1-->F=1 transition, yielding (1 665 401 803 +/-12)Hz. Comparing these laboratory frequencies to those from OH megamasers in interstellar space will allow a sensitivity of 1 ppm for Delta(alpha/alpha) over approximately 10(10) yr.

Interaction of hydrogen chloride with alumina. [atmospheric effluent concentrations and interaction of solid rocket propellants used in space shuttle

NASA Technical Reports Server (NTRS)

Bailey, R. R.; Wightman, J. P.

1978-01-01

The influence of temperature, pressure, and outgas conditions on the absorption of hydrogen chloride and water vapor on both alpha and gamma alumina was studied. Characterization of the adsorbents was performed using X-ray powder diffraction, scanning electron microscopy (SEM), low temperature nitrogen adsorption desorption measurements, BET nitrogen surface area measurements and electron spectroscopy for chemical analysis (ESCA). Water vapor adsorption isotherms at 30, 40, and 50 C were measured on alpha and gamma alumina after outgassing at 80, 200, and 400 C. Both outgas temperature and adsorption temperature influenced the adsorption of water vapor on the aluminas. The water vapor adsorption was completely reversible. Alpha alumina absorbed more water per unit area than gamma alumina. Differences in the adsorption capacity for water vapor of the two aluminas were explained on the basis of ideal surface models of alpha and gamma alumina. Isosteric heats of adsorption for water vapor on the aluminas were determined over a limited range of surface coverage.

Development and irradiation test of lost alpha detection system for ITER.

PubMed

Nishiura, M; Nagasaka, T; Fujioka, K; Fujimoto, Y; Tanaka, T; Ido, T; Yamamoto, S; Kashiwa, S; Sasao, M

2010-10-01

We developed a lost alpha detection system to use in burning plasma experiments. The scintillators of Ag:ZnS and polycrystalline Ce:YAG were designed for a high-temperature environment, and the optical transmission line was designed to transmit from the scintillator to the port plug. The required optical components of lenses and mirrors were irradiated using the fission reactor with the initial result that there was no clear change after the irradiation with a neutron flux of 9.6×10(17) nm(-2)  s(-1) for 48 h. We propose a diagnostic of alpha particle loss, so-called alpha particle induced gamma ray spectroscopy. The initial laboratory test has been carried out by the use of the Ce doped Lu(2)SiO(5) scintillator detector and an Am-Be source to detect the 4.44 MeV high energy gamma ray due to the (9)Be(α,nγ)(12)C reaction.

Evaluating the potential effects of hurricanes on long-term sediment accumulation in two micro-tidal sub-estuaries: Barnegat Bay and Little Egg Harbor, New Jersey, U.S.A.

USGS Publications Warehouse

Marot, Marci E.; Smith, Christopher G.; Ellis, Alisha M.; Wheaton, Cathryn J.

2016-06-23

This report serves as an archive for sedimentological and radiochemical data derived from the surface sediments and box cores. Downloadable data are available as Excel spreadsheets, PDF files, and JPEG files, and include sediment core data plots and x-radiographs, as well as physical-properties, grain-size, alpha-spectroscopy, and gamma-spectroscopy data. Federal Geographic Data Committee metadata are available for analytical datasets in the data downloads page of this report.

The Universe as Viewed from Star Forming Galaxies over the Past Ten Billion Years

NASA Astrophysics Data System (ADS)

Ly, Chun; Malkan, M.; Lee, J. C.; Kashikawa, N.; Hayashi, M.; Motohara, K.; Subaru Deep Field Collaboration; NEWFIRM Narrow-band H-alpha Survey Team

2010-01-01

In this dissertation talk, I will discuss my work to provide improved constraints on the star formation history of the universe by (1) using narrow-band filters to identify galaxies to z 2.2 and (2) extending the Lyman break technique to z=1.5-3. These techniques efficiently isolate a large population of star-forming galaxies and enable measurement of the star formation rate via emission line and ultraviolet indicators. With the SDF team, we have conducted a narrow-band optical survey which yields a sample of 5000 galaxies within 0.25 square degree to z 1.5 detected by H-alpha, [OIII], or [OII]. Diagnostics based on broad-band optical colors are developed to resolve ambiguities in emission-line identification. In addition, with the NEWFIRM H-alpha team, we are working to extend optical studies into the near-infrared with NEWFIRM. We target H-alpha emitting galaxies at z 0.8 and z 2.2, which probes a critical period in the history of the universe during which much of the star formation has occurred. The NEWFIRM H-alpha survey covers over 1 square degree. A total of 300 H-alpha emitting galaxies at z 0.8 has been identified for 60% of the survey volume. Preliminary results from the NEWFIRM H-alpha Survey will be discussed. Spectroscopy for both narrow-band surveys reveals a high reliability of the technique: contamination at the few percent level. Finally, I will describe the first Lyman break survey to select star-forming galaxies at z 2 (limiting magnitude of 27 AB), using deep, wide GALEX near-ultraviolet imaging. A total of 7000 LBGs was identified in 0.25 square degree. Spectroscopy indicates that the success of identifying z 2 galaxies is 80%. I will also compare different z 2 photometric techniques (BzK, DRG, BX/BM) to provide a more comprehensive view of the galaxy population, including dusty star-forming galaxies. The comparison reveals a good but imperfect ( 50%) overlap, indicating that these photometric techniques are complementary.

Multiscale mapping of species diversity under changed land use using imaging spectroscopy.

PubMed

Paz-Kagan, Tarin; Caras, Tamir; Herrmann, Ittai; Shachak, Moshe; Karnieli, Arnon

2017-07-01

Land use changes are one of the most important factors causing environmental transformations and species diversity alterations. The aim of the current study was to develop a geoinformatics-based framework to quantify alpha and beta diversity indices in two sites in Israel with different land uses, i.e., an agricultural system of fruit orchards, an afforestation system of planted groves, and an unmanaged system of groves. The framework comprises four scaling steps: (1) classification of a tree species distribution (SD) map using imaging spectroscopy (IS) at a pixel size of 1 m; (2) estimation of local species richness by calculating the alpha diversity index for 30-m grid cells; (3) calculation of beta diversity for different land use categories and sub-categories at different sizes; and (4) calculation of the beta diversity difference between the two sites. The SD was classified based on a hyperspectral image with 448 bands within the 380-2500 nm spectral range and a spatial resolution of 1 m. Twenty-three tree species were classified with high overall accuracy values of 82.57% and 86.93% for the two sites. Significantly high values of the alpha index characterize the unmanaged land use, and the lowest values were calculated for the agricultural land use. In addition, high values of alpha indices were found at the borders between the polygons related to the "edge-effect" phenomenon, whereas low alpha indices were found in areas with high invasion species rates. The beta index value, calculated for 58 polygons, was significantly lower in the agricultural land use. The suggested framework of this study succeeded in quantifying land use effects on tree species distribution, evenness, and richness. IS and spatial statistics techniques offer an opportunity to study woody plant species variation with a multiscale approach that is useful for managing land use, especially under increasing environmental changes. © 2017 by the Ecological Society of America.

Reducing DRIFT backgrounds with a submicron aluminized-mylar cathode

NASA Astrophysics Data System (ADS)

Battat, J. B. R.; Daw, E.; Dorofeev, A.; Ezeribe, A. C.; Fox, J. R.; Gauvreau, J.-L.; Gold, M.; Harmon, L.; Harton, J.; Lafler, R.; Landers, J.; Lauer, R. J.; Lee, E. R.; Loomba, D.; Lumnah, A.; Matthews, J.; Miller, E. H.; Mouton, F.; Murphy, A. St. J.; Paling, S. M.; Phan, N.; Sadler, S. W.; Scarff, A.; Schuckman, F. G.; Snowden-Ifft, D.; Spooner, N. J. C.; Walker, D.

2015-09-01

Background events in the DRIFT-IId dark matter detector, mimicking potential WIMP signals, are predominantly caused by alpha decays on the central cathode in which the alpha particle is completely or partially absorbed by the cathode material. We installed a 0.9 μm thick aluminized-mylar cathode as a way to reduce the probability of producing these backgrounds. We study three generations of cathode (wire, thin-film, and radiologically clean thin-film) with a focus on the ratio of background events to alpha decays. Two independent methods of measuring the absolute alpha decay rate are used to ensure an accurate result, and agree to within 10%. Using alpha range spectroscopy, we measure the radiologically cleanest cathode version to have a contamination of 3.3±0.1 ppt 234U and 73±2 ppb 238U. This cathode reduces the probability of producing an RPR from an alpha decay by a factor of 70±20 compared to the original stainless steel wire cathode. First results are presented from a texturized version of the cathode, intended to be even more transparent to alpha particles. These efforts, along with other background reduction measures, have resulted in a drop in the observed background rate from 500/day to 1/day. With the recent implementation of full-volume fiducialization, these remaining background events are identified, allowing for background-free operation.

NMR solution structure of the mitochondrial F1beta presequence from Nicotiana plumbaginifolia.

PubMed

Moberg, Per; Nilsson, Stefan; Ståhl, Annelie; Eriksson, Anna-Carin; Glaser, Elzbieta; Mäler, Lena

2004-03-05

We have isolated, characterized and determined the three-dimensional NMR solution structure of the presequence of ATPsynthase F1beta subunit from Nicotiana plumbaginifolia. A general method for purification of presequences is presented. The method is based on overexpression of a mutant precursor containing a methionine residue introduced at the processing site, followed by CNBr-cleavage and purification of the presequence on a cation-exchange column. The F1beta presequence, 53 amino acid residues long, retained its native properties as evidenced by inhibition of in vitro mitochondrial import and processing at micromolar concentrations. CD spectroscopy revealed that the F1beta presequence formed an alpha-helical structure in membrane mimetic environments such as SDS and DPC micelles (approximately 50% alpha-helix), and in acidic phospholipid bicelles (approximately 60% alpha-helix). The NMR solution structure of the F1beta presequence in SDS micelles was determined on the basis of 518 distance and 21 torsion angle constraints. The structure was found to contain two helices, an N-terminal amphipathic alpha-helix (residues 4-15) and a C-terminal alpha-helix (residues 43-53), separated by a largely unstructured 27 residue long internal domain. The N-terminal amphipathic alpha-helix forms the putative Tom20 receptor binding site, whereas the C-terminal alpha-helix is located upstream of the mitochondrial processing peptidase cleavage site.

The effect of particle size on the dehydration/rehydration behaviour of lactose.

PubMed

Crisp, J L; Dann, S E; Edgar, M; Blatchford, C G

2010-05-31

Ethanolic suspensions of spray dried and micronized alpha lactose monohydrate (L(alpha)xH(2)O) with average particle size between 3 and 200 microm, have been prepared and their dehydration behaviour was investigated by (13)C CP-MASNMR spectroscopy. Sub-micron lactose suspension prepared by a novel high pressure homogenisation method has been compared with the standard ethanolic suspensions of (L(alpha).H(2)O prepared by reflux or static room temperature methods. In all cases, suspensions were shown to contain the stable anhydrous form of lactose ((L(alpha)(S)). Several approaches were employed to remove ethanol from these suspensions and the resulting dry lactose powders were then analysed by FT-IR, PXRD and SEM to evaluate the effect of drying procedure on type and distribution of lactose polymorphs and particle size. For samples with mean particle size greater than 1 microm, the stable anhydrous polymorphic form of lactose was retained on removal of the ethanol, although differences in the morphology and particle size of the crystals were apparent depending on method of suspension formation. Sub-micron (L(alpha)(S), while stable in dry conditions, has been shown to be less stable to atmospheric water vapour than (L(alpha)(S) with particle size between 3 and 200 microm. Copyright (c) 2010 Elsevier B.V. All rights reserved.

Modifications of the optical properties for DAM-ADC nuclear track detector exposed to alpha particles

NASA Astrophysics Data System (ADS)

Rammah, Y. S.; Awad, E. M.

2018-05-01

Modifications of the optical properties of diallyl maleate-allyl diglycol carbonate (DAM-ADC) nuclear detector induced by alpha particles are described. DAM-ADC samples were irradiated perpendicularly by thin 241Am disk source that emits alpha particles with 5.48 MeV. The optical absorption has been measured using the ultraviolet-visible (UV-1100) spectroscopy. It was found that DAM-ADC polymer shows substantial modifications in its optical characteristics upon irradiated with alpha particles with different energies. The optical energy band gap (Egap) for the detector was calculated for the direct and the indirect allowed transitions in K-space using two approaches (Tauc's model and absorption spectrum fitting (ASF) method). Urbach's energy (Ea), number of carbon atoms per conjugated length (N), number of carbon atoms per cluster (M), and refractive index (n) for the present samples were determined. Results reveal that the values of energy gap in direct transition are greater than those of indirect, before and after irradiation. (Egap), (Ea), (N), (M), and (n) of the present samples are changed significantly with irradiation time and value of alpha energy. Results reflect the possibility of using DAM-ADC polymer track detectors to estimate alpha particle energies using the variation of the absorbance.

Detecting Circumstellar ``Hydrogen Wall'' Emission Around a Nearby, Sun-like Star

NASA Astrophysics Data System (ADS)

Wood, Brian

1999-07-01

Using the long-slit spectroscopy capabilities of STIS, we propose to try to detect for the first time nebular Lyman- Alpha emission surrounding a Sun-like star produced by the interaction of its stellar wind with the ISM. Such ``hydrogen walls'' have likely been detected in absorption around the Sun and several other nearby stars using GHRS Lyman-Alpha spectra. However, most of these detections are tentative due to the difficulty in separating the H-wall absorption from the interstellar H I absorption. Furthermore, even if one accepts the reality of the detected hot H I absorption components, it is impossible to prove that circumstellar material is in fact responsible. We propose to circumvent these difficulties by detecting a hydrogen wall in emission around 40 Eri A, which is one of the stars for which a tentative H-wall detection already exists. A successful detection of the expected circumstellar emission would validate the previous Lyman-Alpha aborption line studies, a nd the combined spectroscopic and spatial information provided by long-slit spectroscopy would contribute valuable new information on the stellar wind of 40 Eri A and how it interacts with the ISM, especially when compared with models that we will construct of 40 Eri A's ``astrosphere.'' This new information includes a direct measurement of the distance to the stellar bow shock, information that we do not possess for any other nearby star, including the Sun.

Increased oxygen consumption in the somatosensory cortex of alpha-chloralose anesthetized rats during forepaw stimulation determined using MRS at 11.7 Tesla.

PubMed

Yang, Jehoon; Shen, Jun

2006-09-01

The significance of changes in cerebral oxygen consumption in focally activated brain tissue is still controversial. Since the rate of cerebral oxygen consumption is tightly coupled to that of tricarboxylic acid cycle which can be measured from the turnover kinetics of [4-(13)C]glutamate using in vivo (1)H{(13)C} magnetic resonance spectroscopy, changes in tricarboxylic acid cycle flux rate were assessed in primary somatosensory cortex of alpha-chloralose anesthetized rats during electrical forepaw stimulation. With markedly improved (1)H{(13)C} magnetic resonance spectroscopy technique and the use of high magnetic field strength of 11.7 T accessible to the current study, [4-(13)C]glutamate at 2.35 ppm was spectrally resolved from overlapping resonances of [4-(13)C]glutamine at 2.46 ppm and [2-(13)C]GABA at 2.28 ppm as well as the more distal [3-(13)C]glutamate and [3-(13)C]glutamine. The results showed a significantly increased V(TCA) in focally activated primary somatosensory cortex during forepaw stimulation, corresponding to approximately 51 +/- 27% (n = 6, mean +/- SD) increase in cerebral oxygen consumption rate. Considering the high efficiency in producing adenosine triphosphate by oxidative metabolism of glucose, the results demonstrate that aerobic oxidative metabolism provides the majority of energy required for cerebral focal activation in alpha-chloralose anesthetized rats subjected to forepaw stimulation.

A triple-crystal phoswich detector with digital pulse shape discrimination for alpha/beta/gamma spectroscopy

NASA Astrophysics Data System (ADS)

White, Travis L.; Miller, William H.

1999-02-01

Researchers at the University of Missouri - Columbia have developed a three-crystal phoswich detector coupled to a digital pulse shape discrimination system for use in alpha/beta/gamma spectroscopy. Phoswich detectors use a sandwich of scintillators viewed by a single photomultiplier tube to simultaneously detect multiple types of radiation. Separation of radiation types is based upon pulse shape difference among the phosphors, which has historically been performed with analog circuitry. The system uses a GaGe CompuScope 1012, 12 bit, 10 MHz computer-based oscilloscope that digitally captures the pulses from a phoswich detector and subsequently performs pulse shape discrimination with cross-correlation analysis. The detector, based partially on previous phoswich designs by Usuda et al., uses a 10 mg/cm 2 thick layer of ZnS(Ag) for alpha detection, followed by a 0.254 cm CaF 2(Eu) crystal for beta detection, all backed by a 2.54 cm NaI(Tl) crystal for gamma detection. Individual energy spectra and count rate information for all three radiation types are displayed and updated periodically. The system shows excellent charged particle discrimination with an accuracy of greater than 99%. Future development will include a large area beta probe with gamma-ray discrimination, systems for low-energy photon detection (e.g. Bremsstrahlung or keV-range photon emissions), and other health physics instrumentation.

Analysis of internal structure changes in black human hair keratin fibers with aging using Raman spectroscopy.

PubMed

Kuzuhara, Akio; Fujiwara, Nobuki; Hori, Teruo

To investigate the internal structure changes in virgin black human hair keratin fibers due to aging, the structure of cross-sections at various depths of virgin black human hair (sections of new growth hair: 2 mm from the scalp) from a group of eight Japanese females in their twenties and another group of eight Japanese females in their fifties were analyzed using Raman spectroscopy. For the first time, we have succeeded in recording the Raman spectra of virgin black human hair, which had been impossible due to high melanin granule content. The key points of this method are to cross-section hair samples to a thickness of 1.50-microm, to select points at various depths of the cortex with the fewest possible melanin granules, and to optimize laser power, cross slit width as well as total acquisition time. The reproducibility of the Raman bands, namely the alpha-helix (alpha) content, the beta-sheet and/or random coil (beta/R) content, the disulfide (--SS--) content, and random coil content of two adjoining cross-sections of a single hair keratin fiber was clearly good. The --SS-- content of virgin black human hair from the Japanese females in their fifties for the cortex region decreased compared with that of the Japanese females in their twenties. On the other hand, the beta/R and alpha contents of the cortex region did not change.

Starch waxiness in hexaploid wheat (Triticum aestivum L.) by NIR reflectance spectroscopy

USDA-ARS?s Scientific Manuscript database

Starch, the primary energy storage component of plants, consists of two large macromolecules, amylose and amylopectin. Each molecule is composed of long chains of alpha-D-glucopyranosyl units, with branching present in amylopectin and absent in amylose. The relative abundance of these two molecules ...

Kinetics of ozonation. 4. Reactions of ozone with. cap alpha. -tocopherol and oleate and linoleate esters in carbon tetrachloride and in aqueous micellar solvents

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

Giamalva, D.H.; Church, D.F.; Pryor, W.A.

1986-10-15

Vitamin E (..cap alpha..-tocopherol; ..cap alpha..-T) is known to protect animals against the deleterious effects of ozone in polluted air; one such effect is the ozone-initiated autooxidation of polyunsaturated fatty acids (PUFA) that occur in membranes. In order to assess the possibility of a direct reaction of ozone with ..cap alpha..-T competing with the very fast ozone-PUFA reaction, we have measured the rates of reaction of ozone with ..cap alpha..-T, oleic acid, and linoleic acid. I CCl/sub 4/ as solvent, ..cap alpha..-T reacts with ozone with a rate constant of about 5500 M/sup -1/ s/sup -1/; methyl oleate and methylmore » linoleate react 2 orders of magnitude faster. In aqueous micellar solutions the rate constants for ..cap alpha..-T and the fatty acids are more similar. The k for the ozone/..cap alpha..-T reaction is about 1 x 10/sup 6/ M/sup -1/ s/sup -1/ at pH 7, but decreases as the solution becomes more acidic; the k's for oleic acid and linoleic acid are ca. 1 x 10/sup 6/ M/sup -1/ s/sup -1/ and exhibit no significant pH dependence. Since the ratio of fatty acids to ..cap alpha..-T in membranes is typically at least 100-1000 to 1, we conclude that the direct reaction of ozone with ..cap alpha..-T is unlikely. Thus, the protection that vitamin E provides to animals breathing ozone-containing air must result from vitamin E acting as a free radical scavenger. We have also detected the ..cap alpha..-tocopheroxyl radical as an intermediate from the reaction of ozone with ..cap alpha..-T both in CCl/sub 4/ and aqueous micelles using electron spin resonance spectroscopy. The authors suggest that the observation of this intermediate is consistent with an initial electron transfer from ..cap alpha..-T to ozone.« less

Galloylated polyphenols efficiently reduce alpha-tocopherol radicals in a phospholipid model system composed of sodium dodecyl sulfate (SDS) micelles.

PubMed

Pazos, Manuel; Torres, Josep Lluís; Andersen, Mogens L; Skibsted, Leif H; Medina, Isabel

2009-06-10

The ability of several polyphenolic fractions from grape ( Vitis vinifera ) pomace, pine ( Pinus pinaster ) bark, and witch hazel ( Hammamelis virginiana ) bark to repair alpha-tocopherol (alpha-TOH) through reduction of the alpha-tocopheroxyl radical was investigated in a homogeneous hexane system and a phospholipid-like system based on SDS micelles. These natural polyphenols were compared with pure related phenolics (epicatechin, gallic acid, epigallocatechin gallate, quercetin, and rutin) and ascorbic acid, which is a substance with a well-recognized capacity for regenerating alpha-TOH. alpha-Tocopheroxyl radicals were monitored and quantified by electron spin resonance (ESR) spectroscopy in the absence and presence of phenolics. Polyphenols from grape and pine bark were essentially catechin monomers and proanthocyanidins differing in the content of galloyl residues; those from pine bark had a negligible degree of galloylation. Polyphenolic fractions from witch hazel bark were composed of approximately 80% hydrolyzable tannins rich in galloyl moieties, together with a smaller amount of catechin monomers and proanthocyanidins. In the homogeneous hexane system, polyphenols from grape and pine bark exhibited similar activities, reducing the alpha-tocopheroxyl radicals by over 27-40%, whereas phenols from witch hazel were more highly effective, reducing 80% of alpha-TOH. In contrast, pine bark polyphenols were found to be significantly less active than the grape fractions in SDS micelles, reducing 30 and 70% of alpha-tocopheroxyl radicals, respectively. Polyphenolic fractions from witch hazel were also able to reduce the highest amount of alpha-TOH in SDS-micelles. The reducing capacity on alpha-tocopheroxyl radical of polyphenolic fractions was found to be pH-dependent and more effective at higher pH in the range of pH studied (5.8-7.8). These results stress the potential role of polyphenols, in particular those rich in galloyl groups, to maintain intact endogenous alpha-TOH in biological membranes through reduction of alpha-tocopheroxyl radicals.

Crystal Structures of Human Choline Kinase Isoforms in Complex with Hemicholinium-3 Single Amino Acid near the Active Site Influences Inhibitor Sensitivity

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

Hong, Bum Soo; Allali-Hassani, Abdellah; Tempel, Wolfram

2010-07-06

Human choline kinase (ChoK) catalyzes the first reaction in phosphatidylcholine biosynthesis and exists as ChoK{alpha} ({alpha}1 and {alpha}2) and ChoK{beta} isoforms. Recent studies suggest that ChoK is implicated in tumorigenesis and emerging as an attractive target for anticancer chemotherapy. To extend our understanding of the molecular mechanism of ChoK inhibition, we have determined the high resolution x-ray structures of the ChoK{alpha}1 and ChoK{beta} isoforms in complex with hemicholinium-3 (HC-3), a known inhibitor of ChoK. In both structures, HC-3 bound at the conserved hydrophobic groove on the C-terminal lobe. One of the HC-3 oxazinium rings complexed with ChoK{alpha}1 occupied the choline-bindingmore » pocket, providing a structural explanation for its inhibitory action. Interestingly, the HC-3 molecule co-crystallized with ChoK{beta} was phosphorylated in the choline binding site. This phosphorylation, albeit occurring at a very slow rate, was confirmed experimentally by mass spectroscopy and radioactive assays. Detailed kinetic studies revealed that HC-3 is a much more potent inhibitor for ChoK{alpha} isoforms ({alpha}1 and {alpha}2) compared with ChoK{beta}. Mutational studies based on the structures of both inhibitor-bound ChoK complexes demonstrated that Leu-401 of ChoK{alpha}2 (equivalent to Leu-419 of ChoK{alpha}1), or the corresponding residue Phe-352 of ChoK{beta}, which is one of the hydrophobic residues neighboring the active site, influences the plasticity of the HC-3-binding groove, thereby playing a key role in HC-3 sensitivity and phosphorylation.« less

Resolved spectroscopy of adolescent and infant galaxies (1 < z < 10)

NASA Astrophysics Data System (ADS)

Wright, Shelley; IRIS Science Team

2014-07-01

The combination of integral field spectroscopy (IFS) and adaptive optics (AO) on TMT will be revolutionary in studying the distant universe. The high angular resolution exploited by an AO system with this large aperture will be essential for studying high-redshift (1 < z < 5) galaxies' kinematics and chemical abundance histories. At even greater distances, TMT will be essential for conducting follow-up spectroscopy of Ly-alpha emission from first lights galaxies (6 < z < 10) and determining their kinematics and morphologies. I will present simulations and sensitivity calculations for high-z and first light galaxies using the diffraction-limited instrument IRIS coupled with NFIRAOS. I will put these simulations in context with current IFS+AO high-z observations and future capabilities with JWST.

Application of two-dimensional NMR spectroscopy and molecular dynamics simulations to the conformational analysis of oligosaccharides corresponding to the cell-wall polysaccharide of Streptococcus group A.

PubMed

Kreis, U C; Varma, V; Pinto, B M

1995-06-01

This paper describes the use of a protocol for conformational analysis of oligosaccharide structures related to the cell-wall polysaccharide of Streptococcus group A. The polysaccharide features a branched structure with an L-rhamnopyranose (Rhap) backbone consisting of alternating alpha-(1-->2) and alpha-(1-->3) links and D-N-acetylglucosamine (GlcpNAc) residues beta-(1-->3)-connected to alternating rhamnose rings: [formula: see text] Oligomers consisting of three to six residues have been synthesized and nuclear magnetic resonance (NMR) assignments have been made. The protocol for conformational analysis of the solution structure of these oligosaccharides involves experimental and theoretical methods. Two-dimensional NMR spectroscopy methods (TOCSY, ROESY and NOESY) are utilized to obtain chemical shift data and proton-proton distances. These distances are used as constraints in 100 ps molecular dynamics simulations in water using QUANTA and CHARMm. In addition, the dynamics simulations are performed without constraints. ROE build-up curves are computed from the averaged structures of the molecular dynamics simulations using the CROSREL program and compared with the experimental curves. Thus, a refinement of the initial structure may be obtained. The alpha-(1-->2) and the beta-(1-->3) links are unambiguously defined by the observed ROE cross peaks between the A-B',A'-B and C-B,C'-B' residues, respectively. The branch-point of the trisaccharide CBA' is conformationally well-defined. Assignment of the conformation of the B-A linkage (alpha-(1-->3)) was problematic due to TOCSY relay, but could be solved by NOESY and T-ROESY techniques. A conformational model for the polysaccharide is proposed.

LRO Lyman Alpha Mapping Project (LAMP) Far-UV Investigations of Lunar Composition, Porosity, and Space Weathering

NASA Astrophysics Data System (ADS)

Retherford, K. D.; Greathouse, T. K.; Mandt, K. E.; Gladstone, R.; Hendrix, A.; Cahill, J. T.; Liu, Y.; Grava, C.; Hurley, D.; Egan, A.; Kaufmann, D. E.; Raut, U.; Byron, B. D.; Magana, L. O.; Stickle, A. M.; Wyrick, D. Y.; Pryor, W. R.

2017-12-01

Far ultraviolet reflectance measurements of the Moon, icy satellites, comets, and asteroids have proven surprisingly useful for advancing our understanding of planetary surfaces. This new appreciation for planetary far-UV imaging spectroscopy is provided in large part thanks to nearly a decade of investigations with the Lunar Reconnaissance Orbiter (LRO) Lyman Alpha Mapping Project (LAMP). LAMP has demonstrated an innovative nightside observing technique, putting a new light on permanently shadowed regions (PSRs) and other features on the Moon. Dayside far-UV albedo maps complement the nightside data, enabling comparisons of direct and hemispheric (diffuse) illumination derived albedos. We'll discuss the strengths of the far-UV reflectance imaging spectroscopy technique with respect to several new LAMP results. Detections of water frost and hydration signatures near 165 nm, for example, provide constraints on composition that complement infrared spectroscopy, visible imaging, neutron spectroscopy, radar, and other techniques. LRO's polar orbit and high data downlink capabilities enable searches for diurnal variations in spectral signals. At far-UV wavelengths a relatively blue spectral slope is diagnostic of space weathering, which is opposite of the spectral reddening indicator of maturity at wavelengths longward of 180 nm. By utilizing natural diffuse illumination sources on the nightside the far-UV technique is able to identify relative increases in porosity within the PSRs, and provides an additional tool for determining relative surface ages. On October 6, 2016 LAMP enacted a new, more sensitive dayside operating mode that expands its ability to search for diurnally varying hydration signals associated with different regions and features.

Time-resolved FT EPR and optical spectroscopy study on photooxidation of aliphatic alpha-amino acids in aqueous solutions; electron transfer from amino vs carboxylate functional group.

PubMed

Tarabek, Peter; Bonifacić, Marija; Beckert, Dieter

2006-06-08

Using time-resolved Fourier transform electron paramagnetic resonance, FT EPR, and optical spectroscopy, the photooxidation of glycine, alpha-alanine, alpha-aminoisobutyric acid, and model compounds beta-alanine, methylamine and sodium acetate, by excited triplets of anthraquinone-2,6-disulfonate dianion was studied in aqueous solutions in the pH range 5-13. Anthraquinone radical trianions showing strong emissive spin-polarization (CIDEP) were formed, indicating fast electron transfer from the quenchers to the spin-polarized quinone triplet as the primary reaction. None of the primary radicals formed upon one-electron oxidation of quenchers could be detected at the nanosecond time scale of FT EPR measurements because of their very fast transformation into secondary products. The latter were identified to be decarboxylated alpha-aminoalkyl radicals for alpha-amino acids anions and zwitterions, beta-aminoalkyl radicals for beta-alanine zwitterions, and methyl radicals for acetate anions; corresponding aminyl radicals were the first EPR detectable products from beta-alanine anions and methylamine. Thus, anthraquinone-2,6-disulfonate triplet can take an electron from both NH(2)- and -CO(2)(-) functional groups forming aminium ((+*)NH(2)-) and acyloxyl (-CO(2)(*)) radicals, respectively. Aminium radicals derived from beta-alanine anions and CH(3)-NH(2) stabilize by deprotonation into aminyl radicals, whereas these derived from alpha-amino acids anions are known to suffer ultrafast decarboxylation (tau approximately 10 ps). Analysis of the polarization patterns revealed that decarboxylation from acyloxyl radicals are considerably slower (ns < tau < 0.1 micros). Therefore, in the case of alpha-amino acids, the isoelectronic structures NH(2)-CR(2)-CO(2)(*) and (+*)NH(2)-CR(2)-CO(2)(-) probably do not constitute resonance mesomeric forms of one and the same species and the decarboxylation of aminium radicals is not preceded by the intramolecular carboxylate to amino group electron transfer. Absolute triplet quenching rate constants at zero ionic strength were in the range of 2 x 10(8) to 2 x 10(9) M(-1) s(-1) for R-NH(2) and 2 x 10(7) to 10(8) M(-1) s(-1) for R-CO(2)(-) type of electron donors, reflecting in principle their standard reduction potentials. The strengths of acids: (+)NH(3)-(*)CH(2), (+)NH(3)-(*)C(CH(3))H, and (+)NH(3)-(*)C(CH(3))(2), pK(a) <4, >6, and >7, respectively, were found to be remarkably strongly dependent on alpha-C substitution. The conjugate bases of these alpha-aminoalkyl radicals reduce anthraquinone-2,6-disulfonate dianion ground state with k(sec) = 3 x 10(9) M(-1) s(-1).

Spectral and Temporal Properties of the Alpha and Beta Subunits and (alpha Beta) Monomer Isolated from Nostoc SP. Using Picosecond Laser Spectroscopy.

NASA Astrophysics Data System (ADS)

Dagen, Aaron J.

1985-12-01

The fluorescence decay profiles, relative quantum yield and transmission of the (alpha), (beta) and ((alpha)(beta)) complexes from phycoerythrin isolated from the photosynthetic antenna system of Nostoc sp. and measured by single picosecond laser spectroscopic techniques is studied. The fluorescence decay profiles of all three complexes are found to be intensity independent for the intensity range investigated ((TURN)4 x 10('13) to (TURN)4 x 10('15) photons-cm('-2) per pulse). The apparent decrease in the relative quantum yield of all three complexes as intensity increases is offset by a corresponding increase in the relative transmission. This evidence, along with the intensity independent fluorescence kinetics, suggests that exciton annihilation is absent in these complexes. The decay profiles are fit to models assuming energy transfer amongst fluorescing chromophores. The intraprotein transfer rate is found to be 100 ps in the (alpha) subunit, 666 ps in the (beta) subunit. Constraining these rates to be identical in the monomer results in explaining the monomer kinetics by an increase in the nonradiative rate of the f(,(beta)) chromophore, an apparent result of aggregation effects.

Spectral and temporal properties of the alpha and beta subunits and (alpha beta) monomer isolated from Nostoc sp. using picosecond laser spectroscopy

NASA Astrophysics Data System (ADS)

Dagen, A. J.

1985-12-01

The fluorescence decay profiles, relative quantum yield and transmission of the alpha, beta and (alpha beta) complexes from phycoerythrin isolated from the photosynthetic antenna system of Nostoc sp. and measured by single picosecond laser spectroscopic techniques is studied. The fluorescence decay profiles of all three complexes are found to be intensity independent for the intensity range investigated (approx. 4x10 to the 13th power to 4x10 to the 15th power photons/sq cm per pulse). The apparent decrease in the relative quantum yield of all three complexes as intensity increases is offset by a corresponding increase in the relative transmission. This evidence, along with the intensity independent fluorescence kinetics, suggests that exciton annihilation is absent in these complexes. The decay profiles are fit to models assuming energy transfer amongst fluorescing chromophores. The intraprotein transfer rate is found to be 100 ps in the alpha subunit, 666 ps in the beta subunit. Constraining these rates to be identical in the monomer results in explaining the monomer kinetics by an increase in the nonradiative rate of the f beta chromophore, an apparent result of aggregation effects.

Cell wall teichoic acids of actinomycetes of three genera of the order actinomycetales.

PubMed

Streshinskaya, G M; Shashkov, A S; Usov, A I; Evtushenko, L I; Naumova, I B

2002-07-01

The structures of cell wall teichoic acids of the members of newly recognized genera of the order Actinomycetales were studied. Planotetraspora mira VKM Ac-2000T contains two types of teichoic acids: 2,3-poly(glycerol phosphate) substituted with alpha-D-Galp at C-1 of glycerol and 1,3-poly(glycerol phosphate) substituted with alpha-L-Rhap at OH-2 of glycerol (60%). Herbidospora cretacea VKM Ac-1997T contains the chains of 1,3-poly(glycerol phosphate) partially substituted with alpha-D-Galp and alpha-D-GalpNAc at C-2 of glycerol. The majority of alpha-D-galactopyranosyl residues are substituted at OH-3 with a sulfate. The aforementioned teichoic acids have not been found in bacteria thus far. Actinocorallia herbida VKM Ac-1994T contains poly(galactosylglycerol phosphate), with the beta-Galp-(1-->2)-Gro-P repeating units being linked via the phosphodiester bonds between the OH-3 of glycerol and OH-6 of galactose. Earlier, this structure was found in the cell wall of Actinomadura madura. The polymer structures were determined by chemical analysis and using 13C-NMR spectroscopy. The results show that teichoic acids are widespread in the order Actinomycetales.

HREELS to identify electronic structures of organic thin films.

PubMed

Oeter, D; Ziegler, C; Göpel, W

1995-10-01

The electronic structure of alpha-oligothiophene (alphanT) thin films has been investigated for increasing chain lengths of n= 4-8 thiophene units with high resolution electron energy loss spectroscopy (HREELS) in the specular reflection geometry at a primary energy of 15 eV. The great advantage of this technique in contrast to UV/VIS absorption spectroscopy results from the fact, that the impact scattering mechanism of HREELS makes it possible to also detect optically forbidden electronic transitions. On the other hand, the electrons used as probes in HREELS have a wavelength which is two orders of magnitudes smaller if compared to those of photons used in UV/VIS absorption spectroscopy. Therefore individual molecules are excited by HREELS independent from each other and hence the excitation of collective excitons is not possible. As a result, information about the orientation of the molecules cannot be achieved with HREELS, which, however, is possible in polarization-dependent UV/VIS spectroscopy.

Structural elucidation of novel phosphocholine-containing glycosylinositol-phosphoceramides in filamentous fungi and their induction of cell death of cultured rice cells.

PubMed Central

Aoki, Kazuhiro; Uchiyama, Ryosuke; Itonori, Saki; Sugita, Mutsumi; Che, Fang-Sik; Isogai, Akira; Hada, Noriyasu; Hada, Junko; Takeda, Tadahiro; Kumagai, Hidehiko; Yamamoto, Kenji

2004-01-01

Novel ZGLs (zwitterionic glycosphingolipids) have been found in and extracted from the mycelia of filamentous fungi ( Acremonium sp.) isolated from soil. Five ZGLs (ZGL1-ZGL5) were structurally elucidated by sugar compositional analysis, methylation analysis, periodate oxidation, matrix-assisted laser-desorption ionization-time-of-flight MS, (1)H-NMR spectroscopy and fast-atom bombardment MS. Their chemical structures were as follows: GlcN(alpha1-2)Ins1-P-1Cer (ZGL1), Man(alpha1-6)GlcN(alpha1-2)Ins1-P-1Cer (ZGL2), Man(alpha1-6)Man(alpha1-6)GlcN(alpha1-2)Ins1-P-1Cer (ZGL3), PC-->6Man(alpha1-6)GlcN(alpha1-2)Ins1- P -1Cer (ZGL4), and PC-->6Man(alpha1-6)Man(alpha1-6)GlcN(alpha1-2)Ins1-P-1Cer (ZGL5) (where Cer is ceramide and PC is phosphocholine). In addition, one acidic glycosphingolipid, which was the precursor of ZGLs, was also characterized as inositol-phosphoceramide. The core structure of the ZGLs, GlcN(alpha1-2)Ins1- P, is rather different from those found in other fungi, such as Man(alpha1-2)Ins1- P and Man(alpha1-6)Ins1- P. Interestingly, the terminal mannose residue of ZGL4 and ZGL5 was modified further with a PC group. The presence of PC-containing glycosylinositol-phosphoceramides has not been reported previously in any organism. The ceramide constituents of both ZGLs and acidic glycosphingolipid were essentially the same, and consisted of a 4-hydroxyoctadecasphinganine (phytosphingosine) as the sole sphingoid base and 2-hydroxytetracosanoic acid (>90%) as the major fatty acid. ZGLs were found to cause cell death in suspensions of cultured rice cells. The cell death-inducing activity of ZGLs is probably due to the characteristic glycan moiety of Man(alpha1-6)GlcN, and PC-containing ZGLs had high activity. This study is the first to demonstrate that fungal glycosylinositol-phosphoceramides induce cell death in cultured rice cells. PMID:14583095

Hole defects in molecular beam epitaxially grown p-GaAs introduced by alpha irradiation

NASA Astrophysics Data System (ADS)

Goodman, S. A.; Auret, F. D.; Meyer, W. E.

1994-01-01

Epitaxial aluminum Schottky barrier diodes on molecular beam epitaxially grown p-GaAs with a free carrier density of 2×1016 cm-3 were irradiated with alpha particles at room temperature using an americium-241 (Am-241) radio nuclide. For the first time, the radiation induced hole defects are characterized using conventional deep level transient spectroscopy (DLTS). The introduction rates and DLTS ``signatures'' of three prominent radiation induced defects Hα1, Hα4, and Hα5, situated 0.08, 0.20, and 0.30 eV above the valence band, respectively, are calculated and compared to those of similar defects introduced during electron irradiation.

Far-UV Spectral Mapping of Lunar Composition, Porosity, and Space Weathering: LRO Lyman Alpha Mapping Project (LAMP)

NASA Astrophysics Data System (ADS)

Retherford, K. D.; Greathouse, T. K.; Mandt, K.; Gladstone, R.; Liu, Y.; Hendrix, A. R.; Hurley, D.; Cahill, J. T.; Stickle, A. M.; Egan, A.; Kaufmann, D. E.; Grava, C.; Pryor, W. R.

2016-12-01

Far ultraviolet reflectance measurements of the Moon, icy satellites, comets, and asteroids obtained within the last decade have ushered in a new era of scientific advancement for UV surface investigations. The Lunar Reconnaissance Orbiter (LRO) Lyman Alpha Mapping Project (LAMP) has demonstrated an innovative nightside observing technique, putting a new light on permanently shadowed regions (PSRs) and other features on the Moon. Dayside far-UV albedo maps complement the nightside data, and LRO's polar orbit and high data downlink capabilities enable searches for diurnal variations in spectral signals. We'll discuss the strengths of the far-UV reflectance imaging spectroscopy technique with respect to several new LAMP results. Detections of water frost and hydration signatures near 165 nm, for example, provide constraints on composition that complement infrared spectroscopy, visible imaging, neutron spectroscopy, radar, and other techniques. At far-UV wavelengths a relatively blue spectral slope is diagnostic of space weathering, which is opposite of the spectral reddening indicator of maturity at wavelengths longward of 180 nm. By utilizing natural diffuse illumination sources on the nightside the far-UV technique is able to identify relative increases in porosity within the PSRs, and provides an additional tool for determining relative surface ages. Prospects for future studies are further enabled by a new, more sensitive dayside operating mode enacted during the present LRO mission extension.

Characterization of nanoscale oxide and oxyhydroxide powders using EXAFS spectroscopy

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

Darab, J.G.; Linehan, J.C.; Matson, D.W.

1993-06-01

Extended x-ray absorption fine structure (EXAFS) spectroscopy has been used to determine the structural environment local to iron(HI) and zircorium(IV) cations in respectively, nanoscale iron oxyhydroxide and nanoscale zirconium oxide powders. The iron oxyhydroxide powder, produced by the modified reverse micelle (MRM) technology, was found to have a short-range structure most similar to that of goethite ([alpha]-FeOOH). The short-range structure of the zirconium oxide powder, produced using the rapid thermal decomposition of solutes (RTDS) technology, was found to be a mixture of monoclinic zirconia and cubic zirconia environments.

Characterization of nanoscale oxide and oxyhydroxide powders using EXAFS spectroscopy

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

Darab, J.G.; Linehan, J.C.; Matson, D.W.

1993-06-01

Extended x-ray absorption fine structure (EXAFS) spectroscopy has been used to determine the structural environment local to iron(HI) and zircorium(IV) cations in respectively, nanoscale iron oxyhydroxide and nanoscale zirconium oxide powders. The iron oxyhydroxide powder, produced by the modified reverse micelle (MRM) technology, was found to have a short-range structure most similar to that of goethite ({alpha}-FeOOH). The short-range structure of the zirconium oxide powder, produced using the rapid thermal decomposition of solutes (RTDS) technology, was found to be a mixture of monoclinic zirconia and cubic zirconia environments.

Dispersive electron transport in tris(8-hydroxyquinoline) aluminum (Alq3) probed by impedance spectroscopy.

PubMed

Berleb, Stefan; Brütting, Wolfgang

2002-12-31

Electron transport in tris(8-hydroxyquinoline) aluminum (Alq3) is investigated by impedance spectroscopy under conditions of space-charge limited conduction (SCLC). Existing SCLC models are extended to include the field dependence of the charge carrier mobility and energetically distributed trap states. The dispersive nature of electron transport is revealed by a frequency-dependent mobility with a dispersion parameter alpha in the range 0.4-0.5, independent of temperature. This indicates that positional rather than energetic disorder is the dominant mechanism for the dispersive transport of electrons in Alq3.

Annual Report on the Activities and Publications of the DHS-DNDO-NTNFC Sponsored Post-doctoral Fellow at Los Alamos National Laboratory

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

Rim, Jung Ho; Tandon, Lav

This report is a summary of the projects Jung Rim is working on as a DHS postdoctoral fellow at Los Alamos National Laboratory. These research projects are designed to explore different radioanalytical methods to support nuclear forensics applications. The current projects discussed here include development of alpha spectroscopy method for 240/239Pu Isotopic ratio measurement, non-destructive uranium assay method using gamma spectroscopy, and 236U non-destructive uranium analysis using FRAM code. This report documents the work that has been performed since the start of the postdoctoral appointment.

High-resolution X-ray spectroscopy of M87 with the Einstein observatory - The detection of an O VIII emission line

NASA Technical Reports Server (NTRS)

Canizares, C. R.; Clark, G. W.; Markert, T. H.; Berg, C.; Smedira, M.; Bardas, D.; Schnopper, H.; Kalata, K.

1979-01-01

The paper deals with high-resolution X-ray spectroscopy performed to study the extended source surrounding the giant elliptical galaxy, M87, in the Virgo cluster. From observations carried out with a focal plane crystal spectrometer, L-alpha emission was detected from hydrogenic oxygen (O VIII). Upper limits could be set on lines from intermediate ionization states of iron. The presence of a quantity of cooler matter surrounding M87 was revealed, which has important implications for cluster models and favors a radiatively controlled accretion mechanism.

Solution structure for Pandinus toxin K-alpha (PiTX-K alpha), a selective blocker of A-type potassium channels.

PubMed

Tenenholz, T C; Rogowski, R S; Collins, J H; Blaustein, M P; Weber, D J

1997-03-11

PiTX-K alpha, a 35-residue peptide recently isolated from the venom of Pandinus imperator, blocks the rapidly inactivating (A-type) K+ channel(s) in rat brain synaptosomes and the cloned Kv 1.2 potassium channel at very low toxin concentrations (6 nM and 32 pM, respectively) [Rogowski, R. S., Collins, J. H., O'Neil, T. J., Gustafson, T. A., Werkman, T. A., Rogawski, M. A., Tenenholz, T. C., Weber, D. J., & Blaustein, M. P. (1996) Mol. Pharmacol. 50, 1167-1177]. The three-dimensional structure of PiTX-K alpha was determined using NMR spectroscopy in order to understand its selectivity and affinity toward K+ channels. PiTX-K alpha was found to have an alpha-helix from residues 10 to 21 and two beta-strands (betaI, 26-28; betaII, 33-35) connected by a type II beta-turn to form a small antiparallel beta-sheet. Three disulfide bonds, which are conserved in all members of the charybdotoxin family (alpha-K toxins), anchor one face of the alpha-helix to the beta-sheet. The N-terminal portion of PiTX-K alpha has three fewer residues than other alpha-K toxins such as charybdotoxin. Rather than forming a third beta-strand as found for other alpha-K toxins, the N-terminal region of PiTX-K alpha adopts an extended conformation. This structural difference in PiTX-K alpha together with differences in sequence at Pro-10, Tyr-14, and Asn-25 (versus Ser-10, Trp-14, and Arg-25 in CTX) may explain why PiTX-K alpha does not block maxi-K+ channels. Differences in three-dimensional structure between PiTX-K alpha and charybdotoxin are also observed in both the tight turn and the loop that connects the first beta-strand to the alpha-helix. As a result, side chains of two residues (Tyr-23 and Arg-31) are in regions of PiTX-K alpha that probably interact with rapidly inactivating A-type K+ channels. The analogous residues in charybdotoxin are positioned differently on the toxin surface. Thus, the locations of Tyr-23 and Arg-31 side chains in PiTX-K alpha could explain why this toxin blocks A-type channels at much lower concentrations than does charybdotoxin.

Falling number of soft wheat wheat by near-infrared spectroscopy: a challenge revisited

USDA-ARS?s Scientific Manuscript database

Wheat Hagberg falling number is a long-standing quality test that, by means of measuring the viscosity of a heated water-meal or water-flour mixture, characterizes the activity of alpha-amylase, the enzyme primarily responsible for starch hydrolysis. The accuracy, time requirement, and cost of this...

Peptide adsorption to cyanine dye aggregates revealed by cryo-transmission electron microscopy.

PubMed

von Berlepsch, Hans; Brandenburg, Enrico; Koksch, Beate; Böttcher, Christoph

2010-07-06

The binding interaction between aggregates of the 5-chloro-2-[[5-chloro-3-(3-sulfopropyl)-3H-benzothiazol-2-ylidene]methyl]-3-(3-sulfopropyl)benzothiazolium hydroxide inner salt ammonium salt (CD-1) and alpha-helix, as well as beta-sheet forming de novo designed peptides, was investigated by absorption spectroscopy, circular dichroism spectroscopy, and cryogenic transmission electron microscopy. Both pure dye and pure peptides self-assembled into well-defined supramolecular assemblies in acetate buffer at pH = 4. The dye formed sheetlike and tubular H- and J-aggregates and the peptides alpha-helical coiled-coil assemblies or beta-sheet rich fibrils. After mixing dye and peptide solutions, tubular aggregates with an unusual ultrastructure were found, most likely due to the decoration of dye tubes with monolayers of peptide assemblies based on the strong electrostatic attraction between the oppositely charged species. There was neither indication of a transfer of chirality from the peptides to the dye aggregates nor the opposite effect of a structural transfer from dye aggregates onto the peptides secondary structure.

Thoron detection with an active Radon exposure meter—First results

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

Irlinger, J., E-mail: josef.irlinger@helmholtz-muenchen.de; Wielunski, M.; Rühm, W.

For state-of-the-art discrimination of Radon and Thoron several measurement techniques can be used, such as active sampling, electrostatic collection, delayed coincidence method, and alpha-particle-spectroscopy. However, most of the devices available are bulky and show high power consumption, rendering them unfeasible for personal exposition monitoring. Based on a Radon exposure meter previously realized at the Helmholtz Center Munich (HMGU), a new electronic prototype for Radon/Thoron monitoring is currently being developed, which features small size and weight. Operating with pin-diode detectors, the low-power passive-sampling device can be used for continuous concentration measurements, employing alpha-particle-spectroscopy and coincidence event registration to distinguish decays originatingmore » either from Radon or Thoron isotopes and their decay products. In open geometry, preliminary calibration measurements suggest that one count per hour is produced by a 11 Bq m{sup −3} Radon atmosphere or by a 15 Bq m{sup −3} Thoron atmosphere. Future efforts will concentrate on measurements in mixed Radon/Thoron atmospheres.« less

[Compatibility between high-strength dental ceramic (type A) and vintage AL veneering porcelain].

PubMed

Cui, Jun; Chao, Yong-lie; Meng, Yu-kun

2006-05-01

To investigate the interface bond strength and compatibility between High-Strength Dental Ceramic (type A) and Vintage AL veneering porcelain. Twenty bar-shape specimens (ten Vintage AL and ten Vitadur alpha) were fabricated, and shear test was conducted to determine the bond strength. A bilayered composite (1 mm core ceramic and 0.8 mm Vintage AL) was prepared and then fractured for scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS) analysis. Ten all-ceramic anterior crowns were fabricated and the temperatures of thermal shock resistance were tested. The mean values of the bond strength measured were (55.52 +/- 14.64) MPa and (59.37 +/- 13.93) MPa for Vintage AL and Vitadur alpha respectively (P>0.05). SEM showed tight connection between the High-Strength Dental Ceramic (type A) and the veneering porcelain. Element diffusion was also confirmed by energy dispersive spectroscopy (EDS) analysis. The temperature of thermal shock resistance of this system was (179 +/- 15) degrees C. Vintage AL veneering porcelain has good thermal and chemical compatibility with High-Strength Dental Ceramic (type A).

Emission spectroscopy and laser-induced fluorescence measurements on the plume from a 1-kW arcjet operated on simulated ammonia

NASA Technical Reports Server (NTRS)

Ruyten, Wilhelmus M.; Burtner, D.; Keefer, Dennis

1993-01-01

Spectroscopic and laser-induced fluorescence measurements were performed on the exhaust plume from a 1 kW NASA Lewis arcjet, operated on simulated ammonia. In particular, emissions were analyzed from the Balmer lines of atomic hydrogen and from one of the rotational bands of the NH radical. The laser-induced fluorescence measurements were performed on the Balmer-alpha line of atomic hydrogen. We find that exit plane temperatures are in the range 1500 to 3500 K and that the electron density upstream of the exit plane is on the order of 1.5 x 10(exp 14)/cu cm as determined by the Stark width of the Balmer-alpha line. Both emission spectroscopy and laser-induced fluorescence were used to measure the plume velocities of atomic hydrogen. Using either technique, velocities on the order of 4 km/sec were found at the exit plane and significant acceleration of the flow was observed in the first 2 mm beyond the exit plane. This result indicates that the design of the arcjet nozzle may not be optimum.

Interaction of the p85 subunit of PI 3-kinase and its N-terminal SH2 domain with a PDGF receptor phosphorylation site: structural features and analysis of conformational changes.

PubMed Central

Panayotou, G; Bax, B; Gout, I; Federwisch, M; Wroblowski, B; Dhand, R; Fry, M J; Blundell, T L; Wollmer, A; Waterfield, M D

1992-01-01

Circular dichroism and fluorescence spectroscopy were used to investigate the structure of the p85 alpha subunit of the PI 3-kinase, a closely related p85 beta protein, and a recombinant SH2 domain-containing fragment of p85 alpha. Significant spectral changes, indicative of a conformational change, were observed on formation of a complex with a 17 residue peptide containing a phosphorylated tyrosine residue. The sequence of this peptide is identical to the sequence surrounding Tyr751 in the kinase-insert region of the platelet-derived growth factor beta-receptor (beta PDGFR). The rotational correlation times measured by fluorescence anisotropy decay indicated that phosphopeptide binding changed the shape of the SH2 domain-containing fragment. The CD and fluorescence spectroscopy data support the secondary structure prediction based on sequence analysis and provide evidence for flexible linker regions between the various domains of the p85 proteins. The significance of these results for SH2 domain-containing proteins is discussed. Images PMID:1330535

A Combined NMR-Computational Study of the Interaction between Influenza Virus Hemagglutinin and Sialic Derivatives from Human and Avian Receptors on the Surface of Transfected Cells.

PubMed

Vasile, Francesca; Panigada, Maddalena; Siccardi, Antonio; Potenza, Donatella; Tiana, Guido

2018-04-24

The development of small-molecule inhibitors of influenza virus Hemagglutinin could be relevant to the opposition of the diffusion of new pandemic viruses. In this work, we made use of Nuclear Magnetic Resonance (NMR) spectroscopy to study the interaction between two derivatives of sialic acid, Neu5Ac-α-(2,6)-Gal-β-(1⁻4)-GlcNAc and Neu5Ac-α-(2,3)-Gal-β-(1⁻4)-GlcNAc, and hemagglutinin directly expressed on the surface of recombinant human cells. We analyzed the interaction of these trisaccharides with 293T cells transfected with the H5 and H1 variants of hemagglutinin, which thus retain their native trimeric conformation in such a realistic environment. By exploiting the magnetization transfer between the protein and the ligand, we obtained evidence of the binding event, and identified the epitope. We analyzed the conformational features of the glycans with an approach combining NMR spectroscopy and data-driven molecular dynamics simulations, thus obtaining useful information for an efficient drug design.

Detection system for high-resolution gamma radiation spectroscopy with neutron time-of-flight filtering

DOEpatents

Dioszegi, Istvan; Salwen, Cynthia; Vanier, Peter

2014-12-30

A .gamma.-radiation detection system that includes at least one semiconductor detector such as HPGe-Detector, a position-sensitive .alpha.-Detector, a TOF Controller, and a Digitizer/Integrator. The Digitizer/Integrator starts to process the energy signals of a .gamma.-radiation sent from the HPGe-Detector instantly when the HPGe-Detector detects the .gamma.-radiation. Subsequently, it is determined whether a coincidence exists between the .alpha.-particles and .gamma.-radiation signal, based on a determination of the time-of-flight of neutrons obtained from the .alpha.-Detector and the HPGe-Detector. If it is determined that the time-of-flight falls within a predetermined coincidence window, the Digitizer/Integrator is allowed to continue and complete the energy signal processing. If, however, there is no coincidence, the Digitizer/Integrator is instructed to be clear and reset its operation instantly.

Secondary and primary relaxations in hyperbranched polyglycerol: a comparative study in the frequency and time domains.

PubMed

Garcia-Bernabé, Abel; Dominguez-Espinosa, Gustavo; Diaz-Calleja, Ricardo; Riande, Evaristo; Haag, Rainer

2007-09-28

The non-Debye relaxation behavior of hyperbranched polyglycerol was investigated by broadband dielectric spectroscopy. A thorough study of the relaxations was carried out paying special attention to truncation effects on deconvolutions of overlapping processes. Hyperbranched polyglycerol exhibits two relaxations in the glassy state named in increasing order of frequency beta and gamma processes. The study of the evolution of these two fast processes with temperature in the time retardation spectra shows that the beta absorption is swallowed by the alpha in the glass-liquid transition, the gamma absorption being the only relaxation that remains operative in the liquid state. In heating, a temperature is reached at which the alpha absorption vanishes appearing the alphagamma relaxation. Two characteristics of alpha absorptions, decrease of the dielectric strength with increasing temperature and rather high activation energy, are displayed by the alphagamma process. Williams' ansatz seems to hold for these topologically complex macromolecules.

Solid surface dependent layering of self-arranged structures with fibril-like assemblies of alpha-synuclein

NASA Astrophysics Data System (ADS)

Bukauskas, V.; Šetkus, A.; Šimkienė, I.; Tumėnas, S.; Kašalynas, I.; Rėza, A.; Babonas, J.; Časaitė, V.; Povilonienė, S.; Meškys, R.

2012-03-01

In present work the formation of hybrid constructions composed of alpha-synuclein-based colloidal solutions on various solid surfaces (silica coated Si, mica, CaF2 and KBr) is investigated by scanning probe microscopy, spectrocopic ellipsometry, Fourier transformed infrared spectroscopy and vibrational circular dichroism. Prior to the modification of the solids, the proteins were intentionally fibrilled under special conditions. It is proved that the multi-component coatings are self-arranged on the solid substrates. Depending on the substrate material, the interface films consisting of individual biomolecules can be detected on the solid surfaces. The coatings with fibril-like alpha-synuclein objects can be obtained on solid surfaces with negligible or comparatively thick interface films. The results are interpreted in terms of the charged surface-controlled electrostatic interaction between the substrate and the biomolecules. Solubility of solids is considered in this interpretation.

Structural and immunochemical studies of neutral exopolysaccharide produced by Lactobacillus johnsonii 142.

PubMed

Górska, Sabina; Jachymek, Wojciech; Rybka, Jacek; Strus, Magdalena; Heczko, Piotr B; Gamian, Andrzej

2010-01-11

This paper describes the structure of neutral exopolysaccharide (EPS) produced by Lactobacillus johnsonii 142, strain of the lactic acid bacteria isolated from the intestine of mice with experimentally induced inflammatory bowel disease (IBD). Sugar and methylation analyses along with (1)H and (13)C NMR spectroscopy, including two-dimensional (1)H,(1)H COSY, TOCSY, NOESY, and (1)H,(13)C HSQC experiments revealed that the repeating unit of the EPS is a pentasaccharide: -->3)-alpha-D-Galp-(1-->3)-beta-d-Glcp-(1-->5)-beta-D-Galf-(1-->3)-alpha-D-Galp-(1-->3)-alpha-D-Galp-(1--> The rabbit antiserum raised against whole cells of L. johnsonii 142 reacted with homologous EPS, and cross-reacted with exopolysaccharide from Lactobacillus animalis/murinus 148 isolated also from mice with IBD, but not reacted with EPS of L. johnsonii 151 from healthy mice. Copyright 2009 Elsevier Ltd. All rights reserved.

GAS MOTION STUDY OF Ly{alpha} EMITTERS AT z {approx} 2 USING FUV AND OPTICAL SPECTRAL LINES {sup ,}

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

Hashimoto, Takuya; Shimasaku, Kazuhiro; Nakajima, Kimihiko

2013-03-01

We present the results of Magellan/MMIRS and Keck/NIRSPEC spectroscopy for five Ly{alpha} emitters (LAEs) at z {approx_equal} 2.2 for which high-resolution FUV spectra from Magellan/MagE are available. We detect nebular emission lines including H{alpha} on the individual basis and low-ionization interstellar (LIS) absorption lines in a stacked FUV spectrum, and measure average offset velocities of the Ly{alpha} line, {Delta}v {sub Ly{alpha}}, and LIS absorption lines, {Delta}v {sub abs}, with respect to the systemic velocity defined by the nebular lines. For a sample of eight z {approx} 2-3 LAEs without active galactic nucleus from our study and the literature, we obtainmore » {Delta}v {sub Ly{alpha}} = 175 {+-} 35 km s{sup -1}, which is significantly smaller than that of Lyman-break Galaxies (LBGs), {Delta}v {sub Ly{alpha}} {approx_equal} 400 km s{sup -1}. The stacked FUV spectrum gives {Delta}v {sub abs} = -179 {+-} 73 km s{sup -1}, comparable to that of LBGs. These positive {Delta}v {sub Ly{alpha}} and negative {Delta}v {sub abs} suggest that LAEs also have outflows. In contrast to LBGs, however, the LAEs' {Delta}v {sub Ly{alpha}} is as small as |{Delta}v {sub abs}|, suggesting low neutral hydrogen column densities. Such a low column density with a small number of resonant scattering may cause the observed strong Ly{alpha} emission of LAEs. We find an anti-correlation between Ly{alpha} equivalent width (EW) and {Delta}v {sub Ly{alpha}} in a compilation of LAE and LBG samples. Although its physical origin is not clear, this anti-correlation result appears to challenge the hypothesis that a strong outflow, by means of a reduced number of resonant scattering, produces a large EW. If LAEs at z > 6 have similarly small {Delta}v {sub Ly{alpha}} values, constraints on the reionization history derived from the Ly{alpha} transmissivity may need to be revised.« less

Using scaling factors for evaluating spatial and temporal variability of soil hydraulic properties within one elevation transect

NASA Astrophysics Data System (ADS)

Nikodem, Antonín; Kodešová, Radka; Jakšík, Ondřej; Fér, Miroslav; Klement, Aleš

2016-04-01

This study was carried out in Southern Moravia, in the Czech Republic. The original soil unit in the wider area is a Haplic Chernozem developed on loess. The intensive agricultural exploitation in combination with terrain morphology has resulted in a highly diversified soil spatial pattern. Nowadays the original soil unit is preserved only on top of relatively flat parts, and is gradually transformed by water erosion up to Regosols on the steepest slopes, while colluvial soils are formed in terrain depressions and at toe slopes due to sedimentation of previously eroded material. Soils within this area has been intensively investigated during the last several years (e.g. Jakšík et al., 2015; Vašát et al., 2014, 2015a,b). Soil sampling (disturbed and undisturbed 100-cm3 soil samples) was performed at 5 points of one elevation transect in November 2010 (after wheat sowing) and August 2011 (after wheat harvest). Disturbed soil samples were used to determine basic soil properties (grain size distribution and organic carbon content etc.). Undisturbed soil samples were used to determine the soil water retention curves and the hydraulic conductivity functions using the multiple outflow tests in Tempe cells and a numerical inversion with HYDRUS 1-D. Scaling factors (alpha-h for pressure head, alpha-theta for soil water contents and alpha-k for hydraulic conductivities) were used here to express soil hydraulic properties variability. Evaluated scaling factors reflected position within the elevation transect as well as time of soil sampling. In general large values of alpha-h, lower values of alpha-k and similar values of alpha-theta were obtained in 2010 in comparison to values obtained in 2011, which indicates development of soil structure during the vegetation season. Jakšík, O., Kodešová, R., Kubiš, A., Stehlíková, I., Drábek, O., Kapička, A. (2015): Soil aggregate stability within morphologically diverse areas. Catena, 127, 287-299. Vašát, R., Kodešová, R., Borůvka, L., Jakšík, O., Klement, A., Drábek, O. (2015a): Absorption features in soil spectra assessment. Applied Spectroscopy, 69(12), 1425-1431. Vašát, R., Kodešová, R., Borůvka, L., Klement, A., Jakšík, O., Gholizadeh, A. (2014): Consideration of peak parameters derived from continuum-removed spectra to predict extractable nutrients in soils with visible and near-infrared diffuse reflectance spectroscopy (VNIR-DRS). Geoderma, 232-234, 208-218. Vašát, R., Kodešová, R., Klement, A., Jakšík, O. (2015b): Predicting oxidizable carbon content via visible- and near-infrared diffuse reflectance spectroscopy in soils heavily affected by water erosion. Soil and Water Research, 10 (2), 74-77.

Precision atomic spectroscopy for improved limits on variation of the fine structure constant and local position invariance.

PubMed

Fortier, T M; Ashby, N; Bergquist, J C; Delaney, M J; Diddams, S A; Heavner, T P; Hollberg, L; Itano, W M; Jefferts, S R; Kim, K; Levi, F; Lorini, L; Oskay, W H; Parker, T E; Shirley, J; Stalnaker, J E

2007-02-16

We report tests of local position invariance and the variation of fundamental constants from measurements of the frequency ratio of the 282-nm 199Hg+ optical clock transition to the ground state hyperfine splitting in 133Cs. Analysis of the frequency ratio of the two clocks, extending over 6 yr at NIST, is used to place a limit on its fractional variation of <5.8x10(-6) per change in normalized solar gravitational potential. The same frequency ratio is also used to obtain 20-fold improvement over previous limits on the fractional variation of the fine structure constant of |alpha/alpha|<1.3x10(-16) yr-1, assuming invariance of other fundamental constants. Comparisons of our results with those previously reported for the absolute optical frequency measurements in H and 171Yb+ vs other 133Cs standards yield a coupled constraint of -1.5x10(-15)

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

Hopkins, Rebecca J.; Lewis, K.; Desyaterik, Yury

Aerosols generated from burning different plant fuels were characterized to determine relationships between chemical, optical and physical properties. Single scattering albedo ({omega}) and Angstrom absorption coefficients ({alpha}{sub ap}) were measured using a photoacoustic technique combined with a reciprocal nephelometer. Carbon-to-oxygen atomic ratios, sp{sup 2} hybridization, elemental composition and morphology of individual particles were measured using scanning transmission X-ray microscopy coupled with near-edge X-ray absorption fine structure spectroscopy (STXM/NEXAFS) and scanning electron microscopy with energy dispersion of X-rays (SEM/EDX). Particles were grouped into three categories based on sp2 hybridization and chemical composition. Measured {omega} (0.4-1.0 at 405 nm) and {alpha}{sub ap}more » (1.0-3.5) values displayed a fuel dependence. The category with sp{sup 2} hybridization >80% had values of {omega} (<0.5) and {alpha}{sub ap} ({approx}1.25) characteristic of light absorbing soot. Other categories with lower sp2 hybridization (20 to 60%) exhibited higher {omega} (>0.8) and {alpha}{sub ap} (1.0 to 3.5) values, indicating increased absorption spectral selectivity.« less

Cloning and expression of a novel UDP-GlcNAc:alpha-D-mannoside beta1,2-N-acetylglucosaminyltransferase homologous to UDP-GlcNAc:alpha-3-D-mannoside beta1,2-N-acetylglucosaminyltransferase I.

PubMed Central

Zhang, Wenli; Betel, Doron; Schachter, Harry

2002-01-01

A TBLASTN search with human UDP-GlcNAc:alpha-3-d-mannoside beta-1,2-N-acetylglucosaminyltransferase I (GnT I; EC 2.4.1.101) as a probe identified human and mouse Unigenes encoding a protein similar to human GnT I (34% identity over 340 amino acids). The recombinant protein converted Man(alpha1-6)[Man(alpha1-3)]Man(beta1-)O-octyl to Man(alpha1-6)[GlcNAc(beta1-2)Man(alpha1-3)]Man(beta1-)O-octyl, the reaction catalysed by GnT I. The enzyme also added GlcNAc to Man(alpha1-6)[GlcNAc(beta1-2)Man(alpha1-3)]Man(beta1-)O-octyl (the substrate for beta-1,2-N-acetylglucosaminyltransferase II), Man(alpha1-)O-benzyl [with K(m) values of approximately 0.3 and >30 mM for UDP-GlcNAc and Man(alpha1-)O-benzyl respectively] and the glycopeptide CYA[Man(alpha1-)O-T]AV (K(m) approximately 12 mM). The product formed with Man(alpha1-)O-benzyl was identified as GlcNAc(beta1-2)Man(alpha1-)O-benzyl by proton NMR spectroscopy. The enzyme was named UDP-GlcNAc:alpha-d-mannoside beta-1,2-N-acetylglucosaminyltransferase I.2 (GnT I.2). The human gene mapped to chromosome 1. Northern-blot analysis showed a 3.3 kb message with a wide tissue distribution. The cDNA has a 1980 bp open reading frame encoding a 660 amino acid protein with a type-2 domain structure typical of glycosyltransferases. Man(beta1-)O-octyl, Man(beta1-)O-p-nitrophenyl and GlcNAc(beta1-2)Man(alpha1-6)[GlcNAc(beta1-2)Man(alpha1-3)]Man(beta1-4)GlcNAc(beta1-4)GlcNAc(beta1-)O-Asn were not acceptors, indicating that GnT I.2 is specific for alpha-linked terminal Man and does not have N-acetylglucosaminyltransferase III, IV, V, VII or VIII activities. CYA[Man(alpha1-)O-T]AV was between three and seven times more effective as an acceptor than the other substrates, suggesting that GnT I.2 may be responsible for the synthesis of the GlcNAc(beta1-2)Man(alpha1-)O-Ser/Thr moiety on alpha-dystroglycan and other O-mannosylated proteins. PMID:11742540

Conformation, orientation, and adsorption kinetics of dermaseptin B2 onto synthetic supports at aqueous/solid interface.

PubMed

Noinville, S; Bruston, F; El Amri, C; Baron, D; Nicolas, P

2003-08-01

The antimicrobial activity of cationic amphipathic peptides is due mainly to the adsorption of peptides onto target membranes, which can be modulated by such physicochemical parameters as charge and hydrophobicity. We investigated the structure of dermaseptin B2 (Drs B2) at the aqueous/synthetic solid support interface and its adsorption kinetics using attenuated total reflection Fourier transform infrared spectroscopy and surface plasmon resonance. We determined the conformation and affinity of Drs B2 adsorbed onto negatively charged (silica or dextran) and hydrophobic supports. Synthetic supports of differing hydrophobicity were obtained by modifying silica or gold with omega-functionalized alkylsilanes (bromo, vinyl, phenyl, methyl) or alkylthiols. The peptide molecules adsorbed onto negatively charged supports mostly had a beta-type conformation. In contrast, a monolayer of Drs B2, mainly in the alpha-helical conformation, was adsorbed irreversibly onto the hydrophobic synthetic supports. The conformational changes during formation of the adsorbed monolayer were monitored by two-dimensional Fourier transform infrared spectroscopy correlation; they showed the influence of peptide-peptide interactions on alpha-helix folding on the most hydrophobic support. The orientation of the alpha-helical Drs B2 with respect to the hydrophobic support was determined by polarized attenuated total reflection; it was around 15 +/- 5 degrees. This orientation was confirmed and illustrated by a molecular dynamics study. These combined data demonstrate that specific chemical environments influence the structure of Drs B2, which could explain the many functions of antimicrobial peptides.

Raman spectroscopy reveals spectroscopic changes in histologically normal retinas in a mouse model of alpha-synucleinopathy

USDA-ARS?s Scientific Manuscript database

The retina is an extension of the nervous system and is accessible for in vivo assessments. We have previously demonstrated changes in retinal function and pathology associated with scrapie, TME and BSE. The purpose of this work was to determine the utility of the retina to identify early CNS change...

KECK SPECTROSCOPY OF FAINT 3 < z < 8 LYMAN BREAK GALAXIES: EVIDENCE FOR A DECLINING FRACTION OF EMISSION LINE SOURCES IN THE REDSHIFT RANGE 6 < z < 8

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

Schenker, Matthew A.; Ellis, Richard S.; Robertson, Brant E.

2012-01-10

Using deep Keck spectroscopy of Lyman break galaxies selected from infrared imaging data taken with the Wide Field Camera 3 on board the Hubble Space Telescope, we present new evidence for a reversal in the redshift-dependent fraction of star-forming galaxies with detectable Lyman alpha (Ly{alpha}) emission in the redshift range 6.3 < z < 8.8. Our earlier surveys with the DEIMOS spectrograph demonstrated a significant increase with redshift in the fraction of line emitting galaxies over the interval 4 < z < 6, particularly for intrinsically faint systems which dominate the luminosity density. Using the longer wavelength sensitivities of Lowmore » Resolution Imaging Spectrometer and NIRSPEC, we have targeted 19 Lyman break galaxies selected using recent WFC3/IR data whose photometric redshifts are in the range 6.3 < z < 8.8 and which span a wide range of intrinsic luminosities. Our spectroscopic exposures typically reach a 5{sigma} sensitivity of <50 A for the rest-frame equivalent width (EW) of Ly{alpha} emission. Despite the high fraction of emitters seen only a few hundred million years later, we find only two convincing and one possible line emitter in our more distant sample. Combining with published data on a further seven sources obtained using FORS2 on the ESO Very Large Telescope, and assuming continuity in the trends found at lower redshift, we discuss the significance of this apparent reversal in the redshift-dependent Ly{alpha} fraction in the context of our range in continuum luminosity. Assuming all the targeted sources are at their photometric redshift and our assumptions about the Ly{alpha} EW distribution are correct, we would expect to find so few emitters in less than 1% of the realizations drawn from our lower redshift samples. Our new results provide further support for the suggestion that, at the redshifts now being probed spectroscopically, we are entering the era where the intergalactic medium is partially neutral. With the arrival of more sensitive multi-slit infrared spectrographs, the prospects for improving the statistical validity of this result are promising.« less

High molecular weight glucan of the culinary medicinal mushroom Agaricus bisporus is an alpha-glucan that forms complexes with low molecular weight galactan.

PubMed

Smiderle, Fhernanda R; Sassaki, Guilherme L; van Arkel, Jeroen; Iacomini, Marcello; Wichers, Harry J; Van Griensven, Leo J L D

2010-08-25

An alpha-glucan was isolated from the culinary medicinal mushroom A. bisporus by hot water extraction, ethanol precipitation and DEAE-cellulose chromatography. The resulting material showed a single HMW peak excluded from a Sephadex G50 column that could completely be degraded by alpha-amylase treatment. After heating in 1% SDS a small additional peak of low MW eluted from the G50 column. The monosaccharide composition of the main peak was evaluated by HPLC, and was found to consist of a majority of glucose (97.6%), and a minor proportion of galactose (2.4%). Methylation analysis and degradation by alpha-amylase indicated the presence of an alpha-glucan with a main chain consisting of (1(R)4)-linked units, substituted at O-6 by alpha-D-glucopyranose single-units in the relation 1:8. Mono- (13C-, 1H-NMR) and bidimensional [1H (obs.),13C-HSQC] spectroscopy analysis confirmed the alpha-configuration of the Glcp residues by low frequency resonances of C-1 at delta 100.6, 100.2, and 98.8 ppm and H-1 high field ones at delta 5.06, 5.11, and 4.74 ppm. The DEPT-13C-NMR allowed assigning the non-substituted and O-substituted -CH(2) signals at delta 60.3/60.8 and 66.2 ppm, respectively. Other assignments were attributed to C-2, C-3, C-4, C-5 and C-6 of the non-reducing ends at delta 71.8; 72.8; 70.0; 71.3 and 60.3/60.8 ppm, respectively. The minor proportion of galactose that was demonstrated was probably derived from a complex between the alpha-glucan and a low molecular weight galactan.

Study of the Many Fluorescent Lines and the Absorption Variability in GX 301-2 with XMM-Newton

NASA Technical Reports Server (NTRS)

Fuerst, F.; Suchy, S.; Kreykenbohm, I.; Barragan, L.; Wilms, J.; Pottschmidt, K.; Caballero, I.; Kretschmar, P.; Ferrigno, C.; Rothschild, R. E.

2011-01-01

We present an in-depth study of the High Mass X-ray Binary (HMXB) GX 301-2 during its pre-periastron flare using data from the XMM-Newton satellite. The energy spectrum shows a power law continuum absorbed by a large equivalent hydrogen column on the order of 10(exp 24)/ sq cm and a prominent Fe K-alpha fluorescent emission line. Besides the Fe K-alpha line, evidence for Fe K-Beta, Ni K-alpha, Ni K-Beta, S K-alpha, Ar K-alpha, Ca K-alpha, and Cr K-alpha fluorescent lines is found. The observed line strengths are consistent with fluorescence in a cold absorber. This is the first time that Cr K-alpha is seen in emission in the X-ray spectrum of a HMXB. In addition to the modulation by the strong pulse period of approx 685 sec the source is highly variable and shows different states of activity. We perform time-resolved as well as pulse-to-pulse resolved spectroscopy to investigate differences between these states of activity. We find that fluorescent line fluxes are strongly variable and generally follow the overall flux. The N-H value is variable by a factor of 2, but not correlated to continuum normalization. We find an interval of low flux in the light curve in which the pulsations cease almost completely, without any indication of an increasing absorption column. We investigate this dip in detail and argue that it is most likely that during the dip the accretion ceased and the afterglow of the fluorescent iron accounted for the main portion of the X-ray flux. A similar dip was found earlier in RXTE data, and we compare our findings to these results.

Probing alpha-helical and beta-sheet structures of peptides at solid/liquid interfaces with SFG.

PubMed

Chen, Xiaoyun; Wang, Jie; Sniadecki, Jason J; Even, Mark A; Chen, Zhan

2005-03-29

We demonstrated that sum frequency generation (SFG) vibrational spectroscopy can distinguish different secondary structures of proteins or peptides adsorbed at solid/liquid interfaces. The SFG spectrum for tachyplesin I at the polystyrene (PS)/solution interface has a fingerprint peak corresponding to the B1/B3 mode of the antiparallel beta-sheet. This peak disappeared upon the addition of dithiothreitol, which can disrupt the beta-sheet structure. The SFG spectrum indicative of the MSI594 alpha-helical structure was observed at the PS/MSI594 solution interface. This research validates SFG as a powerful technique for revealing detailed secondary structures of interfacial proteins and peptides.

Evaluating bis(2-ethylhexyl) methanediphosphonic acid (H 2DEH[MDP]) based polymer ligand film (PLF) for plutonium and uranium extraction

DOE PAGES

Rim, Jung H.; Armenta, Claudine E.; Gonzales, Edward R.; ...

2015-09-12

This paper describes a new analyte extraction medium called polymer ligand film (PLF) that was developed to rapidly extract radionuclides. PLF is a polymer medium with ligands incorporated in its matrix that selectively and quickly extracts analytes. The main focus of the new technique is to shorten and simplify the procedure for chemically isolating radionuclides for determination through alpha spectroscopy. The PLF system was effective for plutonium and uranium extraction. The PLF was capable of co-extracting or selectively extracting plutonium over uranium depending on the PLF composition. As a result, the PLF and electrodeposited samples had similar alpha spectra resolutions.

Serum albumin and globulin analysis for hepatocellular carcinoma detection avoiding false-negative results from alpha-fetoprotein test negative subjects

NASA Astrophysics Data System (ADS)

Wang, Jing; Feng, Shangyuan; Lin, Juqiang; Zeng, Yongyi; Li, Ling; Huang, Zufang; Li, Buhong; Zeng, Haishan; Chen, Rong

2013-11-01

Surface-enhanced Raman spectroscopy (SERS) of serum albumin and globulin were employed to detect hepatocellular carcinoma (HCC). Tentative assignments of SERS bands show specific biomolecular changes associated with cancer development. These changes include a decrease in relative amounts of tryptophan, glutamine, glycine, and serine, indicating excessive consumption of amino acids for protein duplication. Principal component analysis was also introduced to analyze the obtained spectra, resulting in both diagnostic sensitivity and specificity of 100%. More importantly, it reveals that this method can detect HCC patients with alpha-fetoprotein negative test results, suggesting its great potential as a new alternative to detect HCC.

Sample preparation for the determination of 241Am in sediments utilizing gamma-spectroscopy.

PubMed

Ristic, M; Degetto, S; Ast, T; Cantallupi, C

2002-01-01

This paper describes a procedure developed to separate americium-241 from the bulk of a sample by coprecipitation followed by high sensitivity gamma-counting of the concentrate in a well-type detector. It enables the measurement of 241Am at low concentrations, e.g. fallout levels in soils and sediments, or where large sample sizes are not available. The method is much faster and more reliable than those involving separation from other alpha-emitters, electroplating and alpha-spectrometry. A number of tracer experiments was performed in order to optimize the conditions for coprecipitation of 241Am from sediment leachates. The general outline of the determination of americium is also given.

On the interface between perturbative and nonperturbative QCD

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

Deur, Alexandre; Brodsky, Stanley J.; de Teramond, Guy F.

2016-04-04

The QCD running couplingmore » $$\\alpha_s(Q^2)$$ sets the strength of the interactions of quarks and gluons as a function of the momentum transfer $Q$. The $Q^2$ dependence of the coupling is required to describe hadronic interactions at both large and short distances. In this article we adopt the light-front holographic approach to strongly-coupled QCD, a formalism which incorporates confinement, predicts the spectroscopy of hadrons composed of light quarks, and describes the low-$Q^2$ analytic behavior of the strong coupling $$\\alpha_s(Q^2)$$. The high-$Q^2$ dependence of the coupling $$\\alpha_s(Q^2)$$ is specified by perturbative QCD and its renormalization group equation. The matching of the high and low $Q^2$ regimes of $$\\alpha_s(Q^2)$$ then determines the scale $$Q_0$$ which sets the interface between perturbative and nonperturbative hadron dynamics. The value of $$Q_0$$ can be used to set the factorization scale for DGLAP evolution of hadronic structure functions and the ERBL evolution of distribution amplitudes. We discuss the scheme-dependence of the value of $$Q_0$$ and the infrared fixed-point of the QCD coupling. Our analysis is carried out for the $$\\bar{MS}$$, $$g_1$$, $MOM$ and $V$ renormalization schemes. Our results show that the discrepancies on the value of $$\\alpha_s$$ at large distance seen in the literature can be explained by different choices of renormalization schemes. Lastly, we also provide the formulae to compute $$\\alpha_s(Q^2)$$ over the entire range of space-like momentum transfer for the different renormalization schemes discussed in this article.« less

Employing NMR Spectroscopy To Evaluate Transmission of Electronic Effects in 4-Substituted Chalcones

NASA Astrophysics Data System (ADS)

Wachter-Jurcsak, Nanette; Zamani, Hossein

1999-05-01

Described is an organic synthesis experiment that demonstrates the electronic transmission by substituents. The effect of substitution at the para-position of the styryl ring of 1,3-diphenyl-2-propenones (chalcones) by typical electron-donating or -accepting groups can be observed by proton and carbon-13 NMR spectroscopy. A linear correlation is observed when the differences in chemical shift measurements for H are plotted against the corresponding Hammett substituent constant values. Good correlation between carbon-13 chemical shifts of the alpha carbon are also observed. The syntheses of the 4-substituted chalcones is presented as well as a brief discussion of the theory.

Conformational analysis of the partially disordered measles virus N(TAIL)-XD complex by SDSL EPR spectroscopy.

PubMed

Kavalenka, Aleh; Urbancic, Iztok; Belle, Valérie; Rouger, Sabrina; Costanzo, Stéphanie; Kure, Sandra; Fournel, André; Longhi, Sonia; Guigliarelli, Bruno; Strancar, Janez

2010-03-17

To characterize the structure of dynamic protein systems, such as partly disordered protein complexes, we propose a novel approach that relies on a combination of site-directed spin-labeled electron paramagnetic resonance spectroscopy and modeling of local rotation conformational spaces. We applied this approach to the intrinsically disordered C-terminal domain of the measles virus nucleoprotein (N(TAIL)) both free and in complex with the X domain (XD, aa 459-507) of the viral phosphoprotein. By comparing measured and modeled temperature-dependent restrictions of the side-chain conformational spaces of 12 SL cysteine-substituted N(TAIL) variants, we showed that the 490-500 region of N(TAIL) is prestructured in the absence of the partner, and were able to quantitatively estimate, for the first time to our knowledge, the extent of the alpha-helical sampling of the free form. In addition, we showed that the 505-525 region of N(TAIL) conserves a significant degree of freedom even in the bound form. The latter two findings provide a mechanistic explanation for the reported rather high affinity of the N(TAIL)-XD binding reaction. Due to the nanosecond timescale of X-band EPR spectroscopy, we were also able to monitor the disordering in the 488-525 region of N(TAIL), in particular the unfolding of the alpha-helical region when the temperature was increased from 281 K to 310 K. Copyright 2010 Biophysical Society. Published by Elsevier Inc. All rights reserved.

A Proposed Mechanism for the Thermal Denaturation of a Recombinant Bacillus Halmapalus Alpha-amylase - the Effect of Calcium Ions

NASA Technical Reports Server (NTRS)

Nielsen, Anders D.; Pusey, Marc L.; Fuglsang, Claus C.; Westh, Peter

2003-01-01

The thermal stability of a recombinant alpha-amylase from Bacillus halmapalus alpha-amylase (BHA) has been investigated using circular dichroism spectroscopy (CD) and differential scanning calorimetry (DSC). This alpha-amylase is homologous to other Bacillus alpha-amylases where previous crystallographic studies have identified the existence of 3 calcium binding sites in the structure. Denaturation of BHA is irreversible with a Tm of approximately 89 C, and DSC thermograms can be described using a one-step irreversible model. A 5 C increase in T(sub m) in the presence of 10 fold excess CaCl2 was observed. However, a concomitant increase in the tendency to aggregate was also observed. The presence of 30-40 fold excess calcium chelator (EDTA or EGTA) results in a large destabilization of BHA corresponding to about 40 C lower T(sub m), as determined by both CD and DSC. Ten fold excess EGTA reveals complex DSC thermograms corresponding to both reversible and irreversible transitions, which possibly originate from different populations of BHA:calcium complexes. The observations in the present study have, in combination with structural information of homologous alpha-amylases, provided the basis for the proposal of a simple denaturation mechanism of BHA. The proposed mechanism describes the irreversible thermal denaturation of different BHA:calcium complexes and the calcium binding equilibrium involved. Furthermore, the model accounts for a temperature induced reversible structural change associated with calcium binding.

Larvicidal effect of Eucalyptus grandis essential oil and turpentine and their major components on Aedes aegypti larvae.

PubMed

Lucia, Alejandro; Gonzalez Audino, Paola; Seccacini, Emilia; Licastro, Susana; Zerba, Eduardo; Masuh, Hector

2007-09-01

In the search for new alternatives for the control of Aedes aegypti the larvicidal activity of Eucalyptus grandis essential oil and pine resin essential oil (turpentine) and their major components (alpha- and beta-pinene and 1,8-cineole) was determined. Gas chromatography-mass spectroscopy analysis of E. grandis essential oil revealed that its major components are alpha-pinene and 1,8-cineole. Similar analysis of turpentine obtained by distillation of the resin pitch of conifers showed that alpha- and beta-pinene are the only major components. Third and early 4th instars of the CIPEIN-susceptible strain of Ae. aegypti were exposed to acetonic solutions of E. grandis essential oil, turpentine, and their major components for 24 h. Turpentine, with an LC50 of 14.7 ppm, was more active than the essential oil of E. grandis (LC50: 32.4 ppm). Larvicidal activity of the essential oil components showed that alpha- and beta-pinene present low LC50 values (15.4 and 12.1 ppm, respectively), whereas pure 1,8-cineole showed an LC50 of 57.2 ppm. These results suggest that alpha-pinene in E. grandis and alpha- and beta-pinene in turpentine serve as the principal larvicidal components of both oils. Results obtained on larvicidal effects of essential oil of Eucalyptus grandis and turpentine could be considered a contribution to the search for new biodegradable larvicides of natural origin.

Self-absorption Effects on Alpha-Induced Atmospheric Nitrogen Fluorescence Yield

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

Bachelor, Paula P.; Jordan, David V.; Harper, Warren W.

2009-12-01

Nitrogen fluorescence induced by alpha, beta and gamma radiation can be used to detect the presence of radioactive contamination in the environment. Successful measurement of fluorescence yield involves a number of factors, including: known fluorescence signal rate during the measurement; the effective alpha spectrum of the radioactive sources used in the measurement; optical attenuation length of the fluorescence signal in air during the measurement; the absolute throughput of the instrumentation; calibration of the instrumentation; and radiation transport modeling of the "effective" array exposure rate given the spectrum of the alpha particles. Field testing of optical instrumentation was conducted to measuremore » the nitrogen fluorescence yield from the alpha radiation generated from americium-241 (241Am) decay. The 241Am test sources were prepared by direct evaporation of ~1 mCi in nitric acid solution, and some solids were visible on the surface of the sources. A laboratory study was conducted with lower activities of 241Am to determine whether the presence of solids on the surface of the sources prepared both by direct evaporation and by electrodeposition onto stainless steel disks produced sufficient self-absorption to cause a decrease in expected fluorescence. Alpha spectroscopy was used to determine the apparent activity of the sources versus the known activity deposited on the surface. Results from the self-absorption laboratory studies were used to correct the activity values in the model and calculate the nitrogen fluorescence generated by the 241Am during the field experiments.« less

Interaction of the alpha-subunit of Escherichia coli RNA polymerase with DNA: rigid body nature of the protein-DNA contact.

PubMed

Heyduk, E; Baichoo, N; Heyduk, T

2001-11-30

The alpha-subunit of Escherichia coli RNA polymerase plays an important role in the activity of many promoters by providing a direct protein-DNA contact with a specific sequence (UP element) located upstream of the core promoter sequence. To obtain insight into the nature of thermodynamic forces involved in the formation of this protein-DNA contact, the binding of the alpha-subunit of E. coli RNA polymerase to a fluorochrome-labeled DNA fragment containing the rrnB P1 promoter UP element sequence was quantitatively studied using fluorescence polarization. The alpha dimer and DNA formed a 1:1 complex in solution. Complex formation at 25 degrees C was enthalpy-driven, the binding was accompanied by a net release of 1-2 ions, and no significant specific ion effects were observed. The van't Hoff plot of temperature dependence of binding was linear suggesting that the heat capacity change (Deltac(p)) was close to zero. Protein footprinting with hydroxyradicals showed that the protein did not change its conformation upon protein-DNA contact formation. No conformational changes in the DNA molecule were detected by CD spectroscopy upon protein-DNA complex formation. The thermodynamic characteristics of the binding together with the lack of significant conformational changes in the protein and in the DNA suggested that the alpha-subunit formed a rigid body-like contact with the DNA in which a tight complementary recognition interface between alpha-subunit and DNA was not formed.

Amino acidis derived from Titan tholins

NASA Technical Reports Server (NTRS)

Khare, Bishun N.; Sagan, Carl; Ogino, Hiroshi; Nagy, Bartholomew; Er, Cevat

1986-01-01

The production of amino acids by acid treatment of Titan tholin is experimentally investigated. The synthesis of Titan tholin and the derivatization of amino acids to N-trifluoroacetyl isopropyl esters are described. The gas chromatography/mass spectroscopy analysis of the Titan tholins reveals the presence of glycine, alpha and beta alainine, and aspartic acid, and the total yield of amino acids is about 0.01.

Interest of fluorine-19 nuclear magnetic resonance spectroscopy in the detection, identification and quantification of metabolites of anticancer and antifungal fluoropyrimidine drugs in human biofluids.

PubMed

Martino, Robert; Gilard, Véronique; Desmoulin, Franck; Malet-Martino, Myriam

2006-01-01

The metabolism of fluorouracil and fluorocytosine, two 5-fluoropyrimidine drugs in clinical use, was investigated. (19)F nuclear magnetic resonance (NMR) spectroscopy was used as an analytical technique for the detection, identification and quantification of fluorinated metabolites of these drugs in intact human biofluids as well as fluorinated degradation compounds of fluorouracil in commercial vials. (19)F NMR provides a highly specific tool for the detection and absolute quantification, in a single run, of all the fluorinated species, including unexpected substances, present in biofluids of patients treated with fluorouracil or fluorocytosine. Besides the parent drug and the already known fluorinated metabolites, nine new metabolites were identified for the first time with (19)F NMR in human biofluids. Six of them can only be observed with this technique: fluoride ion, N-carboxy-alpha-fluoro-beta-alanine, alpha-fluoro-beta-alanine conjugate with deoxycholic acid, 2-fluoro-3-hydroxypropanoic acid, fluoroacetic acid, O(2)-beta-glucuronide of fluorocytosine. (19)F NMR studies of biological fluids of patients treated with anticancer fluorouracil or antifungal fluorocytosine have furthered the understanding of their catabolic pathways.

Fluorine nuclear magnetic resonance spectroscopy of human biofluids in the field of metabolic studies of anticancer and antifungal fluoropyrimidine drugs.

PubMed

Malet-Martino, Myriam; Gilard, Véronique; Desmoulin, Franck; Martino, Robert

2006-04-01

Fluorine-19 nuclear magnetic resonance (19F NMR) spectroscopy provides a highly specific tool for the detection, identification and quantification of fluorine-containing drugs and their metabolites in biofluids. The value and difficulties encountered in investigations on drug metabolism are first discussed. Then the metabolism of three fluoropyrimidines in clinical use, 5-fluorouracil, 5-fluorocytosine and capecitabine are reported. Besides the parent drug and the already known fluorinated metabolites, 12 new metabolites were identified for the first time with 19F NMR in human biofluids. Nine of them can only be observed with this technique: fluoride ion, N-carboxy-alpha-fluoro-beta-alanine, alpha-fluoro-beta-alanine conjugate with deoxycholic acid, 2-fluoro-3-hydroxypropanoic acid, fluoroacetic acid, O2-beta-glucuronide of fluorocytosine, fluoroacetaldehyde hydrate and its adduct with urea, fluoromalonic acid semi-aldehyde adducts with urea. This emphasizes the high analytical potential of 19F NMR for the furtherance in the understanding of fluoropyrimidine catabolic pathways. 19F NMR should also play a role in the therapeutic monitoring of FU and its prodrugs in specific groups of patients, e.g. hemodialyzed patients or patients with deficiency in FU catabolic enzymes.

THE MISSING GOLIATH'S SLINGSHOT: MASSIVE BLACK HOLE RECOIL AT M83

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

Dottori, Horacio; Diaz, Ruben J.; Facundo Albacete-Colombo, Juan

2010-07-01

The Fanaroff-Riley II radio source J133658.3-295105, which is also an X-ray source, appears to be projected onto the disk of the barred-spiral galaxy M83 at about 60'' from the galaxy's optical nucleus. J133658.3-295105 and its radio lobes are aligned with the optical nucleus of M 83 and two other radio sources, neither of which are supernova remnants or H II regions. Due to this peculiar on-the-sky projection, J133658.3-295105 was previously studied by Gemini+GMOS optical spectroscopy, which marginally revealed the presence of H{alpha} in emission receding at 130 km s{sup -1} with respect to the optical nucleus. In this Letter, wemore » reanalyze the Chandra spectroscopy carried out in 2000. We show that J133658.3-295105 presents an Fe K{alpha} emission line at a redshift of z = 0.018. This redshift is compatible with a black hole at the distance of M 83. We discuss similarities to the recently reported micro-quasar in NGC 5408. This finding reinforces the kicked-off black hole scenario for J133658.3-295105.« less

Spectroscopic studies of model polar stratospheric cloud films

NASA Technical Reports Server (NTRS)

Tolbert, Margaret A.; Koehler, Birgit G.; Middlebrook, Ann M.

1993-01-01

Fourier transform infrared (FTIR) spectroscopy has been used to study nitric-acid/ice films representative of type I polar stratospheric clouds (PSCs). These studies reveal that in addition to amorphous nitric acid/ice mixtures, there are three stable stoichiometric hydrates of nitric acid: nitric-acid monohydrate (NAM), dihydrate (NAD), and trihydrate (NAT). We also observe two distinct crystalline forms of the trihydrate, which we denote alpha- and beta-NAT. These two forms appear to differ in their concentration of crystalline defects, but not in their chemical composition. In addition to probing the composition of type I PSCs, we have also used FTIR spectroscopy to study the interaction of HCl with model PSC films. In this work we find that for HCl pressures in the range 10 exp -5 to 10 exp -7 Torr, HCl is taken up by ice at 155 K to form a thin layer of HCl.6H2O. At 193 K, the uptake of HCl by ice was consistent with less than or equal to monolayer coverage. Uptake of HCl by alpha and beta-NAT at 175 K was also consistent with less than or equal to monolayer coverage.

Passive radon/thoron personal dosimeter using an electrostatic collector and a diffused-junction detector

NASA Astrophysics Data System (ADS)

Bigu, J.; Raz, R.

1985-01-01

A solid-state alpha dosimeter has been designed and tested suitable for personal and environmental radon/thoron monitoring. The dosimeter basically consists of an electrostatic collector and an alpha-particle counting system with spectroscopy capabilities. The sensitive volume (˜20 cm3) of the electrostatic collector consists of a cylindrically shaped metal wire screen and a diffused-junction silicon alpha-detector covered with a thin aluminized Mylar sheet. A dc voltage (˜500 V) is applied between the wire screen and the Mylar sheet, with the latter held at negative potential relative to the former. Data can be retrieved during or after sampling by means of a microcomputer (Epson HX20) via a RS-232 communication interface unit. The dosimeter has been calibrated in a large (26 m3) radon/thoron test facility. A linear relationship was found between the dosimeter's alpha-count and both radon gas concentration and radon daughter working level. The dosimeter is mounted on top of an ordinary miner's cap lamp battery and is ideally suited for personal monitoring in underground uranium mines and other working areas. The dosimeter presented here is a considerably improved version of an earlier prototype.

Preparation and Characterization of Cellulose Microcrystalline (MCC) from Fiber of Empty Fruit Bunch Palm Oil

NASA Astrophysics Data System (ADS)

Nasution, H.; Yurnaliza; Veronicha; Irmadani; Sitompul, S.

2017-03-01

Alpha cellulose which was isolated from cellulose of fiber empty fruit bunch palm oil was hidrolized with hydrochloric acid (2,5N) at 80°C to produce microcrystalline cellulose (MCC). Microcrystalline cellulose is an important additional ingredient in the pharmaceutical, food, cosmetics, and structural composites. In this study, MCC, alpha cellulose, and cellulose were characterized and thereafter were compared. Characterizations were made using some equipment such as x-ray diffraction (XRD), Fourier transform infrared (FTIR), scanning electron microscopy (SEM) and thermogravimetry analyzer (TGA). X-ray diffraction and infrared spectroscopy were studied to determine crystallinity and molecular structure of MCC, where scanning electron microscopy images were conducted for information about morfology of MCC. Meanwhile, thermal resistance of MCC was determined using thermogravimetry analyzer (TGA). From XRD and FTIR, the obtained results showed that the crystalline part was traced on MCC, where the -OH and C-O groups tended to reduced as alpha cellulose has changed to MCC. From SEM the image showed the reduction of particle size of MCC, while the thermal resistance of MCC was found lower as compared with cellulose and alpha cellulose as well, which was attributed to the lower molecular weight of MCC.

Biocatalytic synthesis of 4-pregnen-20,21-diol-3-one, a selective inhibitor of human 5alpha-reductase type II.

PubMed

Hannemann, Frank; Bernhardt, Rita; Jose, Joachim

2007-10-01

Biocatalysis, the conversion of substrates into valuable products by the use of enzymes, has some striking advantages in comparison to standard organic chemistry for drug synthesis. By biocatalysis, substrates that contain several identical reactive groups at different positions can be converted with high regio-selectivity and enantio-selectivity. In this study, an E. coli isolate (E132) was identified which was able to convert the steroid desoxycorticosterone into the product 4-pregnen-20,21-diol-3-one in real terms. The product was purified from the cell culture supernatant by HPLC and its structure was demonstrated by mass spectrometry and NMR spectroscopy. It was tested on inhibition of human 5alpha-reductases type I and type II. At a concentration of 10 microM, inhibition was 49.0% for type I and 81.8% for type II, whereas there was no inhibition of human aromatase (CYP19) at 20 microM and human 17alpha-hydroxylase-C17,20-lyase (CYP17) at 2.5 microM detectable. The IC50 value of 4-pregnen-20,21-diol-3-one for human 5alpha-reductase type II was determined to be 1.56 microM.

Time-Resolved Ultraviolet Spectroscopy of the M-Dwarf GJ 876 Exoplanetary System

NASA Technical Reports Server (NTRS)

France, Kevin; Linsky, Jeffrey L.; Tian, Feng; Froning, Cynthia S.; Roberge, Aki

2012-01-01

Extrasolar planets orbiting M-stars may represent our best chance to discover habitable worlds in the coming decade. The ultraviolet spectrum incident upon both Earth-like and Jovian planets is critically important for proper modeling of their atmospheric heating and chemistry. In order to provide more realistic inputs for atmospheric models of planets orbiting low-mass stars, we present new near- and far-ultraviolet (NUV and FUV) spectroscopy of the M-dwarf exoplanet host GJ 876 (U4V). Using the COS and STIS spectrographs aboard the Hubble Space Telescope, we have measured the 1150 - 3140 Ang. spectrum of GJ 876. We have reconstructed the stellar H I Ly-alpha emission line profile, and find that the integrated Ly-apha flux is roughly equal to the rest of the integrated flux (1150 - 1210 Ang + 1220 - 3140 Ang) in the entire ultraviolet bandpass (F(Ly-alpha)/F(FUV+NUV) approximately equals 0.7). This ratio is approximately 2500 x greater than the solar value. We describe the ultraviolet line spectrum and report surprisingly strong fluorescent emission from hot H2 (T(H2) > 2000 K). We show the light-curve of a chromospheric + transition region flare observed in several far-UV emission lines, with flare/ quiescent flux ratios :2: 10. The strong FUV radiation field of an M-star (and specifically Ly-alpha) is important for determining the abundance of O2 - and the formation of biomarkers - in the lower atmospheres of Earth-like planets in the habitable zones of low-mass stars.

Photometry and spectroscopy in the open cluster Alpha Persei, 2

NASA Technical Reports Server (NTRS)

Prosser, Charles F.

1993-01-01

Results from a combination of new spectroscopic and photometric observations in the lower main-sequence and pre-main sequence of the open cluster alpha Persei are presented. New echelle spectroscopy has provided radial and rotational velocity information for thirteen candidate members, three of which are nonmembers based on radial velocity, absence of a Li 6707A feature, and absence of H-alpha emission. A set of revised rotational velocity estimates for several slowly rotating candidates identified earlier is given, yielding rotational velocities as low as 7 km/s for two apparent cluster members. VRI photometry for several pre-main sequence members is given; the new (V,V-I(sub K)) photometry yields a more clearly defined pre-main sequence. A list of approximately 43 new faint candidate members based on the (V,V-I(sub K)) CCD photometry is presented in an effort to identify additional cluster members at very low masses. Low-dispersion spectra obtained for several of these candidates provide in some cases supporting evidence for cluster membership. The single brown dwarf candidate in this cluster is for the first time placed in a color-magnitude diagram with other cluster members, providing a better means for establishing its true status. Stars from among the list of new photometric candidates may provide the means for establishing a sequence of cluster members down to very faint magnitudes (V approximately 21) and consequently very low masses. New coordinate determinations for previous candidate members and finding charts for the new photometric candidates are provided in appendices.

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

Schwarz, R.B.; Bach, H.T.; Harms, U.

We used a resonant-ultrasound-spectroscopy technique to measure the three independent elastic constants of PdH{sub x}, PdD{sub x}, and PdT{sub x} single crystals at 300 K. For 0.1x0.62 our PdH{sub x} crystals are two-phase mixtures of coherent {alpha} and {beta} hydride phases. For increasing x in this range, C{sub 44} decreases monotonically whereas C'=12(C11-C12) has a concave parabolic dependence. This difference is because C' is softened by an anelastic relaxation resulting from acoustic-stress-induced changes in the shape of the coherent lenticular-shape precipitates ({beta}-hydride precipitates in {alpha}-hydride matrix and {alpha}-hydride precipitates in {beta}-hydride matrix). In the {beta}-phase C' and C{sub 44} decreasemore » with increasing hydrogen (or deuterium or tritium) content. Furthermore, C' exhibits a strong isotope effect whereas C{sub 44} does not. This effect is attributed to differences in the excitation of optical phonons in Pd-H, Pd-D and Pd-T.« less

24Mg(p, α) 21Na reaction study for spectroscopy of 21Na

DOE PAGES

Cha, S. M.; Chae, K. Y.; Kim, A.; ...

2015-11-03

The Mg-24(p, alpha)Na-21 reaction was measured at the Holifield Radioactive Ion Beam Facility at Oak Ridge National Laboratory in order to better constrain the spins and parities of the energy levels in Na-21 for the astrophysically important F-17(alpha, p)Ne-20 reaction rate calculation. 31-MeV proton beams from the 25-MV tandem accelerator and enriched Mg-24 solid targets were used. When recoiling He-4 particles from the Mg-24(p, alpha)Na-21 reaction we used a highly segmented silicon detector array to detect them; it measured the yields of He-4 particles over a range of angles simultaneously. A observed a new level at 6661 ± 5 keVmore » in the present work. The extracted angular distributions for the first four levels of Na-21 and the results from distorted wave Born approximation (DWBA) calculations were compared to verify and extract the angular momentum transfer.« less

Formation, isomerization, and derivatization of Keggin tungstoaluminates.

PubMed

Cowan, J J; Bailey, A J; Heintz, R A; Do, B T; Hardcastle, K I; Hill, C L; Weinstock, I A

2001-12-17

Trends in the stability of alpha- and beta-Keggin heteropolytungstates of the second-row main-group heteroatoms Al(III), Si(IV), and P(V) are elaborated by data that establish the roles of kinetic and thermodynamic control in the formation and isomerization of Keggin tungstoaluminates. Slow, room-temperature co-condensation of Al(III) and W(VI) (2:11 molar ratio) in water gives a pH 7 solution containing beta(1) and beta(2) isomers of [Al(AlOH(2))W(11)O(39)](6)(-) (beta(1)- and beta(2)-1). Partial equilibration of this kinetic product mixture by gentle heating (2 h at 100 degrees C) or, alternatively, co-condensation of Al(III) and W(VI) for 2.5 h at 100 degrees C both give mixtures of beta(2)-, beta(3)-, and alpha-1. Full equilibration, by prolonged heating (25 days at 100 degrees C), gives an isomerically pure solution of alpha-1, thus demonstrating that isomerization occurs in the direction beta(1) --> beta(2) --> beta(3) --> alpha. Furthermore, kinetically controlled conversions of 1 to H(5)[AlW(12)O(40)] (2)-achieved by heating pH 0-0.2 solutions of 1 for 5 days at 100 degrees C-occur with retention of isomeric integrity, such that alpha-1 is converted to alpha-2 (92%; 8% beta), while mixtures of beta(2)- and beta(3)-1 are converted to beta-2 (87%; 13% alpha). These data, when combined with previously reported observations (equilibria between alpha- and beta-2, kinetically controlled hydrolyses of alpha-2 to alpha-[AlW(11)O(39)](9)(-) (alpha-3) and of beta-2 to beta(2)-3, and equilibria between beta(3)- and alpha-3), provide a comprehensive picture regarding the roles of kinetic and thermodynamic control. Finally, a general method for preparation of the isomerically pure derivatives alpha-K(9)(-)(n)()[AlM(n)()(+)W(11)O(39)] (4), M(n)()(+) = Al(III), [V(IV)O](2+), [V(V)O](3+), Mn(II), Mn(III), Mn(IV), Co(II), and Co(III), is provided. The presence of Mn(IV) is confirmed by cyclic voltammetry, pK(a) values of the aquo ligands on 4 are determined by pH titration, and the isomeric structure of these derivatives is established by (27)Al, (51)V, and (183)W NMR and IR spectroscopies and X-ray crystallography.

Deconvolution of the relaxations associated with local and segmental motions in poly(methacrylate)s containing dichlorinated benzyl moieties in the ester residue.

PubMed

Dominguez-Espinosa, Gustavo; Díaz-Calleja, Ricardo; Riande, Evaristo; Gargallo, Ligia; Radic, Deodato

2005-09-15

The relaxation behavior of poly(2,3-dichlorobenzyl methacrylate) is studied by broadband dielectric spectroscopy in the frequency range of 10(-1)-10(9) Hz and temperature interval of 303-423 K. The isotherms representing the dielectric loss of the glassy polymer in the frequency domain present a single absorption, called beta process. At temperatures close to Tg, the dynamical alpha relaxation already overlaps with the beta process, the degree of overlapping increasing with temperature. The deconvolution of the alpha and beta relaxations is facilitated using the retardation spectra calculated from the isotherms utilizing linear programming regularization parameter techniques. The temperature dependence of the beta relaxation presents a crossover associated with a change in activation energy of the local processes. The distance between the alpha and beta peaks, expressed as log(fmax;beta/fmax;alpha) where fmax is the frequency at the peak maximum, follows Arrhenius behavior in the temperature range of 310-384 K. Above 384 K, the distance between the peaks remains nearly constant and, as a result, the a onset temperature exhibited for many polymers is not reached in this system. The fraction of relaxation carried out through the alpha process, without beta assistance, is larger than 60% in the temperature range of 310-384 K where the so-called Williams ansatz holds.

Carotenoid stoichiometry in the LH2 crystal: no spectral evidence for the presence of the second molecule in the alpha/beta-apoprotein dimer.

PubMed

Gall, Andrew; Gardiner, Alastair T; Cogdell, Richard J; Robert, Bruno

2006-07-10

In this work we have investigated the carotenoid-protein interactions in LH2 complexes of Rhodopseudomonas acidophila both in "free in solution" mixed-micelles and in three-dimensional crystals by Raman spectroscopy in resonance with the carotenoid (Car) molecules. We show that the Car molecules when bound to their binding pockets show no significant differences when the complexes are "free in solution" or packed in crystalline arrays. Furthermore, there is no significant wavelength dependence in the Raman spectrum of the Car molecules of LH2. This indicates that there is only one Car configuration in LH2 and thus only one molecule per alpha/beta-heterodimer.

Solar flares

NASA Technical Reports Server (NTRS)

Zirin, H.

1974-01-01

A review of the knowledge about solar flares which has been obtained through observations from the earth and from space by various methods. High-resolution cinematography is best carried out at H-alpha wavelengths to reveal the structure, time history, and location of flares. The classification flares in H alpha according to either physical or morphological criteria is discussed. The study of flare morphology, which shows where, when, and how flares occur, is important for evaluating theories of flares. Consideration is given to studies of flares by optical spectroscopy, radio emissions, and at X-ray and XUV wavelengths. Research has shown where and possibly why flares occur, but the physics of the instability involved, of the particle acceleration, and of the heating are still not understood.

Electronic and transformation properties of a metastable defect introduced in epitaxially grown boron-doped p-type Si by alpha particle irradiation

NASA Astrophysics Data System (ADS)

Mamor, M.; Auret, F. D.; Goodman, S. A.; Meyer, W. E.; Myburg, G.

1998-06-01

Titanium (Ti) Schottky barrier diodes on epitaxially grown boron-doped p-type Si films with a free carrier density of 6-8×1016cm-3 were irradiated with alpha particles at room temperature using an americium-241 (Am-241) radio nuclide. We report the electronic and transformation characteristics of an α-particle irradiation-induced defect Hα2 in epitaxially grown p-Si with metastable properties. The energy level and apparent capture cross section, as determined by deep-level transient spectroscopy, are Ev+0.43 eV and 1.4×10-15 cm2, respectively. This defect can be removed and re-introduced using a conventional bias-on/off cooling technique.

Transition from overlayer growth to alloying growth of Ga on Si(111)-alpha-(sqrt[3]xsqrt[3])-Au.

PubMed

Yamanaka, T; Ino, S

2002-11-04

Atomic depth distribution and growth modes of Ga on an Si(111)-alpha-(sqrt[3]xsqrt[3])-Au surface at room temperature were studied after each monolayer deposition of Ga via reflection high-energy electron diffraction and characteristic x-ray spectroscopy measurements as functions of glancing angle theta(g) of the incident electron beam. One monolayer of Ga grew on the Au layer, and the sqrt[3]xsqrt[3] periodicity was conserved below the Ga overlayer. Above a critical Ga coverage of about one monolayer, this growth mode drastically changed; i.e., Au atoms dissociated from the sqrt[3]xsqrt[3] structure and Ga grew into islands of Ga-Au alloy.

Serotonergic neurotoxic metabolites of ecstasy identified in rat brain.

PubMed

Jones, Douglas C; Duvauchelle, Christine; Ikegami, Aiko; Olsen, Christopher M; Lau, Serrine S; de la Torre, Rafael; Monks, Terrence J

2005-04-01

The selective serotonergic neurotoxicity of 3,4-methylenedioxyamphetamine (MDA) and 3,4-methylenedioxymethamphetamine (MDMA, ecstasy) depends on their systemic metabolism. We have recently shown that inhibition of brain endothelial cell gamma-glutamyl transpeptidase (gamma-GT) potentiates the neurotoxicity of both MDMA and MDA, indicating that metabolites that are substrates for this enzyme contribute to the neurotoxicity. Consistent with this view, glutathione (GSH) and N-acetylcysteine conjugates of alpha-methyl dopamine (alpha-MeDA) are selective neurotoxicants. However, neurotoxic metabolites of MDMA or MDA have yet to be identified in brain. Using in vivo microdialysis coupled to liquid chromatography-tandem mass spectroscopy and a high-performance liquid chromatography-coulometric electrode array system, we now show that GSH and N-acetylcysteine conjugates of N-methyl-alpha-MeDA are present in the striatum of rats administered MDMA by subcutaneous injection. Moreover, inhibition of gamma-GT with acivicin increases the concentration of GSH and N-acetylcysteine conjugates of N-methyl-alpha-MeDA in brain dialysate, and there is a direct correlation between the concentrations of metabolites in dialysate and the extent of neurotoxicity, measured by decreases in serotonin (5-HT) and 5-hydroxyindole acetic (5-HIAA) levels. Importantly, the effects of acivicin are independent of MDMA-induced hyperthermia, since acivicin-mediated potentiation of MDMA neurotoxicity occurs in the context of acivicin-mediated decreases in body temperature. Finally, we have synthesized 5-(N-acetylcystein-S-yl)-N-methyl-alpha-MeDA and established that it is a relatively potent serotonergic neurotoxicant. Together, the data support the contention that MDMA-mediated serotonergic neurotoxicity is mediated by the systemic formation of GSH and N-acetylcysteine conjugates of N-methyl-alpha-MeDA (and alpha-MeDA). The mechanisms by which such metabolites access the brain and produce selective serotonergic neurotoxicity remain to be determined.

Choline kinase-alpha by regulating cell aggressiveness and drug sensitivity is a potential druggable target for ovarian cancer.

PubMed

Granata, A; Nicoletti, R; Tinaglia, V; De Cecco, L; Pisanu, M E; Ricci, A; Podo, F; Canevari, S; Iorio, E; Bagnoli, M; Mezzanzanica, D

2014-01-21

Aberrant choline metabolism has been proposed as a novel cancer hallmark. We recently showed that epithelial ovarian cancer (EOC) possesses an altered MRS-choline profile, characterised by increased phosphocholine (PCho) content to which mainly contribute over-expression and activation of choline kinase-alpha (ChoK-alpha). To assess its biological relevance, ChoK-alpha expression was downmodulated by transient RNA interference in EOC in vitro models. Gene expression profiling by microarray analysis and functional analysis was performed to identify the pathway/functions perturbed in ChoK-alpha-silenced cells, then validated by in vitro experiments. In silenced cells, compared with control, we observed: (I) a significant reduction of both CHKA transcript and ChoK-alpha protein expression; (II) a dramatic, proportional drop in PCho content ranging from 60 to 71%, as revealed by (1)H-magnetic spectroscopy analysis; (III) a 35-36% of cell growth inhibition, with no evidences of apoptosis or modification of the main cellular survival signalling pathways; (IV) 476 differentially expressed genes, including genes related to lipid metabolism. Ingenuity pathway analysis identified cellular functions related to cell death and cellular proliferation and movement as the most perturbed. Accordingly, CHKA-silenced cells displayed a significant delay in wound repair, a reduced migration and invasion capability were also observed. Furthermore, although CHKA silencing did not directly induce cell death, a significant increase of sensitivity to platinum, paclitaxel and doxorubicin was observed even in a drug-resistant context. We showed for the first time in EOC that CHKA downregulation significantly decreased the aggressive EOC cell behaviour also affecting cells' sensitivity to drug treatment. These observations open the way to further analysis for ChoK-alpha validation as a new EOC therapeutic target to be used alone or in combination with conventional drugs.

Optical and interfacial electronic properties of diamond-like carbon films

NASA Technical Reports Server (NTRS)

Woollam, J. A.; Natarajan, V.; Lamb, J.; Khan, A. A.; Bu-Abbud, G.; Banks, B.; Pouch, J.; Gulino, D. A.; Domitz, S.; Liu, D. C.

1984-01-01

Hard, semitransparent carbon films were prepared on oriented polished crystal wafers of silicon, indium phosphide and gallium arsenide, as well as on KBr and quartz. Properties of the films were determined using IR and visible absorption spectrocopy, ellipsometry, conductance-capacitance spectroscopy and alpha particle-proton recoil spectroscopy. Preparation techniques include RF plasma decomposition of methane (and other hydrocarbons), ion beam sputtering, and dual-ion-beam sputter deposition. Optical energy band gaps as large as 2.7 eV and extinction coefficients lower than 0.1 at long wavelengths are found. Electronic state densities at the interface with silicon as low as 10 to the 10th states/eV sq cm per were found.

Effects of temperature and SDS on the structure of beta-glycosidase from the thermophilic archaeon Sulfolobus solfataricus.

PubMed Central

D'auria, S; Barone, R; Rossi, M; Nucci, R; Barone, G; Fessas, D; Bertoli, E; Tanfani, F

1997-01-01

The effects of temperature and SDS on the three-dimensional organization and secondary structure of beta-glycosidase from the thermophilic archaeon Sulfolobus solfataricus were investigated by CD, IR spectroscopy and differential scanning calorimetry. CD spectra in the near UV region showed that the detergent caused a remarkable change in the protein tertiary structure, and far-UV CD analysis revealed only a slight effect on secondary structure. Infrared spectroscopy showed that low concentrations of the detergent (up to 0.02%) induced slight changes in the enzyme secondary structure, whereas high concentrations caused the alpha-helix content to increase at high temperatures and prevented protein aggregation. PMID:9169619

Disaster Relief and Emergency Medical Services Project (DREAMS TM): Science, Triage and Treatment (STAT)

DTIC Science & Technology

2004-10-01

and necrosis using CT, magnetic resonance, thermal imaging, and near-infrared spectroscopy. These have led to numerous publications, patents, products...Willerson, Buja, Litovsky) 13. Project II.D ....................................... 99 Thermal Detection and Treatment of Inflammation and Necrosis ...2002). ,’Endotoxin stress- response in cardiomyocytes: NF-kappaB• activation and tumor necrosis factor-alpha expression," Am J Physiol Heart Circ Physiol

Raman analysis of ancient pigments on a tile from the Citadel of Algiers.

PubMed

Kock, L D; De Waal, D

2008-12-15

A micro-Raman spectroscopy study of a multi-coloured (yellow, blue, white, redish-brown and brown-black) tile shard from the Citadel of Algiers was undertaken. XRD and EDX were used as complementary techniques. The study shows that the heterogeneous three-shade yellow pigment on the tile is composed largely of the ancient ternary (Pb-Sn-Sb) pyrochlore oxide with a dominant Pb-O vibration at 127 cm(-1) consistent with the Pb2SnSbO6.5 structure as verified by XRD. The literature assignment of this band at 132 cm(-1) probably comes from a mixture of pigments. The redish-brown and the brown-black pigments are found to be Naples yellow (Pb2Sb2O7) and lead(II) stannate (Pb2SnO4), respectively, while cobalt blue (CoAl2O4) gives the blue colour and cassiterite (SnO2) is the origin of the white colour. The bulk of the tile body is composed mainly of hematite (alpha-Fe2O3), maghemite (gamma-Fe2O3), magnetite (Fe3O4) and Quartz (alpha-SiO2) with traces of calcite (CaCO3) and amorphous carbon. Micro-Raman spectroscopy proved to be very useful in the characterization of pigments as well as the tile body. These results further establish Raman spectroscopy as a technique of choice for the analysis of pigments on archaeological artifacts. The results obtained here could be used in the restoration and preservation programme of the Citadel itself which stands today as a symbol of pre-colonial Algerian heritage.

Treatment of solid tumors by interstitial release of recoiling short-lived alpha emitters

NASA Astrophysics Data System (ADS)

Arazi, L.; Cooks, T.; Schmidt, M.; Keisari, Y.; Kelson, I.

2007-08-01

A new method utilizing alpha particles to treat solid tumors is presented. Tumors are treated with interstitial radioactive sources which continually release short-lived alpha emitting atoms from their surface. The atoms disperse inside the tumor, delivering a high dose through their alpha decays. We implement this scheme using thin wire sources impregnated with 224Ra, which release by recoil 220Rn, 216Po and 212Pb atoms. This work aims to demonstrate the feasibility of our method by measuring the activity patterns of the released radionuclides in experimental tumors. Sources carrying 224Ra activities in the range 10-130 kBq were used in experiments on murine squamous cell carcinoma tumors. These included gamma spectroscopy of the dissected tumors and major organs, Fuji-plate autoradiography of histological tumor sections and tissue damage detection by Hematoxylin-Eosin staining. The measurements focused on 212Pb and 212Bi. The 220Rn/216Po distribution was treated theoretically using a simple diffusion model. A simplified scheme was used to convert measured 212Pb activities to absorbed dose estimates. Both physical and histological measurements confirmed the formation of a 5-7 mm diameter necrotic region receiving a therapeutic alpha-particle dose around the source. The necrotic regions shape closely corresponded to the measured activity patterns. 212Pb was found to leave the tumor through the blood at a rate which decreased with tumor mass. Our results suggest that the proposed method, termed DART (diffusing alpha-emitters radiation therapy), may potentially be useful for the treatment of human patients.

A Mossbauer investigation of iron-rich terrestrial hydrothermal vent systems: lessons for Mars exploration.

PubMed

Wade, M L; Agresti, D G; Wdowiak, T J; Armendarez, L P; Farmer, J D

1999-04-25

Hydrothermal spring systems may well have been present on early Mars and could have served as a habitat for primitive life. The integrated instrument suite of the Athena Rover has, as a component on the robotic arm, a Mossbauer spectrometer. In the context of future Mars exploration we present results of Mossbauer analysis of a suite of samples from an iron-rich thermal spring in the Chocolate Pots area of Yellowstone National Park (YNP) and from Obsidian Pool (YNP) and Manitou Springs, Colorado. We have found that Mossbauer spectroscopy can discriminate among the iron-bearing minerals in our samples. Those near the vent and on the surface are identified as ferrihydrite, an amorphous ferric mineraloid. Subsurface samples, collected from cores, which are likely to have undergone inorganic and/or biologically mediated alteration (diagenesis), exhibit spectral signatures that include nontronite (a smectite clay), hematite (alpha-Fe2O3), small-particle/nanophase goethite (alpha-FeOOH), and siderite (FeCO3). We find for iron minerals that Mossbauer spectroscopy is at least as efficient in identification as X-ray diffraction. This observation is important from an exploration standpoint. As a planetary surface instrument, Mossbauer spectroscopy can yield high-quality spectral data without sample preparation (backscatter mode). We have also used field emission scanning electron microscopy (FESEM), in conjunction with energy-dispersive X ray (EDX) fluorescence spectroscopy, to characterize the microbiological component of surface sinters and the relation between the microbiological and the mineralogical framework. Evidence is presented that the minerals found in these deposits can have multi-billion-year residence times and thus may have survived their possible production in a putative early Martian hot spring up to the present day. Examples include the nanophase property and the Mossbauer signature for siderite, which has been identified in a 2.09-billion-year old hematite-rich chert stromatolite. Our research demonstrates that in situ Mossbauer spectroscopy can help determine whether hydrothermal mineral deposits exist on Mars, which is significant for exobiology because of the issue of whether that world ever had conditions conductive to the origin of life. As a useful tool for selection of samples suitable for transport to Earth, Mossbauer spectroscopy will not only serve geological interests but will also have potential for exopaleontology.

A Mossbauer investigation of iron-rich terrestrial hydrothermal vent systems: lessons for Mars exploration

NASA Technical Reports Server (NTRS)

Wade, M. L.; Agresti, D. G.; Wdowiak, T. J.; Armendarez, L. P.; Farmer, J. D.

1999-01-01

Hydrothermal spring systems may well have been present on early Mars and could have served as a habitat for primitive life. The integrated instrument suite of the Athena Rover has, as a component on the robotic arm, a Mossbauer spectrometer. In the context of future Mars exploration we present results of Mossbauer analysis of a suite of samples from an iron-rich thermal spring in the Chocolate Pots area of Yellowstone National Park (YNP) and from Obsidian Pool (YNP) and Manitou Springs, Colorado. We have found that Mossbauer spectroscopy can discriminate among the iron-bearing minerals in our samples. Those near the vent and on the surface are identified as ferrihydrite, an amorphous ferric mineraloid. Subsurface samples, collected from cores, which are likely to have undergone inorganic and/or biologically mediated alteration (diagenesis), exhibit spectral signatures that include nontronite (a smectite clay), hematite (alpha-Fe2O3), small-particle/nanophase goethite (alpha-FeOOH), and siderite (FeCO3). We find for iron minerals that Mossbauer spectroscopy is at least as efficient in identification as X-ray diffraction. This observation is important from an exploration standpoint. As a planetary surface instrument, Mossbauer spectroscopy can yield high-quality spectral data without sample preparation (backscatter mode). We have also used field emission scanning electron microscopy (FESEM), in conjunction with energy-dispersive X ray (EDX) fluorescence spectroscopy, to characterize the microbiological component of surface sinters and the relation between the microbiological and the mineralogical framework. Evidence is presented that the minerals found in these deposits can have multi-billion-year residence times and thus may have survived their possible production in a putative early Martian hot spring up to the present day. Examples include the nanophase property and the Mossbauer signature for siderite, which has been identified in a 2.09-billion-year old hematite-rich chert stromatolite. Our research demonstrates that in situ Mossbauer spectroscopy can help determine whether hydrothermal mineral deposits exist on Mars, which is significant for exobiology because of the issue of whether that world ever had conditions conductive to the origin of life. As a useful tool for selection of samples suitable for transport to Earth, Mossbauer spectroscopy will not only serve geological interests but will also have potential for exopaleontology.

di Synthesis and Characterization of the Platinum-Substituted Keggin Anion alpha-H2SiPtW11O404-

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

Klonowski, P; Goloboy, JC; Uribe-Romo, FJ

2014-12-15

Acidification of an aqueous solution of K8SiW11O39 and K2Pt(OH)(6) to pH 4 followed by addition of excess tetramethylammonium (TMA) chloride yielded a solid mixture of TMA salts of H2SiPtW11O404- (1) and SiW12O404- (2). The former was separated from the latter by extraction into an aqueous solution and converted into tetra-n-butylammonium (TBA) and potassium salts TBA-1 and K-1. The a-H2SiPtW11O404- was identified as a monosubstituted Keggin anion using elemental analysis, IR spectroscopy, X-ray crystallography, electrospray ionization mass spectrometry, Pt-195 NMR spectroscopy, (183)W NMR spectroscopy, and W-183-W-183 2D INADEQUATE NMR spectroscopy. Both TBA-1 and K-1 readily cocrystallized with their unsubstituted Keggin anionmore » salts, TBA-2 and K-2, respectively, providing an explanation for the historical difficulty of isolating certain platinum-substituted heteropolyanions in pure form.« less

CD and MCD of CytC3 and taurine dioxygenase: role of the facial triad in alpha-KG-dependent oxygenases.

PubMed

Neidig, Michael L; Brown, Christina D; Light, Kenneth M; Fujimori, Danica Galonić; Nolan, Elizabeth M; Price, John C; Barr, Eric W; Bollinger, J Martin; Krebs, Carsten; Walsh, Christopher T; Solomon, Edward I

2007-11-21

The alpha-ketoglutarate (alpha-KG)-dependent oxygenases are a large and diverse class of mononuclear non-heme iron enzymes that require FeII, alpha-KG, and dioxygen for catalysis with the alpha-KG cosubstrate supplying the additional reducing equivalents for oxygen activation. While these systems exhibit a diverse array of reactivities (i.e., hydroxylation, desaturation, ring closure, etc.), they all share a common structural motif at the FeII active site, termed the 2-His-1-carboxylate facial triad. Recently, a new subclass of alpha-KG-dependent oxygenases has been identified that exhibits novel reactivity, the oxidative halogenation of unactivated carbon centers. These enzymes are also structurally unique in that they do not contain the standard facial triad, as a Cl- ligand is coordinated in place of the carboxylate. An FeII methodology involving CD, MCD, and VTVH MCD spectroscopies was applied to CytC3 to elucidate the active-site structural effects of this perturbation of the coordination sphere. A significant decrease in the affinity of FeII for apo-CytC3 was observed, supporting the necessity of the facial triad for iron coordination to form the resting site. In addition, interesting differences observed in the FeII/alpha-KG complex relative to the cognate complex in other alpha-KG-dependent oxygenases indicate the presence of a distorted 6C site with a weak water ligand. Combined with parallel studies of taurine dioxygenase and past studies of clavaminate synthase, these results define a role of the carboxylate ligand of the facial triad in stabilizing water coordination via a H-bonding interaction between the noncoordinating oxygen of the carboxylate and the coordinated water. These studies provide initial insight into the active-site features that favor chlorination by CytC3 over the hydroxylation reactions occurring in related enzymes.

Allosteric regulation of tryptophan synthase channeling: the internal aldimine probed by trans-3-indole-3'-acrylate binding.

PubMed

Casino, Patricia; Niks, Dimitri; Ngo, Huu; Pan, Peng; Brzovic, Peter; Blumenstein, Lars; Barends, Thomas Reinier; Schlichting, Ilme; Dunn, Michael F

2007-07-03

Substrate channeling in the tryptophan synthase bienzyme complex from Salmonella typhimurium is regulated by allosteric interactions triggered by binding of ligand to the alpha-site and covalent reaction at the beta-site. These interactions switch the enzyme between low-activity forms with open conformations and high-activity forms with closed conformations. Previously, allosteric interactions have been demonstrated between the alpha-site and the external aldimine, alpha-aminoacrylate, and quinonoid forms of the beta-site. Here we employ the chromophoric l-Trp analogue, trans-3-indole-3'-acrylate (IA), and noncleavable alpha-site ligands (ASLs) to probe the allosteric properties of the internal aldimine, E(Ain). The ASLs studied are alpha-d,l-glycerol phosphate (GP) and d-glyceraldehyde 3-phosphate (G3P), and examples of two new classes of high-affinity alpha-site ligands, N-(4'-trifluoromethoxybenzoyl)-2-aminoethyl phosphate (F6) and N-(4'-trifluoromethoxybenzenesulfonyl)-2-aminoethyl phosphate (F9), that were previously shown to bind to the alpha-site by optical spectroscopy and X-ray crystal structures [Ngo, H., Harris, R., Kimmich, N., Casino, P., Niks, D., Blumenstein, L., Barends, T. R., Kulik, V., Weyand, M., Schlichting, I., and Dunn, M. F. (2007) Synthesis and characterization of allosteric probes of substrate channeling in the tryptophan synthase bienzyme complex, Biochemistry 46, 7713-7727]. The binding of IA to the beta-site is stimulated by the binding of GP, G3P, F6, or F9 to the alpha-site. The binding of ASLs was found to increase the affinity of the beta-site of E(Ain) for IA by 4-5-fold, demonstrating for the first time that the beta-subunit of the E(Ain) species undergoes a switching between low- and high-affinity states in response to the binding of ASLs.

Investigation of storage-phosphor autoradiography for the rapid quantitative screening of air filters for emergency response purposes

NASA Astrophysics Data System (ADS)

Gallardo, Athena Marie

Past nuclear accidents, such as Chernobyl, resulted in a large release of radionuclides into the atmosphere. Radiological assessment of the vicinity of the site of the incident is vital to assess the exposure levels and dose received by the population and workers. Therefore, it is critical to thoroughly understand the situation and risks associated with a particular event in a timely manner in order to properly manage the event. Current atmospheric radiological assessments of alpha emitting radioisotopes include acquiring large quantities of air samples, chemical separation of radionuclides, sample mounting, counting through alpha spectrometry, and analysis of the data. The existing methodology is effective, but time consuming and labor intensive. Autoradiography, and the properties of phosphor imaging films, may be used as an additional technique to facilitate and expedite the alpha analysis process in these types of situations. Although autoradiography is not as sensitive to alpha radiation as alpha spectrometry, autoradiography may benefit alpha analysis by providing information about the activity as well as the spatial distribution of radioactivity in the sample under investigation. The objective for this research was to develop an efficient method for quantification and visualization of air filter samples taken in the aftermath of a nuclear emergency through autoradiography using 241Am and 239Pu tracers. Samples containing varying activities of either 241Am or 239Pu tracers were produced through microprecipitation and assayed by alpha spectroscopy. The samples were subsequently imaged and an activity calibration curve was produced by comparing the digital light units recorded from the image to the known activity of the source. The usefulness of different phosphor screens was examined by exposing each type of film to the same standard nuclide for varying quantities of time. Unknown activity samples created through microprecipiation containing activities of either 241Am or 239Pu as well as air filters doped with beta and alpha emitting nuclides were imaged and activities were determined by comparing the image to the activity calibration curve.

DEEP LBT/LUCI SPECTROSCOPY OF AN Ly{alpha} EMITTER CANDIDATE AT z {approx_equal} 7.7

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

Jiang Linhua; Bian Fuyan; Fan Xiaohui

2013-07-01

We present deep spectroscopic observations of an Ly{alpha} emitter (LAE) candidate at z {approx_equal} 7.7 using the infrared spectrograph LUCI on the 2 Multiplication-Sign 8.4 m Large Binocular Telescope (LBT). The candidate is the brightest among the four z {approx_equal} 7.7 LAE candidates found in a narrowband imaging survey by Krug et al. Our spectroscopic data include a total of 7.5 hr of integration with LBT/LUCI and are deep enough to significantly (3.2{sigma}-4.9{sigma}) detect the Ly{alpha} emission line of this candidate based on its Ly{alpha} flux 1.2 Multiplication-Sign 10{sup -17} erg s{sup -1} cm{sup -2} estimated from the narrowband photometry.more » However, we do not find any convincing signal at the expected position of its Ly{alpha} emission line, suggesting that this source is not an LAE at z {approx_equal} 7.7. The non-detection in this work, together with the previous studies of z {approx_equal} 7.7 LAEs, puts a strong constraint on the bright-end Ly{alpha} luminosity function (LF) at z {approx_equal} 7.7. We find a rapid evolution of the Ly{alpha} LF from z {approx_equal} 6.5 to 7.7: the upper limit of the z {approx_equal} 7.7 LF is more than five times lower than the z {approx_equal} 6.5 LF at the bright end (f{>=} 1.0 Multiplication-Sign 10{sup -17} erg s{sup -1} cm{sup -2} or L{>=} 6.9 Multiplication-Sign 10{sup 42} erg s{sup -1}). This is likely caused by an increasing neutral fraction in the intergalactic medium that substantially attenuates Ly{alpha} emission at z {approx_equal} 7.7.« less

Mapping alpha-helical induced folding within the intrinsically disordered C-terminal domain of the measles virus nucleoprotein by site-directed spin-labeling EPR spectroscopy.

PubMed

Belle, Valérie; Rouger, Sabrina; Costanzo, Stéphanie; Liquière, Elodie; Strancar, Janez; Guigliarelli, Bruno; Fournel, André; Longhi, Sonia

2008-12-01

Using site-directed spin-labeling EPR spectroscopy, we mapped the region of the intrinsically disordered C-terminal domain of measles virus nucleoprotein (N(TAIL)) that undergoes induced folding. In addition to four spin-labeled N(TAIL) variants (S407C, S488C, L496C, and V517C) (Morin et al. (2006), J Phys Chem 110: 20596-20608), 10 new single-site cysteine variants were designed, purified from E. coli, and spin-labeled. These 14 spin-labeled variants enabled us to map in detail the gain of rigidity of N(TAIL) in the presence of either the secondary structure stabilizer 2,2,2-trifluoroethanol or the C-terminal domain X (XD) of the viral phosphoprotein. Different regions of N(TAIL) were shown to contribute to a different extent to the binding to XD, while the mobility of the spin labels grafted at positions 407 and 460 was unaffected upon addition of XD; that of the spin labels grafted within the 488-502 and the 505-522 regions was severely and moderately reduced, respectively. Furthermore, EPR experiments in the presence of 30% sucrose allowed us to precisely map to residues 488-502, the N(TAIL) region undergoing alpha-helical folding. The mobility of the 488-502 region was found to be restrained even in the absence of the partner, a behavior that could be accounted for by the existence of a transiently populated folded state. Finally, we show that the restrained motion of the 505-522 region upon binding to XD is due to the alpha-helical transition occurring within the 488-502 region and not to a direct interaction with XD.

Solid-state NMR characterization of copolymers of nylon 11 and nylon 12.

PubMed

Johnson, C G; Mathias, L J

1997-05-01

Solid-state 13C and 15N NMR spectroscopy, in conjunction with differential scanning calorimetry, wide-angle X-ray diffraction and infrared spectroscopy, were used to characterize a series of nylon 11 and 12 copolymers with mole percentages of nylon 12 monomer of 0, 15, 35, 50, 65, 85, and 100%. Monotonic melting point (Tm) and heat of fusion depressions were observed for the copolymer series with the 65 mol% nylon 12 copolymer having the lowest apparent crystallinity and Tm at 148 degrees C. Solid-state 15N NMR spectra showed a smooth shift of the main peak position for the as-prepared copolymers from 84 ppm for the alpha-form of pure nylon 11 to 89 ppm for the gamma-form of pure nylon 12. Similar behavior was seen for FTIR amide V and VI modes which are also sensitive to the alpha- and gamma-crystal forms. 13C NMR T1 measurements showed that the overall most mobile sample was the 65:35 copolymer. The amide group of the 1:1 copolymer was labelled using 15N-labelled amino acids available through the Gabriel synthesis; an annealed, solution-cast film of this sample showed a T1N value of 349 s, similar to values seen for annealed nylon 11 and nylon 12 homopolymers. The WAXS pattern for the 65 mol% nylon 12 sample showed a sharp peak at 2 theta = 21.3, overlapping a broad peak centered at 2 theta = 21.0. These are consistent with the values seen for gamma-form nylon 12. The 1:1 copolymer (15N labelled) was shown to be polymorphic, like the homopolymers after specific treatments, with a gamma-like phase formed upon solvent casting, and an alpha-like phase dominating for as-polymerized material and precipitated flakes.

223Ra-dichloride spectrometric characterization: Searching for the presence of long-lived isotopes with radiological protection implications.

PubMed

Sánchez-Jiménez, J; López-Montes, A; Núñez-Martínez, L; Villa-Abaunza, A; Fraile, L M; Sánchez-Tembleque, V; Udías, J M

2017-03-01

223 Ra-dichloride was approved with the commercial name of Xofigo in 2014 for treatment of metastatic castration-resistant prostate cancer. 223 Ra is obtained by neutron irradiation of 226 Ra yielding 227 Ac, which decays to 227 Th and 223 Fr, both decaying to 223 Ra. Since 223 Ra is predominantly (95.3%) an alpha emitter with a 11.42days long half-life, the radiopharmaceutical, its remnants, the patient, and waste material can be managed and disposed with low radiation protection requirements. 227 Ac is a long-lived (T 1/2 =21.77years) beta emitter that demands strong radiation protection measures. In particular waste disposal has to follow the International Atomic Energy Agency (IAEA) and European Commission (EC) regulations. Since 227 Ac is involved in the production of 223 Ra, an impurity analysis of each batch is required after production. Due to time restrictions, the manufacturer's detection limit (<0.001%) exceeds the one required to assure that 227 Ac concentrations are below direct disposal levels. To improve the detection limit, long-term accurate spectroscopy is required. Alpha and gamma spectroscopy measurements were carried out at the Complutense University Nuclear Physics Laboratory. After twelve months follow up of a sample, 227 Ac concentration was found to be smaller than 10 -9 . This allows for direct waste disposal and no additional radiation protection restrictions than those required for 223 Ra. The presence of contamination by other radioisotopes was also ruled out by this experiment. Specifically 226 Ra, involved in 223 Ra production as the original parent and with a very long-lived (T 1/2 =1577years) alpha emitter, was also below the experimental detection limit. Copyright © 2017 Associazione Italiana di Fisica Medica. Published by Elsevier Ltd. All rights reserved.

Applying a low energy HPGe detector gamma ray spectrometric technique for the evaluation of Pu/Am ratio in biological samples.

PubMed

Singh, I S; Mishra, Lokpati; Yadav, J R; Nadar, M Y; Rao, D D; Pradeepkumar, K S

2015-10-01

The estimation of Pu/(241)Am ratio in the biological samples is an important input for the assessment of internal dose received by the workers. The radiochemical separation of Pu isotopes and (241)Am in a sample followed by alpha spectrometry is a widely used technique for the determination of Pu/(241)Am ratio. However, this method is time consuming and many times quick estimation is required. In this work, Pu/(241)Am ratio in the biological sample was estimated with HPGe detector based measurements using gamma/X-rays emitted by these radionuclides. These results were compared with those obtained from alpha spectroscopy of sample after radiochemical analysis and found to be in good agreement. Copyright © 2015 Elsevier Ltd. All rights reserved.

New cycloartane-type triterpenes from Marcetia latifolia (Melastomataceae) and in silico studies on Candida parapsilosis protease.

PubMed

Leite, Tonny C C; Leite, Franco H A; Vieira, Ivo J C; Braz Filho, Raimundo; Branco, Alexsandro

2013-08-01

We have previously reported the antimicrobial activity of the ethyl acetate extract of Marcetia latifolia, particularly against Candida parapsilosis. In this work we describe the isolation of two new cycloartane-type triterpenes, 28,29-bis-norcycloartan-3beta,4alpha-diol (1) and 28,29-bis-norcycloart-24-en-3beta,4alpha-diol (2) from the same extract. These compounds were mainly characterized by one- (1H, 13C and APT) and two-dimensional (1H-1H-COSY, 1H-1H-NOESY, HMQC and HMBC) NMR spectroscopy, mass spectrometry and comparison with published structural data. In addition, the activity of triterpenes 1 and 2 on the Candida protease target was investigated by in silico methods using molecular docking.

Biophysical insights into the interaction of clofazimine with human alpha 1-acid glycoprotein: a multitechnique approach.

PubMed

Ajmal, Mohammad Rehan; Almutairi, Fahad; Zaidi, Nida; Alam, Parvez; Siddiqi, Mohammad Khursheed; Khan, Mohsin Vahid; Zaman, Masihuz; Ishtikhar, Mohd; Khan, Rizwan Hasan

2018-04-25

Alpha1-acid glycoprotein (AAG) is a major acute phase protein of human plasma. Binding of clofazimine to AAG is investigated using optical spectroscopy and molecular docking tools. We found significant quenching of intrinsic fluorescence of AAG upon the binding of clofazimine, binding mode is static with binding constant of 3.52 × 10 4 at 298 K. The Gibbs free energy change is found to be negative for the interaction of clofazimine with AAG indicating spontaneity of the binding process. Binding of clofazimine induced ordered structure in protein and lead to molecular compaction. Molecular docking results indicate the binding site is located in the central beta barrel, hydrogen bonding and hydrophobic interactions are main bonding forces between AAG-clofazimine.

In vitro electron paramagnetic resonance characterization of free radicals: relevance to exercise-induced lipid peroxidation and implications of ascorbate prophylaxis.

PubMed

Davison, Gareth W; Ashton, Tony; Davies, Bruce; Bailey, Damian M

2008-04-01

This study tested the hypothesis that exercise-induced oxidative stress is caused by free radical-mediated damage to polyunsaturated fatty acids (PUFA) which can be prevented following ascorbate prophylaxis. Hyperfine coupling constants (HCC) of alpha-phenyl-tert-butylnitrone (PBN)-adducts were measured via room temperature electron paramagnetic resonance (EPR) spectroscopy in the venous blood of 12 subjects at rest and following maximal exercise during a randomized double-blind placebo-controlled trial and compared to those observed following room-air incubation (2 h at 37 degrees C) of L-alpha-phosphatidycholine, linoleic acid, alpha-linolenic acid and arachidonic acid. All adducts exhibited similar HCC [a(N) 13.6 Gauss (G) and a beta(H) 1.8 G] with the exception of L-alpha-phosphatidycholine [a(N1)=13.4 G, a beta(H1)=1.6 G (37%) and a(N2)=14.9 G, a beta(H2)=0.3 G (63%)] consistent with the trapping of lipid-derived alkoxyl and oleate radicals, respectively. Ascorbate pre-treatment ablated radical formation in both systems. These findings identify circulating PUFA as a potential source of secondary radicals that are capable of initiating oxidative stress in the exercising human.

Large Band Gap of alpha-RuCl3 Probed by Photoemission and Inverse Photoemission Spectroscopy

NASA Astrophysics Data System (ADS)

Sinn, Soobin; Kim, Choong Hyun; Sandilands, Luke; Lee, Kyungdong; Won, Choongjae; Oh, Ji Seop; Han, Moonsup; Chang, Young Jun; Hur, Namjung; Sato, Hitoshi; Park, Byeong-Gyu; Kim, Changyoung; Kim, Hyeong-Do; Noh, Tae Won

The Kitaev honeycomb lattice model has attracted great attention because of its possibility to stabilize a quantum spin liquid ground state. Recently, it was proposed that alpha-RuCl3 is its material realization and the first 4 d relativistic Mott insulator from an optical spectrum and LDA + U + SO calculations. Here, we present photoemission and inverse photoemission spectra of alpha-RuCl3. The observed band gap is about 1.8 eV, which suggests that the previously assigned optical gap of 0.3 eV is misinterpreted, and that the strong peak at about 1.2 eV in the optical spectrum may be associated with an actual optical gap. Assuming a strong excitonic effect of 0.6 eV in the optical spectrum, all the structures except for the peak at 0.3 eV are consistent with our electronic spectra. When compared with LDA + U + SO calculations, the value of U should be considerably larger than the previous one, which implies that the spin-orbit coupling is not a necessary ingredient for the insulating mechanism of alpha-RuCl3. We also present angle-resolved photoemission spectra to be compared with LDA + U + SO and LDA +DMFT calculations.

Conformational analysis of HAMLET, the folding variant of human alpha-lactalbumin associated with apoptosis.

PubMed

Casbarra, Annarita; Birolo, Leila; Infusini, Giuseppe; Dal Piaz, Fabrizio; Svensson, Malin; Pucci, Piero; Svanborg, Catharina; Marino, Gennaro

2004-05-01

A combination of hydrogen/deuterium (H/D) exchange and limited proteolysis experiments coupled to mass spectrometry analysis was used to depict the conformation in solution of HAMLET, the folding variant of human alpha-lactalbumin, complexed to oleic acid, that induces apoptosis in tumor and immature cells. Although near- and far-UV CD and fluorescence spectroscopy were not able to discriminate between HAMLET and apo-alpha-lactalbumin, H/D exchange experiments clearly showed that they correspond to two distinct conformational states, with HAMLET incorporating a greater number of deuterium atoms than the apo and holo forms. Complementary proteolysis experiments revealed that HAMLET and apo are both accessible to proteases in the beta-domain but showed substantial differences in accessibility to proteases at specific sites. The overall results indicated that the conformational changes associated with the release of Ca2+ are not sufficient to induce the HAMLET conformation. Metal depletion might represent the first event to produce a partial unfolding in the beta-domain of alpha-lactalbumin, but some more unfolding is needed to generate the active conformation HAMLET, very likely allowing the protein to bind the C18:1 fatty acid moiety. On the basis of these data, a putative binding site of the oleic acid, which stabilizes the HAMLET conformation, is proposed.

Sterol patterns of cultured zooxanthellae isolated from marine invertebrates: Synthesis of gorgosterol and 23-desmethylgorgosterol by aposymbiotic algae.

PubMed

Withers, N W; Kokke, W C; Fenical, W; Djerassi, C

1982-06-01

QUANTITATIVE STEROL COMPOSITIONS OF CULTURED ZOOXANTHELLAE ISOLATED FROM VARIOUS PACIFIC AND ATLANTIC INVERTEBRATE HOSTS: Zoanthus sociatus (a zoanthid), Oculina diffusa (a scleractian coral), Tridacna gigas (a giant clam), Melibe pilosa (a nudibranch), and Aiptasia pulchella (a sea anemone) are reported. The results clearly demonstrate large differences in sterol patterns of zooxanthellae and that there is no obvious relationship between the taxonomic affiliation of the host and the sterol pattern of its isolated symbiont. The sterols of the zooxanthellae of O. diffusa (Cnidaria) and T. gigas (Mollusca) are qualitatively equivalent. Based on the structures of the two major free sterols synthesized by each alga, the zooxanthellae from different hosts were separated into three distinct groups. It was also found that an aposymbiotic alga can synthesize the unique marine sterols gorgosterol and 23-desmethylgorgosterol. Most of the sterols were identified by using mass spectroscopy and 360-MHz proton magnetic resonance. Spectroscopic data are reported for four novel sterols-(23,24R)-dimethyl-5alpha-cholest-(22E)-en-3beta-o l, 23-methyl-5alpha-cholest-22E-en-3beta-ol, cholesta-5,14-dien-3beta-ol, and 4alpha-methyl-5alpha-cholesta-8(14)-24-dien-3beta-ol.

Radiation damage limits to XPCS studies of protein dynamics

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

Vodnala, Preeti, E-mail: preeti.vodnala@gmail.com; Karunaratne, Nuwan; Lurio, Laurence

2016-07-27

The limitations to x-ray photon correlation spectroscopy (XPCS) imposed by radiation damage have been evaluated for suspensions of alpha crystallin. We find that the threshold for radiation damage to the measured protein diffusion rate is significantly lower than the threshold for damage to the protein structure. We provide damage thresholds beyond which the measured diffusion coeffcients have been modified using both XPCS and dynamic light scattering (DLS).

Lattice gauge theory for QCD

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

DeGrand, T.

1997-06-01

These lectures provide an introduction to lattice methods for nonperturbative studies of Quantum Chromodynamics. Lecture 1: Basic techniques for QCD and results for hadron spectroscopy using the simplest discretizations; lecture 2: Improved actions--what they are and how well they work; lecture 3: SLAC physics from the lattice-structure functions, the mass of the glueball, heavy quarks and {alpha}{sub s} (M{sub z}), and B-{anti B} mixing. 67 refs., 36 figs.

A rapid method for quantification of 242Pu in urine using extraction chromatography and ICP-MS

DOE PAGES

Gallardo, Athena Marie; Than, Chit; Wong, Carolyn; ...

2017-01-01

Occupational exposure to plutonium is generally monitored through analysis of urine samples. Typically, plutonium is separated from the sample and other actinides, and the concentration is determined using alpha spectroscopy. Current methods for separations and analysis are lengthy and require long count times. A new method for monitoring occupational exposure levels of plutonium has been developed, which requires fewer steps and overall less time than the alpha spectroscopy method. In this method, the urine is acidified, and a 239Pu internal standard is added. The urine is digested in a microwave oven, and plutonium is separated using an Eichrom TRU Resinmore » column. The plutonium is eluted, and the eluant is injected directly into the Inductively Coupled Plasma–Mass Spectrometer (ICP-MS). Compared to a direct “dilute and shoot” method, a 30-fold improvement in sensitivity is achieved. This method was validated by analyzing several batches of spiked samples. Based on these analyses, a combined standard uncertainty plot, which relates uncertainty to concentration, was produced. As a result, the MDA 95 was calculated to be 7.0 × 10 –7 μg L –1, and the Lc95 was calculated to be 3.5 × 10 –7 μg L –1 for this method.« less

Visible region MCD and MLD spectra of nitrosylferrohemoglobin and oxyhemoglobin.

PubMed

Pearce, Linda L; Bominaar, Emile L; Peterson, Jim

2002-09-20

Magnetic circular dichroism (MCD) and magnetic linear dichroism (MLD) spectroscopies at various applied magnetic fields (0-6T) and temperatures (2.0-31K) have been used to investigate the electronic properties of the visible (Q(0-0), or alpha band) region of oxy- and nitrosylferrohemoglobin (HbNO). OxyHb, a d(6) (S=0) diamagnet, exhibits the expected pseudo-first derivative MCD and pseudo-second derivative MLD temperature-independent features centered at 574nm. HbNO, a d(7) (S=1/2) paramagnet, also exhibits a temperature-independent pseudo-first derivative MCD spectrum, but centered at 571nm. So far as we are aware, this behavior is unprecedented in the MCD spectra of paramagetic iron-porphyrins, which are expected to be dominated by temperature-dependent C(0) terms. The HbNO MCD spectrum does, however, demonstrate limited field-dependent saturation magnetization behavior and the MLD spectrum is currently below the detection limit. In addition, an MCD signal from reoxygenated venous blood is reported and compared with MCD signals from oxy- and HbNO derivatives. Finally, a combination of MCD and MLD spectroscopies has been used to estimate the orbital angular momentum (M(L)) value of the alpha band excited state of oxyHb as 4.2 (+/-0.7).

Design of a beam emission spectroscopy diagnostic for negative ions radio frequency source SPIDER

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

Zaniol, B.; Pasqualotto, R.; Barbisan, M.

2012-04-15

A facility will be built in Padova (Italy) to develop, commission, and optimize the neutral beam injection system for ITER. The full scale prototype negative ion radio frequency source SPIDER, featuring up to 100 kV acceleration voltage, includes a full set of diagnostics, required for safe operation and to measure and optimize the beam performance. Among them, beam emission spectroscopy (BES) will be used to measure the line integrated beam uniformity, divergence, and neutralization losses inside the accelerator (stripping losses). In the absence of the neutralization stage, SPIDER beam is mainly composed by H{sup -} or D{sup -} particles, accordingmore » to the source filling gas. The capability of a spectroscopic diagnostic of an H{sup -} (D{sup -}) beam relies on the interaction of the beam particles with the background gas particles. The BES diagnostic will be able to acquire the H{sub {alpha}} (D{sub {alpha}}) spectrum from up to 40 lines of sight. The system is capable to resolve stripping losses down to 2 keV and to measure beam divergence with an accuracy of about 10%. The design of this diagnostic is reported, with discussion of the layout and its components, together with simulations of the expected performance.« less

Dynamic nuclear protein interactions investigated using fluorescence lifetime and fluorescence fluctuation spectroscopy

NASA Astrophysics Data System (ADS)

Siegel, Amanda P.; Hays, Nicole M.; Day, Richard N.

2012-03-01

The discovery and engineering of novel fluorescent proteins (FPs) from diverse organisms is yielding fluorophores with exceptional characteristics for live-cell imaging. In particular, the development of FPs for Förster resonance energy transfer (FRET) microscopy and fluorescence fluctuation spectroscopy (FFS) provide important tools for monitoring dynamic protein interactions inside living cells. Fluorescence lifetime imaging microscopy (FLIM) quantitatively maps changes in the spatial distribution of donor FP lifetimes that result from FRET with acceptor FPs. FFS probes dynamic protein associations through its capacity to monitor localized protein diffusion. Here, we use FRET-FLIM combined with FFS in living cells to investigate changes in protein mobility due to protein-protein interactions involving transcription factors and chromatin modifying proteins that function in anterior pituitary gene regulation. The heterochromatin protein 1 alpha (HP1α) plays a key role in the establishment and maintenance of heterochromatin through its interactions with histone methyltransferases. Recent studies, however, also highlight the importance of HP1α as a positive regulator of active transcription in euchromatin. Intriguingly, we observed that the transcription factor CCAAT/enhancer-binding protein alpha (C/EBPα) interacts with HP1α in regions of pericentromeric heterochromatin in mouse pituitary cells. These observations prompted us to investigate the relationship between HP1α dynamic interactions in pituitary specific gene regulation.

Solution conformation of a peptide fragment representing a proposed RNA-binding site of a viral coat protein studied by two-dimensional NMR

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

van der Graaf, M.; van Mierlo, C.P.M.; Hemminga, M.A.

1991-06-11

The first 25 amino acids of the coat protein of cowpea chlorotic mottle virus are essential for binding the encapsidated RNA. Although an {alpha}-helical conformation has been predicted for this highly positively charged N-terminal region. No experimental evidence for this conformation has been presented so far. In this study, two-dimensional proton NMR experiments were performed on a chemically synthesized pentacosapeptide containing the first 25 amino acids of this coat protein. All resonances could be assigned by a combined use of two-dimensional correlated spectroscopy and nuclear Overhauser enhancement spectroscopy carried out at four different temperatures. Various NMR parameters indicate the presencemore » of a conformational ensemble consisting of helical structures rapidly converting into more extended states. Differences in chemical shifts and nuclear Overhauser effects indicate that lowering the temperature induces a shift of the dynamic equilibrium toward more helical structures. At 10{degrees}C, a perceptible fraction of the conformational ensemble consists of structures with an {alpha}-helical conformation between residues 9 and 17, likely starting with a turnlike structure around Thr9 and Arg10. Both the conformation and the position of this helical region agree well with the secondary structure predictions mentioned above.« less

Examination of the solventlike nature of zeolites based on a solvatochromic indicator

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

Dutta, P.K.; Turbeville, W.

1991-05-16

Zeolites are crystalline aluminosilicates with cages and channel systems that can host a variety of organic transformations. This intracrystalline space is akin to a solvent, and description of this space in terms of solventlike properties is appropriate. The concept of solvatochromic indicators has been successfully used to define the physicochemical properties of organic solvents. In this study, the authors have investigated the electronic and Raman spectroscopy of the molecule N-(2-hydroxybenzylidene)aniline and established a quantitative correlation between the spectral intensities of the benzenoid and zwitterionic forms of this molecule and the {alpha}-value of various hydroxylic solvents. The {alpha} value is amore » measure of the hydrogen bond donor ability of the solvent. This correlation has been used to establish an {alpha} value scale for a series of faujasitic zeolites with varying Si/Al ratios. It was found that the {alpha} value of the zeolite increased with Si/Al ratio to reach a maximum around 7.8, followed by a decrease at higher Si/Al ratios. Since Na{sup +}-exchanged zeolites were examined in all cases, the interaction of the anil molecule in its zwitterionic form with Lewis acids (Na{sup +}) and bases (oxygen of the framework) was considered to be responsible for its formation. The Si/Al ratio of the framework determines the acid-base character of the zeolite and is reflected in a quantitative manner by the {alpha} value determined in this study.« less

Electrical characterization of deep levels created by bombarding nitrogen-doped 4H-SiC with alpha-particle irradiation

NASA Astrophysics Data System (ADS)

Omotoso, Ezekiel; Meyer, Walter E.; Auret, F. Danie; Paradzah, Alexander T.; Legodi, Matshisa J.

2016-03-01

Deep-level transient spectroscopy (DLTS) and Laplace-DLTS were used to investigate the effect of alpha-particle irradiation on the electrical properties of nitrogen-doped 4H-SiC. The samples were bombarded with alpha-particles at room temperature (300 K) using an americium-241 (241Am) radionuclide source. DLTS revealed the presence of four deep levels in the as-grown samples, E0.09, E0.11, E0.16 and E0.65. After irradiation with a fluence of 4.1 × 1010 alpha-particles-cm-2, DLTS measurements indicated the presence of two new deep levels, E0.39 and E0.62 with energy levels, EC - 0.39 eV and EC - 0.62 eV, with an apparent capture cross sections of 2 × 10-16 and 2 × 10-14 cm2, respectively. Furthermore, irradiation with fluence of 8.9 × 1010 alpha-particles-cm-2 resulted in the disappearance of shallow defects due to a lowering of the Fermi level. These defects re-appeared after annealing at 300 °C for 20 min. Defects, E0.39 and E0.42 with close emission rates were attributed to silicon or carbon vacancy and could only be separated by using high resolution Laplace-DLTS. The DLTS peaks at EC - (0.55-0.70) eV (known as Z1/Z2) were attributed to an isolated carbon vacancy (VC).

Examination of the suitability of alpha-tocopherol as a stabilizer for ultra-high molecular weight polyethylene used for articulating surfaces in joint endoprostheses.

PubMed

Wolf, C; Krivec, T; Blassnig, J; Lederer, K; Schneider, W

2002-02-01

The lifetime of articulating surfaces in joint endoprostheses made of ultra-high molecular weight polyethylene (UHMW-PE), especially of UHMW-PE-cups of hip-endoprostheses, is usually limited to 10-15 years due to material failure as a result of oxidation of the UHMW-PE in vivo. In this study the suitability of the natural antioxidant alpha-tocopherol (vitamin E) as a stabilizer for UHMW-PE in these applications was investigated. Specimens with 0.1%, 0.2%, 0.4% and 0.8% w/w alpha-tocopherol as well as unstabilized samples were sintered and sterilized with gamma-rays at 25 kGy in accordance with standard processing methods of cups for total hip-endoprostheses. These specimens were aged in pure oxygen at 70 degrees C and 5 bar as well as in aqueous H2O2 at 50 degrees C. The degree of oxidation was observed by means of FTIR-spectroscopy, DSC analysis and mechanical testing. The FTIR-measurements showed that alpha-tocopherol can prolong the lifetime of UHMW-PE in an oxidative environment by a factor of more than 2.5. In the mechanical tests no embrittlement could be observed with the stabilized samples. A comparison with the standard antioxidant system Irganox 1010/Irgafos 168 (Ciba-Geigy, Switzerland) was carried out and revealed that alpha-tocopherol can even exceed the stabilization effect of this widely-used antioxidant system.

Semiconducting lithium indium diselenide: Charge-carrier properties and the impacts of high flux thermal neutron irradiation

NASA Astrophysics Data System (ADS)

Hamm, Daniel S.; Rust, Mikah; Herrera, Elan H.; Matei, Liviu; Buliga, Vladimir; Groza, Michael; Burger, Arnold; Stowe, Ashley; Preston, Jeff; Lukosi, Eric D.

2018-06-01

This paper reports on the charge carrier properties of several lithium indium diselenide (LISe) semiconductors. It was found that the charge collection efficiency of LISe was improved after high flux thermal neutron irradiation including the presence of a typically unobservable alpha peak from hole-only collection. Charge carrier trap energies of the irradiated sample were measured using photo-induced current transient spectroscopy. Compared to previous studies of this material, no significant differences in trap energies were observed. Through trap-filled limited voltage measurements, neutron irradiation was found to increase the density of trap states within the bulk of the semiconductor, which created a polarization effect under alpha exposure but not neutron exposure. Further, the charge collection efficiency of the irradiated sample was higher (14-15 fC) than that of alpha particles (3-5 fC), indicating that an increase in hole signal contribution resulted from the neutron irradiation. Finally, it was observed that significant charge loss takes place near the point of generation, producing a significant scintillation response and artificially inflating the W-value of all semiconducting LISe crystals.

Optical and UV spectroscopy of the peculiar RS CVn system RT Lacertae

NASA Technical Reports Server (NTRS)

Huenemoerder, D. P.; Barden, S. C.

1986-01-01

H-alpha and H-beta spectra of the peculiar double-lined RS CVn binary RT Lacertae have been obtained using the IUE, together with a ground-based coude-feed telescope at KPNO. The ground-based spectra show an asymmetry related to the orbital phase in the H-alpha profile. H-beta profiles showed excess emission in one hemisphere and excess absorption in the other, with a broad Gaussian emission component superposed on the excess H-alpha line. A radial velocity curve was derived to estimate the mass ratio and geometry of the system. It is shown that the component of RT Lac fills 80-90 percent of the equilibrium Roche surface. Low-resolution ultraviolet data show that the supposed cooler component is bluer than its companion, suggesting evidence of a scattering shell or a cloud produced by the splash of a gas stream. The phase behavior of the low resolution ultraviolet data support the conclusion that RT Lac is a mass transfer system and that mass transfer is the primary cause of its activity.

Probes of the catalytic site of cysteine dioxygenase.

PubMed

Chai, Sergio C; Bruyere, John R; Maroney, Michael J

2006-06-09

The first major step of cysteine catabolism, the oxidation of cysteine to cysteine sulfinic acid, is catalyzed by cysteine dioxygenase (CDO). In the present work, we utilize recombinant rat liver CDO and cysteine derivatives to elucidate structural parameters involved in substrate recognition and x-ray absorption spectroscopy to probe the interaction of the active site iron center with cysteine. Kinetic studies using cysteine structural analogs show that most are inhibitors and that a terminal functional group bearing a negative charge (e.g. a carboxylate) is required for binding. The substrate-binding site has no stringent restrictions with respect to the size of the amino acid. Lack of the amino or carboxyl groups at the alpha-carbon does not prevent the molecules from interacting with the active site. In fact, cysteamine is shown to be a potent activator of the enzyme without being a substrate. CDO was also rendered inactive upon complexation with the metal-binding inhibitors azide and cyanide. Unlike many non-heme iron dioxygenases that employ alpha-keto acids as cofactors, CDO was shown to be the only dioxygenase known to be inhibited by alpha-ketoglutarate.

The effect of alpha-particle and proton irradiation on the electrical and defect properties of n-GaAs

NASA Astrophysics Data System (ADS)

Goodman, S. A.; Auret, F. D.; Meyer, W. E.

1994-05-01

Radiation damage effects were studied in n-GaAs grown by organo-metallic vapour phase epitaxy (OMVPE) for a wide range of alpha-particle (2.0 MeV and 5.4 MeV) and proton (2.0 MeV) particle fluences, using an americium-241 (Am-241) radio-nuclide and a linear Van de Graaff accelerator as the particle sources. The samples were irradiated at 300 K, after fabricating palladium Schottky barrier diodes (SBDs) on the 1.2 × 10 16 cm 3 Si-doped epitaxial layers. The irradiation-induced defects are characterized using conventional deep level transient spectroscopy (DLTS). A correlation is made between the change in SBD characteristics and the quantity and type of defects introduced during irradiation. It is shown that the two parameters most susceptible to this irradiation are the reverse leakage current of the SBDs and the free carrier density of the epilayer. The introduction rate and the "signatures" of the alpha-particle and proton irradiation-induced defects are calculated and compared to those of similar defects introduced during electron irradiation.

[Peculiarities of secondary structure of serum albumin of some representatives of the animal kingdom].

PubMed

Pekhymenko, G V; Kuchmerovskaia, T M

2011-01-01

Methods of infrared (IR) spectroscopy and circular dichroism (CD) are suitable techniques for detection of proteins structural changes. These methods were used for determinating peculiarities of the secondary structure of serum albumins in some representatives of two classes of reptiles: Horsfield's tortoise (Testudo horsfieldi), water snake (Natrix tessellata) and grass snake (Natrix natrix) and birds: domestic goose (Anser anser), domestic chicken (Gallus domesticus), domestic duck (Anas platyrhyncha) and dove colored (Columba livia). An analysis of IR spectra and spectra obtained by the method of CD of serum albumins of both classes representatives revealed that beta-folding structure and alpha-helical sections that form the alpha-conformation play an important role in conformational structure formation of polypeptide chain and also disordered sites of molecules of these proteins. It was observed that certain redistribution depending on animals species exists, in the formation of secondary structure of serum albumins of the investigated representatives of reptiles and birds classes between the content of beta-folding structure, alpha-helical sections and disordered sites in molecules of these proteins.

Pseudopeptide foldamers: the homo-oligomers of pyroglutamic acid.

PubMed

Bernardi, Fernando; Garavelli, Marco; Scatizzi, Marco; Tomasini, Claudia; Trigari, Valerio; Crisma, Marco; Formaggio, Fernando; Peggion, Cristina; Toniolo, Claudio

2002-06-03

As a part of a program evaluating substituted gamma-lactams as conformationally constrained building blocks of pseudopeptide foldamers, we synthesized the homo-oligomers of L-pyroglutamic acid up to the tetramer level by solution methods. The preferred conformation of this pseudopeptide series in structure-supporting solvents was assessed by FT-IR absorption, 1H NMR and CD techniques. In addition, the crystal structure of the N alpha-protected dimer was established by X-ray diffraction. A high-level DFT computational modeling was performed based on the crystallographic parameters. In this analysis, we demonstrated that an alpha C-H...O=C intramolecular hydrogen bond is responsible for the stabilization of the s-trans L-pGlu-L-pGlu conformation by 1.4 kcal mol-1. This effect can be easily detected by 1H NMR spectroscopy, owing to the anomalous chemical shifts of the alpha CH protons present in all of the oligomers. In summary, we have developed a new polyimide-based, foldameric structure that, if appropriately functionalized, has promise as a rigid scaffold for novel functions and applications.

Structure-based design of potent histatin analogues.

PubMed

Brewer, Dyanne; Lajoie, Gilles

2002-04-30

Conformational studies of human salivary peptide, histatin 3 (Hst3), were performed by nuclear magnetic resonance (NMR) and circular dichroism (CD) spectroscopy in a membrane-mimicking environment. The structural information that was obtained was used in the design of peptide analogues with improved antifungal activity. In the presence of increasing concentrations of L-alpha-dimyristoylphosphatidylcholine (L-alpha-DMPC) lipid vesicles, a dramatic increase in a minimum at 198 nm is observed in the CD spectra of Hst3. The NMR data of Hst3 in the presence of L-alpha-DMPC lipid vesicles reveal the proximity of residues Y(10) and S(20), indicating the existence of a more compact structure. Peptide analogues were designed on the basis of this observation, which incorporated a disulfide bond to stabilize an extended loop in this region of the sequence. One of these, peptide 4, was 100 times more potent than Hst5 against Saccharomyces cerevisiae cells. Conformational analysis of peptide 4 revealed a looped structure with charged residues protruding on the outside surface, while a combination of aromatic residues and histidines are packed into an internal core.

The influence of phase transitions in phosphatidylethanolamine models on the activity of violaxanthin de-epoxidase.

PubMed

Vieler, Astrid; Scheidt, Holger A; Schmidt, Peter; Montag, Cindy; Nowoisky, Janine F; Lohr, Martin; Wilhelm, Christian; Huster, Daniel; Goss, Reimund

2008-04-01

In the present study, the influence of the phospholipid phase state on the activity of the xanthophyll cycle enzyme violaxanthin de-epoxidase (VDE) was analyzed using different phosphatidylethanolamine species as model lipids. By using (31)P NMR spectroscopy, differential scanning calorimetry and temperature dependent enzyme assays, VDE activity could directly be related to the lipid structures the protein is associated with. Our results show that the gel (L beta) to liquid-crystalline (L alpha) phase transition in these single lipid component systems strongly enhances both the solubilization of the xanthophyll cycle pigment violaxanthin in the membrane and the activity of the VDE. This phase transition has a significantly stronger impact on VDE activity than the transition from the L alpha to the inverted hexagonal (HII) phase. Especially at higher temperatures we found increased VDE reaction rates in the presence of the L alpha phase compared to those in the presence of HII phase forming lipids. Our data furthermore imply that the HII phase is better suited to maintain high VDE activities at lower temperatures.

Dehydrogenation of aromatic molecules under a scanning tunneling microscope: pathways and inelastic spectroscopy simulations.

PubMed

Lesnard, Hervé; Bocquet, Marie-Laure; Lorente, Nicolas

2007-04-11

We have performed a theoretical study on the dehydrogenation of benzene and pyridine molecules on Cu(100) induced by a scanning tunneling microscope (STM). Density functional theory calculations have been used to characterize benzene, pyridine, and different dehydrogenation products. The adiabatic pathways for single and double dehydrogenation have been evaluated with the nudge elastic band method. After identification of the transition states, the analysis of the electronic structure along the reaction pathway yields interesting information on the electronic process that leads to H-scission. The adiabatic barriers show that the formation of double dehydrogenated fragments is difficult and probably beyond reach under the actual experimental conditions. However, nonadiabatic processes cannot be ruled out. Hence, in order to identify the final dehydrogenation products, the inelastic spectra are simulated and compared with the experimental ones. We can then assign phenyl (C6H5) and alpha-pyridil (alpha-C5H4N) as the STM-induced dehydrogenation products of benzene and pyridine, respectively. Our simulations permit us to understand why phenyl, pyridine, and alpha-pyridil present tunneling-active C-H stretch modes in opposition to benzene.

alpha-1,4-Glucan lyase, a new class of starch/glycogen degrading enzyme. III. Substrate specificity, mode of action, and cleavage mechanism.

PubMed

Yu, S; Ahmad, T; Kenne, L; Pedersén, M

1995-05-11

The alpha-1,4-glucan lyase (EC 4.2.2.-), purified from the red alga Gracilariopsis lemaneiformis, is a single polypeptide with a molecular mass of 116,654 Da as determined by matrix-assisted laser-desorption mass spectrometry. It degraded maltose, maltosaccharides, amylose, amylopectin and glycogen, forming 1,5-anhydro-D-fructose from the non-reducing end groups. The substrate specificity, mode of action, and cleavage mechanism of the enzyme were studied by using various naturally occurring and synthesized substrates. This enzyme was highly specific for the alpha-1,4-D-glucosidic bond. When a linear alpha-1,4-glucan was used as substrate, the enzyme split the substrate from the non-reducing end and released 1,5-anhydro-D-fructose successively until only one glucose unit was left. When a branched pentasaccharide of 6(2)-alpha-maltosylmaltotriose, obtained from glycogen by alpha-amylase limitation, was used as substrate, the glucose group in the 4-position of the 4,6-branched residue was not cleaved off. Using maltoheptaose as substrate and following the reaction with HPLC and 1H-NMR spectroscopy, it was found that the action mode of the lyase followed a multichain attack mechanism. 1H- and 13C-NMR spectroscopic studies on unlabelled and labelled amylose (1-2H, 2-2H, 1-13C) as substrates indicated that the lyase cleaved the C-(1')-O(4) bond forming a double bond between C-1' and C-2', thus forming the enol form of 1,5-anhydro-D-fructose. It also indicated that the catalytic process of the lyase involved proton exchanges among C-1, C-2, C-3 and the solvent.

A Luminosity Function of Ly(alpha)-Emitting Galaxies at Z [Approx. Equal to] 4.5(Sup 1),(Sup 2)

NASA Technical Reports Server (NTRS)

Dawson, Steve; Rhoads, James E.; Malhotra, Sangeeta; Stern, Daniel; Wang, JunXian; Dey, Arjun; Spinrad, Hyron; Jannuzi, Buell T.

2007-01-01

We present a catalog of 59 z [approx. equal to] 4:5 Ly(alpha)-emitting galaxies spectroscopically confirmed in a campaign of Keck DEIMOS follow-up observations to candidates selected in the Large Are (LALA) narrowband imaging survey.We targeted 97 candidates for spectroscopic follow-up; by accounting for the variety of conditions under which we performed spectroscopy, we estimate a selection reliability of approx.76%. Together with our previous sample of Keck LRIS confirmations, the 59 sources confirmed herein bring the total catalog to 73 spectroscopically confirmed z [approx. equal to] 4:5 Ly(alpha)- emitting galaxies in the [approx. equal to] 0.7 deg(exp 2) covered by the LALA imaging. As with the Keck LRIS sample, we find that a nonnegligible fraction of the co rest-frame equivalent widths (W(sub lambda)(sup rest)) that exceed the maximum predicted for normal stellar populations: 17%-31%(93%confidence) of the detected galaxies show (W(sub lambda)(sup rest)) 12%-27% (90% confidence) show (W(sub lambda)(sup rest)) > 240 A. We construct a luminosity function of z [approx. equal to] 4.5 Ly(alpha) emission lines for comparison to Ly(alpha) luminosity function < 6.6. We find no significant evidence for Ly(alpha) luminosity function evolution from z [approx. equal to] 3 to z [approx. equal to] 6. This result supports the conclusion that the intergalactic me largely reionized from the local universe out to z [approx. equal to] 6.5. It is somewhat at odds with the pronounced drop in the cosmic star formation rate density recently measured between z approx. 3 an z approx. 6 in continuum-selected Lyman-break galaxies, and therefore potentially sheds light on the relationship between the two populations.

Characterization of subunit-specific interactions in a double-stranded RNA virus: Raman difference spectroscopy of the phi6 procapsid.

PubMed

Benevides, James M; Juuti, Jarmo T; Tuma, Roman; Bamford, Dennis H; Thomas, George J

2002-10-08

The icosahedral core of a double-stranded (ds) RNA virus hosts RNA-dependent polymerase activity and provides the molecular machinery for RNA packaging. The stringent requirements of dsRNA metabolism may explain the similarities observed in core architecture among a broad spectrum of dsRNA viruses, from the mammalian rotaviruses to the Pseudomonas bacteriophage phi6. Although the structure of the assembled core has been described in atomic detail for Reoviridae (blue tongue virus and reovirus), the molecular mechanism of assembly has not been characterized in terms of conformational changes and key interactions of protein constituents. In the present study, we address such questions through the application of Raman spectroscopy to an in vitro core assembly system--the procapsid of phi6. The phi6 procapsid, which comprises multiple copies of viral proteins P1 (copy number 120), P2 (12), P4 (72), and P7 (60), represents a precursor of the core that is devoid of RNA. Raman signatures of the procapsid, its purified recombinant core protein components, and purified sub-assemblies lacking either one or two of the protein components have been obtained and interpreted. The major procapsid protein (P1), which forms the skeletal frame of the core, is an elongated and monomeric molecule of high alpha-helical content. The fold of the core RNA polymerase (P2) is also mostly alpha-helical. On the other hand, the folds of both the procapsid accessory protein (P7) and RNA-packaging ATPase (P4) are of the alpha/beta type. Raman difference spectra show that conformational changes occur upon interaction of P1 with either P4 or P7 in the procapsid. These changes involve substantial ordering of the polypeptide backbone. Conversely, conformations of procapsid subunits are not significantly affected by interactions with P2. An assembly model is proposed in which P1 induces alpha-helix in P4 during formation of the nucleation complex. Subsequently, the partially disordered P7 subunit is folded within the context of the procapsid shell.

Phase equilibria and formation of vesicles of dioleoylphosphatidylcholine in glycerol/water mixtures.

PubMed

Johansson, L B; Kalman, B; Wikander, G; Fransson, A; Fontell, K; Bergenståhl, B; Lindblom, G

1993-07-04

The lipid 1,2-dioleoyl-sn-glycero-3-phosphocholine (DOPC) forms a lamellar liquid crystalline phase (L alpha) in arbitrary mixtures of glycerol and water. The phase has been characterized by means of X-ray diffraction, 31P-NMR spectroscopy and differential scanning calorimetry (DSC). In the L alpha state, and for DOPC concentrations greater than 50% (w/w), the thickness of the lipid bilayer decreases, while the area of the polar head group increases with increasing glycerol concentration. The phase transition from gel to L alpha state occurs in the range of 240 to 260 K. Contrary to a previous (McDaniel, R.V., McIntosh, T.J. and Simon, S.A. (1983) Biochim. Biophys. Acta 731, 97) study of 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC) we find that in the gel state, the thickness of the DOPC lipid bilayer is greater than that in the L alpha state. This suggests that in the gel state, the lipid acyl chains of DOPC are in extended configuration. The lamellar phase reaches its maximum swelling at about 50% (w/w) of DOPC. At lower DOPC concentrations a two-phase system is formed where the lamellar phase exists in equilibrium with excess of solvent. Unilamellar vesicles can be prepared from a diluted suspension of the lamellar phase either by using the sonicator or extruder technique. We show this by means of 31P-NMR, EPR and fluorescence spectroscopy. The mean radius of the vesicles, prepared by a sonicator, has been determined at different glycerol/water mixtures. It is found to decrease continuously from 100 A at 100% water to a minimum of 75 A at about 50% water in the solvent mixture. By further decreasing the water content in the solution, the radius rapidly increases, and a mean radius of 450 A is estimated at a water content of 10%. The rotational relaxation times of a fluorescent probe and two EPR spin probes, solubilized in DOPC vesicles, have been measured at different glycerol/water mixtures. It is found that the rotational rates are always much slower in the systems containing glycerol.

Mechanical design of proteins studied by single-molecule force spectroscopy and protein engineering.

PubMed

Carrion-Vazquez, M; Oberhauser, A F; Fisher, T E; Marszalek, P E; Li, H; Fernandez, J M

2000-01-01

Mechanical unfolding and refolding may regulate the molecular elasticity of modular proteins with mechanical functions. The development of the atomic force microscopy (AFM) has recently enabled the dynamic measurement of these processes at the single-molecule level. Protein engineering techniques allow the construction of homomeric polyproteins for the precise analysis of the mechanical unfolding of single domains. alpha-Helical domains are mechanically compliant, whereas beta-sandwich domains, particularly those that resist unfolding with backbone hydrogen bonds between strands perpendicular to the applied force, are more stable and appear frequently in proteins subject to mechanical forces. The mechanical stability of a domain seems to be determined by its hydrogen bonding pattern and is correlated with its kinetic stability rather than its thermodynamic stability. Force spectroscopy using AFM promises to elucidate the dynamic mechanical properties of a wide variety of proteins at the single molecule level and provide an important complement to other structural and dynamic techniques (e.g., X-ray crystallography, NMR spectroscopy, patch-clamp).

A new cytotoxic sterol methoxymethyl ether from a deep water marine sponge Scleritoderma sp. cf. paccardi.

PubMed

Gunasekera, S P; Kelly-Borges, M; Longley, R E

1996-02-01

24(R)-Methyl-5 alpha-cholest-7-enyl 3 beta-methoxymethyl ether (1), a new sterol ether, has been isolated from a deep-water marine sponge Scleritoderma sp. cf. paccardi. Compound 1 exhibited in vitro cytotoxicity against the cultured murine P-388 tumor cell line with an IC50 of 2.3 micrograms/mL. The isolation and structure elucidation of 1 by NMR spectroscopy is described.

Predicting the Redshift 2 H-Alpha Luminosity Function Using [OIII] Emission Line Galaxies

NASA Technical Reports Server (NTRS)

Mehta, Vihang; Scarlata, Claudia; Colbert, James W.; Dai, Y. S.; Dressler, Alan; Henry, Alaina; Malkan, Matt; Rafelski, Marc; Siana, Brian; Teplitz, Harry I.;

QUASARS PROBING QUASARS. IV. JOINT CONSTRAINTS ON THE CIRCUMGALACTIC MEDIUM FROM ABSORPTION AND EMISSION

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

Hennawi, Joseph F.; Prochaska, J. Xavier, E-mail: xavier@ucolick.org

2013-03-20

We have constructed a sample of 29 close projected quasar pairs where the background quasar spectrum reveals absorption from optically thick H I gas associated with the foreground quasar. These unique sightlines allow us to study the quasar circumgalactic medium (CGM) in absorption and emission simultaneously, because the background quasar pinpoints large concentrations of gas where Ly{alpha} emission, resulting from quasar-powered fluorescence, resonant Ly{alpha} scattering, and/or cooling radiation, is expected. A sensitive search (1{sigma} surface-brightness limits of SB{sub Ly{alpha}}{approx_equal}3 Multiplication-Sign 10{sup -18} erg s{sup -1} cm{sup -2} arcsec{sup -2}) for diffuse Ly{alpha} emission in the environments of the foreground (predominantlymore » radio-quiet) quasars is conducted using Gemini/GMOS and Keck/LRIS slit spectroscopy. We fail to detect large-scale {approx}100 kpc Ly{alpha} emission, either at the location of the optically thick absorbers or in the foreground quasar halos, in all cases except a single system. We interpret these non-detections as evidence that the gas detected in absorption is shadowed from the quasar UV radiation due to obscuration effects, which are frequently invoked in unified models of active galactic nuclei. Small-scale R {approx}< 50 kpc extended Ly{alpha} nebulosities are detected in 34% of our sample, which are likely the high-redshift analogs of the extended emission-line regions (EELRs) commonly observed around low-redshift (z < 0.5) quasars. This may be fluorescent recombination radiation from a population of very dense clouds with a low covering fraction illuminated by the quasar. We also detect a compact high rest-frame equivalent width (W{sub Ly{alpha}} > 50 A) Ly{alpha}-emitter with luminosity L{sub Ly{alpha}} = 2.1 {+-} 0.32 Multiplication-Sign 10{sup 41} erg s{sup -1} at small impact parameter R = 134 kpc from one foreground quasar, and argue that it is more likely to result from quasar-powered fluorescence, than simply be a star-forming galaxy clustered around the quasar. Our observations imply that much deeper integrations with upcoming integral-field spectrometers such as MUSE and KCWI will be able to routinely detect a diffuse Ly{alpha} glow around bright quasars on scales R {approx} 100 kpc and thus directly image the CGM.« less

X-ray spectroscopy of SNR E0102-72 with the ASCA satellite

NASA Technical Reports Server (NTRS)

Hayashi, Ichizo; Koyama, Katsuji; Ozaki, Masanobu; Miyata, Emi; Tsumeni, Hiroshi; Hughes, John P.; Petre, Robert

1994-01-01

The Advanced Satellite for Cosmology and Astrophysics (ASCA) satellite has obtained a moderate-resolution energy spectrum of E0102-72, the brightest Supernova Remnant (SNR) in the Small Magellanic Cloud (SMC). This paper reports on the first results of the analysis of the high quality spectrum of E0102-72. The spectrum shows resolved emission lines of He-like K alpha, H-like K alpha and K beta from oxygen, neon, and magnesium. The intensity ratios of these lines cannot be explained by a multi-component plasma model with uniform abundances, but requires abundance inhomogeneity in the plasma. We demonstrate how the spectral capabilities of the ASCA SIS make available new diagnostics of X-ray plasmas in a state of non-equilibrium ionization. Some interpretation based on the spectral analysis is also given.

Rapid measurement of 3J(H N-H alpha) and 3J(N-H beta) coupling constants in polypeptides.

PubMed

Barnwal, Ravi Pratap; Rout, Ashok K; Chary, Kandala V R; Atreya, Hanudatta S

2007-12-01

We present two NMR experiments, (3,2)D HNHA and (3,2)D HNHB, for rapid and accurate measurement of 3J(H N-H alpha) and 3J(N-H beta) coupling constants in polypeptides based on the principle of G-matrix Fourier transform NMR spectroscopy and quantitative J-correlation. These experiments, which facilitate fast acquisition of three-dimensional data with high spectral/digital resolution and chemical shift dispersion, will provide renewed opportunities to utilize them for sequence specific resonance assignments, estimation/characterization of secondary structure with/without prior knowledge of resonance assignments, stereospecific assignment of prochiral groups and 3D structure determination, refinement and validation. Taken together, these experiments have a wide range of applications from structural genomics projects to studying structure and folding in polypeptides.

Interpreting HST observations with simulations of reionization: the ionizing photon budget and the decline of Lyman-alpha emission in z>6 dropouts

NASA Astrophysics Data System (ADS)

D'Aloisio, Anson

2017-08-01

In recent years, HST surveys such as CANDELS, HUDF, BoRG/HIPPIES, ERS, and the Frontier Fields, have made possible the first robust measurements of the rest-frame UV luminosity function of z =6-10 galaxies, spanning much of the redshift range over which reionization likely occurred. These measurements provide an estimate of the galactic ionizing photon output, addressing the critical question of whether these galaxies could have reionized the Universe. In addition, follow-up spectroscopy has measured the fraction of these galaxies that show Lyman-alpha emission. Interestingly, a dramatic decrease in this fraction above z 6 has been observed, and this evolution has (controversially) been interpreted as evidence that much of reionization happened over z=6-8 (as intergalactic neutral gas leads to large damping wings that scatter the Lyman-alpha line). The clumpiness of the IGM and how it self shields to ionizing photons impacts whether the observed population of galaxies can reionize the Universe, as well as the interpretation of the evolving Lyman-alpha emitter fraction. We propose to run fully coupled radiative-hydrodynamics simulations that are the first to resolve the evaporation of small structures by passing ionization fronts and, hence, to accurately assess the level of clumpiness and self-shielding from the IGM. Our study will nail down the clumping factor used to assess whether the observed population of galaxies can drive reionization, and it will address whether neutral self-shielding clumps in recently reionized regions can scatter galaxies' Lyman-alpha lines.

Phosphoenolpyruvate-dependent maltose:phosphotransferase activity in Fusobacterium mortiferum ATCC 25557: specificity, inducibility, and product analysis.

PubMed Central

Robrish, S A; Fales, H M; Gentry-Weeks, C; Thompson, J

1994-01-01

Phosphoenolypyruvate-dependent maltose:phosphotransferase activity was induced in cells of Fusobacterium mortiferum ATCC 25557 during growth on maltose. The disaccharide was rapidly metabolized by washed cells maintained under anaerobic conditions, but fermentation ceased immediately upon exposure of the cell suspension to air. Coincidentally, high levels of a phosphorylated derivative accumulated within the cells. Chemical and enzymatic analyses, in conjunction with data from 1H, 13C, and 31P nuclear magnetic resonance spectroscopy, established the structure of the purified compound as 6-O-phosphoryl-alpha-D-glucopyranosyl-(1-4)-D-glucose (maltose 6-phosphate). A method for the preparation of substrate amounts of this commercially unavailable disaccharide phosphate is described. Permeabilized cells of F. mortiferum catalyzed the phosphoenolpyruvate-dependent phosphorylation of maltose under aerobic conditions. However, the hydrolysis of maltose 6-phosphate (to glucose 6-phosphate and glucose) by permeabilized cells or cell-free preparations required either an anaerobic environment or addition of dithiothreitol to aerobic reaction mixtures. The first step in dissimilation of the phosphorylated disaccharide appears to be catalyzed by an oxygen-sensitive maltose 6-phosphate hydrolase. Cells of F. mortiferum, grown previously on maltose, fermented a variety of alpha-linked glucosides, including maltose, turanose, palatinose, maltitol, alpha-methylglucoside, trehalose, and isomaltose. Conversely, cells grown on the separate alpha-glucosides also metabolized maltose. For this anaerobic pathogen, we suggest that the maltose:phosphotransferase and maltose 6-phosphate hydrolase catalyze the phosphorylative translocation and cleavage not only of maltose but also of structurally analogous alpha-linked glucosides. Images PMID:8195080

Observations of the peculiar object MWC 560 in outburst

NASA Technical Reports Server (NTRS)

Michalitsianos, A. G.; Maran, S. P.; Oliversen, R. J.; Bopp, B.; Kontizas, E.

1991-01-01

The results of ultraviolet spectroscopy, photoelectric photometry, and supplemental high-resolution H(alpha) spectroscopy of a photometric outburst of MWC 560 are discussed. Ultraviolet spectra are shown to be consistent with the ejection of an optically thick shell that produced strong absorption blends of Fe II and Cr II. The velocities reported exceed by far those previously found in symbiotic stars or recurrent novas. In addition to the variable high-velocity system of broad absorption features, a relatively stable system of Mg II, Mg I, Fe II, Cr II, and other ionic absorptions is observed. It is pointed out that the spectroscopic phenomena in MWC 560 resemble those found in XX Ophiuchi, but the velocities in the MWC 560 are an order of magnitude higher than those found in XX Oph.

The role of biomineralization in microbiologically influenced corrosion

NASA Technical Reports Server (NTRS)

Little, B.; Wagner, P.; Hart, K.; Ray, R.; Lavoie, D.; Nealson, K.; Aguilar, C.

1998-01-01

Synthetic iron oxides (goethite, alpha-FeO.OH; hematite, Fe2O3; and ferrihydrite, Fe(OH)3) were used as model compounds to simulate the mineralogy of surface films on carbon steel. Dissolution of these oxides exposed to pure cultures of the metal-reducing bacterium, Shewanella putrefaciens, was followed by direct atomic absorption spectroscopy measurement of ferrous iron coupled with microscopic analyses using confocal laser scanning and environmental scanning electron microscopies. During an 8-day exposure the organism colonized mineral surfaces and reduced solid ferric oxides to soluble ferrous ions. Elemental composition, as monitored by energy dispersive x-ray spectroscopy, indicated mineral replacement reactions with both ferrihydrite and goethite as iron reduction occurred. When carbon steel electrodes were exposed to S. putrefaciens, microbiologically influenced corrosion was demonstrated electrochemically and microscopically.

Li + transport in poly(ethylene oxide) based electrolyte: A combined study of neutron scattering, dielectric spectroscopy, and MD simulation

NASA Astrophysics Data System (ADS)

Do, Changwoo; Lunkenheimer, Peter; Diddens, Diddo; Götz, Marion; Weiß, Matthias; Loidl, Alois; Sun, Xiao-Guang; Allgaier, Jürgen; Ohl, Michael

2013-03-01

Dynamics of Li + transport in polyethylene oxide (PEO) and lithium bis(trifluoromethanesulfonyl)imde (LiTFSI) mixtures are investigated by combining various experimental techniques (neutron spin-echo and dielectric spectroscopy) with molecular dynamics (MD) simulations. Our results suggest that the characteristic live times within the cages formed by oxygens are mainly determined by the alpha-relaxation which corresponds to local segmental motions of polymers, to a much lesser extent by the main chain relaxation, and not at all by the beta-relaxation or any other faster processes. The significant contribution of Li + hopping process to the ion conductivity is also identified. Subsequently, detailed characteristic length and time scales of various Li + transport processes in solid polymer electrolytes are presented and interpreted.

Size-dependent structural transformations of hematite nanoparticles. 1. Phase transition.

PubMed

Chernyshova, I V; Hochella, M F; Madden, A S

2007-04-14

Using Fourier Transform InfraRed (FTIR) spectroscopy, Raman spectroscopy, X-ray diffraction (XRD), and Transmission Electron Microscopy (TEM), we characterize the structure and/or morphology of hematite (alpha-Fe(2)O(3)) particles with sizes of 7, 18, 39 and 120 nm. It is found that these nanoparticles possess maghemite (gamma-Fe(2)O(3))-like defects in the near surface regions, to which a vibrational mode at 690 cm(-1), active both in FTIR and Raman spectra, is assigned. The fraction of the maghemite-like defects and the net lattice disorder are inversely related to the particle size. However, the effect is opposite for nanoparticles grown by sintering of smaller hematite precursors under conditions when the formation of a uniform hematite-like structure throughout the aggregate is restricted by kinetic issues. This means that not only particle size but also the growth kinetics determines the structure of the nanoparticles. The observed structural changes are interpreted as size-induced alpha-Fe(2)O(3)<-->gamma-Fe(2)O(3) phase transitions. We develop a general model that considers spinel defects and absorbed/adsorbed species (in our case, hydroxyls) as dominant controls on structural changes with particle size in hematite nanoparticles, including solid-state phase transitions. These changes are represented by trajectories in a phase diagram built in three phase coordinates-concentrations of spinel defects, absorbed impurities, and adsorbed species. The critical size for the onset of the alpha-->gamma phase transition depends on the particle environment, and for the dry particles used in this study is about 40 nm. The model supports the existence of intermediate phases (protohematite and hydrohematite) during dehydration of goethite. We also demonstrate that the hematite structure is significantly less defective when the nanoparticles are immersed in water or KBr matrix, which is explained by the effects of the electrochemical double layer and increased rigidity of the particle environment. Finally, we revise the problem of applicability of IR spectroscopy to the lattice vibrations of hematite nanoparticles, demonstrating that structural comparison of different samples is much more reliable if it is based on the E(u) band at about 460 cm(-1) and the spinel band at 690 cm(-1), instead of the A(2u)/E(u) band at about 550 cm(-1) used in previous work. The new methodology is applied to analysis of the reported IR spectra of Martian hematite.

THE AGES, METALLICITIES, AND ALPHA ELEMENT ENHANCEMENTS OF GLOBULAR CLUSTERS IN THE ELLIPTICAL NGC 5128: A HOMOGENEOUS SPECTROSCOPIC STUDY WITH GEMINI/GEMINI MULTI-OBJECT SPECTROGRAPH

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

Woodley, Kristin A.; Harris, William E.; Puzia, Thomas H.

2010-01-10

We present new integrated light spectroscopy of globular clusters (GCs) in NGC 5128, a nearby giant elliptical galaxy less than 4 Mpc away, in order to measure radial velocities and derive ages, metallicities, and alpha-element abundance ratios. Using the Gemini South 8 meter telescope with the instrument Gemini Multi-Object Spectrograph, we obtained spectroscopy in the range of approx3400-5700 A for 72 GCs with a signal-to-noise ratio greater than 30 A{sup -1}; and we have also discovered 35 new GCs within NGC 5128 from our radial velocity measurements. We measured and compared the Lick indices from Hdelta{sub A} through Fe5406 withmore » the single stellar population models of Thomas et al. in order to derive age, metallicity, and [alpha/Fe] values. We also measure Lick indices for 41 Milky Way GCs from Puzia et al. and Schiavon et al. with the same methodology for direct comparison. Our results show that 68% of the NGC 5128 GCs have old ages (>8 Gyr), 14% have intermediate ages (5-8 Gyr), and 18% have young ages (<5 Gyr). However, when we look at the metallicity of the GCs as a function of age, we find 92% of metal-poor GCs and 56% of metal-rich GCs in NGC 5128 have ages >8 Gyr, indicating that the majority of both metallicity subpopulations of GCs formed earlier, with a significant population of young and metal-rich GCs forming later. Our metallicity distribution function generated directly from spectroscopic Lick indices is clearly bimodal, as is the color distribution of the same set of GCs. Thus, the metallicity bimodality is real and not an artifact of the color to metallicity conversion. However, the metallicity distribution function obtained from comparison with the single stellar population models is consistent with a unimodal, bimodal, or multimodal shape. The [alpha/Fe] values are supersolar with a mean value of 0.14 +- 0.04, indicating a fast formation timescale. However, the GCs in NGC 5128 are not as [alpha/Fe] enhanced as the Milky Way GCs also examined in this study. Our measured indices also indicate that the GCs in NGC 5128 may have a slight overabundance in nitrogen and a wider range of calcium strength compared to the Milky Way GCs. Our results support a rapid, early formation of the GC system in NGC 5128, with subsequent major accretion and/or GC and star-forming events in more recent times.« less

Evaluation of photostability of solid-state nicardipine hydrochloride polymorphs by using Fourier-transformed reflection-absorption infrared spectroscopy - effect of grinding on the photostability of crystal form.

PubMed

Teraoka, Reiko; Otsuka, Makoto; Matsuda, Yoshihisa

2004-11-22

Photostability and physicochemical properties of nicardipine hydrochloride polymorphs (alpha- and beta-form) were studied by using Fourier-transformed reflection-absorption infrared spectroscopy (FT-IR-RAS) of the tablets, X-ray powder diffraction analysis, differential scanning calorimetry (DSC), and color difference measurement. It was clear from the results of FT-IR-RAS spectra after irradiation that nicardipine hydrochloride in the solid state decomposed to its pyridine derivative when exposed to light. The photostability of the ground samples of two forms was also measured in the same manner. The two crystalline forms of the drug changed to nearly amorphous form after 150 min grinding in a mixer mill. X-ray powder diffraction patterns of those ground samples showed almost halo patterns. The nicardipine hydrochloride content on the surface of the tablet was determined based on the absorbance at 1700 cm(-1) attributable to the C=O stretch vibration in FT-IR-RAS spectra before and after irradiation by fluorescent lamp (3500 lx). The photodegradation followed apparently the first-order kinetics for any sample. The apparent photodegradation rate constant of beta-form was greater than that of alpha-form. The ground samples decomposed rapidly under the same light irradiation as compared with the intact crystalline forms. The photodegradation rate constant decreased with increase of the heat of fusion. copyright 2004 Elsevier B.V.

Sleuthing the Dynamo: the Final Frontier

NASA Astrophysics Data System (ADS)

Ayres, Thomas

1996-07-01

Innovative technologies are opening new windows into the Sun;from its hidden interior to the far reaches of its turbulentouter envelope: rare-earth detectors for solar neutrinos; theGONG project for helioseismology; SOHO for high-resolutionXUV spectroscopy, and YOHKOH for coronal X-ray imaging. Atthe same time, a fleet of space observatories--ROSAT, EUVE,ASCA, and HST itself--are providing unprecedented views ofthe vacuum-UV and X-ray emissions of stars in our Galacticneighborhood. These seemingly unrelated developments are infact deeply connected. A central issue of solar-stellarphysics is the nature and origin of magnetic activity: thelink between the interior dynamics of a late-type star and theviolent state of its outermost coronal layers. As solarphysicists are unlocking the secrets of the hydromagneticDynamo deep inside the Sun, we and others have beendocumenting the early evolution of the Dynamo and itsassociated external gas-dynamic activity. In particular, wehave obtained HST/FOS spectra of ten young solar-type starsin three nearby open clusters--the Hyades, Pleiades, andAlpha Persei--ranging in age from 50 Myr to 600 Myr. We havesupplemented the HST spectroscopy with deep ROSAT pointings, and ground-based studies. Here, we will continue the HSTside of our project by obtaining FUV spectra of two AlphaPerseids from our original program (but not yet observed),and high-S/N follow-up measurements of the hyperactive PleiadH II 314.

Spectroscopic study of the degradation products in the holy water fonts in Santa Maria della Steccata Church in Parma (Italy).

PubMed

Bersani, D; Campani, E; Casoli, A; Lottici, P P; Marino, I-G

2008-03-03

Two holy water fonts (dated at the beginning of the XVII century) in the Santa Maria della Steccata Church in Parma (Italy) have recently been restored. Before the intervention, a detailed investigation on their degradation products was carried out to understand the mechanisms of alteration of the materials and to suggest appropriate restoration procedures. The analyses were performed by means of powder X-ray diffraction (XRD), micro-Fourier transform infrared (FTIR) and micro-Raman spectroscopies. Calcite, iron oxides, silicates and sodium chloride (from salted holy water) were found in the red coloured calcarenite. On and under the lead coverings, different lead oxides (mainly massicot), other lead salts (lead basic carbonate, cerussite, plumbonacrite Pb10O(OH)6(CO3)6 and lead-chlorine compounds as laurionite PbOHCl and phosgenite Pb2CO3Cl2) were identified by Raman spectroscopy and XRD. Haematite alpha-Fe2O3, goethite alpha-FeO(OH) and lepidocrocite gamma-FeO(OH) were found on and around the iron hinges. Lead compounds and sodium chloride, through crystallization and solubilization cycles, were responsible for the stone's degradation, whereas the iron corrosion materials on the hinges produced mechanical stress and cracks in the stone. Various suggestions have been given on how to restore these fonts and to remove the causes of damage.

Binding of transducin and transducin-derived peptides to rhodopsin studies by attenuated total reflection-Fourier transform infrared difference spectroscopy.

PubMed Central

Fahmy, K

1998-01-01

Fourier transform infrared difference spectroscopy combined with the attenuated total reflection technique allows the monitoring of the association of transducin with bovine photoreceptor membranes in the dark. Illumination causes infrared absorption changes linked to formation of the light-activated rhodopsin-transducin complex. In addition to the spectral changes normally associated with meta II formation, prominent absorption increases occur at 1735 cm-1, 1640 cm-1, 1550 cm-1, and 1517 cm-1. The D2O sensitivity of the broad carbonyl stretching band around 1735 cm-1 indicates that a carboxylic acid group becomes protonated upon formation of the activated complex. Reconstitution of rhodopsin into phosphatidylcholine vesicles has little influence on the spectral properties of the rhodopsin-transducin complex, whereas pH affects the intensity of the carbonyl stretching band. AC-terminal peptide comprising amino acids 340-350 of the transducin alpha-subunit reproduces the frequencies and isotope sensitivities of several of the transducin-induced bands between 1500 and 1800 cm-1, whereas an N-terminal peptide (aa 8-23) does not. Therefore, the transducin-induced absorption changes can be ascribed mainly to an interaction between the transducin-alpha C-terminus and rhodopsin. The 1735 cm-1 vibration is also seen in the complex with C-terminal peptides devoid of free carboxylic acid groups, indicating that the corresponding carbonyl group is located on rhodopsin. PMID:9726932

Effects of alpha-zirconium phosphate on thermal degradation and flame retardancy of transparent intumescent fire protective coating

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

Xing, Weiyi; Zhang, Ping; Song, Lei

2014-01-01

Graphical abstract: - Highlights: • A transparent intumescent fire protective coating was obtained by UV-cured technology. • OZrP could enhance the thermal stability and anti-oxidation of the coating. • OZrP could reduce the combustion properties of the coatings. - Abstract: Organophilic alpha-zirconium phosphate (OZrP) was used to improve the thermal and fire retardant behaviors of the phenyl di(acryloyloxyethyl)phosphate (PDHA)-triglycidyl isocyanurate acrylate (TGICA)-2-phenoxyethyl acrylate (PHEA) (PDHA-TGICA-PHEA) coating. The morphology of nanocomposite coating was characterized by X-ray diffraction (XRD) and transmission electron microscopy (TEM). The effect of OZrP on the flame retardancy, thermal stability, fireproofing time and char formation of the coatingsmore » was investigated by microscale combustion calorimeter (MCC), thermogravimetric analysis (TGA), X-ray photoelectron spectroscopy (XPS), laser Raman spectroscopy (LRS) and scanning electric microscope (SEM). The results showed that by adding OZrP, the peak heat release rate and total heat of combustion were significantly reduced. The highest improvement was achieved with 0.5 wt% OZrP. XPS analysis indicated that the performance of anti-oxidation of the coating was improved with the addition of OZrP, and SEM images showed that a good synergistic effect was obtained through a ceramic-like layer produced by OZrP covered on the surface of char.« less

FINAL REPORT: Adopting Biophysics Methods in Pursuit of Biogeophysical Research: Advancing the Measurement and Modeling of Electrical Signatures of Microbe-Mineral Transformations Impacting Contaminant Transport

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

PRODAN, CAMELIA; SLATER, LEE; NTARLAGIANNIS, DIMITRIOS

2012-09-01

This exploratory project involved laboratory experiments to investigate three hypotheses: (H1) Physics-based modeling of low-frequency dispersions (henceforth referred to as alpha) measured in broadband dielectric spectroscopy (DS) data can quantify pore-scale geometric changes impacting contaminant transport resulting from biomineralization; (H2) Physics-based modeling of high-frequency dispersions (henceforth referred to as beta) measured in broadband dielectric spectroscopy data can quantify rates of mineral growth in/on the cell wall; (H3) Application of this measurement and modeling approach can enhance geophysical interpretation of bioremediation experiments conducted at the RIFLE IFC by providing constraints on bioremediation efficiency (biomass concentration, mineral uptake within the cell wall,more » biomineralization rate). We tested H1 by performing DS measurements (alpha and beta range) on iron (Fe) particles of dimensions similar to microbial cells, dispersed within agar gels over a range of Fe concentrations. We have tested the ability of the physics-based modeling to predict volume concentrations of the Fe particles by assuming that the Fe particles are polarizable inclusions within an otherwise nonpolarizable medium. We evaluated the smallest volume concentration that can be detected with the DS method. Similar experiments and modeling have been performed on the sulfate-reducing bacteria D. vulgaris. Synchrotron x-ray absorption measurements were conducted to determine the local structure of biominerals coatings on D. vulgaris which were grown in the presence of different Fe concentrations. We imaged the mineral growth on cell wall using SEM. We used dielectric spectroscopy to differentiate between iron sulfide precipitates of biotic and abiotic nature. Biotic measurements were made on D. vulgaris bacteria grown in the presence of different concentrations of iron to form different thicknesses of iron sulfide precipitates around themselves and abiotic measurements were made on different concentrations of pyrrhotite particles suspended in agar. Results show a decrease in dielectric permittivity as a function of frequency for biotic minerals and an opposite trend is observed for abiotic minerals. Our results suggest that dielectric spectroscopy offers a noninvasive and fast approach for distinguishing between abiotic and biotic mineral precipitates.« less

Adopting Biophysics Methods in Pursuit of Biogeophysical Research: Advancing the measurement and modeling of electrical signatures of microbe-mineral transformations impacting contaminant transport

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

Prodan, Camelia

2013-06-14

This exploratory project involved laboratory experiments to investigate three hypotheses: (H1) Physics-based modeling of low-frequency dispersions (henceforth referred to as alpha) measured in broadband dielectric spectroscopy (DS) data can quantify pore-scale geometric changes impacting contaminant transport resulting from biomineralization; (H2) Physics-based modeling of high-frequency dispersions (henceforth referred to as beta) measured in broadband dielectric spectroscopy data can quantify rates of mineral growth in/on the cell wall; (H3) Application of this measurement and modeling approach can enhance geophysical interpretation of bioremediation experiments conducted at the RIFLE IFC by providing constraints on bioremediation efficiency (biomass concentration, mineral uptake within the cell wall,more » biomineralization rate). We tested H1 by performing DS measurements (alpha and beta range) on iron (Fe) particles of dimensions similar to microbial cells, dispersed within agar gels over a range of Fe concentrations. We have tested the ability of the physics-based modeling to predict volume concentrations of the Fe particles by assuming that the Fe particles are polarizable inclusions within an otherwise nonpolarizable medium. We evaluated the smallest volume concentration that can be detected with the DS method. Similar experiments and modeling have been performed on the sulfate-reducing bacteria D. vulgaris. Synchrotron x-ray absorption measurements were conducted to determine the local structure of biominerals coatings on D. vulgaris which were grown in the presence of different Fe concentrations. We imaged the mineral growth on cell wall using SEM. We used dielectric spectroscopy to differentiate between iron sulfide precipitates of biotic and abiotic nature. Biotic measurements were made on D. vulgaris bacteria grown in the presence of different concentrations of iron to form different thicknesses of iron sulfide precipitates around themselves and abiotic measurements were made on different concentrations of pyrrhotite particles suspended in agar. Results show a decrease in dielectric permittivity as a function of frequency for biotic minerals and an opposite trend is observed for abiotic minerals. Our results suggest that dielectric spectroscopy offers a noninvasive and fast approach for distinguishing between abiotic and biotic mineral precipitates.« less

The effect of temperature on the stability of compounds used as UV-MALDI-MS matrix: 2,5-dihydroxybenzoic acid, 2,4,6-trihydroxyacetophenone, alpha-cyano-4-hydroxycinnamic acid, 3,5-dimethoxy-4-hydroxycinnamic acid, nor-harmane and harmane.

PubMed

Tarzi, Olga I; Nonami, Hiroshi; Erra-Balsells, Rosa

2009-02-01

The thermal stability of several commonly used crystalline matrix-assisted ultraviolet laser desorption/ionization mass spectrometry (UV-MALDI-MS) matrices, 2,5-dihydroxybenzoic acid (gentisic acid; GA), 2,4,6-trihydroxyacetophenone (THA), alpha-cyano-4-hydroxycinnamic acid (CHC), 3,5-dimethoxy-4-hydroxycinnamic acid (sinapinic acid; SA), 9H-pirido[3,4-b]indole (nor-harmane; nor-Ho), 1-methyl-9H-pirido[3,4-b]indole (harmane; Ho), perchlorate of nor-harmanonium ([nor-Ho+H]+) and perchlorate of harmanonium ([Ho+H]+) was studied by heating them at their melting point and characterizing the remaining material by using different MS techniques [electron ionization mass spectrometry (EI-MS), ultraviolet laserdesorption/ionization-time-of-flight-mass spectrometry (UV-LDI-TOF-MS) and electrospray ionization-time-of-flight-mass spectrometry (ESI-TOF-MS)] as well as by thin layer chromatography analysis (TLC), electronic spectroscopy (UV-absorption, fluorescence emission and excitation spectroscopy) and 1H nuclear magnetic resonance spectroscopy (1H-NMR). In general, all compounds, except for CHC and SA, remained unchanged after fusion. CHC showed loss of CO2, yielding the trans-/cis-4-hydroxyphenylacrilonitrile mixture. This mixture was unambiguously characterized by MS and 1H-NMR spectroscopy, and its sublimation capability was demonstrated. These results explain the well-known cluster formation, fading (vanishing) and further recovering of CHC when used as a matrix in UV-MALDI-MS. Commercial SA (SA 98%; trans-SA/cis-SA 5:1) showed mainly cis- to-trans thermal isomerization and, with very poor yield, loss of CO2, yielding (3',5'-dimethoxy-4'-hydroxyphenyl)-1-ethene as the decarboxilated product. These thermal conversions would not drastically affect its behavior as a UV-MALDI matrix as happens in the case of CHC. Complementary studies of the photochemical stability of these matrices in solid state were also conducted. Copyright (c) 2008 John Wiley & Sons, Ltd.

NMR structure of navel orangeworm moth pheromone-binding protein (AtraPBP1): implications for pH-sensitive pheromone detection.

PubMed

Xu, Xianzhong; Xu, Wei; Rayo, Josep; Ishida, Yuko; Leal, Walter S; Ames, James B

2010-02-23

The navel orangeworm, Amyelois transitella (Walker), is an agricultural insect pest that can be controlled by disrupting male-female communication with sex pheromones, a technique known as mating disruption. Insect pheromone-binding proteins (PBPs) provide fast transport of hydrophobic pheromones through the aqueous sensillar lymph and promote sensitive delivery of pheromones to receptors. Here we present the three-dimensional structure of a PBP from A. transitella (AtraPBP1) in solution at pH 4.5 determined by nuclear magnetic resonance (NMR) spectroscopy. Pulsed-field gradient NMR diffusion experiments, multiangle light scattering, and (15)N NMR relaxation analysis indicate that AtraPBP1 forms a stable monomer in solution at pH 4.5 in contrast to forming mostly dimers at pH 7. The NMR structure of AtraPBP1 at pH 4.5 contains seven alpha-helices (alpha1, L8-L23; alpha2, D27-F36; alpha3, R46-V62; alpha4, A73-M78; alpha5, D84-S100; alpha6, R107-L125; alpha7, M131-E141) that adopt an overall main-chain fold similar to that of PBPs found in Antheraea polyphemus and Bombyx mori. The AtraPBP1 structure is stabilized by three disulfide bonds formed by C19/C54, C50/C108, and C97/C117 and salt bridges formed by H69/E60, H70/E57, H80/E132, H95/E141, and H123/D40. All five His residues are cationic at pH 4.5, whereas H80 and H95 become neutral at pH 7.0. The C-terminal helix (alpha7) contains hydrophobic residues (M131, V133, V134, V135, V138, L139, and A140) that contact conserved residues (W37, L59, A73, F76, A77, I94, V111, and V115) suggested to interact with bound pheromone. Our NMR studies reveal that acid-induced formation of the C-terminal helix at pH 4.5 is triggered by a histidine protonation switch that promotes rapid release of bound pheromone under acidic conditions.

THE BALMER-DOMINATED BOW SHOCK AND WIND NEBULA STRUCTURE OF {gamma}-RAY PULSAR PSR J1741-2054

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

Romani, Roger W.; Shaw, Michael S.; Camilo, Fernando

2010-12-01

We have detected an H{alpha} bow shock nebula around PSR J1741-2054, a pulsar discovered through its GeV {gamma}-ray pulsations. The pulsar is only {approx}1.''5 behind the leading edge of the shock. Optical spectroscopy shows that the nebula is non-radiative, dominated by Balmer emission. The H{alpha} images and spectra suggest that the pulsar wind momentum is equatorially concentrated and implies a pulsar space velocity {approx}150 km s{sup -1}, directed 15{sup 0} {+-} 10{sup 0} out of the plane of the sky. The complex H{alpha} profile indicates that different portions of the post-shock flow dominate line emission as gas moves along themore » nebula and provide an opportunity to study the structure of this unusual slow non-radiative shock under a variety of conditions. CXO ACIS observations reveal an X-ray pulsar wind nebula within this nebula, with a compact {approx}2.''5 equatorial structure and a trail extending several arcminutes behind. Together these data support a close ({<=}0.5 kpc) distance, a spin geometry viewed edge-on, and highly efficient {gamma}-ray production for this unusual, energetic pulsar.« less

Optical and UV spectroscopy of the peculiar RS CVn system, RT Lacertae

NASA Technical Reports Server (NTRS)

Huenemoerder, D. P.; Barden, S. C.

1985-01-01

Spectra in the H-alpha and H-beta regions of the peculiar double-lined RS CVn binary, RT Lacertae, were obtained in the fall of 1984. Limited International Ultraviolet Explorer (IUE) long wavelength low and high resolution spectra were obtained concurrently. The ground based spectra have shown an asymmetry with orbital phase in the H-alpha profile. The H-beta profiles were consistent with the same effect. One hemisphere showed excess emission and the other excess absorption, with a broad Gaussian emission component superposed upon the excess H-alpha line. An improved radial velocity curve, giving a better determined mass ratio and geometry was derived. This combined with the radii implied by the rotational broadening of the spectra, showed one component to be 80 to 90% filling the equilibrium Roche surface. The two-faced nature is, therfore, very likely due to mass transfer from the contact component impacting upon its companion. Low resolution ultraviolet data showed that the supposed cooler component is bluer than its companion. High resolution ultraviolet data taken during secondary eclipse showed Mg II emission strength which decreased more slowly than the area visible. The phase behavior of the low resolution data support the former situation, indicating traditional chromospheric activity.

Resting state glutamate predicts elevated pre-stimulus alpha during self-relatedness: A combined EEG-MRS study on "rest-self overlap".

PubMed

Bai, Yu; Nakao, Takashi; Xu, Jiameng; Qin, Pengmin; Chaves, Pedro; Heinzel, Alexander; Duncan, Niall; Lane, Timothy; Yen, Nai-Shing; Tsai, Shang-Yueh; Northoff, Georg

2016-01-01

Recent studies have demonstrated neural overlap between resting state activity and self-referential processing. This "rest-self" overlap occurs especially in anterior cortical midline structures like the perigenual anterior cingulate cortex (PACC). However, the exact neurotemporal and biochemical mechanisms remain to be identified. Therefore, we conducted a combined electroencephalography (EEG)-magnetic resonance spectroscopy (MRS) study. EEG focused on pre-stimulus (e.g., prior to stimulus presentation or perception) power changes to assess the degree to which those changes can predict subjects' perception (and judgment) of subsequent stimuli as high or low self-related. MRS measured resting state concentration of glutamate, focusing on PACC. High pre-stimulus (e.g., prior to stimulus presentation or perception) alpha power significantly correlated with both perception of stimuli judged to be highly self-related and with resting state glutamate concentrations in the PACC. In sum, our results show (i) pre-stimulus (e.g., prior to stimulus presentation or perception) alpha power and resting state glutamate concentration to mediate rest-self overlap that (ii) dispose or incline subjects to assign high degrees of self-relatedness to perceptual stimuli.

Optical and UV spectroscopy of the peculiar RS CVn system, RT Lacertae

NASA Astrophysics Data System (ADS)

Huenemoerder, D. P.; Barden, S. C.

1985-11-01

Spectra in the H-alpha and H-beta regions of the peculiar double-lined RS CVn binary, RT Lacertae, were obtained in the fall of 1984. Limited International Ultraviolet Explorer (IUE) long wavelength low and high resolution spectra were obtained concurrently. The ground based spectra have shown an asymmetry with orbital phase in the H-alpha profile. The H-beta profiles were consistent with the same effect. One hemisphere showed excess emission and the other excess absorption, with a broad Gaussian emission component superposed upon the excess H-alpha line. An improved radial velocity curve, giving a better determined mass ratio and geometry was derived. This combined with the radii implied by the rotational broadening of the spectra, showed one component to be 80 to 90% filling the equilibrium Roche surface. The two-faced nature is, therfore, very likely due to mass transfer from the contact component impacting upon its companion. Low resolution ultraviolet data showed that the supposed cooler component is bluer than its companion. High resolution ultraviolet data taken during secondary eclipse showed Mg II emission strength which decreased more slowly than the area visible. The phase behavior of the low resolution data support the former situation, indicating traditional chromospheric activity.

Structural comparison of arabinoxylans from two barley side-stream fractions.

PubMed

Pitkänen, Leena; Tuomainen, Päivi; Virkki, Liisa; Aseyev, Vladimir; Tenkanen, Maija

2008-07-09

The structures of barley ( Hordeum vulgare) arabinoxylans isolated from two industrial side fractions, barley husks (BH) and barley fiber (BF), were characterized. Arabinoxylans were extracted with saturated barium hydroxide after enzymatic pretreatment. Barium hydroxide was selective toward arabinoxylans, and only a minor amount of glucose-containing material was coextracted. Acid methanolysis followed by gas chromatography, 1H NMR spectroscopy, and specific enzymatic treatments followed by anion exchange chromatography with pulse amperometric detection (HPAEC-PAD) revealed that the chemical structure of barley husk arabinoxylan (BHAX) clearly differed from that of barley fiber arabinoxylan (BFAX). BFAX was more branched, containing more beta-D-xylopyranosyl (beta-D-Xylp) residues carrying alpha-L-arabinofuranosyl (alpha-L-Araf) units at both O-2 and O-3 positions. BHAX, on the other hand, contained more 2-O-beta-D-Xyl p-alpha-L-Ara f substituents than BFAX. BHAX and BFAX also differed with respect to the hydrodynamic properties investigated with multidetector size exclusion chromatography. BFAX had a higher weight-average molar mass and larger hydrodynamic volume, the latter indicating less dense conformation than BHAX. Mn, Mw /Mn, Rh, and the Mark-Houwink a value were also determined for both arabinoxylans.

Do Lyman-alpha photons escape from star-forming galaxies through dust holes?

NASA Astrophysics Data System (ADS)

France, Kevin; Wofford, A.; Leitherer, C.; Fleming, B.; McCandliss, S. R.; Nell, N.

2014-01-01

H I Lyman-alpha (LyA) is commonly used as a signpost for the entire galaxy at redshifts z>2, and yet spatially and kinematically resolved views of the local conditions within galaxies that determine the integrated properties of this line are scarce. We obtained Hubble Space Telescope (HST) images in continuum-subtracted LyA, H-alpha, H-beta, and far-UV continuum of three low-inclination spiral star-forming galaxies located at redshifts z=0.02, 0.03, and 0.05. This was accomplished using the UVIS and SBC channels of the Wide Field Camera 3 (WFC3) and the Advanced Camera for Surveys (ACS), respectively. Previous HST spectroscopy obtained by our team with the Cosmic Origins Spectrograph (COS) showed that the galaxies display different integrated LyA profiles within their central few kiloparsecs, i.e., pure absorption, single emission, and double emission, which are representative of what is observed between redshifts 0-3. This data is useful for establishing the relative importance of starburst phase, dust content, and gas kinematics in determining the LyA escape. We present preliminary results that combine our spectroscopic and imaging observations.

Diagnostics for PLX-alpha

NASA Astrophysics Data System (ADS)

Gilmore, Mark; Hsu, Scott

2015-11-01

The goal of the Plasma Liner eXperiment PLX-alpha at Los Alamos National Laboratory is to establish the viability of creating a spherically imploding plasma liner for MIF and HED applications, using a spherical array of supersonic plasma jets launched by innovative contoured-gap coaxial plasma guns. PLX- α experiments will focus in particular on establishing the ram pressure and uniformity scalings of partial and fully spherical plasma liners. In order to characterize these parameters experimentally, a suite of diagnostics is planned, including multi-camera fast imaging, a 16-channel visible interferometer (upgraded from 8 channels) with reconfigurable, fiber-coupled front end, and visible and VUV high-resolution and survey spectroscopy. Tomographic reconstruction and data fusion techniques will be used in conjunction with interferometry, imaging, and synthetic diagnostics from modeling to characterize liner uniformity in 3D. Diagnostic and data analysis design, implementation, and status will be presented. Supported by the Advanced Research Projects Agency - Energy - U.S. Department of Energy.

Polysaccharide components from the scape of Musa paradisiaca: main structural features of water-soluble polysaccharide component.

PubMed

Anjaneyalu, Y V; Jagadish, R L; Raju, T S

1997-06-01

Polysaccharide components present in the pseudo-stem (scape) of M. paradisiaca were purified from acetone powder of the scape by delignification followed by extraction with aqueous solvents into water soluble polysaccharide (WSP), EDTA-soluble polysaccharide (EDTA-SP), alkali-soluble polysaccharide (ASP) and alkali-insoluble polysaccharide (AISP) fractions. Sugar compositional analysis showed that WSP and EDTA-SP contained only D-Glc whereas ASP contained D-Glc, L-Ara and D-Xyl in approximately 1:1:10 ratio, respectively, and AISP contained D-Glc, L-Ara and D-Xyl in approximately 10:1:2 ratio, respectively. WSP was further purified by complexation with iso-amylalcohol and characterized by specific rotation, IR spectroscopy, Iodine affinity, ferricyanide number, blue value, hydrolysis with alpha-amylase and glucoamylase, and methylation linkage analysis, and shown to be a amylopectin type alpha-D-glucan.

Efficiencies of state and velocity-changing collisions of superthermal CN A(2)Pi with He, Ar, N(2) and O(2).

PubMed

Alagappan, Azhagammai; Ballingall, Iain; Costen, Matthew L; McKendrick, Kenneth G; Paterson, Grant

2007-02-14

Polarized laser photolysis of ICN is combined with saturated optical pumping to prepare state-selected CN Alpha(2)Pi (nu' = 4, J = 0.5, F(2), f) with a well-defined anisotropic superthermal speed distribution. The collisional evolution of the prepared state is observed by Doppler-resolved Frequency Modulated (FM) spectroscopy via stimulated emission on the CN Alpha(2)Pi-Chi(2)Sigma(+) (4,2) band. The phenomenological rate constants for removal of the prepared state in collisions with He, Ar, N(2) and O(2) are reported. The observed collision cross-sections are consistent with attractive forces contributing significantly for all the colliders with the exception of He. The collisional evolution of the prepared velocity distribution demonstrates that no significant back-transfer into the prepared level occurs, and that any elastic scattering is strongly in the forward hemisphere.

Characterization of two minor saponins from Cordia piauhiensis by 1H and 13C NMR spectroscopy.

PubMed

Santos, Renata P; Silveira, Edilberto R; Lemos, Telma Leda G; Viana, Francisco Arnaldo; Braz-Filho, Raimundo; Pessoa, Otília Deusdênia L

2005-06-01

A careful NMR analysis with full assignment of the 1H and 13C spectral data for two minor saponins isolated from stems of Cordia piauhiensis is reported. These saponins were isolated by high-performance liquid chromatography and characterized as 3beta-O-[alpha-L-rhamnopyranosyl-(1 --> 2)-beta-D-glucopyranosyl]pomolic acid 28-O-[beta-D-glucopyranosyl-(1 --> 6)-beta-D-glucopyranosyl] ester (1) and 3beta-O-[alpha-L-rhamnopyranosyl-(1 --> 2)-beta-D-glucopyranosyl]oleanolic acid 28-O-[beta-D-xylopyranosyl-(1 --> 2)-beta-D-glucopyranosyl-(1 --> 6)-beta-D-glucopyranosyl] ester (2). Their structures were established using a combination of 1D and 2D (1H, 1H-COSY, TOCSY, NOESY, gs-HMQC and gs-HMBC) NMR techniques, electrospray ionization mass spectrometry and chemical evidence. Copyright 2005 John Wiley & Sons, Ltd.

Photodissociation dynamics of the 2-propyl radical, C{sub 3}H{sub 7}

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

Noller, Bastian; Fischer, Ingo

2007-04-14

The photodissociation of 2-propyl leading to propene+H was investigated with nanosecond time resolution. A supersonic beam of isolated 2-propyl radicals was produced by pyrolysis of 2-bromopopane. The kinetic energy release of the H-atom photofragment was monitored as a function of excitation wavelength by photofragment Doppler spectroscopy via the Lyman-{alpha} transition. The loss of hydrogen atoms after excitation proceeds in {alpha} position to the radical center with a rate constant of 5.8x10{sup 7} s{sup -1} at 254 nm. Approximately 20% of the excess energy is deposited as translation in the H-atom photofragment. In contrast 1-propyl does not lose H atoms tomore » a significant extent. The experimental results are compared to simple Rice-Ramsperger-Kassel-Marcus calculations. The possible reaction pathways are examined in hybrid density functional theory calculations.« less

Kinetic Energy Distribution of H(2p) Atoms from Dissociative Excitation of H2

NASA Technical Reports Server (NTRS)

Ajello, Joseph M.; Ahmed, Syed M.; Kanik, Isik; Multari, Rosalie

1995-01-01

The kinetic energy distribution of H(2p) atoms resulting from electron impact dissociation of H2 has been measured for the first time with uv spectroscopy. A high resolution uv spectrometer was used for the measurement of the H Lyman-alpha emission line profiles at 20 and 100 eV electron impact energies. Analysis of the deconvolved 100 eV line profile reveals the existence of a narrow line peak and a broad pedestal base. Slow H(2p) atoms with peak energy near 80 meV produce the peak profile, which is nearly independent of impact energy. The wings of H Lyman-alpha arise from dissociative excitation of a series of doubly excited Q(sub 1) and Q(sub 2) states, which define the core orbitals. The fast atom energy distribution peaks at 4 eV.

A study of the dynamics of PTEN proteins in living cells using in vivo fluorescence correlation spectroscopy

NASA Astrophysics Data System (ADS)

Du, Zhixue; Dong, Chaoqing; Ren, Jicun

2017-06-01

PTEN (phosphatase and tensin homolog on chromosome 10) is one of the most important tumor-suppressor proteins, which plays a key role in negative regulation of the PI3K/AKT pathway, and governs many cellular processes including growth, proliferation, survival and migration. The dynamics of PTEN proteins in single living cells is as yet unclear owing to a shortage of suitable in vivo approaches. Here, we report a single-molecule method for in vivo study of the dynamics of PTEN proteins in living cells using fluorescence correlation spectroscopy (FCS). First, we established a monoclonal H1299 stable cell line expressing enhanced green fluorescent protein (EGFP) and PTEN (EGFP-PTEN) fusion proteins; we then developed an in vivo FCS method to study the dynamics of EGFP-PTEN both in the nucleus and the cytoplasm. We investigated the diffusion behaviors of EGFP and EGFP-PTEN in solution, nucleus and cytosol, and observed that the motion of PTEN in living cells was restricted compared with EGFP. Finally, we investigated the protein dynamics in living cells under oxidative stress stimulation and a cellular ATP depletion treatment. Under oxidative stress stimulation, the EGFP-PTEN concentration increased in the nucleus, but slightly decreased in the cytoplasm. The diffusion coefficient and alpha value of EGFP-PTEN reduced significantly both in the nucleus and cytoplasm; the significantly decreased alpha parameter indicates a more restricted Brownian diffusion behavior. Under the cellular ATP depletion treatment, the concentration of EGFP-PTEN remained unchanged in the nucleus and decreased significantly in cytosol. The diffusion coefficient of EGFP-PTEN decreased significantly in cytosol, but showed no significant change in the nucleus; the alpha value decreased significantly in both the nucleus and cytoplasm. These results suggest that the concentration and mobility of PTEN in the nucleus and cytoplasm can be regulated by stimulation methods. Our approach provides a unique method for real-time monitoring of protein dynamics in different subcellular compartments under different stimulation treatments.

Practical aspects of monochromators developed for transmission electron microscopy

PubMed Central

Kimoto, Koji

2014-01-01

A few practical aspects of monochromators recently developed for transmission electron microscopy are briefly reviewed. The basic structures and properties of four monochromators, a single Wien filter monochromator, a double Wien filter monochromator, an omega-shaped electrostatic monochromator and an alpha-shaped magnetic monochromator, are outlined. The advantages and side effects of these monochromators in spectroscopy and imaging are pointed out. A few properties of the monochromators in imaging, such as spatial or angular chromaticity, are also discussed. PMID:25125333

The search for the cause of the low albedo of the moon

NASA Technical Reports Server (NTRS)

Gold, T.; Bilson, E.; Baron, R. L.

1975-01-01

Experimentation concerning lunar weathering and its effect on the albedo of the surface cover consisted of: (1) determination of the surface chemical composition of lunar soil and ground-up rock samples by Auger electron spectroscopy, (2) measurement of the optical albedo of these samples, and (3) proton or alpha-particle irradiation of terrestrial rock chips and rock powders and of ground-up lunar rock samples in order to determine the optical and surface chemical effect of simulated solar wind.

Lattice vibrations and electronic transitions in the rare-earth metals: praseodymium under pressure.

PubMed

Olijnyk, Helmut; Grosshans, Walter A; Jephcoat, Andrew P

2004-12-17

Praseodymium was investigated by Raman spectroscopy under pressure. A negative pressure shift of the E(2g) mode is observed in the dhcp phase, which indicates that the initial structural sequence hcp-->Sm-type-->dhcp-->fcc as a whole in the regular lanthanides is associated with a softening of this mode. The pressure response of the phonon modes, observed in the monoclinic and alpha-uranium phases, where 4f bonding becomes important, is characteristic for anisotropic bonding properties.

Kinetic analysis of reactions of Si-based epoxy resins by near-infrared spectroscopy, 13C NMR and soft-hard modelling.

PubMed

Garrido, Mariano; Larrechi, Maria Soledad; Rius, F Xavier; Mercado, Luis Adolfo; Galià, Marina

2007-02-05

Soft- and hard-modelling strategy was applied to near-infrared spectroscopy data obtained from monitoring the reaction between glycidyloxydimethylphenyl silane, a silicon-based epoxy monomer, and aniline. On the basis of the pure soft-modelling approach and previous chemical knowledge, a kinetic model for the reaction was proposed. Then, multivariate curve resolution-alternating least squares optimization was carried out under a hard constraint, that compels the concentration profiles to fulfil the proposed kinetic model at each iteration of the optimization process. In this way, the concentration profiles of each species and the corresponding kinetic rate constants of the reaction, unpublished until now, were obtained. The results obtained were contrasted with 13C NMR. The joint interval test of slope and intercept for detecting bias was not significant (alpha=5%).

Determining Beta Sheet Crystallinity in Fibrous Proteins by Thermal Analysis and Infrared Spectroscopy

NASA Astrophysics Data System (ADS)

Hu, Xiao; Kaplan, David; Cebe, Peggy

2007-03-01

We report a study of self-assembled beta pleated sheets in Bombyx mori silk fibroin films using thermal analysis and infrared spectroscopy. Crystallization of beta pleated sheets was effected either by heating the films above the glass transition temperature (Tg) and holding isothermally, or by exposure to methanol. The fractions of secondary structural components including random coils, alpha helices, beta pleated sheets, turns, and side chains, were evaluated using Fourier self-deconvolution (FSD) of the infrared absorbance spectra. As crystalline beta sheets form, the heat capacity increment from the TMDSC trace at Tg is systematically decreased and is linearly well correlated with beta sheet content determined from FSD. This analysis of beta sheet content can serve as an alternative to X-ray methods and may have wide applicability to other crystalline beta sheet forming proteins.

THE zCOSMOS-SINFONI PROJECT. I. SAMPLE SELECTION AND NATURAL-SEEING OBSERVATIONS

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

Mancini, C.; Renzini, A.; Foerster Schreiber, N. M.

2011-12-10

The zCOSMOS-SINFONI project is aimed at studying the physical and kinematical properties of a sample of massive z {approx} 1.4-2.5 star-forming galaxies, through SINFONI near-infrared integral field spectroscopy (IFS), combined with the multiwavelength information from the zCOSMOS (COSMOS) survey. The project is based on one hour of natural-seeing observations per target, and adaptive optics (AO) follow-up for a major part of the sample, which includes 30 galaxies selected from the zCOSMOS/VIMOS spectroscopic survey. This first paper presents the sample selection, and the global physical characterization of the target galaxies from multicolor photometry, i.e., star formation rate (SFR), stellar mass, age,more » etc. The H{alpha} integrated properties, such as, flux, velocity dispersion, and size, are derived from the natural-seeing observations, while the follow-up AO observations will be presented in the next paper of this series. Our sample appears to be well representative of star-forming galaxies at z {approx} 2, covering a wide range in mass and SFR. The H{alpha} integrated properties of the 25 H{alpha} detected galaxies are similar to those of other IFS samples at the same redshifts. Good agreement is found among the SFRs derived from H{alpha} luminosity and other diagnostic methods, provided the extinction affecting the H{alpha} luminosity is about twice that affecting the continuum. A preliminary kinematic analysis, based on the maximum observed velocity difference across the source and on the integrated velocity dispersion, indicates that the sample splits nearly 50-50 into rotation-dominated and velocity-dispersion-dominated galaxies, in good agreement with previous surveys.« less

Witnessing the assembly of galaxies in an extended gas-rich structure at z 3.25

NASA Astrophysics Data System (ADS)

Mackenzie, Ruari

2017-08-01

The direct study of star formation in Damped Lyman Alpha systems (DLAs), the reservoirs of the majority of neutral gas at high redshift, has previously been hampered by the lack of deep integral field spectroscopy for sensitive searches of faint host galaxies. Building on our successful HST shot-in-the-dark survey that has probed the in-situ star formation rate of z 2-3 DLAs, we have initiated a MUSE follow-up of 6 DLA signlines to overcome this bottleneck. In the first sightline we have studied, we have uncovered a 40 kpc Lyman alpha emitting nebula, composed of two clumps within 50 kpc of the DLA, suggestive of a merger or an extended protodisk. Within this structure, which is the largest nebula known to be associated with a z 3 DLA, we also found a compact continuum source with spectrophotometry consistent with a Lyman Break Galaxy at the same redshift. Aside from the LBG, the rest of the Lyman alpha structure has no continuum counterpart in deep UV and visible imaging. The LBG alone seems unable to power the Lyman alpha nebula and the morphology supports our conclusion that, most likely, this structure is powered by in-situ star formation below detection limit. However, from the Lyman alpha alone the origin of this incredible structure remains ambiguous. With this proposal, we aim to acquire high resolution, deep infrared imaging with HST to probe the rest-frame optical emission to search for the underlying stellar emission of this object and to infer the stellar mass of the LBG. With the powerful combination of HST and MUSE data, we will unravel the nature of this unique system.

Structures of the glycopeptidolipid antigens of Mycobacterium abscessus and Mycobacterium chelonae and possible chemical basis of the serological cross-reactions in the Mycobacterium fortuitum complex.

PubMed

López-Marín, L M; Gautier, N; Lanéelle, M A; Silve, G; Daffé, M

1994-05-01

Mycobacterium abscessus and Mycobacterium chelonae, two members of the Mycobacterium fortuitum complex, contain five major glycolipids. A combination of NMR spectroscopy, fast atom bombardment mass spectrometry and chemical degradation was used to elucidate their structures. All the compounds belong to the family of glycopeptidolipids. A 6-deoxy-alpha-L-talosyl unit, which may bear one or two acetyl groups, invariably occupies the site of glycosylation on the threonine residue in the various compounds. A 3,4-di-O-methyl- or 2,3,4-tri-O-methyl-alpha-L-rhamnosyl unit modifies the alaninol end of the diglycosylated molecules. Both species also contain a multiglycosylated compound consisting of alpha-L-rhamnosyl-(1-->2)-3,4-di-O-methyl-alpha-L-rhamnosyl linked to alaninol, which belongs to the class of new variants of glycopeptidolipids recently described. Using an ELISA, the latter glycolipid as well as the diglycosylated ones (not previously reported to be antigenic), were shown to react with the serum raised against the whole lipid antigens of M. chelonae. A comparative serologic study of the native and chemically modified glycopeptidolipid antigens allowed the identification of their epitope as the 3,4-di-O-methyl-alpha-L-rhamnosyl residue. Similar experiments conducted on the glycopeptidolipids isolated from the serologically cross-reacting species M. peregrinum led to the conclusion that the epitope identified in M. chelonae and M. abscessus was involved in the cross-reactions and demonstrated the existence of a second haptenic moiety in the glycolipids of M. peregrinum, the 3-O-methyl-alpha-L-rhamnosyl unit. In addition to this latter non-shared epitope, the recently described sulfated glycopeptidolipid antigen of M. peregrinum did not react with the M. chelonae serum, thus further explaining the difference in the seroreactivity within the complex.

Specificity and mechanism of action of alpha-helical membrane-active peptides interacting with model and biological membranes by single-molecule force spectroscopy.

PubMed

Sun, Shiyu; Zhao, Guangxu; Huang, Yibing; Cai, Mingjun; Shan, Yuping; Wang, Hongda; Chen, Yuxin

2016-07-01

In this study, to systematically investigate the targeting specificity of membrane-active peptides on different types of cell membranes, we evaluated the effects of peptides on different large unilamellar vesicles mimicking prokaryotic, normal eukaryotic, and cancer cell membranes by single-molecule force spectroscopy and spectrum technology. We revealed that cationic membrane-active peptides can exclusively target negatively charged prokaryotic and cancer cell model membranes rather than normal eukaryotic cell model membranes. Using Acholeplasma laidlawii, 3T3-L1, and HeLa cells to represent prokaryotic cells, normal eukaryotic cells, and cancer cells in atomic force microscopy experiments, respectively, we further studied that the single-molecule targeting interaction between peptides and biological membranes. Antimicrobial and anticancer activities of peptides exhibited strong correlations with the interaction probability determined by single-molecule force spectroscopy, which illustrates strong correlations of peptide biological activities and peptide hydrophobicity and charge. Peptide specificity significantly depends on the lipid compositions of different cell membranes, which validates the de novo design of peptide therapeutics against bacteria and cancers.

Characterization of Synthetic and Natural Manganese Oxides as Martian Analogues

NASA Technical Reports Server (NTRS)

Fox, V. K.; Arvidson, R. E.; Jolliff, B. L.; Carpenter, P. K.; Catalano, J. G.; Hinkle, M. A. G.; Morris, R. V.

2015-01-01

Recent discoveries of highly concentrated manganese oxides in Gale Crater and on the rim of Endeavour Crater by the Mars Science Laboratory Curiosity and Mars Exploration Rover Opportunity, respectively, imply more highly oxidizing aqueous conditions than previously recognized. Manganese oxides are a significant environmental indicator about ancient aqueous conditions, provided the phases can be characterized reliably. Manganese oxides are typically fine-grained and poorly crystalline, making the mineral structures difficult to determine, and they generally have very low visible reflectance with few distinctive spectral features in the visible to near infrared, making them a challenge for interpretation from remote sensing data. Therefore, these recent discoveries motivate better characterization using methods available on Mars, particularly visible to near infrared (VNIR) spectroscopy, X-ray diffractometry (XRD), and compositional measurements. Both rovers have complementary instruments in this regard. Opportunity is equipped with its multispectral visible imager, Pancam, and an Alpha Particle X-ray Spectrometer (APXS), and Curiosity has the multispectral Mastcam, ChemCam (laser-induced breakdown spectroscopy and passive spectroscopy), and APXS for in situ characterization, and ChemMin (XRD) for collected samples.

Unraveling protein-protein interactions in clathrin assemblies via atomic force spectroscopy.

PubMed

Jin, Albert J; Lafer, Eileen M; Peng, Jennifer Q; Smith, Paul D; Nossal, Ralph

2013-03-01

Atomic force microscopy (AFM), single molecule force spectroscopy (SMFS), and single particle force spectroscopy (SPFS) are used to characterize intermolecular interactions and domain structures of clathrin triskelia and clathrin-coated vesicles (CCVs). The latter are involved in receptor-mediated endocytosis (RME) and other trafficking pathways. Here, we subject individual triskelia, bovine-brain CCVs, and reconstituted clathrin-AP180 coats to AFM-SMFS and AFM-SPFS pulling experiments and apply novel analytics to extract force-extension relations from very large data sets. The spectroscopic fingerprints of these samples differ markedly, providing important new information about the mechanism of CCV uncoating. For individual triskelia, SMFS reveals a series of events associated with heavy chain alpha-helix hairpin unfolding, as well as cooperative unraveling of several hairpin domains. SPFS of clathrin assemblies exposes weaker clathrin-clathrin interactions that are indicative of inter-leg association essential for RME and intracellular trafficking. Clathrin-AP180 coats are energetically easier to unravel than the coats of CCVs, with a non-trivial dependence on force-loading rate. Published by Elsevier Inc.

Low Dose X-Ray Speckle Visibility Spectroscopy Reveals Nanoscale Dynamics in Radiation Sensitive Ionic Liquids

NASA Astrophysics Data System (ADS)

Verwohlt, Jan; Reiser, Mario; Randolph, Lisa; Matic, Aleksandar; Medina, Luis Aguilera; Madsen, Anders; Sprung, Michael; Zozulya, Alexey; Gutt, Christian

2018-04-01

X-ray radiation damage provides a serious bottleneck for investigating microsecond to second dynamics on nanometer length scales employing x-ray photon correlation spectroscopy. This limitation hinders the investigation of real time dynamics in most soft matter and biological materials which can tolerate only x-ray doses of kGy and below. Here, we show that this bottleneck can be overcome by low dose x-ray speckle visibility spectroscopy. Employing x-ray doses of 22-438 kGy and analyzing the sparse speckle pattern of count rates as low as 6.7 ×10-3 per pixel, we follow the slow nanoscale dynamics of an ionic liquid (IL) at the glass transition. At the prepeak of nanoscale order in the IL, we observe complex dynamics upon approaching the glass transition temperature TG with a freezing in of the alpha relaxation and a multitude of millisecond local relaxations existing well below TG . We identify this fast relaxation as being responsible for the increasing development of nanoscale order observed in ILs at temperatures below TG .

Accumulation of a novel glycolipid and a betaine lipid in cells of Rhodobacter sphaeroides grown under phosphate limitation.

PubMed

Benning, C; Huang, Z H; Gage, D A

1995-02-20

Cells of the photosynthetic bacterium Rhodobacter sphaeroides grown under phosphate-limiting conditions accumulated nonphosphorous glycolipids and lipids carrying head groups derived from amino acids. Concomitantly, the relative amount of phosphoglycerolipids decreased from 90 to 22 mol% of total polar lipids in the membranes. Two lipids, not detectable in cells grown under standard conditions, were synthesized during phosphate-limited growth. Fast atom bombardment mass spectroscopy, exact mass measurements, 1H NMR spectroscopy, sugar composition analysis, and methylation analysis of the predominant glycolipid led to the identification of the novel compound 1,2-di-O-acyl-3-O-[alpha-D-glucopyranosyl-(1-->4)-O-beta-D-galactopyr anosyl]glycerol. The second lipid was identified as the betaine lipid 1,2-di-O-acyl-[4'-(N,N,N-trimethyl)-homoserine]glycerol by cochromatography employing an authentic standard from Chlamydomonas reinhardtii, fast atom bombardment mass spectroscopy, exact mass measurements, and 1H NMR spectroscopy. Prior to this observation, the occurrence of this lipid was thought to be restricted to lower plants and algae. Apparently, these newly synthesized nonphosphorous lipids, in addition to the sulfo- and the ornithine lipid also found in R. sphaeroides grown under optimal conditions, take over the role of phosphoglycerolipids in phosphate-deprived cells.

Three-dimensional structure of the NLRP7 pyrin domain: insight into pyrin-pyrin-mediated effector domain signaling in innate immunity.

PubMed

Pinheiro, Anderson S; Proell, Martina; Eibl, Clarissa; Page, Rebecca; Schwarzenbacher, Robert; Peti, Wolfgang

2010-08-27

The innate immune system provides an initial line of defense against infection. Nucleotide-binding domain- and leucine-rich repeat-containing protein (NLR or (NOD-like)) receptors play a critical role in the innate immune response by surveying the cytoplasm for traces of intracellular invaders and endogenous stress signals. NLRs themselves are multi-domain proteins. Their N-terminal effector domains (typically a pyrin or caspase activation and recruitment domain) are responsible for driving downstream signaling and initiating the formation of inflammasomes, multi-component complexes necessary for cytokine activation. However, the currently available structures of NLR effector domains have not yet revealed the mechanism of their differential modes of interaction. Here, we report the structure and dynamics of the N-terminal pyrin domain of NLRP7 (NLRP7 PYD) obtained by NMR spectroscopy. The NLRP7 PYD adopts a six-alpha-helix bundle death domain fold. A comparison of conformational and dynamics features of the NLRP7 PYD with other PYDs showed distinct differences for helix alpha3 and loop alpha2-alpha3, which, in NLRP7, is stabilized by a strong hydrophobic cluster. Moreover, the NLRP7 and NLRP1 PYDs have different electrostatic surfaces. This is significant, because death domain signaling is driven by electrostatic contacts and stabilized by hydrophobic interactions. Thus, these results provide new insights into NLRP signaling and provide a first molecular understanding of inflammasome formation.

Three-dimensional structure of interleukin 8 in solution.

PubMed

Clore, G M; Appella, E; Yamada, M; Matsushima, K; Gronenborn, A M

1990-02-20

The solution structure of the interleukin 8 (IL-8) dimer has been solved by nuclear magnetic resonance (NMR) spectroscopy and hybrid distance geometry-dynamical simulated annealing calculations. The structure determination is based on a total of 1880 experimental distance restraints (of which 82 are intersubunit) and 362 torsion angle restraints (comprising phi, psi, and chi 1 torsion angles). A total of 30 simulated annealing structures were calculated, and the atomic rms distribution about the mean coordinate positions (excluding residues 1-5 of each subunit) is 0.41 +/- 0.08 A for the backbone atoms and 0.90 +/- 0.08 A for all atoms. The three-dimensional solution structure of the IL-8 dimer reveals a structural motif in which two symmetry-related antiparallel alpha-helices, approximately 24 A long and separated by about 14 A, lie on top of a six-stranded antiparallel beta-sheet platform derived from two three-stranded Greek keys, one from each monomer unit. The general architecture is similar to that of the alpha 1/alpha 2 domains of the human class I histocompatibility antigen HLA-A2. It is suggested that the two alpha-helices form the binding site for the cellular receptor and that the specificity of IL-8, as well as that of a number of related proteins involved in cell-specific chemotaxis, mediation of cell growth, and the inflammatory response, is achieved by the distinct distribution of charged and polar residues at the surface of the helices.

Cyclic oligomer of oxide clusters through a siloxane bond. Synthesis and structure of reaction products of alpha2-mono-lacunary Dawson polyoxometalate with tetrachlorosilane and tetraethoxysilane.

PubMed

Kurashina, Takayuki; Aoki, Shotaro; Hirasawa, Ryota; Hasegawa, Takeshi; Kasahara, Yuhki; Yoshida, Shoko; Yoza, Kenji; Nomiya, Kenji

2009-07-28

The title compound with the formula (Me2NH2)13H5[{alpha2-P2W17O61(Si2O)}3(micro-O)3].39H2O Me2NH(2)-1 was obtained in 12.8% (0.258 g scale) yield by a 1:2 molar ratio reaction of alpha2-mono-lacunary Dawson polyoxometalate (POM) [alpha2-P2W17O61]10- with SiCl4 in water and unequivocally characterized by complete elemental analysis, TG/DTA, FTIR, (solution and solid-state) 31P NMR, solid-state 29Si NMR and X-ray crystallography. [Note: the moieties of the polyoxoanions in Me2NH(2)-1 and Me2NH(2)-2 are abbreviated simply as 1 and 2, respectively.] X-Ray crystallography revealed that the molecular structure of polyoxoanion 1 was a cyclic trimer consisting of three alpha2-mono-lacunary Dawson POM subunits constituted through intra- and intermolecular siloxane bonds. The compound resulted in an approximate Cs symmetry, but not the idealized C3v symmetry, because one Dawson unit was unequivalently incorporated into the cyclic framework. This compound is the first example of a siloxane-bonding cyclic trimer of POMs and its formation suggests that the oxygen atoms in the lacunary site of POM are reactive just like the surface oxygen atoms of silica. The formation of the cyclic trimer was also clarified by two control experiments: (1) the reaction of [alpha2-P2W17O61]10- with Si(OEt)4 under acidic conditions (pH 1), and (2) oligomerization under 6 M aqueous HCl acidic conditions (pH approximately 0) of the reactive monomer units (RMUs: tentatively assigned as "[alpha2-P2W17O61{O(SiOH)2}]6-"), derived from the cleavage of Ph-Si bonds by the thermal degradation of [alpha2-P2W17O61{O(SiPh)2}]6-. On the other hand, the reactions of alpha2-mono-lacunary Dawson POMs with GeX4 (X=OEt, Cl) gave the monomeric species of mono-germanium-substituted Dawson POM (Me2NH2)7[alpha2-P2W17O61(GeOH)].5H2O Me2NH(2)-2, which was characterized by CHN analysis, TG/DTA, FTIR, X-ray crystallography, and (solid-state and solution) 31P NMR spectroscopy. X-ray crystallography revealed that compound Me2NH(2)-2 was a monomeric species, but the Ge site per formula unit was not determined due to disorder of alpha-Dawson structure.

The QCD running coupling

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

Deur, Alexandre; Brodsky, Stanley J.; de Téramond, Guy F.

Here, we review present knowledge onmore » $$\\alpha_{s}$$, the Quantum Chromodynamics (QCD) running coupling. The dependence of $$\\alpha_s(Q^2)$$ on momentum transfer $Q$ encodes the underlying dynamics of hadron physics --from color confinement in the infrared domain to asymptotic freedom at short distances. We will survey our present theoretical and empirical knowledge of $$\\alpha_s(Q^2)$$, including constraints at high $Q^2$ predicted by perturbative QCD, and constraints at small $Q^2$ based on models of nonperturbative dynamics. In the first, introductory, part of this review, we explain the phenomenological meaning of the coupling, the reason for its running, and the challenges facing a complete understanding of its analytic behavior in the infrared domain. In the second, more technical, part of the review, we discuss $$\\alpha_s(Q^2)$$ in the high momentum transfer domain of QCD. We review how $$\\alpha_s$$ is defined, including its renormalization scheme dependence, the definition of its renormalization scale, the utility of effective charges, as well as `` Commensurate Scale Relations" which connect the various definitions of the QCD coupling without renormalization scale ambiguity. We also report recent important experimental measurements and advanced theoretical analyses which have led to precise QCD predictions at high energy. As an example of an important optimization procedure, we discuss the ``Principle of Maximum Conformality" which enhances QCD's predictive power by removing the dependence of the predictions for physical observables on the choice of the gauge and renormalization scheme. In last part of the review, we discuss $$\\alpha_s(Q^2)$$ in the low momentum transfer domain, where there has been no consensus on how to define $$\\alpha_s(Q^2)$$ or its analytic behavior. We will discuss the various approaches used for low energy calculations. Among them, we will discuss the light-front holographic approach to QCD in the strongly coupled regime and its prediction for the analytic form of $$\\alpha_s(Q^2)$$. The AdS/QCD light-front holographic analysis predicts the color confinement potential underlying hadron spectroscopy and dynamics, and it gives a remarkable connection between the perturbative QCD scale $$\\Lambda$$ and hadron masses. One can also identify a specific scale $$Q_0$$ which demarcates the division between perturbative and nonperturbative QCD. We also review other important methods for computing the QCD coupling, including Lattice QCD, Schwinger-Dyson equations and the Gribov-Zwanziger analysis. After describing these approaches and enumerating conflicting results, we provide a partial discussion on the origin of these discrepancies and how to remedy them. Our aim is not only to review the advances on this difficult subject, but also to suggest what could be the best definition of $$\\alpha_s(Q^2)$$ in order to bring better unity to the subject.« less

The QCD running coupling

DOE PAGES

Deur, Alexandre; Brodsky, Stanley J.; de Téramond, Guy F.

2016-05-09

Here, we review present knowledge onmore » $$\\alpha_{s}$$, the Quantum Chromodynamics (QCD) running coupling. The dependence of $$\\alpha_s(Q^2)$$ on momentum transfer $Q$ encodes the underlying dynamics of hadron physics --from color confinement in the infrared domain to asymptotic freedom at short distances. We will survey our present theoretical and empirical knowledge of $$\\alpha_s(Q^2)$$, including constraints at high $Q^2$ predicted by perturbative QCD, and constraints at small $Q^2$ based on models of nonperturbative dynamics. In the first, introductory, part of this review, we explain the phenomenological meaning of the coupling, the reason for its running, and the challenges facing a complete understanding of its analytic behavior in the infrared domain. In the second, more technical, part of the review, we discuss $$\\alpha_s(Q^2)$$ in the high momentum transfer domain of QCD. We review how $$\\alpha_s$$ is defined, including its renormalization scheme dependence, the definition of its renormalization scale, the utility of effective charges, as well as `` Commensurate Scale Relations" which connect the various definitions of the QCD coupling without renormalization scale ambiguity. We also report recent important experimental measurements and advanced theoretical analyses which have led to precise QCD predictions at high energy. As an example of an important optimization procedure, we discuss the ``Principle of Maximum Conformality" which enhances QCD's predictive power by removing the dependence of the predictions for physical observables on the choice of the gauge and renormalization scheme. In last part of the review, we discuss $$\\alpha_s(Q^2)$$ in the low momentum transfer domain, where there has been no consensus on how to define $$\\alpha_s(Q^2)$$ or its analytic behavior. We will discuss the various approaches used for low energy calculations. Among them, we will discuss the light-front holographic approach to QCD in the strongly coupled regime and its prediction for the analytic form of $$\\alpha_s(Q^2)$$. The AdS/QCD light-front holographic analysis predicts the color confinement potential underlying hadron spectroscopy and dynamics, and it gives a remarkable connection between the perturbative QCD scale $$\\Lambda$$ and hadron masses. One can also identify a specific scale $$Q_0$$ which demarcates the division between perturbative and nonperturbative QCD. We also review other important methods for computing the QCD coupling, including Lattice QCD, Schwinger-Dyson equations and the Gribov-Zwanziger analysis. After describing these approaches and enumerating conflicting results, we provide a partial discussion on the origin of these discrepancies and how to remedy them. Our aim is not only to review the advances on this difficult subject, but also to suggest what could be the best definition of $$\\alpha_s(Q^2)$$ in order to bring better unity to the subject.« less

The structure of poly(carbonsuboxide) on the atomic scale: a solid-state NMR study.

PubMed

Schmedt auf der Günne, Jörn; Beck, Johannes; Hoffbauer, Wilfried; Krieger-Beck, Petra

2005-07-18

In this contribution we present a study of the structure of amorphous poly(carbonsuboxide) (C3O2)x by 13C solid-state NMR spectroscopy supported by infrared spectroscopy and chemical analysis. Poly(carbonsuboxide) was obtained by polymerization of carbonsuboxide C3O2, which in turn was synthesized from malonic acid bis(trimethylsilylester). Two different 13C labeling schemes were applied to probe inter- and intramonomeric bonds in the polymer by dipolar solid-state NMR methods and also to allow quantitative 13C MAS NMR spectra. Four types of carbon environments can be distinguished in the NMR spectra. Double-quantum and triple-quantum 2D correlation experiments were used to assign the observed peaks using the through-space and through-bond dipolar coupling. In order to obtain distance constraints for the intermonomeric bonds, double-quantum constant-time experiments were performed. In these experiments an additional filter step was applied to suppress contributions from not directly bonded 13C,13C spin pairs. The 13C NMR intensities, chemical shifts, connectivities and distances gave constraints for both the polymerization mechanism and the short-range order of the polymer. The experimental results were complemented by bond lengths predicted by density functional theory methods for several previously suggested models. Based on the presented evidence we can unambiguously exclude models based on gamma-pyronic units and support models based on alpha-pyronic units. The possibility of planar ladder- and bracelet-like alpha-pyronic structures is discussed.

Evidence for Intramolecular Antiparallel Beta-Sheet Structure in Alpha-Synuclein Fibrils from a Combination of Two-Dimensional Infrared Spectroscopy and Atomic Force Microscopy

NASA Astrophysics Data System (ADS)

Roeters, Steven J.; Iyer, Aditya; Pletikapić, Galja; Kogan, Vladimir; Subramaniam, Vinod; Woutersen, Sander

2017-01-01

The aggregation of the intrinsically disordered protein alpha-synuclein (αS) into amyloid fibrils is thought to play a central role in the pathology of Parkinson’s disease. Using a combination of techniques (AFM, UV-CD, XRD, and amide-I 1D- and 2D-IR spectroscopy) we show that the structure of αS fibrils varies as a function of ionic strength: fibrils aggregated in low ionic-strength buffers ([NaCl] ≤ 25 mM) have a significantly different structure than fibrils grown in higher ionic-strength buffers. The observations for fibrils aggregated in low-salt buffers are consistent with an extended conformation of αS molecules, forming hydrogen-bonded intermolecular β-sheets that are loosely packed in a parallel fashion. For fibrils aggregated in high-salt buffers (including those prepared in buffers with a physiological salt concentration) the measurements are consistent with αS molecules in a more tightly-packed, antiparallel intramolecular conformation, and suggest a structure characterized by two twisting stacks of approximately five hydrogen-bonded intermolecular β-sheets each. We find evidence that the high-frequency peak in the amide-I spectrum of αS fibrils involves a normal mode that differs fundamentally from the canonical high-frequency antiparallel β-sheet mode. The high sensitivity of the fibril structure to the ionic strength might form the basis of differences in αS-related pathologies.

Evidence for Intramolecular Antiparallel Beta-Sheet Structure in Alpha-Synuclein Fibrils from a Combination of Two-Dimensional Infrared Spectroscopy and Atomic Force Microscopy

PubMed Central

Roeters, Steven J.; Iyer, Aditya; Pletikapić, Galja; Kogan, Vladimir; Subramaniam, Vinod; Woutersen, Sander

2017-01-01

The aggregation of the intrinsically disordered protein alpha-synuclein (αS) into amyloid fibrils is thought to play a central role in the pathology of Parkinson’s disease. Using a combination of techniques (AFM, UV-CD, XRD, and amide-I 1D- and 2D-IR spectroscopy) we show that the structure of αS fibrils varies as a function of ionic strength: fibrils aggregated in low ionic-strength buffers ([NaCl] ≤ 25 mM) have a significantly different structure than fibrils grown in higher ionic-strength buffers. The observations for fibrils aggregated in low-salt buffers are consistent with an extended conformation of αS molecules, forming hydrogen-bonded intermolecular β-sheets that are loosely packed in a parallel fashion. For fibrils aggregated in high-salt buffers (including those prepared in buffers with a physiological salt concentration) the measurements are consistent with αS molecules in a more tightly-packed, antiparallel intramolecular conformation, and suggest a structure characterized by two twisting stacks of approximately five hydrogen-bonded intermolecular β-sheets each. We find evidence that the high-frequency peak in the amide-I spectrum of αS fibrils involves a normal mode that differs fundamentally from the canonical high-frequency antiparallel β-sheet mode. The high sensitivity of the fibril structure to the ionic strength might form the basis of differences in αS-related pathologies. PMID:28112214

Reactivity of superoxide radical anion and hydroperoxyl radical with alpha-phenyl-N-tert-butylnitrone (PBN) derivatives.

PubMed

Durand, Grégory; Choteau, Fanny; Pucci, Bernard; Villamena, Frederick A

2008-12-04

Nitrones have exhibited pharmacological activity against radical-mediated pathophysiological conditions and as analytical reagents for the identification of transient radical species by electron paramagnetic resonance (EPR) spectroscopy. In this work, competitive spin trapping, stopped-flow kinetics, and density functional theory (DFT) were employed to assess and predict the reactivity of O(2)(*-) and HO(2)(*) with various para-substituted alpha-phenyl-N-tert-butylnitrone (PBN) spin traps. Rate constants of O(2)(*-) trapping by nitrones were determined using competitive UV-vis stopped-flow method with phenol red (PR) as probe, while HO(2)(*) trapping rate constants were calculated using competition kinetics with 5,5-dimethylpyrroline N-oxide (DMPO) by employing EPR spectroscopy. The effects of the para substitution on the charge density of the nitronyl-carbon and on the free energies of nitrone reactivity with O(2)(*-) and HO(2)(*) were computationally rationalized at the PCM/B3LYP/6-31+G(d,p)//B3LYP/6-31G(d) level of theory. Theoretical and experimental data show that the rate of O(2)(*-) addition to PBN derivatives is not affected by the polar effect of the substituents. However, the reactivity of HO(2)(*) follows the Hammett equation and is increased as the substituent becomes more electron withdrawing. This supports the conclusion that the nature of HO(2)(*) addition to PBN derivatives is electrophilic, while the addition of O(2)(*-) to PBN-type compounds is only weakly electrophilic.

Quantitative Analysis of Plutonium Content in Particles Collected from a Certified Reference Material by Total Nuclear Reaction Energy (Q Value) Spectroscopy

NASA Astrophysics Data System (ADS)

Croce, M. P.; Hoover, A. S.; Rabin, M. W.; Bond, E. M.; Wolfsberg, L. E.; Schmidt, D. R.; Ullom, J. N.

2016-08-01

Microcalorimeters with embedded radioisotopes are an emerging category of sensor with advantages over existing methods for isotopic analysis of trace-level nuclear materials. For each nuclear decay, the energy of all decay products captured by the absorber (alpha particles, gamma rays, X-rays, electrons, daughter nuclei, etc.) is measured in one pulse. For alpha-decaying isotopes, this gives a measurement of the total nuclear reaction energy (Q value) and the spectra consist of well-separated, narrow peaks. We have demonstrated a simple mechanical alloying process to create an absorber structure consisting of a gold matrix with small inclusions of a radioactive sample. This absorber structure provides an optimized energy thermalization environment, resulting in high-resolution spectra with minimal tailing. We have applied this process to the analysis of particles collected from the surface of a plutonium metal certified reference material (CRM-126A from New Brunswick Laboratory) and demonstrated isotopic analysis by microcalorimeter Q value spectroscopy. Energy resolution from the Gaussian component of a Bortels function fit was 1.3 keV FWHM at 5244 keV. The collected particles were integrated directly into the detector absorber without any chemical processing. The ^{238}Pu/^{239}Pu and ^{240}Pu/^{239}Pu mass ratios were measured and the results confirmed against the certificate of analysis for the reference material. We also demonstrated inter-element analysis capability by measuring the ^{241}Am/^{239}Pu mass ratio.

Fabrication, characterization and simulation of 4H-SiC Schottky diode alpha particle detectors for pyroprocessing actinide monitoring

NASA Astrophysics Data System (ADS)

Garcia, Timothy Richard

Pyroprocessing is a method of using high-temperature molten salts and electric fields to separate and collect fuel isotopes of used nuclear fuel. It has been has been tested in the U.S. at Idaho National Laboratory as a key step in closing the nuclear fuel cycle. One technical problem with the pyroprocessing method is a lack of knowledge regarding the actinide concentrations in the salt bath during operation, since on-line techniques for measuring these concentrations are not presently available. 4H-SiC Schottky diode detectors can potentially fulfill this need. Such detectors would operate in contact with the molten salt, and measure concentrations via alpha-particle spectroscopy. This work seeks to fabricate and characterize 4H-SiC Schottky diode detectors at high temperature, model the alpha particle spectrum expected in a molten salt, and model the operation of the detectors to confirm the physics of operation is as expected. In this work, 4H-SiC Schottky diode detectors were fabricated at OSU Nanotech West. After fabrication, these detectors were characterized using both I-V curves and Am-241 alpha-particle energy spectra. All measurements were made as a function of temperature, from room temperature up to 500°C. The average energy required to create an electron-hole pair was observed to decrease with an increase of temperature, due to a decrease of both the 4H-SiC bandgap and non-linear energy loss terms. Furthermore, the FWHM of the spectra was observed to be dependent on the leakage current at a certain temperature, and not dependent on the temperature itself. Secondly, the alpha particle energy spectrum in the pyroprocessing environment was modeled using SRIM. The molten salt was modeled in 3 different geometries, with or without a protective cover material on top of the detector. Due to the loss of alpha-particle energy in the molten salt itself, a high-energy alpha emitter may completely cover the spectrum from a lower-energy alpha emitter. Each of the geometries simulated showed a different sensitivity to the lower-energy alpha emitter. Regardless of which geometry was modeled, it was observed that it is possible to measure both the emission energy of the alpha particles, as well as the concentration of the alpha emitter in the liquid. Lastly, Sentaurus TCAD was used to simulate the detection of alpha-particle charge collection in situations that are relevant to the molten salt alpha particle energy spectra. The effect of electric field negation was investigated, as well as velocity saturation. Finally, the dependence of charge recombination on temperature, alpha particle energy, and angle of incidence was investigated. These simulations captured the measurements performed at room temperature. With changed angle of incidence, the change in the amount of charge collected was less than 1 percent, indicating a weak dependence. Also, the amount of charge lost to Auger recombination was seen to increase with temperature. This disagrees with observations from experiment, indicating that the temperature dependence of one or more parameters of the model may not be accurate.

On the anomalous adsorption of [Pd(edta)]2- at the water/Goethite interface: spectroscopic evidence for two types of surface complexes.

PubMed

Kaplun, Marina; Nordin, Agneta; Persson, Per

2008-01-15

The structure of palladium(II) ethylenediaminetetraacetate (edta) in aqueous solutions and its adsorption on the surface of goethite (alpha-FeOOH) were studied using extended X-ray absorption fine structure spectroscopy and attenuated total reflection Fourier transform infrared spectroscopy. The obtained results show that in aqueous solutions, Pd-edta exists as a 1:1 complex, [Pd(edta)]2-, with edta acting as a quadridentate ligand. On the surface of goethite, [Pd(edta)]2- forms two different types of complexes over a pH range of 3.40-8.12. At pH < 5, [Pd(edta)]2- adsorbs as an outer-sphere species with possible hydrogen bonding. At higher pH values, the formation of inner-sphere complexes of the cation-type sets in after a cleavage of one glycinate ring and the formation of an (edta)Pd-O-Fe linkage.

Tomography of a simply magnetized toroidal plasma

NASA Astrophysics Data System (ADS)

Ruggero, BARNI; Stefano, CALDIROLA; Luca, FATTORINI; Claudia, RICCARDI

2018-02-01

Optical emission spectroscopy is a passive diagnostic technique, which does not perturb the plasma state. In particular, in a hydrogen plasma, Balmer-alpha (H α ) emission can be easily measured in the visible range along a line of sight from outside the plasma vessel. Other emission lines in the visible spectral range from hydrogen atoms and molecules can be exploited too, in order to gather complementary pieces of information on the plasma state. Tomography allows us to capture bi-dimensional structures. We propose to adopt an emission spectroscopy tomography for studying the transverse profiles of magnetized plasmas when Abel inversion is not exploitable. An experimental campaign was carried out at the Thorello device, a simple magnetized torus. The characteristics of the profile extraction method, which we implemented for this purpose are discussed, together with a few results concerning the plasma profiles in a simply magnetized torus configuration.

Diagnostics and results from coaxial plasma gun development for the PLX- α project

NASA Astrophysics Data System (ADS)

Case, A.; Brockington, S.; Cruz, E.; Witherspoon, F. D.

2016-10-01

We present results from the diagnostics used during development of the contoured gap coaxial plasma guns for the PLX- α project at LANL. Plasma-jet diagnostics include fast photodiodes for velocimetry, a ballistic pendulum for total plasmoid momentum, and interferometry for line integrated density. Deflectometry will be used for line integrated perpendicular density gradients. Time-resolved high-resolution spectroscopy using a novel detector and time-integrated survey spectroscopy are used for measurements of velocity and temperature, as well as impurities. We will also use a Faraday cup for density, fast imaging for plume geometry, and time-integrated imaging for overall light emission. Experimental results are compared to the desired target parameters for the plasma jets (up to n 2 ×1016cm-3 , v 50km / s , mass 5gm , radius = 4cm , and length 10cm). This work supported by the ARPA-E ALPHA Program.

Hydrophobizing coatings for cultural heritage. A detailed study of resin/stone surface interaction

NASA Astrophysics Data System (ADS)

Fermo, P.; Cappelletti, G.; Cozzi, N.; Padeletti, G.; Kaciulis, S.; Brucale, M.; Merlini, M.

2014-07-01

Conservation of historical buildings is an important issue and the environmental conditions seriously affect the monument's stones. The protection of cultural heritage buildings and monuments by surface treatment with polymers is a common practice due to their ability to form a protective layer on the monument's surface as well as to control the transport of different fluids from the surface to the monument's interior. In this work, three different substrates were used: Carrara marble, Botticino limestone, and Angera stone. A commercially available Si-based resin (Alpha®SI30) was used as protective agent to improve the hydrophobicity features of the different tested materials. The surface properties of the coating and the relative interaction with the adopted stones were studied using different techniques such as contact angle measurements, electron microscope coupled with an energy dispersive spectrometer, X-ray photoelectron spectroscopy, atomic force microscopy, and attenuated total reflection infrared spectroscopy.

Direct detection of ligand binding to Sepharose-immobilised protein using saturation transfer double difference (STDD) NMR spectroscopy

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

Haselhorst, Thomas; Muenster-Kuehnel, Anja K.; Oschlies, Melanie

2007-08-10

We report an easy and direct application of 'Saturation Transfer Double Difference' (STDD) NMR spectroscopy to identify ligands that bind to a Sepharose-immobilised target protein. The model protein, cytidine 5'-monophosphate sialic acid (CMP-Sia) synthetase, was expressed as a Strep-Tag II fusion protein and immobilised on Strep-Tactin Sepharose. STD NMR experiments of the protein-enriched Sepharose matrix in the presence of a binding ligand (cytidine 5'-triphosphate, CTP) and a non-binding ligand ({alpha}/{beta}-glucose) clearly show that CTP binds to the immobilised enzyme, whereas glucose has no affinity. This approach has three major advantages: (a) only low quantities of protein are required, (b) nomore » specialised NMR technology or the application of additional data analysis by non-routine methods is required, and (c) easy multiple use of the immobilised protein is available.« less

Cryogenic mount for mirror and piezoelectric actuator for an optical cavity.

PubMed

Oliveira, A N; Moreira, L S; Sacramento, R L; Kosulic, L; Brasil, V B; Wolff, W; Cesar, C L

2017-06-01

We present the development of a mount that accommodates a mirror and a piezoelectric actuator with emphasis on physical needs for low temperature operation. The design uses a monolithic construction with flexure features that allow it to steadily hold the mirror and the piezoelectric actuator without glue and accommodate differential thermal contraction. The mount is small and lightweight, adding little heat capacity and inertia. It provides a pre-loading of the piezoelectric actuator as well as a good thermal connection to the mirror and a thermal short across the piezoelectric actuator. The performance of the assemblies has been tested by thermally cycling from room temperature down to 3 K more than a dozen times and over one hundred times to 77 K, without showing any derating. Such mounts are proposed for the cryogenic optical enhancement cavities of the ALPHA experiment at CERN for laser spectroscopy of antihydrogen and for hydrogen spectroscopy in our laboratory at UFRJ.

Immune function and brain abnormalities in patients with systemic lupus erythematosus without overt neuropsychiatric manifestations.

PubMed

Kozora, E; Filley, C M; Zhang, L; Brown, M S; Miller, D E; Arciniegas, D B; Pelzman, J L; West, S G

2012-04-01

This study examined the relationship between immune, cognitive and neuroimaging assessments in subjects with systemic lupus erythematosus (SLE) without histories of overt neuropsychiatric (NP) disorders. In total, 84 subjects with nonNPSLE and 37 healthy controls completed neuropsychological testing from the American College of Rheumatology SLE battery. Serum autoantibody and cytokine measures, volumetric magnetic resonance imaging, and magnetic resonance spectroscopy data were collected on a subset of subjects. NonNPSLE subjects had lower scores on measures of visual/complex attention, visuomotor speed and verbal memory compared with controls. No clinically significant differences between nonNPSLE patients and controls were found on serum measures of lupus anticoagulant, anticardiolipin antibodies, beta 2-glycoproteins, or pro-inflammatory cytokines (interleukin (IL)-1, IL-6, interferon alpha (IFN-alpha), and interferon gamma (IFN-gamma)). Higher scores on a global cognitive impairment index and a memory impairment index were correlated with lower IFN-alpha. Few associations between immune functions and neuroimaging parameters were found. Results indicated that nonNPSLE patients demonstrated cognitive impairment but not immune differences compared with controls. In these subjects, who were relatively young and with mild disease, no relationship between cognitive dysfunction, immune parameters, or previously documented neuroimaging abnormalities were noted. Immune measures acquired from cerebrospinal fluid instead of serum may yield stronger associations.

Spectroscopic studies of bacteriorhodopsin fragments dissolved in organic solution.

PubMed Central

Torres, J; Padrós, E

1995-01-01

Fourier transform infrared and UV fourth-derivative spectroscopies were used to study the secondary structure of bacteriorhodopsin and its chymotryptic and one of the sodium borohydride fragments dissolved in chloroform-methanol (1:1, v/v), 0.1 M LiClO4. The C1 fragment (helices C, D, E, F, and G) showed an alpha-helical content of about 53%, whereas C2 (helices A and B) had about 60%, and B2 (helices F and G) about 65% alpha-helix. The infrared main band indicated differences in alpha-helical properties between these fragments. These techniques were also used to obtain information on the interactions among helices. According to the results obtained from the hydrogen/deuterium exchange kinetics, about 40% of the amide protons of C2 are particularly protected against exchange, whereas for the C1 fragment this process is unexpectedly fast. UV fourth-derivative spectra of these samples were used to obtain information about the environment of Trp side chains. The results showed that the Trp residues of C2 are more shielded from the solvent than those of C1 or B2. The results of this work indicate that the specific interactions existing between the transmembrane segments induce different types of helical conformations in native bacteriorhodopsin. PMID:7612847

Higher Signal-to-Noise Measurements of Alpha-element Abundances in the M31 System

NASA Astrophysics Data System (ADS)

Escala, Ivanna; Kirby, Evan N.

2018-06-01

The stellar halo and tidal streams of M31 provide an essential counterpoint to the same structures around the Milky Way (MW). While measurements of [Fe/H] and [$\\alpha$/Fe] have been made in the MW, little is known about the detailed chemical abundances of the M31 system. To make progress with existing telescopes, we expand upon the technique first presented by Kirby et al., applying spectral synthesis to medium-resolution spectroscopy at lower spectral resolution (R $\\sim$ 1800) across an optical range (4100~\\AA \\ $<$ $\\lambda$ $<$ 9100~\\AA) that extends down the blue. We have obtained deep spectra of red giants in the tidal streams, smooth halo, and disk of M31 using the DEIMOS 600ZD grating, resulting in higher signal-to-noise per spectral resolution element (S/N $\\sim$ 30 \\AA$^{-1}$). By applying our technique to red giant stars in MW globular clusters with higher-resolution ($R$ $\\sim$ 6000) spectra in the blue (4100 - 6300 \\AA), we demonstrate that our technique reproduces previous measurements derived from the red side of the optical (6300 - 9100 \\AA). For the first time, we present measurements of [Fe/H] and [$\\alpha$/Fe] of sufficient quality and sample size to construct quantitative models of galactic chemical evolution in the M31 system.

Identification of a novel selenium-containing compound, selenoneine, as the predominant chemical form of organic selenium in the blood of bluefin tuna.

PubMed

Yamashita, Yumiko; Yamashita, Michiaki

2010-06-11

A novel selenium-containing compound having a selenium atom in the imidazole ring, 2-selenyl-N(alpha),N(alpha),N(alpha)-trimethyl-L-histidine, 3-(2-hydroseleno-1H-imidazol-5-yl)-2-(trimethylammonio)propanoate, was identified from the blood and other tissues of the bluefin tuna, Thunnus orientalis. The selenium-containing compound was purified from the tuna blood in several chromatographic steps. High resolution mass spectrometry and nuclear magnetic resonance spectroscopy showed that the exact mass of the [M+H](+) ion of the compound was 533.0562 and the molecular formula was C(18)H(29)N(6)O(4)Se(2). Its gross structure was assigned as the oxidized dimeric form of an ergothioneine selenium analog in which the sulfur of ergothioneine is replaced by selenium. Therefore, we named this novel selenium-containing compound "selenoneine." By speciation analysis of organic selenium compounds using liquid chromatography inductively coupled plasma mass spectrometry, selenoneine was found widely distributed in various tissues of the tuna, with the highest concentration in blood; mackerel blood contained similar levels. Selenoneine was measurable at 2-4 orders of magnitude lower concentration in a limited set of tissues from squid, tilapia, pig, and chicken. Quantitatively, selenoneine is the predominant form of organic selenium in tuna tissues.

Use of EPR Spin-Trapping Techniques to Detect Radicals from Rat Lung Lavage Fluid Following Sulfur Mustard Vapor Exposure

DTIC Science & Technology

1993-05-13

lung injury. Anesthetized rats were intratracheally intubated and exposed to 0.35 mg HD vapor over 50 min, Immediately, 1 hr or 24 hr after exposure...lungs were lavaged with the spin trap, alpha-phenyl-t-butyl nitrone (PBN; 0.35 mg/ml). Recovered lavage fluid was assayed by EPR spectroscopy for...in EtOH (100 Ml), or EtOH alone (control), was placed in a water Jacketed (37° C) vapor generator and the rats .ere exposed for 50 min. by which time

Toward broadband mechanical spectroscopy.

PubMed

Hecksher, Tina; Torchinsky, Darius H; Klieber, Christoph; Johnson, Jeremy A; Dyre, Jeppe C; Nelson, Keith A

2017-08-15

Diverse material classes exhibit qualitatively similar behavior when made viscous upon cooling toward the glass transition, suggesting a common theoretical basis. We used seven different measurement methods to determine the mechanical relaxation kinetics of a prototype molecular glass former over a temporal range of 13 decades and over a temperature range spanning liquid to glassy states. The data conform to time-temperature superposition for the main (alpha) process and to a scaling relation of schematic mode-coupling theory. The broadband mechanical measurements demonstrated have fundamental and practical applications in polymer science, geophysics, multifunctional materials, and other areas.

Development and testing of laser-induced breakdown spectroscopy for the Mars Rover Program : elemental analysis at stand-off distances

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

Cremers, D. A.; Wiens, R. C.; Arp, Z. A.

2003-01-01

One of the most Fundamental pieces of information about any planetary body is the elemental cornposition of its surface materials. The Viking Martian landers employed XRF (x-ray fluorescence) and the MER rovers are carrying APXS (alpha-proton x-ray spectrometer) instruments upgraded from that used on the Pathfinder rover to supply elemental composition information for soils and rocks for which direct contact is possible. These in-situ analyses require that the lander or rover be in contact with the sample

Moderate resolution spectrophotometry of high redshift quasars

NASA Technical Reports Server (NTRS)

Schneider, Donald P.; Schmidt, Maarten; Gunn, James E.

1991-01-01

A uniform set of photometry and high signal-to-noise moderate resolution spectroscopy of 33 quasars with redshifts larger than 3.1 is presented. The sample consists of 17 newly discovered quasars (two with redshifts in excess of 4.4) and 16 sources drawn from the literature. The objects in this sample have r magnitudes between 17.4 and 21.4; their luminosities range from -28.8 to -24.9. Three of the 33 objects are broad absorption line quasars. A number of possible high redshift damped Ly-alpha systems were found.

Hydroxyester disaccharides from fruits of cape gooseberry (Physalis peruviana).

PubMed

Mayorga, Humberto; Duque, Carmenza; Knapp, Holger; Winterhalter, Peter

2002-02-01

The 3-O-beta-D-glucopyranosyl-(1-->6)-beta-D-glucopyranoside of ethyl 3-hydroxyoctanoate and the diastereomeric 3-O-alpha-L-arabinopyranosyl-(1-->6)-beta-D-glucopyranosides of (3R) and (3S)-butyl 3-hydroxybutanoate, respectively, were isolated by chromatographic methods from fruits of cape gooseberry (Physalis peruviana) harvested in Colombia. Their structures were identified by ESI-MS/MS and NMR spectroscopy. The three glycoconjugates can be considered as immediate precursors of ethyl 3-hydroxyoctanoate and butyl 3-hydroxybutanoate, which are important aroma volatiles found in the fruit.

Electronic Structure of Alpha-Quartz and the Influence of Some Local Disorder: A Tight Binding Study,

DTIC Science & Technology

1977-01-01

An s extended summary of the theoretical and ex- perimental work on Si02 is to be found in that paper. The tight-binding basis con- sists of the four... theoretical and experimental works contained therein. 4. B. Fischer, R. A. Pollak, T. H. Distefano and W. D. Grobman, "Electronic Structure of SiO 2, SixGe 1 x...and GeO 2 from Photoemission Spectroscopy," Phys. Rev. BI5, 3193 (1977), and references to earlier works therein. 5. J. H. Scofield , "Hartree-Slater

Next generation laser-based standoff spectroscopy techniques for Mars exploration.

PubMed

Gasda, Patrick J; Acosta-Maeda, Tayro E; Lucey, Paul G; Misra, Anupam K; Sharma, Shiv K; Taylor, G Jeffrey

2015-01-01

In the recent Mars 2020 Rover Science Definition Team Report, the National Aeronautics and Space Administration (NASA) has sought the capability to detect and identify elements, minerals, and most importantly, biosignatures, at fine scales for the preparation of a retrievable cache of samples. The current Mars rover, the Mars Science Laboratory Curiosity, has a remote laser-induced breakdown spectroscopy (LIBS) instrument, a type of quantitative elemental analysis, called the Chemistry Camera (ChemCam) that has shown that laser-induced spectroscopy instruments are not only feasible for space exploration, but are reliable and complementary to traditional elemental analysis instruments such as the Alpha Particle X-Ray Spectrometer. The superb track record of ChemCam has paved the way for other laser-induced spectroscopy instruments, such as Raman and fluorescence spectroscopy. We have developed a prototype remote LIBS-Raman-fluorescence instrument, Q-switched laser-induced time-resolved spectroscopy (QuaLITy), which is approximately 70 000 times more efficient at recording signals than a commercially available LIBS instrument. The increase in detection limits and sensitivity is due to our development of a directly coupled system, the use of an intensified charge-coupled device image detector, and a pulsed laser that allows for time-resolved measurements. We compare the LIBS capabilities of our system with an Ocean Optics spectrometer instrument at 7 m and 5 m distance. An increase in signal-to-noise ratio of at least an order of magnitude allows for greater quantitative analysis of the elements in a LIBS spectrum with 200-300 μm spatial resolution at 7 m, a Raman instrument capable of 1 mm spatial resolution at 3 m, and bioorganic fluorescence detection at longer distances. Thus, the new QuaLITy instrument fulfills all of the NASA expectations for proposed instruments.

Adsorption-induced conformational changes of antifreeze glycoproteins at the ice/water interface.

PubMed

Uda, Yukihiro; Zepeda, Salvador; Kaneko, Fumitoshi; Matsuura, Yoshiki; Furukawa, Yoshinori

2007-12-27

The conformation of antifreeze glycoprotein (AFGP) molecules adsorbed at the ice/water interface was studied by attenuated total reflection (ATR)-FTIR spectroscopy. Measurements were carried out for AFGP/D2O solution films formed on the surface of an ATR prism as a function of temperature. Using the FTIR spectrum from the O-D stretching band of D2O molecules, we monitored the supercooled and frozen states of the film and measured the thickness of the quasi-liquid layer (QLL) at the ice/prism interfaces. The AFGP structure was determined for the liquid, supercooled, and frozen states of the solution film using the amide I band spectra. No noticeable differences in conformation were observed in the solution conformation from room temperature down to the 15 K supercooling studied, whereas the alpha-helical content of AFGP suddenly increased when the supercooled solution film froze at -15 degrees C. This change in conformation can increase the overall interaction between the AFGP molecules and ice surface and allow a stronger adsorption. In contrast, the alpha-helical content of AFGP in the frozen film gradually decreased with increasing temperature and finally returned to its solution-state level at the melting point of D2O ice. This gradual decrease in the alpha-helix content directly correlates with the measured increase in QLL thickness. Finally, we conclude that the differences in the alpha-helix signals between the frozen and supercooled states indicate the conformational change of AFGP molecules upon adsorption at the ice/water interface, emphasizing the importance of the structure-function relationship, even for this highly flexible antifreeze.

Assignment of the sup 1 H and sup 15 N NMR spectra of Rhodobacter capsulatus ferrocytochrome c sub 2

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

Gooley, P.R.; Caffrey, M.S.; Cusanovich, M.A.

1990-03-06

The peptide resonances of the {sup 1}H and {sup 15}N nuclear magnetic resonance spectra of ferrocytochrome c{sub 2} from Rhodobacter capsulatus are sequentially assigned by a combination of 2D {sup 1}H-{sup 1}H and {sup 1}H-{sup 15}N spectroscopy, the latter performed on {sup 15}N-enriched protein. Short-range nuclear Overhauser effect (NOE) data show {alpha}-helices from residues 3-17, 55-65, 69-88, and 103-115. Within the latter two {alpha}-helices, there are three single 3{sub 10} turns, 70-72, 76-78, and 107-109. In addition {alpha}H-NH{sub i+1} and {alpha}H-NH{sub i+2} NOEs indicate that the N-terminal helix (3-17) is distorted. Compared to horse or tuna cytochrome c and cytochromemore » c{sub 2} of Rhodospirillium rubrum, there is a 6-residue insertion at residues 23-29 in R. capsulatus cytochrome c{sub 2}. The NOE data show that this insertion forms a loop, probably an {Omega} loop. {sup 1}H-{sup 15}N heteronuclear multiple quantum correlation experiments are used to follow NH exchange over a period of 40 h. As the 2D spectra are acquired in short time periods (30 min), rates for intermediate exchanging protons can be measured. Comparison of the NH exchange data for the N-terminal helix of cytochrome c{sub 2} of R. capsulatus with the highly homologous horse heart cytochrome c shows that this helix is less stable in cytochrome c{sub 2}.« less

New study on the correlation between carbon dioxide concentration in the environment and radon monitor devices.

PubMed

Shahrokhi, A; Burghele, B D; Fábián, F; Kovács, T

2015-12-01

The influence of high geogenic carbon dioxide concentrations on monitoring devices might present a significant challenge to the measurement of radon concentrations in environments with a high level of carbon dioxide concentration such as volcano sites, mofettes, caves, etc. In this study, the influence of carbon dioxide concentration on several different types of radon monitor devices - including Alpha Spectrometry (Sarad RTM 2200, EQF 3220, RAD7), Ionizing Chamber (AlphaGUARD PQ2000 PRO) and Active Cell (Active scintillation cell, Pylon 300A) - was examined to represent new aspects of radon measuring in environments with carbon dioxide. In light of the results, all measuring devices were exposed to variable conditions affected by carbon dioxide concentration, except for the AlphaGUARD, which was kept in a steady state throughout the experiment. It was observed that alpha spectroscopy devices were affected by carbon dioxide, since measured radon concentrations decreased in the presence of 70% and 90% carbon dioxide concentrations by 26.5 ± 2% and 14.5 ± 2.5% for EQF 3220, and 32 ± 2% and 35.5 ± 2% for RTM 2200. However, the ionizing chamber instrument was unaffected by changes in carbon dioxide concentration. It was determined that the RAD7 performed relatively inefficiently in the presence of carbon dioxide concentrations higher than 67% by an overall efficiency factor of approximately 0.52, confirming that it is not an admissible radon monitor instrument in environments with high carbon dioxide concentrations. Copyright © 2015 Elsevier Ltd. All rights reserved.

ELLERMAN BOMBS AT HIGH RESOLUTION. I. MORPHOLOGICAL EVIDENCE FOR PHOTOSPHERIC RECONNECTION

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

Watanabe, Hiroko; Kitai, Reizaburo; Vissers, Gregal

2011-07-20

High-resolution imaging-spectroscopy movies of solar active region NOAA 10998 obtained with the Crisp Imaging Spectropolarimeter at the Swedish 1-m Solar Telescope show very bright, rapidly flickering, flame-like features that appear intermittently in the wings of the Balmer H{alpha} line in a region with moat flows and likely some flux emergence. They show up at regular H{alpha} blue-wing bright points that outline the magnetic network, but flare upward with much larger brightness and distinct 'jet' morphology seen from aside in the limbward view of these movies. We classify these features as Ellerman bombs and present a morphological study of their appearancemore » at the unprecedented spatial, temporal, and spectral resolution of these observations. The bombs appear along the magnetic network with footpoint extents up to 900 km. They show apparent travel away from the spot along the pre-existing network at speeds of about 1 km s{sup -1}. The bombs flare repetitively with much rapid variation at timescales of seconds only, in the form of upward jet-shaped brightness features. These reach heights of 600-1200 km and tend to show blueshifts; some show bi-directional Doppler signature and some seem accompanied with an H{alpha} surge. They are not seen in the core of H{alpha} due to shielding by overlying chromospheric fibrils. The network where they originate has normal properties. The morphology of these jets strongly supports deep-seated photospheric reconnection of emergent or moat-driven magnetic flux with pre-existing strong vertical network fields as the mechanism underlying the Ellerman bomb phenomenon.« less

Nebular Line Emission and Stellar Mass of Bright z 8 Galaxies "Super-Eights"

NASA Astrophysics Data System (ADS)

Holwerda, Benne; Bouwens, Rychard; Trenti, Michele; Oesch, Pascal; Labbe, Ivo; Smit, Renske; Roberts-Borsani, Guido; Bernard, Stephanie; Bridge, Joanna

2018-05-01

Searches for the Lyman-alpha emission from the very first galaxies ionizing the Universe have proved to be extremely difficult with limited success beyond z 7 (<3% detections). However, a search of all CANDELS yielded four bright z 8 sources with associated strong Lyman-alpha lines, despite the Universe expected to be 70% neutral at this time. The key to their selection is an extremely red IRAC color ([3.6]-[4.5]> 0.5, Roberts-Borsani+ 2016), indicative of very strong nebular line emission. Do such extreme line emitting galaxies produce most of the photons to reionize the Universe? We propose to expand the sample of bright z 8 galaxies with reliable IRAC colors with seven more Y-band dropouts found with HST and confirmed through HST/Spitzer. The Spitzer observations will test how many of bright z 8 galaxies are IRAC-red and measure both their stellar mass and [OIII]+Hbeta line strength. Together with Keck/VLT spectroscopy, they will address these questions: I) Do all luminous z 8 galaxies show such red IRAC colors ([OIII] emission / hard spectra)? II) Is luminosity or a red IRAC color the dominant predictor for Lyman-alpha emission? III) Or are these sources found along exceptionally transparent sightlines into the early Universe? With 11 bright z 8 sources along different lines-of-sight, all prime targets for JWST, we will aim to determine which of the considered factors (luminosity, color, sight-line) drives the high Lyman-alpha prevalence (100%) and insight into the sources reionizing the Universe.

Effect of particle size on hydroxyapatite crystal-induced tumor necrosis factor alpha secretion by macrophages.

PubMed

Nadra, Imad; Boccaccini, Aldo R; Philippidis, Pandelis; Whelan, Linda C; McCarthy, Geraldine M; Haskard, Dorian O; Landis, R Clive

2008-01-01

Macrophages may promote a vicious cycle of inflammation and calcification in the vessel wall by ingesting neointimal calcific deposits (predominantly hydroxyapatite) and secreting tumor necrosis factor (TNF)alpha, itself a vascular calcifying agent. Here we have investigated whether particle size affects the proinflammatory potential of hydroxyapatite crystals in vitro and whether the nuclear factor (NF)-kappaB pathway plays a role in the macrophage TNFalpha response. The particle size and nano-topography of nine different crystal preparations was analyzed by X-ray diffraction, Raman spectroscopy, scanning electron microscopy and gas sorbtion analysis. Macrophage TNFalpha secretion was inversely related to hydroxyapatite particle size (P=0.011, Spearman rank correlation test) and surface pore size (P=0.014). A necessary role for the NF-kappaB pathway was demonstrated by time-dependent I kappaB alpha degradation and sensitivity to inhibitors of I kappaB alpha degradation. To test whether smaller particles were intrinsically more bioactive, their mitogenic activity on fibroblast proliferation was examined. This showed close correlation between TNFalpha secretion and crystal-induced fibroblast proliferation (P=0.007). In conclusion, the ability of hydroxyapatite crystals to stimulate macrophage TNFalpha secretion depends on NF-kappaB activation and is inversely related to particle and pore size, with crystals of 1-2 microm diameter and pore size of 10-50 A the most bioactive. Microscopic calcific deposits in early stages of atherosclerosis may therefore pose a greater inflammatory risk to the plaque than macroscopically or radiologically visible deposits in more advanced lesions.

Understanding of the mechanical and structural changes induced by alpha particles and heavy ions in the French simulated nuclear waste glass

NASA Astrophysics Data System (ADS)

Karakurt, G.; Abdelouas, A.; Guin, J.-P.; Nivard, M.; Sauvage, T.; Paris, M.; Bardeau, J.-F.

2016-07-01

Borosilicate glasses are considered for the long-term confinement of high-level nuclear wastes. External irradiations with 1 MeV He+ ions and 7 MeV Au5+ ions were performed to simulate effects produced by alpha particles and by recoil nuclei in the simulated SON68 nuclear waste glass. To better understand the structural modifications, irradiations were also carried out on a 6-oxides borosilicate glass, a simplified version of the SON68 glass (ISG glass). The mechanical and macroscopic properties of the glasses were studied as function of the deposited electronic and nuclear energies. Alpha particles and gold ions induced a volume change up to -0.7% and -2.7%, respectively, depending on the glass composition. Nano-indentations tests were used to determine the mechanical properties of the irradiated glasses. A decrease of about -22% to -38% of the hardness and a decrease of the reduced Young's modulus by -8% were measured after irradiations. The evolution of the glass structure was studied by Raman spectroscopy, and also 11B and 27Al Nuclear Magnetic Resonance (MAS-NMR) on a 20 MeV Kr irradiated ISG glass powder. A decrease of the silica network connectivity after irradiation with alpha particles and gold ions is deduced from the structural changes observations. NMR spectra revealed a partial conversion of BO4 to BO3 units but also a formation of AlO5 and AlO6 species after irradiation with Kr ions. The relationships between the mechanical and structural changes are also discussed.

Probing the Orientation of Surface-Immobilized Protein G B1 Using ToF-SIMS Sum Frequency Generation and NEXAFS Spectroscopy

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

L Baugh; T Weidner; J Baio

2011-12-31

The ability to orient active proteins on surfaces is a critical aspect of many medical technologies. An important related challenge is characterizing protein orientation in these surface films. This study uses a combination of time-of-flight secondary ion mass spectrometry (ToF-SIMS), sum frequency generation (SFG) vibrational spectroscopy, and near-edge X-ray absorption fine structure (NEXAFS) spectroscopy to characterize the orientation of surface-immobilized Protein G B1, a rigid 6 kDa domain that binds the Fc fragment of IgG. Two Protein G B1 variants with a single cysteine introduced at either end were immobilized via the cysteine thiol onto maleimide-oligo(ethylene glycol)-functionalized gold and baremore » gold substrates. X-ray photoelectron spectroscopy was used to measure the amount of immobilized protein, and ToF-SIMS was used to measure the amino acid composition of the exposed surface of the protein films and to confirm covalent attachment of protein thiol to the substrate maleimide groups. SFG and NEXAFS were used to characterize the ordering and orientation of peptide or side chain bonds. On both substrates and for both cysteine positions, ToF-SIMS data showed enrichment of mass peaks from amino acids located at the end of the protein opposite to the cysteine surface position as compared with nonspecifically immobilized protein, indicating end-on protein orientations. Orientation on the maleimide substrate was enhanced by increasing pH (7.0-9.5) and salt concentration (0-1.5 M NaCl). SFG spectral peaks characteristic of ordered {alpha}-helix and {beta}-sheet elements were observed for both variants but not for cysteine-free wild type protein on the maleimide surface. The phase of the {alpha}-helix and {beta}-sheet peaks indicated a predominantly upright orientation for both variants, consistent with an end-on protein binding configuration. Polarization dependence of the NEXAFS signal from the N 1s to {pi}* transition of {beta}-sheet peptide bonds also indicated protein ordering, with an estimated tilt angle of inner {beta}-strands of 40-50{sup o} for both variants (one variant more tilted than the other), consistent with SFG results. The combined results demonstrate the power of using complementary techniques to probe protein orientation on surfaces.« less

Sulfated and pyruvylated disaccharide alditols obtained from a red seaweed galactan: ESIMS and NMR approaches.

PubMed

Gonçalves, Alan G; Ducatti, Diogo R B; Duarte, M Eugênia R; Noseda, Miguel D

2002-11-29

The water-soluble acid agaran isolated from Acanthophora spicifera (Rhodophyta) was submitted to alkaline treatment for the complete cyclization of alpha-L-Galp 6-sulfate to 3,6-An-alpha-L-Galp units. The modified agaran was then partially depolymerized using partial reductive hydrolysis. The resulting oligosaccharide mixture was fractionated by adsorption and ion-exchange chromatography. Fractions were purified by gel-filtration chromatography and studied by ESIMS and NMR spectroscopy, including 1D 1H, 13C, DEPT and 2D 1H, 1H COSY, TOCSY and 1H, 13C HMQC procedures. The following neutral, pyruvylated, sulfated and sulfated/pyruvylated disaccharide alditols were obtained: beta-D-Galp-(1-->4)-3,6-An-L-GalOH; 4,6-O-(1-carboxyethylidene)-beta-D-Galp-(1-->4)-3,6-An-L-GalOH; beta-D-Galp 2-sulfate-(1-->4)-3,6-An-L-GalOH and 4,6-O-(1-carboxyethylidene)-beta-D-Galp 2-sulfate-(1-->4)-3,6-An-L-GalOH.

Characterization of EDTA-soluble polysaccharides from the scape of Musa paradisiaca (banana).

PubMed

Raju, T S; Jagadish, R L; Anjaneyalu, Y V

2001-02-01

The polysaccharide components present in the scape of Musa paradisiaca (banana) were fractionated into water-soluble (WSP), EDTA-soluble (EDTA-SP), alkali-soluble (ASP) and alkali-insoluble (AISP) polysaccharide fractions [Anjaneyalu, Jagadish and Raju (1997) Glycoconj. J. 14, 507-512]. The EDTA-SP was further fractionated by iso-amyl alcohol into EDTA-SP-A and EDTA-SP-B. The homogeneity of these two polysaccharides was established by repeated precipitation with iso-amyl alcohol, gel-filtration chromatography and sedimentation analysis. The polysaccharides were characterized by monosaccharide composition analysis, methylation linkage analysis, iodine affinity, ferricyanide number, blue value, hydrolysis with alpha-amylase, gold-electron microscopy and X-ray diffraction spectroscopy. Data from all of these studies suggest that EDTA-SP-A is a branched amylose-type alpha-D-glucan and that EDTA-SP-B is a highly branched amylopectin-type polymer. The nature of the branching patterns of these polysaccharides suggests that they are unique to M. paradisiaca.

Imaging of the Field of 4C41.17 Below the Lyman Limit

NASA Technical Reports Server (NTRS)

Lacy, Mark; Rawlings, Steve

1997-01-01

Imaging of zeta greater than or equal to 3.4 radio galaxy fields below the Lyman continuum wavelength allows companion galaxies to be identified on the basis of red colors across the wavelength of redshifted Ly(alpha) and very red colors across the redshifted Lyman continuum. These arise due to a combination of absorption by intervening Ly(alpha) forest and Lyman-limit systems, and intrinsic Lyman-limit breaks in the galaxy spectral energy distribution caused by an Hi screen or breaks in stellar spectra. As a pilot study, we have imaged the field of the zeta = 3.8 radio galaxy 4C41.17 in U, V and R with the Auxiliary Port of the WHT. We find a number of potential companion galaxies, which require confirmation via spectroscopy or narrow-band imaging. The Lyman-limit in the spectrum of the radio galaxy itself and its implications for the origin of the UV flux is also discussed.

Five-minute P Modes Detected in Doppler Shift Measurement on Alpha Centauri

NASA Technical Reports Server (NTRS)

Fossat, E.; Grec, G.; Gelly, B.

1984-01-01

A spectrophotometer using the principle of optical resonance spectroscopy, designed for the goal of identifying radial and weakly non radial eigenmodes in the five minute range in the case of stars, is discussed. The conclusion of the first test of this new instrument was that if the observation can be photon noise limited (i.e., in total absence of any instrumental source of noise), the five-minute solar oscillation could still be detected by removing the Sun far enough for its magnitude to become zero or one. Such a situation is very closely represented by the observation of Alpha Centauri A, because it is a G2 V star, very similar to the Sun, with a mass of 1.1 in solar unit. Six nights were granted to this program on a 3.6m telescope, from 22 to 28 May 1983. Two and half nights provided over 20 hours of data of photometric quality good enough for analysis.

Evaluation of hydrogen absorption cells for observations of the planetary coronas

NASA Astrophysics Data System (ADS)

Kuwabara, M.; Taguchi, M.; Yoshioka, K.; Ishida, T.; de Oliveira, N.; Ito, K.; Kameda, S.; Suzuki, F.; Yoshikawa, I.

2018-02-01

Newly designed Lyman-alpha absorption cells for imaging hydrogen planetary corona were characterized using an ultra high resolution Fourier transform spectrometer installed on the DESIRS (Dichroïsme Et Spectroscopie par Interaction avec le Rayonnement Synchrotron) beamline of Synchrotron SOLEIL in France. The early absorption cell installed in the Japanese Mars orbiter NOZOMI launched in 1998 had not been sufficiently optimized due to its short development time. The new absorption cells are equipped with the ability to change various parameters, such as filament shape, applied power, H2 gas pressure, and geometrical configuration. We found that the optical thickness of the new absorption cell was ˜4 times higher than the earlier one at the center wavelength of Lyman-alpha absorption, by optimizing the condition to promote thermal dissociation of H2 molecules into two H atoms on a hot tungsten filament. The Doppler temperature of planetary coronas could be determined with an accuracy better than 100 K with the performance of the newly developed absorption cell.

Design of a minimal protein oligomerization domain by a structural approach.

PubMed

Burkhard, P; Meier, M; Lustig, A

2000-12-01

Because of the simplicity and regularity of the alpha-helical coiled coil relative to other structural motifs, it can be conveniently used to clarify the molecular interactions responsible for protein folding and stability. Here we describe the de novo design and characterization of a two heptad-repeat peptide stabilized by a complex network of inter- and intrahelical salt bridges. Circular dichroism spectroscopy and analytical ultracentrifugation show that this peptide is highly alpha-helical and 100% dimeric tinder physiological buffer conditions. Interestingly, the peptide was shown to switch its oligomerization state from a dimer to a trimer upon increasing ionic strength. The correctness of the rational design principles used here is supported by details of the atomic structure of the peptide deduced from X-ray crystallography. The structure of the peptide shows that it is not a molten globule but assumes a unique, native-like conformation. This de novo peptide thus represents an attractive model system for the design of a molecular recognition system.

Design of a minimal protein oligomerization domain by a structural approach.

PubMed Central

Burkhard, P.; Meier, M.; Lustig, A.

2000-01-01

Because of the simplicity and regularity of the alpha-helical coiled coil relative to other structural motifs, it can be conveniently used to clarify the molecular interactions responsible for protein folding and stability. Here we describe the de novo design and characterization of a two heptad-repeat peptide stabilized by a complex network of inter- and intrahelical salt bridges. Circular dichroism spectroscopy and analytical ultracentrifugation show that this peptide is highly alpha-helical and 100% dimeric tinder physiological buffer conditions. Interestingly, the peptide was shown to switch its oligomerization state from a dimer to a trimer upon increasing ionic strength. The correctness of the rational design principles used here is supported by details of the atomic structure of the peptide deduced from X-ray crystallography. The structure of the peptide shows that it is not a molten globule but assumes a unique, native-like conformation. This de novo peptide thus represents an attractive model system for the design of a molecular recognition system. PMID:11206050

Environmental and human monitoring of Americium-241 utilizing extraction chromatography and alpha-spectrometry.

PubMed

Goldstein, S J; Hensley, C A; Armenta, C E; Peters, R J

1997-03-01

Recent developments in extraction chromatography have simplified the separation of americium from complex matrices in preparation for alpha-spectroscopy relative to traditional methods. Here we present results of procedures developed/adapted for water, air, and bioassay samples with less than 1 g of inorganic residue. Prior analytical methods required the use of a complex, multistage procedure for separation of americium from these matrices. The newer, simplified procedure requires only a single 2 mL extraction chromatographic separation for isolation of Am and lanthanides from other components of the sample. This method has been implemented on an extensive variety of "real" environmental and bioassay samples from the Los Alamos area, and consistently reliable and accurate results with appropriate detection limits have been obtained. The new method increases analytical throughput by a factor of approximately 2 and decreases environmental hazards from acid and mixed-waste generation relative to the prior technique. Analytical accuracy, reproducibility, and reliability are also significantly improved over the more complex and laborious method used previously.

UV Timing and Spectroscopy of the Crab Nebula Pulsar

NASA Technical Reports Server (NTRS)

Gull, Theodore R.; Lunqvist, Peter; Sollerman, Jesper; Lindler, Don; Fisher, Richard R. (Technical Monitor)

2001-01-01

We have used the Hubble Space Telescope and Space Telescope Imaging Spectrograph to obtain Near Ultraviolet (NUV) (1600-3200 Angstroms) and Far Ultraviolet (FUV) (1140-1720 Angstroms) spectra and pulse profiles of the Crab Nebula's pulsar. The pulse period agrees well with the radio predictions. The NUV and FUV pulse profiles are little changed from the visible wavelength profile. Spectra obtained with the Nordic Optical Telescope were combined with the UV spectra for full coverage from 1140-9250Angstoms. Dereddening the spectrum with a standard extinction curve achieves a flat spectrum for E(B-V)=0.52, R=3.1. Lyman alpha absorption indicates a column density of 3.0=/-0.5 x 10(exp 21) cm -2, consistent with the E(B-V) of 0.52. The dereddened spectrum can be fitted by a power law with spectral index alpha=0.11+/-0.04. A broad, blueshifted absorption is seen in CIV (1550Angstroms), reaching a velocity of about 2500 kilometer per second.

Structural characterization of the cell wall D-glucans isolated from the mycelium of Botryosphaeria rhodina MAMB-05.

PubMed

de Lourdes Corradi da Silva, Maria; Fukuda, Eliane K; Vasconcelos, Ana Flora D; Dekker, Robert F H; Matias, Andreza C; Monteiro, Nilson K; Cardoso, Marilsa S; Barbosa, Aneli M; Silveira, Joana L M; Sassaki, Guilherme L; Carbonero, Elaine R

2008-03-17

Three D-glucans were isolated from the mycelium of the fungus Botryosphaeria rhodina MAMB-05 by sequential extraction with hot-water and hot aqueous KOH (2% w/v) followed by ethanol precipitation. Following their purification by gel permeation chromatography on Sepharose CL-4B, the structural characteristics of the D-glucans were determined by FT-IR and 13C NMR spectroscopy and, after methylation, by GC-MS. The hot-water extract produced a fraction designated Q1A that was a beta-(1-->6)-D-glucan with the following structure: [Formula: see text] The alkaline extract, when subjected to repeated freeze-thawing, yielded two fractions: K1P (insoluble) that comprised a beta-(1-->3)-D-glucan with beta-D-glucose branches at C-6 with the structure: [Formula: see text] and K1SA (soluble) consisting of a backbone chain of alpha-(1-->4)-linked D-glucopyranosyl residues substituted at O-6 with alpha-D-glucopyranosyl residues: [Formula: see text

Astronomical infrared spectroscopy with a Connes-type interferometer. III Alpha Orionis, 2600 to 3450 per cm.

NASA Technical Reports Server (NTRS)

Beer, R.; Hutchison, R. B.; Norton, R. H.; Lambert, D. L.

1972-01-01

Analysis of recent spectra of alpha Ori in the 3 to 4 micron region at a resolving power of about 10,000, showing clear evidence of the delta v = 1 sequence of the rotation-vibration bands of OH. A detailed investigation of the rotational and vibrational populations suggests that the OH is close to being in LTE at an apparent temperature of 4100 plus or minus 200 K. An OH abundance of 1.2 x 10 to the 20th molecules per cu cm and upper limits for H2O and H super 35 Cl of 8 x 10 to the 18th and 8 x 10 to the 17th molecules per cu cm, respectively, are deduced. It is also deduced that the rms turbulence velocity in the region of OH line formation is 11.5 plus or minus 2 km/sec. The implications of these data on abundances in M supergiant atmospheres are discussed.

Rapid acquisition of beta-sheet structure in the prion protein prior to multimer formation.

PubMed

Post, K; Pitschke, M; Schäfer, O; Wille, H; Appel, T R; Kirsch, D; Mehlhorn, I; Serban, H; Prusiner, S B; Riesner, D

1998-11-01

The N-terminally truncated form of the prion protein, PrP 27-30, and the corresponding recombinant protein, rPrP, were solubilized in 0.2% SDS, and the transitions induced by changing the conditions from 0.2% SDS to physiological conditions, i.e. removing SDS, were characterized with respect to solubility, resistance to proteolysis, secondary structure and multimerization. Circular dichroism, electron microscopy and fluorescence correlation spectroscopy were used to study the structural transitions of PrP. Within one minute the alpha-helical structure of PrP was transformed into one that was enriched in beta-sheets and consisted mainly of dimers. Larger oligomers were found after 20 minutes and larger multimers exhibiting resistance to proteolysis were found after several hours. It was concluded that the monomeric alpha-helical conformation was stable in SDS or when attached to the membrane; however, the state of lowest free energy in aqueous solution at neutral pH seems to be the multimeric, beta-sheet enriched conformation.

Spectroscopy of chromospheric lines of giants in the globular cluster

NASA Technical Reports Server (NTRS)

Dupree, A. K.; Hartmann, Lee; Smith, Graeme H.; Rodgers, A. W.; Roberts, W. H.; Zucker, D. B.

1994-01-01

Spectroscopic observations of chromospheric transitions (Mg II, H-alpha, and Ca II K) from two red giants (A31 and A59) in the globular cluster NGC 6572 were made with the Goddard High Resolution Spectrograph on the Hubble Space Telescope and the coude spectrograph of the 1.9 m telescope at the Mount Stromlo Observatory. These measurements give evidence for chromospheric activity and outward motions within the atmospheres. The surface flux of the Mg II emission is comparable to that in disk population giants of similar (B-V) color. The Mg II profiles are asymmetric, which is most likely caused by absorption in an expanding stellar atmosphere and/or by possible interstellar features. Notches are found in the core of the H-alpha line of A59, which are similar to those found in Cepheids. This suggests that shocks are present in the atmosphere of A59 and indicates that hydrodynamic phenomena are influencing the levvel of chromospheric emission and producing upper atmospheric motions which may lead to mass loss.

ALPhA Laboratory Immersion in Plasma Physics

NASA Astrophysics Data System (ADS)

Dominguez, A.; Zwicker, A.; Williams, J. D.

2016-10-01

According to the FESAC, as recently as 2014 there were a total of just 14 universities offering strong curricula in MFE sciences. Similarly, it was reported that 8 and 19 universities offer strong HEDPL and Discovery Plasma programs respectively. At the undergraduate level, there is also a lack of plasma physics in the curricula. This, regardless of its rich insights into the core subfields of physics, i.e., classical mechanics, electrodynamics, statistical mechanics and quantum phenomena. The coauthors have been leading a plasma physics workshop for the last 3 years directed at undergraduate physics professors and lecturers. The workshop is centered around a versatile and relatively inexpensive (< 10 k) plasma discharge experiment which lets students explore Panchen's Law, spectroscopy and Langmuir probes. The workshop is part of the Advanced Laboratory Physics Association (ALPhA) Laboratory Immersions, and its objective is for the participants to become familiar with the experiments and incorporate them into their home institution's curricula as junior labs, senior labs or independent student projects.

Raman and nuclear magnetic resonance investigation of alkali metal vapor interaction with alkene-based anti-relaxation coating

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

Tretiak, O. Yu., E-mail: otretiak@genphys.ru; Balabas, M. V.; Blanchard, J. W.

2016-03-07

The use of anti-relaxation coatings in alkali vapor cells yields substantial performance improvements compared to a bare glass surface by reducing the probability of spin relaxation in wall collisions by several orders of magnitude. Some of the most effective anti-relaxation coating materials are alpha-olefins, which (as in the case of more traditional paraffin coatings) must undergo a curing period after cell manufacturing in order to achieve the desired behavior. Until now, however, it has been unclear what physicochemical processes occur during cell curing, and how they may affect relevant cell properties. We present the results of nondestructive Raman-spectroscopy and magnetic-resonancemore » investigations of the influence of alkali metal vapor (Cs or K) on an alpha-olefin, 1-nonadecene coating the inner surface of a glass cell. It was found that during the curing process, the alkali metal catalyzes migration of the carbon-carbon double bond, yielding a mixture of cis- and trans-2-nonadecene.« less

Scattered light characterization of FORTIS

NASA Astrophysics Data System (ADS)

McCandliss, Stephan R.; Carter, Anna; Redwine, Keith; Teste, Stephane; Pelton, Russell; Hagopian, John; Kutyrev, Alexander; Li, Mary J.; Moseley, S. Harvey

2017-08-01

We describe our efforts to build a Wide-Field Lyman alpha Geocoronal simulator (WFLaGs) for characterizing the end-to-end sensitivity of FORTIS (Far-UV Off Rowland-circle Telescope for Imaging and Spectroscopy) to scattered Lyman α emission from outside of the nominal (1/2 degree)2 field-of-view. WFLaGs is a 50 mm diameter F/1 aluminum parabolic collimator fed by a hollow cathode discharge lamp with a 80 mm clear MgF2 window housed in a vacuum skin. It creates emission over a 10 degree FOV. WFLaGS will allow us to validate and refine a recently developed scattered light model and verify our scatter light mitigation strategies, which will incorporate low scatter baffle materials, and possibly 3-d printed light traps, covering exposed scatter centers. We present measurements of scattering intensity of Lyman alpha as a function of angle with respect to the specular reflectance direction for several candidate baffle materials. Initial testing of WFLaGs will be described.

Cavity-enhanced resonant photoacoustic spectroscopy with optical feedback cw diode lasers: A novel technique for ultratrace gas analysis and high-resolution spectroscopy.

PubMed

Hippler, Michael; Mohr, Christian; Keen, Katherine A; McNaghten, Edward D

2010-07-28

Cavity-enhanced resonant photoacoustic spectroscopy with optical feedback cw diode lasers (OF-CERPAS) is introduced as a novel technique for ultratrace gas analysis and high-resolution spectroscopy. In the scheme, a single-mode cw diode laser (3 mW, 635 nm) is coupled into a high-finesse linear cavity and stabilized to the cavity by optical feedback. Inside the cavity, a build-up of laser power to at least 2.5 W occurs. Absorbing gas phase species inside the cavity are detected with high sensitivity by the photoacoustic effect using a microphone embedded in the cavity. To increase sensitivity further, coupling into the cavity is modulated at a frequency corresponding to a longitudinal resonance of an organ pipe acoustic resonator (f=1.35 kHz and Q approximately 10). The technique has been characterized by measuring very weak water overtone transitions near 635 nm. Normalized noise-equivalent absorption coefficients are determined as alpha approximately 4.4x10(-9) cm(-1) s(1/2) (1 s integration time) and 2.6x10(-11) cm(-1) s(1/2) W (1 s integration time and 1 W laser power). These sensitivities compare favorably with existing state-of-the-art techniques. As an advantage, OF-CERPAS is a "zero-background" method which increases selectivity and sensitivity, and its sensitivity scales with laser power.

Immobilization of alcohol dehydrogenase in phospholipid Langmuir-Blodgett films to detect ethanol.

PubMed

Caseli, Luciano; Perinotto, Angelo C; Viitala, Tapani; Zucolotto, Valtencir; Oliveira, Osvaldo N

2009-03-03

Enzyme immobilization in nanostructured films may be useful for a number of biomimetic systems, particularly if suitable matrixes are identified. Here we show that alcohol dehydrogenase (ADH) has high affinity toward a negatively charged phospholipid, dimyristoylphosphatidic acid (DMPA), which forms a Langmuir monolayer at an air-water interface. Incorporation of ADH into the DMPA monolayer was monitored with surface pressure measurements and polarization-modulation infrared reflection absorption spectroscopy, with the alpha-helices from ADH being mainly oriented parallel to the water surface. ADH remained at the interface even at high surface pressures, thus allowing deposition of Langmuir-Blodgett (LB) films from the DMPA-ADH film. Indeed, interaction with DMPA enhances the transfer of ADH, where the mass transferred onto a solid support increased from 134 ng for ADH on a Gibbs monolayer to 178 ng for an LB film with DMPA. With fluorescence spectroscopy it was possible to confirm that the ADH structure was preserved even after one month of the LB deposition. ADH-containing films deposited onto gold-interdigitated electrodes were employed in a sensor array capable of detecting ethanol at concentrations down to 10 ppb (in volume), using impedance spectroscopy as the method of detection.

Transmutation of a heme protein.

PubMed Central

Barker, P D; Ferrer, J C; Mylrajan, M; Loehr, T M; Feng, R; Konishi, Y; Funk, W D; MacGillivray, R T; Mauk, A G

1993-01-01

Residue Asn57 of bovine liver cytochrome b5 has been replaced with a cysteine residue, and the resulting variant has been isolated from recombinant Escherichia coli as a mixture of four major species: A, BI, BII, and C. A combination of electronic spectroscopy, 1H NMR spectroscopy, resonance Raman spectroscopy, electrospray mass spectrometry, and direct electrochemistry has been used to characterize these four major cytochrome derivatives. The red form A (E(m) = -19 mV) is found to possess a heme group bound covalently through a thioether linkage involving Cys57 and the alpha carbon of the heme 4-vinyl group. Form BI has a covalently bound heme group coupled through a thioether linkage involving the beta carbon of the heme 4-vinyl group. Form BII is similar to BI except that the sulfur involved in the thioether linkage is oxidized to a sulfoxide. The green form C (E(m) = 175 mV) possesses a noncovalently bound prosthetic group with spectroscopic properties characteristic of a chlorin. A mechanism is proposed for the generation of these derivatives, and the implications of these observations for the biosynthesis of cytochrome c and naturally occurring chlorin prosthetic groups are discussed. PMID:8341666

Searching for Lyman-alpha Emitters as a Probe of Cosmic Reionization and Peering Inside Galaxies in the First Two Billion Years

NASA Astrophysics Data System (ADS)

Jung, Intae; Finkelstein, Steven; CANDELS team

2018-01-01

In the reionization era an immediately accessible method for studying the intergalactic medium is to measure the equivalent width distribution of Lyman-alpha emission from galaxies with follow-up spectroscopy. To search for Lyman-alpha emission from galaxies at z ~ 5-8, we perform spectroscopic observations of candidate galaxies from the Cosmic Assembly Near-infrared Deep Extragalactic Legacy Survey (CANDELS). We utilize data from the Keck DEIMOS (optical) and MOSFIRE (near-infrared) spectrographs, ensuring a comprehensive wavelength coverage of Lyman-alpha emission at z ~ 5-8. We have a total of 1170 object-hours of spectroscopic integration of galaxies at z > 5: 118 galaxies with DEIMOS and 69 galaxies with MOSFIRE. The equivalent width distribution of Lyman-alpha emission is constrained with the number of detected objects from our dataset by constructing detailed simulations of mock emission lines, which consider observational conditions and the photometric redshift probability distribution function. We present our robust measure of the evolution of the Lyman-alpha emission equivalent width distribution at z ~ 5-8.Understanding what drives star-formation quenching in the early universe is a long-standing puzzle. To reveal the hidden relation of quenching with galaxy structural properties, particularly central stellar mass density, we perform the first spatially resolved stellar population study of galaxies at z ~ 4, utilizing the CANDELS imaging data set over the GOODS-S field. We examine 166 photometric-redshift-selected galaxies at 3.5 < z < 4.0 with additional deep K-band survey data from the HAWK-I UDS and GOODS Survey which covers the 4000Å break at these redshifts. We estimate the stellar mass, star formation rate, and dust extinction for galaxy inner and outer regions via spatially resolved spectral energy distribution fitting based on a Markov Chain Monte Carlo algorithm. By comparing specific star formation rates (sSFRs) between inner and outer parts of the galaxies we find that the majority of galaxies with high central mass densities show evidence for a preferentially lower sSFR in their centers than in their outer regions, indicative of reduced sSFRs in their central regions.

Reaction of the isosteric methylenephosphonate analog of alpha-D-glucose 1-phosphate with phosphoglucomutase. Induced-fit specificity revisited.

PubMed

Ray, W J; Post, C B; Puvathingal, J M

1993-01-12

The phospho form of phosphoglucomutase reacts with the isosteric methylenephosphonate analog of alpha-D-glucose 1-phosphate to produce the corresponding analog of alpha-D-glucose 1,6-bisphosphate plus the dephosphoenzyme. In a coupled reaction, kcat/Km = 1.7 x 10(3) M-1 s-1, which is about 2 x 10(-5) times that for the corresponding reaction with alpha-D-glucose 1-phosphate. The decrease in kcat/Km is divided more or less evenly between less efficient PO3- transfer and decreased binding, although smaller phosphates and phosphonates bind approximately equally. There is a much smaller difference in the binding of glucose 1-methylenephosphonate 6-phosphate and glucose 1,6-bisphosphate to the dephosphoenzyme: the binding ratio is < 1:35 when the glucose ring is oriented similarly. Preferred binding patterns for a number of substrates/inhibitors, studied by 31P NMR and UV-difference spectroscopy, suggest that in the ground state the phosphonate group is tolerated to a much greater extent at the catalytic subsite than at the phosphate-binding subsite, where binding specificity appears to be directed toward a tetrahedral-PO3(2-) group attached to a bridging atom that can act as a hydrogen-bond acceptor. Binding specificity at the catalytic subsite apparently is directed toward a different array, possibly (-O...PO3...O-)2-. Some of these results are considered in terms of a modified version of the "induced fit" concept of enzymic specificity, which is reexamined in view of implied thermodynamic restrictions. The internal rearrangement whereby the positions of the anionic groups of the phosphate/phosphonate are exchanged is compared with the analogous rearrangements involving glucose 1,6-bisphosphate and 1,4-butanediol bisphosphate. The supplementary material describes a three-step synthesis of 1-deoxy-alpha-D-glucose 1-methylenephosphonate together with a procedure for phosphorylating the phosphonate to produce an analog of alpha-D-glucose 1,6-bisphosphate and also describes a facile procedure for the qualitative conversion of organic phosphonates to inorganic phosphate.

Conformational change of cytochrome P450 1A2 induced by phospholipids and detergents.

PubMed

Yun, C H; Song, M; Kim, H

1997-08-08

Recently, it was reported that the activity of rabbit P450 1A2 is markedly increased at elevated salt concentration (Yun, C-H., Song, M., Ahn, T., and Kim, H. (1996) J. Biol. Chem. 271, 31312-31316). The activity increase of P450 1A2 coincides with the raised alpha-helix content and decreased beta-sheet content. The presence of phospholipid magnified this effect. Here, possible structural change of rabbit P450 1A2 accompanying the phospholipid-induced increase in its enzyme activity was investigated by circular dichroism, fluorescence spectroscopy, and absorption spectroscopy. Studies with the reconstituted system supported by cumene hydroperoxide or NADPH showed that the P450 1A2 activities were found to be dependent on the head group and hydrocarbon chain length of phospholipid. Phosphatidylcholines having short hydrocarbon chains with a carbon number of 8-12 were very efficient for reconstitution of the P450-catalyzed reactions supported by both cumene hydroperoxide and NADPH. It was found that the phospholipid increased the alpha-helix content and lowered the beta-sheet content of P450. Intrinsic fluorescence intensity is also increased in the presence of phospholipid. The low spin iron configuration of P450 1A2 shifted toward the high spin configuration by most of the phospholipids in the endoplasmic reticulum. Some synthetic phospholipids having short hydrocarbon chains with a carbon number of 10-12 caused a shift in the spin equilibrium of P450 1A2 toward low spin. The effect of detergents on the activity and conformation of P450 1A2 was also studied. It was found that the addition of detergents to P450 1A2 solution increased the enzyme activity of P450 1A2. Detergents also increased the alpha-helix content and lowered the beta-sheet content of P450 1A2. Intrinsic fluorescence emissions also increased with the presence of detergents. Octyl glucoside and deoxycholate caused a shift toward high spin. On the other hand, cholate caused a shift toward low spin. It was found that the activity increase of rabbit P450 1A2 coincides with the conformational change including raised alpha-helix content. It is proposed that the interaction with the phospholipid molecules surrounding P450 1A2 in the endoplasmic reticulum is important for a functional conformation of P450 1A2 in a monooxygenase system including NADPH-P450 reductase.

Alpha-Recoil Damage Annealing Effecfs on Zircon Crystallinity and He Diffusivity: Improving Damage-Diffusivity Models

NASA Astrophysics Data System (ADS)

Thurston, O. G.; Guenthner, W.; Garver, J. I.

2017-12-01

The effects of radiation damage on He diffusion in zircon has been a major research focus in thermochronology over the past decade. In the zircon-He system, alpha-recoil damage effects He diffusivity in two ways: a decrease in He diffusivity at low radiation damage levels, and an increase in He diffusivity at high radiation damage levels. The radiation damage accumulation process within zircon is well understood; however, the kinetics of annealing of alpha-recoil damage at geologic timescales as they pertain to damage-diffusivity models, and for metamict zircon (i.e. transition from crystalline to amorphous glass via damage accumulation), has not been well constrained. This study aims to develop a more complete model that describes the annealing kinetics for zircon grains with a broad range of pre-annealing, alpha-induced radiation damage. A suite of zircon grains from the Lucerne pluton, ME were chosen for this study due to their simple thermal history (monotonic cooling), notable range of effective uranium (eU, eU = [U] +0.235*[Th]) (15 - 34,239 ppm eU), and large range of radiation damage as measured by Raman shift from crystalline (>1005 cm-1) to metamict (<1000 cm-1). The zircon grains selected represent the full range of eU and radiation damage present in the pluton. The zircon grains were first mapped for overall crystallinity using Raman spectroscopy, then annealed at different time-temperature (t-T) schedules from 1 hr to 24 hrs at temperatures ranging from 700-1100 °C, followed by remapping with Raman spectroscopy to track the total Raman shift for each t-T step. The temperature window selected is at the "roll-over" point established in prior studies (Zhang et al., 2000), at which most laboratory annealing occurs. Our data show that high radiation damage zircon grains show larger Raman shifts than low radiation damage zircon grains when exposed to the same t-T step. The high damage zircon grains typically show a Raman shift of 4 cm-1 toward crystalline, while low radiation damage grains show a shift of 2 cm-1. These shifts suggest that the annealing process occurs at a faster rate in high damage zircon grains, and slower rates in more crystalline grains. That is, the initial level of radiation damage prior to annealing must be considered in damage-diffusivity models that contain thermal histories from zircon-He dates.

Binding of cationic pentapeptides with modified side chain lengths to negatively charged lipid membranes: Complex interplay of electrostatic and hydrophobic interactions.

PubMed

Hoernke, Maria; Schwieger, Christian; Kerth, Andreas; Blume, Alfred

2012-07-01

Basic amino acids play a key role in the binding of membrane associated proteins to negatively charged membranes. However, side chains of basic amino acids like lysine do not only provide a positive charge, but also a flexible hydrocarbon spacer that enables hydrophobic interactions. We studied the influence of hydrophobic contributions to the binding by varying the side chain length of pentapeptides with ammonium groups starting with lysine to lysine analogs with shorter side chains, namely omithine (Orn), alpha, gamma-diaminobutyric acid (Dab) and alpha, beta-diaminopropionic acid (Dap). The binding to negatively charged phosphatidylglycerol (PG) membranes was investigated by calorimetry, FT-infrared spectroscopy (FT-IR) and monolayer techniques. The binding was influenced by counteracting and sometimes compensating contributions. The influence of the bound peptides on the lipid phase behavior depends on the length of the peptide side chains. Isothermal titration calorimetry (ITC) experiments showed exothermic and endothermic effects compensating to a different extent as a function of side chain length. The increase in lipid phase transition temperature was more significant for peptides with shorter side chains. FTIR-spectroscopy revealed changes in hydration of the lipid bilayer interface after peptide binding. Using monolayer techniques, the contributions of electrostatic and hydrophobic effects could clearly be observed. Peptides with short side chains induced a pronounced decrease in surface pressure of PG monolayers whereas peptides with additional hydrophobic interactions decreased the surface pressure much less or even lead to an increase, indicating insertion of the hydrophobic part of the side chain into the lipid monolayer.

Tryptophan depletion and formation of alpha-aminoadipic and gamma-glutamic semialdehydes in porcine burger patties with added phenolic-rich fruit extracts.

PubMed

Ganhão, Rui; Morcuende, David; Estévez, Mario

2010-03-24

The effect of added fruit extracts on the oxidation of muscle proteins in porcine burger patties subjected to cooking and chill storage was studied. Extracts from arbutus berries (Arbutus unedo L., AU), common hawthorns (Crataegus monogyna L., CM), dog roses (Rosa canina L., RC), and elm-leaf blackberries (Rubus ulmifolius Schott, RU) were prepared, characterized, added to burger patties (3% of total weight), and evaluated as inhibitors of protein oxidation. Negative (no added extract, C) and positive control (added quercetin, 230 mg/kg, Q) groups were also included in the design. Protein oxidation was assessed by means of tryptophan loss using fluorescence spectroscopy (FS) and formation of the specific protein carbonyls alpha-aminoadipic (AAS) and gamma-glutamic semialdehyde (GGS) using liquid chromatography and mass spectroscopy (LC-MS). Both advanced methodologies (FS and LC-MS) were found to be reliable and specific protein oxidation measurements that allow us to gain chemical insight into protein oxidation. The mechanisms likely involved in the oxidative reactions affecting proteins during cooking and storage of burger patties are profusely discussed. Phenolic-rich fruit extracts protected tryptophan residues against oxidation and inhibited the formation of both semialdehydes in burger patties during cooking and subsequent chill storage. In general, RC, RU, and AU were the most effective inhibitors of protein oxidation, with this effect being more intense than that of pure polyphenols like quercetin. These fruit extracts could be considered functional ingredients as their antioxidant actions contribute to the enhancement of the nutritional value of the meat products.

Preparation and characterization of highly water-soluble magnetic Fe3O4 nanoparticles via surface double-layered self-assembly method of sodium alpha-olefin sulfonate

NASA Astrophysics Data System (ADS)

Li, Honghong; Qin, Li; Feng, Ying; Hu, Lihua; Zhou, Chunhua

2015-06-01

A kind of double-layered self-assembly sodium alpha-olefin sulfonate (AOS) capped Fe3O4 magnetic nanoparticles (Fe3O4-AOS-MN) with highly water-solubility was prepared by a wet co-precipitation method with a pH of 4.8. The resulting Fe3O4-AOS-MN could be dispersed into water to form stable magnetic fluid without other treatments. The result of X-ray diffraction (XRD) indicated that the Fe3O4-AOS-MN maintained original crystalline structure and exhibited a diameter of about 7.5 nm. The iron oxide phase of nanoparticles determined by Raman spectroscopy is Fe3O4. Transmission electron microscopy (TEM) analysis confirmed that the Fe3O4-AOS-MN with spherical morphology were uniformly dispersed in water. FT-IR spectroscopy (FT-IR) and thermo-gravimetric analysis (TGA) verified the successful preparation of Fe3O4-AOS-MN capped with double-layered self-assembled AOS. The corresponding capacities of monolayer chemical absorption and the second-layer self-assembly absorption were respectively 4.07 and 14.71 wt% of Fe3O4-MN, which were much lower than those of other surfactants. Vibrating sample magnetometer (VSM) test result showed Fe3O4-AOS-MN possessed superparamagnetic behavior with the saturation magnetization value of about 44.45 emu/g. The blocking temperature TB of Fe3O4-AOS-MN capped with double-layered AOS is 170 K.

Towards Solvation of a Chiral Alpha-Hydroxy Ester: Broadband Chirp and Narrow Band Cavity Fouirier Transform Microwave Spectroscopy of Methyl Lactate-Water Clusters

NASA Astrophysics Data System (ADS)

Thomas, Javix; Sukhorukov, Oleksandr; Jaeger, Wolfgang; Xu, Yunjie

2013-06-01

Methyl lactate (ML), a chiral alpha-hydroxy ester, has attracted much attention as a prototype system in studies of chirality transfer,[1] solvation effects on chiroptical signatures,[2] and chirality recognition.[3] It has multiple functional groups which can serve both as a hydrogen donor and acceptor. By applying rotational spectroscopy and high level ab initio calculations, we examine the delicate competition between inter- and intramolecular hydrogen-bonding in the ML-water clusters. Broadband rotational spectra obtained with a chirp Fourier transform microwave (FTMW) spectrometer, reveal that the insertion conformations are the most favourable ones in the binary and ternary solvated complexes. In the insertion conformations, the water molecule(s) inserts itself (themselves) into the existing intramolecular hydrogen-bonded ring formed between the alcoholic hydroxyl group and the oxygen of the carbonyl group of ML. The final frequency measurements have been carried out using a cavity based FTMW instrument where internal rotation splittings due to the ester methyl group have also been detected. A number of insertion conformers with subtle structural differences for both the binary and ternary complexes have been identified theoretically. The interconversion dynamics of these conformers and the identification of the most favorable conformers will be discussed. 1. C. Merten, Y. Xu, Angew. Chem. Int. Ed., 2013, 52, 2073 -2076. 2. M. Losada, Y. Xu, Phys. Chem. Chem. Phys., 2007, 9, 3127-3135; Y. Liu, G. Yang, M. Losada, Y. Xu, J. Chem. Phys., 2010, 132, 234513/1-11. 3. A. Zehnacker, M. Suhm, Angew. Chem. Int. Ed. 2008, 47, 6970 - 6992.

Research on Spectroscopy, Opacity, and Atmospheres

NASA Technical Reports Server (NTRS)

Kurucz, Robert L.

1999-01-01

To make my calculations more readily accessible I have set up a web site cfaku5.harvard.edu that can also be accessed by FTP. it has 5 9GB disks that hold all of my atomic and diatomic molecular data, my tables of distribution function opacities, my grids of model atmospheres, colors, fluxes, etc, my program that are ready for distribution, most of my recent papers. Atlases and computed spectra will be added as they are completed. New atomic and molecular calculations will be added as they are completed. I got my atomic programs that had been running on a Cray at the San Diego Supercomputer Center to run on my Vaxes and Alpha. I started with Ni and Co because there were new laboratory analyses that included isotopic and hyperfine splitting. Those calculations are described in the appended abstract for the 6th Atomic Spectroscopy and oscillator Strengths meeting in Victoria last summer. A surprising finding is that quadrupole transitions have been grossly in error because mixing with higher levels has not been included. I now have enough memory in my Alpha to treat 3000 x 3000 matrices. I now include all levels up through n=9 for Fe I and 11, the spectra for which the most information is available. I am finishing those calculations right now. After Fe I and Fe 11, all other spectra are "easy", and I will be in mass production. ATL;LS12, my opacity sampling program for computing models with arbitrary abundances, has been put on the web server. I wrote a new distribution function opacity program for workstations that replaces the one I used on the Cray at the San Diego Supercomputer Center. Each set of abundances would take 100 Cray hours costing $100,000. 1 ran 25 cases. Each of my opacity CDs contains three abundances. I have a new program -iinning on the Alpha that takes about a week. I am going to have to get a faster processor or I will have to dedicate a whole workstation just to opacities.

Testing the Crystalline Integrity of Baddeleyite: A Systematic EBSD and Confocal Laser-Raman Spectroscopy Study

NASA Astrophysics Data System (ADS)

DesOrmeau, J. W.; Ibanez-Mejia, M.; Lafuente Valverde, B.; Eddy, M. P.; Trail, D.; Wang, Y.

2017-12-01

The accessory mineral baddeleyite (monoclinic ZrO2) has great potential as a high-precision U-Pb geochronometer in silica-undersaturated rocks. However, due to a lack of understanding of alpha-recoil damage to the crystal structure and the influences on chemical diffusion properties and closed-system behavior, limitations still exist. Studies have shown phase transformations in baddeleyite (monoclinic to tetragonal) resulting from radiation damage due to ion bombardment [e.g., 1], but the effects of self-irradiation on the baddeleyite crystal structure over geologic timescales remain poorly understood. A recent study reported confocal laser-Raman spectra suggesting the presence of a tetragonal phase in a Phalaborwa baddeleyite [2], which has crucial implications for Pb mobility and high-precision U-Pb results. To better understand the physical effects of self-irradiation in baddeleyite over geologic timescales, samples of various ages (ca. 2060-32 Ma) and calculated alpha-doses (0.001-0.901 x 1016 α/mg) were imaged by cathodoluminescence (CL) and subsequently analyzed via electron backscatter diffraction (EBSD) and confocal laser-Raman spectroscopy. Synthetic baddeleyite grown in a one-atmosphere furnace was also analyzed to allow a comparison of EBSD and Raman results of the pure monoclinic phase and the natural unknown samples. Whole grain EBSD maps (n=75) of baddeleyite from the Phalabowra and Kovdor carbonatites, the Ammänpelto sill, and the Duluth, Ogden and Yinmawanshan gabbros show complex twinning that is loosely correlated to CL zoning and identification of the monoclinic phase only, suggesting no evidence for phase transformations within grains of contrasting age and amounts of alpha-doses. Preliminary Raman results show evidence of systematic shifts in the vibrational modes of Phalabowra baddeleyite with respect to the younger crystals, which may be the result of radiation-induced damage accumulation rather than phase transformation. These results aim to better characterize the poorly known effects of radiation damage in natural baddeleyite and assist in improving methods for high-precision U-Pb dating of mafic systems on Earth and other planetary bodies. [1] Valdez et al. (2008), J. Nucl. Mater. 381, pp. 259-266. [2[ Schaltegger and Davies (2017), RIMG 83, pp.297-328.

Effect of intravenous infusion of an alpha-adrenergic blocking agent on the haemodynamic changes in human masseter muscle induced by cold pressor stimulation.

PubMed

Maekawa, K; Kuboki, T; Miyawaki, T; Shimada, M; Yamashita, A; Clark, G T

1999-04-01

This study evaluated the effect of intravenous infusion of a non-selective alpha-adrenergic blocking agent on masseter muscle haemodynamics induced by 4 degrees C cold pressor stimulation (CPS) of the right foot and ankle, which reportedly evokes a rapidly increasing sympathetic nerve activity in human skeletal muscle. Nine healthy non-smoking males (mean age 23.7+/-2.1 year) with no history of chronic muscle pain or migraine participated. The haemoglobin (Hb) concentration in the right masseter was continuously recorded by non-invasive, near-infrared spectroscopy. Heart rate and blood pressure were also recorded. The experiment involved the following sequence: (1) a placebo (physiological saline) with a CPS trial; (2) a 30-sec maximal voluntary clenching (MVC)-only trial; and (3) an alpha-adrenergic blocking agent with a CPS trial. The saline and drug trials each involved continuous recording for 1 min before, 2 min during and 5 min after the CPS. Physiological saline (20 ml) or phentolamine mesylate (20 ml) were infused at the rate of 2 ml/min. This infusion was begun 15 min before baseline recording and participants were not aware which solution (saline or phentolamine) was being infused. For the MVC trial, each participant performed a 30-sec MVC of his jaw-closing muscles followed by a 15-min rest between each trial. The individual Hb data were adjusted so that the baseline at the beginning of the experiment was equal to zero and all data were normalized as a percentage of the individual's highest absolute Hb change seen after the MVC. The mean baseline Hb concentrations 1 min before CPS were significantly higher in the alpha-blocker trial (83.6%) than in the placebo saline trial (P < 0.001). The change in mean Hb concentration from baseline during CPS in the alpha-blocker trial was significantly less than in the placebo trial (P = 0.006). Mean heart rate before CPS was also significantly higher in the alpha-blocker trial (85.2 beats/min) than in the placebo trial (69.6 beats/min) (P < 0.001). There were no significant differences in the mean systolic and diastolic blood pressures between the placebo and alpha-blocker trials in any time period. The results suggest that non-selective alpha-adrenoceptor blockade increases the blood volume in the masseter muscle. This change might be due to a combination of peripheral vasodilation and an increase in cardiac output.

Microstructural characterization and mechanical properties of Excel alloy pressure tube material

NASA Astrophysics Data System (ADS)

Sattari, Mohammad

Microstructural characterization and mechanical properties of Excel (Zr-3.5%Sn-0.8%Mo-0.8%Nb), a dual phase alphaZr -hcp and betaZr-bcc pressure tube material, is discussed in the current study which is presented in manuscript format. Chapter 3 discusses phase transformation temperatures using different techniques such as quantitative metallography, differential scanning calorimetry (DSC), and electrical resistivity. It was found that the alphaZr → alphaZr+beta Zr and alphaZr+betaZr → betaZr transformation temperatures are in the range of 600-690°C and 960-970°C respectively. Also it was observed that upon quenching from temperatures below ˜860°C the martensitic transformation of betaZr to alpha'--hcp is halted and instead the microstructure transforms into retained Zr with o hexagonal precipitates inside betaZr grains. Chapter 4 deals with aging response of Excel alloy. Precipitation hardening was observed in samples water-quenched from high in the alphaZr+beta Zr or betaZr regions followed by aging. The optimum aging conditions were found to be 450°C for 1 hour. Transmission electron microscopy (TEM) showed dispersion of fine precipitates (˜10nm) inside the martensitic phase. Energy dispersive X-ray spectroscopy (EDS) showed the chemical composition of precipitates to be Zr-30wt%Mo-25wt%Nb-2wt%Fe. Electron crystallography using whole pattern symmetry of the convergent beam electron diffraction (CBED) patterns together with selected area diffraction (SAD) polycrystalline ring patterns, suggests the -6m2 point group for the precipitates belonging to hexagonal crystal structure, with a= 2.936 A and c=4.481 A, i.e. c/a =1.526. Crystallographic texture and high temperature tensile properties as well as creep-rupture properties of different microstructures are discussed in Chapter 5. Texture analysis showed that solution treatment high in the alpha Zr+betaZr or betaZr regions followed by water quenching or air cooling results in a more random texture compared to typical pressure tube texture. Variant selection was observed upon water quenching while partial memory effect and some transformation texture with variant selection was observed in the air-cooled sample. The results of creep-rupture tests suggest that fully martensitic and aged microstructure has better creep properties at high stress levels (>700 MPa) while the microstructure from air cooling from high in the alphaZr+betaZr region is less sensitive to stress and shows better creep properties compared to the as-received annealed microstructure at lower stresses (<560 MPa).

Structure and anticoagulant activity of a sulfated galactan from the red alga, Gelidium crinale. Is there a specific structural requirement for the anticoagulant action?

PubMed

Pereira, Maria G; Benevides, Norma M B; Melo, Marcia R S; Valente, Ana Paula; Melo, Fábio R; Mourão, Paulo A S

2005-09-05

Marine red algae are an abundant source of sulfated galactans with potent anticoagulant activity. However, the specific structural motifs that confer biological activity remain to be elucidated. We have now isolated and purified a sulfated galactan from the marine red alga, Gellidium crinale. The structure of this polysaccharide was determined using NMR spectroscopy. It is composed of the repeating structure -4-alpha-Galp-(1-->3)-beta-Galp1--> but with a variable sulfation pattern. Clearly 15% of the total alpha-units are 2,3-di-sulfated and another 55% are 2-sulfated. No evidence for the occurrence of 3,6-anhydro alpha-galactose units was observed in the NMR spectra. We also compared the anticoagulant activity of this sulfated galactan with a polysaccharide from the species, Botryocladia occidentalis, with a similar saccharide chain but with higher amounts of 2,3-di-sulfated alpha-units. The sulfated galactan from G. crinale has a lower anticoagulant activity on a clotting assay when compared with the polysaccharide from B. occidentalis. When tested in assays using specific proteases and coagulation inhibitors, these two galactans showed significant differences in their activity. They do not differ in thrombin inhibition mediated by antithrombin, but in assays where heparin cofactor II replaces antithrombin, the sulfated galactan from G. crinale requires a significantly higher concentration to achieve the same inhibitory effect as the polysaccharide from B. occidentalis. In contrast, when factor Xa instead of thrombin is used as the target protease, the sulfated galactan from G. crinale is a more potent anticoagulant. These observations suggest that the proportion and/or the distribution of 2,3-di-sulfated alpha-units along the galactan chain may be a critical structural motif to promote the interaction of the protease with specific protease and coagulation inhibitors.

Temperature dependence of single-crystal elastic constants of flux-grown alpha-GaPO(4).

PubMed

Armand, P; Beaurain, M; Rufflé, B; Menaert, B; Papet, P

2009-06-01

The lattice parameter change with respect to temperature (T) has been measured using high-temperature powder X-ray diffraction techniques for high-temperature flux-grown GaPO(4) single crystals with the alpha-quartz structure. The lattice and the volume linear thermal expansion coefficients in the temperature range 303-1173 K were computed from the X-ray data. The percentage linear thermal expansions along the a and c axes at 1173 K are 1.5 and 0.51, respectively. The temperature dependence of the mass density rho of flux-grown GaPO(4) single crystals was evaluated using the volume thermal expansion coefficient alpha(V)(T) = 3.291 x 10(-5) - 2.786 x 10(-8) [T] + 4.598 x 10(-11)[T](2). Single-crystal high-resolution Brillouin spectroscopy measurements have been carried out at ambient pressure from 303 to 1123 K to determine the elastic constants C(IJ) of high-temperature flux-grown GaPO(4) material. The single-crystal elastic moduli were calculated using the sound velocities via the measured Brillouin frequency shifts Deltanu(B). These are, to our knowledge, the highest temperatures at which single-crystal elastic constants of alpha-GaPO(4) have been measured. Most of the room-temperature elastic constant values measured on flux-grown GaPO(4) material are higher than the ones found for hydrothermally grown GaPO(4) single crystals. The fourth-order temperature coefficients of both the Brillouin frequency shifts T(nuB)((n)) and the single-crystal elastic moduli T(C(IJ))((n)) were obtained. The first-order temperature coefficients of the C(IJ) are in excellent agreement with previous reports on low-temperature hydrothermally grown alpha-GaPO(4) single crystals, while small discrepancies in the higher-order temperature coefficients are observed. This is explained in terms of the OH content in the GaPO(4) network, which is an important parameter in the crystal thermal behavior.

Proton Resonance Spectroscopy in CALCIUM-40.

NASA Astrophysics Data System (ADS)

Warthen, Barry Joseph

1987-09-01

The differential cross sections for the ^{39}K(p,p_{ rm o})^{39}K and ^{39}K(p,alpha_ {rm o})^{36}Ar reactions have been measured for E_{ rm p} = 1.90 to 4.02 MeV at laboratory angles theta = 90^ circ, 108^circ, 150^circ and 165^ circ. Data were taken with the Triangle Universities Nuclear Laboratory (TUNL) KN Van de Graaff accelerator and the associated high resolution system. The targets consisted of 1-2 mug/cm^2 of potassium carbonate (K_2CO _3), enriched to 99.97% ^{39}K, evaporated onto gold coated carbon backings. Excitation functions were measured in proton energy steps varying from 100 to 400 eV. The energy region studied corresponds to an excitation energy range in the ^{40}Ca nucleus of E_{rm x} = 10.2 to 12.3 MeV. A multi-level multi-channel R-matrix based computer code was used to fit the experimental excitation functions. Resonance parameters obtained include resonance energy, spin, parity, partial widths, and channel spin and orbital angular momentum mixing ratios. Of the 248 resonances observed in the proton channel, 148 were also observed in the alpha channel. A fit to the observed level density yielded a nuclear temperature of 1.5 MeV. The data were compared with predictions of statistical theories of energy levels for both level spacing and reduced width distributions. The alpha reduced widths agree with the Porter-Thomas distribution and suggest that only 5-10% of the states with alpha widths were not observed. The summed strength in each of the alpha channels represents a significant fraction of the Wigner limit for these channels. The proton channels, on the other hand, generally have much smaller fractions. The two proton s-wave strength functions are equal and thus show no evidence for spin-exchange forces in the nucleon-nucleus interaction.

Structure and function of PA4872 from Pseudomonas aeruginosa, a novel class of oxaloacetate decarboxylase from the PEP mutase/isocitrate lyase superfamily.

PubMed

Narayanan, Buvaneswari C; Niu, Weiling; Han, Ying; Zou, Jiwen; Mariano, Patrick S; Dunaway-Mariano, Debra; Herzberg, Osnat

2008-01-08

Pseudomonas aeruginosa PA4872 was identified by sequence analysis as a structurally and functionally novel member of the PEP mutase/isocitrate lyase superfamily and therefore targeted for investigation. Substrate screens ruled out overlap with known catalytic functions of superfamily members. The crystal structure of PA4872 in complex with oxalate (a stable analogue of the shared family alpha-oxyanion carboxylate intermediate/transition state) and Mg2+ was determined at 1.9 A resolution. As with other PEP mutase/isocitrate lyase superfamily members, the protein assembles into a dimer of dimers with each subunit adopting an alpha/beta barrel fold and two subunits swapping their barrel's C-terminal alpha-helices. Mg2+ and oxalate bind in the same manner as observed with other superfamily members. The active site gating loop, known to play a catalytic role in the PEP mutase and lyase branches of the superfamily, adopts an open conformation. The Nepsilon of His235, an invariant residue in the PA4872 sequence family, is oriented toward a C(2) oxygen of oxalate analogous to the C(3) of a pyruvyl moiety. Deuterium exchange into alpha-oxocarboxylate-containing compounds was confirmed by 1H NMR spectroscopy. Having ruled out known activities, the involvement of a pyruvate enolate intermediate suggested a decarboxylase activity of an alpha-oxocarboxylate substrate. Enzymatic assays led to the discovery that PA4872 decarboxylates oxaloacetate (kcat = 7500 s(-1) and Km = 2.2 mM) and 3-methyloxaloacetate (kcat = 250 s(-1) and Km = 0.63 mM). Genome context of the fourteen sequence family members indicates that the enzyme is used by select group of Gram-negative bacteria to maintain cellular concentrations of bicarbonate and pyruvate; however the decarboxylation activity cannot be attributed to a pathway common to the various bacterial species.

Discovery, SAR, and Radiolabeling of Halogenated Benzimidazole Carboxamide Antagonists as Useful Tools for (alpha)4(beta)1 Integrin Expressed on T- and B-cell Lymphomas

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

Carpenter, R D; Natarajan, A; Lau, E Y

2010-02-08

The cell surface receptor {alpha}{sub 4}{beta}{sub 1} integrin is an attractive yet poorly understood target for selective diagnosis and treatment of T- and B-cell lymphomas. This report focuses on the rapid microwave preparation of medicinally pertinent benzimidazole heterocycles, structure-activity relationships (SAR) of novel halobenzimidazole carboxamide antagonists 3-6, and preliminary biological evaluation of radioiodinated agents 7, 8, and 18. The I-125 derivative 18 had good tumor uptake (12 {+-} 1% ID/g at 24 h; 4.5 {+-} 1% ID/g at 48 h) and tumor:kidney ratio ({approx}4:1 at 24 h; 2.5:1 at 48 h) in xenograft murine models of B-cell lymphoma. Molecular homologymore » models of {alpha}{sub 4}{beta}{sub 1} integrin have predicted that docked halobenzimidazole carboxamides have the halogen atom in a suitable orientation for halogen-hydrogen bonding. These high affinity ({approx} pM binding) halogenated ligands are attractive tools for medicinal and biological use; the fluoro and iodo derivatives are potential radiodiagnostic ({sup 18}F) or radiotherapeutic ({sup 131}I) agents, whereas the chloro and bromo analogues could provide structural insight into integrin-ligand interactions through photoaffinity cross-linking/mass spectroscopy experiments, as well as co-crystallization X-ray studies.« less

Reversible conformational transition gives rise to 'zig-zag' temperature dependence of the rate constant of irreversible thermoinactivation of enzymes.

PubMed

Levitsky VYu; Melik-Nubarov, N S; Siksnis, V A; Grinberg VYa; Burova, T V; Levashov, A V; Mozhaev, V V

1994-01-15

We have obtained unusual 'zig-zag' temperature dependencies of the rate constant of irreversible thermoinactivation (k(in)) of enzymes (alpha-chymotrypsin, covalently modified alpha-chymotrypsin, and ribonuclease) in a plot of log k(in) versus reciprocal temperature (Arrhenius plot). These dependencies are characterized by the presence of both ascending and descending linear portions which have positive and negative values of the effective activation energy (Ea), respectively. A kinetic scheme has been suggested that fits best for a description of these zig-zag dependencies. A key element of this scheme is the temperature-dependent reversible conformational transition of enzyme from the 'low-temperature' native state to a 'high-temperature' denatured form; the latter form is significantly more stable against irreversible thermoinactivation than the native enzyme. A possible explanation for a difference in thermal stabilities is that low-temperature and high-temperature forms are inactivated according to different mechanisms. Existence of the suggested conformational transition was proved by the methods of fluorescence spectroscopy and differential scanning calorimetry. The values of delta H and delta S for this transition, determined from calorimetric experiments, are highly positive; this fact underlies a conclusion that this heat-induced transition is caused by an unfolding of the protein molecule. Surprisingly, in the unfolded high-temperature conformation, alpha-chymotrypsin has a pronounced proteolytic activity, although this activity is much smaller than that of the native enzyme.

Diffusion-controlled and "diffusionless" crystal growth near the glass transition temperature: relation between liquid dynamics and growth kinetics of seven ROY polymorphs.

PubMed

Sun, Ye; Xi, Hanmi; Ediger, M D; Richert, Ranko; Yu, Lian

2009-08-21

The liquid dynamics of 5-methyl-2-[(2-nitrophenyl)amino]-3-thiophenecarbonitrile, named ROY for its red, orange, and yellow crystal polymorphs, was characterized by dielectric spectroscopy and differential scanning calorimetry. Four of these polymorphs show fast "diffusionless" crystal growth at low temperatures while three others do not. ROY was found to be a typical fragile organic liquid. Its alpha relaxation process has time-temperature superposition symmetry across the viscous range (tau(alpha)=100 s-100 ns) with the width of the relaxation peak characterized by a constant beta(KWW) of 0.73. No secondary relaxation peak was observed, even with glasses made by fast quenching. For the polymorphs not showing fast crystal growth in the glassy state, the growth rate has a power-law relation with tau(alpha), u proportional to tau(alpha)(-xi), where xi approximately = 0.7. For the polymorphs showing fast crystal growth in the glassy state, the growth is so fast near and below the glass transition temperature T(g) that thousands of molecular layers can be added to the crystalline phase during one structural relaxation time of the liquid. In the glassy state, this mode of growth slows slightly over time. This slowdown is not readily explained by the effect of physical aging on the thermodynamic driving force of crystallization, the glass vapor pressure, or the rate of structural relaxation. This study demonstrates that from the same liquid or glass, the growth of some polymorphs is accurately described as being limited by the rate of structural relaxation or bulk diffusion, whereas the growth of other polymorphs is too fast to be under such control.

Revisiting the structure of the anti-neoplastic glucans of Mycobacterium bovis Bacille Calmette-Guerin. Structural analysis of the extracellular and boiling water extract-derived glucans of the vaccine substrains.

PubMed

Dinadayala, Premkumar; Lemassu, Anne; Granovski, Pierre; Cérantola, Stéphane; Winter, Nathalie; Daffé, Mamadou

2004-03-26

The attenuated strain of Mycobacterium bovis Bacille Calmette-Guérin (BCG), used worldwide to prevent tuberculosis and leprosy, is also clinically used as an immunotherapeutic agent against superficial bladder cancer. An anti-tumor polysaccharide has been isolated from the boiling water extract of the Tice substrain of BCG and tentatively characterized as consisting primarily of repeating units of 6-linked-glucosyl residues. Mycobacterium tuberculosis and other mycobacterial species produce a glycogen-like alpha-glucan composed of repeating units of 4-linked glucosyl residues substituted at some 6 positions by short oligoglucosyl units that also exhibits an anti-tumor activity. Therefore, the impression prevails that mycobacteria synthesize different types of anti-neoplastic glucans or, alternatively, the BCG substrains are singular in producing a unique type of glucan that may confer to them their immunotherapeutic property. The present study addresses this question through the comparative analysis of alpha-glucans purified from the extracellular materials and boiling water extracts of three vaccine substrains. The polysaccharides were purified, and their structural features were established by mono- and two-dimensional NMR spectroscopy and matrix-assisted laser desorption/ionization time-of-flight mass spectrometry of the enzymatic and chemical degradation products of the purified compounds. The glucans isolated by the two methods from the three substrains of BCG were shown to exhibit identical structural features shared with the glycogen-like alpha-glucan of M. tuberculosis and other mycobacteria. Incidentally, we observed an occasional release of dextrans from Sephadex columns that may explain the reported occurrence of 6-substituted alpha-glucans in mycobacteria.

Interaction of cord factor (alpha, alpha'-trehalose-6,6'-dimycolate) with phospholipids.

PubMed

Crowe, L M; Spargo, B J; Ioneda, T; Beaman, B L; Crowe, J H

1994-08-24

We previously reported that cord factor (alpha,alpha'-trehalose-6,6'-dimycolate) isolated from Nocardia asteroides strain GUH-2 strongly inhibits fusion between unilamellar vesicles containing acidic phospholipid. We chose to study the effects of this molecule on liposome fusion since the presence of N. asteroides GUH-2 in the phagosomes of mouse macrophages had been shown to prevent phagosomal acidification and inhibit phagosome-lysosome fusion. A virtually non-virulent strain, N. asteroides 10905, does not prevent acidification or phagosome-lysosome fusion and, further, contains only trace amounts of cord factor. In the present paper, we have investigated the effects of cord factor on phospholipid bilayers that could be responsible for the inhibition of fusion. We show that cord factor increases molecular area, measured by isothermal compression of a monolayer film, in a mixed monolayer more than would be expected based in its individual contribution to molecular area. Cord factor, as well as other glycolipids investigated, increased the overall hydration of bilayers of dipalmitoylphosphatidylcholine by 50%, as estimated from the unfrozen water fraction measured by differential scanning calorimetry. The effect of calcium on this increased molecular area and headgroup hydration was measured by fluorescence anisotropy and FTIR spectroscopy of phosphatidylserine liposomes. Both techniques showed that cord factor, incorporated at 10 mol%, increased acyl chain disorder over controls in the presence of Ca2+. However, FTIR showed that cord factor did not prevent headgroup dehydration by the Ca2+. The other glycolipids tested did not prevent either the Ca(2+)-induced chain crystallization or headgroup dehydration of phosphatidylserine bilayers. These data point to a possible role of the bulky mycolic acids of cord factor in preventing Ca(2+)-induced fusion of liposomes containing acidic phospholipids.

The importance of including local correlation times in the calculation of inter-proton distances from NMR measurements: ignoring local correlation times leads to significant errors in the conformational analysis of the Glc alpha1-2Glc alpha linkage by NMR spectroscopy.

PubMed

Mackeen, Mukram; Almond, Andrew; Cumpstey, Ian; Enis, Seth C; Kupce, Eriks; Butters, Terry D; Fairbanks, Antony J; Dwek, Raymond A; Wormald, Mark R

2006-06-07

The experimental determination of oligosaccharide conformations has traditionally used cross-linkage 1H-1H NOE/ROEs. As relatively few NOEs are observed, to provide sufficient conformational constraints this method relies on: accurate quantification of NOE intensities (positive constraints); analysis of absent NOEs (negative constraints); and hence calculation of inter-proton distances using the two-spin approximation. We have compared the results obtained by using 1H 2D NOESY, ROESY and T-ROESY experiments at 500 and 700 MHz to determine the conformation of the terminal Glc alpha1-2Glc alpha linkage in a dodecasaccharide and a related tetrasaccharide. For the tetrasaccharide, the NOESY and ROESY spectra produced the same qualitative pattern of linkage cross-peaks but the quantitative pattern, the relative peak intensities, was different. For the dodecasaccharide, the NOESY and ROESY spectra at 500 MHz produced a different qualitative pattern of linkage cross-peaks, with fewer peaks in the NOESY spectrum. At 700 MHz, the NOESY and ROESY spectra of the dodecasaccharide produced the same qualitative pattern of peaks, but again the relative peak intensities were different. These differences are due to very significant differences in the local correlation times for different proton pairs across this glycosidic linkage. The local correlation time for each proton pair was measured using the ratio of the NOESY and T-ROESY cross-relaxation rates, leaving the NOESY and ROESY as independent data sets for calculating the inter-proton distances. The inter-proton distances calculated including the effects of differences in local correlation times give much more consistent results.

A New Population of High-z, Dusty Lyman-alpha Emitters and Blobs Discovered by WISE: Feedback Caught in the Act?

NASA Technical Reports Server (NTRS)

Bridge, Carrie R.; Blain, Andrew; Borys, Colin J. K.; Petty, Sara; Benford, Dominic; Eisenhardt, Peter; Farrah, Duncan; Griffith, Roger, L.; Jarrett, Tom; Lonsdale, Carol;

An Accurate Measurement of the IGM HeII Lyman Alpha Forest toward a Newly Discovered UV-bright Quasar at z>3.5

NASA Astrophysics Data System (ADS)

Worseck, Gabor

2016-10-01

The advent of GALEX and COS have revolutionized our view of HeII reionization, the final major phase transition of the intergalactic medium. COS spectra of the HeII Lyman alpha forest have confirmed with high confidence the high HeII transmission that signifies the completion of HeII reionization at z 2.7. However, the handful of z>3.5 quasars observed to date show a set of HeII transmission 'spikes' and larger regions with non-zero transmission that suggest HeII reionization was well underway by z=4. This is in striking conflict with predictions from state-of-the-art radiative transfer simulations of a HeII reionization driven by bright quasars. Explaining these measurements may require either faint quasars or more exotic sources of hard photons at z>4, with concomitant implications for HI reionization. We propose here to observe J2354-2033, an FUV-bright quasar at z=3.786 that we recently discovered in a dedicated survey for likely HeII-transmitting quasars. With this COS/G140L spectrum, we would confirm that the quasar is valuable for studies of the HeII Lyman alpha forest by identifying possible interloping low-z HI absorbers, provide accurate measurements of the IGM HeII opacity, and provide only the third z>3.5 sightline that would allow for high-resolution G130M spectroscopy before the end of HST's mission. The proposed observations would mark only the fourth observation of the HeII Lyman alpha forest at z>3.7 and the source would be the 2nd-brightest known on the sky at these redshifts.

Enduring effects of severe developmental adversity, including nutritional deprivation, on cortisol metabolism in aging Holocaust survivors.

PubMed

Yehuda, Rachel; Bierer, Linda M; Andrew, Ruth; Schmeidler, James; Seckl, Jonathan R

2009-06-01

In animal models, early life exposure to major environmental challenges such as malnutrition and stress results in persisting cardiometabolic, neuroendocrine and affective effects. While such effects have been associated with pathogenesis, the widespread occurrence of 'developmental programming' suggests it has adaptive function. Glucocorticoids may mediate 'programming' and their metabolism is known to be affected by early life events in rodents. To examine these relationships in humans, cortisol metabolism and cardiometabolic disease manifestations were examined in Holocaust survivors in relation to age at exposure and affective dysfunction, notably lifetime posttraumatic stress disorder (PTSD). Fifty-one Holocaust survivors and 22 controls without Axis I disorder collected 24-h urine samples and were evaluated for psychiatric disorders and cardiometabolic diagnoses. Corticosteroids and their metabolites were assayed by gas chromatography-mass spectroscopy (GC-MS); cortisol was also measured by radioimmunoassay (RIA). Holocaust survivors showed reduced cortisol by RIA, and decreased levels of 5alpha-tetrahydrocortisol (5alpha-THF) and total glucocorticoid production by GC-MS. The latter was associated with lower cortisol metabolism by 5alpha-reductase and 11beta-hydroxysteroid dehydrogenase (11beta-HSD) type-2. The greatest decrements were associated with earliest age of Holocaust exposure and less severe PTSD symptomatology. Cardiometabolic manifestations were associated with decreased 11beta-HSD-2 activity. In controls, 5alpha-reductase was positively associated with trauma-related symptoms (i.e., to traumatic exposures unrelated to the Holocaust). Extreme malnutrition and related stress during development is associated with long-lived alterations in specific pathways of glucocorticoid metabolism. These effects may be adaptive and link with lower risks of cardiometabolic and stress-related disorders in later life.

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

Berastegui, P.; Hull, S., E-mail: stephen.hull@stfc.ac.u; Eriksson, S.G.

The compound CsSn{sub 2}F{sub 5} has been investigated over the temperature range from ambient to 545 K using differential scanning calorimetry, impedance spectroscopy and neutron powder diffraction methods. A first-order phase transition is observed from DSC measurements at 510(2) K, to a phase possessing a high ionic conductivity ({sigma}{approx}2.5x10{sup -2} {Omega}{sup -1} cm{sup -1} at 520 K). The crystal structure of the high temperature superionic phase (labelled {alpha}) has been determined to be tetragonal (space group I4/mmm, a=4.2606(10) A, c=19.739(5) A and Z=2) in which the cations form layers perpendicular to the [001] direction, with a stacking sequence CsSnSnCsSnSn... Allmore » the anions are located in two partially occupied sites in the gap between the Cs and Sn layers, whilst the space between the Sn cations is empty, due to the orientation of the lone-pair electrons associated with the Sn{sup 2+}. The structure of {alpha}-CsSn{sub 2}F{sub 5} is discussed in relation to two other layered F{sup -} conducting superionic phases containing Sn{sup 2+} cations, {alpha}-RbSn{sub 2}F{sub 5} and {alpha}-PbSnF{sub 4} and, to facilitate this comparison, an improved structural characterisation of the former is also presented. The wider issue of the role of lone-pair cations such as Sn{sup 2+} in promoting dynamic disorder within an anion substructure is also briefly addressed. - Graphical abstract: CsSn{sub 2}F{sub 5} is shown to undergo a first order phase transition at 510(2) K to a superionic phase in which the specific electronic configuration of the Sn{sup 2+} plays a key role in promoting extensive disorder of the anions.« less

ISOLATED WOLF-RAYET STARS AND O SUPERGIANTS IN THE GALACTIC CENTER REGION IDENTIFIED VIA PASCHEN-{alpha} EXCESS

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

Mauerhan, J. C.; Stolovy, S. R.; Cotera, A.

We report the discovery of 19 hot, evolved, massive stars near the Galactic center region (GCR). These objects were selected for spectroscopy owing to their detection as strong sources of Paschen-{alpha} (P{alpha}) emission-line excess, following a narrowband imaging survey of the central 0.{sup 0}65 x 0.{sup 0}25 (l, b) around Sgr A* with the Hubble Space Telescope. Discoveries include six carbon-type (WC) and five nitrogen-type (WN) Wolf-Rayet stars, six O supergiants, and two B supergiants. Two of the O supergiants have X-ray counterparts having properties consistent with solitary O stars and colliding-wind binaries. The infrared photometry of 17 stars ismore » consistent with the Galactic center distance, but 2 of them are located in the foreground. Several WC stars exhibit a relatively large infrared excess, which is possibly thermal emission from hot dust. Most of the stars appear scattered throughout the GCR, with no relation to the three known massive young clusters; several others lie near the Arches and Quintuplet clusters and may have originated within one of these systems. The results of this work bring the total sample of Wolf-Rayet (WR) stars in the GCR to 88. All sources of strong P{alpha} excess have been identified in the area surveyed with HST, which implies that the sample of WN stars in this region is near completion, and is dominated by late (WNL) types. The current WC sample, although probably not complete, is almost exclusively dominated by late (WCL) types. The observed WR subtype distribution in the GCR is a reflection of the intrinsic rarity of early subtypes (WNE and WCE) in the inner Galaxy, an effect that is driven by metallicity.« less

Biosynthesis of ketomycin. (II) biomimetic model for beta-lactamase catalysis: host-guest interactions in cyclodextrin-penicillin inclusion complex

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

Mak, H.W.

The antibiotic ketomycin is formed from shikimic acid via chorismic acid and prephenic acid. Phenylalanine and 2',5'-dihydrophenylalanine derived from shikimic acid are not intermediates in the biosynthesis. Degradation of ketomycin derived from (1,6-/sup 14/C)shikimic acid showed that prephenic acid is converted into ketomycin with stereospecific discrimination between the two enantiotopic edges of the ring, the pro-S-R edge giving rise to the C-2', C-3' side of the cyclohexane ring of ketomycin. The resistance of pathogenic bacteria to the action of ..beta..-lactam antibiotics is mainly ascribed to their ability to produce ..beta..-lactamase to cleave the ..beta..-lactam ring. It is essential to understandmore » the molecular nature of ..beta..-lactamase-penicillin recognition for designing and formulating more effective ..beta..-lactam antibiotics. A biomimetic study of ..beta..-lactamase is therefore initiated. To meet the requirements of hydrophobic and serine protease characteristics of ..beta..-lactamase, ..cap alpha..-cyclodextrin is chosen as a biomimetic model for ..beta..-lactamase. The structural specificity and the chemical dynamics of ..cap alpha..-cyclodextrin-phenoxymethyl penicillin inclusion complex in solid state and in solution have been determined by IR and NMR spectroscopy. The spectral results strongly indicate that the phenyl portion of the phenoxymethyl penicillin forms a stable inclusion complex with the hydrophobic cavity of ..cap alpha..-cyclodextrin in solution as well as in the solid state. Kinetic studies followed by /sup 1/HNMR and HPLC analyses under alkaline condition have shown that the ..cap alpha..-cyclodextrin mimics the catalytic function of serine of ..beta..-lactamase in the stereospecific hydrolysis of the ..beta..-lactam ring of phenoxymethyl penicillin.« less

A Fourier transform spectrometer for visible and near ultra-violet measurements of atmospheric absorption

NASA Technical Reports Server (NTRS)

Parsons, C. L.; Gerlach, J. C.; Whitehurst, M.

1982-01-01

The development of a prototype, ground-based, Sun-pointed Michelson interferometric spectrometer is described. Its intended use is to measure the atmospheric amount of various gases which absorb in the near-infrared, visible, and near-ultraviolet portions of the electromagnetic spectrum. Preliminary spectra which contain the alpha, 0.8 micrometer, and rho sigma tau water vapor absorption bands in the near-infrared are presented to indicate the present capability of the system. Ultimately, the spectrometer can be used to explore the feasible applications of Fourier transform spectroscopy in the ultraviolet where grating spectrometers were used exclusively.

Enhanced effect of temporal variation of the fine structure constant and the strong interaction in 229Th.

PubMed

Flambaum, V V

2006-09-01

The relative effects of the variation of the fine structure constant alpha = e2/variant Planck's over 2pi c and the dimensionless strong interaction parameter m(q)/LambdaQCD are enhanced by 5-6 orders of magnitude in a very narrow ultraviolet transition between the ground and the first excited states in the 229Th nucleus. It may be possible to investigate this transition with laser spectroscopy. Such an experiment would have the potential of improving the sensitivity to temporal variation of the fundamental constants by many orders of magnitude.

Precision Fe K-Alpha and Fe K-Beta Line Spectroscopy of the Seyfert 1.9 Galaxy NGC 2992 with Suzaku

NASA Technical Reports Server (NTRS)

Yaqoob, Tahir; Murphy, Kendrah D.; Griffiths, Richard E.; Haba, Yoshito; Inoue, Hajime; Itoh, Takeshi; Kelley, Richard; Kokubun, Motohide; Markowitz, Alex; Mushotzky, Richard;

Probing the Lewis acidity and catalytic activity of the metal-organic framework [Cu3(btc)2] (BTC=benzene-1,3,5-tricarboxylate).

PubMed

Alaerts, Luc; Séguin, Etienne; Poelman, Hilde; Thibault-Starzyk, Frédéric; Jacobs, Pierre A; De Vos, Dirk E

2006-09-25

An optimized procedure was designed for the preparation of the microporous metal-organic framework (MOF) [Cu3(btc)2] (BTC=benzene-1,3,5-tricarboxylate). The crystalline material was characterized by X-ray diffraction, optical microscopy, SEM, X-ray photoelectron spectroscopy, N2 sorption, thermogravimetry, and IR spectroscopy of adsorbed CO. CO adsorbs on a small number of Cu2O impurities, and particularly on the free CuII coordination sites in the framework. [Cu3(btc)2] is a highly selective Lewis acid catalyst for the isomerization of terpene derivatives, such as the rearrangement of alpha-pinene oxide to campholenic aldehyde and the cyclization of citronellal to isopulegol. By using the ethylene ketal of 2-bromopropiophenone as a test substrate, it was demonstrated that the active sites in [Cu3(btc)2] are hard Lewis acids. Catalyst stability, re-usability, and heterogeneity are critically assessed.

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

Elihn, K.; Landstroem, L.; Alm, O.

Iron nanoparticles enclosed in carbon shells were formed by laser-assisted chemical vapor decomposition of ferrocene (Fe(C{sub 5}H{sub 5}){sub 2}) vapor in Ar gas atmosphere. The particle size dependence on the total ambient gas pressure and on laser fluence of the pulsed ArF excimer laser was examined and, e.g., an effective size decrease of the iron core was observed at elevated laser fluences. Characterizations of the iron and carbon microstructures were performed by x-ray diffraction and transmission electron microscopy, while relative iron deposition rates were measured by x-ray fluorescence spectroscopy. Both {alpha}-Fe and {gamma}-Fe phases were found for the single crystallinemore » iron cores, surrounded by graphitic (inner) and amorphous (outer) carbon layers. The temperature rise of the laser-excited particles was also determined by optical spectroscopy of the emitted thermal radiation, which allowed an estimation of the iron loss of the nanoparticles due to evaporation. The estimated and measured iron losses are in good agreement.« less

Deciphering molecular interactions of native membrane proteins by single-molecule force spectroscopy.

PubMed

Kedrov, Alexej; Janovjak, Harald; Sapra, K Tanuj; Müller, Daniel J

2007-01-01

Molecular interactions are the basic language of biological processes. They establish the forces interacting between the building blocks of proteins and other macromolecules, thus determining their functional roles. Because molecular interactions trigger virtually every biological process, approaches to decipher their language are needed. Single-molecule force spectroscopy (SMFS) has been used to detect and characterize different types of molecular interactions that occur between and within native membrane proteins. The first experiments detected and localized molecular interactions that stabilized membrane proteins, including how these interactions were established during folding of alpha-helical secondary structure elements into the native protein and how they changed with oligomerization, temperature, and mutations. SMFS also enables investigators to detect and locate molecular interactions established during ligand and inhibitor binding. These exciting applications provide opportunities for studying the molecular forces of life. Further developments will elucidate the origins of molecular interactions encoded in their lifetimes, interaction ranges, interplay, and dynamics characteristic of biological systems.

GLASS: spatially resolved spectroscopy of lensed galaxies in the Frontier Fields

NASA Astrophysics Data System (ADS)

Jones, Tucker; Treu, Tommaso; Brammer, Gabriel; Borello Schmidt, Kasper; Malkan, Matthew A.

2015-08-01

The Grism Lens-Amplified Survey from Space (GLASS) has obtained slitless near-IR spectroscopy of 10 galaxy clusters selected for their strong lensing properties, including all six Hubble Frontier Fields. Slitless grism spectra are ideal for mapping emission lines such as [O II], [O III], and H alpha at z=1-3. The combination of strong gravitational lensing and HST's diffraction limit provides excellent sensitivity with spatial resolution as fine as 100 pc for highly magnified sources, and ~500 pc for less magnified sources near the edge of the field of view. The GLASS survey represents the largest spectroscopic sample with such high resolution at z>1. GLASS and Hubble Frontier Field data provide the distribution of stellar mass, star formation, gas-phase metallicity, and other aspects of the physical structure of high redshift galaxies, reaching unprecedented stellar masses as low as ~10^7 Msun at z=2. I will discuss precise measurements of these physical properties and implications for galaxy evolution.

Assessing the reliability of FTIR spectroscopy measurements and validity of bioelectrical impedance analysis as a surrogate measure of body composition among children and adolescents aged 8-19 years attending schools in Kampala, Uganda.

PubMed

Ndagire, Catherine T; Muyonga, John H; Isabirye, Dan; Odur, Benard; Somda, Serge M A; Bukenya, Richard; Andrade, Juan E; Nakimbugwe, Dorothy

2018-06-04

Accurate measurement of body composition in children and adolescents is important as the quantities of fat and fat-free mass have implications for health risk. The objectives of the present study were: to determine the reliability of Fourier Transform Infrared spectroscopy (FTIR) measurements and; compare the Fat Mass (FM), Fat Free Mass (FFM) and body fat percentage (%BF) values determined by bioelectrical impedance analysis (BIA) to those determined by deuterium dilution method (DDM) to identify correlations and agreement between the two methods. A cross-sectional study was conducted among 203 children and adolescents aged 8-19 years attending schools in Kampala city, Uganda. Pearson product-moment correlation at 5% significance level was considered for assessing correlations. Bland Altman analysis was used to examine the agreement between of FTIR measurements and between estimates by DDM and BIA.. Reliability of measurements was determined by Cronbach's alpha. There was good agreement between the in vivo D 2 O saliva enrichment measurements at 3 and 4 h among the studied age groups based on Bland-Altman plots. Cronbach's alpha revealed that measurements of D 2 O saliva enrichment had very good reliability. For children and young adolescents, DDM and BIA gave similar estimates of FFM, FM, and %BF. Among older adolescents, BIA significantly over-estimated FFM and significantly under-estimated FM and %BF compared to estimates by DDM. The correlation between FFM, FM and %BF estimates by DDM and BIA was high and significant among young and older adolescents and for FFM among children. Reliability of the FTIR spectroscopy measurements was very good among the studied population. BIA is suitable for assessing body composition among children (8-9 years) and young adolescents (10-14 years) but not among older adolescents (15-19 years) in Uganda. The body composition measurements of older adolescents determined by DDM can be predicted using those provided by BIA using population-specific regression equations.

a Combined Molecular Dynamics and NMR Spectroscopic Protocol for the Conformational Analysis of Oligosaccharides.

NASA Astrophysics Data System (ADS)

Varma, Vikram

A combined experimental and theoretical protocol for the conformational analysis of oligosaccharides is presented. Three disaccharides, methyl alpha - scD-mannopyranosyl-(1 to 3)-alpha- scD-mannopyranoside, methyl beta- scD-galactopyranosyl-(1 to 4)-beta- scD-glucopyranoside, and propyl beta- scD-2-acetamido -2-deoxy glucopyranosyl-(1 to 3)- alpha- scL-rhamnopyranoside, are used to evaluate a protocol for conformational analysis that makes use of molecular dynamics calculations with the CHARMM force field. Dynamics trajectories computed in vacuo and in water are used to calculate time-averaged NMR parameters such as spin-lattice relaxation times (T_1 ), Nuclear Overhauser Enhancements (NOE), and heteronuclear spin-spin coupling constants (^3J _{rm CH}). The calculated NMR parameters are then compared to experimental values and used to evaluate the computational procedure. The energetically accessible conformations are effectively sampled by the simulations. The method has been extended to the conformational analysis of higher-order oligosaccharides corresponding to the cell-wall polysaccharide of the Streptococcus Group A, and the Shigella flexneri Y O-antigen. The Streptococcus Group A cell-wall polysaccharide is comprised of a backbone of rhamnopyranosyl units connected by alternating alpha- scL-(1 to 3) and alpha- scL -(1 to 2) linkages, to which are attached N-acetyl-beta- scD-glucosamine ( beta- scD-GlcpNAc) residues at the 3 positions of the rhamnose backbone.rm A&rm B^'qquad A^'& rm Bqquad Acr[{-alpha}{-}L{-}Rha {it p}{-}(1to2){-alpha }{-}L{-}Rha{it p} {-}(1to3){-alpha}{ -}L{-}Rha{it p}-(1to2) -alpha-L-Rha{it p}{-}(1 to3){-alpha}{-}L{- }Rha{it p}{-}cr&uparrow(1 to3)&uparrow(1to3)crbeta {-}D{-}&rm Glc{it p }NAcqquadbeta{-}D{-}& rm Glc{it p}NAccr&rm C ^'&rm C] A branched trisaccharide (A^' -(C)B), a tetrasaccharide (A^' -(C)B-A), a pentasaccharide (C^' -B^'-A ^'-(C)B), and two hexasaccharides (C^'-B^ '-A^' -(C)B-A) and (A-(C^')B ^'-A^' -(C)B), have been chosen for study. The Shigella flexneri Y O-antigen is a linear polysaccharide that is composed of rhamnose units linked alpha- scL-(1 to 3) and alpha- scL-(1 to 2), interspersed by N-acetyl-beta - scD-glucosamine (beta- scD -GlcpNAc) to form a periodic repeating unit ABCD. &rm A&rm B&rm C&rm Dcr [{-alpha}{-}L {-}Rha{it p}-(1to2){ -alpha}{-}L{-}Rha{it p}{-}(1to3){-alpha} {-}L{-}Rha{it p}{ -}(1to3){-}beta{-}D {-}Glc{it p}NAc{-}(1 to2){-}]_{it n}A heptasaccharide corresponding to the fragment (ABCDA^'B ^'C^' ) of the Shigella flexneri Y polysaccharide has been investigated. The conformational properties of all of the oligosaccharides have been studied using molecular dynamics simulations. Interproton distances derived from ROESY spectra are used to determine the starting conformations of the oligosaccharides used in the dynamics calculations, and dynamics simulations are computed with proton pairs constrained to the ROESY -derived distances, as well as with the constraints removed. These dynamics trajectories are used to calculate ROESY buildup curves with CROSREL, a program that treats cross relaxation by means of a full matrix relaxation approach. The calculated buildup curves compare favorably with the experimental buildup curves. The study demonstrates that molecular dynamics, in conjunction with NMR spectroscopy, can be a useful tool in the understanding of the conformational behavior of oligosaccharides in solution. The results provide a model for antigen topology that can be used to infer some of the critical features of antibody-antigen interactions.

Molecular and structural characteristics in toxic algae cultures of Ostreopsis ovata and Ostreopsis spp. evidenced by FTIR and FTNIR spectroscopy

NASA Astrophysics Data System (ADS)

Mecozzi, Mauro; Pietroletti, Marco; Tornambè, Andrea

2011-05-01

In this article we investigated the compositional and structural characteristics of the principal biomolecules such as carbohydrates, proteins, lipids, nucleic acids and chlorophyll pigments present in biofilm cultures of Ostreopsis spp. and in batch cultures of Ostreopsis ovata. Our approach based on the use of infrared (FTIR) and near infrared (FTNIR) spectroscopy showed the marked differences existing between biofilm cultures and batch cultures. FTIR spectroscopy showed the higher contents of polysaccharides and chlorophyll pigments in O. ovata from batch cultures with respect to Ostreopsis spp. Second derivative FTIR spectroscopy showed different features concerning the secondary structure of proteins because in O. ovata samples the beta sheet and beta turn structures were observed whereas in Ostreopsis spp. samples the alpha helix structure was the most evident. FTNIR spectroscopy showed other structural differences observed existing between O. ovata and Ostreopsis spp. mainly related to hydrogen bond interactions determining more packed structures in the nucleus of O. ovata. In addition, the interpretation of FTIR and FTNIR spectral information was also supported by the application of two statistical methods, the independent component analysis (ICA) and the spectral cross correlation analysis (SCCA). ICA was used as spectral deconvolution technique to separate the effects of the interference bicarbonate ion from algal FTIR spectra so to verify the high similar qualitative composition of the three biofilm samples of Ostreopsis spp. At last, SCCA applied to FTIR and FTNIR spectra was useful to evidence some structural differences involving -CH and CH 2 groups of aliphatic chains in O. ovata and Ostreopsis spp. samples. Though preliminary, these results agree with some previous studies suggesting that the presence of different ecophysiological characteristics in O. ovata and Ostreopsis spp. depending on the parameters related to the condition growth.

Time-resolved Spectroscopy of RS CVn Binaries and dMe Flare Stars

NASA Astrophysics Data System (ADS)

Brown, Alexander

One of the most striking feature of the first two years of EUVE spectroscopy is the frequent occurrence of largescale coronal variability, in the form of stellar flares and slower changes in activity level due to rotational modulation and evolution of active regions. We propose EUVE observations of a set of RS CVn and dMe star binaries, most with short (< 2 days) periods, to investigate the coronal conditions and physical processes associated with this variability. EUVE flare outbursts have mostly been long duration events lasting many satellite orbits and been readily studied using time-resolved spectroscopy. Our targets are the dMe binaries YY Gem, CC Eri and Gliese 2123, and the RS CVn systems EI Eri, AR Psc, and TY Pyx. YY Gem and TY Pyx are eclipsing systems and Deep Survey photometry will be used to investigate the size of the coronal emitting regions. Situated 73 arcmin from YY Gem is Castor (Alpha Gem) another X-ray source that can be observed (and spatially resolved) simultaneously. We shall use the DS lightcurve to guide our time resolved spectral analysis. Changes in the coronal emission measure as a function of temperature and possibly changes in coronal density will be used to constrain magnetic loop models.

The processing and characterization of animal-derived bone to yield materials with biomedical applications. Part II: milled bone powders, reprecipitated hydroxyapatite and the potential uses of these materials.

PubMed

Johnson, G S; Mucalo, M R; Lorier, M A; Gieland, U; Mucha, H

2000-11-01

Further studies on the processing and use of animal-bone-derived calcium phosphate materials in biomedical applications are presented. Bone powders sourced either from the direct crushing and milling of bovine, ovine and cervine bone or after being subjected to defatting and acid digestion/NaOH reprecipitation and sodium hypochlorite hydrogen peroxide treatment of animal bones were characterized using Fourier transform infra-red (FTIR) spectroscopy, 13C solid state magic angle spinning (MAS) nuclear magnetic resonance (NMR) spectroscopy, atomic absorption (AA) and inductively coupled plasma (ICP) spectrometric techniques. Bone powders were trialled for their potential use as a substrate for phosphine coupling and enzyme immobilization as well as a feedstock powder for plasma spraying on titanium metal substrates. Results indicated that enzyme immobilization by phosphine coupling could be successfully achieved on milled cervine bone with the immobilized enzyme retaining some activity. It was found that the presence of impurities normally carried down with the processing of the bone materials (viz., fat and collagen) played an important role in influencing the adsorbency and reactivity of the powders. Plasma spraying studies using reprecipitated bovine-derived powders produced highly adherent coatings on titanium metal, the composition of which was mostly hydroxyapatite (Ca10(PO4)6(OH)2) with low levels of alpha-tricalcium phosphate (alpha-Ca3(PO4)2) and tetracalcium phosphate (Ca4P2O9) also detected. In general, animal derived calcium phosphate materials constitute a potentially cheaper source of calcium phosphate materials for biomedical applications and make use of a largely under-utilized resource from abattoir wastes. Copyright 2000 Kluwer Academic Publishers

Isolation and characterisation of EfeM, a periplasmic component of the putative EfeUOBM iron transporter of Pseudomonas syringae pv. syringae

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

Rajasekaran, Mohan B; Structural Biology Unit at The BioCentre, University of Reading, Harborne Building, Whiteknights Campus, Reading, RG6 6AS; Mitchell, Sue A

2010-07-30

Research highlights: {yields} Bioinformatic analysis reveals EfeM is a metallopeptidase with conserved HXXE motif. {yields} Mass spectrometry confirms EfeM consists of 251 residues, molecular weight 27,772Da. {yields} SRCD spectroscopy shows an {alpha}-helical secondary structure. {yields} Single crystals of EfeM are orthorhombic and diffract to 1.6A resolution. {yields} Space group is P22{sub 1}2{sub 1} with cell dimensions a = 46.74, b = 95.17 and c = 152.61 A. -- Abstract: The EfeM protein is a component of the putative EfeUOBM iron-transporter of Pseudomonas syringae pathovar syringae and is thought to act as a periplasmic, ferrous-iron binding protein. It contains a signalmore » peptide of 34 amino acid residues and a C-terminal 'Peptidase{sub M}75' domain of 251 residues. The C-terminal domain contains a highly conserved 'HXXE' motif thought to act as part of a divalent cation-binding site. In this work, the gene (efeM or 'Psyr{sub 3}370') encoding EfeM was cloned and over-expressed in Escherichia coli, and the mature protein was purified from the periplasm. Mass spectrometry confirmed the identity of the protein (M{sub W} 27,772 Da). Circular dichroism spectroscopy of EfeM indicated a mainly {alpha}-helical structure, consistent with bioinformatic predictions. Purified EfeM was crystallised by hanging-drop vapor diffusion to give needle-shaped crystals that diffracted to a resolution of 1.6 A. This is the first molecular study of a peptidase M75 domain with a presumed iron transport role.« less

Structural and functional properties of hemoglobins from unicellular organisms as revealed by resonance Raman spectroscopy.

PubMed

Egawa, Tsuyoshi; Yeh, Syun-Ru

2005-01-01

Hemoglobins have been discovered in organisms from virtually all kingdoms. Their presence in unicellular organisms suggests that the gene for hemoglobin is very ancient and that the hemoglobins must have functions other than oxygen transport, in view of the fact that O2 delivery is a diffusion-controlled process in these organisms. Based on sequence alignment, three groups of hemoglobins have been characterized in unicellular organisms. The group-one hemoglobins, termed truncated hemoglobins, consist of proteins with 110-140 amino acid residues and a novel two-over-two alpha-helical sandwich motif. The group-two hemoglobins, termed flavohemoglobins, consist of a hemoglobin domain, with a classical three-over-three alpha-helical sandwich motif, and a flavin-containing reductase domain that is covalently attached to it. The group-three hemoglobins consist of myoglobin-like proteins that have high sequence homology and structural similarity to the hemoglobin domain of flavohemoglobins. In this review, recent resonance Raman studies of each group of these proteins are presented. Their implications are discussed in the context of the structural and functional properties of these novel hemoglobins.

Sterols isolated from Nuruk (Rhizopus oryzae KSD-815) inhibit the migration of cancer cells.

PubMed

Lee, Dae-Young; Lee, Sang-Jin; Kwak, Ho-Young; Jung, Lakoon; Heo, Jieun; Hong, Sungyoul; Kim, Gye-Won; Baek, Nam-In

2009-11-01

An activity-guided fractionation method was used to isolate anticancer components from Nuruk (Rhizopus oryzae KSD-815:KSD-815). Dried powder of KSD-815 was extracted with 80% methanol and partitioned successively using nhexane, ethyl acetate, n-butanol, and water. The n-hexane and n-butanol fractions showed a strong antimigratory effect on human cancer cells. Both of these fractions were subjected to separation and purification procedures using silica gel, octadecyl silica gel, and Sephadex LH-20 column chromatographies to afford four purified compounds. These were identified as ergosterol peroxide (1), stigmast- 5-en-3beta,7beta-diol (2), ergosta-7,22-dien-3beta,5alpha,6beta,9alpha-tetraol (3), and daucosterol (4), respectively, by spectroscopic methods such as nuclear magnetic resonance spectrometry, mass spectrometry, and infrared spectroscopy, and comparison with those in the literature. Compounds 1-4 were isolated from KSD-815 for the first time. Compounds 1 and 4 inhibited the migration of MDA-MB-231 cells at concentrations lower than 20 micronM.

A Theoretical Investigation of the Charge Transfer System TCNQ-F4 and Alpha-Sexithiophene

NASA Astrophysics Data System (ADS)

Braun, Kai-Felix

2005-03-01

The electronic and geometrical structures of the charge-transfer system of alpha-sexihiophene and tetrafluorotetracyanoquinodimethane are calculated self-consistently from first principles. By means of density functional theory (DFT) methods several configurations of the free molecules are calculated within LDA and B3LYP employing a plane wave basis and different atomic orbital sets. The combined system exhibits preferential binding of the center of the TCNQ-F4 on top of a c-c bond of the sexithiophene, thereby the central configuration having the lowest energy. As opposed to the periodic arrangement in a crystal of the related system dimethylquaterthiophene and TCNQ-F4, the free system exhibits a strong interaction going along with a substantial polarization of both molecules. For comparison with scanning tunneling spectroscopy results, the molecules were adsorbed in a parallel geometry on a Au(111) slab. To take into account the voltage applied to the STM tip the system was finally calculated within an electric field. This work is financially supported by the US-DOE grant no. DE-FG02-02ER46012.

Diffusion bonding of Ti-48Ni-2Mn-2Nb (at.%)

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

Godfrey, S.P.; Strangwood, M.; Threadgill, P.L.

The diffusion bonding behavior of Ti-48at. % Al-2at. % Mn-2at. %Nb has been studied as a function of temperature (in the range 1,200--1,350C), time (15--45 minutes) and starting microstructure (lamellar, duplex and near {gamma}) at constant bonding pressure of 10 MPa. It was found, that under the above conditions, small twin related {gamma} grains, approximately 10-20 {mu}m in size, nucleated at the original interface and grew into the matrix forming a double necklace grain structure. Particles of {alpha}{sub 2} were observed around the interface, the formation of {alpha}{sub 2} particles was believed to be related to oxygen partitioning and stabilizationmore » effects from dissolved oxide films during the bonding process. Evidence for this mechanism was obtained from parallel electron energy loss spectroscopy (PEELS), which identified oxygen partitioning in the (X2) particles. For the fully lamellar structure bonded at 1,250 C for 45 minutes the failure strength of the bond was found to be 250 MPa, approximately 50 MPa lower than the failure strength of the base material.« less

Structure-activity relationships in the fusion of small unilamellar phosphatidylcholine vesicles induced by a model peptide.

PubMed

da Costa, M H; Chaimovich, H

1997-09-01

Limited proteolysis of fatty acid-free bovine serum albumin by pepsin yields several well characterized peptides, one of which (P9, M(r) 9,000), induces fusion of small unilamellar vesicles (SUV) of phosphatidylcholine at pH 3.6. Circular dichroism (CD) of P9 solutions confirmed that the peptide undergoes a reversible transition between pH 7 and pH 3.6. The spectral changes observed with CD suggest that in the low pH conformation there is a decrease in the alpha-helical contents and an exposure of hydrophobic residues. CD and differential ultraviolet spectroscopy demonstrated that P9 binds to micelles of hexadecylphosphorylcholine and the binding produces changes in the tertiary structure of the peptide. Reduction and carboxymethylation of the two disulfide bridges of P9 produced loss of the ability to induce fusion of SUV, although the reduced peptide binds to vesicles, induces loss of entrapped marker and produces vesicle disruption. In the active form P9 exposes hydrophobic groups, one amphiphilic alpha-helix and requires the integrity of the disulfide bridge-stabilized tertiary structure.

Studying Cosmic Dawn with WFIRST

NASA Astrophysics Data System (ADS)

Rhoads, James; Malhotra, Sangeeta; Jansen, Rolf A.; Windhorst, Rogier; Tilvi, Vithal; Finkelstein, Steven; Wold, Isak; Papovich, Casey; Fan, Xiaohui; Mellema, Garrelt; Zackrisson, Erik; Jensen, Hannes; T

2018-01-01

Our understanding of Cosmic Dawn can be revolutionized using WFIRST's combination of wide-field, sensitive, high resolution near-infrared imaging and spectroscopy. Guest investigator studies of WFIRST's high latitude imaging survey and supernova search fields will yield orders of magnitude increases in our samples of Lyman break galaxies from z=7 to z>12. The high latitude spectrsocopic survey will enable an unprecedented search for z>7 quasars. Guest observer deep fields can extend these studies to flux levels of Hubble's deepest fields, over regions measured in square degrees. The resulting census of luminous objects in the Cosmic Dawn will provide key insights into the sources of the ultraviolet photons that powered reionization. Moreover, because WFIRST has a wide field (slitless) spectroscopic capability, it can be used to search for Lyman alpha emitting galaxies over the full history of reionization. By comparing the Lyman alpha galaxy statistics to those of continuum sources, we can directly probe the transparency of the intergalactic gas and chart reionization history.Our team is planning for both Guest Investigator and Guest Observer applications of WFIRST to studying Cosmic Dawn, and welcomes dialog with other interested members of the community.

Environmental and human monitoring of Americium-241 utilizing extraction chromatography and {alpha}-Spectrometry

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

Goldstein, S.J.; Hensley, C.A.; Armenta, C.E.

1997-03-01

Recent developments in extraction chromatography have simplified the separation of americium from complex matrices in preparation for {alpha}-spectroscopy relative to traditional methods. Here we present results of procedures developed/adapted for water, air, and bioassay samples with less than 1 g of inorganic residue. Prior analytical methods required the use of a complex, multistage procedure for separation of americium from these matrices. The newer, simplified procedure requires only a single 2 mL extraction chromatographic separation for isolation of Am and lanthanides from other components of the sample. This method has been implemented on an extensive variety of `real` environmental and bioassaymore » samples from the Los Alamos area, and consistently reliable and accurate results with appropriate detection limits have been obtained. The new method increases analytical throughput by a factor of {approx}2 and decreases environmental hazards from acid and mixed-waste generation relative to the prior technique. Analytical accuracy, reproducibility, and reliability are also significantly improved over the more complex and laborious method used previously. 24 refs., 2 figs., 2 tabs.« less

Low temperature synthesis of monolithic transparent Ta2O5 gels from hydrolysis of metal alkoxide

NASA Technical Reports Server (NTRS)

Bansal, Narottam P.

1993-01-01

Tantalum oxide gels in the form of transparent monoliths and powder were prepared from hydrolysis of tantalum pentaethoxide under controlled conditions using different mole ratios of Ta(OC2H5)5:C2H50H:H20:HCl. Alcohol acts as the mutual solvent and HCl as the deflocculating agent. For a fixed alkoxide:water:HCl ratio, time of gel formation increased with the alcohol to alkoxide mole ratio. Thermal evolution of the physical and structural changes in the gel was monitored by differential thermal analysis, thermogravimetric analysis, x-ray diffraction, and infrared spectroscopy. On heating to approximately 400 C, the amorphous gel crystallized into the low temperature orthorhombic phase Beta-Ta2O5, which transformed into the high temperature tetragonal phase Alpha-Ta2O5 when further heated to approximately 1450 C. The volume fraction of the crystalline phase increased with the firing temperature. The Alpha-Ta205 converted back into the low temperature phase, Beta-Ta2O5, on slow cooling through the transformation temperature of 1360 C indicating a slow but reversible transformation.

Complex stability of single proteins explored by forced unfolding experiments.

PubMed

Janovjak, Harald; Sapra, K Tanuj; Müller, Daniel J

2005-05-01

In the last decade atomic force microscopy has been used to measure the mechanical stability of single proteins. These force spectroscopy experiments have shown that many water-soluble and membrane proteins unfold via one or more intermediates. Recently, Li and co-workers found a linear correlation between the unfolding force of the native state and the intermediate in fibronectin, which they suggested indicated the presence of a molecular memory or multiple unfolding pathways (1). Here, we apply two independent methods in combination with Monte Carlo simulations to analyze the unfolding of alpha-helices E and D of bacteriorhodopsin (BR). We show that correlation analysis of unfolding forces is very sensitive to errors in force calibration of the instrument. In contrast, a comparison of relative forces provides a robust measure for the stability of unfolding intermediates. The proposed approach detects three energetically different states of alpha-helices E and D in trimeric BR. These states are not observed for monomeric BR and indicate that substantial information is hidden in forced unfolding experiments of single proteins.

High-resolution laser absorption spectroscopy of ozone near 1129.4 cm (-1)

NASA Technical Reports Server (NTRS)

Majorana, L. N.

1981-01-01

A Beer's Law experiment was performed with a tunable diode laser to determine self broadened line shape parameters of one infrared absorption ozone line in the nu1 band for ten pressures from 0.26 to 6.29 torr at 285 K. The SO2 line positions were used for wavelength calibration. Line shapes were iteratively fitted to the Voigt function at a Doppler width of 29.54 MHz (HWHM) resulting in values for the integrated line strength, (S), of (0.144 +/- 0.007) x 10 to the minus 20th/cm molecule/cu cm, line center frequency, nu sub o, of 1129.426/cm and the Lorentzian contributions to halfwidth. A linear least squares fit of (alpha sub L)5 as a function of pressure yielded a zero intercept of 15.27 +/- 0.29 MHz (rho = 0.99) and a broadening parameter, (alpha sub L)5, of 5.71 +/- 0.29 MHz/Torr. This results in a line width (FWHM) of 0.144 +/- .007/cm at 760 torr and 285 K.

Fouling-release coatings prepared from alpha,omega-dihydroxypoly(dimethylsiloxane) cross-linked with (heptadecafluoro-1,1,2,2-tetrahydrodecyl)triethoxysilane.

PubMed

Berglin, Mattias; Wynne, Kenneth J; Gatenholm, Paul

2003-01-15

Surface properties of pristine and water-aged polymeric films made of alpha,omega-dihydroxypoly(dimethylsiloxane) (PDMS) cross-linked with (heptadecafluoro-1,1,2,2-tetrahydrodecyl)triethoxysilane (FTEOS17) or tetraethoxysilane (TEOS) were investigated. The FTEOS17-cured coatings showed stable advancing and receding contact angles over a period of 3 months of water exposure, compared to a 70 degrees decrease in receding contact angle for the TEOS-cured coatings. After immersion in water, hydroxyl groups were detected on the TEOS-cured coatings with attenuated total reflection infrared spectroscopy (ATR-FT/IR). Tapping-mode atomic force microscopy (TM-AFM) on pristine FTEOS17-cured coatings showed surfaces topologies ranging from smooth and featureless to topologically complex, depending on FTEOS17 concentration. The fluorinated coatings showed a stable surface morphology after water immersion, which we believe is due to the formation of a fluorinated siliceous phase that prevented the surface reconstruction, water penetration, and hydrolysis. The smooth pristine TEOS-cured coatings showed an increased roughness with cracks and erosion pits present on the surface after water immersion.

Measurements of Photo-induced Changes in Conjugated Polymers

DOE R&D Accomplishments Database

Seager, C. H.; Sinclair, M. B.; Mc Branch, D.; Heeger, A. J.; Baker, G. L.

1991-01-01

We have used the highly sensitive technique of Photothermal Deflection Spectroscopy (PDS) to measure changes in the infrared absorption spectra of MEHPPV, P3HT and Polydiacetylene-4BCMU induced by pumping these polymers with light above the {pi} - {pi}* transition energy. In contrast to previous chopped light transmission measurements of these effects, the PDS technique can directly measure the buildup or decay of the absorption coefficient, {alpha}, on the time scale of second to days. In the case of MEHPPV we observe that the time scale of seconds to days. In the case of MEHPPV we observe that above-gap light causes the appearance of a broad infrared peak in {alpha}, which continues to grow-in hours after the pump light is first applied. For this polymer the general shape of the absorption spectra in the unpumped state mimics the photo-induced changes, suggesting that remnant photo-induced states determine the maximum transparency observed under normal experimental conditions. For P3HT and to a lesser extent, MEHPPV, we also observe irreversible photo-induced absorption components which we tentatively identify with photo-induced oxidation of the polymer matrix.

Isolation and structures of glycoprotein-derived free oligosaccharides from the unfertilized eggs of Scyliorhinus caniculus. Characterization of the sequences galactose(alpha 1-4)galactose(beta 1-3)-N-acetylglucosamine and N-acetylneuraminic acid(alpha 2-6)galactose(beta 1-3)-N-acetylglucosamine.

PubMed

Plancke, Y; Delplace, F; Wieruszeski, J M; Maes, E; Strecker, G

1996-01-15

As previously reported [Ishii, K., Iwasaki, M., Inoue, S., Kenny, P. T. M., Komura, H. & Inoue, Y. (1989) J. Biol. Chem. 264, 1623-1630; Inoue, S., Iwasaki, M., Ishii, K., Kitajima, K. & Inoue, Y. (1989) J. Biol. Chem. 264, 18520-185261, the unfertilized eggs of two different species of fresh-water fish, Plecoglossus altivelis and Tribodolon hakonensis, contain relatively large amounts of free sialooligosaccharides. These oligosaccharides were found to derive from glycophosphoproteins, owing to the activity of a peptide - N4-(N-acetyl-beta-D-glucosaminyl)asparagine amidase [Iwasaki, M., Seko, A., Kitajima, K., Inoue, Y. & Inoue, S. (1992) J. Biol. Chem. 267, 24287-24296; Seko, A., Kitajima, K., Inoue, Y. & Inoue, S. (1991) J. Biol. Chem. 266, 22110-22114]. Here we describe a new type of free oligosaccharides, isolated from unfertilized eggs of Scyliorhinus caniculus. From the structural analysis, based upon 1H-NMR spectroscopy, the following glycan units are proposed.[Formula: see text

Formation of insulin amyloid fibrils followed by FTIR simultaneously with CD and electron microscopy.

PubMed Central

Bouchard, M.; Zurdo, J.; Nettleton, E. J.; Dobson, C. M.; Robinson, C. V.

2000-01-01

Fourier transform infrared spectroscopy (FTIR), circular dichroism (CD), and electron microscopy (EM) have been used simultaneously to follow the temperature-induced formation of amyloid fibrils by bovine insulin at acidic pH. The FTIR and CD data confirm that, before heating, insulin molecules in solution at pH 2.3 have a predominantly native-like alpha-helical structure. On heating to 70 degrees C, partial unfolding occurs and results initially in aggregates that are shown by CD and FT-IR spectra to retain a predominantly helical structure. Following this step, changes in the CD and FTIR spectra occur that are indicative of the extensive conversion of the molecular conformation from alpha-helical to beta-sheet structure. At later stages, EM shows the development of fibrils with well-defined repetitive morphologies including structures with a periodic helical twist of approximately 450 A. The results indicate that formation of fibrils by insulin requires substantial unfolding of the native protein, and that the most highly ordered structures result from a slow evolution of the morphology of the initially formed fibrillar species. PMID:11106169

Thermodynamics of melittin binding to lipid bilayers. Aggregation and pore formation.

PubMed

Klocek, Gabriela; Schulthess, Therese; Shai, Yechiel; Seelig, Joachim

2009-03-31

Lipid membranes act as catalysts for protein folding. Both alpha-helical and beta-sheet structures can be induced by the interaction of peptides or proteins with lipid surfaces. Melittin, the main component of bee venom, is a particularly well-studied example for the membrane-induced random coil-to-alpha-helix transition. Melittin in water adopts essentially a random coil conformation. The cationic amphipathic molecule has a high affinity for neutral and anionic lipid membranes and exhibits approximately 50-65% alpha-helix conformation in the membrane-bound state. At higher melittin concentrations, the peptide forms aggregates or pores in the membrane. In spite of the long-standing interest in melittin-lipid interactions, no systematic thermodynamic study is available. This is probably caused by the complexity of the binding process. Melittin binding to lipid vesicles is fast and occurs within milliseconds, but the binding process involves at least four steps, namely, (i) the electrostatic attraction of the cationic peptide to an anionic membrane surface, (ii) the hydrophobic insertion into the lipid membrane, (iii) the conformational change from random coil to alpha-helix, and (iv) peptide aggregation in the lipid phase. We have combined microelectrophoresis (measurement of the zeta potential), isothermal titration calorimetry, and circular dichroism spectroscopy to provide a thermodynamic analysis of the individual binding steps. We have compared melittin with a synthetic analogue, [D]-V(5,8),I(17),K(21)-melittin, for which alpha-helix formation is suppressed and replaced by beta-structure formation. The comparison reveals that the thermodynamic parameters for the membrane-induced alpha-helix formation of melittin are identical to those observed earlier for other peptides with an enthalpy h(helix) of -0.7 kcal/mol and a free energy g(helix) of -0.2 kcal/mol per peptide residue. These thermodynamic parameters hence appear to be of general validity for lipid-induced membrane folding. As g(helix) is negative, it further follows that helix formation leads to an enhanced membrane binding for the peptides or proteins involved. In this study, melittin binds by approximately 2 orders of magnitude better to the lipid membrane than [D]-V(5,8),I(17),K(21)-melittin which cannot form an alpha-helix. We also found conditions under which the isothermal titration experiment reports only the aggregation process. Melittin aggregation is an entropy-driven process with an endothermic heat of reaction (DeltaH(agg)) of approximately 2 kcal/mol and an aggregation constant of 20-40 M(-1).

Calorimetric and spectroscopic studies of the thermotropic phase behavior of lipid bilayer model membranes composed of a homologous series of linear saturated phosphatidylserines.

PubMed Central

Lewis, R N; McElhaney, R N

2000-01-01

The thermotropic phase behavior of lipid bilayer model membranes composed of the even-numbered, N-saturated 1,2-diacyl phosphatidylserines was studied by differential scanning calorimetry and by Fourier-transform infrared and (31)P-nuclear magnetic resonance spectroscopy. At pH 7.0, 0.1 M NaCl and in the absence of divalent cations, aqueous dispersions of these lipids, which have not been incubated at low temperature, exhibit a single calorimetrically detectable phase transition that is fully reversible, highly cooperative, and relatively energetic, and the transition temperatures and enthalpies increase progressively with increases in hydrocarbon chain length. Our spectroscopic observations confirm that this thermal event is a lamellar gel (L(beta))-to-lamellar liquid crystalline (L(alpha)) phase transition. However, after low temperature incubation, the L(beta)/L(alpha) phase transition of dilauroyl phosphatidylserine is replaced by a higher temperature, more enthalpic, and less cooperative phase transition, and an additional lower temperature, less enthalpic, and less cooperative phase transition appears in the longer chain phosphatidylserines. Our spectroscopic results indicate that this change in thermotropic phase behavior when incubated at low temperatures results from the conversion of the L(beta) phase to a highly ordered lamellar crystalline (L(c)) phase. Upon heating, the L(c) phase of dilauroyl phosphatidylserine converts directly to the L(alpha) phase at a temperature slightly higher than that of its original L(beta)/L(alpha) phase transition. Calorimetrically, this process is manifested by a less cooperative but considerably more energetic, higher-temperature phase transition, which replaces the weaker L(beta)/L(alpha) phase transition alluded to above. However, with the longer chain compounds, the L(c) phase first converts to the L(beta) phase at temperatures some 10-25 degrees C below that at which the L(beta) phase converts to the L(alpha) phase. Our results also suggest that shorter chain homologues form L(c) phases that are structurally related to, but more ordered than, those formed by the longer chain homologues, but that these L(c) phases are less ordered than those formed by other phospholipids. These studies also suggest that polar/apolar interfaces of the phosphatidylserine bilayers are more hydrated than those of other glycerolipid bilayers, possibly because of interactions between the polar headgroup and carbonyl groups of the fatty acyl chains. PMID:11023908

Shape of intrinsic alpha pulse height spectra in lanthanide halide scintillators

NASA Astrophysics Data System (ADS)

Wolszczak, W.; Dorenbos, P.

2017-06-01

Internal contamination with actinium-227 and its daughters is a serious drawback in low-background applications of lanthanide-based scintillators. In this work we showed the important role of nuclear γ de-excitations on the shape of the internal alpha spectrum measured in scintillators. We calculated with Bateman equations the activities of contamination isotopes and the time evolution of actinium-227 and its progenies. Next, we measured the intrinsic background spectra of LaBr3(Ce), LaBr3(Ce,Sr) and CeBr3 with a digital spectroscopy technique, and we analyzed them with a pulse shape discrimination method (PSD) and a time-amplitude analysis. Finally, we simulated the α background spectrum with Geant4 tool-kit, consequently taking into account complex α-γ-electron events, the α / β ratio dependence on the α energy, and the electron/γ nonproportionality. We found that α-γ mixed events have higher light yield than expected for alpha particles alone, which leads to overestimation of the α / β ratio when it is measured with internal 227Th and 223Ra isotopes. The time-amplitude analysis showed that the α peaks of 219Rn and 215Po in LaBr3(Ce) and LaBr3(Ce,Sr) are not symmetric. We compared the simulation results with the measured data and provided further evidence of the important role of mixed α-γ-electron events for understanding the shape of the internal α spectrum in scintillators.

A designed glycoprotein analogue of Gc-MAF exhibits native-like phagocytic activity.

PubMed

Bogani, Federica; McConnell, Elizabeth; Joshi, Lokesh; Chang, Yung; Ghirlanda, Giovanna

2006-06-07

Rational protein design has been successfully used to create mimics of natural proteins that retain native activity. In the present work, de novo protein engineering is explored to develop a mini-protein analogue of Gc-MAF, a glycoprotein involved in the immune system activation that has shown anticancer activity in mice. Gc-MAF is derived in vivo from vitamin D binding protein (VDBP) via enzymatic processing of its glycosaccharide to leave a single GalNAc residue located on an exposed loop. We used molecular modeling tools in conjunction with structural analysis to splice the glycosylated loop onto a stable three-helix bundle (alpha3W, PDB entry 1LQ7). The resulting 69-residue model peptide, MM1, has been successfully synthesized by solid-phase synthesis both in the aglycosylated and the glycosylated (GalNAc-MM1) form. Circular dichroism spectroscopy confirmed the expected alpha-helical secondary structure. The thermodynamic stability as evaluated from chemical and thermal denaturation is comparable with that of the scaffold protein, alpha3W, indicating that the insertion of the exogenous loop of Gc-MAF did not significantly perturb the overall structure. GalNAc-MM1 retains the macrophage stimulation activity of natural Gc-MAF; in vitro tests show an identical enhancement of Fc-receptor-mediated phagocytosis in primary macrophages. GalNAc-MM1 provides a framework for the development of mutants with increased activity that could be used in place of Gc-MAF as an immunomodulatory agent in therapy.

Gross alpha and beta activity analyses in urine-a routine laboratory method for internal human radioactivity detection.

PubMed

Chen, Xiaowen; Zhao, Luqian; Qin, Hongran; Zhao, Meijia; Zhou, Yirui; Yang, Shuqiang; Su, Xu; Xu, Xiaohua

2014-05-01

The aim of this work was to develop a method to provide rapid results for humans with internal radioactive contamination. The authors hypothesized that valuable information could be obtained from gas proportional counter techniques by screening urine samples from potentially exposed individuals rapidly. Recommended gross alpha and beta activity screening methods generally employ gas proportional counting techniques. Based on International Standards Organization (ISO) methods, improvements were made in the evaporation process to develop a method to provide rapid results, adequate sensitivity, and minimum sample preparation and operator intervention for humans with internal radioactive contamination. The method described by an American National Standards Institute publication was used to calibrate the gas proportional counter, and urine samples from patients with or without radionuclide treatment were measured to validate the method. By improving the evaporation process, the time required to perform the assay was reduced dramatically. Compared with the reference data, the results of the validation samples were very satisfactory with respect to gross-alpha and gross-beta activities. The gas flow proportional counting method described here has the potential for radioactivity monitoring in the body. This method was easy, efficient, and fast, and its application is of great utility in determining whether a sample should be analyzed by a more complicated method, for example radiochemical and/or γ-spectroscopy. In the future, it may be used commonly in medical examination and nuclear emergency treatment.Health Phys. 106(5):000-000; 2014.

Amyloid-beta-sheet formation at the air-water interface.

PubMed Central

Schladitz, C; Vieira, E P; Hermel, H; Möhwald, H

1999-01-01

An amyloid(1-40) solution rich in coil, turn, and alpha-helix, but poor in beta-sheet, develops monolayers with a high beta-sheet content when spread at the air-water interface. These monolayers are resistant to repeated compression-dilatation cycles and interaction with trifluoroethanol. The secondary structure motifs were detected by circular dichroism (CD) in solution and with infrared reflection-absorption spectroscopy (IRRAS) at the interface. Hydrophobic influences are discussed for the structure conversion in an effort to understand the completely unknown reason for the natural change of the normal prion protein cellular (PrP(C)) into the abnormal prion protein scrapie (PrP(Sc)). PMID:10585952

Results from the X-ray polychromator on SMM

NASA Astrophysics Data System (ADS)

Culhane, J. L.; Acton, L. W.; Gabriel, A. H.

Observations of the soft X-ray emitting plasma by means of the X-Ray Polychromator (XRP) on the Solar Maximum Mission satellite are described. The scientific advances achieved by use of the XRP are in the areas of: (1) flare morphology, (2) spectroscopy and plasma diagnostics, (3) chromospheric evaporation and the physics of flare loops, (4) studies of the microwave emission mechanisms of active regions, (5) the fluorescent excitation of Fe II K-alpha radiation, (6) measurement of variations of calcium abundance for X-ray plasmas, and (7) soft X-ray observations of spray transients. The findings in each of these areas are discussed.

Results from the X-ray polychromator on SMM

NASA Technical Reports Server (NTRS)

Culhane, J. L.; Acton, L. W.; Gabriel, A. H.

1984-01-01

Observations of the soft X-ray emitting plasma by means of the X-Ray Polychromator (XRP) on the Solar Maximum Mission satellite are described. The scientific advances achieved by use of the XRP are in the areas of: (1) flare morphology, (2) spectroscopy and plasma diagnostics, (3) chromospheric evaporation and the physics of flare loops, (4) studies of the microwave emission mechanisms of active regions, (5) the fluorescent excitation of Fe II K-alpha radiation, (6) measurement of variations of calcium abundance for X-ray plasmas, and (7) soft X-ray observations of spray transients. The findings in each of these areas are discussed.

Influence of pH and method of crystallization on the solid physical form of indomethacin.

PubMed

Dubbini, Alessandra; Censi, Roberta; Martena, Valentina; Hoti, Ela; Ricciutelli, Massimo; Malaj, Ledjan; Di Martino, Piera

2014-10-01

The purpose of this study was to investigate the effect of pH and method of crystallization on the solid physical form of indomethacin (IDM). IDM, a non steroidal anti-inflammatory drug poorly soluble in water, underwent two different crystallization methods: crystallization by solvent evaporation under reduced pressure at 50.0°C (method A), and crystallization by cooling of solution from 50.0 to 5.0°C (method B). In both cases, several aqueous ethanolic solutions of IDM of different pHs were prepared. pHs were adjusted by adding acidic solutions (HCl 2M) or alkali (NaOH or NH4OH 2M) to an aqueous ethanolic solution of IDM. Thus, several batches were recovered after crystallization. The chemical stability of IDM was verified through (1)H NMR and mass spectroscopy (FIA-ESI-MS), that revealed that IDM degraded in strong alkali media (pH ≥ 12). Crystals obtained under different crystallization conditions at pHs of 1.0, 4.5, 7.0, 8.0, 10.0 and chemically stable were thus characterized for crystal habit by scanning electron microscopy, for thermal behaviour by differential scanning calorimetry, and thermogravimetry, and for solid state by X-ray powder diffractometry. Under the Method A, IDM always crystallized into pure metastable alpha form when solutions were acidified or alkalized respectively with HCl and NH4OH. On the contrary, in presence of NaOH, IDM crystallized under a mixture of alpha and sodium trihydrate form, because the presence of the sodium counter ion orientates the crystallization towards the formation of the trihydrate salt. Under the method B, at pH of 1.0, IDM crystallized under the alpha form; at pH 4.5, IDM crystallized under the form alpha in presence of some nuclei of gamma form; at pH 7.0, 8.0, and 10.0 for NH4OH, IDM crystallized under the most stable polymorph gamma form, whereas in presence of NaOH, a mix of alpha, and salt forms was formed whatever the pH of the solution. Copyright © 2014 Elsevier B.V. All rights reserved.

Product kinetic and internal energy distributions via velocity-aligned Doppler spectroscopy: Technical report, May 1985-January 1987

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

Wittig, C.

1987-01-01

We developed a method of sub-Doppler resolution spectroscopy that is useful for determining kinetic energy distributions. With 'conventional' Doppler spectroscopy, it is almost impossible to obtain an accurate distribution from a line profile, even with the highest resolution, except when the distribution is quite simple (e.g., a delta function). This is due to the lineshape deriving from velocity components along the wave-vector of the probe radiation, k/sub probe/. However, by choosing only those species whose velocities are essentially parallel (or antiparallel) to k/sub probe/, this handicap is overcome. Here, one obtains the kinetic energy distribution along k/sub probe/, and themore » resolution is limited only by our ability to reject species with velocity components perpendicular to k/sub probe/. This rejection is done by spatial and temporal discrimination, using counterpropagating, overlapped, pulsed photolysis and probe sources. At long delays, molecules are detected which are aligned with k/sub probe/. We call the method velocity-aligned Doppler spectroscopy (VADS). We have perused several cases involving photodissociation of small molecules, in each case detecting H-atoms using sequential 2-photon ionization via Lyman-..cap alpha... We discern structure in the kinetic energy distribution which is attributed to internal excitation of the 'other' fragment, and resolution is limited by the dye laser bandwidth. In the case of HBr, we resolve the Br spin-orbit states, and with H/sub 2/S, we resolve the SH vibrational levels. 38 refs., 7 figs.« less

Noninvasive noble metal nanoparticle arrays for surface-enhanced Raman spectroscopy of proteins

NASA Astrophysics Data System (ADS)

Inya-Agha, Obianuju; Forster, Robert J.; Keyes, Tia E.

2007-02-01

Noble metal nanoparticles arrays are well established substrates for surface enhanced Raman spectroscopy (SERS). Their ability to enhance optical fields is based on the interaction of their surface valence electrons with incident electromagnetic radiation. In the array configuration, noble metal nanoparticles have been used to produce SER spectral enhancements of up to 10 8 orders of magnitude, making them useful for the trace analysis of physiologically relevant analytes such as proteins and peptides. Electrostatic interactions between proteins and metal surfaces result in the preferential adsorption of positively charged protein domains onto metal surfaces. This preferential interaction has the effect of disrupting the native conformation of the protein fold, with a concomitant loss of protein function. A major historic advantage of Raman microspectroscopy has been is its non-invasive nature; protein denaturation on the metal surfaces required for SER spectroscopy renders it a much more invasive technique. Further, part of the analytical power of Raman spectroscopy lies in its use as a secondary conformation probe. The protein structural loss which occurs on the metal surface results in secondary conformation readings which are not true to the actual native state of the analyte. This work presents a method for chemical fabrication of noble metal SERS arrays with surface immobilized layers which can protect protein native conformation without excessively mitigating the electromagnetic enhancements of spectra. Peptide analytes are used as model systems for proteins. Raman spectra of alpha lactalbumin on surfaces and when immobilized on these novel arrays are compared. We discuss the ability of the surface layer to protect protein structure whilst improving signal intensity.

Surface plasmon resonance spectroscopy studies of membrane proteins: transducin binding and activation by rhodopsin monitored in thin membrane films.

PubMed Central

Salamon, Z; Wang, Y; Soulages, J L; Brown, M F; Tollin, G

1996-01-01

Surface plasmon resonance (SPR) spectroscopy can provide useful information regarding average structural properties of membrane films supported on planar solid substrates. Here we have used SPR spectroscopy for the first time to monitor the binding and activation of G-protein (transducin or Gt) by bovine rhodopsin incorporated into an egg phosphatidylcholine bilayer deposited on a silver film. Rhodopsin incorporation into the membrane, performed by dilution of a detergent solution of the protein, proceeds in a saturable manner. Before photolysis, the SPR data show that Gt binds tightly (Keq approximately equal to 60 nM) and with positive cooperativity to rhodopsin in the lipid layer to form a closely packed film. A simple multilayer model yields a calculated average thickness of about 57 A, in good agreement with the structure of Gt. The data also demonstrate that Gt binding saturates at a Gt/rhodopsin ratio of approximately 0.6. Moreover, upon visible light irradiation, characteristic changes occur in the SPR spectrum, which can be modeled by a 6 A increase in the average thickness of the lipid/protein film caused by formation of metarhodopsin II (MII). Upon subsequent addition of GTP, further SPR spectral changes are induced. These are interpreted as resulting from dissociation of the alpha-subunit of Gt, formation of new MII-Gt complexes, and possible conformational changes of Gt as a consequence of complex formation. The above results clearly demonstrate the ability of SPR spectroscopy to monitor interactions among the proteins associated with signal transduction in membrane-bound systems. Images FIGURE 1 PMID:8804611

Design of beta-domain swapping, alpha/beta-protein, environmentally sensitive coiled coil and peptide functionalized titania materials

NASA Astrophysics Data System (ADS)

Nagarkar, Radhika P.

2009-12-01

The objective of this dissertation is to apply rational peptide design to fabricate nanomaterials via self-assembly. This has been demonstrated in structurally diverse systems with an aim of deciphering the underlying principles governing how sequence affects the peptide's ability to adopt a specific secondary structure and ultimate material properties that are realized from the association of these secondary structural elements. Several amyloidogenic proteins have been shown to self-assemble into fibrils using a mechanism known as domain swapping. Here, discreet units of secondary structure are exchanged among discreet proteins during self-assembly to form extended networks with precise three dimensional organization. The possibility of using these mechanisms to design peptides capable of controlled assembly and fibril formation leading to materials with targeted properties is explored. By altering the placement of a beta-turn sequence that varies the size and location of the exchanged strand, twisting, non-twisting and laminated fibrillar nanostructures are obtained. Hydrogels prepared from these strand swapping beta-hairpins have varied rheological properties due to differences in their fibrillar nanostructures. In a second distinct design, alpha/beta-proteins are used to prepare environmentally sensitive hydrogels. Here, multiple distinct motifs for structural integrity and dynamic response within a single self-assembling peptide allow the amyloid-like fibrils formed to controllably alter their nano-topography in response to an external stimulus such as temperature. The development of these self-assembling alpha/beta-protein motifs also necessitated the design of pH sensitive antiparallel coiled coils. Exploring the basic principles responsible for pH dependent conformational changes in coiled coils can lead to new insights in the control of protein structure and function. Lastly, this dissertation discusses the interface between biomolecules and inorganic materials. Here, a new methodology of functionalizing titania nanoparticles with peptides is developed. In all of these different material forming systems, extensive biophysical characterization by circular dichroism spectroscopy, fourier transform infrared spectroscopy, X-ray diffraction and analytical ultracentrifugation is performed to understand peptide folding and self-assembly. Careful nanostructural characterization by electron and force microscopies is performed to elucidate self-assembly mechanisms and has proved to be vital in applying the iterative design process to develop responsive nanomaterials.

Assessment of brain metabolite correlates of adeno-associated virus-mediated over-expression of human alpha-synuclein in cortical neurons by in vivo (1) H-MR spectroscopy at 9.4 T.

PubMed

Cuellar-Baena, Sandra; Landeck, Natalie; Sonnay, Sarah; Buck, Kerstin; Mlynarik, Vladimir; In 't Zandt, René; Kirik, Deniz

2016-06-01

In this study, we used proton-localized spectroscopy ((1) H-MRS) for the acquisition of the neurochemical profile longitudinally in a novel rat model of human wild-type alpha-synuclein (α-syn) over-expression. Our goal was to find out if the increased α-syn load in this model could be linked to changes in metabolites in the frontal cortex. Animals injected with AAV vectors encoding for human α-syn formed the experimental group, whereas green fluorescent protein expressing animals were used as the vector-treated control group and a third group of uninjected animals were used as naïve controls. Data were acquired at 2, 4, and 8 month time points. Nineteen metabolites were quantified in the MR spectra using LCModel software. On the basis of 92 spectra, we evaluated any potential gender effect and found that lactate (Lac) levels were lower in males compared to females, while the opposite was observed for ascorbate (Asc). Next, we assessed the effect of age and found increased levels of GABA, Tau, and GPC+PCho. Finally, we analyzed the effect of treatment and found that Lac levels (p = 0.005) were specifically lower in the α-syn group compared to the green fluorescent protein and control groups. In addition, Asc levels (p = 0.05) were increased in the vector-injected groups, whereas glucose levels remained unchanged. This study indicates that the metabolic switch between glucose-lactate could be detectable in vivo and might be modulated by Asc. No concomitant changes were found in markers of neuronal integrity (e.g., N-acetylaspartate) consistent with the fact that α-syn over-expression in cortical neurons did not result in neurodegeneration in this model. We acquired the neurochemical profile longitudinally in a rat model of human wild-type alpha-synuclein (α-syn) over-expression in cortical neurons. We found that Lactate levels were reduced in the α-syn group compared to the control groups and Ascorbate levels were increased in the vector-injected groups. No changes were found in markers of neuronal integrity consistent with the fact that α-syn over-expression did not result in frank neurodegeneration. © 2016 International Society for Neurochemistry.

Biosynthesis of titanium dioxide nanoparticles using Bacillus amyloliquefaciens culture and enhancement of its photocatalytic activity for the degradation of a sulfonated textile dye Reactive Red 31.

PubMed

Khan, Razia; Fulekar, M H

2016-08-01

The present study aims at exploiting Bacillus amyloliquefaciens for the biosynthesis of titanium dioxide nanoparticles and also investigates role of bacterial enzymes in the biosynthesis of titanium dioxide nanoparticles. Bacterial synthesized as well as metal doped titanium dioxide nanoparticles were characterized by X-ray diffractometer (XRD), Fourier transform infrared spectroscopy (FTIR), Transmission electron microscopy (TEM), Energy dispersive X-ray spectroscopy (EDAX). Amylase activity (43.37IU) in culture supernatant evinced a potential involvement of extracellular enzyme in TiO2 nanoparticle biosynthesis. Crystallite size of bio-synthesized nanoparticles was found to be in the range of 15.23-87.6nm. FTIR spectroscopy and native-PAGE (Polyacrylamide Gel Electrophoresis) clearly indicated involvement of alpha amylase in biosynthesis of TiO2 nanoparticles and in their stabilization. TEM micrographs of the synthesized titanium dioxide nanoparticles revealed the formation of spherical nanoparticles with a size range of 22.11-97.28nm. Photocatalytic degradation of Reactive Red 31 (RR31) dye was carried out using bio-synthesized TiO2 nanoparticles under UV radiation. Photocatalytic activity of synthesized nanoparticles was enhanced by Ag, La, Zn and Pt doping. Platinum doped TiO2 showed highest potential (90.98%) in RR31 degradation as compared to undoped (75.83%). Copyright © 2016 Elsevier Inc. All rights reserved.

Two-dimensional infrared correlation spectroscopy study of the aggregation of cytochrome c in the presence of dimyristoylphosphatidylglycerol.

PubMed Central

Paquet, M J; Laviolette, M; Pézolet, M; Auger, M

2001-01-01

Two-dimensional infrared correlation spectroscopy (2D-IR) was used in this study to investigate the aggregation of cytochrome c in the presence of dimyristoylphosphatidylglycerol. The influence of temperature on the aggregation has been evaluated by monitoring the intensity of a band at 1616 cm(-1), which is characteristic of aggregated proteins, and the 2D-IR analysis has been used to determine the various secondary structure components of cytochrome c involved before and during its aggregation. The 2D-IR correlation analysis clearly reveals for the first time that aggregation starts to occur between nearly native proteins, which then unfold, yielding to further aggregation of the protein. Later in the aggregation process, the formation of intermolecular bonds and unfolding of the alpha-helices appear to be simultaneous. These results lead us to propose a two-step aggregation process. Finally, the results obtained during the heating period clearly indicate that before the protein starts to aggregate, there is a loosening of the tertiary structure of cytochrome c, resulting in a decrease of the beta-sheet content and an increase of the amount of beta-turns. This study clearly demonstrates the potential of 2D-IR spectroscopy to investigate the aggregation of proteins and this technique could therefore be applied to other proteins such as those involved in fibrilogenesis. PMID:11423415

Characterization of the near native conformational states of the SAM domain of Ste11 protein by NMR spectroscopy.

PubMed

Gupta, Sebanti; Bhattacharjya, Surajit

2014-11-01

The sterile alpha motif or SAM domain is one of the most frequently present protein interaction modules with diverse functional attributions. SAM domain of the Ste11 protein of budding yeast plays important roles in mitogen-activated protein kinase cascades. In the current study, urea-induced, at subdenaturing concentrations, structural, and dynamical changes in the Ste11 SAM domain have been investigated by nuclear magnetic resonance spectroscopy. Our study revealed that a number of residues from Helix 1 and Helix 5 of the Ste11 SAM domain display plausible alternate conformational states and largest chemical shift perturbations at low urea concentrations. Amide proton (H/D) exchange experiments indicated that Helix 1, loop, and Helix 5 become more susceptible to solvent exchange with increased concentrations of urea. Notably, Helix 1 and Helix 5 are directly involved in binding interactions of the Ste11 SAM domain. Our data further demonstrate that the existence of alternate conformational states around the regions involved in dimeric interactions in native or near native conditions. © 2014 Wiley Periodicals, Inc.

Fluorescence correlation spectroscopy to study antibody binding and stoichiometry of complexes

NASA Astrophysics Data System (ADS)

Swift, Kerry M.; Matayoshi, Edmund D.

2008-02-01

FCS (fluorescence correlation spectroscopy) was used to study the association at the single molecule level of tumor necrosis factor alpha (TNF-α) and two of its protein antagonists Humira (TM) (adalimumab), a fully humanized monoclonal antibody, and Enbrel (TM) (etanercept), a soluble form of the TNF receptor. Single molecule approaches potentially have the advantage not only of enhanced sensitivity, but also of observing at equilibrium the details that would otherwise be lost in classical ensemble experiments where heterogeneity is averaged. We prepared fluorescent conjugates of the protein drugs and their biological target, the trimeric soluble form of TNF-α. The bivalency of adalimumab and the trimeric nature of TNF-α potentially allow several forms of associative complexes that may differ in stoichiometry. Detailed knowledge of this reaction may be relevant to understanding adalimumab's pharmacological properties. Our FCS data showed that a single trimeric TNF-α can bind up to three adalimumab molecules. Under some conditions even larger complexes are formed, apparently the result of cross-linking of TNF-α trimers by adalimumab. In addition, distinct differences between Humira and Enbrel were observed in their association with TNF-α.

Infrared spectroscopy as a screening technique for colitis

NASA Astrophysics Data System (ADS)

Titus, Jitto; Ghimire, Hemendra; Viennois, Emilie; Merlin, Didier; Perera, A. G. Unil

2017-05-01

There remains a great need for diagnosis of inflammatory bowel disease (IBD), for which the current technique, colonoscopy, is not cost-effective and presents a non-negligible risk for complications. Attenuated Total Reflectance Fourier Transform Infrared (ATR-FTIR) spectroscopy is a new screening technique to evaluate colitis. Comparing infrared spectra of sera to study the differences between them can prove challenging due to the complexity of its biological constituents giving rise to a plethora of vibrational modes. Overcoming these inherent infrared spectral analysis difficulties involving highly overlapping absorbance peaks and the analysis of the data by curve fitting to improve the resolution is discussed. The proposed technique uses colitic and normal wild type mice dried serum to obtain ATR/FTIR spectra to effectively differentiate colitic mice from normal mice. Using this method, Amide I group frequency (specifically, alpha helix to beta sheet ratio of the protein secondary structure) was identified as disease associated spectral signature in addition to the previously reported glucose and mannose signatures in sera of chronic and acute mice models of colitis. Hence, this technique will be able to identify changes in the sera due to various diseases.

Atomic and Molecular Spectroscopic Studies of the DIII-D Neutral Beam Ion Source and Neutralizer

NASA Astrophysics Data System (ADS)

Crowley, B.; Rauch, J.; Scoville, J. T.; Sharma, S. K.; Choksi, B.

2015-11-01

The neutral beam system is interesting in that it comprises two distinct low temperature plasmas. Firstly, the ion source is typically a filament or RF driven plasma from which ions are extracted by a high voltage accelerator grid system. Secondly the neutralizer is essentially a low temperature plasma system with the beam serving as the primary ionization source and the neutralizer walls serving as conducting boundaries. Atomic spectroscopy of Doppler shifted D-alpha light emanating from the fast atoms is studied to determine the composition of the source and the divergence of the beam. Molecular spectroscopy involves measuring fine structure in electron-vibrational rotational bands. The technique has applications in low temperature plasmas and here it is used to determine gas temperature in the neutralizer. We describe the experimental set-up and the physics model used to relate the spectroscopic data to the plasma parameters and we present results of recent experiments exploring how to increase neutralization efficiency. Supported by the US DOE under DE-FC02-04ER54698.

Cotranslational structure acquisition of nascent polypeptides monitored by NMR spectroscopy.

PubMed

Eichmann, Cédric; Preissler, Steffen; Riek, Roland; Deuerling, Elke

2010-05-18

The folding of proteins in living cells may start during their synthesis when the polypeptides emerge gradually at the ribosomal exit tunnel. However, our current understanding of cotranslational folding processes at the atomic level is limited. We employed NMR spectroscopy to monitor the conformation of the SH3 domain from alpha-spectrin at sequential stages of elongation via in vivo ribosome-arrested (15)N,(13)C-labeled nascent polypeptides. These nascent chains exposed either the entire SH3 domain or C-terminally truncated segments thereof, thus providing snapshots of the translation process. We show that nascent SH3 polypeptides remain unstructured during elongation but fold into a compact, native-like beta-sheet assembly when the entire sequence information is available. Moreover, the ribosome neither imposes major conformational constraints nor significantly interacts with exposed unfolded nascent SH3 domain moieties. Our data provide evidence for a domainwise folding of the SH3 domain on ribosomes without significant population of folding intermediates. The domain follows a thermodynamically favorable pathway in which sequential folding units are stabilized, thus avoiding kinetic traps during the process of cotranslational folding.

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

Fogh, R.H.; Mabbutt, B.C.; Kem, W.R.

Sequence-specific assignments are reported for the 500-MHz H nuclear magnetic resonance (NMR) spectrum of the 48-residue polypeptide neurotoxin I from the sea anemone Stichodactyla helianthus (Sh I). Spin systems were first identified by using two-dimensional relayed or multiple quantum filtered correlation spectroscopy, double quantum spectroscopy, and spin lock experiments. Specific resonance assignments were then obtained from nuclear Overhauser enhancement (NOE) connectivities between protons from residues adjacent in the amino acid sequence. Of a total of 265 potentially observable resonances, 248 (i.e., 94%) were assigned, arising from 39 completely and 9 partially assigned amino acid spin systems. The secondary structure ofmore » Sh I was defined on the basis of the pattern of sequential NOE connectivities. NOEs between protons on separate strands of the polypeptide backbone, and backbone amide exchange rates. Sh I contains a four-stranded antiparallel {beta}-sheet encompassing residues 1-5, 16-24, 30-33, and 40-46, with a {beta}-bulge at residues 17 and 18 and a reverse turn, probably a type II {beta}-turn, involving residues 27-30. No evidence of {alpha}-helical structure was found.« less

Observations of GAIA-identified Cataclysmic Variables Using the TUBITAK National Observatory

NASA Astrophysics Data System (ADS)

Esenoglu, Hasan H.; Kirbiyik, Halil; Kaynar, Suleyman; Okuyan, Oguzhan; Hamitoglu, Irek; Galeev, Almaz; Uluc, Kadir; Kocak, Murat; Kilic, Sila E.; Parmaksizoglu, Murat; Erece, Orhan; Ozisik, Tuncay; Gulsecen, Hulusi

2016-07-01

TUBITAK National Observatory supports the GAIA alerts with observations using three telescopes (RTT150, T100, T60) at the site with a limited time quota. We have observed 10 variable stars among GAIA sources discovered in the years 2014-2016 that may be candidate Cataclysmic Variables (CVs). Our TUG observations at this stage involve photometry and spectroscopy to aid the identification of these sources. The first preliminary result of our observations of Gaia14aat among them showed a dwarf nova outburst with an amplitude of 2.69 mag. We aim to construct a GAIA astrophysics group to study CVs along with supported studies using the SRG (Spectrum Roentgen Gamma astrophysical observatory) after the year of 2016. These observations will basically involve spectroscopy, narrow-band CCD imaging and photometry using several filters to aid the identification of these sources. RTT150 observations with very narrow filters (like H-alpha, SII, OIII with band width of range of 2 to 5 nm) will reveal whether shell around the SRG sources to aid identification novae among them.

Alpha Recoil Flux of Radon in Groundwater and its Experimental Measurement

NASA Astrophysics Data System (ADS)

Mehta, N.; Harvey, C. F.; Kocar, B. D.

2016-12-01

Groundwater Radon (Rn222) activity is primarily controlled by alpha recoil process (radioactive decay), however, evaluating the rate and extent of this process, and its impact on porewater radioactivity, remains uncertain. Numerous factors contribute to this uncertainty, including the spatial distribution of parent radionuclides (e.g. U238, Th232 , Ra226 and Ra228) within native materials, differences in nuclide recoil length in host matrix and the physical structure of the rock strata (pore size distribution and porosity). Here, we experimentally measure Radon activities within porewater contributed through alpha recoil, and analyze its variations as a function of pore structure and parent nuclide distribution within host matrices, including Marcellus shale rock and Serrie-Copper Pegmatite. The shale cores originate from the Marcellus formation in Mckean, Pennsylvania collected at depths ranging from 1000-7000 feet, and the U-Th-rich Pegmatite is obtained from South Platte District, Colorado. Columns are packed with granulated rock of varying surface area (30,000-60,000 cm2/g) and subjected to low salinity sodium chloride solution in a close loop configuration. The activity of Radon (Rn222) and radium (Ra226) in the saline fluid is measured over time to determine recoil supply rates. Mineralogical and trace element data for rock specimens are characterized using XRD and XRF, and detailed geochemical profiles are constructed through total dissolution and analysis using ICP-MS and ICP-OES. Naturally occurring Radium nuclides and its daughters are quantified using a low-energy Germanium detector. The parent nuclide (U238 and Th232) distribution in the host rock is studied using X-Ray Absorption Spectroscopy (XAS). Our study elucidates the contribution of alpha recoil on the appearance and distribution of Radon (Rn222) within porewater of representative rock matrices. Further, we illustrate the effects of chemical and physical heterogeneity on the rate of this process, which may inform models predicting the fate and transport of radionuclides in subsurface environments.

SPIDER. IV. OPTICAL AND NEAR-INFRARED COLOR GRADIENTS IN EARLY-TYPE GALAXIES: NEW INSIGHT INTO CORRELATIONS WITH GALAXY PROPERTIES

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

La Barbera, F.; De Carvalho, R. R.; De La Rosa, I. G.

2010-11-15

We present an analysis of stellar population gradients in 4546 early-type galaxies (ETGs) with photometry in grizYHJK along with optical spectroscopy. ETGs were selected as bulge-dominated systems, displaying passive spectra within the SDSS fibers. A new approach is described which utilizes color information to constrain age and metallicity gradients. Defining an effective color gradient, {nabla}{sub *}, which incorporates all of the available color indices, we investigate how {nabla}{sub *} varies with galaxy mass proxies, i.e., velocity dispersion, stellar (M{sub *}) and dynamical (M{sub dyn}) masses, as well as age, metallicity, and [{alpha}/Fe]. ETGs with M{sub dyn} larger than 8.5 xmore » 10{sup 10} M{sub sun} have increasing age gradients and decreasing metallicity gradients with respect to mass, metallicity, and enhancement. We find that velocity dispersion and [{alpha}/Fe] are the main drivers of these correlations. ETGs with 2.5 x 10{sup 10} M{sub sun} {<=} M{sub dyn} {<=} 8.5 x 10{sup 10} M{sub sun} show no correlation of age, metallicity, and color gradients with respect to mass, although color gradients still correlate with stellar population parameters, and these correlations are independent of each other. In both mass regimes, the striking anti-correlation between color gradient and {alpha}-enhancement is significant at {approx}5{sigma} and results from the fact that metallicity gradient decreases with [{alpha}/Fe]. This anti-correlation may reflect the fact that star formation and metallicity enrichment are regulated by the interplay between the energy input from supernovae, and the temperature and pressure of the hot X-ray gas in ETGs. For all mass ranges, positive age gradients are associated with old galaxies (>5-7 Gyr). For galaxies younger than {approx}5 Gyr, mostly at low mass, the age gradient tends to be anti-correlated with the Age parameter, with more positive gradients at younger ages.« less

Structure and Function of PA4872 from Pseudomonas aeruginosa, a Novel Class of Oxaloacetate Decarboxylase from the PEP Mutase/Isocitrate Lyase Superfamily

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

Narayanan, Buvaneswari C.; Niu, Weiling; Han, Ying

2008-06-30

Pseudomonas aeruginosa PA4872 was identified by sequence analysis as a structurally and functionally novel member of the PEP mutase/isocitrate lyase superfamily and therefore targeted for investigation. Substrate screens ruled out overlap with known catalytic functions of superfamily members. The crystal structure of PA4872 in complex with oxalate (a stable analogue of the shared family R-oxyanion carboxylate intermediate/transition state) and Mg{sup 2+} was determined at 1.9 {angstrom} resolution. As with other PEP mutase/isocitrate lyase superfamily members, the protein assembles into a dimer of dimers with each subunit adopting an {alpha}/{beta} barrel fold and two subunits swapping their barrel's C-terminal {alpha}-helices. Mg2+more » and oxalate bind in the same manner as observed with other superfamily members. The active site gating loop, known to play a catalytic role in the PEP mutase and lyase branches of the superfamily, adopts an open conformation. The N{sup {epsilon}} of His235, an invariant residue in the PA4872 sequence family, is oriented toward a C(2) oxygen of oxalate analogous to the C(3) of a pyruvyl moiety. Deuterium exchange into {alpha}-oxocarboxylate-containing compounds was confirmed by {sup 1}H NMR spectroscopy. Having ruled out known activities, the involvement of a pyruvate enolate intermediate suggested a decarboxylase activity of an {alpha}-oxocarboxylate substrate. Enzymatic assays led to the discovery that PA4872 decarboxylates oxaloacetate (k{sub cat}) = 7500 s{sup -1} and K{sub m} = 2.2 mM) and 3-methyloxaloacetate (k{sub cat}) = 250 s{sup -1} and K{sub m} = 0.63 mM). Genome context of the fourteen sequence family members indicates that the enzyme is used by select group of Gram-negative bacteria to maintain cellular concentrations of bicarbonate and pyruvate; however the decarboxylation activity cannot be attributed to a pathway common to the various bacterial species.« less

Determination of human serum alpha1-acid glycoprotein and albumin binding of various marketed and preclinical kinase inhibitors.

PubMed

Zsila, Ferenc; Fitos, Ilona; Bencze, Gyula; Kéri, György; Orfi, László

2009-01-01

There are about 380 protein kinase inhibitors in drug development as of today and 15 drugs have been marketed already for the treatment of cancer. This time 139 validated kinase targets are in the focus of drug research of pharmaceutical companies and big efforts are made for the development of new, druglike kinase inhibitors. Plasma protein binding is an important factor of the ADME profiling of a drug compound. Human serum albumin (HSA) and alpha(1)-acid glycoprotein (AAG) are the most relevant drug carriers in blood plasma. Since previous literature data indicated that AAG is the principal plasma binding component of some kinase inhibitors the present work focuses on the comprehensive evaluation of AAG binding of a series of marketed and experimental kinase inhibitors by using circular dichroism (CD) spectroscopy approach. HSA binding was also evaluated by affinity chromatography. Protein binding interactions of twenty-six kinase inhibitors are characterized. The contribution of AAG and HSA binding data to the pharmacokinetic profiles of the investigated therapeutic agents is discussed. Structural, biological and drug binding properties of AAG as well as the applicability of the CD method in studying drug-protein binding interactions are also briefly reviewed.

Mental stress assessment using simultaneous measurement of EEG and fNIRS

PubMed Central

Al-Shargie, Fares; Kiguchi, Masashi; Badruddin, Nasreen; Dass, Sarat C.; Hani, Ahmad Fadzil Mohammad; Tang, Tong Boon

2016-01-01

Previous studies reported mental stress as one of the major contributing factors leading to various diseases such as heart attack, depression and stroke. An accurate stress assessment method may thus be of importance to clinical intervention and disease prevention. We propose a joint independent component analysis (jICA) based approach to fuse simultaneous measurement of electroencephalography (EEG) and functional near-infrared spectroscopy (fNIRS) on the prefrontal cortex (PFC) as a means of stress assessment. For the purpose of this study, stress was induced by using an established mental arithmetic task under time pressure with negative feedback. The induction of mental stress was confirmed by salivary alpha amylase test. Experiment results showed that the proposed fusion of EEG and fNIRS measurements improves the classification accuracy of mental stress by +3.4% compared to EEG alone and +11% compared to fNIRS alone. Similar improvements were also observed in sensitivity and specificity of proposed approach over unimodal EEG/fNIRS. Our study suggests that combination of EEG (frontal alpha rhythm) and fNIRS (concentration change of oxygenated hemoglobin) could be a potential means to assess mental stress objectively. PMID:27867700

Energy-transfer processes in neon-hydrogen mixtures excited by electron beams

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

Morozov, A.; Kruecken, R.; Ulrich, A.

2005-12-15

Energy- and charge-transfer processes in neon-hydrogen mixtures (500-1400 hPa neon and 0.001-3 hPa hydrogen partial pressures) excited by a pulsed low-energy ({approx}10 keV) electron beam were investigated using time-resolved spectroscopy. Time spectra of the hydrogen Lyman-{alpha} line, neon excimer emission (second continuum), and neon atomic lines (3p-3s transitions) were recorded. The time-integrated intensity of the Lyman-{alpha} emission was measured for the same range of gas mixtures. It is shown that direct energy transfer from Ne{sub 2}* excimers and neon atoms in the four lowest excited states as well as recombination of H{sub 3}{sup +} ions are the main channels populatingmore » atomic hydrogen in the n=2 state. A rate constant of (4.2{+-}1.4)x10{sup -11} cm{sup 3} s{sup -1} was obtained for the charge transfer from Ne{sub 2}{sup +} ions to molecular hydrogen. A lower limit for the depopulation rate constant of Ne{sub 2}* excimers by molecular hydrogen (combination of energy transfer and ionization) was found to be 1.0x10{sup -10} cm{sup 3} s{sup -1}.« less

Crab shell chitin whiskers reinforced natural rubber nanocomposites. 3. Effect of chemical modification of chitin whiskers.

PubMed

Gopalan Nair, Kalaprasad; Dufresne, Alain; Gandini, Alessandro; Belgacem, Mohamed Naceur

2003-01-01

The purpose of this study was to chemically modify the surface of chitin whiskers and to investigate the effect of the incorporation of these modified whiskers into a natural rubber (NR) matrix on the properties of the ensuing nanocomposite. Different chemical coupling agents were tested, namely, phenyl isocyanate (PI), alkenyl succinic anhydride (ASA) (Accosize 18 from American Cyanamid), and 3-isopropenyl-alpha,alpha'-dimethylbenzyl isocyanate (TMI). The extent of chemical modification was evaluated by Fourier transform infrared (FTIR) spectroscopy, transmission electron microscopy (TEM), and surface energy analysis. After chemical modification, nanocomposite films were obtained using a toluene natural rubber solution in which the whiskers were dispersed. Their mechanical properties were found to be inferior to those of unmodified chitin/NR composites presented in our previous study. In fact, even though there is an increase in filler-matrix interaction as a result of chemical modification of the chitin whiskers, this does not contribute to the improvement in the mechanical properties of the resulting nanocomposite. It is concluded that this loss of performance is due to the partial destruction of the three-dimensional network of chitin whiskers assumed to be present in the unmodified composites.

Physical and chemical properties of pyropheophorbide-a methyl ester in ethanol, phosphate buffer and aqueous dispersion of small unilamellar dimyristoyl-L-alpha-phosphatidylcholine vesicles.

PubMed

Delanaye, Lisiane; Bahri, Mohamed Ali; Tfibel, Francis; Fontaine-Aupart, Marie-Pierre; Mouithys-Mickalad, Ange; Heine, Bélinda; Piette, Jacques; Hoebeke, Maryse

2006-03-01

The aggregation process of pyropheophorbide-a methyl ester (PPME), a second-generation photosensitizer, was investigated in various solvents. Absorption and fluorescence spectra showed that the photosensitizer was under a monomeric form in ethanol as well as in dimyristoyl-L-alpha-phosphatidylcholine liposomes while it was strongly aggregated in phosphate buffer. A quantitative determination of reactive oxygen species production by PPME in these solvents has been undertaken by electron spin resonance associated with spin trapping technique and absorption spectroscopy. In phosphate buffer, both electron spin resonance and absorption measurements led to the conclusion that singlet oxygen production was not detectable while hydroxyl radical production was very weak. In liposomes and ethanol, singlet oxygen and hydroxyl radical production increased highly; the singlet oxygen quantum yield was determined to be 0.2 in ethanol and 0.13 in liposomes. The hydroxyl radical production origin was also investigated. Singlet oxygen was formed from PPME triplet state deactivation in the presence of oxygen. Indeed, the triplet state formation quantum yield of PPME was found to be about 0.23 in ethanol, 0.15 in liposomes (too small to be measured in PBS).

Characterization of compositional modifications in metal-organic frameworks using carbon and alpha particle microbeams

NASA Astrophysics Data System (ADS)

Paneta, V.; Fluch, U.; Petersson, P.; Ott, S.; Primetzhofer, D.

2017-08-01

Zirconium-oxide based metal-organic frameworks (MOFs) were grown on p-type Si wafers. A modified linker molecule containing iodine was introduced by post synthetic exchange (PSE). Samples have been studied using Rutherford Backscattering Spectrometry (RBS) and Particle Induced X-ray Emission (PIXE) techniques, employing the 5 MV 15SDH-2 Pelletron Tandem accelerator at the Ångström laboratory. The degree of post synthetic uptake of the iodine-containing linker has been investigated with both a broad beam and a focused beam of carbon and alpha particles targeting different kind of MOF crystals which were of ∼1-10 μm in size, depending on the linker used. Iodine concentrations in MOF crystallites were also measured by Nuclear Magnetic Resonance Spectroscopy (NMR) and are compared to the RBS results. In parallel to the ion beam studies, samples were investigated by Scanning Electron Microscopy (SEM) to quantify possible crystallite clustering, develop optimum sample preparation routines and to characterize the potential ion beam induced sample damage and its dependence on different parameters. Based on these results the reliability and accuracy of ion beam data is assessed.

Morphological and compositional study of 238U thin film targets for nuclear experiments

NASA Astrophysics Data System (ADS)

Sibbens, Goedele; Ernstberger, Markus; Gouder, Thomas; Marouli, Maria; Moens, André; Seibert, Alice; Vanleeuw, David; Zúñiga, Martin Vargas; Wiss, Thierry; Zampella, Mariavittoria; Zuleger, Evelyn

2018-05-01

The uncertainty in neutron cross section values strongly depends on the quality and characteristics of the deposited actinide films which are used as "targets" in the nuclear experiments. Until recently, at the Joint Research Centre in Geel (JRC-Geel), mass and areal densities of actinide layers were determined by measuring activity (using alpha-particle counting), isotopic composition (using thermal ionisation mass spectrometry) and diameter. In this study a series of 238U deposits, prepared by molecular plating and vacuum deposition on different substrates, were characterized with additional non-destructive and destructive analysis techniques. The quality of the deposits was investigated by autoradiography, high-resolution alpha-particle spectrometry, and scanning electron microscopy. The elemental composition was determined by x-ray photoelectron spectroscopy and inductively coupled plasma mass spectrometry. The latter technique was also applied on the U3O8 starting material and the converted UF4 powder. This paper compares the quality and morphology of deposited 238U films prepared by molecular plating and vacuum deposition on various backings, including their elemental composition determined by different characterization techniques. Also discussed are problems in target preparation and characterization.

Identifying compositional and structural changes in spongy and subchondral bone from the hip joints of patients with osteoarthritis using Raman spectroscopy.

PubMed

Buchwald, Tomasz; Niciejewski, Krzysztof; Kozielski, Marek; Szybowicz, Mirosław; Siatkowski, Marcin; Krauss, Hanna

2012-01-01

Raman microspectroscopy was used to examine the biochemical composition and molecular structure of extracellular matrix in spongy and subchondral bone collected from patients with clinical and radiological evidence of idiopathic osteoarthritis of the hip and from patients who underwent a femoral neck fracture, as a result of trauma, without previous clinical and radiological evidence of osteoarthritis. The objectives of the study were to determine the levels of mineralization, carbonate accumulation and collagen quality in bone tissue. The subchondral bone from osteoarthritis patients in comparison with control subject is less mineralized due to a decrease in the hydroxyapatite concentration. However, the extent of carbonate accumulation in the apatite crystal lattice increases, most likely due to deficient mineralization. The alpha helix to random coil band area ratio reveals that collagen matrix in subchondral bone is more ordered in osteoarthritis disease. The hydroxyapatite to collagen, carbonate apatite to hydroxyapatite and alpha helix to random coil band area ratios are not significantly changed in the differently loaded sites of femoral head. The significant differences also are not visible in mineral and organic constituents' content in spongy bone beneath the subchondral bone in osteoarthritis disease.

Identifying compositional and structural changes in spongy and subchondral bone from the hip joints of patients with osteoarthritis using Raman spectroscopy

NASA Astrophysics Data System (ADS)

Buchwald, Tomasz; Niciejewski, Krzysztof; Kozielski, Marek; Szybowicz, Mirosław; Siatkowski, Marcin; Krauss, Hanna

2012-01-01

Raman microspectroscopy was used to examine the biochemical composition and molecular structure of extracellular matrix in spongy and subchondral bone collected from patients with clinical and radiological evidence of idiopathic osteoarthritis of the hip and from patients who underwent a femoral neck fracture, as a result of trauma, without previous clinical and radiological evidence of osteoarthritis. The objectives of the study were to determine the levels of mineralization, carbonate accumulation and collagen quality in bone tissue. The subchondral bone from osteoarthritis patients in comparison with control subject is less mineralized due to a decrease in the hydroxyapatite concentration. However, the extent of carbonate accumulation in the apatite crystal lattice increases, most likely due to deficient mineralization. The alpha helix to random coil band area ratio reveals that collagen matrix in subchondral bone is more ordered in osteoarthritis disease. The hydroxyapatite to collagen, carbonate apatite to hydroxyapatite and alpha helix to random coil band area ratios are not significantly changed in the differently loaded sites of femoral head. The significant differences also are not visible in mineral and organic constituents' content in spongy bone beneath the subchondral bone in osteoarthritis disease.

Characterization of flavonols in cranberry (Vaccinium macrocarpon) powder.

PubMed

Vvedenskaya, Irina O; Rosen, Robert T; Guido, Jane E; Russell, David J; Mills, Kent A; Vorsa, Nicholi

2004-01-28

Flavonoids were extracted from cranberry powder with acetone and ethyl acetate and subsequently fractionated with Sephadex LH-20 column chromatography. The fraction eluted with a 60% methanol solution was composed primarily of phenolic constituents with maximum absorbance at 340 nm. A high-performance liquid chromatography procedure was developed, which resolved 22 distinct peaks with UV/vis and mass spectra corresponding to flavonol glycoside conjugates. Six new constituents not previously reported in cranberry or in cranberry products were determined through NMR spectroscopy to be myricetin-3-beta-xylopyranoside, quercetin-3-beta-glucoside, quercetin-3-alpha-arabinopyranoside, 3'-methoxyquercetin-3-alpha-xylopyranoside, quercetin-3-O-(6' '-p-coumaroyl)-beta-galactoside, and quercetin-3-O-(6' '-benzoyl)-beta-galactoside. Quercetin-3-O-(6' '-p-coumaroyl)-beta-galactoside and quercetin-3-O-(6' '-benzoyl)-beta-galactoside represent a new class of cranberry flavonol compounds with three conjugated components consisting of a flavonol, sugar, and carboxylic acid (benzoic or hydroxycinnamic acids). This is also the first report identifying quercetin-3-arabinoside in both furanose and pyranose forms in cranberry. Elucidation of specific flavonol glycosides in cranberry is significant since the specificity of the sugar moiety may play a role in the bioavailability of the flavonol glycosides in vivo.

Distribution of glycolipid and unsaturated fatty acids in human hair.

PubMed

Takahashi, Toshie; Yoshida, Satoshi

2014-09-01

It has been recognized that human hair lipids play crucial roles in the integrity of cells and matrices, while the details of distribution and structure of the minor lipids are hardly known. Here we investigated the lipids at the hair surface, at the interface between cuticle and cortex and in the interior of hair (cortex, medulla and melanin granules). Hair lipids and fatty acids and their metabolites were detected and characterized by using infrared spectroscopy and several mass spectrometry techniques (FTIR, ToF-SIMS, GCMS, and ESI-MS). As a result, it was found that unsaturated fatty acids were present more in the cortex of hair than at the hair surface. At the interface between cuticle and cortex, it is suggested that steryl glycoside-like lipids containing N-acetylglucosamine were present, and contributing to the adhesion between the cuticle and cortex of hair. Oxidative metabolites derived from integral fatty acids such as linoleic and alpha-linolenic acids were found in the hair bulb and melanin granules. Especially the oxidative metabolites of alpha-linolenic acid were integrated into the lipids non-covalently and tightly bound to melanin granules (namely, melanin lipids) and suggested as being involved in the biosynthetic processes of melanosome.

Highly efficient Cu-decorated iron oxide nanocatalyst for low pressure CO 2 conversion

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

Halder, Avik; Kilianová, Martina; Yang, Bing

We report a nanoparticulate iron oxide based catalyst for CO2 conversion with high efficiency at low pressures and on the effect of the presence of copper on the catalyst's restructuring and its catalytic performance. In situ X-ray scattering reveals the restructuring of the catalyst at the nanometer scale. In situ X-ray absorption near edge structure (XANES) shows the evolution of the composition and oxidation state of the iron and copper components under reaction conditions along with the promotional effect of copper on the chemical transformation of the iron component. X-ray diffraction (XRD), XANES and Raman spectroscopy proved that the startingmore » nano catalyst is composed of iron oxides differing in chemical nature (alpha-Fe2O3, Fe3O4, FeO(OH)) and dimensionality, while the catalyst after CO2 conversion was identified as a mixture of alpha-Fe, Fe3C, and traces of Fe5C2. The significant increase of the rate CO2 is turned over in the presence of copper nanoparticles indicates that Cu nanoparticles activate hydrogen, which after spilling over to the neighbouring iron sites, facilitate a more efficient conversion of carbon dioxide.« less

Two distinct structures of alpha-conotoxin GI in aqueous solution.

PubMed

Maslennikov, I V; Sobol, A G; Gladky, K V; Lugovskoy, A A; Ostrovsky, A G; Tsetlin, V I; Ivanov, V T; Arseniev, A S

1998-06-01

The detailed analysis of conformational space of alpha-conotoxin GI in aqueous solution has been performed on the basis of two-dimensional NMR spectroscopy data using multiconformational approach. As the result, two topologically distinct interconvertible sets of GI conformations (populations of 78% and 22%) have been found. A common feature of the two sets is the Asn4-Cys7 beta-turn. The Gly8 to Tyrll region has a structure of right-handed helical turn in the major set and two sequential bends in the minor one. N-terminus and C-terminus also have different orientations, anti-parallel in the major conformational set and parallel in the minor one. An average pairwise rmsd for backbone heavy atoms is 0.56 A in the major set, 0.23 A in the minor, and 1.85 A between the structures of the two sets. The X-ray structure of GI [Guddat, L. W., Martin, J. A., Shan, L., Edmundson, A. B. & Gray, W. R. (1996) Biochemistry 35, 11329 - 11335] has the same folding pattern as the major NMR set, the average backbone rmsd between the two structures being 0.77 A.

Fourier transform mid-infrared (MIR) and near-infrared (NIR) spectroscopy for rapid quality assessment of Chinese medicine preparation Honghua Oil.

PubMed

Wu, Yan-Wen; Sun, Su-Qin; Zhou, Qun; Leung, Hei-Wun

2008-02-13

Honghua Oil (HHO), a traditional Chinese medicine (TCM) oil preparation, is a mixture of several plant essential oils. In this text, the extended ranges of Fourier transform mid-infrared (FT-MIR) and near infrared (FT-NIR) were recorded for 48 commercially available HHOs of different batches from nine manufacturers. The qualitative and quantitative analysis of three marker components, alpha-pinene, methyl salicylate and eugenol, in different HHO products were performed rapidly by the two vibrational spectroscopic methods, i.e. MIR with horizontal attenuated total reflection (HATR) accessory and NIR with direct sampling technique, followed by partial least squares (PLS) regression treatment of the set of spectra obtained. The results indicated that it was successful to identify alpha-pinene, methyl salicylate and eugenol in all of the samples by simple inspection of the MIR-HATR spectra. Both PLS models established with MIR-HATR and NIR spectral data using gas chromatography (GC) peak areas as calibration reference showed a good linear correlation for each of all three target substances in HHO samples. The above spectroscopic techniques may be the promising methods for the rapid quality assessment/quality control (QA/QC) of TCM oil preparations.

Effect of radiation-induced amorphization on smectite dissolution.

PubMed

Fourdrin, C; Allard, T; Monnet, I; Menguy, N; Benedetti, M; Calas, G

2010-04-01

Effects of radiation-induced amorphization of smectite were investigated using artificial irradiation. Beams of 925 MeV Xenon ions with radiation dose reaching 73 MGy were used to simulate the effects generated by alpha recoil nuclei or fission products in the context of high level nuclear waste repository. Amorphization was controlled by X-ray diffraction, transmission electron microscopy, and Fourier transform infrared spectroscopy. An important coalescence of the smectite sheets was observed which lead to a loss of interparticle porosity. The amorphization is revealed by a loss of long-range structure and accompanied by dehydroxylation. The dissolution rate far-from-equilibrium shows that the amount of silica in solution is two times larger in the amorphous sample than in the reference clay, a value which may be enhanced by orders of magnitude when considering the relative surface area of the samples. Irradiation-induced amorphization thus facilitates dissolution of the clay-derived material. This has to be taken into account for the safety assessment of high level nuclear waste repository, particularly in a scenario of leakage of the waste package which would deliver alpha emitters able to amorphize smectite after a limited period of time.

Adsorption of fibrinogen on a biomedical-grade stainless steel 316LVM surface: a PM-IRRAS study of the adsorption thermodynamics, kinetics and secondary structure changes.

PubMed

Desroches, Marie-Josee; Omanovic, Sasha

2008-05-14

Polarization-modulation infrared reflection-absorption spectroscopy (PM-IRRAS) was employed to investigate the interaction of serum protein fibrinogen with a biomedical-grade 316LVM stainless steel surface, in terms of the adsorption thermodynamics, kinetics and secondary structure changes of the protein. Apparent Gibbs energy of adsorption values indicated a highly spontaneous and strong adsorption of fibrinogen onto the surface. The kinetics of fibrinogen adsorption were successfully modeled using a pseudo first-order kinetic model. Deconvolution of the amide I bands indicated that the adsorption of fibrinogen on 316LVM results in significant changes in the protein's secondary structure that occur predominantly within the first minute of adsorption. Among the investigated structures, the alpha-helix structure undergoes the smallest changes, while the beta-sheet and beta-turns structures undergo significant changes. It was shown that lateral interactions between the adsorbed molecules do not play a role in controlling the secondary structure changes. An increase in temperature induced changes in the secondary structure of the protein, characterized by a loss of the alpha-helical content and its transformation into the beta-turns structure.

Alpha-amylase inhibitory activity and sterol composition of the marine algae, Sargassum glaucescens

PubMed Central

Payghami, Nasrin; Jamili, Shahla; Rustaiyan, Abdolhossein; Saeidnia, Soodabeh; Nikan, Marjan; Gohari, Ahmad Reza

2015-01-01

Background: Sargassum species (phaeophyceae) are economically important brown algae in southern parts of Iran. Sargassum is mainly harvested as a row material in alginate production industries and is a source of plant foods or plant bio-stimulants even a component of animal foods. Objective: In this study, Sargassum glaucescens, collected from the seashore of Chabahar, was employed for phytochemical and biological evaluations. Materials and Methods: For that purpose, the dried algae was extracted by methanol and subjected to different chromatographic separation methods. Results: Six sterols, fucosterol (1), 24(S)-hydroxy-24-vinylcholesterol (2), 24(R)-hydroxy-24-vinylcholesterol (3), stigmasterol (4), β-sitosterol (5) and cholesterol (6) were identified by spectroscopic methods including 1H-NMR, 13C-NMR and mass spectroscopy. In vitro alpha-amylase inhibitory test was performed on the methanolic extract and the results revealed a potent inhibition (IC50 = 8.9 ± 2.4 mg/mL) of the enzyme compared to acarbose as a positive control. Conclusion: Various biological activities and distribution of sterols in Sargassum genus have been critically reviewed here. The results concluded that these algae are a good candidate for further anti-diabetic investigations in animals and human. PMID:26692744

Differences in the electrostatic surfaces of the type III secretion needle proteins PrgI, BsaL, and MxiH.

PubMed

Wang, Yu; Ouellette, Andrew N; Egan, Chet W; Rathinavelan, Thenmalarchelvi; Im, Wonpil; De Guzman, Roberto N

2007-08-31

Gram-negative bacteria use a needle-like protein assembly, the type III secretion apparatus, to inject virulence factors into target cells to initiate human disease. The needle is formed by the polymerization of approximately 120 copies of a small acidic protein that is conserved among diverse pathogens. We previously reported the structure of the BsaL needle monomer from Burkholderia pseudomallei by nuclear magnetic resonance (NMR) spectroscopy and others have determined the crystal structure of the Shigella flexneri MxiH needle. Here, we report the NMR structure of the PrgI needle protein of Salmonella typhimurium, a human pathogen associated with food poisoning. PrgI, BsaL, and MxiH form similar two helix bundles, however, the electrostatic surfaces of PrgI differ radically from those of BsaL or MxiH. In BsaL and MxiH, a large negative area is on a face formed by the helix alpha1-alpha2 interface. In PrgI, the major negatively charged surface is not on the "face" but instead is on the "side" of the two-helix bundle, and only residues from helix alpha1 contribute to this negative region. Despite being highly acidic proteins, these molecules contain large basic regions, suggesting that electrostatic contacts are important in needle assembly. Our results also suggest that needle-packing interactions may be different among these bacteria and provide the structural basis for why PrgI and MxiH, despite 63% sequence identity, are not interchangeable in S. typhimurium and S. flexneri.

ADP binding to TF1 and its subunits induces ultraviolet spectral changes.

PubMed

Hisabori, T; Yoshida, M; Sakurai, H

1986-09-01

Adenine nucleotide binding sites on the coupling factor ATPase of thermophilic bacterium PS3 (TF1) were investigated by UV spectroscopy and by equilibrium dialysis. When ADP was mixed with TF1 in the presence and in the absence of Mg2+, an UV absorbance change was induced (t1/2 approximately 1 min) with a peak at about 278 nm and a trough at about 250 nm. Similar spectral changes were induced by ADP with the isolated beta subunits in the presence and in the absence of Mg2+, and with the isolated alpha subunits in the presence of Mg2+ although the magnitudes of the changes were different. From equilibrium dialysis measurement we identified two classes of nucleotide binding sites in TF1 in the presence of Mg2+, three high-affinity sites (Kd = 61 nM) and three low-affinity sites (Kd = 87 microM). In the absence of Mg2+, TF1 has one high-affinity site (Kd less than 10 nM) and five low-affinity sites (Kd = 100 microM). Moreover, we found a single Mg2+-dependent ADP binding site on the isolated alpha subunit and a single Mg2+-independent ADP binding site on the isolated beta subunit. From the above observations, we concluded that the three Mg2+-dependent high-affinity sites for ADP are located on the alpha subunit in TF1 and that the single high-affinity site is located on one of the beta subunits in TF1 in the absence of Mg2+.

Do Lyman-alpha photons escape from star-forming galaxies through dust-holes?

NASA Astrophysics Data System (ADS)

Wofford, Aida

2012-10-01

The hydrogen Lyman-alpha line is arguably the most important signature of galaxies undergoing their first violent burst of star formation. Although Lya photons are easily destroyed by dust, candidate Lya emitters have been detected at z>5. Thus the line can potentially be used to probe galaxy formation and evolution, as long as the astrophysical processes that regulate the escape of Lya photons from star-forming galaxies are well understood.We request 15 orbits for imaging in Lya and the FUV continuum with ACS/SBC, and in the H-beta/H-alpha ratio {proxy for dust extinction} with WFC3/UVIS, a sample of isolated non-AGN face-on spirals for which our team previously obtained and analyzed COS FUV spectroscopy of the central regions. Each target shows a different Lya profile, i.e., pure absorption, P-Cygni like, and multiple-emission. From the COS data, we already know the starburst phase and H I gas velocity. The images would greatly increase the impact of our spectroscopic study by enabling us to 1} conclusively determine if Lya photons escape through dust-holes, 2} assess the relative importance of dust extinction, ISM kinematics, and starburst phase in regulating the Lya escape, 3} clarify what we can really learn from the Lya equivalent width, and 4} provide constraints on the dust extinction to Lya 3D radiative transfer models. Ultimately this program will inform our understanding of the Lya escape at high redshift by providing spatially resolved views of the local conditions within star-forming galaxies that favor escape.

Spectroscopic CCD surveys for quasars at large redshift. 3: The Palomar Transit Grism Survey catalog

NASA Technical Reports Server (NTRS)

Schneider, Donald P.; Schmidt, Maarten; Gunn, James E.

1994-01-01

This paper reports the initial results of the Palomar Transit Grism Survey (PTGS). The PTGS was designed to produce a sample of z greater than 2.7 quasars that were identified by well-defined selection criteria. The survey consists of six narrow (approximately equal to 8.5 min wide) strips of sky; the total effective area is 61.47 sq deg. Low-resolution slitless spectra, covering the wavelength range from 4400 to 7500 A, were obtained for approximately 600 000 objects. The wavelength- and flux-calibrated spectra were searched for emission lines with an automatic software algorithm. A total to 1655 emission features in the grism data satisfied our signal-to-noise ratio and equivalent width selection criteria; subsequent slit spectroscopy of the candidates confirmed the existence of 1052 lines (928 different objects). Six groups of emission lines were detected in the survey: Lyman alpha + N V, C IV, C III1, Mg II, H Beta + (O III), and H alpha + (S II). More than two-thirds of the candidates are low-redshift (z less than 0.45) emission-line galaxies; ninety objects are high-redshift quasars (z greater than 2.7) detected via their Lyman alpha + N V emission lines. The survey contains three previously unknown quasars brighter than 17th magnitude; all three have redshifts of approximately equal to 1.3. In this paper we present the observational properties of the survey, the algorithms used to select the emission-line candidates, and the catalog of emission-line objects.

Implementation of a process analytical technology system in a freeze-drying process using Raman spectroscopy for in-line process monitoring.

PubMed

De Beer, T R M; Allesø, M; Goethals, F; Coppens, A; Heyden, Y Vander; De Diego, H Lopez; Rantanen, J; Verpoort, F; Vervaet, C; Remon, J P; Baeyens, W R G

2007-11-01

The aim of the present study was to propose a strategy for the implementation of a Process Analytical Technology system in freeze-drying processes. Mannitol solutions, some of them supplied with NaCl, were used as models to freeze-dry. Noninvasive and in-line Raman measurements were continuously performed during lyophilization of the solutions to monitor real time the mannitol solid state, the end points of the different process steps (freezing, primary drying, secondary drying), and physical phenomena occurring during the process. At-line near-infrared (NIR) and X-ray powder diffractometry (XRPD) measurements were done to confirm the Raman conclusions and to find out additional information. The collected spectra during the processes were analyzed using principal component analysis and multivariate curve resolution. A two-level full factorial design was used to study the significant influence of process (freezing rate) and formulation variables (concentration of mannitol, concentration of NaCl, volume of freeze-dried sample) upon freeze-drying. Raman spectroscopy was able to monitor (i) the mannitol solid state (amorphous, alpha, beta, delta, and hemihydrate), (ii) several process step end points (end of mannitol crystallization during freezing, primary drying), and (iii) physical phenomena occurring during freeze-drying (onset of ice nucleation, onset of mannitol crystallization during the freezing step, onset of ice sublimation). NIR proved to be a more sensitive tool to monitor sublimation than Raman spectroscopy, while XRPD helped to unravel the mannitol hemihydrate in the samples. The experimental design results showed that several process and formulation variables significantly influence different aspects of lyophilization and that both are interrelated. Raman spectroscopy (in-line) and NIR spectroscopy and XRPD (at-line) not only allowed the real-time monitoring of mannitol freeze-drying processes but also helped (in combination with experimental design) us to understand the process.

A ``delayed'' counting method to determine indoor Rn-222 levels indirectly

NASA Astrophysics Data System (ADS)

Iannopollo, V.; Licandro, M.; Trimarchi, M.; Tripepi, M. G.; Vermiglio, G.

2001-08-01

A new indirect and "delayed" way is presented to determine indoor concentration of Rn-222 by best-fitting methods. If a rapid knowledge of Rn-222 levels is required and if a detection system is not available in situ, it is possible to obtain concentration of radioactive gas by determining of "delayed" counts of Po-214. The "delay" time consists of two or three hours. The method is based on the use of cellulose filters for particulate collection and on the analysis of samples by alpha spectroscopy. It is also possible to obtain concentrations of short-lived radon daughters Po-218, Pb-214, Bi-214, which are very important quantities in a medical framework.

Development of a high resolution liquid xenon imaging chamber for gamma-ray astronomy

NASA Technical Reports Server (NTRS)

Aprile, Elena

1991-01-01

The objective was to develop the technology of liquid xenon (LXe) detectors for spectroscopy and imaging of gamma rays from astrophysical sources emitting in the low to medium energy regime. In particular, the technical challenges and the physical processes relevant to the realization of the LXe detector operated as a Time Projection Chamber (TPC) were addressed and studied. Experimental results were obtained on the following topics: (1) long distance drift of free electrons in LXe (purity); (2) scintillation light yield for electrons and alphas in LXe (triggering); and (3) ionization yield for electrons and gamma rays in LXe (energy resolution). The major results from the investigations are summarized.

Samarium electrodeposited acetate and oxide thin films on stainless steel substrate characterized by XPS

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

Myhre, Kristian; Burns, Jonathan; Meyer, Harry

Characterization of a samarium thin film deposited on a stainless steel substrate using molecular electrodeposition was carried out using a Thermo Scientific K-Alpha X-ray photoelectron spectrometer. We studied two types of samarium electrodeposition samples, one as-deposited and one heated to 700 °C in an air flow. Survey scans include peaks coming from the stainless steel substrate, such as Fe and Cr. An X-ray photoelectron spectroscopy (XPS) survey spectrum, Sm 3d, C 1s, and O 1s narrow scans are shown. It was determined that the heating process decomposed the deposited Sm acetate to Sm 2O 3 using XPS.

High Resolution Emission Spectroscopy of the Alpha Pi-1 - Chi Sigma-1(+) Fourth Positive Band System of CO from Electron Impact

NASA Technical Reports Server (NTRS)

Beegle, Luther W.; Ajello, Joseph M.; James, Geoffrey K.; Alvarez, Marcos; Dziczek, Dariusz

2000-01-01

We report electron-impact induced fluorescence spectra [300 mA full width at half maximum (FWHM)] of CO for 20 and 100 eV impact energies of the spectral region of 1300 to 2050 A and high resolution spectra (FWHM) of the v'=5 to v"=l and the v'=3 to v"=O bands showing that the rotational structure of the band system are modeled accurately. The excitation function of the (0,1) band (1597 A) was measured from electron impact in the energy range from threshold to 750 eV and placed on an absolute scale from modem calibration standards.

Time-resolved x-ray spectra from laser-generated high-density plasmas

NASA Astrophysics Data System (ADS)

Andiel, U.; Eidmann, Klaus; Witte, Klaus-Juergen

2001-04-01

We focused frequency doubled ultra short laser pulses on solid C, F, Na and Al targets, K-shell emission was systematically investigated by time resolved spectroscopy using a sub-ps streak camera. A large number of laser shots can be accumulated when triggering the camera with an Auston switch system at very high temporal precision. The system provides an outstanding time resolution of 1.7ps accumulating thousands of laser shots. The time duration of the He-(alpha) K-shell resonance lines was observed in the range of (2-4)ps and shows a decrease with the atomic number. The experimental results are well reproduced by hydro code simulations post processed with an atomic kinetics code.

New benzophenone and quercetin galloyl glycosides from Psidium guajava L.

PubMed

Matsuzaki, Keiichi; Ishii, Rie; Kobiyama, Kaori; Kitanaka, Susumu

2010-07-01

New benzophenone and flavonol galloyl glycosides were isolated from an 80% MeOH extract of Psidium guajava L. (Myrtaceae) together with five known quercetin glycosides. The structures of the novel glycosides were elucidated to be 2,4,6-trihydroxybenzophenone 4-O-(6''-O-galloyl)-beta-D: -glucopyranoside (1, guavinoside A), 2,4,6-trihydroxy-3,5-dimethylbenzophenone 4-O-(6''-O-galloyl)-beta-D: -glucopyranoside (2, guavinoside B), and quercetin 3-O-(5''-O-galloyl)-alpha-L: -arabinofuranoside (3, guavinoside C) by NMR, MS, UV, and IR spectroscopies. Isolated phenolic glycosides showed significant inhibitory activities against histamine release from rat peritoneal mast cells, and nitric oxide production from a murine macrophage-like cell line, RAW 264.7.

Samarium electrodeposited acetate and oxide thin films on stainless steel substrate characterized by XPS

DOE PAGES

Myhre, Kristian; Burns, Jonathan; Meyer, Harry; ...

2016-06-01

Characterization of a samarium thin film deposited on a stainless steel substrate using molecular electrodeposition was carried out using a Thermo Scientific K-Alpha X-ray photoelectron spectrometer. We studied two types of samarium electrodeposition samples, one as-deposited and one heated to 700 °C in an air flow. Survey scans include peaks coming from the stainless steel substrate, such as Fe and Cr. An X-ray photoelectron spectroscopy (XPS) survey spectrum, Sm 3d, C 1s, and O 1s narrow scans are shown. It was determined that the heating process decomposed the deposited Sm acetate to Sm 2O 3 using XPS.

Ion and electron temperatures in the SUMMA mirror device by emission spectroscopy

NASA Technical Reports Server (NTRS)

Patch, R. W.; Voss, D. E.; Reinmann, J. J.; Snyder, A.

1974-01-01

Ion and electron temperatures, and ion drift were measured in a superconducting magnetic mirror apparatus by observing the Doppler-broadened charge-exchange component of the 667.8 and 587.6 nanometer He lines in He plasma, and the H sub alpha and H sub beta lines in H2 plasma. The second moment of the line profiles was used as the parameter for determining ion temperature. Corrections for magnetic splitting, fine structure, monochromator slit function, and variation in charge-exchange cross section with energy are included. Electron temperatures were measured by the line ratio method for the corona model, and correlations of ion and electron temperatures with plasma parameters are presented.

Mitigating Backgrounds with a Novel Thin-Film Cathode in the DRIFT-IId Dark Matter Detector

NASA Astrophysics Data System (ADS)

Miller, Eric H.

The nature of dark matter, which comprises 85% of the matter density in the universe, is a major outstanding question in physics today. The standard hypothesis is that the dark matter is a new weakly interacting massive particle, which is present throughout the galaxy. These particles could interact within detectors on Earth, producing low-energy nuclear recoils. Two distinctive signatures arise from the solar motion through the galaxy. The DRIFT experiment aims to measure one of these, the directional signature that is based on the sidereal modulation of the nuclear recoil directions. Although DRIFT has demonstrated its capability for detecting this signature, it has been plagued by a large number of backgrounds that have limited its reach. The focus of this thesis is on characterizing these backgrounds and describing techniques that have essentially eliminated them. The background events in the DRIFT-IId detector are predominantly caused by alpha decays on the central cathode in which the alpha particles completely or partially absorbed by the cathode material. This thesis describes the installation a 0.9 mum thick aluminized-mylar cathode as a way to reduce the probability of producing these backgrounds. We study three generations of cathode (wire, thin-film, and radiologically clean thin-film) with a focus on identifying and quantifying the sources of alpha decay backgrounds, as well as their contributions to the background rate in the detector. This in-situ study is based on alpha range spectroscopy and the determination of the absolute alpha detection efficiency. The results for the final radiologically clean version of the cathode give a contamination of 3.3 +/- 0.1 ppt 234U and 73 +/- 2 ppb 238U, and an efficiency for rejecting an RPR from an alpha decay that is a factor 70 +/- 20 higher than for the original wire cathode. Along with other background reduction measures, the thin-film cathode has reduced the observed background rate from 130/day to 1.7/day in the DRIFT experiment. The complete elimination of the remaining RPR backgrounds requires fiducialization of the detector along the drift direction. We describe two methods for doing this: one involving the detection of positive ions at the cathode, and the other using multiple species of charge carriers with variable drift speeds. With the recent successful implementation of the latter technique, the DRIFT experiment has run background-free for 46 days.

Diffusion and phase transformation behavior in poly-synthetically-twinned (PST) titanium-aluminum/titanium diffusion couple

NASA Astrophysics Data System (ADS)

Pan, Ling

Motivated by the great potential applications of gamma titanium aluminide based alloys and the important effect of diffusion on the properties of gamma-TiAl/alpha2-Ti3Al two-phase lamellar structure, we conduct this thesis research to explore the microstructural evolution and interdiffusion behavior, and their correlations in multi-phase solid state diffusion couples made up of pure titanium and polysynthetically-twinned (PST) Ti-49.3 at.% Al "single" crystal, in the temperature range of 973--1173 K. The diffusion couples are prepared by high vacuum hot-pressing, with the diffusion direction parallel to the lamellar planes. Scanning electron microscopy (SEM), transmission electron microscopy (TEM) and high-resolution transmission electron microscopy (HRTEM) are employed to observe the microstructure at various interfaces/interphases. A reaction zone (RZ) of polycrystalline alpha 2-Ti3Al phase forms along the PST Ti-Al/Ti bonding interface having a wavy interface with the PST crystal and exhibits deeper penetration in alpha2 lamellae, consisting of many fine alpha2 and secondary gamma laths, than in primary gamma lamellae. Direct measurement of the RZ thickness on SEM back-scattered electron images reveals a parabolic growth of the RZ, indicating a macroscopically diffusion-controlled growth. Concentration profiles from Ti, through the RZ, into the alpha2 lamellae of the PST crystal are measured by quantitative energy-dispersive x-ray spectroscopy (EDS) in a scanning transmission electron microscope (STEM). A plateau of composition adjacent to the RZ/(mixed alpha2 lath in PST) interface forms in the deeply penetrated RZ grains, implying a diffusion barrier crossing the interface and some extent of interface control in the RZ grain growth. The interdiffusion coefficient is evaluated both independent of composition and as a function of composition. No significant concentration dependence of the interdiffusion coefficients is observed using Boltzmann-Matano analysis. The temperature dependence of the interdiffusion coefficients obeys the Arrhenius relationship with a pre-exponential factor of D 0 = (7.56 +/- 7.14) x 10-5 m2/s and an activation enthalpy of Q = 255.6+8.9-8.3 kJ/mol = (2.65 +/- 0.09) eV/atom. The initial nucleation stage of the RZ grains plays an important role in the later microstructural evolution as does the local mass balance. The interfacial energy and the strain energy in the deeply penetrated RZ grains are possible reasons for the plateau.

Intensity mapping the Universe

NASA Astrophysics Data System (ADS)

Croft, Rupert

Intensity mapping (IM) is the use of one or more emission lines to trace out the structure of the Universe without needing to resolve individual objects (such as galaxies or gas clouds). It is one of the most promising ways to radically extend the sky survey revolution in cosmology. By making spectra of the entire sky, rather than the one part in one million captured by current fiber spectrographs, one would be sensitive to all structure. There are potentially huge discoveries to be made in the vast majority of the sky that is currently spectrally unmapped, and also great gains in signal to noise of cosmological clustering measurements. Intensity mapping with the 21cm radio line has been explored theoretically by many and instruments are being built, particularly targeting the epoch of reionization. In the UV, visible and infrared, however other lines have enormous promise, and will be exploited by a range of future NASA missions including WFIRST, Euclid, and the proposed SPHEREx instrument, a dedicated intensity mapping satellite. The first measurement of large-scale structure outside the radio (using Lyman-alpha emission) was recently made by the PI and collaborators. The Ly-a absorption line also traces a continuous cosmological field, the Lyman-alpha forest, and the enormous recent increase in the number of observed quasar spectra have made it possible to interpolate between quasar sightlines to create three-dimensional maps. Being able to trace the same cosmic structure in emission and absorption offers huge advantages when we seek to understand the processes involved. It will help us make comprehensive maps of the Universe's contents and offer us the opportunity to create new powerful cosmological tests. In our proposed work we will explore the possibilities afforded by taking grism and integral field spectra of large volumes of the Universe, using state-of-the-art cosmological hydrodynamic simulations. We will make use of analysis techniques developed for the Lyman-alpha forest, as well as forest data itself to test them. Our aim is to develop intensity mapping as a cosmological tool and show how it can be used to answer questions about the contents of the Universe and the formation of structure that are not accessible to traditional techniques. The project will involve both direct sampling of cosmic structure and cross-correlations of line intensity and objects (including galaxies, quasars and absorption lines). Emission (e.g., H-alpha emission) and absorption (Ly alpha forest) will be viewed as continuous fields. Using large volume cosmological simulations combined with population synthesis techniques we will make simulated spectral data sets. The techniques to analyse these cosmological data cubes will be developed. The expected outcomes are the following: (a) Predictions for the large-scale structure of strong emission lines (including Ha, Hb, Lya, OII, OIII) in the Universe using hydrodynamic simulations including the contribution from all components, from quasars to diffuse emssion. (b) Simulations of realistic examples of the use of IM as a cosmological probe, including Baryon Oscillations and weak gravitational lensing. (c) Tests of techniques to detection and quantify the low surface brightness Universe, leading to a complete census of the cosmic intensity in specific lines such as OII and Ha. (d) Development of techniques to extract redshifts for individual galaxies from low angular resolution IM spectroscopy. (e) Mock catalogs for SPHEREx, Euclid and WFIRST spectroscopy of diffuse emission, as well as for the Galex grism survey and tests of analysis techniques on data from the latter.

1 H MR spectroscopy in cervical carcinoma using external phase array body coil at 3.0 Tesla: Prediction of poor prognostic human papillomavirus genotypes.

PubMed

Lin, Gigin; Lai, Chyong-Huey; Tsai, Shang-Yueh; Lin, Yu-Chun; Huang, Yu-Ting; Wu, Ren-Chin; Yang, Lan-Yan; Lu, Hsin-Ying; Chao, Angel; Wang, Chiun-Chieh; Ng, Koon-Kwan; Ng, Shu-Hang; Chou, Hung-Hsueh; Yen, Tzu-Chen; Hung, Ji-Hong

2017-03-01

To assess the clinical value of proton ( 1 H) MR spectroscopy in cervical carcinomas, in the prediction of poor prognostic human papillomavirus (HPV) genotypes as well as persistent disease following concurrent chemoradiotherapy (CCRT). 1 H MR spectroscopy using external phase array coil was performed in 52 consecutive cervical cancer patients at 3 Tesla (T). Poor prognostic HPV genotypes (alpha-7 species or absence of HPV infection) and persistent cervical carcinoma after CCRT were recorded. Statistical significance was calculated with the Mann-Whitney two-sided nonparametric test and areas under the receiver operating characteristics curve (AUC) analysis. A 4.3-fold (P = 0.032) increased level of methyl resonance at 0.9 ppm was found in the poor prognostic HPV genotypes, mainly attributed to the presence of HPV18, with a sensitivity of 75%, a specificity of 81%, and an AUC of 0.76. Poor prognostic HPV genotypes were more frequently observed in patients with adeno-/adenosquamous carcinoma (Chi-square, P < 0.0001). In prediction of the four patients with persistent disease after CCRT, elevated methyl resonance demonstrated a sensitivity of 100%, a specificity of 74%, and an AUC of 0.82. 1 H MR spectroscopy at 3T can be used to depict the elevated lipid resonance levels in cervical carcinomas, as well as help to predict the poor prognostic HPV genotypes and persistent disease following CCRT. Further large studies with longer follow up times are warranted to validate our initial findings. 1 J. Magn. Reson. Imaging 2017;45:899-907. © 2016 International Society for Magnetic Resonance in Medicine.

Interfacial behavior of N-nitrosodiethylamine/bovine serum albumin complexes at the air-water and the chloroform-water interfaces by axisymmetric drop tensiometry.

PubMed

Juárez, J; Galaz, J G; Machi, L; Burboa, M; Gutiérrez-Millán, L E; Goycoolea, F M; Valdez, M A

2007-03-15

Interfacial properties of N-nitrosodiethylamine/bovine serum albumin (NDA/BSA) complexes were investigated at the air-water interface. The interfacial behavior at the chloroform-water interface of the interaction product of phospholipid 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC), dissolved in the chloroform phase, and NDA/BSA complex, in the aqueous phase, were also analyzed by using a drop tensiometer. The secondary structure changes of BSA with different NDA concentrations were monitored by circular dichroism spectroscopy at different pH and the NDA/BSA interaction was probed by fluorescence spectroscopy. Different NDA/BSA mixtures were prepared from 0, 7.5 x 10(-5), 2.2 x 10(-4), 3.7 x 10(-4), 5 x 10(-4), 1.6 x 10(-3), and 3.1 x 10(-3) M NDA solutions in order to afford 0, 300/1, 900/1, 1 500/1, 2 000/1, 6 000/1, and 12 500/1 NDA/BSA molar ratios, respectively, in the aqueous solutions. Increments of BSA alpha-helix contents were obtained up to the 2 000/1 NDA/BSA molar ratio, but at ratios beyond this value, the alpha-helix content practically disappeared. These BSA structure changes produced an increment of the surface pressure at the air-water interface, as the alpha-helix content increased with the concentration of NDA. On the contrary, when alpha-helix content decreased, the surface pressure also appeared lower than the one obtained with pure BSA solutions. The interaction of DPPC with NDA/BSA molecules at the chloroform-water interface produced also a small, but measurable, pressure increment with the addition of NDA molecules. Dynamic light scattering measurements of the molecular sizes of NDA/BSA complex at pH 4.6, 7.1, and 8.4 indicated that the size of extended BSA molecules at pH 4.6 increased in a greater proportion with the increment in NDA concentration than at the other studied pH values. Diffusion coefficients calculated from dynamic surface tension values, using a short-term solution of the general adsorption model of Ward and Tordai, also showed differences with pH and the NDA concentration. Both, the storage and loss dilatational elastic modulus were obtained at the air-water and at the chloroform-water interfaces. The interaction of NDA/BSA with DPPC at the chloroform-water produced a less rigid monolayer than the one obtained with pure DPPC (1 x 10(-5) M), indicating a significant penetration of NDA/BSA molecules at the interface. At short times and pH 4.6, the values of the storage elastic modulus were larger and more sensible to the NDA addition than the ones at pH 7.1 and 8.4, probably due to a gel-like network formation at the air-water interface.

Diagnostics and Degradation Investigations of Li-Ion Battery Electrodes using Single Nanowire Electrochemical Cells

NASA Astrophysics Data System (ADS)

Palapati, Naveen Kumar Reddy

Portable energy storage devices, which drive advanced technological devices, are improving the productivity and quality of our everyday lives. In order to meet the growing needs for energy storage in transportation applications, the current lithium-ion (Li-ion) battery technology requires new electrode materials with performance improvements in multiple aspects: (1) energy and power densities, (2) safety, and (3) performance lifetime. While a number of interesting nanomaterials have been synthesized in recent years with promising performance, accurate capabilities to probe the intrinsic performance of these high-performance materials within a battery environment are lacking. Most studies on electrode nanomaterials have so far used traditional, bulk-scale techniques such as cyclic voltammetry, electrochemical impedance spectroscopy, and Raman spectroscopy. These approaches give an ensemble-average estimation of the electrochemical properties of a battery electrode and does not provide a true indication of the performance that is intrinsic to its material system. Thus, new techniques are essential to understand the changes happening at a single particle level during the operation of a battery. The results from this thesis solve this need and study the electrical, mechanical and size changes that take place in a battery electrode at a single particle level. Single nanowire lithium cells are built by depositing nanowires in carefully designed device regions of a silicon chip using Dielectrophoresis (DEP). This work has demonstrated the assembly of several NW cathode materials like LiFePO 4, pristine and acid-leached alpha-MnO2, todorokite - MnO2, acid and nonacid-leached Na0.44MnO2. Within these materials, alpha-MnO2 was chosen as the model material system for electrochemical experiments. Electrochemical lithiation of pristine alpha-MnO 2 was performed inside a glove box. The volume, elasticity and conductivity changes were measured at each state-of-charge (SOC) to understand the performance of the material system. The NW size changes due to lithiation were measured using an Atomic Force Microscope (AFM) in the tapping mode. Electronic conductivity changes as a function of lithiation was also studied in the model alpha-MnO 2 NWs and was found to decrease substantially with lithium loading. In other measurements involving a comparison between the alpha and todorokite phases of this material system, it was observed that the rate capability of these materials is limited not by the electronic but, by the ionic conductivity. Mechanical degradation of a battery cathode represents an important failure mode, which results in an irreversible loss of capacity with cycling. To analyze and understand these degradation mechanisms, this thesis has tested the evolution of nanomechanical properties of a battery cathode. Specifically, contact-mode AFM measurements have focused on the SOC-dependent changes in the Young's modulus and fracture strength of an alpha-MnO2 NW electrode, which are critical parameters that determine its mechanical stability. These changes have been studied at the end of the first discharge step, 1 full electrochemical cycle, and 20 cycles. The observations show an increase in Young's modulus at low concentrations of lithium loading and this is attributed to the formation of new Li-O bonds within the tunnel-structured cathode. As the lithium loading increases further, the Young's modulus was observed to reduce and this is hypothesized to occur due to the distortions of the crystal at high lithium concentrations. The experimental-to-theoretical fracture strength ratio, which points to the defect density in the crystal at a given stoichiometry, was observed to reduce with electrochemical lithium insertion / cycling. This capability has demonstrated lithiation-dependent mechanical property measurements for the first time and represents an important contribution since degradation models, which are currently in use for materials at any size scale, always assume constant values regardless of the change in stoichiometry.

Europium III binding and the reorientation of magnetically aligned bicelles: insights from deuterium NMR spectroscopy.

PubMed Central

Crowell, K J; Macdonald, P M

2001-01-01

Solid-state deuterium ((2)H) NMR spectroscopy was used to study the reorientation of magnetically ordered bicelles in the presence of the paramagnetic lanthanide Eu(3+). Bicelles were composed of 1,2-dimyristoyl-sn-glycero-3-phosphocholine (DMPC) plus 1,2-dihexanoyl-sn-glycero-3-phosphocholine plus either the anionic lipid 1,2-dimyristoyl-sn-3-phosphoglycerol, or the cationic lipid 1,2-dimyristoyl-3-trimethyl ammonium propane. Alignment of the bicelles in the magnetic field produced (2)H NMR spectra consisting of a pair of quadrupole doublets, one from the alpha-deuterons and one from the beta-deuterons of DMPC-alpha,beta-d(4). Eu(3+) addition induced the appearance of a second set of quadrupole doublets, having approximately twice the quadrupolar splittings of the originals, and growing progressively in intensity with increasing Eu(3+), at the expense of the intensity of the originals. The new resonances were attributed to bicelles having a parallel alignment with respect to the magnetic field, as opposed to the perpendicular alignment preferred in the absence of Eu(3+). Therefore, the equilibrium degree and kinetics of reorientation could be evaluated from the (2)H NMR spectra. For more cationic initial surface charges, higher amounts of added Eu(3+) were required to induce a given degree of reorientation. However, the equilibrium degree of bicellar reorientation was found to depend solely on the amount of bound Eu(3+), regardless of the bicelle composition. The kinetics of reorientation were a function of lipid concentration. At high lipid concentration, a single fast rate of reorientation (minutes) described the approach to the equilibrium degree of orientation. At lower lipid concentrations, two rates processes were discernible: one fast (minutes) and one slow (hours). The data indicate, therefore, that bicelle reorientation is a phase transition made critical by bicelle-bicelle interactions. PMID:11423411

Structural and superionic properties of Ag+-rich ternary phases within the AgI-MI2 systems

NASA Astrophysics Data System (ADS)

Hull, S.; Keen, D. A.; Berastegui, P.

2002-12-01

The effects of temperature on the crystal structure and ionic conductivity of the compounds Ag2CdI4, Ag2ZnI4 and Ag3SnI5 have been investigated by powder diffraction and impedance spectroscopy techniques. varepsilon-Ag2CdI4 adopts a tetragonal crystal structure under ambient conditions and abrupt increases in the ionic conductivity are observed at 407(2), 447(3) and 532(4) K, consistent with the sequence of transitions varepsilon-Ag2CdI 4 rightarrow beta-Ag2CdI 4 + beta-AgI + CdI2 rightarrow alpha-AgI + CdI2 rightarrow alpha-Ag2CdI4. Hexagonal beta-Ag2CdI4 is metastable at ambient temperature. The ambient-temperature beta phase of Ag2ZnI4 is orthorhombic and the structures of beta-Ag2CdI4 and beta-Ag2ZnI4 can, respectively, be considered as ordered derivatives of the wurtzite (beta) and zincblende (gamma) phases of AgI. On heating Ag2ZnI4, there is a 12-fold increase in ionic conductivity at 481(1) K and a further eightfold increase at 542(3) K. These changes result from decomposition of beta-Ag2ZnI4 into alpha-AgI + ZnI2, followed by the appearance of superionic alpha-Ag2ZnI4 at the higher temperature. The hexagonal crystal structure of alpha-Ag2ZnI4 is a dynamically disordered counterpart to the beta modification. Ag3SnI5 is only stable at temperatures in excess of 370(3) K and possesses a relatively high ionic conductivity (sigma approx 0.19Omega-1 cm-1 at 420 K) due to dynamic disorder of the Ag+ and Sn2+ within a cubic close packed I- sublattice. The implications of these findings for the wider issue of high ionic conductivity in AgI-MI2 compounds is discussed, with reference to recently published studies of Ag4PbI6 and Ag2HgI4 and new data for the temperature dependence of the ionic conductivity of the latter compound.

Innovative diagnostics for ITER physics addressed in JET

NASA Astrophysics Data System (ADS)

Murari, A.; Edlington, T.; Alfier, A.; Alonso, A.; Andrew, Y.; Arnoux, G.; Beurskens, M.; Coad, P.; Crombe, C.; Gauthier, E.; Giroud, C.; Hidalgo, C.; Hong, S.; Kempenaars, M.; Kiptily, V.; Loarer, T.; Meigs, A.; Pasqualotto, R.; Tala, T.; Contributors, JET-EFDA

2008-12-01

In recent years, JET diagnostic capability has been significantly improved to widen the range of physical phenomena that can be studied and thus contribute to the understanding of some ITER relevant issues. The most significant results reported in this paper refer to the plasma wall interactions, the interplay between core and edge physics and fast particles. A synergy between new infrared cameras, visible cameras and spectroscopy diagnostics has allowed investigating a series of new aspects of the plasma wall interactions. The power loads on the plasma facing components of JET main chambers have been assessed at steady state and during transient events like ELMs and disruptions. Evidence of filaments in the edge region of the plasma has been collected with a new fast visible camera and high resolution Thomson scattering. The physics of detached plasmas and some new aspects of dust formation have also been devoted particular attention. The influence of the edge plasma on the core has been investigated with upgraded active spectroscopy, providing new information on momentum transport and the effects of impurity injection on ELMs and ITBs and their interdependence. Given the fact that JET is the only machine with a plasma volume big enough to confine the alphas, a coherent programme of diagnostic developments for the energetic particles has been undertaken. With upgraded γ-ray spectroscopy and a new scintillator probe, it is now possible to study both the redistribution and the losses of the fast particles in various plasma conditions.

Insulin amyloid fibrillation studied by terahertz spectroscopy and other biophysical methods

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

Liu, Rui; He, Mingxia; Su, Rongxin, E-mail: surx@tju.edu.cn

2010-01-01

Assembly and fibrillation of amyloid proteins are believed to play a key role in the etiology of various human diseases, including Alzheimer's, Parkinson's, Huntington's and type II diabetes. Insights into conformational changes and formation processes during amyloid fibrillation are essential for the clinical diagnosis and drug discovery. To study the changes in secondary, tertiary, quaternary structures, and the alteration in the collective vibrational mode density of states during the amyloid fibrillation, bovine insulin in 20% acetic acid was incubated at 60 {sup o}C, and its multi-level structures were followed by various biophysical techniques, including circular dichroism (CD), thioflavin T fluorescencemore » (ThT), dynamic light scattering (DLS), electron microscopy, and terahertz (THz) absorption spectroscopy. The experimental data demonstrated a transformation of {alpha}-helix into {beta}-sheet starting at 26 h. This was followed by the aggregation of insulin, as shown by ThT binding, with a transition midpoint at 41 h, and by the bulk formation of mature aggregates after about 71 h. THz is a quick and non-invasive technique, which has the advantage of allowing the study of the conformational state of biomolecules and tissues. We first applied THz spectroscopy to study the amyloid fibrillation. At the terahertz frequency range of 0.2-2.0 THz, there was an apparent increase in both the absorbance and refractive index in THz spectra. Thus, THz is expected to provide a new way of looking into amyloid fibrillation.« less

INEL BNCT Research Program annual report, 1992

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

Venhuizen, J.R.

1993-05-01

This report is a summary of the progress and research produced for the Idaho National Engineering Laboratory Boron Neutron Capture Therapy (BNCT) Research Program for calendar year 1992. Contributions from all the principal investigators about their individual projects are included, specifically, chemistry (pituitary tumor targeting compounds, boron drug development including liposomes, lipoproteins, and carboranylalanine derivatives), pharmacology (murine screenings, toxicity testing, inductively coupled plasma-atomic emission spectroscopy (ICP-AES) analysis of biological samples), physics (radiation dosimetry software, neutron beam and filter design, neutron beam measurement dosimetry), and radiation biology (small and large animal models tissue studies and efficacy studies). Information on the potentialmore » toxicity of borocaptate sodium and boronophenylalanine is presented, results of 21 spontaneous-tumor-bearing dogs that have been treated with BNCT at the Brookhaven National Laboratory (BNL) Medical Research Reactor (BMRR) are discussed, and predictions for an epithermal-neutron beam at the Georgia Tech Research Reactor (GTRR) are shown. Cellular-level boron detection and localization by secondary ion mass spectrometry, sputter-initiated resonance ionization spectroscopy, low atomization resonance ionization spectroscopy, and alpha track are presented. Boron detection by ICP-AES is discussed in detail. Several boron carrying drugs exhibiting good tumor uptake are described. Significant progress in the potential of treating pituitary tumors with BNCT is presented. Measurement of the epithermal-neutron flux at BNL and comparison to predictions are shown. Calculations comparing the GTRR and BMRR epithermal-neutron beams are also presented. Individual progress reports described herein are separately abstracted and indexed for the database.« less

Hobby-Eberly Telescope Optical Transmission Spectroscopy of the Hot Jupiter WASP-12b

NASA Astrophysics Data System (ADS)

Jensen, Adam G.; Redfield, Seth; Cauley, Paul W.; Endl, Michael; Cochran, William D.

2017-01-01

Transmission spectroscopy of exoplanetary atmospheres is an extremely useful tool that can be used for understanding exoplanetary composition as well as potentially revealing star-planet interactions from radiation, magnetic fields, and more. The hot Jupiter planet WASP-12b is interesting in that it is very close to its star (0.02 AU), has a large calculated scale height, has had water and metals detected in its atmosphere, and has had varying observational and theoretical constraints placed on its C/O ratio. Here we present a preliminary analysis of the optical transmission spectrum of WASP-12b taken with the Hobby-Eberly Telescope (HET). Our data covers the optical wavelength range from approximately 4800 to 6850 Angstroms. Most notably this includes two Balmer lines of hydrogen (H-alpha at 6563 Angstroms and H-beta at 4861 Angstroms) and the sodium D doublet (at 5890 and 5896 Angstroms). Due to the relative faintness of the system's central star and different instrumental settings, the analysis involves several challenges that are not present in previous transmission spectroscopy observations with the HET.This work is supported by NASA Exoplanet Research Program grant 14-XRP14_2-0090 to the University of Nebraska-Kearney. The Hobby-Eberly Telescope is a joint project of the University of Texas at Austin, the Pennsylvania State University, Stanford University, Ludwig-Maximilians-Universitat Munchen, and Georg-August-Universitat Gottingen and is named in honor of its principal benefactors, William P. Hobby and Robert E. Eberly.

High-Resolution Spectroscopy of some very Active Southern Stars

NASA Technical Reports Server (NTRS)

Soderblom, David R.; King, Jeremy R.; Henry, Todd J.

1998-01-01

We have obtained high-resolution echelle spectra of 18 solar-type stars that an earlier survey showed to have very high levels of Ca II H and K emission. Most of these stars belong to close binary systems, but five remain as probable single stars or well-separated binaries that are younger than the Pleiades on the basis of their lithium abundances and H.alpha emission. Three of these probable single stars also lie more than 1 mag above the main sequence in a color-magnitude diagram, and appear to have ages of 10 to 15 Myr. Two of them, HD 202917 and HD 222259, also appear to have a kinematic association with the pre-main-sequence multiple system HD 98800.

Nuclear Bragg scattering studies in [sup 57]Fe with synchrotron radiation

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

Haustein, P.E.

1993-01-01

Studies of nuclear Bragg x-ray scattering of synchrotron radiation, using crystals of [alpha]-[sup 57]Fe[sub 2]O[sub 3], have been carried out at the NSLS at Brookhaven National Laboratory and at the Cornell University CHESS facility. These studies have demonstrated that nuclear resonance states can be used to produce filtered x-ray beams which have extremely narrow bandwidth, small angular divergence and unique polarization and temporal properties. this combination of characteristics, unobtainable with radioactive sources, makes synchrotron-based Moessbauer spectroscopy feasible and is an important complement to existing methods. A review of the experimental methodology is presented. As well as come suggestions for fullermore » exploitation of this new technique.« less

Nuclear Bragg scattering studies in {sup 57}Fe with synchrotron radiation

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

Haustein, P.E.

1993-03-01

Studies of nuclear Bragg x-ray scattering of synchrotron radiation, using crystals of {alpha}-{sup 57}Fe{sub 2}O{sub 3}, have been carried out at the NSLS at Brookhaven National Laboratory and at the Cornell University CHESS facility. These studies have demonstrated that nuclear resonance states can be used to produce filtered x-ray beams which have extremely narrow bandwidth, small angular divergence and unique polarization and temporal properties. this combination of characteristics, unobtainable with radioactive sources, makes synchrotron-based Moessbauer spectroscopy feasible and is an important complement to existing methods. A review of the experimental methodology is presented. As well as come suggestions for fullermore » exploitation of this new technique.« less

MR Persei - A new rotating, spotted flare star

NASA Technical Reports Server (NTRS)

Honeycutt, R. K.; Turner, G. W.; Vesper, D. N.; Schlegel, E. M.

1992-01-01

Spectroscopy and photometry are used to show that MR Persei, an object originally classified as a dwarf nova, is in fact a flare star. The automated CCD photometry consists of sequences of exposures within a single night as well as long-term photometry over a five-month interval. One sequence shows a 30-min flare, accompanied by post-flare 'dips'. A 0.2 mag variation with a period of about one-half day is also seen in this sequence. The long-term photometry is used to refine the period to 0.45483 d, which we attribute to the rotation of a spotted star. Evidence for membership of MR Per in the young Alpha Per cluster is considered, and found to be inconclusive.

Analysis of Fusarium mycotoxins by gas chromatography--Fourier transform infrared spectroscopy.

PubMed

Young, J C; Games, D E

1994-03-11

The Fourier transform infrared (FTIR) spectra of selected Fusarium mycotoxins of various structure types were determined. Absorptions were observed for the following functionalities: hydroxyl at 3625-65 cm-1 and 3482 cm-1, the latter being associated with a 7 alpha-hydroxyl adjacent to an 8-carbonyl in keto trichothecenes; carbonyl at 1760-6 cm-1 for 5-membered rings and at 1695-8 cm-1 for those conjugated to a single C = C in a six-membered ring; acetate carbonyl at 1765 cm-1 and acetate C-O at 1220-9 cm-1; and C = C at 1680 cm-1. Gas chromatography combined with FTIR and mass spectrometry was applied to the identification of some mycotoxins in a F. roseum liquid culture extract.

Host-guest complex formation in cyclotrikis-(1-->6).

PubMed

Cescutti, P; Utille, J P; Rizzo, R

2000-11-17

The possibility that cyclotrikis-(1-->6)-[alpha-D-glucopyranosyl-(1-->4)-beta-D-glucopyranosyl] (CGM6) forms inclusion complexes, like cycloamyloses (cyclodextrins), was investigated by means of electrospray mass spectrometry and fluorescence spectroscopy. The complexing ability of both 1-anilinonaphthalene-8-sulfonate (ANS) and 2-p-toluidinylnaphthalene-6-sulfonate (TNS), which were already used with cyclodextrins, was investigated. The former showed very little or no tendency to be complexed by CGM6, while the latter produced detectable adducts with CGM6. Fixed 90 degree angle light scattering experiments supported the findings obtained by molecular modelling calculations, which indicated a polar character for the CGM6 internal cavity. CGM6-TNS complexes were probably formed throughout interaction of the polar regions of the two molecules.

High-resolution nuclear magnetic resonance studies of proteins.

PubMed

Jonas, Jiri

2002-03-25

The combination of advanced high-resolution nuclear magnetic resonance (NMR) techniques with high-pressure capability represents a powerful experimental tool in studies of protein folding. This review is organized as follows: after a general introduction of high-pressure, high-resolution NMR spectroscopy of proteins, the experimental part deals with instrumentation. The main section of the review is devoted to NMR studies of reversible pressure unfolding of proteins with special emphasis on pressure-assisted cold denaturation and the detection of folding intermediates. Recent studies investigating local perturbations in proteins and the experiments following the effects of point mutations on pressure stability of proteins are also discussed. Ribonuclease A, lysozyme, ubiquitin, apomyoglobin, alpha-lactalbumin and troponin C were the model proteins investigated.

Gas Analysis Using Auroral Spectroscopy.

NASA Astrophysics Data System (ADS)

Alozie, M.; Thomas, G.; Medillin, M.

2017-12-01

As part of the Undergraduate Student Instrumentation Project at the University of Houston, an Auroral spectroscope was designed and built. This visible light spectroscope was constructed out of carbon fiber, aluminum, and 3D printed parts. The spectroscope was designed to calculate the wavelengths of the spectral lines and analyze the emitted light spectrum of the gases. The spectroscope contains a primary parabolic 6" mirror and a smaller secondary 2.46" mirror. The light captured through these mirrors will be guided to an optical train that consist of five lenses (1" in diameter and focal length), a slit, and a visible transmission grating. The light will then be led to a Sony Alpha A6000 camera to take images of the spectral lines.

Photoelectron spectroscopy and electronic structure of ScO{sub n}{sup {minus}}(n = 1--4) and YO{sub n}{sup {minus}}(n = 1--5): Strong electron correlation effects in ScO{sup {minus}} and YO{sup {minus}}

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

Wu, H.; Wang, L.S.

A photoelectron spectroscopic study of ScO{sub n}{sup {minus}} (n = 1--4) and YO{sub n}{sup {minus}} (n = 1--5) was carried out at three photon energies: 532, 355, and 266 nm. Vibrationally resolved photoelectron spectra were obtained for ScO{sup {minus}} and YO{sup {minus}}. The electron affinities of both ScO and YO were measured to be identical (1.35 eV) within the experimental accuracy ({+-}0.02 eV). Three low-lying excited states were observed for the monoxides, {Alpha}{prime}{sup 2}{Delta}, {Alpha}{sup 2}{Pi}, and {Beta}{sup 2}{Sigma}{sup +}. The latter two excited states resulted from two-electron detachment, suggesting unusually strong electron correlation (configuration interaction) effects in the groundmore » state of the anions. The excitation energies of the low-lying states were also found to be similar for the two monoxides except that YO has a smaller vibrational frequency and larger spin-orbit splitting. The {Alpha}{prime}{sup 2}{Delta} states of both ScO and YO show very strong photon energy-dependent detachment cross sections. Four similar photoelectron features were observed for the dioxides with those of YO{sub 2}{sup {minus}} having lower binding energies. A second isomer due to an O{sub 2} complex was also observed for Sc and Y. Broad and featureless spectra were observed for the higher oxides. At least two isomers were present for the higher oxides, one with low and one with high binding energies.« less

Beacons in the dark: using the most distant galaxies to probe cosmic reionization

NASA Astrophysics Data System (ADS)

De Barros, Stephane

2017-08-01

One of the major unresolved problems in modern cosmology is when and how the universe was ionized. The consensus scenario is that ultra-faint, low-mass galaxies contributed most to the UV background at high-redshift and that reionization was an inhomogeneous process, with ionized bubbles created first around galaxy overdensities. The very surprising discovery of Ly-alpha emission lines around a large fraction of the most luminous galaxies at z=7.4-8.7, when we expect the universe to be highly neutral, could thus be explained by the fact that they lie in large HII bubbles which were ionized thanks to yet undetected fainter neighbors. Theoretical models indeed predict a boost of up to 6x larger galaxy counts around the brightest sources compared to the general field, when probing down to luminosities as faint as 0.1L_UV of the central source. Here we propose a direct test of these models by searching for fainter neighbors around three bright z>7.4 galaxies emitting Ly-alpha, including two sources that lie only 9 Mpc from each other and could share the same ionized bubble, as well as the most distant confirmed Ly-alpha emitter EGSY-8p7 at z=8.68. Given the expected overdensities, we have the opportunity to detect 20 (and up to 50) new z 7-9 galaxies with only a modest investment of HST time. These observations are thus maximally efficient at providing a large number of precious high-redshift targets for early JWST spectroscopy to directly study the galaxies that are in the process of ionizing the universe. Our imaging will further enhance the legacy of the CANDELS/EGS field, and we will make the reduced data available to the community immediately for JWST follow-up.

Effect of autoclaving on the surfaces of TiN -coated and conventional nickel-titanium rotary instruments.

PubMed

Spagnuolo, G; Ametrano, G; D'Antò, V; Rengo, C; Simeone, M; Riccitiello, F; Amato, M

2012-12-01

To evaluate the effects of repeated autoclave sterilization cycles on surface topography of conventional nickel-titanium ( NiTi ) and titanium nitride ( TiN )-coated rotary instruments. A total of 60 NiTi rotary instruments, 30 ProTaper (Dentsply Maillefer) and 30 TiN -coated AlphaKite (Komet/Gebr. Brasseler), were analysed. Instruments were evaluated in the as-received condition and after 1, 5 and 10 sterilization cycles. After sterilization, the samples were observed using scanning electron microscope (SEM), and surface chemical analysis was performed on each instrument with energy dispersive X-ray spectroscopy (EDS). Moreover, the samples were analysed by atomic force microscopy (AFM), and roughness average (Ra) and the root mean square value (RMS) of the scanned surface profiles were recorded. Data were analysed by means of anova followed by Tukey's test. Scanning electron microscope observations revealed the presence of pitting and deep milling marks in all instruments. EDS analysis confirmed that both types of instruments were composed mainly of nickel and titanium, whilst AlphaKite had additional nitride. After multiple autoclave sterilization cycles, SEM examinations revealed an increase in surface alterations, and EDS values indicated changes in chemical surface composition in all instruments. Ra and RMS values of ProTaper significantly increased after 5 (P = 0.006) and 10 cycles (P = 0.002) with respect to the as-received instruments, whilst AlphaKite showed significant differences compared with the controls after 10 cycles (P = 0.03). Multiple autoclave sterilization cycles modified the surface topography and chemical composition of conventional and TiN -coated NiTi rotary instruments. © 2012 International Endodontic Journal.

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

Devereux, Nick, E-mail: devereux@erau.edu

Dual epoch spectroscopy of the lenticular galaxy, NGC 4203, obtained with the Hubble Space Telescope has revealed that the double-peaked component of the broad H{alpha} emission line is time variable, increasing by a factor of 2.2 in brightness between 1999 and 2010. Modeling the gas distribution responsible for the double-peaked profiles indicates that a ring is a more appropriate description than a disk and most likely represents the contrail of a red supergiant star that is being tidally disrupted at a distance of {approx}1500 AU from the central black hole. There is also a bright core of broad H{alpha} linemore » emission that is not time variable and identified with a large-scale inflow from an outer radius of {approx}1 pc. If the gas number density is {>=}10{sup 6} cm{sup -3}, as suggested by the absence of similarly broad [O I] and [O III] emission lines, then the steady state inflow rate is {approx} 2 Multiplication-Sign 10{sup -2} M{sub Sun} yr{sup -1}, which exceeds the inflow requirement to explain the X-ray luminosity in terms of radiatively inefficient accretion by a factor of {approx}6. The central active galactic nucleus (AGN) is unable to sustain ionization of the broad-line region; the discrepancy is particularly acute in 2010 when the broad H{alpha} emission line is dominated by the contrail of the infalling supergiant star. However, ram pressure shock ionization produced by the interaction of the infalling supergiant with the ambient interstellar medium may help alleviate the ionizing deficit by generating a mechanical source of ionization supplementing the photoionization provided by the AGN.« less

TIDAL TAILS OF MINOR MERGERS. II. COMPARING STAR FORMATION IN THE TIDAL TAILS OF NGC 2782

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

Knierman, Karen A.; Scowen, Paul; Veach, Todd

2013-09-10

The peculiar spiral NGC 2782 is the result of a minor merger with a mass ratio {approx}4: 1 occurring {approx}200 Myr ago. This merger produced a molecular and H I-rich, optically bright eastern tail and an H I-rich, optically faint western tail. Non-detection of CO in the western tail by Braine et al. suggested that star formation had not yet begun. However, deep UBVR and H{alpha} narrowband images show evidence of recent star formation in the western tail, though it lacks massive star clusters and cluster complexes. Using Herschel PACS spectroscopy, we discover 158 {mu}m [C II] emission at themore » location of the three most luminous H{alpha} sources in the eastern tail, but not at the location of the even brighter H{alpha} source in the western tail. The western tail is found to have a normal star formation efficiency (SFE), but the eastern tail has a low SFE. The lack of CO and [C II] emission suggests that the western tail H II region may have a low carbon abundance and be undergoing its first star formation. The western tail is more efficient at forming stars, but lacks massive clusters. We propose that the low SFE in the eastern tail may be due to its formation as a splash region where gas heating is important even though it has sufficient molecular and neutral gas to make massive star clusters. The western tail, which has lower gas surface density and does not form high-mass star clusters, is a tidally formed region where gravitational compression likely enhances star formation.« less

Physical Conditions of the Interstellar Medium in Star-forming Galaxies at z1.5

NASA Technical Reports Server (NTRS)

Hayashi, Masao; Ly, Chun; Shimasaku, Kazuhiro; Motohara, Kentaro; Malkan, Matthew A.; Nagao, Tohru; Kashikawa, Nobunari; Goto, Ryosuke; Naito, Yoshiaki

2015-01-01

We present results from Subaru/FMOS near-infrared (NIR) spectroscopy of 118 star-forming galaxies at z approximately equal to 1.5 in the Subaru Deep Field. These galaxies are selected as [O II] lambda 3727 emitters at z approximately equal to 1.47 and 1.62 from narrow-band imaging. We detect H alpha emission line in 115 galaxies, [O III] lambda 5007 emission line in 45 galaxies, and H Beta, [N II] lambda 6584, and [S II]lambda lambda 6716, 6731 in 13, 16, and 6 galaxies, respectively. Including the [O II] emission line, we use the six strong nebular emission lines in the individual and composite rest-frame optical spectra to investigate physical conditions of the interstellar medium in star-forming galaxies at z approximately equal to 1.5. We find a tight correlation between H alpha and [O II], which suggests that [O II] can be a good star formation rate (SFR) indicator for galaxies at z approximately equal to 1.5. The line ratios of H alpha / [O II] are consistent with those of local galaxies. We also find that [O II] emitters have strong [O III] emission lines. The [O III]/[O II] ratios are larger than normal star-forming galaxies in the local Universe, suggesting a higher ionization parameter. Less massive galaxies have larger [O III]/[O II] ratios. With evidence that the electron density is consistent with local galaxies, the high ionization of galaxies at high redshifts may be attributed to a harder radiation field by a young stellar population and/or an increase in the number of ionizing photons from each massive star.

Anger induced by interferon-alpha is moderated by ratio of arachidonic acid to omega-3 fatty acids.

PubMed

Lotrich, Francis E; Sears, Barry; McNamara, Robert K

2013-11-01

Anger worsens in some patients during interferon-alpha (IFN-α) therapy. Elevated anger has also been associated with lower long-chain omega-3 (LCn-3) fatty acid levels. We examined whether fatty acids could influence vulnerability to anger during IFN-α exposure. Plasma arachidonic acid (AA), eicosapentaenoic acid (EPA), and docosahexaenoic acid (DHA) levels were determined prior to IFN-α therapy by mass spectroscopy. Repeated-measure analyses examined the relationship between AA/EPA+DHA and the subsequent development of labile anger and irritability in 82 subjects who prospectively completed the Anger, Irritability, and Assault Questionnaire (AIAQ) during the first eight weeks of IFN-α therapy. Prior to IFN-α therapy, AA/EPA+DHA did not correlate with either labile anger or irritability. Pre-treatment AA/EPA+DHA did correlate with the subsequent maximal increase in labile anger during IFN-α therapy (r=0.33; p=0.005). Over time, labile anger increased more in subjects with above median AA/EPA+DHA ratios (p<0.05). Of the 17 subjects ultimately requiring psychiatric intervention for anger, 14/17 had above-median AA/EPA+DHA ratios (p=0.009). There was also an interaction with the tumor necrosis factor-alpha (TNF-α) promoter polymorphism (A-308G), such that only those with both elevated AA/EPA+DHA and the A allele had increased labile anger (p=0.001). In an additional 18 subjects, we conversely observed that selective serotonin reuptake inhibitor treatment was associated with increased irritability during IFN-α therapy. LCn-3 fatty acid status may influence anger development during exposure to elevated inflammatory cytokines, and may interact with genetic risk for increased brain TNF-α. LCn-3 supplements may be one strategy for minimizing this adverse side effect of IFN-α. © 2013.

Relatedness of the O-polysaccharide structures of Escherichia coli O123 and Salmonella enterica O58, both containing 4,6-dideoxy-4-{N-[(S)-3-hydroxybutanoyl]-D-alanyl}amino-D-glucose; revision of the E. coli O123 O-polysaccharide structure.

PubMed

Perepelov, Andrei V; Liu, Bin; Shevelev, Sergei D; Senchenkova, Sof'ya N; Shashkov, Alexander S; Feng, Lu; Knirel, Yuriy A; Wang, Lei

2010-04-19

O-Polysaccharides were isolated by mild acid degradation of the lipopolysaccharides of Escherichia coli O123 and Salmonella enterica O58 and studied by chemical methods and 2D (1)H and (13)C NMR spectroscopy, including experiments in a H(2)O/D(2)O mixture, which enabled observation of correlations for nitrogen-linked protons. The following structure of the O-polysaccharide of E. coli O123 was established: -->3)-beta-D-Quip4NAlaHb-(1-->6)-alpha-D-GlcpNAc-(1-->3)-alpha-L-QuipNAc-(1-->3)-alpha-D-Glcp (6)(approx. 30% OAc)NAc-(1--> where L-QuipNAc stands for 2-acetamido-2,6-dideoxy-L-glucose and D-Qui4NAlaHb for 4-{N-[(S)-3-hydroxybutanoyl]-D-alanyl}amino-4,6-dideoxy-D-glucose. The latter was isolated as an ethylene glycol glycoside by three sequential Smith degradations of the O-deacetylated O-polysaccharide. The structure established in this work is at variance with the E. coli O123-polysaccharide structure reported earlier [Clark, C. G.; Kropinski, A. M.; Parolis, H.; Grant, C. C.; Trout-Yakel, K. M.; Franklin, K.; Ng, L. K.; Paramonov, N. A.; Parolis, L. A.; Rahn, K.; Tabor, H. J. Med. Microbiol.2009, 58, 884-894]. In accordance with the genetic data, the O-polysaccharide of S. enterica O58 has the same structure, except for it lacks the O-acetylation. Copyright (c) 2010 Elsevier Ltd. All rights reserved.

A Magnified View of the Kinematics and Morphology of RCSGA 032727-132609: Zooming in on a Merger at z = 1.7

NASA Technical Reports Server (NTRS)

Wuyts, Eva; Rigby, Jane R.; Gladders, Michael D.; Sharon, Keren

2014-01-01

We present a detailed analysis of multi-wavelength Hubble Space Telescope/Wide Field Camera 3 (WFC3) imaging and Keck/OSIRIS near-infrared adaptive optics-assisted integral field spectroscopy for a highly magnified lensed galaxy at z = 1.70. This young starburst is representative of ultraviolet-selected star-forming galaxies (SFGs) at z approx. 2 and contains multiple individual star-forming regions. Due to the lensing magnification, we can resolve spatial scales down to 100 pc in the source plane of the galaxy. The velocity field shows disturbed kinematics suggestive of an ongoing interaction and there is a clear signature of a tidal tail. We constrain the age, reddening, star formation rate, and stellar mass of the star-forming clumps from spectral energy distribution (SED) modeling of the WFC3 photometry and measure their H(alpha) luminosity, metallicity, and outflow properties from the OSIRIS data.With strong star-formation-driven outflows in four clumps, RCSGA0327 is the first high-redshift SFG at stellar mass <10(exp 10) Stellar Mass with spatially resolved stellar winds. We compare the H(alpha) luminosities, sizes, and dispersions of the star-forming regions with other high-z clumps as well as local giant H(II) regions and find no evidence for increased clump star formation surface densities in interacting systems, unlike in the local universe. Spatially resolved SED modeling unveils an established stellar population at the location of the largest clump and a second mass concentration near the edge of the system that is not detected in H(alpha) emission. This suggests a picture of an equal-mass mixed major merger, which has not triggered a new burst of star formation or caused a tidal tail in the gas-poor component.

Alpha Alumina Nanoparticle Conjugation to Cysteine Peptidase A and B: An Efficient Method for Autophagy Induction

PubMed Central

Beyzay, Fatemeh; Zavaran Hosseini, Ahmad; Soudi, Sara

2017-01-01

Background: Autophagy as a cellular pathway facilitates several immune responses against infection. It also eliminates invading pathogens through transferring content between the cytosol and the lysosomal vesicles and contributes to the cross-presentation of exogenous antigens to T lymphocytes via MHC class I pathway. Autophagy induction is one of the main targets for new drugs and future vaccine formulations. Nanoparticles are one of the candidates for autophagy induction. Cysteine Peptidase A (CPA) and Cysteine Peptidase B (CPB) are two members of papain family (Clan CA, family C1) enzyme that have been considered as a virulence factor of Leishmania (L.) major, making them suitable vaccine candidates. In this research, Leishmania major cysteine peptidase A and B (CPA and CPB) conjugation to alpha alumina nanoparticle was the main focus and their entrance efficacy to macrophages was assessed. Methods: For this purpose, CPA and CPB genes were cloned in expression vectors. Related proteins were extracted from transformed Escherichia coli (E. coli) and purified using Ni affinity column. Alpha alumina nanoparticles were conjugated to CPA/CPB proteins using Aldehyde/Hydrazine Reaction. Autophagy induction in macrophages was assessed using acridine orange staining. Results: CPA/CPB protein loading to nanoparticles was confirmed by Fourier Transform Infrared Spectroscopy. α-alumina conjugated CPA/CPB antigen uptake by macrophages at different concentrations was confirmed using fluorescence microscope and flowcytometry. Highly efficient CPA/CPB protein loading to α-alumina nanoparticles and rapid internalization to macrophages introduced these nanocarriers as a delivery tool. Acridine orange staining demonstrated higher autophagy induction in CPA/CPB protein conjugated with α-alumina nanoparticles. Conclusion: α-alumina nanoparticles may be a promising adjuvant in the development of therapeutic leishmania vaccines through antigen delivery to intracellular compartments, induction of autophagy and cross presentation to CD8 lymphocytes. PMID:28496946

Structural elucidation of the Brucella melitensis M antigen by high-resolution NMR at 500 MHz

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

Bundle, D.R.; Cherwonogrodzky, J.W.; Perry, M.B.

The Brucella M antigen from the species type strain Brucella melitensis 16M has been identified as a component of the cell wall lipopolysaccharide (LPS). O polysaccharide liberated from this LPS by mild acid hydrolysis exhibited M activity in serological tests and was shown to be a homopolymer of 4-formamido-4,6-dideoxy-..cap alpha..-D-mannopyranosyl residues arranged in an oligosaccharide repeating unit as judged by sodium dodecyl sulfate-polyacrylamide gel electrophoresis of the native lipopolysaccharide. Structural analysis of the O polysaccharide by NMR methods was difficult due to apparent microheterogeneity of the repeating unit, which was in fact caused by the presence of rotational isomers ofmore » the N-formyl moiety. This problem was resolved by chemical modification of the polysaccharide to its amino and N-acetyl derivatives, the 500-MHz /sup 1/H and 125-MHz /sup 13/C NMR spectra of which could be analyzed in terms of a unique structure through application of pH-dependent ..beta..-shifts and two-dimensional techniques that included COSY, relayed COSY, and NOESY experiments together with heteronuclear C/H shift correlation spectroscopy. On the basis of these experiments and supported by methylation and periodate oxidation data, the structure of the M polysaccharide was determined as a linear polymer of unbranched pentasaccharide repeating units consisting of four 1,2-linked and one 1,3-lined 4,6-dideoxy-4-formamido-..cap alpha..-D-mannopyranosyl residues. The marked structural similarity of the M antigen and the A antigen, which is known to be a 1,2-linked homopolysaccharide of 4,6-dideoxy-4-formamido-..cap alpha..-D-mannopyranosyl units, accounts for cross-serological reactions of the two and the long-standing confusion surrounding the nature of their antigenic determinants.« less

Atomic Scale Structure-Chemistry Relationships at Oxide Catalyst Surfaces and Interfaces

NASA Astrophysics Data System (ADS)

McBriarty, Martin E.

Oxide catalysts are integral to chemical production, fuel refining, and the removal of environmental pollutants. However, the atomic-scale phenomena which lead to the useful reactive properties of catalyst materials are not sufficiently understood. In this work, the tools of surface and interface science and electronic structure theory are applied to investigate the structure and chemical properties of catalytically active particles and ultrathin films supported on oxide single crystals. These studies focus on structure-property relationships in vanadium oxide, tungsten oxide, and mixed V-W oxides on the surfaces of alpha-Al2O3 and alpha-Fe2O 3 (0001)-oriented single crystal substrates, two materials with nearly identical crystal structures but drastically different chemical properties. In situ synchrotron X-ray standing wave (XSW) measurements are sensitive to changes in the atomic-scale geometry of single crystal model catalyst surfaces through chemical reaction cycles, while X-ray photoelectron spectroscopy (XPS) reveals corresponding chemical changes. Experimental results agree with theoretical calculations of surface structures, allowing for detailed electronic structure investigations and predictions of surface chemical phenomena. The surface configurations and oxidation states of V and W are found to depend on the coverage of each, and reversible structural shifts accompany chemical state changes through reduction-oxidation cycles. Substrate-dependent effects suggest how the choice of oxide support material may affect catalytic behavior. Additionally, the structure and chemistry of W deposited on alpha-Fe 2O3 nanopowders is studied using X-ray absorption fine structure (XAFS) measurements in an attempt to bridge single crystal surface studies with real catalysts. These investigations of catalytically active material surfaces can inform the rational design of new catalysts for more efficient and sustainable chemistry.

Effect of double-tailed surfactant architecture on the conformation, self-assembly, and processing in polypeptide-surfactant complexes.

PubMed

Junnila, Susanna; Hanski, Sirkku; Oakley, Richard J; Nummelin, Sami; Ruokolainen, Janne; Faul, Charl F J; Ikkala, Olli

2009-10-12

This work describes the solid-state conformational and structural properties of self-assembled polypeptide-surfactant complexes with double-tailed surfactants. Poly(L-lysine) was complexed with three dialkyl esters of phosphoric acid (i.e., phosphodiester surfactants), where the surfactant tail branching and length was varied to tune the supramolecular architecture in a facile way. After complexation with the branched surfactant bis(2-ethylhexyl) phosphate in an aqueous solution, the polypeptide chains adopted an alpha-helical conformation. These rod-like helices self-assembled into cylindrical phases with the amorphous alkyl tails pointing outward. In complexes with dioctyl phosphate and didodecyl phosphate, which have two linear n-octyl or n-dodecyl tails, respectively, the polypeptide formed antiparallel beta-sheets separated by alkyl layers, resulting in well-ordered lamellar self-assemblies. By heating, it was possible to trigger a partial opening of the beta-sheets and disruption of the lamellar phase. After repeated heating/cooling, all of these complexes also showed a glass transition between 37 and 50 degrees C. Organic solvent treatment and plasticization by overstoichiometric amount of surfactant led to structure modification in poly(L-lysine)-dioctyl phosphate complexes, PLL(diC8)(x) (x = 1.0-3.0). Here, the alpha-helical PLL is surrounded by the surfactants and these bottle-brush-like chains self-assemble in a hexagonal cylindrical morphology. As x is increased, the materials are clearly plasticized and the degree of ordering is improved: The stiff alpha-helical backbones in a softened surfactant matrix give rise to thermotropic liquid-crystalline phases. The complexes were examined by Fourier transform infrared spectroscopy, small- and wide-angle X-ray scattering, transmission electron microscopy, differential scanning calorimetry, polarized optical microscopy, and circular dichroism.

Dwarf Galaxies: Laboratories for Nucleosynthesis and Chemical Evolution

NASA Astrophysics Data System (ADS)

Kirby, Evan N.

2018-06-01

The dwarf galaxies in the Local Group are excellent laboratories for studying the creation of the elements (nucleosynthesis) and the build-up of those elements over time (chemical evolution). The galaxies' proximity permits spectroscopy of individual stars, from which detailed elemental abundances can be measured. Their small sizes and, in some cases, short star formation lifetimes imprinted chemical histories that are easy to interpret relative to larger, more complex galaxies, like the Milky Way.I will briefly review some techniques for measuring elemental abundances from medium-resolution spectroscopy of individual stars. I will show how the metallicity distributions of dwarf galaxies reflect their gas content at the time they were forming stars. Then, I will show how the ratio of alpha elements (for example, magnesium) to iron reveals the star formation history. Finally, I will use certain elements to tease out details of nucleosynthetic events. For example, low manganese and cobalt abundances indicate that the typical Type Ia supernova in dwarf galaxies was a low-density white dwarf, and the evolution of barium suggests that neutron star mergers were most likely responsible for the majority of neutron-capture elements in smaller dwarf galaxies.

Interaction of the replication terminator protein of Bacillus subtilis with DNA probed by NMR spectroscopy

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

Hastings, Adam F.; Otting, Gottfried; Folmer, Rutger H.A.

2005-09-23

Termination of DNA replication in Bacillus subtilis involves the polar arrest of replication forks by a specific complex formed between the dimeric 29 kDa replication terminator protein (RTP) and DNA terminator sites. We have used NMR spectroscopy to probe the changes in {sup 1}H-{sup 15}N correlation spectra of a {sup 15}N-labelled RTP.C110S mutant upon the addition of a 21 base pair symmetrical DNA binding site. Assignment of the {sup 1}H-{sup 15}N correlations was achieved using a suite of triple resonance NMR experiments with {sup 15}N,{sup 13}C,70% {sup 2}H enriched protein recorded at 800 MHz and using TROSY pulse sequences. Perturbationsmore » to {sup 1}H-{sup 15}N spectra revealed that the N-termini, {alpha}3-helices and several loops are affected by the binding interaction. An analysis of this data in light of the crystallographically determined apo- and DNA-bound forms of RTP.C110S revealed that the NMR spectral perturbations correlate more closely to protein structural changes upon complex formation rather than to interactions at the protein-DNA interface.« less

The influence of atomic alignment on absorption and emission spectroscopy

NASA Astrophysics Data System (ADS)

Zhang, Heshou; Yan, Huirong; Richter, Philipp

2018-06-01

Spectroscopic observations play essential roles in astrophysics. They are crucial for determining physical parameters in the universe, providing information about the chemistry of various astronomical environments. The proper execution of the spectroscopic analysis requires accounting for all the physical effects that are compatible to the signal-to-noise ratio. We find in this paper the influence on spectroscopy from the atomic/ground state alignment owing to anisotropic radiation and modulated by interstellar magnetic field, has significant impact on the study of interstellar gas. In different observational scenarios, we comprehensively demonstrate how atomic alignment influences the spectral analysis and provide the expressions for correcting the effect. The variations are even more pronounced for multiplets and line ratios. We show the variation of the deduced physical parameters caused by the atomic alignment effect, including alpha-to-iron ratio ([X/Fe]) and ionisation fraction. Synthetic observations are performed to illustrate the visibility of such effect with current facilities. A study of PDRs in ρ Ophiuchi cloud is presented to demonstrate how to account for atomic alignment in practice. Our work has shown that due to its potential impact, atomic alignment has to be included in an accurate spectroscopic analysis of the interstellar gas with current observational capability.

Investigation of structural, morphological, luminescent and thermal properties of combusted aluminium-based iron oxide

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

Shinde, S.S.; Rajpure, K.Y., E-mail: rajpure@yahoo.co

Nanocomposites of aluminium integrated hematite {alpha}-Fe{sub 2}O{sub 3} are synthesized by combustion route using aqueous solutions of AR grade ferric trichloride and aluminium nitrate as precursors. The influence of aluminium incorporation on to the morphology, XPS, photoluminescence and thermal properties has been investigated. The FESEM and AFM micrographs depict that the samples are compact and have homogeneously distributed grains of varying sizes ({approx}20-60 nm). Chemical composition and valence states of constituent elements in hematite are analyzed by XPS. In room temperature photoluminescence (PL) study, we observed strong violet emission around 436 nm without any deep-level emission and a small PLmore » FWHM indicating that the concentrations of defects are responsible for deep-level emissions. The specific heat and thermal conductivity study shows the phonon conduction behavior is dominant. We studied interparticle interactions using complex impedance spectroscopy. We report a new potential candidate for its possible applications in optoelectronics and magnetic devices. -- Graphical abstract: Frequency and temperature dependent interparticle interactions like grains, grain boundary effects using complex impedance spectroscopy of pure and 10 at% Al:Fe{sub 2}O{sub 3} have been studied. Display Omitted« less

The microscopic protein structure of the lens with a theory for cataract formation as determined by Raman spectroscopy of intact bovine lenses.

PubMed

Schachar, R A; Solin, S A

1975-05-01

Intact bovine lenses have been studied using the polarized Raman spectroscopic technique. A brief theoretical and experimental review of Raman spectroscopy is presented. From the dependence of the Raman depolarization ratio on the propagation direction of the incident radiation we have determined that the uniaxial qualities of the lens result from microscopic anisotropy and have established the quantitative positional correlation of specific chemical bonds with respect to the lens optic axis. In particular, the hydrogen bonded linear CONH groups of the antiparallel beta-pleated sheet are preferentially oriented in directions orthogonal to the lens optic axis. The Raman spectra of intact lenses do not exhibit bands at positions characteristic of either the alpha-helix or the random coil protein structure. The antiparallel beta-pleated sheet protein microstructure and the lens fiber cross-sectional macrostructure exhibit a remarkable similarity. This similarity may be causal and is consistent with the protein concentration of the lens, the birefringent properties observed by both Lenhard and Brewster, the CONH bond angle distribution with respect to the optic axis, and the lens anatomy. It is suggested that cortical cataracts are caused by fluctuations in protein orientational order.

Fast-ion transport in low density L-mode plasmas at TCV using FIDA spectroscopy and the TRANSP code

NASA Astrophysics Data System (ADS)

Geiger, B.; Karpushov, A. N.; Duval, B. P.; Marini, C.; Sauter, O.; Andrebe, Y.; Testa, D.; Marascheck, M.; Salewski, M.; Schneider, P. A.; the TCV Team; the EUROfusion MST1 Team

2017-11-01

Experiments with the new neutral beam injection source of TCV have been performed with high fast-ion fractions (>20%) that exhibit a clear reduction of the loop voltage and a clear increase of the plasma pressure in on- and off-axis heating configurations. However, good quantitative agreement between the experimental data and TRANSP predictions is only found when including strong additional fast-ion losses. These losses could in part be caused by turbulence or MHD activity as, e.g. high frequency modes near the frequency of toroidicity induced Alfvén eignmodes are observed. In addition, a newly installed fast-ion D-alpha (FIDA) spectroscopy system measures strong passive radiation and, hence, indicates the presence of high background neutral densities such that charge-exchange losses are substantial. Also the active radiation measured with the FIDA diagnostic, as well as data from a neutral particle analyzer, suggest strong fast-ion losses and large neutral densities. The large neutral densities can be justified since high electron temperatures (3-4 keV), combined with low electron densities (about 2× {10}19 m-3) yield long mean free paths of the neutrals which are penetrating from the walls.

Zinc sorption to three gram-negative bacteria: combined titration, modeling, and EXAFS study.

PubMed

Guiné, V; Spadini, L; Sarret, G; Muris, M; Delolme, C; Gaudet, J P; Martins, J M F

2006-03-15

The acid-base and Zn sorption properties of three bacteria, Cupriavidus metallidurans CH34, Pseudomonas putida ATCC12633, and Escherichia coli K12DH5alpha, were investigated through an original combination of extended X-ray absorption fine structure (EXAFS) spectroscopy and equilibrium titration studies. Acid-base titration curves of the three strains were fitted with a model accounting for three conceptual reactive sites: an acidic (carboxyl and/or phosphodiester), a neutral (phosphomonoester), and a basic (amine and/or hydroxyl) group. Calculated proton and Zn equilibrium constants and site densities compare with literature data. The nature of Zn binding sites was studied by EXAFS spectroscopy. Phosphoester, carboxyl, and unexpectedly sulfhydryl ligands were identified. Their proportions depended on Zn loading and bacterial strain and were consistent with the titration results. These findings were compared to the structure and site density of the major cell wall components. It appeared that the cumulated theoretical site density of these structures (<2 Zn nm(-2)) was much lower than the total site density of the investigated strains (16-56 Zn nm(-2)). These results suggest a dominant role of extracellular polymeric substances in Zn retention processes, although Zn binding to inner cell components cannot be excluded.

HIGH-RESOLUTION SPECTROSCOPY OF EXTREMELY METAL-POOR STARS IN THE LEAST EVOLVED GALAXIES: LEO IV

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

Simon, Joshua D.; McWilliam, Andrew; Thompson, Ian B.

2010-06-10

We present high-resolution Magellan/MIKE spectroscopy of the brightest star in the ultra-faint dwarf galaxy Leo IV. We measure an iron abundance of [Fe/H] = -3.2, adding to the rapidly growing sample of extremely metal-poor (EMP) stars being identified in Milky Way satellite galaxies. The star is enhanced in the {alpha} elements Mg, Ca, and Ti by {approx}0.3 dex, very similar to the typical Milky Way halo abundance pattern. All of the light and iron-peak elements follow the trends established by EMP halo stars, but the neutron-capture elements Ba and Sr are significantly underabundant. These results are quite similar to thosemore » found for stars in the ultra-faint dwarfs Ursa Major II, Coma Berenices, Booetes I, and Hercules, suggesting that the chemical evolution of the lowest-luminosity galaxies may be universal. The abundance pattern we observe is consistent with predictions for nucleosynthesis from a Population III supernova explosion. The extremely low metallicity of this star also supports the idea that a significant fraction ({approx}>10%) of the stars in the faintest dwarfs have metallicities below [Fe/H] = -3.0.« less