Spectroscopic evidence for an engineered, catalytically active Trp radical that creates the unique reactivity of lignin peroxidase.

PubMed

Smith, Andrew T; Doyle, Wendy A; Dorlet, Pierre; Ivancich, Anabella

2009-09-22

The surface oxidation site (Trp-171) in lignin peroxidase (LiP) required for the reaction with veratryl alcohol a high-redox-potential (1.4 V) substrate, was engineered into Coprinus cinereus peroxidase (CiP) by introducing a Trp residue into a heme peroxidase that has similar protein fold but lacks this activity. To create the catalytic activity toward veratryl alcohol in CiP, it was necessary to reproduce the Trp site and its negatively charged microenvironment by means of a triple mutation. The resulting D179W+R258E+R272D variant was characterized by multifrequency EPR spectroscopy. The spectra unequivocally showed that a new Trp radical [g values of g(x) = 2.0035(5), g(y) = 2.0027(5), and g(z) = 2.0022(1)] was formed after the [Fe(IV)=O Por(*+)] intermediate, as a result of intramolecular electron transfer between Trp-179 and the porphyrin. Also, the EPR characterization crucially showed that [Fe(IV)=O Trp-179(*)] was the reactive intermediate with veratryl alcohol. Accordingly, our work shows that it is necessary to take into account the physicochemical properties of the radical, fine-tuned by the microenvironment, as well as those of the preceding [Fe(IV)=O Por(*+)] intermediate to engineer a catalytically competent Trp site for a given substrate. Manipulation of the microenvironment of the Trp-171 site in LiP allowed the detection by EPR spectroscopy of the Trp-171(*), for which direct evidence has been missing so far. Our work also highlights the role of Trp residues as tunable redox-active cofactors for enzyme catalysis in the context of peroxidases with a unique reactivity toward recalcitrant substrates that require oxidation potentials not realized at the heme site.

Variations in protein/flavin hydrogen bonding in a LOV domain produce non-Arrhenius kinetics of adduct decay†

PubMed Central

Zoltowski, Brian D.; Nash, Abigail I.; Gardner, Kevin H.

2011-01-01

Light Oxygen Voltage (LOV) domains utilize a conserved blue light-dependent mechanism to control a diverse array of effector domains in biological and engineered proteins. Variations in the kinetics and efficiency of LOV photochemistry fine tune various aspects of the photic response. Characterization of the kinetics of a key aspect of this photochemical mechanism in EL222, a blue-light responsive DNA binding protein from Erythrobacter litoralis HTCC2594, reveals unique non-Arrhenius behavior in the rate of dark state cleavage of the photochemically-generated adduct. Sequence analysis and mutagenesis studies establish that this effect stems from a Gln to Ala mutation unique to EL222 and homologous proteins from marine bacteria. Kinetic and spectroscopic analyses reveal that hydrogen bonding interactions between the FMN N1, O2 and ribityl hydroxyls with the surrounding protein regulate photocycle kinetics and stabilize the LOV active site from temperature-induced alteration in local structure. Substitution of residues interacting with the N1-O2 locus modulates adduct stability, structural flexibility and sequestration of the active site from bulk solvent without perturbation of light-activated DNA binding. Together, these variants link non-Arrhenius behavior to specific alteration of an H-bonding network, while affording tunability of photocycle kinetics. PMID:21923139

Variations in protein-flavin hydrogen bonding in a light, oxygen, voltage domain produce non-Arrhenius kinetics of adduct decay.

PubMed

Zoltowski, Brian D; Nash, Abigail I; Gardner, Kevin H

2011-10-18

Light, oxygen, voltage (LOV) domains utilize a conserved blue light-dependent mechanism to control a diverse array of effector domains in biological and engineered proteins. Variations in the kinetics and efficiency of LOV photochemistry fine-tune various aspects of the photic response. Characterization of the kinetics of a key aspect of this photochemical mechanism in EL222, a blue light responsive DNA binding protein from Erythrobacter litoralis HTCC2594, reveals unique non-Arrhenius behavior in the rate of dark-state cleavage of the photochemically generated adduct. Sequence analysis and mutagenesis studies establish that this effect stems from a Gln to Ala mutation unique to EL222 and homologous proteins from marine bacteria. Kinetic and spectroscopic analyses reveal that hydrogen bonding interactions between the FMN N1, O2, and ribityl hydroxyls and the surrounding protein regulate photocycle kinetics and stabilize the LOV active site from temperature-induced alteration in local structure. Substitution of residues interacting with the N1-O2 locus modulates adduct stability, structural flexibility, and sequestration of the active site from bulk solvent without perturbation of light-activated DNA binding. Together, these variants link non-Arrhenius behavior to specific alteration of an H-bonding network, while affording tunability of photocycle kinetics. © 2011 American Chemical Society

Sensing site-specific structural characteristics and chirality using vibrational circular dichroism of isotope labeled peptides.

PubMed

Keiderling, Timothy A

2017-12-01

Isotope labeling has a long history in chemistry as a tool for probing structure, offering enhanced sensitivity, or enabling site selection with a wide range of spectroscopic tools. Chirality sensitive methods such as electronic circular dichroism are global structural tools and have intrinsically low resolution. Consequently, they are generally insensitive to modifications to enhance site selectivity. The use of isotope labeling to modify vibrational spectra with unique resolvable frequency shifts can provide useful site-specific sensitivity, and these methods have been recently more widely expanded in biopolymer studies. While the spectral shifts resulting from changes in isotopic mass can provide resolution of modes from specific parts of the molecule and can allow detection of local change in structure with perturbation, these shifts alone do not directly indicate structure or chirality. With vibrational circular dichroism (VCD), the shifted bands and their resultant sign patterns can be used to indicate local conformations in labeled biopolymers, particularly if multiple labels are used and if their coupling is theoretically modeled. This mini-review discusses selected examples of the use of labeling specific amides in peptides to develop local structural insight with VCD spectra. © 2017 Wiley Periodicals, Inc.

VESUVIO: a novel instrument for performing spectroscopic studies in condensed matter with eV neutrons at the ISIS facility

NASA Astrophysics Data System (ADS)

Senesi, R.; Andreani, C.; Bowden, Z.; Colognesi, D.; Degiorgi, E.; Fielding, A. L.; Mayers, J.; Nardone, M.; Norris, J.; Praitano, M.; Rhodes, N. J.; Stirling, W. G.; Tomkinson, J.; Uden, C.

2000-03-01

The VESUVIO project aims to provide unique prototype instrumentation at the ISIS-pulsed neutron source and to establish a routine experimental and theoretical program in neutron scattering spectroscopy at eV energies. This instrumentation will be specifically designed for high momentum, (20 Å-11 eV) inelastic neutron scattering studies of microscopic dynamical processes in materials and will represent a unique facility for EU researchers. It will allow to derive single-particle kinetic energies and single-particle momentum distributions, n(p), providing additional and/or complementary information to other neutron inelastic spectroscopic techniques.

Electron transfer and reaction mechanism of laccases.

PubMed

Jones, Stephen M; Solomon, Edward I

2015-03-01

Laccases are part of the family of multicopper oxidases (MCOs), which couple the oxidation of substrates to the four electron reduction of O2 to H2O. MCOs contain a minimum of four Cu's divided into Type 1 (T1), Type 2 (T2), and binuclear Type 3 (T3) Cu sites that are distinguished based on unique spectroscopic features. Substrate oxidation occurs near the T1, and electrons are transferred approximately 13 Å through the protein via the Cys-His pathway to the T2/T3 trinuclear copper cluster (TNC), where dioxygen reduction occurs. This review outlines the electron transfer (ET) process in laccases, and the mechanism of O2 reduction as elucidated through spectroscopic, kinetic, and computational data. Marcus theory is used to describe the relevant factors which impact ET rates including the driving force, reorganization energy, and electronic coupling matrix element. Then, the mechanism of O2 reaction is detailed with particular focus on the intermediates formed during the two 2e(-) reduction steps. The first 2e(-) step forms the peroxide intermediate, followed by the second 2e(-) step to form the native intermediate, which has been shown to be the catalytically relevant fully oxidized form of the enzyme.

Identification of a Unique Fe-S Cluster Binding Site in a Glycyl-Radical Type Microcompartment Shell Protein

PubMed Central

Thompson, Michael C.; Wheatley, Nicole M.; Jorda, Julien; Sawaya, Michael R.; Gidaniyan, Soheil D.; Ahmed, Hoda; Yang, Zhongyu; McCarty, Krystal N.; Whitelegge, Julian P.; Yeates, Todd O.

2014-01-01

Recently, progress has been made toward understanding the functional diversity of bacterial microcompartment (MCP) systems, which serve as protein-based metabolic organelles in diverse microbes. New types of MCPs have been identified, including the glycyl-radical propanediol (Grp) MCP. Within these elaborate protein complexes, BMC-domain shell proteins assemble to form a polyhedral barrier that encapsulates the enzymatic contents of the MCP. Interestingly, the Grp MCP contains a number of shell proteins with unusual sequence features. GrpU is one such shell protein, whose amino acid sequence is particularly divergent from other members of the BMC-domain superfamily of proteins that effectively defines all MCPs. Expression, purification, and subsequent characterization of the protein showed, unexpectedly, that it binds an iron-sulfur cluster. We determined X-ray crystal structures of two GrpU orthologs, providing the first structural insight into the homohexameric BMC-domain shell proteins of the Grp system. The X-ray structures of GrpU, both obtained in the apo form, combined with spectroscopic analyses and computational modeling, show that the metal cluster resides in the central pore of the BMC shell protein at a position of broken 6-fold symmetry. The result is a structurally polymorphic iron-sulfur cluster binding site that appears to be unique among metalloproteins studied to date. PMID:25102080

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

PubMed

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

2009-07-01

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

Functional Studies on Oligotropha carboxidovorans Molybdenum-Copper CO Dehydrogenase Produced in Escherichia coli.

PubMed

Kaufmann, Paul; Duffus, Benjamin R; Teutloff, Christian; Leimkühler, Silke

2018-04-30

The Mo/Cu-dependent CO dehydrogenase (CODH) from Oligotropha carboxidovorans is an enzyme that is able to catalyze both the oxidation of CO to CO 2 and the oxidation of H 2 to protons and electrons. Despite the close to atomic resolution structure (1.1 Å), significant uncertainties have remained with regard to the reaction mechanism of substrate oxidation at the unique Mo/Cu center, as well as the nature of intermediates formed during the catalytic cycle. So far, the investigation of the role of amino acids at the active site was hampered by the lack of a suitable expression system that allowed for detailed site-directed mutagenesis studies at the active site. Here, we report on the establishment of a functional heterologous expression system of O. carboxidovorans CODH in Escherichia coli. We characterize the purified enzyme in detail by a combination of kinetic and spectroscopic studies and show that it was purified in a form with characteristics comparable to those of the native enzyme purified from O. carboxidovorans. With this expression system in hand, we were for the first time able to generate active-site variants of this enzyme. Our work presents the basis for more detailed studies of the reaction mechanism for CO and H 2 oxidation of Mo/Cu-dependent CODHs in the future.

Fragment-based identification of determinants of conformational and spectroscopic change at the ricin active site

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

Carra,J.; McHugh, C.; Mulligan, S.

2007-01-01

We found that amide ligands can bind weakly but specifically to the ricin active site, producing significant shifts in positions of the critical active site residues Arg180 and Tyr80. These results indicate that fragment-based drug discovery methods are capable of identifying minimal bonding determinants of active-site side-chain rearrangements and the mechanistic origins of spectroscopic shifts. Our results suggest that tryptophan fluorescence provides a sensitive probe for the geometric relationship of arginine-tryptophan pairs, which often have significant roles in protein function. Using the unusual characteristics of the RTA system, we measured the still controversial thermodynamic changes of site-specific urea binding tomore » a protein, results that are relevant to understanding the physical mechanisms of protein denaturation.« less

Spectroscopic characterisation of interaction of ferulic acid with aldehyde dehydrogenase (ALDH).

PubMed

Kolawole, Ayodele O; Agaba, Ruth J; Oluwole, Matthew O

2017-05-01

Interaction of a pharmacological important phenolic, ferulic acid, with Aldehyde dehydrogenase (ALDH) at the simulative pH condition, was studied using spectroscopic approach. Ferulic acid caused a decrease in the fluorescence intensity formed from ALDH-ferulic acid complex resulting in mixed inhibition of ALDH activity (IC 50 =30.65μM). The intrinsic quenching was dynamic and induced altered conformation of ALDH and made the protein less compact but might not unfold it. ALDH has two binding sites for ferulic acid at saturating concentrations having association constant of 1.35×10 3 Lmol -1 and a dissociation constant of 9.7×10 7 Lmol -1 at 25°C indicating ALDH-ferulic acid complex formation is more favourable than its dissociation. The interaction was not spontaneous and endothermic and suggests the involvement of hydrophobic interactions with a FRET binding distance of 4.49nm. Change in pH near and far from isoelectric points of ferulic acid did not affect the bonding interaction. Using trehalose as viscosogen, the result from Stoke-Einstein hypothesis showed that ferulic acid-ALDH binding and dissociation equilibrium was diffusion controlled. These results clearly suggest the unique binding properties and lipophilicity influence of ferulic acid. Copyright © 2017 Elsevier B.V. All rights reserved.

Spectroscopically Enhanced Method and System for Multi-Factor Biometric Authentication

NASA Astrophysics Data System (ADS)

Pishva, Davar

This paper proposes a spectroscopic method and system for preventing spoofing of biometric authentication. One of its focus is to enhance biometrics authentication with a spectroscopic method in a multifactor manner such that a person's unique ‘spectral signatures’ or ‘spectral factors’ are recorded and compared in addition to a non-spectroscopic biometric signature to reduce the likelihood of imposter getting authenticated. By using the ‘spectral factors’ extracted from reflectance spectra of real fingers and employing cluster analysis, it shows how the authentic fingerprint image presented by a real finger can be distinguished from an authentic fingerprint image embossed on an artificial finger, or molded on a fingertip cover worn by an imposter. This paper also shows how to augment two widely used biometrics systems (fingerprint and iris recognition devices) with spectral biometrics capabilities in a practical manner and without creating much overhead or inconveniencing their users.

Dioxygen Binding, Activation, and Reduction to H2O by Cu Enzymes.

PubMed

Solomon, Edward I

2016-07-05

Oxygen intermediates in copper enzymes exhibit unique spectroscopic features that reflect novel geometric and electronic structures that are key to reactivity. This perspective will describe: (1) the bonding origin of the unique spectroscopic features of the coupled binuclear copper enzymes and how this overcomes the spin forbiddenness of O2 binding and activates monooxygenase activity, (2) how the difference in exchange coupling in the non-coupled binuclear Cu enzymes controls the reaction mechanism, and (3) how the trinuclear Cu cluster present in the multicopper oxidases leads to a major structure/function difference in enabling the irreversible reductive cleavage of the O-O bond with little overpotential and generating a fully oxidized intermediate, different from the resting enzyme studied by crystallography, that is key in enabling fast PCET in the reductive half of the catalytic cycle.

Art, Meet Chemistry; Chemistry, Meet Art: Case Studies, Current Literature, and Instrumental Methods Combined to Create a Hands-On Experience for Nonmajors and Instrumental Analysis Students

ERIC Educational Resources Information Center

Nivens, Delana A.; Padgett, Clifford W.; Chase, Jeffery M.; Verges, Katie J.; Jamieson, Deborah S.

2010-01-01

Case studies and current literature are combined with spectroscopic analysis to provide a unique chemistry experience for art history students and to provide a unique inquiry-based laboratory experiment for analytical chemistry students. The XRF analysis method was used to demonstrate to nonscience majors (art history students) a powerful…

Role of proton magnetic resonance spectroscopy in the diagnosis of gliomatosis cerebri: a unique pattern of normal choline but elevated Myo-inositol metabolite levels.

PubMed

Mohana-Borges, Aurea V R; Imbesi, Steven G; Dietrich, Rosalind; Alksne, John; Amjadi, Darius K

2004-01-01

A patient with histologically proven gliomatosis cerebri presented with a normal choline level but a markedly abnormal elevated myo-inositol level on magnetic resonance (MR) spectroscopy. We describe the case presentation, imaging findings (in particular, the unique MR spectroscopic pattern), and their significance regarding the diagnosis of this relatively rare neoplasm.

Multiple active site residues are important for photochemical efficiency in the light-activated enzyme protochlorophyllide oxidoreductase (POR).

PubMed

Menon, Binuraj R K; Hardman, Samantha J O; Scrutton, Nigel S; Heyes, Derren J

2016-08-01

Protochlorophyllide oxidoreductase (POR) catalyzes the light-driven reduction of protochlorophyllide (Pchlide), an essential, regulatory step in chlorophyll biosynthesis. The unique requirement of the enzyme for light has provided the opportunity to investigate how light energy can be harnessed to power biological catalysis and enzyme dynamics. Excited state interactions between the Pchlide molecule and the protein are known to drive the subsequent reaction chemistry. However, the structural features of POR and active site residues that are important for photochemistry and catalysis are currently unknown, because there is no crystal structure for POR. Here, we have used static and time-resolved spectroscopic measurements of a number of active site variants to study the role of a number of residues, which are located in the proposed NADPH/Pchlide binding site based on previous homology models, in the reaction mechanism of POR. Our findings, which are interpreted in the context of a new improved structural model, have identified several residues that are predicted to interact with the coenzyme or substrate. Several of the POR variants have a profound effect on the photochemistry, suggesting that multiple residues are important in stabilizing the excited state required for catalysis. Our work offers insight into how the POR active site geometry is finely tuned by multiple active site residues to support enzyme-mediated photochemistry and reduction of Pchlide, both of which are crucial to the existence of life on Earth. Copyright © 2016 The Authors. Published by Elsevier B.V. All rights reserved.

Dynamics of hybrid amoeba proteus containing zoochlorellae studied using fluorescence spectroscopy

NASA Astrophysics Data System (ADS)

Liu, C.-H.; Fong, B. A.; Alfano, S. A., Jr.; Rakhlin, I.; Wang, W. B.; Ni, X. H.; Yang, Y. L.; Zhou, F.; Zuzolo, R. C.; Alfano, R. R.

2011-03-01

The microinjection of organelles, plants, particles or chemical solutions into Amoeba proteus coupled with spectroscopic analysis and observed for a period of time provides a unique new model for cancer treatment and studies. The amoeba is a eukaryote having many similar features of mammalian cells. The amoeba biochemical functions monitored spectroscopically can provide time sequence in vivo information about many metabolic transitions and metabolic exchanges between cellar organelles and substances microinjected into the amoeba. It is possible to microinject algae, plant mitochondria, drugs or carcinogenic solutions followed by recording the native fluorescence spectra of these composites. This model can be used to spectroscopically monitor the pre-metabolic transitions in developing diseased cells such as a cancer. Knowing specific metabolic transitions could offer solutions to inhibit cancer or reverse it as well as many other diseases. In the present study a simple experiment was designed to test the feasibility of this unique new model by injecting algae and chloroplasts into amoeba. The nonradiative dynamics found from these composites are evidence in terms of the emission ratios between the intensities at 337nm and 419nm; and 684nm bands. There were reductions in the metabolic and photosynthetic processes in amoebae that were microinjected with chloroplasts and zoochlorellae as well of those amoebae that ingested the algae and chloroplasts. The changes in the intensity of the emissions of the peaks indicate that the zoochlorellae lived in the amoebae for ten days. Spectral changes in intensity under the UV and 633nm wavelength excitation are from the energy transfer of DNA and RNA, protein-bound chromophores and chlorophylls present in zoochlorellae undergoing photosynthesis. The fluorescence spectroscopic probes established the biochemical interplay between the cell organelles and the algae present in the cell cytoplasm. This hybrid state is indicative that a symbiotic system is in place and the results definitely support the potential use of this unique new model. This model many help in plant / animal and cancer processes.

Calibration Efforts and Unique Capabilities of the HST Space Telescope Imaging Spectrograph

NASA Astrophysics Data System (ADS)

Monroe, TalaWanda R.; Proffitt, Charles R.; Welty, Daniel; Branton, Doug; Carlberg, Joleen K.; debes, John Henry; Lockwood, Sean; Riley, Allyssa; Sohn, Sangmo Tony; Sonnentrucker, Paule G.; Walborn, Nolan R.; Jedrzejewski, Robert I.

2018-01-01

The Space Telescope Imaging Spectrograph (STIS) continues to offer the astronomy community the ability to carry out innovative UV and optical spectroscopic and imaging studies, two decades after its deployment on the Hubble Space Telescope (HST). Most notably, STIS provides spectroscopy in the FUV and NUV, including high spectral resolution echelle modes, imaging in the FUV, optical spectroscopy, and coronagraphic capabilities. Additionally, spatial scanning on the CCD with the long-slits is now possible to enable very high S/N spectroscopic observations without saturation while mitigating telluric and fringing concerns in the far red and near-IR. This new mode may especially benefit the diffuse interstellar bands and exoplanet transiting communities. We present recent calibration efforts for the instrument, including work to optimize the calibration of the echelle spectroscopic modes by improving the flux agreement of overlapping spectral orders affected by changes in the grating blaze function since HST Servicing Mission 4. We also discuss considerations to maintain the wavelength precision of the spectroscopic modes, and the current capabilities of CCD spectroscopic spatial trails.

The Copper Active Site of CBM33 Polysaccharide Oxygenases

PubMed Central

2013-01-01

The capacity of metal-dependent fungal and bacterial polysaccharide oxygenases, termed GH61 and CBM33, respectively, to potentiate the enzymatic degradation of cellulose opens new possibilities for the conversion of recalcitrant biomass to biofuels. GH61s have already been shown to be unique metalloenzymes containing an active site with a mononuclear copper ion coordinated by two histidines, one of which is an unusual τ-N-methylated N-terminal histidine. We now report the structural and spectroscopic characterization of the corresponding copper CBM33 enzymes. CBM33 binds copper with high affinity at a mononuclear site, significantly stabilizing the enzyme. X-band EPR spectroscopy of Cu(II)-CBM33 shows a mononuclear type 2 copper site with the copper ion in a distorted axial coordination sphere, into which azide will coordinate as evidenced by the concomitant formation of a new absorption band in the UV/vis spectrum at 390 nm. The enzyme’s three-dimensional structure contains copper, which has been photoreduced to Cu(I) by the incident X-rays, confirmed by X-ray absorption/fluorescence studies of both aqueous solution and intact crystals of Cu-CBM33. The single copper(I) ion is ligated in a T-shaped configuration by three nitrogen atoms from two histidine side chains and the amino terminus, similar to the endogenous copper coordination geometry found in fungal GH61. PMID:23540833

Absolute vibrational numbering from isotope shifts in fragmentary spectroscopic data

NASA Astrophysics Data System (ADS)

Pashov, A.; Kowalczyk, P.; Jastrzebski, W.

2018-05-01

We discuss application of the isotope effect to establish the absolute vibrational numbering in electronic states of diatomic molecules. This is illustrated by examples of states with potential energy curves of both regular and irregular shape, with one or two potential minima. The minimum number of spectroscopic data (either term values or spectral line positions) necessary to provide a unique numbering is considered. We show that at favourable conditions just four term energies (or spectral lines) in one isotopologue and one term energy in the other suffice.

KSC-2012-3525

NASA Image and Video Library

2012-06-13

KWAJALEIN ATOLL, Marshall Islands - Orbital Sciences' L-1011 "Stargazer" aircraft takes off from the runway at Kwajalein Atoll with the company's Pegasus rocket to launch NASA's Nuclear Spectroscopic Telescope Array, or NuSTAR, payload strapped to the belly of the plane. The plane left Kwajalein one hour before launch. At 9:00:35 a.m. PDT 12:00:35 p.m. EDT), June 13, 2012, the rocket dropped with the NuSTAR payload 117 nautical miles south of Kwajalein. NuSTAR will use a unique set of “eyes” to see the highest energy X-ray light from the cosmos to reveal black holes lurking in our Milky Way galaxy, as well as those hidden in the hearts of faraway galaxies. Kwajalein is located in the Marshall Islands chain in the Pacific Ocean and is part of the Reagan Test Site and used for launches of NASA, commercial and military missions. For more information, visit http://www.nasa.gov/nustar. Photo credit: NASA

KSC-2012-3524

NASA Image and Video Library

2012-06-13

KWAJALEIN ATOLL, Marshall Islands - Orbital Sciences' L-1011 "Stargazer" aircraft takes off from the runway at Kwajalein Atoll with the company's Pegasus rocket to launch NASA's Nuclear Spectroscopic Telescope Array, or NuSTAR. The plane left Kwajalein one hour before launch. At 9:00:35 a.m. PDT 12:00:35 p.m. EDT), June 13, 2012, the rocket dropped with the NuSTAR payload 117 nautical miles south of Kwajalein. NuSTAR will use a unique set of “eyes” to see the highest energy X-ray light from the cosmos to reveal black holes lurking in our Milky Way galaxy, as well as those hidden in the hearts of faraway galaxies. Kwajalein is located in the Marshall Islands chain in the Pacific Ocean and is part of the Reagan Test Site and used for launches of NASA, commercial and military missions. For more information, visit http://www.nasa.gov/nustar. Photo credit: NASA

KSC-2012-3523

NASA Image and Video Library

2012-06-13

KWAJALEIN ATOLL, Marshall Islands - The lights of Orbital Sciences' L-1011 "Stargazer" aircraft illuminates the night sky as it takes off from the runway at Kwajalein Atoll with the company's Pegasus rocket to launch NASA's Nuclear Spectroscopic Telescope Array, or NuSTAR. The plane left Kwajalein one hour before launch. At 9:00:35 a.m. PDT 12:00:35 p.m. EDT), June 13, 2012, the rocket dropped with the NuSTAR payload 117 nautical miles south of Kwajalein. NuSTAR will use a unique set of “eyes” to see the highest energy X-ray light from the cosmos to reveal black holes lurking in our Milky Way galaxy, as well as those hidden in the hearts of faraway galaxies. Kwajalein is located in the Marshall Islands chain in the Pacific Ocean and is part of the Reagan Test Site and used for launches of NASA, commercial and military missions. For more information, visit http://www.nasa.gov/nustar. Photo credit: NASA

Low dielectric response in enzyme active site

PubMed Central

Mertz, Edward L.; Krishtalik, Lev I.

2000-01-01

The kinetics of charge transfer depend crucially on the dielectric reorganization of the medium. In enzymatic reactions that involve charge transfer, atomic dielectric response of the active site and of its surroundings determines the efficiency of the protein as a catalyst. We report direct spectroscopic measurements of the reorganization energy associated with the dielectric response in the active site of α-chymotrypsin. A chromophoric inhibitor of the enzyme is used as a spectroscopic probe. We find that water strongly affects the dielectric reorganization in the active site of the enzyme in solution. The reorganization energy of the protein matrix in the vicinity of the active site is similar to that of low-polarity solvents. Surprisingly, water exhibits an anomalously high dielectric response that cannot be described in terms of the dielectric continuum theory. As a result, sequestering the active site from the aqueous environment inside low-dielectric enzyme body dramatically reduces the dielectric reorganization. This reduction is particularly important for controlling the rate of enzymatic reactions. PMID:10681440

Deformation-related spectroscopic features in natural Type Ib-IaA diamonds from Zimmi (West African craton)

NASA Astrophysics Data System (ADS)

Smit, Karen V.; D'Haenens-Johansson, Ulrika F. S.; Howell, Daniel; Loudin, Lorne C.; Wang, Wuyi

2018-06-01

Zimmi diamonds (Sierra Leone) have 500 million year mantle residency times whose origin is best explained by rapid tectonic exhumation to shallower depths in the mantle, associated with continental collision but prior to kimberlite eruption. Here we present spectroscopic data for a new suite of Zimmi sulphide-bearing diamonds that allow us to evaluate the link between their spectroscopic features and their unusual geological history. Cathodoluminesence (CL) imaging of these diamonds revealed irregular patterns with abundant deformation lamellae, associated with the diamonds' tectonic exhumation. Vacancies formed during deformation were subsequently naturally annealed to form vacancy clusters, NV0/- centres and H3 (NVN0). The brownish-yellow to greenish-yellow colours observed in Zimmi Ib-IaA diamonds result from visible absorption by a combination of isolated substitutional nitrogen ( {N}S^0 ) and deformation-related vacancy clusters. Colour-forming centres and other spectroscopic features can all be attributed to the unique geological history of Zimmi Ib-IaA diamonds and their rapid exhumation after formation.

Interaction of Flavonoids from Woodwardia unigemmata with Bovine Serum Albumin (BSA): Application of Spectroscopic Techniques and Molecular Modeling Methods.

PubMed

Ma, Rui; Pan, Hong; Shen, Tao; Li, Peng; Chen, Yanan; Li, Zhenyu; Di, Xiaxia; Wang, Shuqi

2017-08-09

Phytochemical investigation on the methanol extract of Woodwardia unigemmata resulted in the isolation of seven flavonoids, including one new flavonol acylglycoside ( 1 ). The structures of these compounds were elucidated on the basis of extensive spectroscopic analysis and comparison of literature data. The multidrug resistance (MDR) reversing activity was evaluated for the isolated compounds using doxorubicin-resistant K562/A02 cells model. Compound 6 showed comparable MDR reversing effect to verapamil. Furthermore, the interaction between compounds and bovine serum albumin (BSA) was investigated by spectroscopic methods, including steady-state fluorescence, synchronous fluorescence, circular dichroism (CD) spectroscopies, and molecular docking approach. The experimental results indicated that the seven flavonoids bind to BSA by static quenching mechanisms. The negative ΔH and ΔS values indicated that van der Waals interactions and hydrogen bonds contributed in the binding of compounds 2 - 6 to BSA. In the case of compounds 1 and 7 systems, the hydrophobic interactions play a major role. The binding of compounds to BSA causes slight changes in the secondary structure of BSA. There are two binding sites of compound 6 on BSA and site I is the main site according to the molecular docking studies and the site marker competitive binding assay.

An ALMA Survey of Submillimeter Galaxies in the Extended Chandra Deep Field South: Spectroscopic Redshifts

NASA Astrophysics Data System (ADS)

Danielson, A. L. R.; Swinbank, A. M.; Smail, Ian; Simpson, J. M.; Casey, C. M.; Chapman, S. C.; da Cunha, E.; Hodge, J. A.; Walter, F.; Wardlow, J. L.; Alexander, D. M.; Brandt, W. N.; de Breuck, C.; Coppin, K. E. K.; Dannerbauer, H.; Dickinson, M.; Edge, A. C.; Gawiser, E.; Ivison, R. J.; Karim, A.; Kovacs, A.; Lutz, D.; Menten, K.; Schinnerer, E.; Weiß, A.; van der Werf, P.

2017-05-01

We present spectroscopic redshifts of {\\text{}}{S}870μ {{m}} ≳ 2 mJy submillimeter galaxies (SMGs), which have been identified from the ALMA follow-up observations of 870 μm detected sources in the Extended Chandra Deep Field South (the ALMA-LESS survey). We derive spectroscopic redshifts for 52 SMGs, with a median of z = 2.4 ± 0.1. However, the distribution features a high-redshift tail, with ˜23% of the SMGs at z≥slant 3. Spectral diagnostics suggest that the SMGs are young starbursts, and the velocity offsets between the nebular emission and UV ISM absorption lines suggest that many are driving winds, with velocity offsets of up to 2000 km s-1. Using the spectroscopic redshifts and the extensive UV-to-radio photometry in this field, we produce optimized spectral energy distributions (SEDs) using Magphys, and use the SEDs to infer a median stellar mass of {M}\\star = (6 ± 1)× 1010 M {}⊙ for our SMGs with spectroscopic redshift. By combining these stellar masses with the star formation rates (measured from the far-infrared SEDs), we show that SMGs (on average) lie a factor of ˜5 above the so-called “main sequence” at z˜ 2. We provide this library of 52 template fits with robust and uniquely well-sampled SEDs as a resource for future studies of SMGs, and also release the spectroscopic catalog of ˜2000 (mostly infrared-selected) galaxies targeted as part of the spectroscopic campaign.

Solar System Science with the Twinkle Space Mission

NASA Astrophysics Data System (ADS)

Bowles, N.; Lindsay, S.; Tessenyi, M.; Tinetti, G.; Savini, G.; Tennyson, J.; Pascale, E.; Jason, S.; Vora, A.

2017-09-01

Twinkle is a space-based telescope mission designed for the spectroscopic observation (0.4 to 4.5 μm) of exoplanet atmospheres and Solar System objects. The system design and mission implementation are based on existing, well studied concepts pioneered by Surrey Satellite Technology Ltd for low-Earth orbit Earth Observation satellites, supported by a novel international access model to allow facility access to researchers worldwide. Whilst Twinkle's primary science goal is the observation of exoplanet atmospheres its wide spectroscopic range and photometric stability also make it a unique platform for the observation of Solar system objects.

A model for the spectroscopic variations of the peculiar symbiotic star MWC 560

NASA Technical Reports Server (NTRS)

Shore, Steven N.; Aufdenberg, Jason P.; Michalitsianos, A. G.

1994-01-01

In this note, we show that the ultraviolet and optical spectroscopic variability of this unique symbiotic star can be understood in terms of a time variable collimated stellar wind with a rapid acceleration near the source. Using the radial velocities observed during the ultraviolet bright phase, we find that a variation in the mass loss rate of a factor of ten can explain the ultraviolet spectral changes. The acceleration is far faster than normally observed in radiatively driven stellar winds and may be due to mechanical driving of the outflow from the disk.

Spectroscopic studies reveal that the heme regulatory motifs of heme oxygenase-2 are dynamically disordered and exhibit redox-dependent interaction with heme

DOE PAGES

Bagai, Ireena; Sarangi, Ritimukta; Fleischhacker, Angela S.; ...

2015-05-05

Heme oxygenase (HO) catalyzes a key step in heme homeostasis: the O₂₋ and NADPH-cytochrome P450 reductase-dependent conversion of heme to biliverdin, Fe, and CO through a process in which the heme participates both as a prosthetic group and as a substrate. Mammals contain two isoforms of this enzyme, HO2 and HO1, which share the same α-helical fold forming the catalytic core and heme binding site, as well as a membrane spanning helix at their C-termini. However, unlike HO1, HO2 has an additional 30-residue N-terminus as well as two cysteine-proline sequences near the C-terminus that reside in heme regulatory motifs (HRMs).more » While the role of the additional N-terminal residues of HO2 is not yet understood, the HRMs have been proposed to reversibly form a thiol/disulfide redox switch that modulates the affinity of HO2 for ferric heme as a function of cellular redox poise. To further define the roles of the N- and C-terminal regions unique to HO2, we used multiple spectroscopic techniques to characterize these regions of the human HO2. Nuclear magnetic resonance spectroscopic experiments with HO2 demonstrate that, when the HRMs are in the oxidized state (HO2 O), both the extra N-terminal and the C-terminal HRM-containing regions are disordered. However, protein NMR experiments illustrate that, under reducing conditions, the C-terminal region gains some structure as the Cys residues in the HRMs undergo reduction (HO2 R) and, in experiments employing a diamagnetic protoporphyrin, suggest a redox-dependent interaction between the core and the HRM domains. Further, electron nuclear double resonance and X-ray absorption spectroscopic studies demonstrate that, upon reduction of the HRMs to the sulfhydryl form, a cysteine residue from the HRM region ligates to a ferric heme. Taken together with EPR measurements, which show the appearance of a new low-spin heme signal in reduced HO2, it appears that a cysteine residue(s) in the HRMs directly interacts with a second bound heme.« less

Spectroscopic studies reveal that the heme regulatory motifs of heme oxygenase-2 are dynamically disordered and exhibit redox-dependent interaction with heme

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

Bagai, Ireena; Sarangi, Ritimukta; Fleischhacker, Angela S.

Heme oxygenase (HO) catalyzes a key step in heme homeostasis: the O₂₋ and NADPH-cytochrome P450 reductase-dependent conversion of heme to biliverdin, Fe, and CO through a process in which the heme participates both as a prosthetic group and as a substrate. Mammals contain two isoforms of this enzyme, HO2 and HO1, which share the same α-helical fold forming the catalytic core and heme binding site, as well as a membrane spanning helix at their C-termini. However, unlike HO1, HO2 has an additional 30-residue N-terminus as well as two cysteine-proline sequences near the C-terminus that reside in heme regulatory motifs (HRMs).more » While the role of the additional N-terminal residues of HO2 is not yet understood, the HRMs have been proposed to reversibly form a thiol/disulfide redox switch that modulates the affinity of HO2 for ferric heme as a function of cellular redox poise. To further define the roles of the N- and C-terminal regions unique to HO2, we used multiple spectroscopic techniques to characterize these regions of the human HO2. Nuclear magnetic resonance spectroscopic experiments with HO2 demonstrate that, when the HRMs are in the oxidized state (HO2 O), both the extra N-terminal and the C-terminal HRM-containing regions are disordered. However, protein NMR experiments illustrate that, under reducing conditions, the C-terminal region gains some structure as the Cys residues in the HRMs undergo reduction (HO2 R) and, in experiments employing a diamagnetic protoporphyrin, suggest a redox-dependent interaction between the core and the HRM domains. Further, electron nuclear double resonance and X-ray absorption spectroscopic studies demonstrate that, upon reduction of the HRMs to the sulfhydryl form, a cysteine residue from the HRM region ligates to a ferric heme. Taken together with EPR measurements, which show the appearance of a new low-spin heme signal in reduced HO2, it appears that a cysteine residue(s) in the HRMs directly interacts with a second bound heme.« less

Interstellar problems and matrix solutions

NASA Technical Reports Server (NTRS)

Allamandola, Louis J.

1987-01-01

The application of the matrix isolation technique to interstellar problems is described. Following a brief discussion of the interstellar medium (ISM), three areas are reviewed in which matrix experiments are particularly well suited to contribute the information which is sorely needed to further understanding of the ISM. The first involves the measurement of the spectroscopic properties of reactive species. The second is the determination of reaction rates and the elucidation of reaction pathways involving atoms, radicals, and ions which are likely to interact on grain surfaces and in grain mantles. The third entails the determiantion of the spectroscopic, photochemical, and photophysical properties of interstellar and cometary ice analogs. Significant, but limited, progress has been made in these three areas, and a tremendous amount of work is required to fully address the variety of unique chemical and spectroscopic questions posed by the astronomical observations.

Spectroscopic determination of the distribution of Cr3+ sites in mullite ceramics

NASA Astrophysics Data System (ADS)

Liu, Huimin; Knutson, Robert; Jia, Weiyi; Strauss, Eugen; Yen, W. M.

1990-06-01

Excitation spectra and lifetime measurements were used to distinguish high-field-site (HFS) and low-field-site (LFS) Cr3+-ion behaviors. A theoretical analysis of site distribution gives an adequate fit to the luminescent spectra. The residual content of LFS in the glass ceramic was found to depend on the extent of the heat treatment.

Using non-invasive molecular spectroscopic techniques to detect unique aspects of protein Amide functional groups and chemical properties of modeled forage from different sourced-origins

NASA Astrophysics Data System (ADS)

Ji, Cuiying; Zhang, Xuewei; Yu, Peiqiang

2016-03-01

The non-invasive molecular spectroscopic technique-FT/IR is capable to detect the molecular structure spectral features that are associated with biological, nutritional and biodegradation functions. However, to date, few researches have been conducted to use these non-invasive molecular spectroscopic techniques to study forage internal protein structures associated with biodegradation and biological functions. The objectives of this study were to detect unique aspects and association of protein Amide functional groups in terms of protein Amide I and II spectral profiles and chemical properties in the alfalfa forage (Medicago sativa L.) from different sourced-origins. In this study, alfalfa hay with two different origins was used as modeled forage for molecular structure and chemical property study. In each forage origin, five to seven sources were analyzed. The molecular spectral profiles were determined using FT/IR non-invasive molecular spectroscopy. The parameters of protein spectral profiles included functional groups of Amide I, Amide II and Amide I to II ratio. The results show that the modeled forage Amide I and Amide II were centered at 1653 cm- 1 and 1545 cm- 1, respectively. The Amide I spectral height and area intensities were from 0.02 to 0.03 and 2.67 to 3.36 AI, respectively. The Amide II spectral height and area intensities were from 0.01 to 0.02 and 0.71 to 0.93 AI, respectively. The Amide I to II spectral peak height and area ratios were from 1.86 to 1.88 and 3.68 to 3.79, respectively. Our results show that the non-invasive molecular spectroscopic techniques are capable to detect forage internal protein structure features which are associated with forage chemical properties.

Towards a mechanistic and physiological understanding of a ferredoxin disulfide reductase from the domains Archaea and Bacteria.

PubMed

Prakash, Divya; Walters, Karim A; Martinie, Ryan J; McCarver, Addison C; Kumar, Adepu K; Lessner, Daniel J; Krebs, Carsten; Golbeck, John H; Ferry, James G

2018-05-02

Disulfide reductases reduce other proteins and are critically important for cellular redox signaling and homeostasis. Methanosarcina acetivorans is a methane-producing microbe from the domain Archaea that produces a ferredoxin:disulfide reductase (FDR) for which the crystal structure has been reported, yet its biochemical mechanism and physiological substrates are unknown. FDR and the extensively characterized plant-type ferredoxin:thioredoxin reductase (FTR) belong to a distinct class of disulfide reductases that contain a unique active-site [4Fe-4S] cluster. The results reported here support a mechanism for FDR similar to that reported for FTR with notable exceptions. Unlike FTR, FDR contains a rubredoxin [1Fe-0S] center postulated to mediate electron transfer from ferredoxin to the active-site [4Fe-4S] cluster.  UV-Vis, EPR and Mӧssbauer spectroscopic data indicated that two-electron reduction of the active-site disulfide in FDR involves a one-electron-reduced [4Fe-4S]1+ intermediate previously hypothesized for FTR. Our results support a role for an active-site tyrosine in FDR that occupies the equivalent position of an essential histidine in the active-site of FTR. Of note, one of seven Trxs encoded in the genome (Trx5) and methanoredoxin, a glutaredoxin-like enzyme from M. acetivorans, were reduced by FDR advancing the physiological understanding of FDRs role in the redox metabolism of methanoarchaea. Finally, bioinformatics analyses show FDR homologs are widespread in diverse microbes from the domain Bacteria. Published under license by The American Society for Biochemistry and Molecular Biology, Inc.

Multi-Vendor Implementation and Comparison of Volumetric Whole-Brain Echo-Planar MR Spectroscopic Imaging

PubMed Central

Sabati, Mohammad; Sheriff, Sulaiman; Gu, Meng; Wei, Juan; Zhu, Henry; Barker, Peter B.; Spielman, Daniel M.; Alger, Jeffry R.; Maudsley, Andrew A.

2014-01-01

Purpose To assess volumetric proton MR spectroscopic imaging of the human brain on multi-vendor MRI instruments. Methods Echo-planar spectroscopic imaging (EPSI) was developed on instruments from three manufacturers, with matched specifications and acquisition protocols that accounted for differences in sampling performance, RF power, and data formats. Inter-site reproducibility was evaluated for signal-normalized maps of N-acetylaspartate (NAA), Creatine (Cre) and Choline using phantom and human subject measurements. Comparative analyses included metrics for spectral quality, spatial coverage, and mean values in atlas-registered brain regions. Results Inter-site differences for phantom measurements were under 1.7% for individual metabolites and 0.2% for ratio measurements. Spatial uniformity ranged from 79% to 91%. The human studies found differences of mean values in the temporal lobe, but good agreement in other white-matter regions, with maximum differences relative to their mean of under 3.2%. For NAA/Cre, the maximum difference was 1.8%. In grey-matter a significant difference was observed for frontal lobe NAA. Primary causes of inter-site differences were attributed to shim quality, B0 drift, and accuracy of RF excitation. Correlation coefficients for measurements at each site were over 0.60, indicating good reliability. Conclusion A volumetric intensity-normalized MRSI acquisition can be implemented in a comparable manner across multi-vendor MR instruments. PMID:25354190

Alteration of fluorescent protein spectroscopic properties upon cryoprotection.

PubMed

von Stetten, David; Batot, Gaëlle O; Noirclerc-Savoye, Marjolaine; Royant, Antoine

2012-11-01

Cryoprotection of a protein crystal by addition of small-molecule compounds may sometimes affect the structure of its active site. The spectroscopic and structural effects of the two cryoprotectants glycerol and ethylene glycol on the cyan fluorescent protein Cerulean were investigated. While glycerol had almost no noticeable effect, ethylene glycol was shown to induce a systematic red shift of the UV-vis absorption and fluorescence emission spectra. Additionally, ethylene glycol molecules were shown to enter the core of the protein, with one of them binding in close vicinity to the chromophore, which provides a sound explanation for the observed spectroscopic changes. These results highlight the need to systematically record spectroscopic data on crystals of light-absorbing proteins and reinforce the notion that fluorescent proteins must not been seen as rigid structures.

Study of spectroscopic properties of nanosized particles of core-shell morphology

NASA Astrophysics Data System (ADS)

Bzhalava, T. N.; Kervalishvili, P. J.

2018-03-01

Method of studying spectroscopic properties of nanosized particles and estimation of resonance wavelength range for determination of specific and unique “spectral” signatures in purpose of sensing, identification of nanobioparticles, viruses is proposed. Elaboration of relevant models of viruses, estimation of spectral response on interaction of electromagnetic (EM) field and viral nanoparticle is the goal of proposed methodology. Core-shell physical model is used as the first approximation of shape-structure of virion. Theoretical solution of EM wave scattering on single spherical virus-like particle (VLP) is applied for determination of EM fields in the areas of core, shell and surrounding medium of (VLP), as well as scattering and absorption characteristics. Numerical results obtained by computer simulation for estimation of EM “spectra” of bacteriophage T7 demonstrate the strong dependence of spectroscopic characteristics on core-shell related electric and geometric parameters of VLP in resonance wavelengths range. Expected spectral response is observable on far-field characterizations. Obtained analytical EM field expressions, modelling technique in complement with experimental spectroscopic methods should be the way of providing the virus spectral signatures, important in bioparticles characterization.

A glutamate is the essential proton transfer gate during the catalytic cycle of the [NiFe] hydrogenase.

PubMed

Dementin, Sébastien; Burlat, Bénédicte; De Lacey, Antonio L; Pardo, Alejandro; Adryanczyk-Perrier, Géraldine; Guigliarelli, Bruno; Fernandez, Victor M; Rousset, Marc

2004-03-12

Kinetic, EPR, and Fourier transform infrared spectroscopic analysis of Desulfovibrio fructosovorans [NiFe] hydrogenase mutants targeted to Glu-25 indicated that this amino acid participates in proton transfer between the active site and the protein surface during the catalytic cycle. Replacement of that glutamic residue by a glutamine did not modify the spectroscopic properties of the enzyme but cancelled the catalytic activity except the para-H(2)/ortho-H(2) conversion. This mutation impaired the fast proton transfer from the active site that allows high turnover numbers for the oxidation of hydrogen. Replacement of the glutamic residue by the shorter aspartic acid slowed down this proton transfer, causing a significant decrease of H(2) oxidation and hydrogen isotope exchange activities, but did not change the para-H(2)/ortho-H(2) conversion activity. The spectroscopic properties of this mutant were totally different, especially in the reduced state in which a non-photosensitive nickel EPR spectrum was obtained.

High pressure reaction cell and transfer mechanism for ultrahigh vacuum spectroscopic chambers

NASA Astrophysics Data System (ADS)

Nelson, A. E.; Schulz, K. H.

2000-06-01

A novel high pressure reaction cell and sample transfer mechanism for ultrahigh vacuum (UHV) spectroscopic chambers is described. The design employs a unique modification of a commercial load-lock transfer system to emulate a tractable microreactor. The reaction cell has an operating pressure range of <1×10-4 to 1000 Torr and can be evacuated to UHV conditions to enable sample transfer into the spectroscopic chamber. Additionally, a newly designed sample holder equipped with electrical and thermocouple contacts is described. The sample holder is capable of resistive specimen heating to 400 and 800 °C with current requirements of 14 A (2 V) and 25 A (3.5 V), respectively. The design enables thorough material science characterization of catalytic reactions and the surface chemistry of catalytic materials without exposing the specimen to atmospheric contaminants. The system is constructed primarily from readily available commercial equipment allowing its rapid implementation into existing laboratories.

Application of Spectroscopic Methods for Structural Analysis of Chitin and Chitosan

PubMed Central

Kumirska, Jolanta; Czerwicka, Małgorzata; Kaczyński, Zbigniew; Bychowska, Anna; Brzozowski, Krzysztof; Thöming, Jorg; Stepnowski, Piotr

2010-01-01

Chitin, the second most important natural polymer in the world, and its N-deacetylated derivative chitosan, have been identified as versatile biopolymers for a broad range of applications in medicine, agriculture and the food industry. Two of the main reasons for this are firstly the unique chemical, physicochemical and biological properties of chitin and chitosan, and secondly the unlimited supply of raw materials for their production. These polymers exhibit widely differing physicochemical properties depending on the chitin source and the conditions of chitosan production. The presence of reactive functional groups as well as the polysaccharide nature of these biopolymers enables them to undergo diverse chemical modifications. A complete chemical and physicochemical characterization of chitin, chitosan and their derivatives is not possible without using spectroscopic techniques. This review focuses on the application of spectroscopic methods for the structural analysis of these compounds. PMID:20559489

The science enabled by the Maunakea Spectroscopic Explorer

NASA Astrophysics Data System (ADS)

Martin, N. F.; Babusiaux, C.

2017-12-01

With its unique wide-field, multi-object, and dedicated spectroscopic capabilities, the Maunakea Spectroscopic Explorer (MSE) is a powerful facility to shed light on the faint Universe. Built around an upgrade of the Canada-France Hawaii Telescope (CFHT) to a 11.25-meter telescope with a dedicated ˜1.5 deg^2, 4,000-fiber wide-field spectrograph that covers the optical and near-infrared wavelengths at resolutions between 2,500 and 40,000, the MSE is the essential follow-up complement to the current and next generations of multi-wavelength imaging surveys, such as the LSST, Gaia, Euclid, eROSITA, SKA, and WFIRST, and is an ideal feeder facility for the extremely large telescopes that are currently being built (E-ELT, GMT, and TMT). The science enabled by the MSE is vast and would have an impact on almost all aspects of astronomy research.

Biometal binding-site mimicry with modular, hetero-bifunctionally modified architecture encompassing a Trp/His motif: insights into spatiotemporal noncovalent interactions from a comparative spectroscopic study.

PubMed

Yang, Chi Ming

2011-03-28

Metal-site Trp/His interactions are crucial to diverse metalloprotein functions. This paper presents a study using metal-motif mimicry to capture and dissect the static and transient components of physicochemical properties underlying the Trp/His aromatic side-chain noncovalent interactions across the first- and second-coordination spheres of biometal ions. Modular biomimetic constructs, EDTA-(L-Trp, L-His) or EWH and DTPA-(L-Trp, L-His) or DWH, featuring a function-significant Trp/His pair, enabled extracting the putative hydrophobic/hydrophilic aromatic interactions surrounding metal centers. Fluorescence, circular dichroism (CD) spectroscopic titrations and ESI mass spectrometry demonstrated that both the constructs stoichiometrically bind to Ca(2+), Co(2+), Cu(2+), Ni(2+), Mn(2+), Zn(2+), Cd(2+), and Fe(2+), and such binding was strongly coupled to stereospecific side-chain structure reorientations of the Trp indole and His imidazole rings. A mechanistic dichotomy corresponding to the participation of the indole unit in the binding event was revealed by a scaffold-platform correlation of steady-state fluorescence-response landscape, illuminating that secondary-coordination-sphere ligand cation-π interactions were immediately followed by subsequent transient physicochemical processes including through-space energy transfer, charge transfer and/or electron transfer, depending on the type of metals. The fluorescence quenching of Trp side chain by 3d metal ions can be ascribed to through-space d-π interactions. While the fluorescence titration was capable of illuminating a two-component energetic model, clean isosbestic/isodichroic points in the CD titration spectra indicated that the metallo-constructs, such as Cu(2+)-EWH complex, fold thermodynamically by means of a two-state equilibrium. Further, the metal-ion dependence of Trp conformational variation in the modular architecture of metal-bound scaffolds was evidenced unambiguously by the CD spectra and supported by MMFF calculations; both were capable of distinguishing between the coordination geometry and the preference for metal binding mode. The study thus helps understand how aromatic rings around metal-sites have unique capabilities through the control of the spatiotemporal distribution of noncovalent interaction elements to achieve diverse chemical functionality.

On the magnetic polarizability tensor of US coinage

NASA Astrophysics Data System (ADS)

Davidson, John L.; Abdel-Rehim, Omar A.; Hu, Peipei; Marsh, Liam A.; O'Toole, Michael D.; Peyton, Anthony J.

2018-03-01

The magnetic dipole polarizability tensor of a metallic object gives unique information about the size, shape and electromagnetic properties of the object. In this paper, we present a novel method of coin characterization based on the spectroscopic response of the absolute tensor. The experimental measurements are validated using a combination of tests with a small set of bespoke coin surrogates and simulated data. The method is applied to an uncirculated set of US coins. Measured and simulated spectroscopic tensor responses of the coins show significant differences between different coin denominations. The presented results are encouraging as they strongly demonstrate the ability to characterize coins using an absolute tensor approach.

Polypropionate lactones of deoxysugars glycosides from slime mold Lycogala epidendrum.

PubMed

Rezanka, Tomás; Dvoráková, Radmila

2003-08-01

Two novel polypropionate lactone glycosides (1 and 2, i.e. lycogalinosides A and B) were isolated from the slime mold Lycogala epidendrum. Their structures, including the absolute configurations of the hydroxyl and methyls groups, were determined by means of extensive spectroscopic data such as mass, IR, UV, and 1D and 2D NMR spectra and chemical degradation followed by spectroscopic and chromatographic analysis. Compounds 1 and 2 are unique in structure containing a 2-deoxy-alpha-L-fucopyranosyl-(1-4)-6-deoxy-beta-D-gulopyranosyl unit and a beta-D-olivopyranosyl-(1-4)-beta-D-fucopyranosyl unit, respectively, and showed growth inhibitory activities against Gram-positive bacteria.

Critical insight into the interaction of naringenin with human haemoglobin: A combined spectroscopic and computational modeling approaches

NASA Astrophysics Data System (ADS)

Maity, Subhajit; Chakraborty, Sandipan; Chakraborti, Abhay Sankar

2017-02-01

The present study demonstrates critical insight into the binding of a bioactive flavanone naringenin with normal human haemoglobin (NHb). Both spectrophotometric and spectrofluorimetric studies reveal that naringenin interacts with NHb. The binding affinity constant and number of binding sites appear to be approximately (1.5 ± 0.2) × 104 M-1 and 1, respectively. Static quenching seems to be an important factor in binding process, as evident from steady-state and time-resolved fluorescence spectroscopic studies. Far UV circular dichroism spectroscopy depicts that binding of naringenin to NHb causes no change in the secondary structure of the protein, which is also evident from Fourier transform infrared spectroscopic study. Free energy change (ΔG0) for naringenin-NHb interaction, determined by spectroscopic and isothermal calorimetric method, appears to be -5.67 kcal/mol and -6.90 kcal/mol, respectively, and is close to the docking energy -6.84 kcal/mol. Molecular docking suggests that naringenin binds near the cavity of the tetrameric heme protein, forming hydrogen bonds with surrounding amino acid residues. The binding site is away from the heme moieties, implicating naringenin binding does not affect the oxygen binding capacity of NHb, which makes the protein a suitable carrier of the flavonoid.

Raman spectroscopy in the analysis of cellulose nanomaterials

Treesearch

Umesh P. Agarwal

2017-01-01

Cellulose nanomaterials (CNs) are new types of materials derived from celluloses and offer unique challenges and opportunities for Raman spectroscopic investigations. CNs can be classified into the categories of cellulose nanocrystals (CNCs, also known as cellulose whisker) and cellulose nanofibrils (CNFs, also known as nanofibrillated cellulose or NFCs) which when...

Metal-Metal Interactions in Heterobimetallic Complexes with Dinucleating Redox-Active Ligands.

PubMed

Broere, Daniël L J; Modder, Dieuwertje K; Blokker, Eva; Siegler, Maxime A; van der Vlugt, Jarl Ivar

2016-02-12

The tuning of metal-metal interactions in multinuclear assemblies is a challenge. Selective P coordination of a redox-active PNO ligand to Au(I) followed by homoleptic metalation of the NO pocket with Ni(II) affords a unique trinuclear Au-Ni-Au complex. This species features two antiferromagnetically coupled ligand-centered radicals and a double intramolecular d(8)-d(10) interaction, as supported by spectroscopic, single-crystal X-ray diffraction, and computational data. A corresponding cationic dinuclear Au-Ni analogue with a stronger d(8)-d(10) interaction is also reported. Although both heterobimetallic structures display rich electrochemistry, only the trinuclear Au-Ni-Au complex facilitates electrocatalytic C-X bond activation of alkyl halides in its doubly reduced state. Hence, the presence of a redox-active ligand framework, an available coordination site at gold, and the nature of the nickel-gold interaction appear to be essential for this reactivity. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Investigating the intermediates in the reaction of ribonucleoside triphosphate reductase from Lactobacillus leichmannii : An application of HF EPR-RFQ technology

NASA Astrophysics Data System (ADS)

Manzerova, Julia; Krymov, Vladimir; Gerfen, Gary J.

2011-12-01

In this investigation high-frequency electron paramagnetic resonance spectroscopy (HFEPR) in conjunction with innovative rapid freeze-quench (RFQ) technology is employed to study the exchange-coupled thiyl radical-cob(II)alamin system in ribonucleotide reductase from a prokaryote Lactobacillus leichmannii. The size of the exchange coupling ( Jex) and the values of the thiyl radical g tensor are refined, while confirming the previously determined (Gerfen et al. (1996) [20]) distance between the paramagnets. Conclusions relevant to ribonucleotide reductase catalysis and the architecture of the active site are presented. A key part of this work has been the development of a unique RFQ apparatus for the preparation of millisecond quench time RFQ samples which can be packed into small (0.5 mm ID) sample tubes used for CW and pulsed HFEPR - lack of this ability has heretofore precluded such studies. The technology is compatible with a broad range of spectroscopic techniques and can be readily adopted by other laboratories.

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

Utschig, L. M.; Dalosto, S. D.; Thurnauer, M. C.

Metal ion binding to a surface site on photosynthetic reaction centers (RCs) modulates light-induced electron and proton transfer events in the RC. Whereas many studies have elucidated aspects of metal ion modulation events in Rhodobacter sphaeroides RCs, much less is understood about the surface site in Blastochloris viridis (Blc. viridis) RCs. Interestingly, electron paramagnetic resonance studies revealed two spectroscopically distinct Cu{sup 2+} surface site environments in Blc. viridis RCs. Herein, Cu{sup 2+} has been used to spectroscopically probe the structure of these Cu{sup 2+} site(s) in response to freezing conditions, temperature, and charge separation. One Cu{sup 2+} environment in Blc.more » viridis RCs, termed CuA, exhibits temperature-dependent conformational flexibility. Different conformation states of the CuA{sup 2+} site are trapped when the RC is frozen in the dark either by fast-freeze or slow-freeze procedure. The second Cu{sup 2+} environment, termed CuB, is structurally invariant to different freezing conditions and shows resolved hyperfine coupling to three nitrogen atoms. Cu{sup 2+} is most likely binding at the same location on the RC, but in different coordination environments which may reflect two distinct conformational states of the isolated Blc. viridis RC protein.« less

Electronic structure of the unique [4Fe-3S] cluster in O2-tolerant hydrogenases characterized by 57Fe Mössbauer and EPR spectroscopy

PubMed Central

Pandelia, Maria-Eirini; Bykov, Dmytro; Izsak, Robert; Infossi, Pascale; Giudici-Orticoni, Marie-Thérèse; Bill, Eckhard; Neese, Frank; Lubitz, Wolfgang

2013-01-01

Iron–sulfur clusters are ubiquitous electron transfer cofactors in hydrogenases. Their types and redox properties are important for H2 catalysis, but, recently, their role in a protection mechanism against oxidative inactivation has also been recognized for a [4Fe-3S] cluster in O2-tolerant group 1 [NiFe] hydrogenases. This cluster, which is uniquely coordinated by six cysteines, is situated in the proximity of the catalytic [NiFe] site and exhibits unusual redox versatility. The [4Fe-3S] cluster in hydrogenase (Hase) I from Aquifex aeolicus performs two redox transitions within a very small potential range, forming a superoxidized state above +200 mV vs. standard hydrogen electrode (SHE). Crystallographic data has revealed that this state is stabilized by the coordination of one of the iron atoms to a backbone nitrogen. Thus, the proximal [4Fe-3S] cluster undergoes redox-dependent changes to serve multiple purposes beyond classical electron transfer. In this paper, we present field-dependent 57Fe-Mössbauer and EPR data for Hase I, which, in conjunction with spectroscopically calibrated density functional theory (DFT) calculations, reveal the distribution of Fe valences and spin-coupling schemes for the iron–sulfur clusters. The data demonstrate that the electronic structure of the [4Fe-3S] core in its three oxidation states closely resembles that of corresponding conventional [4Fe-4S] cubanes, albeit with distinct differences for some individual iron sites. The medial and distal iron–sulfur clusters have similar electronic properties as the corresponding cofactors in standard hydrogenases, although their redox potentials are higher. PMID:23267108

Aqua-vanadyl ion interaction with Nafion® membranes

DOE PAGES

Vijayakumar, Murugesan; Govind, Niranjan; Li, Bin; ...

2015-03-23

Lack of comprehensive understanding about the interactions between Nafion membrane and battery electrolytes prevents the straightforward tailoring of optimal materials for redox flow battery applications. In this work, we analyzed the interaction between aqua-vanadyl cation and sulfonic sites within the pores of Nafion membranes using combined theoretical and experimental X-ray spectroscopic methods. Molecular level interactions, namely, solvent share and contact pair mechanisms are discussed based on Vanadium and Sulfur K-edge spectroscopic analysis.

Spectroscopic characterization and O2 reactivity of the trinuclear Cu cluster of mutants of the multicopper oxidase Fet3p.

PubMed

Palmer, Amy E; Quintanar, Liliana; Severance, Scott; Wang, Tzu-Pin; Kosman, Daniel J; Solomon, Edward I

2002-05-21

Fet3p is a multicopper oxidase that uses four copper ions (one type 1, one type 2, and one type 3 binuclear site) to couple substrate oxidation to the reduction of O(2) to H(2)O. The type 1 Cu site shuttles electrons between the substrate and the type 2/type 3 Cu sites which form a trinuclear Cu cluster that is the active site for O(2) reduction. This study extends the spectroscopic and reactivity studies that have been conducted with type 1-substituted Hg (T1Hg) laccase to Fet3p and a mutant of Fet3p in which the trinuclear Cu cluster is perturbed. To examine the reaction between the trinuclear Cu cluster and O(2), the type 1 Cu Cys(484) was mutated to Ser, resulting in a type 1-depleted (T1D) form of the enzyme. Additional His to Gln mutations were made at the trinuclear cluster to further probe specific contributions to reactivity. One of these mutants (His(126)Gln) produces the first stable but perturbed trinuclear Cu cluster (T1DT3' Fet3p). Spectroscopic characterization (absorption, circular dichroism, magnetic circular dichroism, and electron paramagnetic resonance) of the resting trinuclear sites in T1D and T1DT3' Fet3p reveal that the His(126)Gln mutation changes the electronic structure of both the type 3 and type 2 Cu sites. The trinuclear clusters in T1D and T1DT3' Fet3p react with O(2) to produce peroxide intermediates analogous to that observed in T1Hg laccase. Spectroscopic data on the peroxide intermediates in the three forms provide further insight into the structure of this intermediate. In T1D Fet3p, the decay of this peroxide intermediate is pH-dependent, and the rate of decay is 10-fold higher at low pH. In T1DT3' Fet3p, the decay of the peroxide intermediate is pH-independent and is slow at all pH's. This change in the pH dependence provides new insight into the mechanism of intermediate decay involving reductive cleavage of the O-O bond.

Spectroscopic investigation on structure and pH dependent Cocrystal formation between gamma-aminobutyric acid and benzoic acid

NASA Astrophysics Data System (ADS)

Du, Yong; Xue, Jiadan; Cai, Qiang; Zhang, Qi

2018-02-01

Vibrational spectroscopic methods, including terahertz absorption and Raman scattering spectroscopy, were utilized for the characterization and analysis of gamma-aminobutyric acid (GABA), benzoic acid (BA), and the corresponding GABA-BA cocrystal formation under various pH values of aqueous solution. Vibrational spectroscopic results demonstrated that the solvent GABA-BA cocrystal, similar as grinding counterpart, possessed unique characteristic features compared with that of starting parent compounds. The change of vibrational modes for GABA-BA cocrystal comparing with starting components indicates there is strong inter-molecular interaction between GABA and BA molecules during its cocrystallization process. Formation of GABA-BA cocrystal under slow solvent evaporation is impacted by the pH value of aqueous solution. Vibrational spectra indicate that the GABA-BA cocrystal could be stably formed with the solvent condition of 2.00 ≤ pH ≤ 7.00. In contrast, such cocrystallization did not occur and the cocrystal would dissociate into its parent components when the pH value of solvent is lower than 2.00. This study provides experimental benchmark to discriminate and identify the structure of cocrystal and also pH-dependent cocrystallization effect with vibrational spectroscopic techniques in solid-state pharmaceutical fields.

New concepts in multidentate ligand chemistry: effects of multidentarity on catalytic and spectroscopic properties of ferrocenyl polyphosphines.

PubMed

Hierso, Jean-Cyrille; Smaliy, Radomyr; Amardeil, Régine; Meunier, Philippe

2007-11-01

This tutorial review devoted to ligand chemistry deals with the design and properties of ferrocenyl polyphosphines, an original class of multidentate ligands. The development of a varied library of ferrocenyl tetra-, tri- and diphosphine ligands is reviewed. The multidentate nature of these species has led to unique spectroscopic and catalytic properties, in which the spatial proximity of phosphorus atoms is crucial. Regarding their catalytic applications, the key issues of catalyst longevity and ultralow catalyst loadings are discussed. Another part is concerned with fundamental advances gained in physical chemistry for structure elucidation by the study of the intriguing "through-space" NMR spin-spin J couplings existing within several of these polyphosphines.

Time-resolved spectroscopic imaging reveals the fundamentals of cellular NADH fluorescence.

PubMed

Li, Dong; Zheng, Wei; Qu, Jianan Y

2008-10-15

A time-resolved spectroscopic imaging system is built to study the fluorescence characteristics of nicotinamide adenine dinucleotide (NADH), an important metabolic coenzyme and endogenous fluorophore in cells. The system provides a unique approach to measure fluorescence signals in different cellular organelles and cytoplasm. The ratios of free over protein-bound NADH signals in cytosol and nucleus are slightly higher than those in mitochondria. The mitochondrial fluorescence contributes about 70% of overall cellular fluorescence and is not a completely dominant signal. Furthermore, NADH signals in mitochondria, cytosol, and the nucleus respond to the changes of cellular activity differently, suggesting that cytosolic and nuclear fluorescence may complicate the well-known relationship between mitochondrial fluorescence and cellular metabolism.

A Fermi-degenerate three-dimentional optical lattice clock

NASA Astrophysics Data System (ADS)

Goban, Akihisa; Campbell, Sara; Hutson, Ross; Marti, G. Edward; Sonderhouse, Lindsay; Robinson, John; Zhang, Wei; Ye, Jun

2017-04-01

The pursuit of better atomic clocks has advanced many research areas, providing better quantum state control, tighter limits on fundamental constant variation, and improved tests of relativity. Recent progress in optical lattice clock to the accuracy of 2E-18 has benefited from the understanding of atomic interactions. Also the precision of clock spectroscopy has been applied to explore many-body interactions including SU(N) symmetry. In our previous 1D optical lattice, atomic interactions cause suppression and broadening of the atomic resonance, limiting the clock stability. To overcome this limitation, we demonstrate a scalable solution that takes advantage of the high density of a degenerate Fermi gas in a three-dimensional optical lattice to protect against on-site interaction shifts. Using an ultrastable laser, we achieve an unprecedented level of atom-light coherence, reaching a spectroscopic quality factor 5.2E15. We investigate clock systematics unique to this design; on-site interactions are resolved so that their contribution to clock shifts is orders of magnitude suppressed compared to the 1D optical lattice experiments. Also, we measure the combined scalar and tensor magic wavelengths for state-independent trapping along all three lattice axes. We acknowledge support from NIST, DARPA and the NSF JILA Physics Frontier Center.

RED EYES ON WOLF-RAYET STARS: 60 NEW DISCOVERIES VIA INFRARED COLOR SELECTION

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

Mauerhan, Jon C.; Van Dyk, Schuyler D.; Morris, Patrick W., E-mail: mauerhan@ipac.caltech.edu

We have spectroscopically identified 60 Galactic Wolf-Rayet (WR) stars, including 38 nitrogen types (WN) and 22 carbon types (WC). Using photometry from the Spitzer/GLIMPSE and Two Micron All Sky Survey databases, the new WRs were selected via a method we have established that exploits their unique infrared colors, which is mainly the result of excess radiation generated by free-free scattering within their dense ionized winds. The selection criterion has been refined since the last report, resulting in a WR detection rate of {approx}20% in spectroscopic follow-up of candidates that comprise a broad color space defined by the color distribution ofmore » all known WRs having B > 14 mag. However, there are smaller regions within this color space that yield WRs at a rate of >50% in spectroscopic follow-up. Candidates that are not WRs are mainly Be stars, which is possibly attributable to the physical similarities between the free-free emission parameters of Be disks and WR winds. As an additional selection experiment, the list of WR candidates was cross-correlated with archival X-ray point-source catalogs, which increases the WR detection rate of the broad color space to {approx}40%; 10 new WR X-ray sources have been found in addition to a previously unrecognized X-ray counterpart to a known WR. The extinction values, distances, and Galactocentric radii of all new WRs are calculated using the method of spectroscopic parallax. Although the majority of the new WRs have no obvious association with stellar clusters, two WC8 stars reside in a previously unknown massive-star cluster, in which five OB supergiants were also identified. The new system lies at an estimated distance of {approx}6.1 kpc, near the intersection of the Scutum-Centaurus Arm with the Galaxy's bar. In addition, two WC and four WN stars, all but one of which are X-ray sources, were identified in association with the stellar clusters Danks 1 and 2. A WN9 star has also been associated with the cluster [DBS2003] 179. This work brings the total number of known Galactic WRs to 476, or {approx}7%-8% of the total empirically estimated population. An examination of their Galactic distribution reveals an approximate tracing of the spiral arms and an enhanced WR surface density toward several massive-star formation sites.« less

Red Eyes on Wolf-Rayet Stars: 60 New Discoveries via Infrared Color Selection

NASA Astrophysics Data System (ADS)

Mauerhan, Jon C.; Van Dyk, Schuyler D.; Morris, Patrick W.

2011-08-01

We have spectroscopically identified 60 Galactic Wolf-Rayet (WR) stars, including 38 nitrogen types (WN) and 22 carbon types (WC). Using photometry from the Spitzer/GLIMPSE and Two Micron All Sky Survey databases, the new WRs were selected via a method we have established that exploits their unique infrared colors, which is mainly the result of excess radiation generated by free-free scattering within their dense ionized winds. The selection criterion has been refined since the last report, resulting in a WR detection rate of ≈20% in spectroscopic follow-up of candidates that comprise a broad color space defined by the color distribution of all known WRs having B > 14 mag. However, there are smaller regions within this color space that yield WRs at a rate of >50% in spectroscopic follow-up. Candidates that are not WRs are mainly Be stars, which is possibly attributable to the physical similarities between the free-free emission parameters of Be disks and WR winds. As an additional selection experiment, the list of WR candidates was cross-correlated with archival X-ray point-source catalogs, which increases the WR detection rate of the broad color space to ≈40% 10 new WR X-ray sources have been found in addition to a previously unrecognized X-ray counterpart to a known WR. The extinction values, distances, and Galactocentric radii of all new WRs are calculated using the method of spectroscopic parallax. Although the majority of the new WRs have no obvious association with stellar clusters, two WC8 stars reside in a previously unknown massive-star cluster, in which five OB supergiants were also identified. The new system lies at an estimated distance of ≈6.1 kpc, near the intersection of the Scutum-Centaurus Arm with the Galaxy's bar. In addition, two WC and four WN stars, all but one of which are X-ray sources, were identified in association with the stellar clusters Danks 1 and 2. A WN9 star has also been associated with the cluster [DBS2003] 179. This work brings the total number of known Galactic WRs to 476, or ≈7%-8% of the total empirically estimated population. An examination of their Galactic distribution reveals an approximate tracing of the spiral arms and an enhanced WR surface density toward several massive-star formation sites.

In situ characterization of cofacial Co(IV) centers in Co4O4 cubane: Modeling the high-valent active site in oxygen-evolving catalysts.

PubMed

Brodsky, Casey N; Hadt, Ryan G; Hayes, Dugan; Reinhart, Benjamin J; Li, Nancy; Chen, Lin X; Nocera, Daniel G

2017-04-11

The Co 4 O 4 cubane is a representative structural model of oxidic cobalt oxygen-evolving catalysts (Co-OECs). The Co-OECs are active when residing at two oxidation levels above an all-Co(III) resting state. This doubly oxidized Co(IV) 2 state may be captured in a Co(III) 2 (IV) 2 cubane. We demonstrate that the Co(III) 2 (IV) 2 cubane may be electrochemically generated and the electronic properties of this unique high-valent state may be probed by in situ spectroscopy. Intervalence charge-transfer (IVCT) bands in the near-IR are observed for the Co(III) 2 (IV) 2 cubane, and spectroscopic analysis together with electrochemical kinetics measurements reveal a larger reorganization energy and a smaller electron transfer rate constant for the doubly versus singly oxidized cubane. Spectroelectrochemical X-ray absorption data further reveal systematic spectral changes with successive oxidations from the cubane resting state. Electronic structure calculations correlated to experimental data suggest that this state is best represented as a localized, antiferromagnetically coupled Co(IV) 2 dimer. The exchange coupling in the cofacial Co(IV) 2 site allows for parallels to be drawn between the electronic structure of the Co 4 O 4 cubane model system and the high-valent active site of the Co-OEC, with specific emphasis on the manifestation of a doubly oxidized Co(IV) 2 center on O-O bond formation.

The inner workings of the hydrazine synthase multiprotein complex.

PubMed

Dietl, Andreas; Ferousi, Christina; Maalcke, Wouter J; Menzel, Andreas; de Vries, Simon; Keltjens, Jan T; Jetten, Mike S M; Kartal, Boran; Barends, Thomas R M

2015-11-19

Anaerobic ammonium oxidation (anammox) has a major role in the Earth's nitrogen cycle and is used in energy-efficient wastewater treatment. This bacterial process combines nitrite and ammonium to form dinitrogen (N2) gas, and has been estimated to synthesize up to 50% of the dinitrogen gas emitted into our atmosphere from the oceans. Strikingly, the anammox process relies on the highly unusual, extremely reactive intermediate hydrazine, a compound also used as a rocket fuel because of its high reducing power. So far, the enzymatic mechanism by which hydrazine is synthesized is unknown. Here we report the 2.7 Å resolution crystal structure, as well as biophysical and spectroscopic studies, of a hydrazine synthase multiprotein complex isolated from the anammox organism Kuenenia stuttgartiensis. The structure shows an elongated dimer of heterotrimers, each of which has two unique c-type haem-containing active sites, as well as an interaction point for a redox partner. Furthermore, a system of tunnels connects these active sites. The crystal structure implies a two-step mechanism for hydrazine synthesis: a three-electron reduction of nitric oxide to hydroxylamine at the active site of the γ-subunit and its subsequent condensation with ammonia, yielding hydrazine in the active centre of the α-subunit. Our results provide the first, to our knowledge, detailed structural insight into the mechanism of biological hydrazine synthesis, which is of major significance for our understanding of the conversion of nitrogenous compounds in nature.

In situ characterization of cofacial Co(IV) centers in Co 4O 4 cubane: Modeling the high-valent active site in oxygen-evolving catalysts

DOE PAGES

Brodsky, Casey N.; Hadt, Ryan G.; Hayes, Dugan; ...

2017-03-27

The Co 4O 4 cubane is a representative structural model of oxidic cobalt oxygen evolving catalysts (Co-OECs). The Co-OECs are active when residing at two oxidation levels above an all Co(III) resting state. This doubly oxidized Co(IV) 2 state may be captured in a Co(III) 2(IV) 2 cubane. We demonstrate that the Co(III) 2(IV) 2 cubane may be electrochemically generated and the electronic properties of this unique high-valent state may be probed by in situ spectroscopy. Intervalence charge transfer (IVCT) bands in the near-IR are observed for the Co(III) 2(IV) 2 cubane, and spectroscopic analysis together with electrochemical kinetics measurementsmore » reveal a larger reorganization energy and a smaller electron transfer rate constant for the doubly versus singly oxidized cubane. Spectroelectrochemical X-ray absorption data further reveal systematic spectral changes with successive oxidations from the cubane resting state. Electronic structure calculations correlated to experimental data suggest that this state is best represented as a localized, antiferromagnetically coupled Co(IV) 2 dimer. The exchange coupling in the cofacial Co(IV) 2 site allows for parallels to be drawn between the electronic structure of the Co 4O 4 cubane model system and the high valent active site of the Co-OEC, with specific emphasis on the manifestation of a doubly oxidized Co(IV) 2 center on O–O bond formation.« less

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

B Akabayov; C Richardson

Divalent metal ions are crucial as cofactors for a variety of intracellular enzymatic activities. Mg{sup 2+}, as an example, mediates binding of deoxyribonucleoside 5'-triphosphates followed by their hydrolysis in the active site of DNA polymerase. It is difficult to study the binding of Mg{sup 2+} to an active site because Mg{sup 2+} is spectroscopically silent and Mg{sup 2+} binds with low affinity to the active site of an enzyme. Therefore, we substituted Mg{sup 2+} with Mn{sup 2+}:Mn{sup 2+} that is not only visible spectroscopically but also provides full activity of the DNA polymerase of bacteriophage T7. In order to demonstratemore » that the majority of Mn{sup 2+} is bound to the enzyme, we have applied site-directed titration analysis of T7 DNA polymerase using X-ray near edge spectroscopy. Here we show how X-ray near edge spectroscopy can be used to distinguish between signal originating from Mn{sup 2+} that is free in solution and Mn{sup 2+} bound to the active site of T7 DNA polymerase. This method can be applied to other enzymes that use divalent metal ions as a cofactor.« less

Studies on rock characteristics and timing of creep at selected landslide sites in Taiwan

Treesearch

Cheng-Yi Lee

2000-01-01

A study was conducted to investigate the causes of and rock characteristics at three landslide sites in the Tesngwen Reservoir watershed of southern Taiwan. Research methods used included the petrographic microscope, X-ray diffraction (XRD), scanning electron microscope (SEM), inductively coupled plasma spectroscope (ICP), constant head permeameter in triaxial...

A Simple Surface-Enhanced Raman Spectroscopic Method for on-Site Screening of Tetracycline Residue in Whole Milk

PubMed Central

Dhakal, Sagar; Chao, Kuanglin; Huang, Qing; Kim, Moon; Schmidt, Walter; Qin, Jianwei; Broadhurst, C. Leigh

2018-01-01

Therapeutic and subtherapeutic use of veterinary drugs has increased the risk of residue contamination in animal food products. Antibiotics such as tetracycline are used for mastitis treatment of lactating cows. Milk expressed from treated cows before the withdrawal period has elapsed may contain tetracycline residue. This study developed a simple surface-enhanced Raman spectroscopic (SERS) method for on-site screening of tetracycline residue in milk and water. Six batches of silver colloid nanoparticles were prepared for surface enhancement measurement. Milk-tetracycline and water-tetracycline solutions were prepared at seven concentration levels (1000, 500, 100, 10, 1, 0.1, and 0.01 ppm) and spiked with silver colloid nanoparticles. A 785 nm Raman spectroscopic system was used for spectral measurement. Tetracycline vibrational modes were observed at 1285, 1317 and 1632 cm−1 in water-tetracycline solutions and 1322 and 1621 cm−1 (shifted from 1317 and 1632 cm−1, respectively) in milk-tetracycline solutions. Tetracycline residue concentration as low as 0.01 ppm was detected in both the solutions. The peak intensities at 1285 and 1322 cm−1 were used to estimate the tetracycline concentrations in water and milk with correlation coefficients of 0.92 for water and 0.88 for milk. Results indicate that this SERS method is a potential tool that can be used on-site at field production for qualitative and quantitative detection of tetracycline residues. PMID:29389871

A Simple Surface-Enhanced Raman Spectroscopic Method for on-Site Screening of Tetracycline Residue in Whole Milk.

PubMed

Dhakal, Sagar; Chao, Kuanglin; Huang, Qing; Kim, Moon; Schmidt, Walter; Qin, Jianwei; Broadhurst, C Leigh

2018-02-01

Therapeutic and subtherapeutic use of veterinary drugs has increased the risk of residue contamination in animal food products. Antibiotics such as tetracycline are used for mastitis treatment of lactating cows. Milk expressed from treated cows before the withdrawal period has elapsed may contain tetracycline residue. This study developed a simple surface-enhanced Raman spectroscopic (SERS) method for on-site screening of tetracycline residue in milk and water. Six batches of silver colloid nanoparticles were prepared for surface enhancement measurement. Milk-tetracycline and water-tetracycline solutions were prepared at seven concentration levels (1000, 500, 100, 10, 1, 0.1, and 0.01 ppm) and spiked with silver colloid nanoparticles. A 785 nm Raman spectroscopic system was used for spectral measurement. Tetracycline vibrational modes were observed at 1285, 1317 and 1632 cm -1 in water-tetracycline solutions and 1322 and 1621 cm -1 (shifted from 1317 and 1632 cm -1 , respectively) in milk-tetracycline solutions. Tetracycline residue concentration as low as 0.01 ppm was detected in both the solutions. The peak intensities at 1285 and 1322 cm -1 were used to estimate the tetracycline concentrations in water and milk with correlation coefficients of 0.92 for water and 0.88 for milk. Results indicate that this SERS method is a potential tool that can be used on-site at field production for qualitative and quantitative detection of tetracycline residues.

Lesion-induced DNA weak structural changes detected by pulsed EPR spectroscopy combined with site-directed spin labelling.

PubMed

Sicoli, Giuseppe; Mathis, Gérald; Aci-Sèche, Samia; Saint-Pierre, Christine; Boulard, Yves; Gasparutto, Didier; Gambarelli, Serge

2009-06-01

Double electron-electron resonance (DEER) was applied to determine nanometre spin-spin distances on DNA duplexes that contain selected structural alterations. The present approach to evaluate the structural features of DNA damages is thus related to the interspin distance changes, as well as to the flexibility of the overall structure deduced from the distance distribution. A set of site-directed nitroxide-labelled double-stranded DNA fragments containing defined lesions, namely an 8-oxoguanine, an abasic site or abasic site analogues, a nick, a gap and a bulge structure were prepared and then analysed by the DEER spectroscopic technique. New insights into the application of 4-pulse DEER sequence are also provided, in particular with respect to the spin probes' positions and the rigidity of selected systems. The lesion-induced conformational changes observed, which were supported by molecular dynamics studies, confirm the results obtained by other, more conventional, spectroscopic techniques. Thus, the experimental approaches described herein provide an efficient method for probing lesion-induced structural changes of nucleic acids.

Using non-invasive molecular spectroscopic techniques to detect unique aspects of protein Amide functional groups and chemical properties of modeled forage from different sourced-origins.

PubMed

Ji, Cuiying; Zhang, Xuewei; Yu, Peiqiang

2016-03-05

The non-invasive molecular spectroscopic technique-FT/IR is capable to detect the molecular structure spectral features that are associated with biological, nutritional and biodegradation functions. However, to date, few researches have been conducted to use these non-invasive molecular spectroscopic techniques to study forage internal protein structures associated with biodegradation and biological functions. The objectives of this study were to detect unique aspects and association of protein Amide functional groups in terms of protein Amide I and II spectral profiles and chemical properties in the alfalfa forage (Medicago sativa L.) from different sourced-origins. In this study, alfalfa hay with two different origins was used as modeled forage for molecular structure and chemical property study. In each forage origin, five to seven sources were analyzed. The molecular spectral profiles were determined using FT/IR non-invasive molecular spectroscopy. The parameters of protein spectral profiles included functional groups of Amide I, Amide II and Amide I to II ratio. The results show that the modeled forage Amide I and Amide II were centered at 1653 cm(-1) and 1545 cm(-1), respectively. The Amide I spectral height and area intensities were from 0.02 to 0.03 and 2.67 to 3.36 AI, respectively. The Amide II spectral height and area intensities were from 0.01 to 0.02 and 0.71 to 0.93 AI, respectively. The Amide I to II spectral peak height and area ratios were from 1.86 to 1.88 and 3.68 to 3.79, respectively. Our results show that the non-invasive molecular spectroscopic techniques are capable to detect forage internal protein structure features which are associated with forage chemical properties. Copyright © 2015 Elsevier B.V. All rights reserved.

Life in the Outer Limits: Insight into Hierarchical Merging from the Outermost Structure of the Andromeda Stellar Halo

NASA Astrophysics Data System (ADS)

Beaton, Rachael; Majewski, S. R.; Patterson, R. J.; Guhathakurta, P.; Gilbert, K.; Kalirai, J. S.; Tollerud, E. J.; SPLASH Team

2014-01-01

Owing to their large dynamical timescales, the stellar haloes of Milky Way (MW) sized galaxies represent ideal environments to test modern theories of galaxy formation in the Lambda-CDM paradigm. Only in stellar haloes can the remnants of hierarchical accretion be preserved over long timescales as in-tact dwarf satellites or as tidal debris and can be easily distinguished from the underlying smooth structure. Stellar haloes, however, remain some of the most difficult galactic structures to constrain due to their large angular extent and extremely low surface brightness. Thus, the basic properties of stellar haloes -- the overall stellar distribution, substructure fraction, global kinematics and detailed stellar content -- remained relatively unconstrained. In this thesis, we present several projects designed to understand the current structure and the the formation of the Andromeda (M31) stellar halo, the only stellar halo -- besides our own -- that is within reach of current ground based facilities on the large scale required to constrain the basic properties of stellar haloes. First, we describe a seven season imaging campaign comprising the backbone of the Spectroscopic and Photometric Landscape of the Andromeda Stellar Halo (SPLASH) program. This survey is unique in its application of the Washington + DDO51 filter system to select individual M31 RGB stars without spectroscopic follow up. Second, we use the SPLASH photometric survey to identify sample of halo stars at projected radii of 120 kpc, for which we have obtained spectroscopic follow-up. Third, we add this large radius sample to the existing spectroscopic results from SPLASH, and use this unique sample to explore the stellar kinematics of the halo at large radii with full azimuthal coverage. Lastly, we preview on-going work to constrain the formation of the Andromeda stellar halo, using both in-tact satellites and resolved M31 halo members as tracers of its accretion history.

Scavenging performance and antioxidant activity of γ-alumina nanoparticles towards DPPH free radical: Spectroscopic and DFT-D studies.

PubMed

Zamani, Mehdi; Moradi Delfani, Ali; Jabbari, Morteza

2018-05-03

The radical scavenging performance and antioxidant activity of γ-alumina nanoparticles towards 2,2-diphenyl-1-picrylhydrazyl (DPPH) free radical were investigated by spectroscopic and computational methods. The radical scavenging ability of γ-alumina nanoparticles in the media with different polarity (i.e. i-propanol and n-hexane) was evaluated by measuring the DPPH absorbance in UV-Vis absorption spectra. The structure and morphology of γ-alumina nanoparticles before and after adsorption of DPPH were studied using XRD, FT-IR and UV-Vis spectroscopic techniques. The adsorption of DPPH free radical on the clean and hydrated γ-alumina (1 1 0) surface was examined by dispersion corrected density functional theory (DFT-D) and natural bond orbital (NBO) calculations. Also, time-dependent density functional theory (TD-DFT) was used to predict the absorption spectra. The adsorption was occurred through the interaction of radical nitrogen N and NO 2 groups of DPPH with the acidic and basic sites of γ-alumina surface. The high potential for the adsorption of DPPH radical on γ-alumina nanoparticles was investigated. Interaction of DPPH with Brønsted and Lewis acidic sites of γ-alumina was more favored than Brønsted basic sites. The following order for the adsorption of DPPH over the different active sites of γ-alumina was predicted: Brønsted base < Lewis acid < Brønsted acid. These results are of great significance for the environmental application of γ-alumina nanoparticles in order to remove free radicals. Copyright © 2018. Published by Elsevier B.V.

Measuring the Impact of Rising CO2 and CH4 on the Surface Energy Balance

NASA Astrophysics Data System (ADS)

Feldman, D.; Collins, W.; Biraud, S.; Turner, D. D.; Mlawer, E. J.; Gero, P. J.; Xie, S.; Shippert, T.; Torn, M. S.

2015-12-01

We use observations at the North Slope of Alaska (NSA) and Southern Great Plains (SGP) ARM sites to improve understanding both of the distribution of CO2 and CH4and their influence on the surface energy balance. We use aircraft and ground-based in situ data to characterize the temporal distribution of these greenhouse gases, and spectroscopic observations to derive their collocated surface radiative forcing. The spectroscopically-measured surface radiative forcing from rising CO2 is 0.2 W/m2/decade at both sites, with a seasonal cycle of 0.2 W/m2. This finding is largely consistent with theoretical predictions, providing robust evidence of radiative perturbations to the Earth's surface energy budget due to anthropogenic influences. The contribution from CH4 to the surface energy balance is more spatially and temporally heterogeneous. The ground-based measurements of CH4 at NSA and SGP indicate rising atmospheric concentrations except for a hiatus from 1995-2005, while more recent aircraft profiles indicate that concentrations in the boundary layer and free troposphere are correlated at NSA and decorrelated at SGP. The probability density functions of boundary layer concentrations of CH4 at NSA show little skew, but at SGP show positive skewness, which increased with the introduction of nearby fossil-fuel extraction. The correlated increases in atmospheric measurements of C2H6 and CH4that only occur at SGP are consistent with an anthropogenic influence there. Time-series of spectroscopically-measured CH4 surface radiative forcing at SGP and NSA also indicate positive trends of 0.1 W/m2/decade associated with the end of the hiatus, marked seasonal cycles, and little skew at NSA and a positive skew at SGP. The combination of in situ and spectroscopic measurements at these sites enables the quantification of surface radiative forcing from anthropogenic CH4. Implications are discussed for how advanced spectroscopic remote sensing measurements of CH4 can be used to quantify the impact of fossil fuel extraction on surface energy budget.

Hybrid pigments resulting from several guest dyes onto γ-alumina host: A spectroscopic analysis

NASA Astrophysics Data System (ADS)

Pérez, Erik; Ibarra, Ilich A.; Guzmán, Ariel; Lima, Enrique

2017-02-01

The synthesis of hybrid pigments was made from combination of γ-Al2O3 and some organic chromophores such as carminic acid, alizarin, purpurin, curcumin, fluorescein and betacyanins. The γ-Al2O3 was obtained through sol-gel synthesis with 2-propanol and aluminium tri-sec-butoxide (ATB). This article presents some spectroscopic evidences related to the formation of aluminium complexes between coordinative unsaturated sites (CUS) of aluminium and some organic groups (carboxylic acid, quaternary ammonium and β-keto enol) present in the chromophores structure. The physicochemical properties upcoming from a spectroscopic analysis point out that these materials can be applied in the design of new materials with potential uses in artworks and in the field of cultural heritage.

Spectroscopic Studies of Perturbed T1 Cu Sites in the Multicopper Oxidases Saccharomyces Cerevisiae Fet3p And Rhus Vernicifera Laccase: Allosteric Coupling Between the T1 And Trinuclear Cu Sites

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

Augustine, A.J.; Kragh, M.E.; Sarangi, R.

2009-04-30

The multicopper oxidases catalyze the 4e{sup -} reduction of O{sub 2} to H{sub 2}O coupled to the 1e{sup -} oxidation of 4 equiv of substrate. This activity requires four Cu atoms, including T1, T2, and coupled binuclear T3 sites. The T2 and T3 sites form a trinuclear cluster (TNC) where O{sub 2} is reduced. The T1 is coupled to the TNC through a T1-Cys-His-T3 electron transfer (ET) pathway. In this study the two T3 Cu coordinating His residues which lie in this pathway in Fet3 have been mutated, H483Q, H483C, H485Q, and H485C, to study how perturbation at the TNCmore » impacts the T1 Cu site. Spectroscopic methods, in particular resonance Raman (rR), show that the change from His to Gln to Cys increases the covalency of the T1 Cu?S Cys bond and decreases its redox potential. This study of T1?TNC interactions is then extended to Rhus vernicifera laccase where a number of well-defined species including the catalytically relevant native intermediate (NI) can be trapped for spectroscopic study. The T1 Cu?S covalency and potential do not change in these species relative to resting oxidized enzyme, but interestingly the differences in the structure of the TNC in these species do lead to changes in the T1 Cu rR spectrum. This helps to confirm that vibrations in the cysteine side chain of the T1 Cu site and the protein backbone couple to the Cu?S vibration. These changes in the side chain and backbone provide a possible mechanism for regulating intramolecular T1 to TNC ET in NI and partially reduced enzyme forms for efficient turnover.« less

Binary Cepheids From High-Angular Resolution

NASA Astrophysics Data System (ADS)

Gallenne, A.; Mérand, A.; Kervella, P.

2015-12-01

Optical interferometry is the only technique giving access to milli-arcsecond (mas) spatial resolution. This is a powerful and unique tool to detect the close orbiting companions of Cepheids, and offers an unique opportunity to make progress in resolving the Cepheid mass discrepancy. Our goal in studying binary Cepheids is to measure the astrometric position of the high-contrast companion, and then combine them with spectroscopic measurements to derive the orbital elements, distances, and dynamical masses. In the course of this program, we developed a new tool, CANDID, to search for high-contrast companions and set detection limits from interferometric observations

Identification of biological agents using surface enhanced Raman scattering

NASA Astrophysics Data System (ADS)

Paxon, Tracy L.; Duthie, R. Scott; Renko, Casey; Burns, Andrew A.; Lesaicherre, Marie L.; Mondello, Frank J.

2011-05-01

GE Global Research Center, in collaboration with Morpho Detection, Inc. has developed an assay scheme for the identification of biological agents using Surface Enhanced Raman Scattering (SERS). Specifically, unique spectroscopic signatures are generated using SERS tags consisting of individual glass-encapsulated gold nanoparticles and surfacebound reporter molecules. These SERS tags are modified with a capture moiety specific to the antigen of interest, and serve as a spectroscopic label in a bead-based sandwich assay. Assays are being developed for a variety of pathogens and this paper will focus on aspects of assay development, optimization, stabilization and validation. Results on the development of an assay to detect Ricin toxin will be presented, and preliminary feasibility studies for the detection of additional pathogens will be discussed.

Structural Characteristics and Reactivity Relationships of Nitroaromatic and Nitramine Explosives – A Review of Our Computational Chemistry and Spectroscopic Research

PubMed Central

Qasim, Mohammad M.; Moore, Brett; Taylor, Lyssa; Honea, Patricia; Gorb, Leonid; Leszczynski, Jerzy

2007-01-01

Although much has been discovered, discussed and written as to problems of contamination by various military unique compounds, particularly by the nitrogen based energetics (NOCs), remaining problems dictate further evaluation of actual and potential risk to the environment by these energetics and their derivatives and metabolites through determination of their environmental impact—transport, fate and toxicity. This work comprises an effort to understand structural relationships and degradation mechanisms of current and emerging explosives, including nitroaromatic; cyclic and cage cyclic nitramine; and a nitrocubane. This review of our computational chemistry and spectroscopic research describes and compares competitive degradation mechanisms by free radical oxidative, reductive and alkali hydrolysis, relating them, when possible, to environmental risk.

Spectroscopic investigation on structure and pH dependent Cocrystal formation between gamma-aminobutyric acid and benzoic acid.

PubMed

Du, Yong; Xue, Jiadan; Cai, Qiang; Zhang, Qi

2018-02-15

Vibrational spectroscopic methods, including terahertz absorption and Raman scattering spectroscopy, were utilized for the characterization and analysis of gamma-aminobutyric acid (GABA), benzoic acid (BA), and the corresponding GABA-BA cocrystal formation under various pH values of aqueous solution. Vibrational spectroscopic results demonstrated that the solvent GABA-BA cocrystal, similar as grinding counterpart, possessed unique characteristic features compared with that of starting parent compounds. The change of vibrational modes for GABA-BA cocrystal comparing with starting components indicates there is strong inter-molecular interaction between GABA and BA molecules during its cocrystallization process. Formation of GABA-BA cocrystal under slow solvent evaporation is impacted by the pH value of aqueous solution. Vibrational spectra indicate that the GABA-BA cocrystal could be stably formed with the solvent condition of 2.00≤pH≤7.00. In contrast, such cocrystallization did not occur and the cocrystal would dissociate into its parent components when the pH value of solvent is lower than 2.00. This study provides experimental benchmark to discriminate and identify the structure of cocrystal and also pH-dependent cocrystallization effect with vibrational spectroscopic techniques in solid-state pharmaceutical fields. Copyright © 2017 Elsevier B.V. All rights reserved.

Binding of copper to lysozyme: Spectroscopic, isothermal titration calorimetry and molecular docking studies

NASA Astrophysics Data System (ADS)

Jing, Mingyang; Song, Wei; Liu, Rutao

2016-07-01

Although copper is essential to all living organisms, its potential toxicity to human health have aroused wide concerns. Previous studies have reported copper could alter physical properties of lysozyme. The direct binding of copper with lysozyme might induce the conformational and functional changes of lysozyme and then influence the body's resistance to bacterial attack. To better understand the potential toxicity and toxic mechanisms of copper, the interaction of copper with lysozyme was investigated by biophysical methods including multi-spectroscopic measurements, isothermal titration calorimetry (ITC), molecular docking study and enzyme activity assay. Multi-spectroscopic measurements proved that copper quenched the intrinsic fluorescence of lysozyme in a static process accompanied by complex formation and conformational changes. The ITC results indicated that the binding interaction was a spontaneous process with approximately three thermodynamical binding sites at 298 K and the hydrophobic force is the predominant driven force. The enzyme activity was obviously inhibited by the addition of copper with catalytic residues Glu 35 and Asp 52 locating at the binding sites. This study helps to elucidate the molecular mechanism of the interaction between copper and lysozyme and provides reference for toxicological studies of copper.

Single-Molecule Interfacial Electron Transfer

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

Lu, H. Peter

This project is focused on the use of single-molecule high spatial and temporal resolved techniques to study molecular dynamics in condensed phase and at interfaces, especially, the complex reaction dynamics associated with electron and energy transfer rate processes. The complexity and inhomogeneity of the interfacial ET dynamics often present a major challenge for a molecular level comprehension of the intrinsically complex systems, which calls for both higher spatial and temporal resolutions at ultimate single-molecule and single-particle sensitivities. Combined single-molecule spectroscopy and electrochemical atomic force microscopy approaches are unique for heterogeneous and complex interfacial electron transfer systems because the static andmore » dynamic inhomogeneities can be identified and characterized by studying one molecule at a specific nanoscale surface site at a time. The goal of our project is to integrate and apply these spectroscopic imaging and topographic scanning techniques to measure the energy flow and electron flow between molecules and substrate surfaces as a function of surface site geometry and molecular structure. We have been primarily focusing on studying interfacial electron transfer under ambient condition and electrolyte solution involving both single crystal and colloidal TiO 2 and related substrates. The resulting molecular level understanding of the fundamental interfacial electron transfer processes will be important for developing efficient light harvesting systems and broadly applicable to problems in fundamental chemistry and physics. We have made significant advancement on deciphering the underlying mechanism of the complex and inhomogeneous interfacial electron transfer dynamics in dyesensitized TiO 2 nanoparticle systems that strongly involves with and regulated by molecule-surface interactions. We have studied interfacial electron transfer on TiO 2 nanoparticle surfaces by using ultrafast single-molecule spectroscopy and electrochemical AFM metal tip scanning microscopy, focusing on understanding the interfacial electron transfer dynamics at specific nanoscale electron transfer sites with high-spatially and temporally resolved topographic-and-spectroscopic characterization at individual molecule basis, characterizing single-molecule rate processes, reaction driving force, and molecule-substrate electronic coupling. One of the most significant characteristics of our new approach is that we are able to interrogate the complex interfacial electron transfer dynamics by actively pin-point energetic manipulation of the surface interaction and electronic couplings, beyond the conventional excitation and observation.« less

Hydrogen-induced structural changes at the nickel site of the regulatory [NiFe] hydrogenase from Ralstonia eutropha detected by X-ray absorption spectroscopy.

PubMed

Haumann, Michael; Porthun, Antje; Buhrke, Thorsten; Liebisch, Peter; Meyer-Klaucke, Wolfram; Friedrich, Bärbel; Dau, Holger

2003-09-23

For the first time, the nickel site of the hydrogen sensor of Ralstonia eutropha, the regulatory [NiFe] hydrogenase (RH), was investigated by X-ray absorption spectroscopy (XAS) at the nickel K-edge. The oxidation state and the atomic structure of the Ni site were investigated in the RH in the absence (air-oxidized, RH(ox)) and presence of hydrogen (RH(+H2)). Incubation with hydrogen is found to cause remarkable changes in the spectroscopic properties. The Ni-C EPR signal, indicative of Ni(III), is detectable only in the RH(+H2) state. XANES and EXAFS spectra indicate a coordination of the Ni in the RH(ox) and RH(+H2) that pronouncedly differs from the one in standard [NiFe] hydrogenases. Also, the changes induced by exposure to H(2) are unique. A drastic modification in the XANES spectra and an upshift of the K-edge energy from 8339.8 (RH(ox)) to 8341.1 eV (RH(+H2)) is observed. The EXAFS spectra indicate a change in the Ni coordination in the RH upon exposure to H(2). One likely interpretation of the data is the detachment of one sulfur ligand in RH(+H2) and the binding of additional (O,N) or H ligands. The following Ni oxidation states and coordinations are proposed: five-coordinated Ni(II)(O,N)(2)S(3) for RH(ox) and six-coordinated Ni((III))(O,N)(3)X(1)S(2) [X being either an (O,N) or H ligand] for RH(+H2). Implications of the structural features of the Ni site of the RH in relation to its function, hydrogen sensing, are discussed.

Chandra’s first decade of discovery

PubMed Central

Swartz, Douglas A.; Wolk, Scott J.; Fruscione, Antonella

2010-01-01

We review some of the many scientific results reported at a symposium held in September 2009 celebrating the 10th anniversary of National Aeronautics and Space Administration's (NASA's) Chandra X-ray Observatory. These results were contributed by scientists who were among the more than 300 symposium participants. We highlight those results that most emphasize the unique imaging and spectroscopic capabilities of Chandra. PMID:20406906

Quantitative Determination of Iron in Limonite Using Spectroscopic Methods with Senior and General Chemistry Students: Geology-Inspired Chemistry Lab Explorations

ERIC Educational Resources Information Center

Bopegedera, A. M. R. P.; Coughenour, Christopher L.; Oswalt, Andrew J.

2016-01-01

Limonite is the field term for a mixed assemblage of ferric oxyhydroxides, often containing nonferric silicate impurities. It is abundant on Earth's surface, possesses variable iron content, and is easily recognized by distinctive yellow and ochre hues. Limonite is a unique centerpiece for undergraduate chemistry laboratories because each sample…

Spectroscopic and Physical Characterization of Functionalized Au Nanoparticles: A Multiweek Experimental Project

ERIC Educational Resources Information Center

Masson, Jean-Francois; Yockell-Lelièvre, Hélène

2014-01-01

A term project was introduced in teaching advanced spectroscopy and notions of nanotechnology to chemistry students at the graduate level (M.Sc. and Ph.D.). This project could also be suited for an honor's thesis at the undergraduate level. Students were assigned a unique combination of nanoparticle synthesis (13 nm Au nanospheres, ~100 nm…

Infrared and Raman spectroscopic studies of structural variations in minerals from Apollo 11, 12, 14 and 15 samples, volume 3

NASA Technical Reports Server (NTRS)

Estep, P. A.; Kovach, J. J.; Waldstein, P.; Karr, C., Jr.

1972-01-01

Infrared and Raman vibrational spectroscopic data, yielding direct information on molecular structure, were obtained for single grains ( 150 microns) of minerals, basalts, and glasses isolated from Apollo 11, 12, 14, and 15 rock and dust samples, and for grains in Apollo 14 polished butt samples. From the vibrational data, specification substitutions were determined for the predominant silicate minerals of plagioclase, pyroxene, and olivine. Unique spectral variations for grains of K-feldspar, orthopyroxene, pyroxenoid, and ilmenite were observed to exceed the ranges of terrestrial samples, and these variations may be correlatable with formation histories. Alpha-quartz was isolated as pure single grains, in granitic grains composited with sanidine, and in unique grains that were intimately mixed with varying amounts of glass. Accessory minerals of chromite and ulvospinel were isolated as pure grains and structurally characterized from their distinctive infrared spectra. Fundamental vibrations of the SiO4 tetrahedra in silicate minerals were used to classify bulk compositions in dust sieved fractions, basalt grains and glass particles, and to compare modal characteristics for maria, highland and rille samples. No hydrated minerals were found in any of the samples studied, indicating anhydrous formation conditions.

A Hidden Active Site in the Potential Drug Target Mycobacterium tuberculosis dUTPase Is Accessible through Small Amplitude Protein Conformational Changes*

PubMed Central

Lopata, Anna; Leveles, Ibolya; Bendes, Ábris Ádám; Viskolcz, Béla; Vértessy, Beáta G.; Jójárt, Balázs; Tóth, Judit

2016-01-01

dUTPases catalyze the hydrolysis of dUTP into dUMP and pyrophosphate to maintain the proper nucleotide pool for DNA metabolism. Recent evidence suggests that dUTPases may also represent a selective drug target in mycobacteria because of the crucial role of these enzymes in maintaining DNA integrity. Nucleotide-hydrolyzing enzymes typically harbor a buried ligand-binding pocket at interdomain or intersubunit clefts, facilitating proper solvent shielding for the catalyzed reaction. The mechanism by which substrate binds this hidden pocket and product is released in dUTPases is unresolved because of conflicting crystallographic and spectroscopic data. We sought to resolve this conflict by using a combination of random acceleration molecular dynamics (RAMD) methodology and structural and biochemical methods to study the dUTPase from Mycobacterium tuberculosis. In particular, the RAMD approach used in this study provided invaluable insights into the nucleotide dissociation process that reconciles all previous experimental observations. Specifically, our data suggest that nucleotide binding takes place as a small stretch of amino acids transiently slides away and partially uncovers the active site. The in silico data further revealed a new dUTPase conformation on the pathway to a relatively open active site. To probe this model, we developed the Trp21 reporter and collected crystallographic, spectroscopic, and kinetic data that confirmed the interaction of Trp21 with the active site shielding C-terminal arm, suggesting that the RAMD method is effective. In summary, our computational simulations and spectroscopic results support the idea that small loop movements in dUTPase allow the shuttlingof the nucleotides between the binding pocket and the solvent. PMID:27815500

Deciphering the complexation process of a fluoroquinolone antibiotic, levofloxacin, with bovine serum albumin in the presence of additives

NASA Astrophysics Data System (ADS)

Kaur, Amandeep; Khan, Imran Ahmd; Banipal, Parampaul Kaur; Banipal, Tarlok Singh

2018-02-01

The current work aims to explore the thermodynamic and conformational aspects for the binding of fluoroquinolone antibacterial drug, levofloxacin (LFC), with bovine serum albumin (BSA) using calorimetric, spectroscopic (UV-visible, fluorescence, circular dichroism, and 1H NMR), dynamic light scattering (DLS) and computational methods (molecular docking). The binding of LFC with BSA at two sequential sites with higher affinity ( 103 M- 1) at the first site has been explored by calorimetry whereas the binding at a single site with affinity of the order of 104 M- 1 has been observed from fluorescence spectroscopy. The calorimetric study in the presence of additives along with docking analysis reveals the significant role of electrostatic, hydrogen bonding, and hydrophobic interactions in the association process. The slight conformational changes in protein as well as the changes in the water network structure around the binding cavity of protein have been observed from spectroscopic and DLS measurements. The LFC induced quenching of BSA fluorescence was observed to be initiated mainly through the static quenching process and this suggests the formation of ground state LFC-BSA association complex. The stronger interactions of LFC in the cavity of Sudlow site I (subdomain IIA) of protein have been explored from site marker calorimetric and molecular docking study.

Binding of dinitrogen to an iron-sulfur-carbon site

NASA Astrophysics Data System (ADS)

Čorić, Ilija; Mercado, Brandon Q.; Bill, Eckhard; Vinyard, David J.; Holland, Patrick L.

2015-10-01

Nitrogenases are the enzymes by which certain microorganisms convert atmospheric dinitrogen (N2) to ammonia, thereby providing essential nitrogen atoms for higher organisms. The most common nitrogenases reduce atmospheric N2 at the FeMo cofactor, a sulfur-rich iron-molybdenum cluster (FeMoco). The central iron sites that are coordinated to sulfur and carbon atoms in FeMoco have been proposed to be the substrate binding sites, on the basis of kinetic and spectroscopic studies. In the resting state, the central iron sites each have bonds to three sulfur atoms and one carbon atom. Addition of electrons to the resting state causes the FeMoco to react with N2, but the geometry and bonding environment of N2-bound species remain unknown. Here we describe a synthetic complex with a sulfur-rich coordination sphere that, upon reduction, breaks an Fe-S bond and binds N2. The product is the first synthetic Fe-N2 complex in which iron has bonds to sulfur and carbon atoms, providing a model for N2 coordination in the FeMoco. Our results demonstrate that breaking an Fe-S bond is a chemically reasonable route to N2 binding in the FeMoco, and show structural and spectroscopic details for weakened N2 on a sulfur-rich iron site.

Alternative ground states enable pathway switching in biological electron transfer

DOE PAGES

Abriata, Luciano A.; Alvarez-Paggi, Damian; Ledesma, Gabirela N.; ...

2012-10-10

Electron transfer is the simplest chemical reaction and constitutes the basis of a large variety of biological processes, such as photosynthesis and cellular respiration. Nature has evolved specific proteins and cofactors for these functions. The mechanisms optimizing biological electron transfer have been matter of intense debate, such as the role of the protein milieu between donor and acceptor sites. Here we propose a mechanism regulating long-range electron transfer in proteins. Specifically, we report a spectroscopic, electrochemical, and theoretical study on WT and single-mutant CuA redox centers from Thermus thermophilus, which shows that thermal fluctuations may populate two alternative ground-state electronicmore » wave functions optimized for electron entry and exit, respectively, through two different and nearly perpendicular pathways. In conclusion, these findings suggest a unique role for alternative or “invisible” electronic ground states in directional electron transfer. Moreover, it is shown that this energy gap and, therefore, the equilibrium between ground states can be fine-tuned by minor perturbations, suggesting alternative ways through which protein–protein interactions and membrane potential may optimize and regulate electron–proton energy transduction.« less

Hexameric supramolecular scaffold orients carbohydrates to sense bacteria.

PubMed

Grünstein, Dan; Maglinao, Maha; Kikkeri, Raghavendra; Collot, Mayeul; Barylyuk, Konstantin; Lepenies, Bernd; Kamena, Faustin; Zenobi, Renato; Seeberger, Peter H

2011-09-07

Carbohydrates are integral to biological signaling networks and cell-cell interactions, yet the detection of discrete carbohydrate-lectin interactions remains difficult since binding is generally weak. A strategy to overcome this problem is to create multivalent sensors, where the avidity rather than the affinity of the interaction is important. Here we describe the development of a series of multivalent sensors that self-assemble via hydrophobic supramolecular interactions. The multivalent sensors are comprised of a fluorescent ruthenium(II) core surrounded by a heptamannosylated β-cyclodextrin scaffold. Two additional series of complexes were synthesized as proof-of-principle for supramolecular self-assembly, the fluorescent core alone and the core plus β-cyclodextrin. Spectroscopic analyses confirmed that the three mannosylated sensors displayed 14, 28, and 42 sugar units, respectively. Each complex adopted original and unique spatial arrangements. The sensors were used to investigate the influence of carbohydrate spatial arrangement and clustering on the mechanistic and qualitative properties of lectin binding. Simple visualization of binding between a fluorescent, multivalent mannose complex and the Escherichia coli strain ORN178 that possesses mannose-specific receptor sites illustrates the potential for these complexes as biosensors.

Diagnostic Chemical Analysis of Exhaled Human Breath Using a Novel Sub-Millimeter Spectroscopic Approach

NASA Astrophysics Data System (ADS)

Fosnight, Alyssa M.; Moran, Benjamin L.; Branco, Daniela R.; Thomas, Jessica R.; Medvedev, Ivan R.

2013-06-01

As many as 3000 chemicals are reported to be found in exhaled human breath. Many of these chemicals are linked to certain health conditions and environmental exposures. Present state of the art techniques used for analysis of exhaled human breath include mass spectrometry based methods, infrared spectroscopic sensors, electro chemical sensors and semiconductor oxide based testers. Some of these techniques are commercially available but are somewhat limited in their specificity and exhibit fairly high probability of false alarm. Here, we present the results of our most recent study which demonstrated a novel application of a terahertz high resolutions spectroscopic technique to the analysis of exhaled human breath, focused on detection of ethanol in the exhaled breath of a person which consumed an alcoholic drink. This technique possesses nearly ``absolute'' specificity and we demonstrated its ability to uniquely identify ethanol, methanol, and acetone in human breath. This project is now complete and we are looking to extend this method of chemical analysis of exhaled human breath to a broader range of chemicals in an attempt to demonstrate its potential for biomedical diagnostic purposes.

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

Brodsky, Casey N.; Hadt, Ryan G.; Hayes, Dugan

The Co 4O 4 cubane is a representative structural model of oxidic cobalt oxygen evolving catalysts (Co-OECs). The Co-OECs are active when residing at two oxidation levels above an all Co(III) resting state. This doubly oxidized Co(IV) 2 state may be captured in a Co(III) 2(IV) 2 cubane. We demonstrate that the Co(III) 2(IV) 2 cubane may be electrochemically generated and the electronic properties of this unique high-valent state may be probed by in situ spectroscopy. Intervalence charge transfer (IVCT) bands in the near-IR are observed for the Co(III) 2(IV) 2 cubane, and spectroscopic analysis together with electrochemical kinetics measurementsmore » reveal a larger reorganization energy and a smaller electron transfer rate constant for the doubly versus singly oxidized cubane. Spectroelectrochemical X-ray absorption data further reveal systematic spectral changes with successive oxidations from the cubane resting state. Electronic structure calculations correlated to experimental data suggest that this state is best represented as a localized, antiferromagnetically coupled Co(IV) 2 dimer. The exchange coupling in the cofacial Co(IV) 2 site allows for parallels to be drawn between the electronic structure of the Co 4O 4 cubane model system and the high valent active site of the Co-OEC, with specific emphasis on the manifestation of a doubly oxidized Co(IV) 2 center on O–O bond formation.« less

Duality based direct resolution of unique profiles using zero concentration region information.

PubMed

Tavakkoli, Elnaz; Rajkó, Róbert; Abdollahi, Hamid

2018-07-01

Self Modeling Curve Resolution (SMCR) is a class of techniques concerned with estimating pure profiles underlying a set of measurements on chemical systems. In general, the estimated profiles are ambiguous (non-unique) except if some special conditions fulfilled. Implementing the adequate information can reduce the so-called rotational ambiguity effectively, and in the most desirable cases lead to the unique solution. Therefore, studies on circumstances resulting in unique solution are of particular importance. The conditions of unique solution can particularly be studied based on duality principle. In bilinear chemical (e.g., spectroscopic) data matrix, there is a natural duality between its row and column vector spaces using minimal constraints (non-negativity of concentrations and absorbances). In this article, the conditions of the unique solution according to duality concept and using zero concentration region information is intended to show. A simulated dataset of three components and an experimental system with synthetic mixtures containing three amino acids tyrosine, phenylalanine and tryptophan are analyzed. It is shown that in the presence of sufficient information, the reliable unique solution is obtained that is valuable in analytical qualification and for quantitative verification analysis. Copyright © 2018 Elsevier B.V. All rights reserved.

Design of a Mechanical-Tunable Filter Spectrometer for Noninvasive Glucose Measurement

NASA Astrophysics Data System (ADS)

Saptari, Vidi; Youcef-Toumi, Kamal

2004-05-01

The development of an accurate and reliable noninvasive near-infrared (NIR) glucose sensor hinges on the success in addressing the sensitivity and the specificity problems associated with the weak glucose signals and the overlapping NIR spectra. Spectroscopic hardware parameters most relevant to noninvasive blood glucose measurement are discussed, which include the optical throughput, integration time, spectral range, and the spectral resolution. We propose a unique spectroscopic system using a continuously rotating interference filter, which produces a signal-to-noise ratio of the order of 10^5 and is estimated to be the minimum required for successful in vivo glucose sensing. Using a classical least-squares algorithm and a spectral range between 2180 and 2312 nm, we extracted clinically relevant glucose concentrations in multicomponent solutions containing bovine serum albumin, triacetin, lactate, and urea.

X-ray astronomical spectroscopy

NASA Technical Reports Server (NTRS)

Holt, S. S.

1980-01-01

The current status of the X-ray spectroscopy of celestial X-ray sources, ranging from nearby stars to distant quasars, is reviewed. Particular emphasis is placed on the role of such spectroscopy as a useful and unique tool in the elucidation of the physical parameters of the sources. The spectroscopic analysis of degenerate and nondegenerate stellar systems, galactic clusters and active galactic nuclei, and supernova remnants is discussed.

Spectroscopic neutron detection using composite scintillators

NASA Astrophysics Data System (ADS)

Jovanovic, I.; Foster, A.; Kukharev, V.; Mayer, M.; Meddeb, A.; Nattress, J.; Ounaies, Z.; Trivelpiece, C.

2016-09-01

Shielded special nuclear material (SNM), especially highly enriched uranium, is exceptionally difficult to detect without the use of active interrogation (AI). We are investigating the potential use of low-dose active interrogation to realize simultaneous high-contrast imaging and photofission of SNM using energetic gamma-rays produced by low-energy nuclear reactions, such as 11B(d,nγ)12C and 12C(p,p‧)12C. Neutrons produced via fission are one reliable signature of the presence of SNM and are usually identified by their unique timing characteristics, such as the delayed neutron die-away. Fast neutron spectroscopy may provide additional useful discriminating characteristics for SNM detection. Spectroscopic measurements can be conducted by recoil-based or thermalization and capture-gated detectors; the latter may offer unique advantages since they facilitate low-statistics and event-by-event neutron energy measurements without spectrum unfolding. We describe the results of the development and characterization of a new type of capture-gated spectroscopic neutron detector based on a composite of scintillating polyvinyltoluene and lithium-doped scintillating glass in the form of millimeter-thick rods. The detector achieves >108 neutron-gamma discrimination resulting from its geometric properties and material selection. The design facilitates simultaneous pulse shape and pulse height discrimination, despite the fact that no materials intrinsically capable of pulse shape discrimination have been used to construct the detector. Accurate single-event measurements of neutron energy may be possible even when the energy is relatively low, such as with delayed fission neutrons. Simulation and preliminary measurements using the new composite detector are described, including those conducted using radioisotope sources and the low-dose active interrogation system based on low-energy nuclear reactions.

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

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

Miller, Terry

2015-06-04

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

A 'first principles' potential energy surface for liquid water from VRT spectroscopy of water clusters.

PubMed

Goldman, Nir; Leforestier, Claude; Saykally, R J

2005-02-15

We present results of gas phase cluster and liquid water simulations from the recently determined VRT(ASP-W)III water dimer potential energy surface (the third fitting of the Anisotropic Site Potential with Woermer dispersion to vibration-rotation-tunnelling data). VRT(ASP-W)III is shown to not only be a model of high 'spectroscopic' accuracy for the water dimer, but also makes accurate predictions of vibrational ground-state properties for clusters up through the hexamer. Results of ambient liquid water simulations from VRT(ASP-W)III are compared with those from ab initio molecular dynamics, other potentials of 'spectroscopic' accuracy and with experiment. The results herein represent the first time to the authors' knowledge that a 'spectroscopic' potential surface is able to correctly model condensed phase properties of water.

Isolated, well-defined organovanadium(iii) on silica: Single-site catalyst for hydrogenation of alkenes and alkynes

DOE PAGES

Sohn, H.; Camacho-Bunquin, J.; Langeslay, R. R.; ...

2017-05-03

Well-defined, isolated, single-site organovanadium(III) catalyst on SiO 2 [(SiO 2)V(Mes)(THF)] were synthesized via surface organometallic chemistry, and fully characterized using a combination of analytical and spectroscopic techniques (EA, ICP, 1H NMR, TGA-MS, EPR, XPS, DR-UV/Vis, UV-Raman, DRIFTS, XAS). The catalysts exhibit unprecedented reactivity in liquid- and gas-phase alkene/alkyne hydrogenation. Catalyst poisoning experiments revealed that 100% of the V sites are active for hydrogenation.

Mapping the geographic distribution of canopy species communities in lowland Amazon rainforest with CAO-AToMS (Invited)

NASA Astrophysics Data System (ADS)

Feret, J.; Asner, G. P.

2013-12-01

Mapping regional canopy diversity will greatly advance our understanding as well as the conservation of tropical rainforests. Changes in species composition across space and time are particularly important to understand the influence of climate, human activity and environmental factors on these ecosystems, but to date such monitoring is extremely challenging and is facing a scale gap between small-scale, highly detailed field studies and large-scale, low-resolution satellite observations. Advances were recently made in the field of spectroscopic imagery for the estimation of canopy alpha-diversity, and an original approach based on the segmentation of the spectral space proved its ability to estimate Shannon diversity index with unprecedented accuracy. We adapted this method in order to estimate spectral dissimilarity across landscape as a proxy for changes in species composition. We applied this approach and mapped species composition over four sites located in lowland rainforest of Peruvian Amazon. This study was based on spectroscopic imagery acquired using the Carnegie Airborne Observatory (CAO) Airborne Taxonomic Mapping System (AToMS), operating a unique sensor combining the fine spectral and spatial resolution required for such task. We obtained accurate estimation of Bray-Curtis distance between pairs of plots, which is the most commonly used metric to estimate dissimilarity in species composition (n=497 pairs, r=0.63). The maps of species composition were then compared to topo-hydrographic properties. Our results indicated a strong shift in species composition and community diversity between floodplain and terra firme terrain conditions as well as a significantly higher diversity of species communities within Amazonian floodplains. These results pave the way for global mapping of tropical canopy diversity at fine geographic resolution.

The Rio Tinto Mars analogue site: an extremophilic Raman spectroscopic study.

PubMed

Edwards, Howell G M; Vandenabeele, Peter; Jorge-Villar, Susana E; Carter, Elizabeth A; Perez, Fernando Rull; Hargreaves, Michael D

2007-12-15

The Rio Tinto site is recognised as a terrestrial Mars analogue because of the presence of jarosite and related sulfates which have recently been identified by the NASA Mars Exploration Rover "Opportunity" in the El Capitan region of Meridiani Planum on Mars. It has long been known that acidophilic microbial action is responsible for the deep blood-red colour of the water in Rio Tinto, where the pH varies from about 1.5 to 3.0 and the water is rich in iron and sulfur. Following recent Raman spectroscopic characterisation of the mineral phases of the Rio Tinto system, we report here a study of the biological components found in several specimens of deposited minerals and near the waterside that were collected during a GeoRaman VI Conference organized field trip in 2006. Key biosignatures were found for carotenoids, scytonemin and mycosporine-like amino acids, which are indicative of the biological colonisation of exposed mineral substrates; information from this study will be useful for targeting Martian sites using a miniaturized Raman instrument where the biosignatures of relict or extant life could remain in the geological record.

Molecular modeling and spectroscopic studies on the interaction of the chiral drug venlafaxine hydrochloride with bovine serum albumin

NASA Astrophysics Data System (ADS)

Shahabadi, Nahid; Hadidi, Saba

2014-03-01

This study was designed to examine the interaction of racemic antidepressant drug "S,R-venlafaxine hydrochloride (VEN)" with bovine serum albumin (BSA) under physiological conditions. The mechanism of interaction was studied by spectroscopic techniques combination with molecular modeling. Stern-Volmer analysis of fluorescence quenching data shows the presence of the static quenching mechanism. The thermodynamic parameters indicated that the hydrogen bonding and weak van der Waals interactions are the predominant intermolecular forces stabilizing the complex. The number of binding sites (n) was calculated. Through the site marker competitive experiment, VEN was confirmed to be located in subdomain IIIA of BSA. The binding distance (r = 4.93 nm) between the donor BSA and acceptor VEN was obtained according to Förster's non-radiative energy transfer theory. According to UV-vis spectra and CD data binding of VEN leaded to conformational changes of BSA. Molecular docking simulations of S and R-VEN revealed that both isomers have similar interaction and the same binding sites, from this point of view S and R isomers are equal.

Analysis of Black Bearing Balls from a Space Shuttle Body Flap Actuator

NASA Technical Reports Server (NTRS)

Sovinski, Marjorie F.; Street, Kenneth W.

2005-01-01

A significantly deteriorated ball bearing mechanism from a body flap actuator on Space Shuttle OV-103 was disassembled and the balls submitted for analysis in conjunction with Return to Flight activities. The OV-103 balls, referred to as the "black balls", were subjected to X-ray photoelectron spectroscopy (XPS), Fourier transform infrared (FT-IR) and Raman micro spectroscopy, surface profilometry, and optical and electron microscopy. The spectroscopic results in combination with microscopy analysis allowed a determination of the lubricant degradation pathway. The chemical attack mechanism does not adequately explain the unique visual appearance of the black balls. Numerous efforts have unsuccessfully focused on duplication of the phenomena causing this unique surface structure and appearance of the black balls. Further detail will be presented supporting these conclusions along with plausible explanations of the unique black appearance to the balls.

The Maunakea Spectroscopic Explorer: Design and Project Status

NASA Astrophysics Data System (ADS)

Murowinski, Rick

2015-08-01

The Maunakea Spectroscopic Explorer (MSE) will be a 10-m class telescope feeding a dedicated massively-multiplexed multi-object spectrometer. The project formally kicked off in March 2014, with a Project Office hosted at the Canada France Hawaii Telescope's (CFHT's) Waimea office facility. The MSE observatory will be ultimately realized my means of an upgrade to the CFHT telescope and partnership, resulting in a new observatory with forefront transformational capability and serving a new international partnership. This new observatory will be housed within the facade of the current CFHT and using the same summit site that CFHT now occupies. We present a description, and the status, of the project. We will show the level one design choices that have been made and those under consideration. We will show our progress in gaining permitting permission as the first major observatory that will re-use an existing Maunakea telescope site.

SUMMARY OF TECNIQUES AND UNIQUE USES FOR DIRECT PUSH METHODS IN SITE CHARACTERIZATION ON CONTAMINATED FIELD SITES

EPA Science Inventory

At many of the sites where we have been asked to assist in site characterization, we have discovered severe discrepancies that new technologies may be able to prevent. This presentation is designed to illustrate these new technologies or unique uses of existing technology and the...

A Combined Probe-Molecule, Mössbauer, Nuclear Resonance Vibrational Spectroscopy, and Density Functional Theory Approach for Evaluation of Potential Iron Active Sites in an Oxygen Reduction Reaction Catalyst

DOE PAGES

Kneebone, Jared L.; Daifuku, Stephanie L.; Kehl, Jeffrey A.; ...

2017-07-06

While non-precious metal M-N-C (M = Fe or Co) catalysts have been developed that are effective for the oxygen reduction reaction in polymer electrolyte fuel cells, no consensus has yet been reached regarding the nature of the M sites in these heterogeneous catalysts that are responsible for reaction with dioxygen (O 2). While multiple studies have developed correlations between Fe distributions in as-prepared catalysts and ORR activity, the direct identification of sites reactive towards O 2 or O 2-analog molecules remains a significant challenge. In the present study, we demonstrate a new approach to identifying and characterizing potential Fe activemore » sites in complex ORR catalysts that combines an effective probe molecule (NO (g)) Mössbauer spectroscopy and nuclear resonance vibrational spectroscopy (NRVS) with density functional theory (DFT) calculations. Mössbauer spectroscopic studies demonstrate that NO (g) treatment of electrochemically reduced PANI-57Fe-C leads to selective reaction with only a sub-set of the Fe species present. Nuclear resonance vibrational spectroscopic studies identified new Fe-ligand vibrations associated with the site reactive towards NO (g). DFT calculations of vibrational properties of a small selection of previously proposed active site structures suggest that graphene zig-zag edge hosted Fe-N structures may be responsible for the observed vibrational behavior with NO (g) probe molecules. Moreover, such sites are likely also reactive to O 2, possibly serving as the ORR active sites in the synthesized materials.« less

A Combined Probe-Molecule, Mössbauer, Nuclear Resonance Vibrational Spectroscopy, and Density Functional Theory Approach for Evaluation of Potential Iron Active Sites in an Oxygen Reduction Reaction Catalyst

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

Kneebone, Jared L.; Daifuku, Stephanie L.; Kehl, Jeffrey A.

While non-precious metal M-N-C (M = Fe or Co) catalysts have been developed that are effective for the oxygen reduction reaction in polymer electrolyte fuel cells, no consensus has yet been reached regarding the nature of the M sites in these heterogeneous catalysts that are responsible for reaction with dioxygen (O 2). While multiple studies have developed correlations between Fe distributions in as-prepared catalysts and ORR activity, the direct identification of sites reactive towards O 2 or O 2-analog molecules remains a significant challenge. In the present study, we demonstrate a new approach to identifying and characterizing potential Fe activemore » sites in complex ORR catalysts that combines an effective probe molecule (NO (g)) Mössbauer spectroscopy and nuclear resonance vibrational spectroscopy (NRVS) with density functional theory (DFT) calculations. Mössbauer spectroscopic studies demonstrate that NO (g) treatment of electrochemically reduced PANI-57Fe-C leads to selective reaction with only a sub-set of the Fe species present. Nuclear resonance vibrational spectroscopic studies identified new Fe-ligand vibrations associated with the site reactive towards NO (g). DFT calculations of vibrational properties of a small selection of previously proposed active site structures suggest that graphene zig-zag edge hosted Fe-N structures may be responsible for the observed vibrational behavior with NO (g) probe molecules. Moreover, such sites are likely also reactive to O 2, possibly serving as the ORR active sites in the synthesized materials.« less

Insight into the binding mechanism of imipenem to human serum albumin by spectroscopic and computational approaches.

PubMed

Rehman, Md Tabish; Shamsi, Hira; Khan, Asad U

2014-06-02

The mechanism of interaction between imipenem and HSA was investigated by various techniques like fluorescence, UV.vis absorbance, FRET, circular dichroism, urea denaturation, enzyme kinetics, ITC, and molecular docking. We found that imipenem binds to HSA at a high affinity site located in subdomain IIIA (Sudlow's site I) and a low affinity site located in subdomain IIA.IIB. Electrostatic interactions played a vital role along with hydrogen bonding and hydrophobic interactions in stabilizing the imipenem.HSA complex at subdomain IIIA, while only electrostatic and hydrophobic interactions were present at subdomain IIA.IIB. The binding and thermodynamic parameters obtained by ITC showed that the binding of imipenem to HSA was a spontaneous process (ΔGD⁰(D)= -32.31 kJ mol(-1) for high affinity site and ΔGD⁰(D) = -23.02 kJ mol(-1) for low affinity site) with binding constants in the range of 10(4)-10(5) M(-1). Spectroscopic investigation revealed only one binding site of imipenem on HSA (Ka∼10(4) M(-1)). FRET analysis showed that the binding distance between imipenem and HSA (Trp-214) was optimal (r = 4.32 nm) for quenching to occur. Decrease in esterase-like activity of HSA in the presence of imipenem showed that Arg-410 and Tyr-411 of subdomain IIIA (Sudlow's site II) were directly involved in the binding process. CD spectral analysis showed altered conformation of HSA upon imipenem binding. Moreover, the binding of imipenem to subdomain IIIA (Sudlow's site II) of HSA also affected its folding pathway as clear from urea-induced denaturation studies.

Growth, structure, Hirshfeld surface and spectroscopic properties of 2-amino-4-hydroxy-6-methylpyrimidinium-2,3-pyrazinedicorboxylate single crystal

NASA Astrophysics Data System (ADS)

Faizan, Mohd; Alam, Mohammad Jane; Afroz, Ziya; Rodrigues, Vítor Hugo Nunes; Ahmad, Shabbir

2018-03-01

The present work is focused on the crystal structure, vibrational spectroscopy and DFT calculations of hydrogen bonded 2,3-pyrazinedicorboxylic acid and 2-amino-4-hydroxy-6-methylpyrimidine (PDCA-.AHMP+) crystal. The crystal structure has been determined using single crystal X-ray diffraction analysis which shows that the crystal belongs to monoclinic space group P21/n. The PDCA-.AHMP+ crystal has been characterized by FTIR, FT-Raman and FT-NMR spectroscopic techniques. The FTIR and FT-Raman spectra of the complex have unique spectroscopic feature as compared with those of the starting material to confirm salt formation. The theoretical vibrational studies have been performed to understand the modes of the vibrations of asymmetric unit of the complex by DFT methods. Hirschfeld surface and 2D fingerprint plots analyses were carried out to investigate the intermolecular interactions and its contribution in the building of PDCA-.AHMP+ crystal. The experimental and simulated 13C and 1H NMR studies have assisted in structural analysis of PDCA-.AHMP+ crystal. The electronic spectroscopic properties of the complex were explored by the experimental as well as theoretical electronic spectra simulated using TD-DFT/IEF-PCM method at B3LYP/6-311++G (d,p) level of theory. In addition, frontier molecular orbitals, molecular electrostatic potential map (MEP) and nonlinear optical (NLO) properties using DFT method have been also presented.

Characterization of the recombinant copper chaperone (CCS) from the plant Glycine (G.) max.

PubMed

Sagasti, Sara; Yruela, Inmaculada; Bernal, Maria; Lujan, Maria A; Frago, Susana; Medina, Milagros; Picorel, Rafael

2011-02-01

The goal of the present work was to characterize the recombinant copper chaperone (CCS) from soybean. Very little is known about plant copper chaperones, which makes this study of current interest, and allows for a comparison with the better known homologues from yeast and humans. To obtain sizeable amounts of pure protein suitable for spectroscopic characterization, we cloned and overexpressed the G. max CCS chaperone in E. coli in the presence of 0.5 mM CuSO(4) and 0.5 mM ZnSO(4) in the broth. A pure protein preparation was obtained by using two IMAC steps and pH gradient chromatography. Most of the proteins were obtained as apo-form, devoid of copper atoms. The chaperone showed a high content (i.e., over 40%) of loops, turns and random coil as determined both by circular dichroism and homology modelling. The homology 3-D structural model suggests the protein might fold in three structural protein domains. The 3-D model along with the primary structure and spectroscopic data may suggest that copper atoms occupy the two metal binding sites, MKCEGC and CTC, within the N-terminal domain I and C-terminal domain III, respectively. But only one Zn-binding site was obtained spectroscopically.

Reduction and Reoxidation of Humic Acid: Influence on Spectroscopic Properties and Proton Binding

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

Maurer, F.; Christl, I; Kretzschmar, R

2010-01-01

Previous studies on proton and metal binding to humic substances have not considered a potential influence of reduction and oxidation of functional groups. Therefore, we investigated how proton binding of a purified soil humic acid was affected by reduction. Reduction of the humic acid was carried out using an electrochemical cell that allowed us to measure the amounts of electrons and protons involved in reduction reactions. We further applied spectroscopic methods (UV-vis, fluorescence, FT-IR, C-1s NEXAFS) to detect possible chemical changes in the humic acid induced by reduction and reoxidation. The effect of reduction on proton binding was determined withmore » acid-base titrations in the pH range 4-10 under controlled redox conditions. During reduction, 0.54 mol kg{sup -1} protons and 0.55 mol kg{sup -1} electrons were transferred to humic acid. NICA-Donnan modeling revealed an equivalent increase in proton-reactive sites (0.52 mol kg{sup -1}) in the alkaline pH-range. Our results indicate that reduction of humic acid increased the amount of proton-reactive sites by 15% compared to the untreated state. Spectroscopic differences between the untreated and reduced humic acid were minor, apart from a lower UV-vis absorption of the reduced humic acid between 400 and 700 nm.« less

Efficient spectroscopic imaging by an optimized encoding of pre-targeted resonances

PubMed Central

Zhang, Zhiyong; Shemesh, Noam; Frydman, Lucio

2016-01-01

A “relaxation-enhanced” (RE) selective-excitation approach to acquire in vivo localized spectra with flat baselines and very good signal-to-noise ratios –particularly at high fields– has been recently proposed. As RE MRS targets a subset of a priori known resonances, new possibilities arise to acquire spectroscopic imaging data in a faster, more efficient manner. Hereby we present one such opportunity based on what we denominate Relaxation-Enhanced Chemical-shift-Encoded Spectroscopically-Separated (RECESS) imaging. RECESS delivers spectral/spatial correlations of various metabolites, by collecting a gradient echo train whose timing is defined by the chemical shifts of the various selectively excited resonances to be disentangled. Different sites thus impart distinct, coherent phase modulations on the images; condition number considerations allow one to disentangle these contributions of the various sites by a simple matrix inversion. The efficiency of the ensuing spectral/spatial correlation method is high enough to enable the examination of additional spatial axes via their phase encoding in CPMG-like spin-echo trains. The ensuing single-shot 1D spectral / 2D spatial RECESS method thus accelerates the acquisition of quality MRSI data by factors that, depending on the sensitivity, range between 2 and 50. This is illustrated with a number of phantom, of ex vivo and of in vivo acquisitions. PMID:26910285

THE NASA AMES PAH IR SPECTROSCOPIC DATABASE VERSION 2.00: UPDATED CONTENT, WEB SITE, AND ON(OFF)LINE TOOLS

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

Boersma, C.; Mattioda, A. L.; Allamandola, L. J.

A significantly updated version of the NASA Ames PAH IR Spectroscopic Database, the first major revision since its release in 2010, is presented. The current version, version 2.00, contains 700 computational and 75 experimental spectra compared, respectively, with 583 and 60 in the initial release. The spectra span the 2.5-4000 μm (4000-2.5 cm{sup -1}) range. New tools are available on the site that allow one to analyze spectra in the database and compare them with imported astronomical spectra as well as a suite of IDL object classes (a collection of programs utilizing IDL's object-oriented programming capabilities) that permit offline analysismore » called the AmesPAHdbIDLSuite. Most noteworthy among the additions are the extension of the computational spectroscopic database to include a number of significantly larger polycyclic aromatic hydrocarbons (PAHs), the ability to visualize the molecular atomic motions corresponding to each vibrational mode, and a new tool that allows one to perform a non-negative least-squares fit of an imported astronomical spectrum with PAH spectra in the computational database. Finally, a methodology is described in the Appendix, and implemented using the AmesPAHdbIDLSuite, that allows the user to enforce charge balance during the fitting procedure.« less

Comparison of spectroscopically measured finger and forearm tissue ethanol concentration to blood and breath ethanol measurements

NASA Astrophysics Data System (ADS)

Ridder, Trent D.; Hull, Edward L.; Ver Steeg, Benjamin J.; Laaksonen, Bentley D.

2011-02-01

Previous works investigated a spectroscopic technique that offered a promising alternative to blood and breath assays for determining in vivo alcohol concentration. Although these prior works measured the dorsal forearm, we report the results of a 26-subject clinical study designed to evaluate the spectroscopic technique at a finger measurement site through comparison to contemporaneous forearm spectroscopic, venous blood, and breath measurements. Through both Monte Carlo simulation and experimental data, it is shown that tissue optical probe design has a substantial impact on the effective path-length of photons through the skin and the signal-to-noise ratio of the spectroscopic measurements. Comparison of the breath, blood, and tissue assays demonstrated significant differences in alcohol concentration that are attributable to both assay accuracy and alcohol pharmacokinetics. Similar to past works, a first order kinetic model is used to estimate the fraction of concentration variance explained by alcohol pharmacokinetics (72.6-86.7%). A significant outcome of this work was significantly improved pharmacokinetic agreement with breath (arterial) alcohol of the finger measurement (mean kArt-Fin = 0.111 min-1) relative to the forearm measurement (mean kArt-For = 0.019 min-1) that is likely due to the increased blood perfusion of the finger.

Spectroscopic and Density Functional Theory Studies of the Blue–Copper Site in M121SeM and C112SeC Azurin: Cu–Se Versus Cu–S Bonding

PubMed Central

Sarangi, Ritimukta; Gorelsky, Serge I.; Basumallick, Lipika; Hwang, Hee Jung; Pratt, Russell C.; Stack, T. Daniel P.; Lu, Yi; Hodgson, Keith O.; Hedman, Britt; Solomon, Edward I.

2009-01-01

S K-edge X-ray absorption, UV–vis absorption, magnetic circular dichroism (MCD), and resonance Raman spectroscopies are used to investigate the electronic structure differences among WT, M121SeM, and C112SeC Pseudomonas aeruginosa (P.a) azurin. A comparison of S K-edge XAS of WT and M121SeM azurin and a CuII–thioether model complex shows that the 38% S character in the ground state wave function of the blue–copper (BC) sites solely reflects the Cu–SCys bond. Resonance Raman (rR) data on WT and C112SeC azurin give direct evidence for the kinematic coupling between the Cu–SCys stretch and the cysteine deformation modes in WT azurin, which leads to multiple features in the rR spectrum of the BC site. The UV–vis absorption and MCD data on WT, M121SeM, and C112SeC give very similar C0/D0 ratios, indicating that the C-term MCD intensity mechanism involves Cu-centered spin–orbit coupling (SOC). The spectroscopic data combined with density functional theory (DFT) calculations indicate that SCys and SeCys have similar covalent interactions with Cu at their respective bond lengths of 2.1 and 2.3 Å. This reflects the similar electronegativites of S and Se in the thiolate/selenolate ligand fragment and explains the strong spectroscopic similarities between WT and C112SeC azurin. PMID:18314977

A Raman Spectroscopic Study of Samples from the May 2001 FIDO Test Site

NASA Technical Reports Server (NTRS)

Kuebler, K.; Jolliff, B. L.; Wang, A.; Haskin, L. A.

2002-01-01

Last May, a rover field test was conducted in the Mojave desert. This study shows what mineralogy a rover-deployed Raman spectrometer might have observed. Additional information is contained in the original extended abstract.

Molecular interaction of 2,4-diacetylphloroglucinol (DAPG) with human serum albumin (HSA): The spectroscopic, calorimetric and computational investigation

NASA Astrophysics Data System (ADS)

Pragna Lakshmi, T.; Mondal, Moumita; Ramadas, Krishna; Natarajan, Sakthivel

2017-08-01

Drug molecule interaction with human serum albumin (HSA) affects the distribution and elimination of the drug. The compound, 2,4-diacetylphloroglucinol (DAPG) has been known for its antimicrobial, antiviral, antihelminthic and anticancer properties. However, its interaction with HSA is not yet reported. In this study, the interaction between HSA and DAPG was investigated through steady-state fluorescence, time-resolved fluorescence (TRF), circular dichroism (CD), Fourier transform infrared (FT-IR) spectroscopy, isothermal titration calorimetry (ITC), molecular docking and molecular dynamics simulation (MDS). Fluorescence spectroscopy results showed the strong quenching of intrinsic fluorescence of HSA due to interaction with DAPG, through dynamic quenching mechanism. The compound bound to HSA with reversible and moderate affinity which explained its easy diffusion from circulatory system to target tissue. The thermodynamic parameters from fluorescence spectroscopic data clearly revealed the contribution of hydrophobic forces but, the role of hydrogen bonds was not negligible according to the ITC studies. The interaction was exothermic and spontaneous in nature. Binding with DAPG reduced the helical content of protein suggesting the unfolding of HSA. Site marker fluorescence experiments revealed the change in binding constant of DAPG in the presence of site I (warfarin) but not site II marker (ibuprofen) which confirmed that the DAPG bound to site I. ITC experiments also supported this as site I marker could not bind to HSA-DAPG complex while site II marker was accommodated in the complex. In silico studies further showed the lowest binding affinity and more stability of DAPG in site I than in site II. Thus the data presented in this study confirms the binding of DAPG to the site I of HSA which may help in further understanding of pharmacokinetic properties of DAPG.

Seafloor massive sulfide deposits support unique megafaunal assemblages: Implications for seabed mining and conservation.

PubMed

Boschen, Rachel E; Rowden, Ashley A; Clark, Malcolm R; Pallentin, Arne; Gardner, Jonathan P A

2016-04-01

Mining of seafloor massive sulfides (SMS) is imminent, but the ecology of assemblages at SMS deposits is poorly known. Proposed conservation strategies include protected areas to preserve biodiversity at risk from mining impacts. Determining site suitability requires biological characterisation of the mine site and protected area(s). Video survey of a proposed mine site and protected area off New Zealand revealed unique megafaunal assemblages at the mine site. Significant relationships were identified between assemblage structure and environmental conditions, including hydrothermal features. Unique assemblages occurred at both active and inactive chimneys and are particularly at risk from mining-related impacts. The occurrence of unique assemblages at the mine site suggests that the proposed protected area is insufficient alone and should instead form part of a network. These results provide support for including hydrothermally active and inactive features within networks of protected areas and emphasise the need for quantitative survey data of proposed sites. Copyright © 2016 The Authors. Published by Elsevier Ltd.. All rights reserved.

Evidence that Chemical Chaperone 4-Phenylbutyric Acid Binds to Human Serum Albumin at Fatty Acid Binding Sites

PubMed Central

James, Joel; Shihabudeen, Mohamed Sham; Kulshrestha, Shweta; Goel, Varun; Thirumurugan, Kavitha

2015-01-01

Endoplasmic reticulum stress elicits unfolded protein response to counteract the accumulating unfolded protein load inside a cell. The chemical chaperone, 4-Phenylbutyric acid (4-PBA) is a FDA approved drug that alleviates endoplasmic reticulum stress by assisting protein folding. It is found efficacious to augment pathological conditions like type 2 diabetes, obesity and neurodegeneration. This study explores the binding nature of 4-PBA with human serum albumin (HSA) through spectroscopic and molecular dynamics approaches, and the results show that 4-PBA has high binding specificity to Sudlow Site II (Fatty acid binding site 3, subdomain IIIA). Ligand displacement studies, RMSD stabilization profiles and MM-PBSA binding free energy calculation confirm the same. The binding constant as calculated from fluorescence spectroscopic studies was found to be kPBA = 2.69 x 105 M-1. Like long chain fatty acids, 4-PBA induces conformational changes on HSA as shown by circular dichroism, and it elicits stable binding at Sudlow Site II (fatty acid binding site 3) by forming strong hydrogen bonding and a salt bridge between domain II and III of HSA. This minimizes the fluctuation of HSA backbone as shown by limited conformational space occupancy in the principal component analysis. The overall hydrophobicity of W214 pocket (located at subdomain IIA), increases upon occupancy of 4-PBA at any FA site. Descriptors of this pocket formed by residues from other subdomains largely play a role in compensating the dynamic movement of W214. PMID:26181488

Multi-spectroscopic and molecular modeling approaches to elucidate the binding interaction between bovine serum albumin and darunavir, a HIV protease inhibitor

NASA Astrophysics Data System (ADS)

Shi, Jie-Hua; Zhou, Kai-Li; Lou, Yan-Yue; Pan, Dong-Qi

2018-01-01

Darunavir (DRV), a second-generation HIV protease inhibitor, is widely used across the world as an important component of HIV therapy. The interaction of DRV with bovine serum albumin (BSA), a major carrier protein, has been studied under simulated physiological conditions (pH 7.4) by multi-spectroscopic techniques in combination with molecular modeling. Fluorescence data revealed that the intrinsic fluorescence of BSA was quenched by DRV in terms of a static quenching procedure due to the formation of the DRV-BSA complex. The results indicated the presence of single weak affinity binding site ( 103 M- 1, 310 K) on protein. The thermodynamic parameters, namely enthalpy change (ΔH0), entropy change (ΔS0) and Gibbs free energy change (ΔG0) were calculated, which signified that the binding reaction was spontaneous, the main binding forces were hydrogen bonding and van der Waals forces. Importantly, competitive binding experiments with three site probes, phenylbutazone (in sub-domain IIA, site I), ibuprofen (in sub-domain IIIA, site II) and artemether (in the interface between sub-domain IIA and IIB, site II'), suggested that DRV was preferentially bound to the hydrophobic cavity in site II' of BSA, and this finding was validated by the docking results. Additionally, synchronous fluorescence, three-dimensional fluorescence and Resonance Rayleigh Scattering (RRS) spectroscopy gave qualitative information on the conformational changes of BSA upon adding DRV, while quantitative data were obtained with Fourier transform infrared spectroscopy (FT-IR).

Spectroscopic Assessment of the Reliability of Metal/Metal Oxide Interfaces

DTIC Science & Technology

1994-10-01

vapor deposition(LCVD)1, 2 of thin films, clusters and ultrafine particles offers many unique opportunities in materials synthesis. As precursors for LCVD...films, the chemistry is directly applicable to other oxidizable metals. Puretsky and Demyanenko9 reported that gas phase clusters and ultrafine ... particles can be synthesized using excimer laser dissociation of all group six metal hexacarbonyls. Our earlier work on platinum clusters and our current

Penicillipyrones A and B, meroterpenoids from a marine-derived Penicillium sp. fungus.

PubMed

Liao, Lijuan; Lee, Jung-Ho; You, Minjung; Choi, Tae Joon; Park, Wanki; Lee, Sang Kook; Oh, Dong-Chan; Oh, Ki-Bong; Shin, Jongheon

2014-02-28

Penicillipyrones A (1) and B (2), two novel meroterpenoids, were isolated from the marine-derived fungus Penicillium sp. On the basis of the results of combined spectroscopic analyses, these compounds were structurally elucidated to be sesquiterpene γ-pyrones from a new skeletal class derived from a unique linkage pattern between the drimane sesquiterpene and pyrone moieties. Compound 2 elicited significant induction of quinone reductase.

VizieR Online Data Catalog: Spectroscopically identified white dwarfs (McCook+, 2014)

NASA Astrophysics Data System (ADS)

McCook, G. P.; Sion, E. M.

2016-10-01

This is an update of the Villanova catalog published in the ApJS paper, corresponding to the Web version of the catalog in Apr 2014 (see http://www.astronomy.villanova.edu/WDCatalog/index.html). The introduction to the 1999 catalog is in the file "preface.tex". This updated version lists 14294 unique white dwarfs for a total of 27975 rows (multiple observations). (5 data files).

Two streptothricins with a cis-streptolidine lactam moiety from Streptomyces sp. I08A 1776.

PubMed

Gan, Maoluo; Guan, Yan; Zheng, Xudong; Yang, Yanhui; Hao, Xueqin; Liu, Yishuang; Yu, Liyan; Xiao, Chunling

2012-10-01

Two unique cis-fused streptothricins (1 and 2) were isolated from the culture broth of Streptomyces sp. I08A 1776. Their structures were determined by MS, CD, and 1D and 2D NMR spectroscopic data analysis. Compound 2 showed weak antibacterial activities against Bacillus subtilis and Enterococcus faecalis with MIC values of 32 and 64 μg ml(-1), respectively.

Biological water oxidation.

PubMed

Cox, Nicholas; Pantazis, Dimitrios A; Neese, Frank; Lubitz, Wolfgang

2013-07-16

Photosystem II (PSII), a multisubunit pigment-protein supercomplex found in cyanobacteria, algae, and plants, catalyzes a unique reaction in nature: the light-driven oxidation of water. Remarkable recent advances in the structural analysis of PSII now give a detailed picture of the static supercomplex on the molecular level. These data provide a solid foundation for future functional studies, in particular the mechanism of water oxidation and oxygen release. The catalytic core of the PSII is a tetramanganese-calcium cluster (Mn₄O₅Ca), commonly referred to as the oxygen-evolving complex (OEC). The function of the OEC rests on its ability to cycle through five metastable states (Si, i = 0-4), transiently storing four oxidizing equivalents, and in so doing, facilitates the four electron water splitting reaction. While the latest crystallographic model of PSII gives an atomic picture of the OEC, the exact connectivity within the inorganic core and the S-state(s) that the X-ray model represents remain uncertain. In this Account, we describe our joint experimental and theoretical efforts to eliminate these ambiguities by combining the X-ray data with spectroscopic constraints and introducing computational modeling. We are developing quantum chemical methods to predict electron paramagnetic resonance (EPR) parameters for transition metal clusters, especially focusing on spin-projection approaches combined with density functional theory (DFT) calculations. We aim to resolve the geometric and electronic structures of all S-states, correlating their structural features with spectroscopic observations to elucidate reactivity. The sequence of manganese oxidations and concomitant charge compensation events via proton transfer allow us to rationalize the multielectron S-state cycle. EPR spectroscopy combined with theoretical calculations provides a unique window into the tetramangenese complex, in particular its protonation states and metal ligand sphere evolution, far beyond the scope of static techniques such as X-ray crystallography. This approach has led, for example, to a detailed understanding of the EPR signals in the S₂-state of the OEC in terms of two interconvertible, isoenergetic structures. These two structures differ in their valence distribution and spin multiplicity, which has important consequences for substrate binding and may explain its low barrier exchange with solvent water. New experimental techniques and innovative sample preparations are beginning to unravel the complex sequence of substrate uptake/inclusion, which is coupled to proton release. The introduction of specific site perturbations, such as replacing Ca²⁺ with Sr²⁺, provides discrete information about the ligand environment of the individual Mn ions. In this way, we have identified a potential open coordination site for one Mn center, which may serve as a substrate binding site in the higher S-states, such as S₃ and S₄. In addition, we can now monitor the binding of the substrate water in the lower S-states (S₁ and S₂) using new EPR-detected NMR spectroscopies. These studies provided the first evidence that one of the substrates is subsumed into the complex itself and forms an oxo-bridge between two Mn ions. This result places important new restrictions on the mechanism of O-O bond formation. These new insights from nature's water splitting catalyst provide important criteria for the rational design of bioinspired synthetic catalysts.

The application of thermodynamic and spectroscopic techniques to adhesion in the polyimide/Ti 6-4 and polyphenylquinoxaline/Ti 6-4 systems

NASA Technical Reports Server (NTRS)

Dias, S.; Wightman, J. P.

1984-01-01

The results of calorimetric measurements of Ti adherend surfaces are presented. The measurements were carried out after several chemical pretreatments and after fracture of several lap shear samples aged at high temperature. The exact composition of the Ti samples was Ti(6 percent Al-4 percent V). The adhesives used were polyimides and polyphenylquinoxalines (PPQ). Each chemical pretreatment was accompanied by a unique spectroscopic feature which was characterized by XPS, SEM, and specular reflectance infrared spectroscopy. The energetics of the interaction between primer solutions and the Ti adherend were evaluated by microcalorimetry. Changes in the structure of the surface oxide layer upon heating of the adherend were deduced from immersion temperatures of the PI and PPQ solutions. The XPS and SEM data are given is a table.

Caspase-2 Is Localized at the Golgi Complex and Cleaves Golgin-160 during Apoptosis

PubMed Central

Mancini, Marie; Machamer, Carolyn E.; Roy, Sophie; Nicholson, Donald W.; Thornberry, Nancy A.; Casciola-Rosen, Livia A.; Rosen, Antony

2000-01-01

Caspases are an extended family of cysteine proteases that play critical roles in apoptosis. Animals deficient in caspases-2 or -3, which share very similar tetrapeptide cleavage specificities, exhibit very different phenotypes, suggesting that the unique features of individual caspases may account for distinct regulation and specialized functions. Recent studies demonstrate that unique apoptotic stimuli are transduced by distinct proteolytic pathways, with multiple components of the proteolytic machinery clustering at distinct subcellular sites. We demonstrate here that, in addition to its nuclear distribution, caspase-2 is localized to the Golgi complex, where it cleaves golgin-160 at a unique site not susceptible to cleavage by other caspases with very similar tetrapeptide specificities. Early cleavage at this site precedes cleavage at distal sites by other caspases. Prevention of cleavage at the unique caspase-2 site delays disintegration of the Golgi complex after delivery of a pro-apoptotic signal. We propose that the Golgi complex, like mitochondria, senses and integrates unique local conditions, and transduces pro-apoptotic signals through local caspases, which regulate local effectors. PMID:10791974

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

Sohn, H.; Camacho-Bunquin, J.; Langeslay, R. R.

Well-defined, isolated, single-site organovanadium(III) catalyst on SiO 2 [(SiO 2)V(Mes)(THF)] were synthesized via surface organometallic chemistry, and fully characterized using a combination of analytical and spectroscopic techniques (EA, ICP, 1H NMR, TGA-MS, EPR, XPS, DR-UV/Vis, UV-Raman, DRIFTS, XAS). The catalysts exhibit unprecedented reactivity in liquid- and gas-phase alkene/alkyne hydrogenation. Catalyst poisoning experiments revealed that 100% of the V sites are active for hydrogenation.

A comparative study of the spectroscopic properties of Mn4+ in the garnet Y2Mg3Ge3O12 and the commercial Mg28Ge7.55O32F15.04 phosphor

NASA Astrophysics Data System (ADS)

Srivastava, A. M.

2018-05-01

The spectroscopic properties of Mn4+ (3 d3) ions in the garnet Y2Mg3Ge3O12 and in the commercial Mg28Ge7.55O32F15.04 (MFG) phosphors are compared. We find that despite the differences in host crystal composition and crystal structures, the 4A2g→ 4T1g and 2Eg→4A2g optical transitions of the Mn4+ ion occur at similar energies. We provide some insights into the nature of chemical bonding that is responsible for the observed similarity in the spectroscopic data. Additionally, discussion is given to the site preference of the Mn4+ ion in the MFG host crystal.

A comparison of on-line and off-line bioaerosol measurements at a biowaste site.

PubMed

Feeney, Patrick; Rodríguez, Santiago Fernández; Molina, Rafael; McGillicuddy, Eoin; Hellebust, Stig; Quirke, Michael; Daly, Shane; O'Connor, David; Sodeau, John

2018-06-01

An air measurement campaign was carried out at a green-waste composting site in the South of Ireland during Spring 2016. The aim was to quantify and identify the levels of Primary Biological Aerosol Particles (PBAP) that were present using the traditional off-line, impaction/optical microscopy method alongside an on-line, spectroscopic approach termed WIBS (Wideband Integrated Bioaerosol Sensor), which can provide number concentrations, sizes and "shapes" of airborne PBAP in real-time by use of Light Induced Fluorescence (LIF). The results from the two techniques were compared in order to validate the use of the spectroscopic method for determining the releases of the wide-range of PBAP present there as a function of site activity and meteorological conditions. The seven-day monitoring period undertaken was much longer than any real-time studies that have been previously performed and allowed due comparison between weekday (working) activities at the site and weekend (closed) releases. The time-span also allowed relationships between site activities like turning, agitation or waste delivery and the WIBS data to be determined in a quantitative manner. This information cannot be obtained with the Andersen Sampling methods generally employed at green-waste management sites. Furthermore, few specific bioaerosol types other than Aspergillus fumigatus, are identified using the traditional protocols employed for site licensing purposes. Here though the co-location of WIBS with the impaction instrument made it possible to identify the real-time release behaviour of a specific plant pathogenic spore, Ustilago maydis, present after green-waste deliveries were made by a local distillery. Copyright © 2018 Elsevier Ltd. All rights reserved.

Complementing asteroseismology with 4MOST spectroscopy

NASA Astrophysics Data System (ADS)

de Jong, R. S.; 4MOST Consortium; 4MOST Spectroscopy Consortium

2016-09-01

4MOST is a wide-field, high-multiplex spectroscopic survey facility under development for the VISTA telescope of the European Southern Observatory (ESO). Its main science drivers are in the areas of galactic archeology, high-energy physics, galaxy evolution and cosmology. 4MOST will in particular provide the spectroscopic complements to the large area surveys coming from space missions like Gaia, eROSITA, Euclid, and PLATO. 4MOST will have an unique operations concept in which 5-years public surveys from both the consortium and the ESO community will be combined and observed in parallel during each exposure, resulting in more than 25 million spectra of targets spread over a large fraction of the southern sky. As a dedicated spectroscopic survey facility with a large field-of-view, a high multiplex that can be reconfigured quickly, and with a broad wavelength coverage, 4MOST is particularly well suited to complement the upcoming asteroseismology space missions like TESS and PLATO. Here we show that, by dedicating the observing time during twilight and poor observing conditions to bright stars, 4MOST will obtain resolution {R>18 000} spectra of nearly all stars brighter than ˜ 12th magnitude at Dec < 30o every ˜ 2 years. 4MOST is also expected to spectroscopically complement any fainter asteroseismology target to be observed with PLATO. These observations will provide a chemical characterization of nearly all stars to be observed with the TESS and PLATO missions and place any planets found in a full chemo-dynamical context of the star formation history of the Galaxy, yield very accurate ages and masses for all stars that can be characterized with asteroseismology, and allow removal of contaminants from target samples (e.g., spectroscopic binaries).

Spectroscopic photon localization microscopy: breaking the resolution limit of single molecule localization microscopy (Conference Presentation)

NASA Astrophysics Data System (ADS)

Dong, Biqin; Almassalha, Luay Matthew; Urban, Ben E.; Nguyen, The-Quyen; Khuon, Satya; Chew, Teng-Leong; Backman, Vadim; Sun, Cheng; Zhang, Hao F.

2017-02-01

Distinguishing minute differences in spectroscopic signatures is crucial for revealing the fluorescence heterogeneity among fluorophores to achieve a high molecular specificity. Here we report spectroscopic photon localization microscopy (SPLM), a newly developed far-field spectroscopic imaging technique, to achieve nanoscopic resolution based on the principle of single-molecule localization microscopy while simultaneously uncovering the inherent molecular spectroscopic information associated with each stochastic event (Dong et al., Nature Communications 2016, in press). In SPLM, by using a slit-less monochromator, both the zero-order and the first-order diffractions from a grating were recorded simultaneously by an electron multiplying charge-coupled device to reveal the spatial distribution and the associated emission spectra of individual stochastic radiation events, respectively. As a result, the origins of photon emissions from different molecules can be identified according to their spectral differences with sub-nm spectral resolution, even when the molecules are within close proximity. With the newly developed algorithms including background subtraction and spectral overlap unmixing, we established and tested a method which can significantly extend the fundamental spatial resolution limit of single molecule localization microscopy by molecular discrimination through spectral regression. Taking advantage of this unique capability, we demonstrated improvement in spatial resolution of PALM/STORM up to ten fold with selected fluorophores. This technique can be readily adopted by other research groups to greatly enhance the optical resolution of single molecule localization microscopy without the need to modify their existing staining methods and protocols. This new resolving capability can potentially provide new insights into biological phenomena and enable significant research progress to be made in the life sciences.

A Spectroscopic Survey and Analysis of Bright, Hydrogen-rich White Dwarfs

NASA Astrophysics Data System (ADS)

Gianninas, A.; Bergeron, P.; Ruiz, M. T.

2011-12-01

We have conducted a spectroscopic survey of over 1300 bright (V <= 17.5), hydrogen-rich white dwarfs based largely on the last published version of the McCook & Sion catalog. The complete results from our survey, including the spectroscopic analysis of over 1100 DA white dwarfs, are presented. High signal-to-noise ratio optical spectra were obtained for each star and were subsequently analyzed using our standard spectroscopic technique where the observed Balmer line profiles are compared to synthetic spectra computed from the latest generation of model atmospheres appropriate for these stars. First, we present the spectroscopic content of our sample, which includes many misclassifications as well as several DAB, DAZ, and magnetic white dwarfs. Next, we look at how the new Stark broadening profiles affect the determination of the atmospheric parameters. When necessary, specific models and analysis techniques are used to derive the most accurate atmospheric parameters possible. In particular, we employ M dwarf templates to obtain better estimates of the atmospheric parameters for those white dwarfs that are in DA+dM binary systems. Certain unique white dwarfs and double-degenerate binary systems are also analyzed in greater detail. We then examine the global properties of our sample including the mass distribution and their distribution as a function of temperature. We then proceed to test the accuracy and robustness of our method by comparing our results to those of other surveys such as SPY and Sloan Digital Sky Survey. Finally, we revisit the ZZ Ceti instability strip and examine how the determination of its empirical boundaries is affected by the latest line profile calculations. Based on observations made with ESO Telescopes at the La Silla or Paranal Observatories under program ID 078.D-0824(A).

The selection function of the LAMOST Spectroscopic Survey of the Galactic Anti-centre

NASA Astrophysics Data System (ADS)

Chen, B.-Q.; Liu, X.-W.; Yuan, H.-B.; Xiang, M.-S.; Huang, Y.; Wang, C.; Zhang, H.-W.; Tian, Z.-J.

2018-05-01

We present a detailed analysis of the selection function of the LAMOST Spectroscopic Survey of the Galactic Anti-centre (LSS-GAC). LSS-GAC was designed to obtain low-resolution optical spectra for a sample of more than 3 million stars in the Galactic anti-centre. The second release of value-added catalogues of the LSS-GAC (LSS-GAC DR2) contains stellar parameters, including radial velocity, atmospheric parameters, elemental abundances, and absolute magnitudes deduced from 1.8 million spectra of 1.4 million unique stars targeted by the LSS-GAC between 2011 and 2014. For many studies using this data base, such as those investigating the chemodynamical structure of the Milky Way, a detailed understanding of the selection function of the survey is indispensable. In this paper, we describe how the selection function of the LSS-GAC can be evaluated to sufficient detail and provide selection function corrections for all spectroscopic measurements with reliable parameters released in LSS-GAC DR2. The results, to be released as new entries in the LSS-GAC value-added catalogues, can be used to correct the selection effects of the catalogue for scientific studies of various purposes.

A Single-Site Platinum CO Oxidation Catalyst in Zeolite KLTL: Microscopic and Spectroscopic Determination of the Locations of the Platinum Atoms

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

Kistler, Joseph D.; Chotigkrai, Nutchapon; Xu, Pinghong

2014-07-01

A stable site-isolated mononuclear platinum catalyst with a well-defined structure is presented. Platinum complexes supported in zeolite KLTL were synthesized from [Pt(NH 3) 4](NO 3) 2, oxidized at 633 K, and used to catalyze CO oxidation. Finally, IR and X-ray absorption spectra and electron micrographs determine the structures and locations of the platinum complexes in the zeolite pores, demonstrate the platinum-support bonding, and show that the platinum remained site isolated after oxidation and catalysis.

Proton Magnetic Resonance Spectroscopic Imaging in Newly Diagnosed Glioblastoma: Predictive Value for the Site of Postradiotherapy Relapse in a Prospective Longitudinal Study

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

Laprie, Anne; Laboratory of Biophysics and Medical Imaging, Universite Toulouse III Paul Sabatier, Toulouse; Catalaa, Isabelle

Purpose: To investigate the association between magnetic resonance spectroscopic imaging (MRSI)-defined, metabolically abnormal tumor regions and subsequent sites of relapse in data from patients treated with radiotherapy (RT) in a prospective clinical trial. Methods and Materials: Twenty-three examinations were performed prospectively for 9 patients with newly diagnosed glioblastoma multiforme studied in a Phase I trial combining Tipifarnib and RT. The patients underwent magnetic resonance imaging (MRI) and MRSI before treatment and every 2 months until relapse. The MRSI data were categorized by the choline (Cho)/N-acetyl-aspartate (NAA) ratio (CNR) as a measure of spectroscopic abnormality. CNRs corresponding to T1 and T2more » MRI for 1,207 voxels were evaluated before RT and at recurrence. Results: Before treatment, areas of CNR2 (CNR {>=}2) represented 25% of the contrast-enhancing (T1CE) regions and 10% of abnormal T2 regions outside T1CE (HyperT2). The presence of CNR2 was often an early indicator of the site of relapse after therapy. In fact, 75% of the voxels within the T1CE+CNR2 before therapy continued to exhibit CNR2 at relapse, compared with 22% of the voxels within the T1CE with normal CNR (p < 0.05). The location of new contrast enhancement with CNR2 corresponded in 80% of the initial HyperT2+CNR2 vs. 20.7% of the HyperT2 voxels with normal CNR (p < 0.05). Conclusion: Metabolically active regions represented a small percentage of pretreatment MRI abnormalities and were predictive for the site of post-RT relapse. The incorporation of MRSI data in the definition of RT target volumes for selective boosting may be a promising avenue leading to increased local control of glioblastomas.« less

Geochemical and Mineralogical Analyses of Cold Spring Deposits at Borup Fiord Pass, a Sulfur-Dominated Arctic Analog for Planetary Environments on Mars and Europa

NASA Astrophysics Data System (ADS)

Lau, Graham Elliot

Sulfur is one of the most ubiquitous elements in the universe and one of those that is crucial for life, as we know it. This graduate dissertation presents the culmination of work conducted to better understand biological and geochemical processes related to sulfur cycling at a sulfur-dominated field site in the Canadian High Arctic. This site, situated in a valley called Borup Fiord Pass, provides a unique environment where sulfide-rich fluids emerge from a glacier and form large deposits of ice that become covered in elemental sulfur. The role of biology is compelling and yet challenging to define in each step of sulfur cycling at Borup Fiord pass, whether one considers the origin of the sulfide (presumed biological sulfate reduction in the subsurface) or one focuses on the processes driving sulfur oxidation and stabilization at the glacier's surface. This dissertation presents results from a field expedition in 2014 as well as detailed mineralogical and spectroscopic analyses of sulfur-rich materials returned from the field. The importance of sulfur and carbonate minerals at this site is considered. Also, analyses of materials within pyrite alteration features in the valley are explored. These features appear to represent emplaced subsurface sulfide ores, which have been subsequently leached near the surface, forming gossanous structures. The geochemistry and mineralogy of these features is explored, as well as is their potential to serve as analogs for the exploration of Mars. The dissertation then concludes with some consideration of potential future work to be considered as well as a recapitulation of the current state of knowledge of processes at Borup Fiord Pass.

Infrared spectra of proton transfer complexes of the cycleanine alkaloid in solid state

NASA Astrophysics Data System (ADS)

Kasende, Okuma E.; de Waal, D.

2003-01-01

Proton transfer complexes obtained between the cycleanine alkaloid and hydrogen chloride, hydrogen bromide and nitric acids have been investigated by infrared spectroscopic technique between 4000 and 400 cm -1 in KBr. The vibrational perturbations brought about by proton transfer complex formation, discussed in terms of preferred site of interaction, show that the proton of the inorganic acids is transferred to cycleanine through one of its N sites.

Efficient catalysis of Nazarov cyclization using a cationic iridium complex possessing adjacent labile coordination sites.

PubMed

Janka, Mesfin; He, Wei; Frontier, Alison J; Eisenberg, Richard

2004-06-09

The dicationic Ir(III) complex [IrMe(CO)(dppe)(DIB)](BARF)2 having adjacent labile sites has been found to be a very effective catalyst for promoting the Nazarov cyclization of aryl vinyl and divinyl ketones. Spectroscopic evidence for a substate-catalyst complex before cyclization is presented. The efficiency of the cyclization is attributed to the electrophilicity of the Ir(III) complex and substrate activation via chelation.

New metabolites of C-glycosidic ellagitannin from Japanese oak sapwood.

PubMed

Omar, Mohamed; Matsuo, Yosuke; Maeda, Hajime; Saito, Yoshinori; Tanaka, Takashi

2014-03-07

Two unusual ellagitannin metabolites, quercusnins A (3) and B (4), have been isolated from the sapwood of Quercus crispula, and their structures determined by spectroscopic methods, as well as DFT calculations of (1)H and (13)C NMR chemical shifts of the possible four diastereomers. Treatment of the major ellagitannin species, vescalagin, with Shiitake mushroom (Lentinula edodes) gave 3, which indicated that these unique ellagitannins were the fungal metabolites of ellagitannins.

The Gaia-ESO Survey: double-, triple-, and quadruple-line spectroscopic binary candidates

NASA Astrophysics Data System (ADS)

Merle, T.; Van Eck, S.; Jorissen, A.; Van der Swaelmen, M.; Masseron, T.; Zwitter, T.; Hatzidimitriou, D.; Klutsch, A.; Pourbaix, D.; Blomme, R.; Worley, C. C.; Sacco, G.; Lewis, J.; Abia, C.; Traven, G.; Sordo, R.; Bragaglia, A.; Smiljanic, R.; Pancino, E.; Damiani, F.; Hourihane, A.; Gilmore, G.; Randich, S.; Koposov, S.; Casey, A.; Morbidelli, L.; Franciosini, E.; Magrini, L.; Jofre, P.; Costado, M. T.; Jeffries, R. D.; Bergemann, M.; Lanzafame, A. C.; Bayo, A.; Carraro, G.; Flaccomio, E.; Monaco, L.; Zaggia, S.

2017-12-01

Context. The Gaia-ESO Survey (GES) is a large spectroscopic survey that provides a unique opportunity to study the distribution of spectroscopic multiple systems among different populations of the Galaxy. Aims: Our aim is to detect binarity/multiplicity for stars targeted by the GES from the analysis of the cross-correlation functions (CCFs) of the GES spectra with spectral templates. Methods: We developed a method based on the computation of the CCF successive derivatives to detect multiple peaks and determine their radial velocities, even when the peaks are strongly blended. The parameters of the detection of extrema (DOE) code have been optimized for each GES GIRAFFE and UVES setup to maximize detection. The DOE code therefore allows to automatically detect multiple line spectroscopic binaries (SBn, n ≥ 2). Results: We apply this method on the fourth GES internal data release and detect 354 SBn candidates (342 SB2, 11 SB3, and even one SB4), including only nine SBs known in the literature. This implies that about 98% of these SBn candidates are new because of their faint visual magnitude that can reach V = 19. Visual inspection of the SBn candidate spectra reveals that the most probable candidates have indeed a composite spectrum. Among the SB2 candidates, an orbital solution could be computed for two previously unknown binaries: CNAME 06404608+0949173 (known as V642 Mon) in NGC 2264 and CNAME 19013257-0027338 in Berkeley 81 (Be 81). A detailed analysis of the unique SB4 (four peaks in the CCF) reveals that CNAME 08414659-5303449 (HD 74438) in the open cluster IC 2391 is a physically bound stellar quadruple system. The SB candidates belonging to stellar clusters are reviewed in detail to discard false detections. We suggest that atmospheric parameters should not be used for these system components; SB-specific pipelines should be used instead. Conclusions: Our implementation of an automatic detection of spectroscopic binaries within the GES has allowed the efficient discovery of many new multiple systems. With the detection of the SB1 candidates that will be the subject of a forthcoming paper, the study of the statistical and physical properties of the spectroscopic multiple systems will soon be possible for the entire GES sample. Based on data products from observations made with ESO Telescopes at the La Silla Paranal Observatory under programme ID 188.B-3002. These data products have been processed by the Cambridge Astronomy Survey Unit (CASU) at the Institute of Astronomy, University of Cambridge, and by the FLAMES/UVES reduction team at INAF/Osservatorio Astrofisico di Arcetri. These data have been obtained from the Gaia-ESO Survey Data Archive, prepared and hosted by the Wide Field Astronomy Unit, Institute for Astronomy, University of Edinburgh, which is funded by the UK Science and Technology Facilities Council.

Interaction of methotrexate with trypsin analyzed by spectroscopic and molecular modeling methods

NASA Astrophysics Data System (ADS)

Wang, Yanqing; Zhang, Hongmei; Cao, Jian; Zhou, Qiuhua

2013-11-01

Trypsin is one of important digestive enzymes that have intimate correlation with human health and illness. In this work, the interaction of trypsin with methotrexate was investigated by spectroscopic and molecular modeling methods. The results revealed that methotrexate could interact with trypsin with about one binding site. Methotrexate molecule could enter into the primary substrate-binding pocket, resulting in inhibition of trypsin activity. Furthermore, the thermodynamic analysis implied that electrostatic force, hydrogen bonding, van der Waals and hydrophobic interactions were the main interactions for stabilizing the trypsin-methotrexate system, which agreed well with the results from the molecular modeling study.

Mg co-ordination with potential carcinogenic molecule acrylamide: Spectroscopic, computational and cytotoxicity studies

NASA Astrophysics Data System (ADS)

Singh, Ranjana; Mishra, Vijay K.; Singh, Hemant K.; Sharma, Gunjan; Koch, Biplob; Singh, Bachcha; Singh, Ranjan K.

2018-03-01

Acrylamide (acr) is a potential toxic molecule produced in thermally processed food stuff. Acr-Mg complex has been synthesized chemically and characterized by spectroscopic techniques. The binding sites of acr with Mg were identified by experimental and computational methods. Both experimental and theoretical results suggest that Mg coordinated with the oxygen atom of Cdbnd O group of acr. In-vitro cytotoxicity studies revealed significant decrease in the toxic level of acr-Mg complex as compared to pure acr. The decrease in toxicity on complexation with Mg may be a useful step for future research to reduce the toxicity of acr.

Imaging open-path Fourier transform infrared spectrometer for 3D cloud profiling

NASA Astrophysics Data System (ADS)

Rentz Dupuis, Julia; Mansur, David J.; Vaillancourt, Robert; Carlson, David; Evans, Thomas; Schundler, Elizabeth; Todd, Lori; Mottus, Kathleen

2009-05-01

OPTRA is developing an imaging open-path Fourier transform infrared (I-OP-FTIR) spectrometer for 3D profiling of chemical and biological agent simulant plumes released into test ranges and chambers. An array of I-OP-FTIR instruments positioned around the perimeter of the test site, in concert with advanced spectroscopic algorithms, enables real time tomographic reconstruction of the plume. The approach is intended as a referee measurement for test ranges and chambers. This Small Business Technology Transfer (STTR) effort combines the instrumentation and spectroscopic capabilities of OPTRA, Inc. with the computed tomographic expertise of the University of North Carolina, Chapel Hill.

Intermolecular interaction of fosinopril with bovine serum albumin (BSA): The multi-spectroscopic and computational investigation.

PubMed

Zhou, Kai-Li; Pan, Dong-Qi; Lou, Yan-Yue; Shi, Jie-Hua

2018-04-16

The intermolecular interaction of fosinopril, an angiotensin converting enzyme inhibitor with bovine serum albumin (BSA), has been investigated in physiological buffer (pH 7.4) by multi-spectroscopic methods and molecular docking technique. The results obtained from fluorescence and UV absorption spectroscopy revealed that the fluorescence quenching mechanism of BSA induced by fosinopril was mediated by the combined dynamic and static quenching, and the static quenching was dominant in this system. The binding constant, K b , value was found to lie between 2.69 × 10 3 and 9.55 × 10 3  M -1 at experimental temperatures (293, 298, 303, and 308 K), implying the low or intermediate binding affinity between fosinopril and BSA. Competitive binding experiments with site markers (phenylbutazone and diazepam) suggested that fosinopril preferentially bound to the site I in sub-domain IIA on BSA, as evidenced by molecular docking analysis. The negative sign for enthalpy change (ΔH 0 ) and entropy change (ΔS 0 ) indicated that van der Waals force and hydrogen bonds played important roles in the fosinopril-BSA interaction, and 8-anilino-1-naphthalenesulfonate binding assay experiments offered evidence of the involvements of hydrophobic interactions. Moreover, spectroscopic results (synchronous fluorescence, 3-dimensional fluorescence, and Fourier transform infrared spectroscopy) indicated a slight conformational change in BSA upon fosinopril interaction. Copyright © 2018 John Wiley & Sons, Ltd.

Spectroscopic insights into the oxygen-tolerant membrane-associated [NiFe] hydrogenase of Ralstonia eutropha H16.

PubMed

Saggu, Miguel; Zebger, Ingo; Ludwig, Marcus; Lenz, Oliver; Friedrich, Bärbel; Hildebrandt, Peter; Lendzian, Friedhelm

2009-06-12

This study provides the first spectroscopic characterization of the membrane-bound oxygen-tolerant [NiFe] hydrogenase (MBH) from Ralstonia eutropha H16 in its natural environment, the cytoplasmic membrane. The H2-converting MBH is composed of a large subunit, harboring the [NiFe] active site, and a small subunit, capable in coordinating one [3Fe4S] and two [4Fe4S] clusters. The hydrogenase dimer is electronically connected to a membrane-integral cytochrome b. EPR and Fourier transform infrared spectroscopy revealed a strong similarity of the MBH active site with known [NiFe] centers from strictly anaerobic hydrogenases. Most redox states characteristic for anaerobic [NiFe] hydrogenases were identified except for one remarkable difference. The formation of the oxygen-inhibited Niu-A state was never observed. Furthermore, EPR data showed the presence of an additional paramagnetic center at high redox potential (+290 mV), which couples magnetically to the [3Fe4S] center and indicates a structural and/or redox modification at or near the proximal [4Fe4S] cluster. Additionally, significant differences regarding the magnetic coupling between the Nia-C state and [4Fe4S] clusters were observed in the reduced form of the MBH. The spectroscopic properties are discussed with regard to the unusual oxygen tolerance of this hydrogenase and in comparison with those of the solubilized, dimeric form of the MBH.

Recent advances in biosynthetic modeling of nitric oxide reductases and insights gained from nuclear resonance vibrational and other spectroscopic studies

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

Chakraborty, Saumen; Reed, Julian; Sage, Timothy

This Forum Article focuses on recent advances in structural and spectroscopic studies of biosynthetic models of nitric oxide reductases (NORs). NORs are complex metalloenzymes found in the denitrification pathway of Earth's nitrogen cycle where they catalyze the proton-dependent twoelectron reduction of nitric oxide (NO) to nitrous oxide (N 2O). While much progress has been made in biochemical and biophysical studies of native NORs and their variants, a. clear mechanistic understanding of this important metalloenzyme related to its function is still elusive. We report herein UV vis and nuclear resonance vibrational spectroscopy (NRVS) studies of mononitrosylated intermediates of the NOR reactionmore » of a biosynthetic model. The ability to selectively substitute metals at either heme or nonheme metal sites allows the introduction of independent 57Fe probe atoms at either site, as well as allowing the preparation of analogues of stable reaction intermediates by replacing either metal with a redox inactive metal. Together with previous structural and spectroscopic results, we summarize insights gained from studying these biosynthetic models toward understanding structural features responsible for the NOR activity and its mechanism. As a result, the outlook on NOR modeling is also discussed, with an emphasis on the design of models capable of catalytic turnovers designed based on close mimics of the secondary coordination sphere of native NORs.« less

S&MPO - An information system for ozone spectroscopy on the WEB

NASA Astrophysics Data System (ADS)

Babikov, Yurii L.; Mikhailenko, Semen N.; Barbe, Alain; Tyuterev, Vladimir G.

2014-09-01

Spectroscopy and Molecular Properties of Ozone ("S&MPO") is an Internet accessible information system devoted to high resolution spectroscopy of the ozone molecule, related properties and data sources. S&MPO contains information on original spectroscopic data (line positions, line intensities, energies, transition moments, spectroscopic parameters) recovered from comprehensive analyses and modeling of experimental spectra as well as associated software for data representation written in PHP Java Script, C++ and FORTRAN. The line-by-line list of vibration-rotation transitions and other information is organized as a relational database under control of MySQL database tools. The main S&MPO goal is to provide access to all available information on vibration-rotation molecular states and transitions under extended conditions based on extrapolations of laboratory measurements using validated theoretical models. Applications for the S&MPO may include: education/training in molecular physics, radiative processes, laser physics; spectroscopic applications (analysis, Fourier transform spectroscopy, atmospheric optics, optical standards, spectroscopic atlases); applications to environment studies and atmospheric physics (remote sensing); data supply for specific databases; and to photochemistry (laser excitation, multiphoton processes). The system is accessible via Internet on two sites: http://smpo.iao.ru and http://smpo.univ-reims.fr.

Applications of time-of-flight secondary ion mass spectrometry (TOF-SIMS) and X-ray photoelectron spectroscopy (XPS) to study interactions of genetically engineered proteins with noble metal films

NASA Astrophysics Data System (ADS)

Suzuki, Noriaki

Genetically engineered proteins for inorganics (GEPIs) belong to a new class of polypeptides that are designed to have specific affinities to inorganic materials. A "gold binding protein (GBP)" was chosen as a model protein for GEPIs to study the molecular origins of binding specificity to gold using Time-of-flight secondary ion mass spectrometry (TOF-SIMS) and X-ray photoelectron spectroscopy (XPS). TOF-SIMS, a surface-sensitive analytical instrument with extremely high mass resolutions, provides information on specific amino acid-surface interactions. We used "principal component analysis (PCA)" to analyze the data. We also introduced a new multivariate technique, "hierarchical cluster analysis (HCA)" to organize the data into meaningful structures by measuring a degree of "similarity" and "dissimilarity" of the data. This report discusses a combined use of PCA and HCA to elucidate the binding specificity of GBP to Au. Based on the knowledge gained from TOF-SIMS measurements, we further investigated the nature of the interaction between selected amino acids and noble metal surfaces by using X-ray photoelectron spectroscopy (XPS). We developed a unique capability to introduce water vapor during the adsorption of a single amino acid and applied this method to study the intrinsic nature of sidechain/Au interactions. To further apply this unique research protocol, we characterized another type of GEPI, "quartz binding protein (QBP)," to identify the possible binding sites. This thesis research aims to provide experimental protocols for analyzing short peptide-substrate interface from complex spectroscopic data by using multivariate analysis techniques.

Label-Free Molecular Imaging of Biological Cells and Tissues by Linear and Nonlinear Raman Spectroscopic Approaches.

PubMed

Krafft, Christoph; Schmitt, Michael; Schie, Iwan W; Cialla-May, Dana; Matthäus, Christian; Bocklitz, Thomas; Popp, Jürgen

2017-04-10

Raman spectroscopy is an emerging technique in bioanalysis and imaging of biomaterials owing to its unique capability of generating spectroscopic fingerprints. Imaging cells and tissues by Raman microspectroscopy represents a nondestructive and label-free approach. All components of cells or tissues contribute to the Raman signals, giving rise to complex spectral signatures. Resonance Raman scattering and surface-enhanced Raman scattering can be used to enhance the signals and reduce the spectral complexity. Raman-active labels can be introduced to increase specificity and multimodality. In addition, nonlinear coherent Raman scattering methods offer higher sensitivities, which enable the rapid imaging of larger sampling areas. Finally, fiber-based imaging techniques pave the way towards in vivo applications of Raman spectroscopy. This Review summarizes the basic principles behind medical Raman imaging and its progress since 2012. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

The calibration of photographic and spectroscopic films: Reciprocity failure and thermal responses of IIaO film at liquid nitrogen temperatures

NASA Technical Reports Server (NTRS)

Hammond, E. C., Jr.; Peters, K. A.; Gunther, S. O.; Cunningham, L. M.; Wright, D. D.

1985-01-01

Reciprocity failure was examined for IIaO spectroscopic film. The results indicate reciprocity failure occurs at three distinct minimum points in time; 15 min, 30 min and 90 min. The results are unique because theory suggests only one minimum reciprocity failure point should occur. When incubating 70mm IIaO film for 15 and 30 min at temperatures of 30, 40, 50, and 60 C and then placing in a liquid nitrogen bath at a temperature of -190 C the film demonstrated an increase of the optical density when developed at a warm-up time of 30 min. Longer warm-up periods of 1, 2 and 3 hrs yield a decrease in optical density of the darker wedge patterns; whereas, shorter warm-up times yield an overall increase in the optical densities.

Material parameter estimation with terahertz time-domain spectroscopy.

PubMed

Dorney, T D; Baraniuk, R G; Mittleman, D M

2001-07-01

Imaging systems based on terahertz (THz) time-domain spectroscopy offer a range of unique modalities owing to the broad bandwidth, subpicosecond duration, and phase-sensitive detection of the THz pulses. Furthermore, the possibility exists for combining spectroscopic characterization or identification with imaging because the radiation is broadband in nature. To achieve this, we require novel methods for real-time analysis of THz waveforms. This paper describes a robust algorithm for extracting material parameters from measured THz waveforms. Our algorithm simultaneously obtains both the thickness and the complex refractive index of an unknown sample under certain conditions. In contrast, most spectroscopic transmission measurements require knowledge of the sample's thickness for an accurate determination of its optical parameters. Our approach relies on a model-based estimation, a gradient descent search, and the total variation measure. We explore the limits of this technique and compare the results with literature data for optical parameters of several different materials.

Synthesis, spectroscopic and electrochemical characterization of secnidazole esters

NASA Astrophysics Data System (ADS)

Shahid, Hafiz Abdullah; Jahangir, Sajid; Hanif, Muddasir; Xiong, Tianrou; Muhammad, Haji; Wahid, Sana; Yousuf, Sammer; Qureshi, Naseem

2017-12-01

We report a low-cost, less toxic to environment and simple method for the esterification of secnidazole. This is first comprehensive structural characterization of novel secnidazole esters by the spectroscopic and electrochemical methods. The important EIMS fragmentation analysis showed unique contribution of heteroatom bonds explained by the fragmentation patterns. These peaks originate from the loss of single electron, loss of HCN, M-O, M-NO, M-NO2, M-C7H10N3O3, and M-C8H10N3O4. The comparison of 13C NMR predicted values with the experimental values showed that ChemBioDraw Ultra 14.0 has advantage of predicting aromatic (sp2) carbons, while MestReNova 6.1 predicts sp3 hybrid carbons more accurately. The electrochemical properties indicated an irreversible oxidation process and reversible reduction process in these ester molecules similar to the parent secnidazole.

Spectroscopic observations with the Stratospheric Observatory for Infrared Astronomy (SOFIA)

NASA Astrophysics Data System (ADS)

Becklin, E. E.; Tielens, A. G. G. M.; Callis, H. H. S.

The joint US and German SOFIA project to develop and operate a 2.5-meter infrared airborne telescope in a Boeing 747-SP is now in its final stages of development. Flying in the stratosphere, SOFIA allows observations through the infrared and submillimeter region, with an average transmission of greater than 80%. SOFIA is characterized by a wide instrument complement ranging from broadband imagers, through moderate resolution spectrographs capable of resolving broad features due to dust and large molecules, to high-resolution spectrometers suitable for kinematic studies of molecular and atomic gas lines at km/s resolution. This broad range in instruments will enable SOFIA to make unique contributions to a broad array of science topics. First science flights will begin in 2009 and the observatory is expected to operate for over 20 years. The sensitivity, characteristics, science instrument complement, and examples of first light spectroscopic science are discussed.

Multi-spectroscopic and molecular modeling approaches to elucidate the binding interaction between bovine serum albumin and darunavir, a HIV protease inhibitor.

PubMed

Shi, Jie-Hua; Zhou, Kai-Li; Lou, Yan-Yue; Pan, Dong-Qi

2018-01-05

Darunavir (DRV), a second-generation HIV protease inhibitor, is widely used across the world as an important component of HIV therapy. The interaction of DRV with bovine serum albumin (BSA), a major carrier protein, has been studied under simulated physiological conditions (pH7.4) by multi-spectroscopic techniques in combination with molecular modeling. Fluorescence data revealed that the intrinsic fluorescence of BSA was quenched by DRV in terms of a static quenching procedure due to the formation of the DRV-BSA complex. The results indicated the presence of single weak affinity binding site (~10 3 M -1 , 310K) on protein. The thermodynamic parameters, namely enthalpy change (ΔH 0 ), entropy change (ΔS 0 ) and Gibbs free energy change (ΔG 0 ) were calculated, which signified that the binding reaction was spontaneous, the main binding forces were hydrogen bonding and van der Waals forces. Importantly, competitive binding experiments with three site probes, phenylbutazone (in sub-domain IIA, site I), ibuprofen (in sub-domain IIIA, site II) and artemether (in the interface between sub-domain IIA and IIB, site II'), suggested that DRV was preferentially bound to the hydrophobic cavity in site II' of BSA, and this finding was validated by the docking results. Additionally, synchronous fluorescence, three-dimensional fluorescence and Resonance Rayleigh Scattering (RRS) spectroscopy gave qualitative information on the conformational changes of BSA upon adding DRV, while quantitative data were obtained with Fourier transform infrared spectroscopy (FT-IR). Copyright © 2017 Elsevier B.V. All rights reserved.

Effects of advanced selection methods on sperm quality and ART outcome.

PubMed

Yetunde, I; Vasiliki, M

2013-10-01

In assisted reproductive technology (ART), the role of spermatozoa has evolved over the years. In the past, early methods of selecting sperm for ART only focused on selecting motile and morphologically normal appearing sperm. It has become evident that these methods are inefficient in identifying the most suitable sperm for fertilization. Novel methods have thus been created to identify highly motile, morphologically normal, viable non-apoptotic spermatozoa with intact membranes and high DNA integrity for use in ART. These advanced methods of selection utilize our knowledge of unique characteristics of sperm, such as sperm surface charge, the presence of hyaluronic acid binding sites on sperm, sperm ultramorphology, markers of apoptosis and zona pellucida binding on sperm. These methods have shown potential promise in improving ART outcomes. Future developments may include Raman spectroscopy, confocal light absorption and scattering spectroscopic microscopy, and polarization microscopy. While these novel techniques have potential, they come with a cost burden and further studies are required to demonstrate their impact on ART outcomes. Furthermore, clinicians and human reproductive scientists need to continue to gather knowledge about human fertilization and determine the most physiological methods of sperm selection.

Raman spectroscopic evaluation of DNA adducts of a platinum containing anticancer drug.

PubMed

Jangir, Deepak K; Mehrotra, Ranjana

2014-09-15

Mechanistic understanding of the interaction of drugs with their target molecules is important for better understanding of their mode of action and to improve their efficacy. Carboplatin is a platinum containing anticancer drug, used to treat different type of tumors. In the present work, we applied Raman spectroscopy to study the interaction of carboplatin with DNA at molecular level using different carboplatin-DNA molar ratios. These Raman spectroscopic results provide comprehensive understanding on the carboplatin-DNA interactions and indicate that DNA cross-linked adducts formed by carboplatin are similar to cisplatin adducts. The results indicate that guanine N7 and adenine N7 are the putative sites for carboplatin interaction. It is observed that carboplatin has some affinity toward cytosine in DNA. Phosphate sugar backbone of DNA showed conformation perturbation in DNA which were easily sensible at higher concentrations of carboplatin. Most importantly, carboplatin interaction induces intermediate A- and B-DNA conformations at the cross-linking sites. Copyright © 2014 Elsevier B.V. All rights reserved.

In vitro drug interaction of levocetirizine and diclofenac: Theoretical and spectroscopic studies.

PubMed

Abo Dena, Ahmed S; Abdel Gaber, Sara A

2017-06-15

Levocetirizine dihydrochloride is known to interact with some anti-inflammatory drugs. We report here a comprehensive integrated theoretical and experimental study for the in vitro drug interaction between levocetirizine dihydrochloride (LEV) and diclofenac sodium (DIC). The interaction of the two drugs was confirmed by the molecular ion peak obtained from the mass spectrum of the product. Moreover, FTIR and 1 HNMR spectra of the individual drugs and their interaction product were inspected to allocate the possible sites of interaction. In addition, quantum mechanical DFT calculations were performed to search for the interaction sites and to verify the types of interactions deduced from the spectroscopic studies such as charge-transfer and non-bonding π-π interactions. It was found that the studied drugs interact with each other in aqueous solution via four types of interactions, namely, ion-pair formation, three weak hydrogen bonds, non-bonding π-π interactions and charge-transfer from DIC to LEV. Copyright © 2017 Elsevier B.V. All rights reserved.

Synthesis, crystal structure and optical properties of two new layered cadmium iodates: Cd(IO{sub 3})X (X=Cl, OH)

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

Yang, Bing-Ping, E-mail: ybp@fjirsm.ac.cn; Mao, Jiang-Gao

Systematic explorations of new compounds in the cadmium iodate system by hydrothermal reactions led to two layered iodates, namely, Cd(IO{sub 3})X (X=Cl, OH). Cd(IO{sub 3})Cl crystallizes in the orthorhombic space group Cmca (No. 64) whereas Cd(IO{sub 3})(OH) crystallizes in the orthorhombic space group Pnma (No. 62). Cd(IO{sub 3})Cl displays a unique double layered structure composed of {sup 1}{sub ∞}[Cd−O{sub 3}Cl]{sub n} chains. Cadmium octahedrons form a 1D chain along the a-axis through edge sharing, and such chains are further interconnected via IO{sub 3} groups to form a special double layer on (020) plane. Cd(IO{sub 3})(OH) also exhibits a layered structuremore » that is composed of cadmium cations, IO{sub 3} groups and hydroxyl ions. Within a layer, chains of CdO{sub 6} edge-shared octahedra are observed along the b-axis. And these chains are connected by IO{sub 3} groups into a layer parallel to the bc plane. Spectroscopic characterizations, elemental analysis, and thermogravimetric analysis for the reported two compounds are also presented. - Graphical abstract: Two new layered cadmium iodates Cd(IO{sub 3})X (X=Cl, OH) are reported. Cd(IO{sub 3})Cl features a unique double layered structure whereas Cd(IO{sub 3})(OH) displays an ordinary layered structure. - Highlights: • Two new layered cadmium iodates Cd(IO{sub 3})X (X=Cl, OH) are reported. • Cd(IO{sub 3})Cl features a unique double layered structure. • Cd(IO{sub 3})(OH) displays an ordinary layered structure. • The spectroscopic and thermal properties have been studied in detail.« less

Social Inquiry and Social Action: Priorities for Preparing School Leaders

ERIC Educational Resources Information Center

Gale, Trevor

2010-01-01

Schools are uniquely placed in democracies. Among other things, they are sites of learning about things democratic, including learning "through" as one (important) way of learning "about." There are other sites in which to learn about and through democracies but schooling's uniqueness is that it is a site through which all must pass. So…

Cu(1+) in HKUST-1: selective gas adsorption in the presence of water.

PubMed

Nijem, Nour; Bluhm, Hendrik; Ng, May L; Kunz, Martin; Leone, Stephen R; Gilles, Mary K

2014-09-11

Spectroscopic evidence for an enhanced binding of Nitric Oxide (NO) to metal centers with lower oxidation states (open Cu(1+) sites) in Cu3(btc)2 (HKUST-1) is presented. The Cu(1+) sites created by thermal treatment or X-ray exposure exhibit a preferential adsorption of NO compared to H2O. This phenomenon demonstrates the potential use of MOFs with lower oxidation state metal centers for selective gas separation.

The effect of Berberine on the secondary structure of human serum albumin

NASA Astrophysics Data System (ADS)

Li, Ying; He, WenYing; Tian, Jianniao; Tang, Jianghong; Hu, Zhide; Chen, Xingguo

2005-05-01

The presence of several high affinity binding sites on human serum albumin (HSA) makes it a possible target for many drugs. This study is designed to examine the effect of Berberine (an ancient Chinese drug used for antimicrobial, antiplasmodial, antidiarrheal and cardiovascular) on the solution structure of HSA using fluorescence, Fourier transform infrared (FT-IR), circular dichroism (CD) spectroscopic methods. The fluorescence spectroscopic results show that the fluorescence intensity of HSA was significantly decreased in the presence of Berberine. The Scatchard's plots indicated that the binding of Berberine to HSA at 296, 303, 318 K is characterized by one binding site with the binding constant is 4.071(±0.128)×10 4, 3.741(±0.089)×10 4, 3.454(±0.110)×10 4 M -1, respectively. The protein conformation is altered (FT-IR and CD data) with reductions of α-helices from 54 to 47% for free HSA to 45-32% and with increases of turn structure5% for free HSA to 18% in the presence of Berberine. The binding process was exothermic, enthalpy driven and spontaneous, as indicated by the thermodynamic analyses, Berberine bound to HSA was mainly based on hydrophobic interaction and electrostatic interaction cannot be excluded from the binding. Furthermore, the displace experiments indicate that Berberine can bind to the subdomain IIA, that is, high affinity site (site II).

Competitive interactions of anti-carcinogens with serum albumin: a spectroscopic study of bendamustine and dexamethasone with the aid of chemometrics.

PubMed

Wang, Yong; Zhu, Ruirui; Ni, Yongnian; Kokot, Serge

2014-04-05

Interactions between the anti-carcinogens, bendamustine (BDM) and dexamethasone (DXM), with bovine serum albumin (BSA) were investigated with the use of fluorescence and UV-vis spectroscopies under pseudo-physiological conditions (Tris-HCl buffer, pH 7.4). The static mechanism was responsible for the fluorescence quenching during the interactions; the binding formation constant of the BSA-BDM complex and the binding number were 5.14×10(5)Lmol(-1) and 1.0, respectively. Spectroscopic studies for the formation of BDM-BSA complex were interpreted with the use of multivariate curve resolution - alternating least squares (MCR-ALS), which supported the complex formation. The BSA samples treated with site markers (warfarin - site I and ibuprofen - site II) were reacted separately with BDM and DXM; while both anti-carcinogens bound to site I, the binding constants suggested that DXM formed a more stable complex. Relative concentration profiles and the fluorescence spectra associated with BDM, DXM and BSA, were recovered simultaneously from the full fluorescence excitation-emission data with the use of the parallel factor analysis (PARAFAC) method. The results confirmed that on addition of DXM to the BDM-BSA complex, the BDM was replaced and the DXM-BSA complex formed; free BDM was released. This finding may have consequences for the transport of these drugs during any anti-cancer treatment. Copyright © 2013 Elsevier B.V. All rights reserved.

Iron loading site on the Fe-S cluster assembly scaffold protein is distinct from the active site.

PubMed

Rodrigues, Andria V; Kandegedara, Ashoka; Rotondo, John A; Dancis, Andrew; Stemmler, Timothy L

2015-06-01

Iron-sulfur (Fe-S) cluster containing proteins are utilized in almost every biochemical pathway. The unique redox and coordination chemistry associated with the cofactor allows these proteins to participate in a diverse set of reactions, including electron transfer, enzyme catalysis, DNA synthesis and signaling within several pathways. Due to the high reactivity of the metal, it is not surprising that biological Fe-S cluster assembly is tightly regulated within cells. In yeast, the major assembly pathway for Fe-S clusters is the mitochondrial ISC pathway. Yeast Fe-S cluster assembly is accomplished using the scaffold protein (Isu1) as the molecular foundation, with assistance from the cysteine desulfurase (Nfs1) to provide sulfur, the accessory protein (Isd11) to regulate Nfs1 activity, the yeast frataxin homologue (Yfh1) to regulate Nfs1 activity and participate in Isu1 Fe loading possibly as a chaperone, and the ferredoxin (Yah1) to provide reducing equivalents for assembly. In this report, we utilize calorimetric and spectroscopic methods to provide molecular insight into how wt-Isu1 from S. cerevisiae becomes loaded with iron. Isothermal titration calorimetry and an iron competition binding assay were developed to characterize the energetics of protein Fe(II) binding. Differential scanning calorimetry was used to identify thermodynamic characteristics of the protein in the apo state or under iron loaded conditions. Finally, X-ray absorption spectroscopy was used to characterize the electronic and structural properties of Fe(II) bound to Isu1. Current data are compared to our previous characterization of the D37A Isu1 mutant, and these suggest that when Isu1 binds Fe(II) in a manner not perturbed by the D37A substitution, and that metal binding occurs at a site distinct from the cysteine rich active site in the protein.

The spectroscopic evolution of novae in the bulge of M31 and a search for their possible origin in the M31 globular cluster system

NASA Astrophysics Data System (ADS)

Tomaney, Austin Bede

Results are presented from a three year (1987 to 1989) spectroscopic and photometric survey of novae in M3l's bulge, the first comprehensive study of novae outside the Galactic and Magellanic Cloud systems. Nine novae were detected and monitored and their spectra cover a range of outburst states from early decline to the early nebular phases. Broad agreement in spectral morphology and evolution is found with Galactic novae. Since Galactic novae are mainly disk objects, this indicates that novae outburst properties are not critically dependent on the metallicity of the progenitor population. However, in this sample, and in a sample of four M31 nova spectra taken in 1983, no fast, violent outbursts frequently associated with nova systems containing ONeMg white dwarfs were found, suggestive of a systematic difference between the observed proportion of such outbursts between Galactic and M31 bulge novae. Three novae in the sample were observed on succeeding nights during the transition phase of their evolution. Extraordinary variations in some nightly line strengths, particularly the N III lines, were discovered. It is argued that this variability reflects the deposition of drag energy by the secondary star during the common envelope phase of nova evolution and is indicative of a key phase in mass loss from nova systems. Observations include the spectroscopic coverage of an extremely slow nova from 1987 to l990, during the object's evolution in the nebula phase. This provided a unique opportunity to make the first detailed comparison of the evolution and properties of an extra galactic nova with those in our own Galaxy. The roughly solar abundances obtained are typical of similar slow Galactic novae. Further observations are also presented of a unique outburst in 1988 that was independently discovered and reported by Rich et al. These data confirm the inferences of other observers that the outburst differed markedly from that of a typical classical nova. Finally an extensive spectroscopic survey of the M31 globular cluster system was made in an effort to find evidence of a previously suggested enhanced nova rate in these objects. No outbursts were detected during an effective survey time of one year for the entire system.

Spectroscopic studies of transition-metal ions in molten alkali-metal carboxylates

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

Maroni, V.A.; Maciejewski, M.L.

This paper presents the results of electronic absorption and /sup 13/C-NMR measurements on molten alkali metal formates and acetates and on solutions of selected 3d transition metal ions therein. These studies provide a unique opportunity to explore (1) the highly ordered nature of alkali carboxylates, (2) the ligand field properties of acetate and formate ions, and (3) the coordination chemistry of the 3d transition metals in molten carboxylates. 1 figure, 2 tables.

Spectroscopy of Exoplanet Atmospheres with the FINESSE Explorer

NASA Technical Reports Server (NTRS)

Deroo, Pieter; Swain, Mark R.; Green, Robert O.

2012-01-01

FINESSE (Fast INfrared Exoplanet Spectroscopic Survey Explorer) will provide uniquely detailed information on the growing number of newly discovered planets by characterizing their atmospheric composition and temperature structure. This NASA Explorer mission, selected for a competitive Phase A study, is unique in its breath and scope thanks to broad instantaneous spectroscopy from the optical to the mid-IR (0.7 - 5 micron), with a survey of exoplanets measured in a consistent, uniform way. For 200 transiting exoplanets ranging from Terrestrial to Jovians, FINESSE will measure the chemical composition and temperature structure of their atmospheres and trace changes over time with exoplanet longitude. The mission will do so by measuring the spectroscopic time series for a primary and secondary eclipse over the exoplanet orbital phase curve. With spectrophotometric precision being a key enabling aspect for combined light exoplanet characterization, FINESSE is designed to produce spectrophotometric precision of better than 100 parts-per-million per spectral channel without the need for decorrelation. The exceptional stability of FINESSE will even allow the mission to characterize non-transiting planets, potentially as part of FINESSE's Participating Scientist Program. In this paper, we discuss the flow down from the target availability to observations and scheduling to the analysis and calibration of the data and how it enables FINESSE to be the mission that will truly expand the new field of comparative exoplanetology.

A 2MASS/AllWISE Search for Extremely Red L Dwarfs: The Discovery of Several Likely L Type Members of β Pic, AB Dor, Tuc-Hor, Argus, and the Hyades

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

Schneider, Adam C.; Shkolnik, Evgenya L.; Windsor, James

Young brown dwarfs share many properties with directly imaged giant extrasolar planets. They therefore provide unique laboratories for investigating the full range of temperature and mass encompassed by the growing collection of planets discovered outside our Solar System. Furthermore, if they can be tied to a particular group of coeval stars, they also provide vital anchor points for low-mass empirical isochrones. We have developed a novel procedure for identifying such objects based on their unique 2MASS and AllWISE colors. Using our search criteria, we have identified 50 new, late-type L dwarf candidates, 47 of which are spectroscopically confirmed as Lmore » dwarfs with follow-up near-infrared spectroscopy. We evaluate the potential membership of these objects in nearby, young moving groups using their proper motions, photometric distance estimates, and spectroscopic indicators of youth, and find seven likely L-type members belonging to the β Pictoris moving group, the AB Doradus moving group, the Tucana-Horologium association, or the Argus association, in addition to several lower probability members. Also found are two late-type (L5 and L6) potential members of the nearby Hyades cluster (WISEA J043642.75+190134.8 and WISEA J044105.56+213001.5).« less

Spectroscopy of disordered low-field sites in Cr3+: Mullite glass ceramic

NASA Astrophysics Data System (ADS)

Knutson, Robert; Liu, Huimin; Yen, W. M.; Morgan, T. V.

1989-09-01

In this article we present results of optical and ESR studies that have allowed us to study the behavior of Cr3+ at disordered low-field sites within a mullite ceramic host. The results indicate that the existence of these low-field ions, which are likely at sites in regions of disorder, accounts for most of the spectroscopic anomalies previously noted in these materials. Furthermore, energy transfer from ordered high-field to disordered low-field ions is observed. The resulting complex spectra are deconvoluted by means of the recently developed technique of saturation-resolved fluorescence spectroscopy.

Polyvalent Display of Heme on Hepatitis B Virus Capsid Protein through Coordination to Hexahistidine Tags

PubMed Central

Prasuhn, Duane E.; Kuzelka, Jane; Strable, Erica; Udit, Andrew K.; Cho, So-Hye; Lander, Gabriel C.; Quispe, Joel D.; Diers, James R.; Bocian, David F.; Potter, Clint; Carragher, Bridget; Finn, M.G.

2009-01-01

SUMMARY The addition of a hexahistidine tag to the N terminus of the hepatitis B capsid protein gives rise to a self-assembled particle with 80 sites of high local density of histidine side chains. Iron protoporphyrin IX has been found to bind tightly at each of these sites, making a polyvalent system of well-defined spacing between metalloporphyrin complexes. The spectroscopic and redox properties of the resulting particle are consistent with the presence of 80 site-isolated bis(histidine)-bound heme centers, comprising a polyvalent b-type cytochrome mimic. PMID:18482703

Sorption of trivalent lanthanides and actinides onto montmorillonite: Macroscopic, thermodynamic and structural evidence for ternary hydroxo and carbonato surface complexes on multiple sorption sites.

PubMed

Fernandes, M Marques; Scheinost, A C; Baeyens, B

2016-08-01

The credibility of long-term safety assessments of radioactive waste repositories may be greatly enhanced by a molecular level understanding of the sorption processes onto individual minerals present in the near- and far-fields. In this study we couple macroscopic sorption experiments to surface complexation modelling and spectroscopic investigations, including extended X-ray absorption fine structure (EXAFS) and time-resolved laser fluorescence spectroscopies (TRLFS), to elucidate the uptake mechanism of trivalent lanthanides and actinides (Ln/An(III)) by montmorillonite in the absence and presence of dissolved carbonate. Based on the experimental sorption isotherms for the carbonate-free system, the previously developed 2 site protolysis non electrostatic surface complexation and cation exchange (2SPNE SC/CE) model needed to be complemented with an additional surface complexation reaction onto weak sites. The fitting of sorption isotherms in the presence of carbonate required refinement of the previously published model by reducing the strong site capacity and by adding the formation of Ln/An(III)-carbonato complexes both on strong and weak sites. EXAFS spectra of selected Am samples and TRLFS spectra of selected Cm samples corroborate the model assumptions by showing the existence of different surface complexation sites and evidencing the formation of Ln/An(III) carbonate surface complexes. In the absence of carbonate and at low loadings, Ln/An(III) form strong inner-sphere complexes through binding to three Al(O,OH)6 octahedra, most likely by occupying vacant sites in the octahedral layers of montmorillonite, which are exposed on {010} and {110} edge faces. At higher loadings, Ln/An(III) binds to only one Al octahedron, forming a weaker, edge-sharing surface complex. In the presence of carbonate, we identified a ternary mono- or dicarbonato Ln/An(III) complex binding directly to one Al(O,OH)6 octahedron, revealing that type-A ternary complexes form with the one or two carbonate groups pointing away from the surface into the solution phase. Within the spectroscopically observable concentration range these complexes could only be identified on the weak sites, in line with the small strong site capacity suggested by the refined sorption model. When the solubility of carbonates was exceeded, formation of an Am carbonate hydroxide could be identified. The excellent agreement between the thermodynamic model parameters obtained by fitting the macroscopic data, and the spectroscopically identified mechanisms, demonstrates the mature state of the 2SPNE SC/CE model for predicting and quantifying the retention of Ln/An(III) elements by montmorillonite-rich clay rocks. Copyright © 2016 Elsevier Ltd. All rights reserved.

Unravelling Site-Specific Photo-Reactions of Ethanol on Rutile TiO2(110)

PubMed Central

Hansen, Jonas Ø.; Bebensee, Regine; Martinez, Umberto; Porsgaard, Soeren; Lira, Estephania; Wei, Yinying; Lammich, Lutz; Li, Zheshen; Idriss, Hicham; Besenbacher, Flemming; Hammer, Bjørk; Wendt, Stefan

2016-01-01

Finding the active sites of catalysts and photo-catalysts is crucial for an improved fundamental understanding and the development of efficient catalytic systems. Here we have studied the photo-activated dehydrogenation of ethanol on reduced and oxidized rutile TiO2(110) in ultrahigh vacuum conditions. Utilizing scanning tunnelling microscopy, various spectroscopic techniques and theoretical calculations we found that the photo-reaction proceeds most efficiently when the reactants are adsorbed on regular Ti surface sites, whereas species that are strongly adsorbed at surface defects such as O vacancies and step edges show little reaction under reducing conditions. We propose that regular Ti surface sites are the most active sites in photo-reactions on TiO2. PMID:26915303

An S-Oxygenated [NiFe] Complex Modelling Sulfenate Intermediates of an O2 -Tolerant Hydrogenase.

PubMed

Lindenmaier, Nils J; Wahlefeld, Stefan; Bill, Eckhard; Szilvási, Tibor; Eberle, Christopher; Yao, Shenglai; Hildebrandt, Peter; Horch, Marius; Zebger, Ingo; Driess, Matthias

2017-02-13

To understand the molecular details of O 2 -tolerant hydrogen cycling by a soluble NAD + -reducing [NiFe] hydrogenase, we herein present the first bioinspired heterobimetallic S-oxygenated [NiFe] complex as a structural and vibrational spectroscopic model for the oxygen-inhibited [NiFe] active site. This compound and its non-S-oxygenated congener were fully characterized, and their electronic structures were elucidated in a combined experimental and theoretical study with emphasis on the bridging sulfenato moiety. Based on the vibrational spectroscopic properties of these complexes, we also propose novel strategies for exploring S-oxygenated intermediates in hydrogenases and similar enzymes. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

SPECTROSCOPIC SPECIATION AND QUANTIFICATION ON ALTERATIONS OF PB IN PHOSPHATE AMENDED SOILS

EPA Science Inventory

Lead-bearing soils are a source of lead (Pb) contamination at a number of sites across the nation and pose a risk for our most sensitive population, children. The In-place Inactivation and Natural Ecological Restoration Team (IINERT) has demonstrated the feasibility of reducing ...

Perspectives and challenges of photon-upconversion nanoparticles - Part I: routes to brighter particles and quantitative spectroscopic studies.

PubMed

Resch-Genger, Ute; Gorris, Hans H

2017-10-01

Lanthanide-doped photon-upconversion nanoparticles (UCNPs) have been the focus of many research activities in materials and life sciences in the last 15 years because of their potential to convert light between different spectral regions and their unique photophysical properties. To fully exploit the application potential of these fascinating nanomaterials, a number of challenges have to be overcome, such as the low brightness, particularly of small UCNPs, and the reliable quantification of the excitation-power-density-dependent upconversion luminescence. In this series of critical reviews, recent developments in the design, synthesis, optical-spectroscopic characterization, and application of UCNPs are presented with special focus on bioanalysis and the life sciences. Here we guide the reader from the synthesis of UCNPs to different concepts to enhance their luminescence, including the required optical-spectroscopic assessment to quantify material performance; surface modification strategies and bioanalytical applications as well as selected examples of the use of UCNPs as reporters in different assay formats are addressed in part II. Future trends and challenges in the field of upconversion are discussed with special emphasis on UCNP synthesis and material characterization, particularly quantitative luminescence studies. Graphical Abstract Both synthesis and spectroscopy as well bioanalytical applications of UCNPs are driven and supported by COST Action CM1403 "The European Upconversion Network".

Spectroscopic investigation on cocrystal formation between adenine and fumaric acid based on infrared and Raman techniques

NASA Astrophysics Data System (ADS)

Du, Yong; Fang, Hong Xia; Zhang, Qi; Zhang, Hui Li; Hong, Zhi

2016-01-01

As an important component of double-stranded DNA, adenine has powerful hydrogen-bond capability, due to rich hydrogen bond donors and acceptors existing within its molecular structure. Therefore, it is easy to form cocrystal between adenine and other small molecules with intermolecular hydrogen-bond effect. In this work, cocrystal of adenine and fumaric acid has been characterized as model system by FT-IR and FT-Raman spectral techniques. The experimental results show that the cocrystal formed between adenine and fumaric acid possesses unique spectroscopical characteristic compared with that of starting materials. Density functional theory (DFT) calculation has been performed to optimize the molecular structures and simulate vibrational modes of adenine, fumaric acid and the corresponding cocrystal. Combining the theoretical and experimental vibrational results, the characteristic bands corresponding to bending and stretching vibrations of amino and carbonyl groups within cocrystal are shifted into lower frequencies upon cocrystal formation, and the corresponding bond lengths show some increase due to the effect of intermolecular hydrogen bonding. Different vibrational modes shown in the experimental spectra have been assigned based on the simulation DFT results. The study could provide experimental and theoretical benchmarks to characterize cocrystal formed between active ingredients and cocrystal formers and also the intermolecular hydrogen-bond effect within cocrystal formation process by vibrational spectroscopic techniques.

Spectroscopic identification of individual fluorophores using photoluminescence excitation spectra.

PubMed

Czerski, J; Colomb, W; Cannataro, F; Sarkar, S K

2018-01-25

The identity of a fluorophore can be ambiguous if other fluorophores or nonspecific fluorescent impurities have overlapping emission spectra. The presence of overlapping spectra makes it difficult to differentiate fluorescent species using discrete detection channels and unmixing of spectra. The unique absorption and emission signatures of fluorophores provide an opportunity for spectroscopic identification. However, absorption spectroscopy may be affected by scattering, whereas fluorescence emission spectroscopy suffers from signal loss by gratings or other dispersive optics. Photoluminescence excitation spectra, where excitation is varied and emission is detected at a fixed wavelength, allows hyperspectral imaging with a single emission filter for high signal-to-background ratio without any moving optics on the emission side. We report a high throughput method for measuring the photoluminescence excitation spectra of individual fluorophores using a tunable supercontinuum laser and prism-type total internal reflection fluorescence microscope. We used the system to measure and sort the photoluminescence excitation spectra of individual Alexa dyes, fluorescent nanodiamonds (FNDs), and fluorescent polystyrene beads. We used a Gaussian mixture model with maximum likelihood estimation to objectively separate the spectra. Finally, we spectroscopically identified different species of fluorescent nanodiamonds with overlapping spectra and characterized the heterogeneity of fluorescent nanodiamonds of varying size. © 2018 The Authors Journal of Microscopy © 2018 Royal Microscopical Society.

Spectroscopically determined force field for water dimer: physically enhanced treatment of hydrogen bonding in molecular mechanics energy functions.

PubMed

Mannfors, Berit; Palmo, Kim; Krimm, Samuel

2008-12-11

Our ab initio transformed spectroscopically determined force field (SDFF) methodology emphasizes, in addition to accurate structure and energy performance, comparable prediction of vibrational properties in order to improve reproduction of interaction forces. It is now applied to the determination of a molecular mechanics (MM) force field for the water monomer and dimer as an initial step in developing a more physically based treatment of the hydrogen bonding that not only underlies condensed-phase water but also must be important in molecular-level protein-water interactions. Essential electrical components of the SDFF for monomer water are found to be the following: an off-plane charge distribution, this distribution consisting of four off-atom charge sites in traditional lone pair (LP) but also in inverted lone pair (ILP) positions; allowance for a diffuse size to these off-atom sites; and the incorporation of charge fluxes (i.e., the change in charge with change in internal coordinate). Parametrization of such an LP/ILP model together with the SDFF analytically transformed valence force field results in essentially exact agreement with ab initio (in this case MP2/6-31++G(d,p)) structure, electrical, and vibrational properties. Although we demonstrate that the properties of this monomer electrical model together with its van der Waals and polarization interactions are transferable to the dimer, this is not sufficient in reproducing comparable dimer properties, most notably the huge increase in infrared intensity of a donor OH stretch mode. This deficiency, which can be eliminated by a large dipole-derivative-determined change in the effective charge flux of the donor hydrogen-bonded OH bond, is not accounted for by the charge flux change in this bond due to the induction effects of the acceptor electric field alone, and can only be fully removed by an added bond flux associated with the extent of overlap of the wave functions of the two molecules. We show that this overlap charge flux (OCF) emulates an actual O-H...LP-O intermolecular dipole flux, reflecting the unitary nature of the hydrogen-bonded system in the context of MM-separable molecules. The effectiveness of incorporating the OCF noncanonical character demonstrates that a distinctively QM-unique property can be substantively represented in MM energy functions.

Hybrid genetic algorithm with an adaptive penalty function for fitting multimodal experimental data: application to exchange-coupled non-Kramers binuclear iron active sites.

PubMed

Beaser, Eric; Schwartz, Jennifer K; Bell, Caleb B; Solomon, Edward I

2011-09-26

A Genetic Algorithm (GA) is a stochastic optimization technique based on the mechanisms of biological evolution. These algorithms have been successfully applied in many fields to solve a variety of complex nonlinear problems. While they have been used with some success in chemical problems such as fitting spectroscopic and kinetic data, many have avoided their use due to the unconstrained nature of the fitting process. In engineering, this problem is now being addressed through incorporation of adaptive penalty functions, but their transfer to other fields has been slow. This study updates the Nanakorrn Adaptive Penalty function theory, expanding its validity beyond maximization problems to minimization as well. The expanded theory, using a hybrid genetic algorithm with an adaptive penalty function, was applied to analyze variable temperature variable field magnetic circular dichroism (VTVH MCD) spectroscopic data collected on exchange coupled Fe(II)Fe(II) enzyme active sites. The data obtained are described by a complex nonlinear multimodal solution space with at least 6 to 13 interdependent variables and are costly to search efficiently. The use of the hybrid GA is shown to improve the probability of detecting the global optimum. It also provides large gains in computational and user efficiency. This method allows a full search of a multimodal solution space, greatly improving the quality and confidence in the final solution obtained, and can be applied to other complex systems such as fitting of other spectroscopic or kinetics data.

Proton Transfer in the Catalytic Cycle of [NiFe] Hydrogenases: Insight from Vibrational Spectroscopy

PubMed Central

2017-01-01

Catalysis of H2 production and oxidation reactions is critical in renewable energy systems based around H2 as a clean fuel, but the present reliance on platinum-based catalysts is not sustainable. In nature, H2 is oxidized at minimal overpotential and high turnover frequencies at [NiFe] catalytic sites in hydrogenase enzymes. Although an outline mechanism has been established for the [NiFe] hydrogenases involving heterolytic cleavage of H2 followed by a first and then second transfer of a proton and electron away from the active site, details remain vague concerning how the proton transfers are facilitated by the protein environment close to the active site. Furthermore, although [NiFe] hydrogenases from different organisms or cellular environments share a common active site, they exhibit a broad range of catalytic characteristics indicating the importance of subtle changes in the surrounding protein in controlling their behavior. Here we review recent time-resolved infrared (IR) spectroscopic studies and IR spectroelectrochemical studies carried out in situ during electrocatalytic turnover. Additionally, we re-evaluate the significant body of IR spectroscopic data on hydrogenase active site states determined through more conventional solution studies, in order to highlight mechanistic steps that seem to apply generally across the [NiFe] hydrogenases, as well as steps which so far seem limited to specific groups of these enzymes. This analysis is intended to help focus attention on the key open questions where further work is needed to assess important aspects of proton and electron transfer in the mechanism of [NiFe] hydrogenases. PMID:28413691

In vivo Raman spectroscopic identification of premalignant lesions in oral buccal mucosa

NASA Astrophysics Data System (ADS)

Singh, S. P.; Deshmukh, Atul; Chaturvedi, Pankaj; Murali Krishna, C.

2012-10-01

Cancers of oral cavities are one of the most common malignancies in India and other south-Asian countries. Tobacco habits are the main etiological factors for oral cancer. Identification of premalignant lesions is required for improving survival rates related to oral cancer. Optical spectroscopy methods are projected as alternative/adjunct for cancer diagnosis. Earlier studies have demonstrated the feasibility of classifying normal, premalignant, and malignant oral ex-vivo tissues. We intend to evaluate potentials of Raman spectroscopy in detecting premalignant conditions. Spectra were recorded from premalignant patches, contralateral normal (opposite to tumor site), and cancerous sites of subjects with oral cancers and also from age-matched healthy subjects with and without tobacco habits. A total of 861 spectra from 104 subjects were recorded using a fiber-optic probe-coupled HE-785 Raman spectrometer. Spectral differences in the 1200- to 1800-cm-1 region were subjected to unsupervised principal component analysis and supervised linear discriminant analysis followed by validation with leave-one-out and an independent test data set. Results suggest that premalignant conditions can be objectively discriminated with both normal and cancerous sites as well as from healthy controls with and without tobacco habits. Findings of the study further support efficacy of Raman spectroscopic approaches in oral-cancer applications.

Fluorescence spectroscopic and molecular docking studies of the binding interaction between the new anaplastic lymphoma kinase inhibitor crizotinib and bovine serum albumin

NASA Astrophysics Data System (ADS)

Abdelhameed, Ali S.; Alanazi, Amer M.; Bakheit, Ahmed H.; Darwish, Hany W.; Ghabbour, Hazem A.; Darwish, Ibrahim A.

2017-01-01

Binding of the recently introduced anti-cancer drug, crizotinib (CRB) with the bovine serum albumin (BSA) was comprehensively studied with the aid of fluorescence and UV-Vis spectroscopic as well as molecular docking techniques. The collective results of the study under the simulated physiological conditions proposed a static type of binding occurring between the CRB and BSA with binding constants of 104 L mol- 1. BSA conformational changes were investigated using three dimensional (3D) and synchronous fluorescence measurements. Moreover, the results of site marker competitive experiments and molecular docking, it could be deduced that CRB was inserted into the subdomain IIA (site I) of BSA yielding a more stabilized system. This was further confirmed with the molecular docking results which revealed that CRB is located in the active site residues Try149, Glu152, Ser191, Arg194, Arg198, Trp213, Arg217, Arg256, His287, Ala290, Glu291, Ser343, Asp450 within a radius of 6 Å. Combining the molecular docking studies and the computed thermodynamic parameters, it can be inferred that hydrophobic and electrostatic interactions are the major binding forces involved in formation of the CRB-BSA complex.

Two-Color Resonant Four-Wave Mixing Spectroscopy: New Perspectives for Direct Studies of Collisional State-to-State Transfer

NASA Astrophysics Data System (ADS)

Chen, X.; Settersten, T. B.; Radi, P. P.; Kouzov, A. P.

2008-10-01

The two-color resonant four-wave mixing (TC-RFWM) is advertised as a unique spectroscopic device enabling one to directly measure the collisional state-to-state transfer characteristics (rates and correlation times). In contrast to the laser-induced fluorescence, these characteristics are phase-sensitive and open wider opportunities to study the rotational relaxation processes. Further perspectives are offered by the recently recorded collision-induced picosecond TC-RFWM signals of OH. Their quantitative interpretation is now under development.

(+)- and (-)-Cajanusine, a pair of new enantiomeric stilbene dimers with a new skeleton from the leaves of Cajanus cajan.

PubMed

Li, Xiao-Long; Zhao, Bing-Xin; Huang, Xiao-Jun; Zhang, Dong-Mei; Jiang, Ren-Wang; Li, Ying-Jie; Jian, Yu-Qing; Wang, Ying; Li, Yao-Lan; Ye, Wen-Cai

2014-01-03

A pair of new enantiomeric stilbene dimers, (+)- and (-)-cajanusine [(+)-1 and (-)-1], with a unique coupling pattern were isolated from the leaves of Cajanus cajan . Their structures including absolute configurations were elucidated on the basis of comprehensive spectroscopic and single-crystal X-ray diffraction analyses, as well as CD calculations. The plausible biogenetic pathway of 1 was also proposed. Additionally, (±)-1, (+)-1, and (-)-1 exhibited inhibitory activities on the growth of human hepatocellular carcinoma cells.

Applications of infrared free electron lasers in picosecond and nonlinear spectroscopy

NASA Astrophysics Data System (ADS)

Fann, W. S.; Benson, S. V.; Madey, J. M. J.; Etemad, S.; Baker, G. L.; Rothberg, L.; Roberson, M.; Austin, R. H.

1990-10-01

In this paper we describe two different types of spectroscopic experiments that exploit the characteristics of the infrared FEL, Mark III, for studies of condensed matter: - the spectrum of χ(3)(-3ω; ω, ω, ω) in polyacetylene: an application of the free electron laser in nonlinear optical spectroscopy, and - a dynamical test of Davydov-like solitons in acetanilide using a picosecond free electron laser. These two studies highlight the unique contributions FELs can make to condensed-matter spectroscopy.

Constraints on early-type galaxy structure from spectroscopically selected gravitational lenses

NASA Astrophysics Data System (ADS)

Bolton, Adam Stallard

2005-11-01

This thesis describes all aspects of a unique spectroscopic survey for strong galaxy-galaxy gravitational lenses: motivation, candidate selection, ground- based spectroscopic follow-up, Hubble Space Telescope imaging, data analysis, and results on the radial density profile of the lens galaxies. The lens candidates are selected from within the spectroscopic database of the Sloan Digital Sky Survey (SDSS) based on the appearance of two significantly different redshifts along the same line of sight, and lenses are confirmed within the candidate sample by follow-up imaging and spectroscopy. The sample of [approximate]20 early-type lenses presented in this thesis represents the largest single strong-lens galaxy sample discovered and published to date. These lenses probe the mass of the lens galaxies on scales roughly equal to one-half effective radius. We find a dynamical normalization between isothermal lens-model velocity dispersions and aperture-corrected SDSS stellar velocity dispersions of f = s lens /s stars = 0.95 +/- 0.03. By combining lens-model Einstein radii and de Vaucouleurs effective radii with stellar velocity dispersions through the Jeans equation, we find that the logarithmic slope [Special characters omitted.] of the density profile in our lens galaxies (r 0 ( [Special characters omitted.] ) is on average slightly steeper than isothermal ([Special characters omitted.] = 2) with a modest intrinsic scatter. Parameterizing the intrinsic distribution in [Special characters omitted.] as Gaussian, we find a maximum-likelihood mean of [Special characters omitted. ] and standard deviation of s[Special characters omitted.] = [Special characters omitted.] (68% confidence, for isotropic velocity-dispersion models). Our results rule out a single universal logarithmic density slope at >99.995% confidence. The success of this spectroscopic lens survey suggests that similar projects should be considered as an explicit science goal of future redshift surveys. (Copies available exclusively from MIT Libraries, Rm. 14-0551, Cambridge, MA 02139-4307. Ph. 617-253-5668; Fax 617-253-1690.)

Studying the Ultraviolet Spectrum of the First Spectroscopically Confirmed Supernova at redshift two

DOE PAGES

Smith, M.

2017-12-11

Here, we present observations of DES16C2nm, the first spectroscopically confirmed hydrogen-free superluminous supernova (SLSN-I) at redshift z~2. DES16C2nm was discovered by the Dark Energy Survey (DES) Supernova Program, with follow-up photometric data from the Hubble Space Telescope, Gemini, and the European Southern Observatory Very Large Telescope supplementing the DES data. Spectroscopic observations confirm DES16C2nm to be at z=1.998, and spectroscopically similar to Gaia16apd (a SLSN-I at z=0.102), with a peak absolute magnitude of U=-22.26more » $$\\pm$$0.06. The high redshift of DES16C2nm provides a unique opportunity to study the ultraviolet (UV) properties of SLSNe-I. Combining DES16C2nm with ten similar events from the literature, we show that there exists a homogeneous class of SLSNe-I in the UV (~2500A), with peak luminosities in the (rest-frame) U band, and increasing absorption to shorter wavelengths. There is no evidence that the mean photometric and spectroscopic properties of SLSNe-I differ between low (z<1) and high redshift (z>1), but there is clear evidence of diversity in the spectrum at <2000A, possibly caused by the variations in temperature between events. No significant correlations are observed between spectral line velocities and photometric luminosity. Using these data, we estimate that SLSNe-I can be discovered to z=3.8 by DES. While SLSNe-I are typically identified from their blue observed colors at low redshift (z<1), we highlight that at z>2 these events appear optically red, peaking in the observer-frame z-band. Such characteristics are critical to identify these objects with future facilities such as the Large Synoptic Survey Telescope, Euclid, and the Wide-Field Infrared Survey Telescope, which should detect such SLSNe-I to z=3.5, 3.7, and 6.6, respectively.« less

Studying the Ultraviolet Spectrum of the First Spectroscopically Confirmed Supernova at Redshift Two

NASA Astrophysics Data System (ADS)

Smith, M.; Sullivan, M.; Nichol, R. C.; Galbany, L.; D’Andrea, C. B.; Inserra, C.; Lidman, C.; Rest, A.; Schirmer, M.; Filippenko, A. V.; Zheng, W.; Cenko, S. Bradley; Angus, C. R.; Brown, P. J.; Davis, T. M.; Finley, D. A.; Foley, R. J.; González-Gaitán, S.; Gutiérrez, C. P.; Kessler, R.; Kuhlmann, S.; Marriner, J.; Möller, A.; Nugent, P. E.; Prajs, S.; Thomas, R.; Wolf, R.; Zenteno, A.; Abbott, T. M. C.; Abdalla, F. B.; Allam, S.; Annis, J.; Bechtol, K.; Benoit-Lévy, A.; Bertin, E.; Brooks, D.; Burke, D. L.; Carnero Rosell, A.; Carrasco Kind, M.; Carretero, J.; Castander, F. J.; Crocce, M.; Cunha, C. E.; da Costa, L. N.; Davis, C.; Desai, S.; Diehl, H. T.; Doel, P.; Eifler, T. F.; Flaugher, B.; Fosalba, P.; Frieman, J.; García-Bellido, J.; Gaztanaga, E.; Gerdes, D. W.; Goldstein, D. A.; Gruen, D.; Gruendl, R. A.; Gschwend, J.; Gutierrez, G.; Honscheid, K.; James, D. J.; Johnson, M. W. G.; Kuehn, K.; Kuropatkin, N.; Li, T. S.; Lima, M.; Maia, M. A. G.; Marshall, J. L.; Martini, P.; Menanteau, F.; Miller, C. J.; Miquel, R.; Ogando, R. L. C.; Petravick, D.; Plazas, A. A.; Romer, A. K.; Rykoff, E. S.; Sako, M.; Sanchez, E.; Scarpine, V.; Schindler, R.; Schubnell, M.; Sevilla-Noarbe, I.; Smith, R. C.; Soares-Santos, M.; Sobreira, F.; Suchyta, E.; Swanson, M. E. C.; Tarle, G.; Walker, A. R.; The DES Collaboration

2018-02-01

We present observations of DES16C2nm, the first spectroscopically confirmed hydrogen-free superluminous supernova (SLSN-I) at redshift z≈ 2. DES16C2nm was discovered by the Dark Energy Survey (DES) Supernova Program, with follow-up photometric data from the Hubble Space Telescope, Gemini, and the European Southern Observatory Very Large Telescope supplementing the DES data. Spectroscopic observations confirm DES16C2nm to be at z = 1.998, and spectroscopically similar to Gaia16apd (a SLSN-I at z = 0.102), with a peak absolute magnitude of U=-22.26+/- 0.06. The high redshift of DES16C2nm provides a unique opportunity to study the ultraviolet (UV) properties of SLSNe-I. Combining DES16C2nm with 10 similar events from the literature, we show that there exists a homogeneous class of SLSNe-I in the UV ({λ }{rest}≈ 2500 Å), with peak luminosities in the (rest-frame) U band, and increasing absorption to shorter wavelengths. There is no evidence that the mean photometric and spectroscopic properties of SLSNe-I differ between low (z< 1) and high redshift (z> 1), but there is clear evidence of diversity in the spectrum at {λ }{rest}< 2000 \\mathringA , possibly caused by the variations in temperature between events. No significant correlations are observed between spectral line velocities and photometric luminosity. Using these data, we estimate that SLSNe-I can be discovered to z = 3.8 by DES. While SLSNe-I are typically identified from their blue observed colors at low redshift (z< 1), we highlight that at z> 2 these events appear optically red, peaking in the observer-frame z-band. Such characteristics are critical to identify these objects with future facilities such as the Large Synoptic Survey Telescope, Euclid, and the Wide-field Infrared Survey Telescope, which should detect such SLSNe-I to z = 3.5, 3.7, and 6.6, respectively.

HST Grism Confirmation of 16 Structures at 1.4 < z < 2.8 from the Clusters Around Radio-Loud AGN (CARLA) Survey

NASA Astrophysics Data System (ADS)

Noirot, Gaël; Stern, Daniel; Mei, Simona; Wylezalek, Dominika; Cooke, Elizabeth A.; De Breuck, Carlos; Galametz, Audrey; Hatch, Nina A.; Vernet, Joël; Brodwin, Mark; Eisenhardt, Peter; Gonzalez, Anthony H.; Jarvis, Matt; Rettura, Alessandro; Seymour, Nick; Stanford, S. A.

2018-05-01

We report spectroscopic results from our 40-orbit Hubble Space Telescope slitless grism spectroscopy program observing the 20 densest Clusters Around Radio-Loud AGN (CARLA) candidate galaxy clusters at 1.4 < z < 2.8. These candidate rich structures, among the richest and most distant known, were identified on the basis of [3.6]–[4.5] color from a 408 hr multi-cycle Spitzer program targeting 420 distant radio-loud AGN. We report the spectroscopic confirmation of 16 distant structures at 1.4 < z < 2.8 associated with the targeted powerful high-redshift radio-loud AGN. We also report the serendipitous discovery and spectroscopic confirmation of seven additional structures at 0.87 < z < 2.12 not associated with the targeted radio-loud AGN. We find that 1010–1011 M ⊙ member galaxies of our confirmed CARLA structures form significantly fewer stars than their field counterparts at all redshifts within 1.4 ≤ z ≤ 2. We also observe higher star-forming activity in the structure cores up to z = 2, finding similar trends as cluster surveys at slightly lower redshifts (1.0 < z < 1.5). By design, our efficient strategy of obtaining just two grism orbits per field only obtains spectroscopic confirmation of emission line galaxies. Deeper spectroscopy will be required to study the population of evolved, massive galaxies in these (forming) clusters. Lacking multi-band coverage of the fields, we adopt a very conservative approach of calling all confirmations “structures,” although we note that a number of features are consistent with some of them being bona fide galaxy clusters. Together this survey represents a unique and large homogenous sample of spectroscopically confirmed structures at high redshifts, potentially more than doubling the census of confirmed, massive clusters at z > 1.4.

Studying the Ultraviolet Spectrum of the First Spectroscopically Confirmed Supernova at redshift two

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

Smith, M.

Here, we present observations of DES16C2nm, the first spectroscopically confirmed hydrogen-free superluminous supernova (SLSN-I) at redshift z~2. DES16C2nm was discovered by the Dark Energy Survey (DES) Supernova Program, with follow-up photometric data from the Hubble Space Telescope, Gemini, and the European Southern Observatory Very Large Telescope supplementing the DES data. Spectroscopic observations confirm DES16C2nm to be at z=1.998, and spectroscopically similar to Gaia16apd (a SLSN-I at z=0.102), with a peak absolute magnitude of U=-22.26more » $$\\pm$$0.06. The high redshift of DES16C2nm provides a unique opportunity to study the ultraviolet (UV) properties of SLSNe-I. Combining DES16C2nm with ten similar events from the literature, we show that there exists a homogeneous class of SLSNe-I in the UV (~2500A), with peak luminosities in the (rest-frame) U band, and increasing absorption to shorter wavelengths. There is no evidence that the mean photometric and spectroscopic properties of SLSNe-I differ between low (z<1) and high redshift (z>1), but there is clear evidence of diversity in the spectrum at <2000A, possibly caused by the variations in temperature between events. No significant correlations are observed between spectral line velocities and photometric luminosity. Using these data, we estimate that SLSNe-I can be discovered to z=3.8 by DES. While SLSNe-I are typically identified from their blue observed colors at low redshift (z<1), we highlight that at z>2 these events appear optically red, peaking in the observer-frame z-band. Such characteristics are critical to identify these objects with future facilities such as the Large Synoptic Survey Telescope, Euclid, and the Wide-Field Infrared Survey Telescope, which should detect such SLSNe-I to z=3.5, 3.7, and 6.6, respectively.« less

Targeting of Repeated Sequences Unique to a Gene Results in Significant Increases in Antisense Oligonucleotide Potency

PubMed Central

Vickers, Timothy A.; Freier, Susan M.; Bui, Huynh-Hoa; Watt, Andrew; Crooke, Stanley T.

2014-01-01

A new strategy for identifying potent RNase H-dependent antisense oligonucleotides (ASOs) is presented. Our analysis of the human transcriptome revealed that a significant proportion of genes contain unique repeated sequences of 16 or more nucleotides in length. Activities of ASOs targeting these repeated sites in several representative genes were compared to those of ASOs targeting unique single sites in the same transcript. Antisense activity at repeated sites was also evaluated in a highly controlled minigene system. Targeting both native and minigene repeat sites resulted in significant increases in potency as compared to targeting of non-repeated sites. The increased potency at these sites is a result of increased frequency of ASO/RNA interactions which, in turn, increases the probability of a productive interaction between the ASO/RNA heteroduplex and human RNase H1 in the cell. These results suggest a new, highly efficient strategy for rapid identification of highly potent ASOs. PMID:25334092

Proposal of AAA-battery-size one-shot ATR Fourier spectroscopic imager for on-site analysis: Simultaneous measurement of multi-components with high accuracy

NASA Astrophysics Data System (ADS)

Hosono, Satsuki; Qi, Wei; Sato, Shun; Suzuki, Yo; Fujiwara, Masaru; Hiramatsu, Hiroyuki; Suzuki, Satoru; Abeygunawardhana, P. K. W.; Wada, Kenji; Nishiyama, Akira; Ishimaru, Ichiro

2015-03-01

For simultaneous measurement of multi-components on-site like factories, the ultra-compact (diameter: 9[mm], length: 45[mm], weight: 200[g]) one-shot ATR (Attenuated Total Reflection) Fourier spectroscopic imager was proposed. Because the proposed one-shot Fourier spectroscopic imaging is based on spatial-phase-shift interferometer, interferograms could be obtained with simple optical configurations. We introduced the transmission-type relativeinclined phase-shifter, that was constructed with a cuboid prism and a wedge prism, onto the optical Fourier transform plane of infinity corrected optical systems. And also, small light-sources and cameras in the mid-infrared light region, whose size are several millimeter on a side, are essential components for the ultra-compact spectroscopic configuration. We selected the Graphite light source (light source area: 1.7×1.7[mm], maker: Hawkeye technologies) whose radiation factor was high. Fortunately, in these days we could apply the cost-effective 2-dimensional light receiving device for smartphone (e.g. product name: LEPTON, maker: FLIR, price: around 400USD). In the case of alcoholic drinks factory, conventionally workers measure glucose and ethanol concentrations by bringing liquid solution back to laboratories every day. The high portable spectroscopy will make it possible to measure multi-components simultaneously on manufacturing scene. But we found experimentally that absorption spectrum of glucose and water and ethanol were overlapped each other in near infrared light region. But for mid-infrared light region, we could distinguish specific absorption peaks of glucose (@10.5[μm]) and ethanol (@11.5[μm]) independently from water absorption. We obtained standard curve between absorption (@9.6[μm]) and ethanol concentration with high correlation coefficient 0.98 successfully by ATR imaging-type 2-dimensional Fourier spectroscopy (wavelength resolution: 0.057[μm]) with the graphite light source (maker: Hawkeye technologies, type: IR-75).

Protonation state of the Cu4S2 CuZ site in nitrous oxide reductase: redox dependence and insight into reactivity

PubMed Central

Johnston, Esther M.; Dell’Acqua, Simone; Pauleta, Sofia R.; Moura, Isabel; Solomon, Edward I.

2015-01-01

Spectroscopic and computational methods have been used to determine the protonation state of the edge sulfur ligand in the Cu4S2 CuZ form of the active site of nitrous oxide reductase (N2OR) in its 3CuICuII (1-hole) and 2CuI2CuII (2-hole) redox states. The EPR, absorption, and MCD spectra of 1-hole CuZ indicate that the unpaired spin in this site is evenly delocalized over CuI, CuII, and CuIV. 1-hole CuZ is shown to have a μ2-thiolate edge ligand from the observation of S-H bending modes in the resonance Raman spectrum at 450 and 492 cm−1 that have significant deuterium isotope shifts (−137 cm−1) and are not perturbed up to pH 10. 2-hole CuZ is characterized with absorption and resonance Raman spectroscopies as having two Cu-S stretching vibrations that profile differently. DFT models of the 1-hole and 2-hole CuZ sites are correlated to these spectroscopic features to determine that 2-hole CuZ has a μ2-sulfide edge ligand at neutral pH. The slow two electron (+1 proton) reduction of N2O by 1-hole CuZ is discussed and the possibility of a reaction between 2-hole CuZ and O2 is considered. PMID:26417423

Atomistic interpretation of the ac-dc crossover frequency in crystalline and glassy ionic conductors

NASA Astrophysics Data System (ADS)

Marple, M. A. T.; Avila-Paredes, H.; Kim, S.; Sen, S.

2018-05-01

A comprehensive analysis of the ionic dynamics in a wide variety of crystalline and glassy ionic conductors, obtained in recent studies using a combination of electrochemical impedance and nuclear magnetic resonance spectroscopic techniques, is presented. These results demonstrate that the crossover frequency, between the frequency-independent dc conductivity and the frequency-dependent ac conductivity, corresponds to the time scale of "successful" diffusive hops of the mobile ions between the trapping sites in the structure. These inter-site hops are typically compound in nature and consist of several elementary hops in the intervening region between the neighboring trapping sites.

Atomistic interpretation of the ac-dc crossover frequency in crystalline and glassy ionic conductors.

PubMed

Marple, M A T; Avila-Paredes, H; Kim, S; Sen, S

2018-05-28

A comprehensive analysis of the ionic dynamics in a wide variety of crystalline and glassy ionic conductors, obtained in recent studies using a combination of electrochemical impedance and nuclear magnetic resonance spectroscopic techniques, is presented. These results demonstrate that the crossover frequency, between the frequency-independent dc conductivity and the frequency-dependent ac conductivity, corresponds to the time scale of "successful" diffusive hops of the mobile ions between the trapping sites in the structure. These inter-site hops are typically compound in nature and consist of several elementary hops in the intervening region between the neighboring trapping sites.

Metal–organic and covalent organic frameworks as single-site catalysts

PubMed Central

Rogge, S. M. J.; Bavykina, A.; Hajek, J.; Garcia, H.; Olivos-Suarez, A. I.; Sepúlveda-Escribano, A.; Vimont, A.; Clet, G.; Bazin, P.; Kapteijn, F.

2017-01-01

Heterogeneous single-site catalysts consist of isolated, well-defined, active sites that are spatially separated in a given solid and, ideally, structurally identical. In this review, the potential of metal–organic frameworks (MOFs) and covalent organic frameworks (COFs) as platforms for the development of heterogeneous single-site catalysts is reviewed thoroughly. In the first part of this article, synthetic strategies and progress in the implementation of such sites in these two classes of materials are discussed. Because these solids are excellent playgrounds to allow a better understanding of catalytic functions, we highlight the most important recent advances in the modelling and spectroscopic characterization of single-site catalysts based on these materials. Finally, we discuss the potential of MOFs as materials in which several single-site catalytic functions can be combined within one framework along with their potential as powerful enzyme-mimicking materials. The review is wrapped up with our personal vision on future research directions. PMID:28338128

Dissecting the active site of a photoreceptor protein

NASA Astrophysics Data System (ADS)

Hoff, Wouter; Hara, Miwa; Ren, Jie; Moghadam, Farzaneh; Xie, Aihua; Kumauchi, Masato

While enzymes are quite large molecules, functionally important chemical events are often limited to a small region of the protein: the active site. The physical and chemical properties of residues at such active sites are often strongly altered compared to the same groups dissolved in water. Understanding such effects is important for unraveling the mechanisms underlying protein function and for protein engineering, but has proven challenging. Here we report on our ongoing efforts on using photoactive yellow protein (PYP), a bacterial photoreceptor, as a model system for such effects. We will report on the following questions: How many residues affect active site properties? Are these residues in direct physical contact with the active site? Can functionally important residues be recognized in the crystal structure of a protein? What structural resolution is needed to understand active sites? What spectroscopic techniques are most informative? Which weak interactions dominate active site properties?

A simple surface-enhanced Raman spectroscopic method for on-site screening of tetracycline residue in whole milk

USDA-ARS?s Scientific Manuscript database

Therapeutic and sub-therapeutic use of veterinary drugs has increased the risk of residue contamination in animal food products. Antibiotics such as tetracycline are used for mastitis treatment of lactating cows. Milk expressed from treated cows before the withdrawal period has elapsed may contain t...

IN-SITU SEQUESTRATION OF ZINC: SPECTROSCOPIC OBSERVATIONS FROM A FIELD STUDY

EPA Science Inventory

Zinc concentrations in the soil and groundwater at the Indian Head Naval Warfare Center, located in Charles County Maryland, have been observed at levels exceeding 20 g/kg and 25 mg/L respectively due to the operation of a zinc recovery furnace during WWI. Erosion of the site due...

Binding modes of environmental endocrine disruptors to human serum albumin: insights from STD-NMR, ITC, spectroscopic and molecular docking studies.

PubMed

Yang, Hongqin; Huang, Yanmei; Liu, Jiuyang; Tang, Peixiao; Sun, Qiaomei; Xiong, Xinnuo; Tang, Bin; He, Jiawei; Li, Hui

2017-09-11

Given that bisphenols have an endocrine-disrupting effect on human bodies, thoroughly exposing their potential effects at the molecular level is important. Saturation transfer difference (STD) NMR-based binding studies were performed to investigate the binding potential of two bisphenol representatives, namely, bisphenol B (BPB) and bisphenol E (BPE), toward human serum albumin (HSA). The relative STD (%) suggested that BPB and BPE show similar binding modes and orientations, in which the phenolic rings were spatially close to HSA binding site. ITC analysis results showed that BPB and BPE were bound to HSA with moderately strong binding affinity through electrostatic interactions and hydrogen bonds. The order of binding affinity of HSA for two test bisphenols is as follows: BPE > BPB. The results of fluorescence competitive experiments using 5-dimethylaminonaphthalene-1-sulfonamide and dansylsarcosine as competitors, combined with molecular docking indicated that both bisphenols are prone to attach to the binding site II in HSA. Spectroscopic results (FT-IR, CD, synchronous and 3D fluorescence spectra) showed that BPB/BPE induces different degrees of microenvironmental and conformational changes to HSA.

Dissection of the binding of hydrogen peroxide to trypsin using spectroscopic methods and molecular modeling

NASA Astrophysics Data System (ADS)

Song, Wei; Yu, Zehua; Hu, Xinxin; Liu, Rutao

2015-02-01

Studies on the effects of environmental pollutants to protein in vitro has become a global attention. Hydrogen peroxide (H2O2) is used as an effective food preservative and bleacher in industrial production. The toxicity of H2O2 to trypsin was investigated by multiple spectroscopic techniques and the molecular docking method at the molecular level. The intrinsic fluorescence of trypsin was proved to be quenched in a static process based on the results of fluorescence lifetime experiment. Hydrogen bonds interaction and van der Waals forces were the main force to generate the trypsin-H2O2 complex on account of the negative ΔH0 and ΔS0. The binding of H2O2 changed the conformational structures and internal microenvironment of trypsin illustrated by UV-vis absorption, fluorescence, synchronous fluorescence, three-dimensional (3D) fluorescence and circular dichroism (CD) results. However, the binding site was far away from the active site of trypsin and the trypsin activity was only slightly affected by H2O2, which was further explained by molecular docking investigations.

Development of quality control and instrumentation performance metrics for diffuse optical spectroscopic imaging instruments in the multi-center clinical environment

NASA Astrophysics Data System (ADS)

Keene, Samuel T.; Cerussi, Albert E.; Warren, Robert V.; Hill, Brian; Roblyer, Darren; Leproux, AnaÑ--s.; Durkin, Amanda F.; O'Sullivan, Thomas D.; Haghany, Hosain; Mantulin, William W.; Tromberg, Bruce J.

2013-03-01

Instrument equivalence and quality control are critical elements of multi-center clinical trials. We currently have five identical Diffuse Optical Spectroscopic Imaging (DOSI) instruments enrolled in the American College of Radiology Imaging Network (ACRIN, #6691) trial located at five academic clinical research sites in the US. The goal of the study is to predict the response of breast tumors to neoadjuvant chemotherapy in 60 patients. In order to reliably compare DOSI measurements across different instruments, operators and sites, we must be confident that the data quality is comparable. We require objective and reliable methods for identifying, correcting, and rejecting low quality data. To achieve this goal, we developed and tested an automated quality control algorithm that rejects data points below the instrument noise floor, improves tissue optical property recovery, and outputs a detailed data quality report. Using a new protocol for obtaining dark-noise data, we applied the algorithm to ACRIN patient data and successfully improved the quality of recovered physiological data in some cases.

Spectroscopic studies on the interaction of bovine serum albumin with surfactants and apigenin

NASA Astrophysics Data System (ADS)

Zhao, Xu-Na; Liu, Yi; Niu, Li-Yuan; Zhao, Chen-Ping

The binding of apigenin (Ap) to bovine serum albumin (BSA) has been studied using the methods of fluorescence spectroscopy and UV-vis absorption spectroscopy. The spectroscopic analysis of the quenching mechanism indicates that the quenching constants are inversely correlated with the temperatures and the quenching process could result from a static interaction. The type of interaction force was discussed and the binding site of Ap was in site I (subdomain IIA) of BSA. The thermodynamic parameters ΔH and ΔS are -42.02 kJ mol-1 and -48.31 J mol-1 K-1, respectively and the negative ΔG implying that the binding interaction was spontaneous. The distance r between BSA and Ap was calculated according to Förster's theory and the value is 3.44 nm. The synchronous and three-dimensional fluorescence spectra show that the binding of Ap to BSA could lead to the changes in the conformation and microenvironment of BSA. At the same time, the effects of ionic surfactants on the interaction of Ap and BSA have also been investigated.

Binding interaction of atorvastatin with bovine serum albumin: Spectroscopic methods and molecular docking

NASA Astrophysics Data System (ADS)

Wang, Qi; Huang, Chuan-ren; Jiang, Min; Zhu, Ying-yao; Wang, Jing; Chen, Jun; Shi, Jie-hua

2016-03-01

The interaction of atorvastatin with bovine serum albumin (BSA) was investigated using multi-spectroscopic methods and molecular docking technique for providing important insight into further elucidating the store and transport process of atorvastatin in the body and the mechanism of action and pharmacokinetics. The experimental results revealed that the fluorescence quenching mechanism of BSA induced atorvastatin was a combined dynamic and static quenching. The binding constant and number of binding site of atorvastatin with BSA under simulated physiological conditions (pH = 7.4) were 1.41 × 105 M- 1 and about 1 at 310 K, respectively. The values of the enthalpic change (ΔH0), entropic change (ΔS0) and Gibbs free energy (ΔG0) in the binding process of atorvastatin with BSA at 310 K were negative, suggesting that the binding process of atorvastatin and BSA was spontaneous and the main interaction forces were van der Waals force and hydrogen bonding interaction. Moreover, atorvastatin was bound into the subdomain IIA (site I) of BSA, resulting in a slight change of the conformation of BSA.

Investigation into the interaction of losartan with human serum albumin and glycated human serum albumin by spectroscopic and molecular dynamics simulation techniques: A comparison study.

PubMed

Moeinpour, Farid; Mohseni-Shahri, Fatemeh S; Malaekeh-Nikouei, Bizhan; Nassirli, Hooriyeh

2016-09-25

The interaction between losartan and human serum albumin (HSA), as well as its glycated form (gHSA) was studied by multiple spectroscopic techniques and molecular dynamics simulation under physiological conditions. The binding information, including the binding constants, effective quenching constant and number of binding sites showed that the binding partiality of losartan to HSA was higher than to gHSA. The findings of three-dimensional fluorescence spectra demonstrated that the binding of losartan to HSA and gHSA would alter the protein conformation. The distances between Trp residue and the binding sites of the drug were evaluated on the basis of the Förster theory, and it was indicated that non-radiative energy transfer from HSA and gHSA to the losartan happened with a high possibility. According to molecular dynamics simulation, the protein secondary and tertiary structure changes were compared in HSA and gHSA for clarifying the obtained results. Copyright © 2016 Elsevier Ireland Ltd. All rights reserved.

Integration of genotoxicity and population genetic analyses in kangaroo rats (Dipodomys merriami) exposed to radionuclide contamination at the Nevada Test Site, USA

USGS Publications Warehouse

Theodorakis, Christopher W.; Bickham, John W.; Lamb, Trip; Medica, Philip A.; Lyne, T. Barrett

2001-01-01

We examined effects of radionuclide exposure at two atomic blast sites on kangaroo rats (Dipodomys merriami) at the Nevada Test Site, Nevada, USA, using genotoxicity and population genetic analyses. We assessed chromosome damage by micronucleus and flow cytometric assays and genetic variation by randomly amplified polymorphic DNA (RAPD) and mitochondrial DNA (mtDNA) analyses. The RAPD analysis showed no population structure, but mtDNA exhibited differentiation among and within populations. Genotoxicity effects were not observed when all individuals were analyzed. However, individuals with mtDNA haplotypes unique to the contaminated sites had greater chromosomal damage than contaminated-site individuals with haplotypes shared with reference sites. When interpopulation comparisons used individuals with unique haplotypes, one contaminated site had greater levels of chromosome damage than one or both of the reference sites. We hypothesize that shared-haplotype individuals are potential migrants and that unique-haplotype individuals are potential long-term residents. A parsimony approach was used to estimate the minimum number of migration events necessary to explain the haplotype distributions on a phylogenetic tree. The observed predominance of migration events into the contaminated sites supported our migration hypothesis. We conclude the atomic blast sites are ecological sinks and that immigration masks the genotoxic effects of radiation on the resident populations.

Spectroscopic Results from the Life in the Atacama (LITA) Project 2004 Field Season

NASA Technical Reports Server (NTRS)

Piatek, J. L.; Moersch, J. E.; Wyatt, M.; Rampey, M.; Cabrol, N. A.; Wettergreen, D. S.; Whittaker, R.; Grin, E. A.; Diaz, G. Chong

2005-01-01

Introduction: The Life in the Atacama (LITA) project includes rover field tests designed to look for life in the arid environment of the Atacama Desert (Chile). Field instruments were chosen to help remote observers identify potential habitats and the presence of life in these habitats, and included two spectrometers for help in identifying the mineralogy of the field sites. Two field trials were undertaken during the 2004 field season. The remote science team had no prior knowledge of the local geology, and relied entirely on orbital images and rover-acquired data to make interpretations. Each field trial lasted approximately one week: the sites for these trials were in different locations, and are designated "Site B" and "Site C."

Spectroscopic study of N-acetylcysteine and N-acetylcystine/hydrogen peroxide complexation

NASA Astrophysics Data System (ADS)

Picquart, Michel; Abedinzadeh, Zohreh; Grajcar, Lydie; Baron, Marie Héléne

1998-03-01

A spectroscopic study of N-acetylcysteine (RSH) and N-acetylcystine (RSSR) has been performed using infrared absorption and Raman scattering in order to pinpoint the sites of complexation of these two species with H 2O 2. Molecules of RSH and RSSR were studied in KBr pellets, and in aqueous solutions of H 2O, D 2O and H 2O with H 2O 2 (1 mol l -1) to characterize the specific influence of the solvent molecules. A time-resolved Raman study was performed for RSH-H 2O 2 in aqueous solution at 1:1 molar ratio in order to observe the formation of RSSR and to discuss the mechanism of this redox reaction.

Bio-important antipyrine derived Schiff bases and their transition metal complexes: Synthesis, spectroscopic characterization, antimicrobial, anthelmintic and DNA cleavage investigation

NASA Astrophysics Data System (ADS)

Manjunath, M.; Kulkarni, Ajaykumar D.; Bagihalli, Gangadhar B.; Malladi, Shridhar; Patil, Sangamesh A.

2017-01-01

Spectroscopic (IR, NMR, UV-vis, ESR, ESI-mass), magnetic and TGA studies suggests octahedral geometry for all the CoII, NiII and CuII complexes of the Schiff bases, derived from 4-aminoantipyrine and 8-formyl-7-Hydroxy-4-methylcoumarin/5-formyl-6-hydroxycoumarin, coordinated through ONO donor sites. Antibacterial (Escherichia coli, Staphylococcus aureus, Pseudomonas aeruginosa and Salmonella typhi), antifungal (Aspergillus niger, Aspergillus flavus and Cladosporium) and DNA cleavage properties of the metal complexes are investigated. The results suggested that some of the synthesized compounds are potential antimicrobials. The synthesized compounds tested for their anthelmintic activities and it was found that CoII and NiII complexes exhibited good anthelmintic properties.

Raman spectroscopic analysis of the Maya wall paintings in Ek'Balam, Mexico

NASA Astrophysics Data System (ADS)

Vandenabeele, P.; Bodé, S.; Alonso, A.; Moens, L.

2005-08-01

Raman spectroscopy has been applied to the examination of wall painting fragments from the archaeological site of Ek'Balam (Yucatán, Mexico). Thirty-three samples have been studied, all originating from room 23 of the Acropolis, and being representative of the painting technique at Ek'Balam during the late Classic Maya period. Several pigments such as haematite, calcite, carbon, cinnabar and indigo were identified in these samples. The latter pigment was presumed to be present as 'Maya blue', which is an intercalation product of indigo and palygorskite clay. The observed Raman spectra are reported and some band assignments have been made. This survey is the first Raman spectroscopic examination of a whole set of pigments in archaeological Maya wall painting fragments.

A single-solenoid pulsed-magnet system for single-crystal scattering studies

NASA Astrophysics Data System (ADS)

Islam, Zahirul; Capatina, Dana; Ruff, Jacob P. C.; Das, Ritesh K.; Trakhtenberg, Emil; Nojiri, Hiroyuki; Narumi, Yasuo; Welp, Ulrich; Canfield, Paul C.

2012-03-01

We present a pulsed-magnet system that enables x-ray single-crystal diffraction in addition to powder and spectroscopic studies with the magnetic field applied on or close to the scattering plane. The apparatus consists of a single large-bore solenoid, cooled by liquid nitrogen. A second independent closed-cycle cryostat is used for cooling samples near liquid helium temperatures. Pulsed magnetic fields close to ˜30 T with a zero-to-peak-field rise time of ˜2.9 ms are generated by discharging a 40 kJ capacitor bank into the magnet coil. The unique characteristic of this instrument is the preservation of maximum scattering angle (˜23.6°) on the entrance and exit sides of the magnet bore by virtue of a novel double-funnel insert. This instrument will facilitate x-ray diffraction and spectroscopic studies that are impractical, if not impossible, to perform using split-pair and narrow-opening solenoid magnets. Furthermore, it offers a practical solution for preserving optical access in future higher-field pulsed magnets.

A Spectroscopic Survey of Lensed Dwarf Galaxies at 1

NASA Astrophysics Data System (ADS)

Alavi, Anahita; Siana, Brian; gburek, Timothy; Richard, Johan; Teplitz, Harry; Rafelski, Marc; Stark, Daniel P.; Anahita Alavi

2018-01-01

High-redshift dwarf galaxies (M<109 M⊙) are one of the primary targets of the James Web Space Telescope. Recent studies have suggested that these galaxies are different than their bright counterparts, as they follow a divergent evolutionary history of star formation. In our previous study, utilizing the magnification from massive clusters of galaxies (Hubble Frontier Fields), we found a large sample of dwarf star-forming galaxies at the peak epoch of star formation (1

Tests of various colorants for application of a Fourier transform infrared imaging system to deciphering obliterated writings

NASA Astrophysics Data System (ADS)

Sugawara, Shigeru

2015-10-01

Obliterated writing is writing that has been obscured by different-colored materials. There are obliterated writings that cannot be detected by conventional methods. A method for deciphering such obliterated writings was developed in this study. Mid-infrared spectroscopic imaging in the wavelength range of 2.5-14 μm was used for deciphering because the infrared spectrum differs among different brands of colorants. Obliterated writings were made by pressing information protection stamps onto characters written by 4 kinds of colorants. The samples were tested for deciphering by the Fourier-transform infrared imaging system. Two peak areas of two specific wavenumber regions of each reflectance spectrum were calculated and the ratio of the two values is displayed as a unique gray scale in the spectroscopic image. As a result, the absorption peak at various wavenumbers could be used to decipher obliterated writings that could not be detected by the conventional methods. Ten different parameters for deciphering obliterated writing were found in this study.

Phosphorus dendrimers and photodynamic therapy. Spectroscopic studies on two dendrimer-photosensitizer complexes: Cationic phosphorus dendrimer with rose bengal and anionic phosphorus dendrimer with methylene blue.

PubMed

Dabrzalska, Monika; Zablocka, Maria; Mignani, Serge; Majoral, Jean Pierre; Klajnert-Maculewicz, Barbara

2015-08-15

Dendrimers due to their unique architecture may play an important role in drug delivery systems including chemotherapy, gene therapy and recently, photodynamic therapy as well. We investigated two dendrimer-photosensitizer systems in context of potential use of these systems in photodynamic therapy. The mixtures of an anionic phosphorus dendrimer of the second generation and methylene blue were studied by UV-vis spectroscopy while that of a cationic phosphorus dendrimer (third generation) and rose bengal were investigated by spectrofluorimetric methods. Spectroscopic analysis of these two systems revealed the formation of dendrimer-photosensitizer complexes via electrostatic interactions as well as π stacking. The stoichiometry of the rose bengal-cationic dendrimer complex was estimated to be 7:1 and 9:1 for the methylene blue-anionic dendrimer complex. The results suggest that these polyanionic or polycationic phosphorus dendrimers can be promising candidates as carriers in photodynamic therapy. Copyright © 2015 Elsevier B.V. All rights reserved.

An Ab Initio Description of the Excitonic Properties of LH2 and Their Temperature Dependence.

PubMed

Cupellini, Lorenzo; Jurinovich, Sandro; Campetella, Marco; Caprasecca, Stefano; Guido, Ciro A; Kelly, Sharon M; Gardiner, Alastair T; Cogdell, Richard; Mennucci, Benedetta

2016-11-10

The spectroscopic properties of light-harvesting (LH) antennae in photosyntehtic organisms represent a fingerprint that is unique for each specific pigment-protein complex. Because of that, spectroscopic observations are generally combined with structural data from X-ray crystallography to obtain an indirect representation of the excitonic properties of the system. Here, an alternative strategy is presented which goes beyond this empirical approach and introduces an ab initio computational description of both structural and electronic properties and their dependence on the temperature. The strategy is applied to the peripheral light-harvesting antenna complex (LH2) present in purple bacteria. By comparing this model with the one based on the crystal structure, a detailed, molecular level explanation of the absorption and circular dichroism (CD) spectra and their temperature dependence is achieved. The agreement obtained with the experiments at both low and room temperature lays the groundwork for an atomistic understanding of the excitation dynamics in the LH2 system.

Cytotoxic macrolides from a new species of the deep-water marine sponge Leiodermatium.

PubMed

Sandler, Joel S; Colin, Patrick L; Kelly, Michelle; Fenical, William

2006-09-15

Chemical investigation of a new species of the deep-water marine sponge Leiodermatium, collected by manned submersible at a depth of 740 feet in Palau, resulted in the isolation of two cytotoxic macrolides, leiodolides A (1) and B (2). The leiodolides represent the first members of a new class of 19-membered ring macrolides, incorporating several unique functional groups including a conjugated oxazole ring, a bromine substituent, and an alpha-hydroxy-alpha-methyl carboxylic acid side-chain terminus. The structures of these new metabolites were established by spectroscopic analysis, chemical modification, and degradation. The relative and absolute stereochemistries at most chiral centers were assigned on detailed interpretation of spectroscopic data, coupled with chemical degradation and application of the modified Mosher ester method. Leiodolide A showed significant cytotoxicity (average GI(50) = 2.0 microM) in the National Cancer Institute's 60 cell line panel with enhanced activity against HL-60 leukemia and OVCAR-3 ovarian cancer cell lines.

Raman and terahertz spectroscopical investigation of cocrystal formation process of piracetam and 3-hydroxybenzoic acid.

PubMed

Du, Yong; Zhang, Huili; Xue, Jiadan; Fang, Hongxia; Zhang, Qi; Xia, Yi; Li, Yafang; Hong, Zhi

2015-03-15

Cocrystallization can improve physical and chemical properties of active pharmaceutical ingredient, and this feature has great potential in pharmaceutical development. In this study, the cocrystal of piracetam and 3-hydroxybenzoic acid under grinding condition has been characterized by Raman and terahertz spectroscopical techniques. The major vibrational modes of individual starting components and cocrystal are obtained and assigned. Spectral results show that the vibrational modes of the cocrystal are different from those of the corresponding parent materials. The dynamic process of such pharmaceutical cocrystal formation has also been monitored directly with Raman and THz spectra. The formation rate is pretty fast in first several 20 min grinding time, and then it becomes slow. After ∼35 min, such process has been almost completed. These results offer us the unique means and benchmark for characterizing the cocrystal conformation from molecule-level and also provide us rich information about the reaction dynamic during cocrystal formation process in pharmaceutical fields. Copyright © 2014 Elsevier B.V. All rights reserved.

Raman and terahertz spectroscopical investigation of cocrystal formation process of piracetam and 3-hydroxybenzoic acid

NASA Astrophysics Data System (ADS)

Du, Yong; Zhang, Huili; Xue, Jiadan; Fang, Hongxia; Zhang, Qi; Xia, Yi; Li, Yafang; Hong, Zhi

2015-03-01

Cocrystallization can improve physical and chemical properties of active pharmaceutical ingredient, and this feature has great potential in pharmaceutical development. In this study, the cocrystal of piracetam and 3-hydroxybenzoic acid under grinding condition has been characterized by Raman and terahertz spectroscopical techniques. The major vibrational modes of individual starting components and cocrystal are obtained and assigned. Spectral results show that the vibrational modes of the cocrystal are different from those of the corresponding parent materials. The dynamic process of such pharmaceutical cocrystal formation has also been monitored directly with Raman and THz spectra. The formation rate is pretty fast in first several 20 min grinding time, and then it becomes slow. After ∼35 min, such process has been almost completed. These results offer us the unique means and benchmark for characterizing the cocrystal conformation from molecule-level and also provide us rich information about the reaction dynamic during cocrystal formation process in pharmaceutical fields.

Optimal methodologies for terahertz time-domain spectroscopic analysis of traditional pigments in powder form

NASA Astrophysics Data System (ADS)

Ha, Taewoo; Lee, Howon; Sim, Kyung Ik; Kim, Jonghyeon; Jo, Young Chan; Kim, Jae Hoon; Baek, Na Yeon; Kang, Dai-ill; Lee, Han Hyoung

2017-05-01

We have established optimal methods for terahertz time-domain spectroscopic analysis of highly absorbing pigments in powder form based on our investigation of representative traditional Chinese pigments, such as azurite [blue-based color pigment], Chinese vermilion [red-based color pigment], and arsenic yellow [yellow-based color pigment]. To accurately extract the optical constants in the terahertz region of 0.1 - 3 THz, we carried out transmission measurements in such a way that intense absorption peaks did not completely suppress the transmission level. This required preparation of pellet samples with optimized thicknesses and material densities. In some cases, mixing the pigments with polyethylene powder was required to minimize absorption due to certain peak features. The resulting distortion-free terahertz spectra of the investigated set of pigment species exhibited well-defined unique spectral fingerprints. Our study will be useful to future efforts to establish non-destructive analysis methods of traditional pigments, to construct their spectral databases, and to apply these tools to restoration of cultural heritage materials.

Towards Breath Gas Analysis Based on Millimeter-Wave Molecular Spectroscopy

NASA Astrophysics Data System (ADS)

Rothbart, Nick; Hübers, Heinz-Wilhelm; Schmalz, Klaus; Borngräber, Johannes; Kissinger, Dietmar

2018-03-01

Breath gas analysis is a promising non-invasive tool for medical diagnosis as there are thousands of Volatile Organic Compounds (VOCs) in human breath that can be used as health monitoring markers. Millimeter-wave/terahertz molecular spectroscopy is highly suitable for breath gas analysis due to unique fingerprint spectra of many VOCs in that frequency range. We present our recent work on sensor systems for gas spectroscopy based on integrated transmitters (TX) and receivers (RX) fabricated in IHP's 0.13 μm SiGe BiCMOS technology. For a single-band system, spectroscopic measurements and beam profiles are presented. The frequency is tuned by direct voltage-frequency tuning and by a fractional-n PLL, respectively. The spectroscopic system includes a folded gas absorption cell with gas pre-concentration abilities demonstrating the detection of a 50 ppm mixture of ethanol in ambient air corresponding to a minimum detectable concentration of 260 ppb. Finally, the design of a 3-band system covering frequencies from 225 to 273 GHz is introduced.

The 3D-HST Survey: An Introduction

NASA Astrophysics Data System (ADS)

Momcheva, Ivelina G.; Van Dokkum, P. G.; Brammer, G.; Franx, M.; Skelton, R.; Lundgren, B.; Whitaker, K. E.; 3D-HST Team

2013-01-01

3D-HST is a near-IR spectroscopic survey with the Hubble Space Telescope designed to study galaxy evolution at 11. In this talk, I will review the observational details, reduction pipeline, data quality and the wide range of public data products, including added-value photometric and spectroscopic catalogs. Data from the 3D-HST survey are non-proprietary and are useful for a wide variety of science investigations. Our first public data release will be in early 2013 and we would like to advertise this unique data set to the community.

Astronomers Set a New Galaxy Distance Record

NASA Image and Video Library

2015-05-06

This is a Hubble Space Telescope image of the farthest spectroscopically confirmed galaxy observed to date (inset). It was identified in this Hubble image of a field of galaxies in the CANDELS survey (Cosmic Assembly Near-infrared Deep Extragalactic Legacy Survey). NASA’s Spitzer Space Telescope also observed the unique galaxy. The W. M. Keck Observatory was used to obtain a spectroscopic redshift (z=7.7), extending the previous redshift record. Measurements of the stretching of light, or redshift, give the most reliable distances to other galaxies. This source is thus currently the most distant confirmed galaxy known, and it appears to also be one of the brightest and most massive sources at that time. The galaxy existed over 13 billion years ago. The near-infrared light image of the galaxy (inset) has been colored blue as suggestive of its young, and hence very blue, stars. The CANDELS field is a combination of visible-light and near-infrared exposures. Credits: NASA, ESA, P. Oesch (Yale U.)

Spectroscopic investigation of phenolic groups ionization in the vipoxin neurotoxic phospholipase A 2: comparison with the X-ray structure in the region of the tyrosyl residues

NASA Astrophysics Data System (ADS)

Georgieva, Dessislava Nikolova; Genov, Nicolay; Rajashankar, Kanagalaghatta R.; Aleksiev, Boris; Betzel, Christian

1998-12-01

The neurotoxin vipoxin is the major lethal component of the venom of Vipera ammodites meridionalis, the most toxic snake in Europe. It is a complex between a toxic phospholipase A 2 (PLA 2) and a non-toxic protein inhibitor (Inh). Tyrosyl residues are involved in the catalytic site (Tyr 52 and 73) and in the substrate binding (Tyr 22). Spectroscopic studies demonstrated differences in the ionization behavior of the various phenolic hydroxyl groups in the toxic PLA 2. The tyrosyl side chains of the enzyme can be classified into three groups: (a) three phenolic hydroxyls are accessible to the solvent and titrate normally, with a p Keff=10.45; (b) three residues are partially 'buried' and participate in hydrogen bonds with neighboring functional groups. They titrate anomalously with a p Keff=12.17; (c) two tyrosines with a p Keff=13.23 are deeply 'buried' in the hydrophobic interior of PLA 2. They became accessible to the titrating agent only after alkaline denaturation of the protein molecule. The spectroscopic data are related to the X-ray structure of the vipoxin PLA 2. The refined model was investigated in the region of the tyrosyl side chains. The accessible surface area of each tyrosyl residue and each phenolic hydroxyl group was calculated. A good correlation between the spectrophotometric and the crystallographic data was observed. The ionization behavior of the phenolic groups is explained by peculiarities of the protein three-dimensional structure and the participation of tyrosines in the catalytic site hydrogen bond network. Attempts are made to assign the calculated p Keff values to individual residues. The high degree of 'exposure' on the protein surface of Tyr 22 and 75 is probably important for their function as parts of the substrate binding and pharmacological sites.

β-SiH-containing tris(silazido) rare-earth complexes as homogeneous and grafted single-site catalyst precursors for hydroamination

DOE PAGES

Eedugurala, Naresh; Wang, Zhuoran; Yan, KaKing; ...

2017-01-25

A series of homoleptic rare-earth silazido compounds and their silica-grafted derivatives were prepared to compare spectroscopic and catalytic features under homogeneous and interfacial conditions. Trivalent tris(silazido) compounds Ln{N(SiHMe 2) tBu} 3 (Ln = Sc (1), Y (2), Lu (3)) are prepared in high yield by salt metathesis reactions. Solution-phase and solid-state characterization of 1–3 by NMR and IR spectroscopy and X-ray diffraction reveals Ln←H–Si interactions. These features are retained in solvent-coordinated 2·Et 2O, 2·THF, and 3·THF. The change in spectroscopic features characterizing the secondary interactions (ν SiH, 1 J SiH) from the unactivated SiH in the silazane HN(SiHMe 2) tBumore » follows the trend 3 > 2 > 1 ≈ 2·Et 2O > 2·THF ≈ 3·THF. Ligand lability follows the same pattern, with Et 2O readily dissociating from 2·Et 2O while THF is displaced only during surface grafting reactions. 1 and 2·THF graft onto mesoporous silica nanoparticles (MSN) to give Ln{N(SiHMe 2) tBu} n@MSN (Ln = Sc (1@MSN), Y (2@MSN)) along with THF and protonated silazido as HN(SiHMe 2) tBu and H 2N tBu. The surface species are characterized by multinuclear and multidimensional solid-state (SS) NMR spectroscopic techniques, as well as diffuse reflectance FTIR, elemental analysis, and reaction stoichiometry. A key 1 J SiH SSNMR measurement reveals that the grafted sites most closely resemble Ln·THF adducts, suggesting that siloxane coordination occurs in grafted compounds. These species catalyze the hydroamination/bicyclization of aminodialkenes, and both solution-phase and interfacial conditions provide the bicyclized product with equivalent cis:trans ratios. As a result, similar diastereoselectivities mediated by catalytic sites under the two conditions suggest similar effective environments.« less

Spectroscopic and E-tongue evaluation of medicinal plants: A taste of how rasa can be studied.

PubMed

Jayasundar, Rama; Ghatak, Somenath

The use of medicinal plants in Ayurveda is based on rasa, generally taken to represent taste as a sensory perception. This chemosensory parameter plays an important role in Ayurvedic pharmacology. The aim is to explore the use of structuro-functional information deduced from analytical techniques for the rasa-based classification of medicinal plants in Ayurveda. Methods of differential sensing and spectroscopic metabolomics have been used in select medicinal plants from three different taste categories (sweet, pungent and multiple taste): Tribulus terrestris, Vitis vinifera and Glycyrrhiza glabra from sweet category; Piper longum, Cuminum cyminum and Capsicum annum from pungent group; Emblica officinalis with five tastes. While Electronic tongue was used for evaluation of the sensorial property of taste, the chemical properties were studied with Nuclear Magnetic Resonance (NMR), Fourier Transform InfraRed (FTIR) and Laser Induced Breakdown Spectroscopy (LIBS). In terms of taste and phytochemical profiles, all samples were unique but with similarities within each group. While the sensor response in E-tongue showed similarities within the sweet and pungent categories, NMR spectra in the aromatic region showed close similarities between the plants in the sweet category. The sensory, phytochemical and phytoelemental profiles of E. officinalis (with five rasa) in particular, were unique. A combination of sensorial and chemical descriptors is a promising approach for a comprehensive evaluation and fingerprinting of the Ayurvedic pharmacological parameter rasa. Copyright © 2016 Transdisciplinary University, Bangalore and World Ayurveda Foundation. Published by Elsevier B.V. All rights reserved.

An accessible echelle pipeline and its application to a binary star

NASA Astrophysics Data System (ADS)

Carmichael, Theron; Johnson, John Asher

2018-01-01

Nearly every star observed in the Galaxy has one or more companions that play an integral role in the evolution of the star. Whether it is a planet or another star, a companion opens up opportunities for unique forms of analysis to be done on a system. Some 2400 lightyears away, there is a 3-10 Myr old binary system called KH 15D, which not only includes two T Tauri K-type stars in a close orbit of 48 days, but also a truncated, coherently precessing warped disk in a circumbinary orbit.In binary systems, a double-lined spectroscopic binary may be observable in spectra. This is a spectrum that contains a mixture of each star's properties and manifests as two sets of spectral emission and absorption lines that correspond to each star. Slightly different is a single-lined spectroscopic binary, where only one set of spectral lines from one star is visible. The data of KH 15D are studied in the form of a double single-lined spectroscopic binary. This means that at two separate observing times, a single-lined spectroscopic binary is obtained from one of the stars of KH 15D. This is possible because of the circumbinary disk that blocks one star at a time from view.Here, we study this binary system with a combination of archival echelle data from the Keck Observatory and new echelle data from Las Campanas Observatory. This optical data is reduced with a new Python-based pipeline available on GitHub. The objective is to measure the mass function of the binary star and refine the current values of each star's properties.

Convergence of QM/MM and Cluster Models for the Spectroscopic Properties of the Oxygen-Evolving Complex in Photosystem II.

PubMed

Retegan, Marius; Neese, Frank; Pantazis, Dimitrios A

2013-08-13

The latest crystal structure of photosystem II at 1.9 Å resolution, which resolves the topology of the Mn4CaO5 oxygen evolving complex (OEC) at atomistic detail, enables a better correlation between structural features and spectroscopic properties than ever before. Building on the refined crystallographic model of the OEC and the protein, we present combined quantum mechanical/molecular mechanical (QM/MM) studies of the spectroscopic properties of the natural catalyst embedded in the protein matrix. Focusing on the S2 state of the catalytic cycle, we examine the convergence of not only structural parameters but also of the intracluster magnetic interactions in terms of exchange coupling constants and of experimentally relevant (55)Mn, (17)O, and (14)N hyperfine coupling constants with respect to QM/MM partitioning using five QM regions of increasing size. This enables us to assess the performance of the method and to probe second sphere effects by identifying amino acid residues that principally affect the spectroscopic properties of the OEC. Comparison between QM-only and QM/MM treatments reveals that whereas QM/MM models converge quickly to stable values, the QM cluster models need to incorporate significantly larger parts of the second coordination sphere and surrounding water molecules to achieve convergence for certain properties. This is mainly due to the sensitivity of the QM-only models to fluctuations in the hydrogen bonding network and ligand acidity. Additionally, a hydrogen bond that is typically omitted in QM-only treatments is shown to determine the hyperfine coupling tensor of the unique Mn(III) ion by regulating the rotation plane of the ligated D1-His332 imidazole ring, the only N-donor ligand of the OEC.

ALA-induced fluorescence in the canine oral cavity.

PubMed

Vaidyanathan, Vijay; Wiggs, Robert; Stohl, Josh; Baxi, Mehul

2006-06-01

We examined whether 5-aminolevulinic acid (ALA) could enhance the spectroscopic contrast between normal and diseased oral tissues, without prolonged photosensitivity. ALA is a promising photosensitizing agent. Adose of 25 mg/kg of ALA was administered intravenously to five dogs with gingivitis and three dogs with oral cancer, respectively. Fluorescence was recorded from the diseased sites in the oral cavity in addition to normal sites. ALA-induced proto-porphyrin IX fluorescence at all gingivitis sites reached a peak in 2-3 h and returned to baseline in 24 h. Fluorescence from the gingivitis site was observed earlier and was higher than the fluorescence from the normal site. For dogs with cancer, fluorescence from the cancerous sites occurred earlier in time compared to gingivitis sites and was comparatively higher in intensity. The fluorescence from the diseased sites was found to be higher than the normal site. Clinical and fluorescence data suggest that a dose of 25 mg/kg may be satisfactory for diagnostic purposes and would have minimal side effects.

Communication between Thiamin Cofactors in the Escherichia coli Pyruvate Dehydrogenase Complex E1 Component Active Centers EVIDENCE FOR A DIRECT PATHWAY BETWEEN THE 4′-AMINOPYRIMIDINE N1′ ATOMS

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

Nemeria, Natalia S; Arjunan, Palaniappa; Chandrasekhar, Krishnamoorthy

2010-11-03

Kinetic, spectroscopic, and structural analysis tested the hypothesis that a chain of residues connecting the 4{prime}-aminopyrimidine N1{prime} atoms of thiamin diphosphates (ThDPs) in the two active centers of the Escherichia coli pyruvate dehydrogenase complex E1 component provides a signal transduction pathway. Substitution of the three acidic residues (Glu{sup 571}, Glu{sup 235}, and Glu{sup 237}) and Arg{sup 606} resulted in impaired binding of the second ThDP, once the first active center was filled, suggesting a pathway for communication between the two ThDPs. (1) Steady-state kinetic and fluorescence quenching studies revealed that upon E571A, E235A, E237A, and R606A substitutions, ThDP binding inmore » the second active center was affected. (2) Analysis of the kinetics of thiazolium C2 hydrogen/deuterium exchange of enzyme-bound ThDP suggests half-of-the-sites reactivity for the E1 component, with fast (activated site) and slow exchanging sites (dormant site). The E235A and E571A variants gave no evidence for the slow exchanging site, indicating that only one of two active sites is filled with ThDP. (3) Titration of the E235A and E237A variants with methyl acetylphosphonate monitored by circular dichroism suggested that only half of the active sites were filled with a covalent predecarboxylation intermediate analog. (4) Crystal structures of E235A and E571A in complex with ThDP revealed the structural basis for the spectroscopic and kinetic observations and showed that either substitution affects cofactor binding, despite the fact that Glu{sup 235} makes no direct contact with the cofactor. The role of the conserved Glu{sup 571} residue in both catalysis and cofactor orientation is revealed by the combined results for the first time.« less

A nearly on-axis spectroscopic system for simultaneously measuring UV-visible absorption and X-ray diffraction in the SPring-8 structural genomics beamline.

PubMed

Sakaguchi, Miyuki; Kimura, Tetsunari; Nishida, Takuma; Tosha, Takehiko; Sugimoto, Hiroshi; Yamaguchi, Yoshihiro; Yanagisawa, Sachiko; Ueno, Go; Murakami, Hironori; Ago, Hideo; Yamamoto, Masaki; Ogura, Takashi; Shiro, Yoshitsugu; Kubo, Minoru

2016-01-01

UV-visible absorption spectroscopy is useful for probing the electronic and structural changes of protein active sites, and thus the on-line combination of X-ray diffraction and spectroscopic analysis is increasingly being applied. Herein, a novel absorption spectrometer was developed at SPring-8 BL26B2 with a nearly on-axis geometry between the X-ray and optical axes. A small prism mirror was placed near the X-ray beamstop to pass the light only 2° off the X-ray beam, enabling spectroscopic analysis of the X-ray-exposed volume of a crystal during X-ray diffraction data collection. The spectrometer was applied to NO reductase, a heme enzyme that catalyzes NO reduction to N2O. Radiation damage to the heme was monitored in real time during X-ray irradiation by evaluating the absorption spectral changes. Moreover, NO binding to the heme was probed via caged NO photolysis with UV light, demonstrating the extended capability of the spectrometer for intermediate analysis.

Highly Selective Adsorption of Ethylene over Ethane in a MOF Featuring the Combination of Open Metal Site and -Complexation

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

Zhang, Yiming; Li, Baiyan; Wu, Zili

The introduction of the combination of open metal site (OMS) and -complexation into MOF has led to very high ethylene/ethane adsorption selectivity at 318K, as illustrated in the context of MIL-101-Cr-SO 3Ag. The interactions with ethylene from both OMS and -complexation in MIL-101-Cr-SO 3Ag have been investigated by in situ IR spectroscopic studies and computational calculations, which suggest -complexation contributes dominantly to the high ethylene/ethane adsorption selectivity.

Pyrrole based Schiff bases as colorimetric and fluorescent chemosensors for fluoride and hydroxide anions.

PubMed

Velmathi, Sivan; Reena, Vijayaraghavan; Suganya, Sivalingam; Anandan, Sambandam

2012-01-01

An efficient colorimetric sensor with pyrrole-NH moiety as binding site and nitro group as a signaling unit has been synthesized by a one step procedure and characterized by spectroscopic techniques, which displays excellent selectivity and sensitivity for fluoride and hydroxide ions. The hydrogen bonding with these anions provides remarkable colorimetric responses. (1)H NMR and FT IR studies has been carried out to confirm the hydrogen bonding. UV-vis and fluorescence spectral changes can be exploited for real time and on site application.

Highly Selective Adsorption of Ethylene over Ethane in a MOF Featuring the Combination of Open Metal Site and -Complexation

DOE PAGES

Zhang, Yiming; Li, Baiyan; Wu, Zili; ...

2015-01-09

The introduction of the combination of open metal site (OMS) and -complexation into MOF has led to very high ethylene/ethane adsorption selectivity at 318K, as illustrated in the context of MIL-101-Cr-SO 3Ag. The interactions with ethylene from both OMS and -complexation in MIL-101-Cr-SO 3Ag have been investigated by in situ IR spectroscopic studies and computational calculations, which suggest -complexation contributes dominantly to the high ethylene/ethane adsorption selectivity.

In-situ Optical Spectroscopy Investigation of Water and Its influence on Forsterite Transformation in Supercritical CO2

NASA Astrophysics Data System (ADS)

Wang, Z.; Thompson, C. J.; Joly, A. G.; Sklarew, D. S.; Poindexter, L.; Rosso, K. M.

2009-12-01

Carbon capture and sequestration (CCS) from coal/gas-burning power plants is currently viewed as one of the most promising technologies for mitigating green house gas emissions. This strategy involves injection of supercritical CO2 (scCO2) into deep geological formations such as depleted oil and gas reservoirs and deep saline aquifers. The feasibility of this approach and the ultimate fate of the stored CO2 are determined by the interactions between scCO2, various minerals in the rock formations, and the host fluids. Currently, there is only limited knowledge about both the thermodynamic and kinetic aspects of the physical and chemical processes that occur between scCO2 and relevant minerals, such as metal silicates and metal aluminosilicates, and the role of water activity for catalyzing mineral transformation reactions. In this work, we have developed a modular in situ optical spectroscopic platform that integrates a scCO2 generation and manipulation system with an array of optical and laser spectroscopies including UV-visible, IR, Raman and laser fluorescence spectroscopy. We have used the system to study i) the dissolution and quantification of H2O/D2O in scCO2 and ii) interaction between scCO2 and a model metal silicate, forsterite (Mg2SiO4), and the effects of the presence of water under variable pressure, temperature and water content. Our results showed that H2O and D2O have unique IR spectral features over a broad spectral range from 700 cm-1 to ~ 2900 cm-1 in scCO2 and their concentrations are directly proportional to the characteristic IR bands that correspond to their stretching (D2O) and bending frequencies (both D2O and H2O). These bands offer a unique spectroscopic signature useful for qualitative and quantitative analysis of the properties and reactivity of small amounts of H2O in scCO2.

In-situ multianalytical approach to analyze and compare the degradation pathways jeopardizing two murals exposed to different environments (Ariadne House, Pompeii, Italy).

PubMed

Veneranda, M; Prieto-Taboada, N; Fdez-Ortiz de Vallejuelo, S; Maguregui, M; Morillas, H; Marcaida, I; Castro, K; Garcia-Diego, F-J; Osanna, M; Madariaga, J M

2018-05-29

This study aimed at using portable analytical techniques to characterize original and decayed materials from two murals paintings of Ariadne House (archaeological site of Pompeii, Italy) and define the degradation pathways threatening their conservation. The first wall, located in an outdoor environment, has been directly exposed to degradation processes triggered by weathering and atmospheric pollution. The second wall, placed in a basement under the ground floor, has been constantly sheltered from sunlight exposure and drastic temperature fluctuations. The analytical data obtained in-situ by using Raman spectroscopy and Laser Induced Breakdown Spectroscopy (LIBS) correlates the degradation patterns affecting the two surfaces to their environmental context. The deterioration processes detected on the outdoor wall, which entailed the complete loss of the paint layer, were mostly related to leaching and thermal fluctuation phenomena. The mural painting from the basement instead, showed deep degradation issues due to soluble salt infiltration and biological colonization. The results obtained from this unique case of study highlight the indispensable role of in-situ spectroscopic analysis to understand and predict the degradation pathways jeopardizing the cultural heritage and provide to the Archaeological Park of Pompeii important inference to consider in future conservation projects. Copyright © 2018. Published by Elsevier B.V.

Correlating Transport with Nanostructure and Chemical Identity in Radical Polymer Conducting Glasses

NASA Astrophysics Data System (ADS)

Boudouris, Bryan; Rostro, Lizbeth; Baradwaj, Aditya; Hay, Martha

2015-03-01

Radical polymers are an emerging class of macromolecules that are composed of non-conjugated backbones which bear stable radical groups at the pendant positions. Because of these stable radical sites, these glassy materials are able to conduct charge in the solid state through a series of oxidation-reduction (redox) reactions. Importantly, the redox-active behavior is controlled by both the local chemical environment of the radical polymer groups and by the nanoscale structure of the materials. Here, we demonstrate that proper control of the pendant group chemical functionality allows for the fabrication of transparent and conducting amorphous thin films which have solid-state hole mobility and electrical conductivity values on the same order as those seen in common conjugated, semicrystalline polymer systems [e.g., poly(3-hexylthiophene) (P3HT)]. Furthermore, we show that control of the nanostructure of the materials aids in facilitating transport in these radical polymer thin films. In turn, we implement simultaneous spectroscopic and electrical characterization measurements in order to elucidate the exact mechanism of charge transport in radical polymers. Finally, we demonstrate that, because there is ready control over the molecular properties of these materials, developing bendable and stretchable transparent conducting thin films is relatively straightforward with this unique class of organic electronic materials.

One Moon, many measurements 1: Radiance values

NASA Astrophysics Data System (ADS)

Pieters, C. M.; Boardman, J. W.; Ohtake, M.; Matsunaga, T.; Haruyama, J.; Green, R. O.; Mall, U.; Staid, M. I.; Isaacson, P. J.; Yokota, Y.; Yamamoto, S.; Besse, S.; Sunshine, J. M.

2013-09-01

Several modern optical instruments orbited the Moon during 2008 and 2009 onboard the SELENE and Chandrayaan-1 spacecraft and provided a welcomed feast of spectroscopic data to be used for scientific analyses. The different spatial and spectral resolutions of these sensors along with diverse illumination geometry during data acquisition make each set of data unique, and each instrument contributes special value to integrated science analyses. In order to provide the maximum science benefit, we have undertaken a careful cross-validation of radiance data among these orbital instruments and also a set of systematic data acquired using Earth-based telescopes. Most radiance values at 750 nm fall between 0 and 100 W/(m2 μm sr), but a small important fraction can be up to ×2 to ×3 that value, with the largest values occurring at the highest spatial resolution. All instruments are in agreement about overall spectral properties of lunar materials, but small systematic differences are documented between instruments. Lunar radiance values measured with remote sensors for landing sites are all not as high as that estimated from laboratory measurements of returned soil. This is largely because laboratory measurements of lunar soils cannot retain or duplicate the fine structure of lunar regolith found in the natural space environment.

Tantallacyclopentadiene as a unique metal-containing diene ligand coordinated to nickel for preparing tantalum-nickel heterobimetallic complexes.

PubMed

Laskar, Payel; Yamamoto, Keishi; Srinivas, Anga; Mifleur, Alexis; Nagae, Haruki; Tsurugi, Hayato; Mashima, Kazushi

2017-10-03

A mononuclear tantallacyclopentadiene complex, TaCl 3 (C 4 H 2 tBu 2 ) (3), serves as a unique ligand to nickel: the addition of Ni(COD) 2 to 3 selectively afforded heterobimetallic Ta-Ni complex 4. The cyclooctadiene ligand bound to the nickel center in complex 4 was readily substituted by monodentate and bidentate phosphine ligands, such as dimethylphenylphosphine, 1,2-bis(diphenylphosphino)ethane, and 1,2-bis(diethylphosphino)ethane, to give the corresponding phosphine complexes 5, 6a, and 6b. We also examined a ligand substitution reaction with 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene (IPr) to produce the corresponding Ta-Ni complex 7. These newly prepared Ta-Ni heterobimetallic complexes were characterized spectroscopically together with the crystal structures of 4, 6a, and 7.

Spectro-Interferometry Studies of Velocity-Related Phenomena at the Surface of Stars: Pulsation and Rotation

NASA Astrophysics Data System (ADS)

Mérand, Antoine; Patru, Fabien; Aufdenberg, Jason

We illustrate here two applications of spectro-interferometry to the study of velocity fields at the surface of stars: pulsation and rotation. Stellar pulsation has been resolved spectroscopically for a long time, and interferometry has resolved stellar diameters variations due to pulsation. Combining the two provides unique insights to the study of Cepheids, in particular regarding the structure of the photosphere or investigating the infamous projection factor which biases distances measured by the Baade-Wesselink method. On the other hand, resolving the surface velocity field of rotating stars offers a unique opportunity to potentially study differential rotation in other cases than for the Sun. We also present the model we have implemented recently, as well as two applications to VLTI/AMBER Data: the pulsation of Cepheids and the rotation of intermediate mass main sequence stars.

Interactions of cephalexin with bovine serum albumin: displacement reaction and molecular docking.

PubMed

Hamishehkar, Hamed; Hosseini, Soheila; Naseri, Abdolhossein; Safarnejad, Azam; Rasoulzadeh, Farzaneh

2016-01-01

Introduction: The drug-plasma protein interaction is a fundamental issue in guessing and checking the serious drug side effects related with other drugs. The purpose of this research was to study the interaction of cephalexin with bovine serum albumin (BSA) and displacement reaction using site probes. Methods: The interaction mechanism concerning cephalexin (CPL) with BSA was investigated using various spectroscopic methods and molecular modeling method. The binding sites number, n, apparent binding constant, K, and thermodynamic parameters, ΔG 0 , ΔH 0 , and ΔS 0 were considered at different temperatures. To evaluate the experimental results, molecular docking modeling was calculated. Results: The distance, r=1.156 nm between BSA and CPL were found in accordance with the Forster theory of non-radiation energy transfer (FRET) indicating energy transfer occurs between BSA and CPL. According to the binding parameters and ΔG 0 = negative values and ΔS 0 = 28.275 j mol -1 K -1 , a static quenching process is effective in the CPL-BSA interaction spontaneously. ΔG 0 for the CPL-BSA complex obtained from the docking simulation is -28.99 kj mol -1 , which is close to experimental ΔG of binding, -21.349 kj mol -1 that indicates a good agreement between the results of docking methods and experimental data. Conclusion: The outcomes of spectroscopic methods revealed that the conformation of BSA changed during drug-BSA interaction. The results of FRET propose that CPL quenches the fluorescence of BSA by static quenching and FRET. The displacement study showed that phenylbutazon and ketoprofen displaced CPL, indicating that its binding site on albumin is site I and Gentamicin cannot be displaced from the binding site of CPL. All results of molecular docking method agreed with the results of experimental data.

Geological characterization of remote field sites using visible and infrared spectroscopy: Results from the 1999 Marsokhod field test

USGS Publications Warehouse

Johnson, J. R.; Ruff, S.W.; Moersch, J.; Roush, T.; Horton, K.; Bishop, J.; Cabrol, N.A.; Cockell, C.; Gazis, P.; Newsom, Horton E.; Stoker, C.

2001-01-01

Upcoming Mars Surveyor lander missions will include extensive spectroscopic capabilities designed to improve interpretations of the mineralogy and geology of landing sites on Mars. The 1999 Marsokhod Field Experiment (MFE) was a Mars rover simulation designed in part to investigate the utility of visible/near-infrared and thermal infrared field spectrometers to contribute to the remote geological exploration of a Mars analog field site in the California Mojave Desert. The experiment simultaneously investigated the abilities of an off-site science team to effectively analyze and acquire useful imaging and spectroscopic data and to communicate efficiently with rover engineers and an on-site field team to provide meaningful input to rover operations and traverse planning. Experiences gained during the MFE regarding effective communication between different mission operation teams will be useful to upcoming Mars mission teams. Field spectra acquired during the MFE mission exhibited features interpreted at the time as indicative of carbonates (both dolomitic and calcitic), mafic rocks and associated weathering products, and silicic rocks with desert varnish-like coatings. The visible/near-infrared spectra also suggested the presence of organic compounds, including chlorophyll in one rock. Postmission laboratory petrologic and spectral analyses of returned samples confirmed that all rocks identified as carbonates using field measurements alone were calc-silicates and that chlorophyll associated with endolithic organisms was present in the one rock for which it was predicted. Rocks classified from field spectra as silicics and weathered mafics were recognized in the laboratory as metamorphosed monzonites and diorite schists. This discrepancy was likely due to rock coatings sampled by the field spectrometers compared to fresh rock interiors analyzed petrographically, in addition to somewhat different surfaces analyzed by laboratory thermal spectroscopy compared to field spectra. Copyright 2001 by the American Geophysical Union.

Preparation and infrared/raman classification of 630 spectroscopically encoded styrene copolymers.

PubMed

Fenniri, Hicham; Chun, Sangki; Terreau, Owen; Bravo-Vasquez, Juan-Pablo

2008-01-01

The barcoded resins (BCRs) were introduced recently as a platform for encoded combinatorial chemistry. One of the main challenges yet to be overcome is the demonstration that a large number of BCRs could be generated and classified with high confidence. Here, we describe the synthesis and classification of 630 polystyrene-based copolymers prepared from the combinatorial association of 15 spectroscopically active styrene monomers. Each of the 630 copolymers displayed a unique vibrational fingerprint (infrared and Raman), which was converted into a spectral vector. To each of the 630 copolymers, a vector of the known (reference) composition was assigned. Unknown (prediction) vectors were decoded using multivariate data analysis. From the inner product of the reference and prediction vectors, a correlation map comparing 396 900 copolymer pairs (630 x 630) was generated. In 100% of the cases, the highest correlation was obtained for polymer pairs in which the reference and prediction vectors correspond to copolymers prepared from identical styrene monomers, thus demonstrating the high reliability of this encoding strategy. We have also established that the spectroscopic barcodes generated from the Raman and infrared spectra are independent of the copolymers' morphology (beaded versus bulk polymers). Besides the demonstration of the generality of the polymer barcoding strategy, the analytical methods developed here could in principle be extended to the investigation of the composition and purity of any other synthetic polymer and biopolymer library, or even scaffold-based combinatorial libraries.

Introducing cymantrene labels into scattering scanning near-field infrared microscopy.

PubMed

Kopf, Ilona; N'Dongo, Harmel W Peindy; Ballout, Fouad; Schatzschneider, Ulrich; Bründermann, Erik; Havenith, Martina

2012-11-07

In this paper we investigate metal-organic compounds as infrared (IR) active labels by scattering scanning near-field infrared microscopy (IR s-SNOM, often also abbreviated as s-SNIM) with a lateral resolution of 90 × 90 nm(2). Tailor-made IR spectroscopic probes based on cymantrene (CpMn(CO)(3) with Cp = η(5)-C(5)H(5)) conjugated to a cysteine-modified pseudoneurotensin (pNT-Cys-OH) peptide were prepared by automated microwave-assisted solid phase peptide synthesis (SPPS) and characterized by HPLC, ESI-MS and IR. Well-defined patterned self-assembled monolayers on a gold surface were prepared by microcontact printing of 1-octadecanethiol (ODT) followed by additional incubation in ethanolic solution of the cymantrene-peptide derivative. The self-assembled monolayers have been evidenced by infrared reflection absorption spectroscopy (IRRAS) and AFM. CO laser source radiation was tuned (1944, 1900, 1798 and 1658 cm(-1)) for imaging contrast with good matching correlation between spectroscopic and topographic patterns at specific characteristic metal carbonyl and amide bands (1944 cm(-1) (λ = 5.14 μm) and 1658 cm(-1) (λ = 6.03 μm)). Cymantrene probes provide an attractive method to tag a unique spectroscopic feature on any bio(macro)molecule. Introducing such probes into super-resolution IR s-SNOM will enable molecular tracking and distribution studies even in complex biological systems.

FTIR and Raman spectroscopic studies of selenium nanoparticles synthesised by the bacterium Azospirillum thiophilum

NASA Astrophysics Data System (ADS)

Tugarova, Anna V.; Mamchenkova, Polina V.; Dyatlova, Yulia A.; Kamnev, Alexander A.

2018-03-01

Vibrational (Fourier transform infrared (FTIR) and Raman) spectroscopic techniques can provide unique molecular-level information on the structural and compositional characteristics of complicated biological objects. Thus, their applications in microbiology and related fields are steadily increasing. In this communication, biogenic selenium nanoparticles (Se NPs) were obtained via selenite (SeO32-) reduction by the bacterium Azospirillum thiophilum (strain VKM B-2513) for the first time, using an original methodology for obtaining extracellular NPs. Dynamic light scattering (DLS) and transmission electron microscopy (TEM) showed the Se NPs to have average diameters within 160-250 nm; their zeta potential was measured to be minus 18.5 mV. Transmission FTIR spectra of the Se NPs separated from bacterial cells showed typical proteinacious, polysaccharide and lipid-related bands, in line with TEM data showing a thin layer covering the Se NPs surface. Raman spectra of dried Se NPs layer in the low-frequency region (under 500 cm-1 down to 150 cm-1) showed a single very strong band with a maximum at 250 cm-1 which, in line with its increased width (ca. 30 cm-1 at half intensity), can be attributed to amorphous elementary Se. Thus, a combination of FTIR and Raman spectroscopic approaches is highly informative in non-destructive analysis of structural and compositional properties of biogenic Se NPs.

Spectroscopic investigation on cocrystal formation between adenine and fumaric acid based on infrared and Raman techniques.

PubMed

Du, Yong; Fang, Hong Xia; Zhang, Qi; Zhang, Hui Li; Hong, Zhi

2016-01-15

As an important component of double-stranded DNA, adenine has powerful hydrogen-bond capability, due to rich hydrogen bond donors and acceptors existing within its molecular structure. Therefore, it is easy to form cocrystal between adenine and other small molecules with intermolecular hydrogen-bond effect. In this work, cocrystal of adenine and fumaric acid has been characterized as model system by FT-IR and FT-Raman spectral techniques. The experimental results show that the cocrystal formed between adenine and fumaric acid possesses unique spectroscopical characteristic compared with that of starting materials. Density functional theory (DFT) calculation has been performed to optimize the molecular structures and simulate vibrational modes of adenine, fumaric acid and the corresponding cocrystal. Combining the theoretical and experimental vibrational results, the characteristic bands corresponding to bending and stretching vibrations of amino and carbonyl groups within cocrystal are shifted into lower frequencies upon cocrystal formation, and the corresponding bond lengths show some increase due to the effect of intermolecular hydrogen bonding. Different vibrational modes shown in the experimental spectra have been assigned based on the simulation DFT results. The study could provide experimental and theoretical benchmarks to characterize cocrystal formed between active ingredients and cocrystal formers and also the intermolecular hydrogen-bond effect within cocrystal formation process by vibrational spectroscopic techniques. Copyright © 2015 Elsevier B.V. All rights reserved.

Optoacoustic multispectral imaging of radiolucent foreign bodies in tissue.

PubMed

Page, Leland; Maswadi, Saher; Glickman, Randolph D

2013-01-01

Optoacoustic imaging is an emerging medical technology that uniquely combines the absorption contrast of optical imaging and the penetration depth of ultrasound. While it is not currently employed as a clinical imaging modality, the results of current research strongly support the use of optoacoustic-based methods in medical imaging. One such application is the diagnosis of the presence of soft tissue foreign bodies. Because many radiolucent foreign bodies have sufficient contrast for imaging in the optical domain, laser-induced optoacoustic imaging could be advantageous for the detection of such objects. Common foreign bodies have been scanned over a range of visible and near infrared wavelengths by using an optoacoustic method to obtain the spectroscopic properties of the materials commonly associated with these foreign bodies. The derived optical absorption spectra compared quite closely to the absorption spectra generated when using a conventional spectrophotometer. By using the probe-beam deflection technique, a novel, pressure-wave detection method, we successfully generated optoacoustic spectroscopic plots of a wooden foreign body embedded in a tissue phantom, which closely resembled the spectrum of the same object obtained in isolation. A practical application of such spectra is to assemble a library of spectroscopic data for radiolucent materials, from which specific characteristic wavelengths can be selected for use in optimizing imaging instrumentation and provide a basis for the identification of the material properties of particular foreign bodies.

Spectroscopic redshifts and age dating of a first statistical sample of passive galaxies at z 3

NASA Astrophysics Data System (ADS)

Daddi, Emanuele

2017-08-01

Ultradeep WFC3/G141 observations from one of our past HST programs allowed us to confirm the redshift and measure the age of a quiescent galaxy at z=3. This unique object was found inside a single WFC3 pointing (4 sq. arcmin) suggesting that massive old galaxies even at z 3 are more common than previously thought. The strong correlation observed between evolved stellar populations and a bulge-dominated morphology at least up to z 2 may also imply that the Hubble sequence comes into place at very early times. Guided by the properties of this spectroscopically confirmed z=3 passive galaxy, we have identified a substantial sample of 2.5

Double-lined M dwarf eclipsing binaries from Catalina Sky Survey and LAMOST

NASA Astrophysics Data System (ADS)

Lee, Chien-Hsiu; Lin, Chien-Cheng

2017-02-01

Eclipsing binaries provide a unique opportunity to determine fundamental stellar properties. In the era of wide-field cameras and all-sky imaging surveys, thousands of eclipsing binaries have been reported through light curve classification, yet their basic properties remain unexplored due to the extensive efforts needed to follow them up spectroscopically. In this paper we investigate three M2-M3 type double-lined eclipsing binaries discovered by cross-matching eclipsing binaries from the Catalina Sky Survey with spectroscopically classified M dwarfs from the Large Sky Area Multi-Object Fiber Spectroscopic Telescope survey data release one and two. Because these three M dwarf binaries are faint, we further acquire radial velocity measurements using GMOS on the Gemini North telescope with R˜ 4000, enabling us to determine the mass and radius of individual stellar components. By jointly fitting the light and radial velocity curves of these systems, we derive the mass and radius of the primary and secondary components of these three systems, in the range between 0.28-0.42M_⊙ and 0.29-0.67R_⊙, respectively. Future observations with a high resolution spectrograph will help us pin down the uncertainties in their stellar parameters, and render these systems benchmarks to study M dwarfs, providing inputs to improving stellar models in the low mass regime, or establishing an empirical mass-radius relation for M dwarf stars.

Interaction of lafutidine in binding to human serum albumin in gastric ulcer therapy: STD-NMR, WaterLOGSY-NMR, NMR relaxation times, Tr-NOESY, molecule docking, and spectroscopic studies.

PubMed

Yang, Hongqin; Huang, Yanmei; He, Jiawei; Li, Shanshan; Tang, Bin; Li, Hui

2016-09-15

In this study, lafutidine (LAF) was used as a model compound to investigate the binding mechanism between antiulcer drugs and human serum albumin (HSA) through various techniques, including STD-NMR, WaterLOGSY-NMR, (1)H NMR relaxation times, tr-NOESY, molecule docking calculation, FT-IR spectroscopy, and CD spectroscopy. The analyses of STD-NMR, which derived relative STD (%) intensities, and WaterLOGSY-NMR, determined that LAF bound to HSA. In particular, the pyridyl group of LAF was in close contact with HSA binding pocket, whereas furyl group had a secondary binding. Competitive STD-NMR and WaterLOGSY-NMR experiments, with warifarin and ibuprofen as site-selective probes, indicated that LAF preferentially bound to site II in the hydrophobic subdomains IIIA of HSA. The bound conformation of LAF at the HSA binding site was further elucidated by transferred NOE effect (tr-NOESY) experiment. Relaxation experiments provided quantitative information about the relationship between the affinity and structure of LAF. The molecule docking simulations conducted with AutoDock and the restraints derived from STD results led to three-dimensional models that were consistent with the NMR spectroscopic data. The presence of hydrophobic forces and hydrogen interactions was also determined. Additionally, FT-IR and CD spectroscopies showed that LAF induced secondary structure changes of HSA. Copyright © 2016 Elsevier Inc. All rights reserved.

The useful potential of using existing data to uniquely identify predictable wind events and regimes, part 1

NASA Technical Reports Server (NTRS)

Trettel, D. W.; Aquino, J. T.; Piazza, T. R.; Taylor, L. E.; Trask, D. C.

1982-01-01

Correlations between standard meteorological data and wind power generation potential were developed. Combined with appropriate wind forecasts, these correlations can be useful to load dispatchers to supplement conventional energy sources. Hourly wind data were analyzed for four sites, each exhibiting a unique physiography. These sites are Amarillo, Texas; Ludington, Michigan; Montauk Point, New York; and San Gorgonio, California. Synoptic weather maps and tables are presented to illustrate various wind 'regimes' at these sites.

Light-driven, proton-controlled, catalytic aerobic C-H oxidation mediated by a Mn(III) porphyrinoid complex.

PubMed

Neu, Heather M; Jung, Jieun; Baglia, Regina A; Siegler, Maxime A; Ohkubo, Kei; Fukuzumi, Shunichi; Goldberg, David P

2015-04-15

The visible light-driven, catalytic aerobic oxidation of benzylic C-H bonds was mediated by a Mn(III) corrolazine complex. To achieve catalytic turnovers, a strict selective requirement for the addition of protons was established. The resting state of the catalyst was unambiguously characterized by X-ray diffraction as [Mn(III)(H2O)(TBP8Cz(H))](+), in which a single, remote site on the ligand is protonated. If two remote sites are protonated, however, reactivity with O2 is shut down. Spectroscopic methods revealed that the related Mn(V)(O) complex is also protonated at the same remote site at -60 °C, but undergoes valence tautomerization upon warming.

The novel fluorescent CDP-analogue (Pbeta)MABA-CDP is a specific probe for the NMP binding site of UMP/CMP kinase.

PubMed

Rudolph, M G; Veit, T J; Reinstein, J

1999-12-01

Direct thermodynamic and kinetic investigations of the binding of nucleotides to the nucleoside monophosphate (NMP) site of NMP kinases have not been possible so far because a spectroscopic probe was not available. By coupling a fluorescent N-methylanthraniloyl- (mant) group to the beta-phosphate of CDP via a butyl linker, a CDP analogue [(Pbeta)MABA-CDP] was obtained that still binds specifically to the NMP site of UmpKdicty, because the base and the ribose moieties, which are involved in specific interactions, are not modified. This allows the direct determination of binding constants for its substrates in competition experiments.

The novel fluorescent CDP-analogue (Pbeta)MABA-CDP is a specific probe for the NMP binding site of UMP/CMP kinase.

PubMed Central

Rudolph, M. G.; Veit, T. J.; Reinstein, J.

1999-01-01

Direct thermodynamic and kinetic investigations of the binding of nucleotides to the nucleoside monophosphate (NMP) site of NMP kinases have not been possible so far because a spectroscopic probe was not available. By coupling a fluorescent N-methylanthraniloyl- (mant) group to the beta-phosphate of CDP via a butyl linker, a CDP analogue [(Pbeta)MABA-CDP] was obtained that still binds specifically to the NMP site of UmpKdicty, because the base and the ribose moieties, which are involved in specific interactions, are not modified. This allows the direct determination of binding constants for its substrates in competition experiments. PMID:10631985

Structural comparison of nickel electrodes and precursor phases

NASA Technical Reports Server (NTRS)

Cornilsen, Bahne C.; Shan, Xiaoyin; Loyselle, Patricia

1989-01-01

Researchers summarize previous Raman spectroscopic results and discuss important structural differences in the various phases of active mass and active mass precursors. Raman spectra provide unique signatures for these phases, and allow one to distinguish each phase, even when the compound is amorphous to x rays (i.e., does not scatter x rays because of a lack of order and/or small particle size). The structural changes incurred during formation, charge and discharge, cobalt addition, and aging are discussed. The oxidation states and dopant contents are explained in terms of the nonstoichiometric structures.

MOSAIC: A Multi-Object Spectrograph for the E-ELT

NASA Astrophysics Data System (ADS)

Kelz, A.; Hammer, F.; Jagourel, P.; MOSAIC Consortium

2016-10-01

The instrumentation plan for the European Extremely Large Telescope foresees a Multi-Object Spectrograph (E-ELT MOS). The MOSAIC project is proposed by a European-Brazilian consortium, to provide a unique MOS facility for astrophysics, studies of the inter-galactic medium and for cosmology. The science cases range from spectroscopy of the most distant galaxies, mass assembly and evolution of galaxies, via resolved stellar populations and galactic archaeology, to planet formation studies. A further strong driver is spectroscopic follow-up observations of targets that will be discovered with the James Webb Space Telescope.

Double Beta Decays and Neutrinos - Experiments and MOON

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

Ejiri, H.; National Institute of Radiological Sciences, Chiba, 263-8555

2008-01-24

This is a brief review of the present and future experiments of neutrino-less double beta decays (0{nu}{beta}{beta}) and the MOON (Mo Observatory Of Neutrinos) project. High sensitivity 0{nu}{beta}{beta} experiments are unique and realistic probes for studying the Majorana nature of neutrinos and the absolute mass scale as suggested by neutrino oscillation experiments. MOON aims at spectroscopic 0{nu}{beta}{beta} studies with the {nu}-mass sensitivity of 100-30 meV by means of a super ensemble of multilayer modules of scintillator plates and tracking detector planes.

Cajanusflavanols A-C, Three Pairs of Flavonostilbene Enantiomers from Cajanus cajan.

PubMed

He, Qi-Fang; Wu, Zhen-Long; Huang, Xiao-Jun; Zhong, Yuan-Lin; Li, Man-Mei; Jiang, Ren-Wang; Li, Yao-Lan; Ye, Wen-Cai; Wang, Ying

2018-02-02

Three pairs of new flavonostilbene enantiomers, cajanusflavanols A-C (1-3), along with their putative biogenetic precursors 4-6, were isolated from Cajanus cajan. Compound 1 possesses an unprecedented carbon skeleton featuring a unique highly functionalized cyclopenta[1,2,3-de]isobenzopyran-1-one tricyclic core. Compounds 2 and 3 are the first examples of methylene-unit-linked flavonostilbenes. Their structures with absolute configurations were elucidated by spectroscopic analyses, X-ray diffraction, and computational calculations. Compounds 1 and 2 exhibited significant in vitro anti-inflammatory activities.

NuSTAR Seeks Hidden Black Holes

NASA Image and Video Library

2015-07-06

Top: An illustration of NASA's Nuclear Spectroscopic Telescope Array, or NuSTAR, in orbit. The unique school bus-long mast allows NuSTAR to focus high energy X-rays. Lower-left: A color image from NASA's Hubble Space Telescope of one of the nine galaxies targeted by NuSTAR in search of hidden black holes. Bottom-right: An artist's illustration of a supermassive black hole, actively feasting on its surroundings. The central black hole is hidden from direct view by a thick layer of encircling gas and dust. http://photojournal.jpl.nasa.gov/catalog/PIA19348

4MOST systems engineering: from conceptual design to preliminary design review

NASA Astrophysics Data System (ADS)

Bellido-Tirado, Olga; Frey, Steffen; Barden, Samuel C.; Brynnel, Joar; Giannone, Domenico; Haynes, Roger; de Jong, Roelof S.; Phillips, Daniel; Schnurr, Olivier; Walcher, Jakob; Winkler, Roland

2016-08-01

The 4MOST Facility is a high-multiplex, wide-field, brief-fed spectrograph system for the ESO VISTA telescope. It aims to create a world-class spectroscopic survey facility unique in its combination of wide-field multiplex, spectral resolution, spectral coverage, and sensitivity. At the end of 2014, after a successful concept optimization design phase, 4MOST entered into its Preliminary Design Phase. Here we present the process and tools adopted during the Preliminary Design Phase to define the subsystems specifications, coordinate the interface control documents and draft the system verification procedures.

Solaris: a global network of autonomous observatories in the southern hemisphere

NASA Astrophysics Data System (ADS)

Kozłowski, S. K.; Sybilski, P.; Konacki, Maciej; Pawłaszek, R. K.; Ratajczak, Milena; Helminiak, K. G.

2014-07-01

We present Project Solaris, a network of four autonomous observatories in the Southern Hemisphere. The Project's primary goal is to detect and characterize circumbinary planets using the eclipse timing approach. This method requires high-cadence and long time-span photometric coverage of the binaries' eclipses, hence the observatories are located at sites having similar separation in longitude and nearly identical latitudes: South African Astronómical Observatory, Republic of South Africa (Solaris-1 and -2), Siding Spring Observatory, Australia (Solaris-3) and Complejo Astronomico El Leoncito, Argentina (Solaris-4). The headquarters coordinating and monitoring the network is based in Toruń, Poland. All four sites are operational as of December 2013. The instrument and hardware configurations are nearly identical. Each site is equipped with a 0.5-m Ritchey-Chrétien or Schmidt-Cassegrain optical tube assembly mounted on a direct-drive modified German equatorial mount along with a set of instruments. Computer, power and networking components are installed in rack cabinets. Everything is housed in sandwiched fiberglass clamshell 3.5-m diameter robotized domes. The Argentinian site is additionally equipped with a 20-ft office container. We discuss the design requirements of robotic observatories aimed to operate autonomously as a global network with concentration on efficiency, robustness and modularity. We also present a newly introduced spectroscopic mode of operation commissioned on the Solaris-1 telescope. Using a compact échelle spectrograph (20 000 resolution) mounted directly on the imaging train of the telescope, we are able to remotely acquire spectra. A fully robotic spectroscopic mode is planned for 2015.

Built-in hyperspectral camera for smartphone in visible, near-infrared and middle-infrared lights region (third report): spectroscopic imaging for broad-area and real-time componential analysis system against local unexpected terrorism and disasters

NASA Astrophysics Data System (ADS)

Hosono, Satsuki; Kawashima, Natsumi; Wollherr, Dirk; Ishimaru, Ichiro

2016-05-01

The distributed networks for information collection of chemical components with high-mobility objects, such as drones or smartphones, will work effectively for investigations, clarifications and predictions against unexpected local terrorisms and disasters like localized torrential downpours. We proposed and reported the proposed spectroscopic line-imager for smartphones in this conference. In this paper, we will mention the wide-area spectroscopic-image construction by estimating 6 DOF (Degrees Of Freedom: parallel movements=x,y,z and rotational movements=θx, θy, θz) from line data to observe and analyze surrounding chemical-environments. Recently, smartphone movies, what were photographed by peoples happened to be there, had worked effectively to analyze what kinds of phenomenon had happened around there. But when a gas tank suddenly blew up, we did not recognize from visible-light RGB-color cameras what kinds of chemical gas components were polluting surrounding atmospheres. Conventionally Fourier spectroscopy had been well known as chemical components analysis in laboratory usages. But volatile gases should be analyzed promptly at accident sites. And because the humidity absorption in near and middle infrared lights has very high sensitivity, we will be able to detect humidity in the sky from wide field spectroscopic image. And also recently, 6-DOF sensors are easily utilized for estimation of position and attitude for UAV (Unmanned Air Vehicle) or smartphone. But for observing long-distance views, accuracies of angle measurements were not sufficient to merge line data because of leverage theory. Thus, by searching corresponding pixels between line spectroscopic images, we are trying to estimate 6-DOF in high accuracy.

Chromatographic and spectroscopic methods for the determination of solvent properties of room temperature ionic liquids.

PubMed

Poole, Colin F

2004-05-28

Room temperature ionic liquids are novel solvents with favorable environmental and technical features. Synthetic routes to over 200 room temperature ionic liquids are known but for most ionic liquids physicochemical data are generally lacking or incomplete. Chromatographic and spectroscopic methods afford suitable tools for the study of solvation properties under conditions that approximate infinite dilution. Gas-liquid chromatography is suitable for the determination of gas-liquid partition coefficients and activity coefficients as well as thermodynamic constants derived from either of these parameters and their variation with temperature. The solvation parameter model can be used to define the contribution from individual intermolecular interactions to the gas-liquid partition coefficient. Application of chemometric procedures to a large database of system constants for ionic liquids indicates their unique solvent properties: low cohesion for ionic liquids with weakly associated ions compared with non-ionic liquids of similar polarity; greater hydrogen-bond basicity than typical polar non-ionic solvents; and a range of dipolarity/polarizability that encompasses the same range as occupied by the most polar non-ionic liquids. These properties can be crudely related to ion structures but further work is required to develop a comprehensive approach for the design of ionic liquids for specific applications. Data for liquid-liquid partition coefficients is scarce by comparison with gas-liquid partition coefficients. Preliminary studies indicate the possibility of using the solvation parameter model for interpretation of liquid-liquid partition coefficients determined by shake-flask procedures as well as the feasibility of using liquid-liquid chromatography for the convenient and rapid determination of liquid-liquid partition coefficients. Spectroscopic measurements of solvatochromic and fluorescent probe molecules in room temperature ionic liquids provide insights into solvent intermolecular interactions although interpretation of the different and generally uncorrelated "polarity" scales is sometimes ambiguous. All evidence points to the ionic liquids as a unique class of polar solvents suitable for technical development. In terms of designer solvents, however, further work is needed to fill the gaps in our knowledge of the relationship between ion structures and physicochemical properties.

Metalloprotein Crystallography: More than a Structure.

PubMed

Bowman, Sarah E J; Bridwell-Rabb, Jennifer; Drennan, Catherine L

2016-04-19

Metal ions and metallocofactors play important roles in a broad range of biochemical reactions. Accordingly, it has been estimated that as much as 25-50% of the proteome uses transition metal ions to carry out a variety of essential functions. The metal ions incorporated within metalloproteins fulfill functional roles based on chemical properties, the diversity of which arises as transition metals can adopt different redox states and geometries, dictated by the identity of the metal and the protein environment. The coupling of a metal ion with an organic framework in metallocofactors, such as heme and cobalamin, further expands the chemical functionality of metals in biology. The three-dimensional visualization of metal ions and complex metallocofactors within a protein scaffold is often a starting point for enzymology, highlighting the importance of structural characterization of metalloproteins. Metalloprotein crystallography, however, presents a number of implicit challenges including correctly incorporating the relevant metal or metallocofactor, maintaining the proper environment for the protein to be purified and crystallized (including providing anaerobic, cold, or aphotic environments), and being mindful of the possibility of X-ray induced damage to the proteins or incorporated metal ions. Nevertheless, the incorporated metals or metallocofactors also present unique advantages in metalloprotein crystallography. The significant resonance that metals undergo with X-ray photons at wavelengths used for protein crystallography and the rich electronic properties of metals, which provide intense and spectroscopically unique signatures, allow a metalloprotein crystallographer to use anomalous dispersion to determine phases for structure solution and to use simultaneous or parallel spectroscopic techniques on single crystals. These properties, coupled with the improved brightness of beamlines, the ability to tune the wavelength of the X-ray beam, the availability of advanced detectors, and the incorporation of spectroscopic equipment at a number of synchrotron beamlines, have yielded exciting developments in metalloprotein structure determination. Here we will present results on the advantageous uses of metals in metalloprotein crystallography, including using metallocofactors to obtain phasing information, using K-edge X-ray absorption spectroscopy to identify metals coordinated in metalloprotein crystals, and using UV-vis spectroscopy on crystals to probe the enzymatic activity of the crystallized protein.

Infrared Imaging, Spectroscopic, and Photometric Studies of Comets

NASA Technical Reports Server (NTRS)

Gehrz, Robert D.

1997-01-01

We have continued our program of infrared (IR) photometric, imaging, spectroscopic, and polarimetric temporal observations of comets to study the properties of comet dust and comet nuclei. During the first two years we digitized our IR data base on P/Halley and other recent comets to facilitate further analysis and comparison with other data bases, and found compelling evidence for the emission of a burst of small grains from P/Halley's nucleus at perihelion. We reported imaging and photometric observations of Comets Austin 1990 V and Swift-Tuttle 1992. The Swift-Tuttle 1992t observations included IR photometry, several 7-14 micron long-slit spectra of the coma and a time-sequence of more than 150 10 micron broadband images of the coma. An analysis of near-IR images of the inner coma of P/Halley obtained on three consecutive nights in 1986 March showed sunwardjets. We completed our analysis of IR imaging spectrosco-photometric data on comets. We also obtained observations of Comets Hyakutake 1996 B2 and Hale/Bopp 1995 01. We obtained infrared imaging, photometric, spectroscopic and polarimetric temporal observations of bright comets using a network of five telescopes, with emphasis on simultaneous observations of comets at many wavelengths with different instruments. Our program offers several unique advantages: 1) rapid observational response to new comets with dedicated infrared telescopes; 2) observations within a few degrees of the sun when comets are near perihelion and 3) access to advanced infrared array imagers and spectrometers. In particular, reduction, analysis, publication and archiving of our Jupiter/sl-9 and Comet Hyakutake infrared data received special emphasis. Instrumentation development included installation of the latest version of the innovative FORTH telescope control and a data acquisition system that enables us to control three telescopes remotely by telephone from anywhere in the world for comet observations in broad daylight. We have acquired more than 3000 256x256 images totaling nearly two gigabytes of data detailing the near-IR development of the impact sites of the S-L9 fragments on Jupiter. These data were obtained using the University of Rochester Imaging IR Camera at the cassegrain focus of the 92" at WIRO. The WIRO data set covers 8 days and is, to our knowledge, one of the most extensive observational records of the S-L/Jupiter encounter obtained by any ground-based telescope. This program benefitted from the compilation during these last few months of an upgrade to the data acquisition program at WIRO with support of this NASA contract.

VISA--Vector Integration Site Analysis server: a web-based server to rapidly identify retroviral integration sites from next-generation sequencing.

PubMed

Hocum, Jonah D; Battrell, Logan R; Maynard, Ryan; Adair, Jennifer E; Beard, Brian C; Rawlings, David J; Kiem, Hans-Peter; Miller, Daniel G; Trobridge, Grant D

2015-07-07

Analyzing the integration profile of retroviral vectors is a vital step in determining their potential genotoxic effects and developing safer vectors for therapeutic use. Identifying retroviral vector integration sites is also important for retroviral mutagenesis screens. We developed VISA, a vector integration site analysis server, to analyze next-generation sequencing data for retroviral vector integration sites. Sequence reads that contain a provirus are mapped to the human genome, sequence reads that cannot be localized to a unique location in the genome are filtered out, and then unique retroviral vector integration sites are determined based on the alignment scores of the remaining sequence reads. VISA offers a simple web interface to upload sequence files and results are returned in a concise tabular format to allow rapid analysis of retroviral vector integration sites.

Acid-base titrations of functional groups on the surface of the thermophilic bacterium Anoxybacillus flavithermus: comparing a chemical equilibrium model with ATR-IR spectroscopic data.

PubMed

Heinrich, Hannah T M; Bremer, Phil J; Daughney, Christopher J; McQuillan, A James

2007-02-27

Acid-base functional groups at the surface of Anoxybacillus flavithermus (AF) were assigned from the modeling of batch titration data of bacterial suspensions and compared with those determined from in situ infrared spectroscopic titration analysis. The computer program FITMOD was used to generate a two-site Donnan model (site 1: pKa = 3.26, wet concn = 2.46 x 10(-4) mol g(-1); site 2: pKa = 6.12, wet concn = 6.55 x 10(-5) mol g(-1)), which was able to describe data for whole exponential phase cells from both batch acid-base titrations at 0.01 M ionic strength and electrophoretic mobility measurements over a range of different pH values and ionic strengths. In agreement with information on the composition of bacterial cell walls and a considerable body of modeling literature, site 1 of the model was assigned to carboxyl groups, and site 2 was assigned to amino groups. pH difference IR spectra acquired by in situ attenuated total reflection infrared (ATR-IR) spectroscopy confirmed the presence of carboxyl groups. The spectra appear to show a carboxyl pKa in the 3.3-4.0 range. Further peaks were assigned to phosphodiester groups, which deprotonated at slightly lower pH. The presence of amino groups could not be confirmed or discounted by IR spectroscopy, but a positively charged group corresponding to site 2 was implicated by electrophoretic mobility data. Carboxyl group speciation over a pH range of 2.3-10.3 at two different ionic strengths was further compared to modeling predictions. While model predictions were strongly influenced by the ionic strength change, pH difference IR data showed no significant change. This meant that modeling predictions agreed reasonably well with the IR data for 0.5 M ionic strength but not for 0.01 M ionic strength.

Spectroscopic and Theoretical Study of CuI Binding to His111 in the Human Prion Protein Fragment 106–115

PubMed Central

2016-01-01

The ability of the cellular prion protein (PrPC) to bind copper in vivo points to a physiological role for PrPC in copper transport. Six copper binding sites have been identified in the nonstructured N-terminal region of human PrPC. Among these sites, the His111 site is unique in that it contains a MKHM motif that would confer interesting CuI and CuII binding properties. We have evaluated CuI coordination to the PrP(106–115) fragment of the human PrP protein, using NMR and X-ray absorption spectroscopies and electronic structure calculations. We find that Met109 and Met112 play an important role in anchoring this metal ion. CuI coordination to His111 is pH-dependent: at pH >8, 2N1O1S species are formed with one Met ligand; in the range of pH 5–8, both methionine (Met) residues bind to CuI, forming a 1N1O2S species, where N is from His111 and O is from a backbone carbonyl or a water molecule; at pH <5, only the two Met residues remain coordinated. Thus, even upon drastic changes in the chemical environment, such as those occurring during endocytosis of PrPC (decreased pH and a reducing potential), the two Met residues in the MKHM motif enable PrPC to maintain the bound CuI ions, consistent with a copper transport function for this protein. We also find that the physiologically relevant CuI-1N1O2S species activates dioxygen via an inner-sphere mechanism, likely involving the formation of a copper(II) superoxide complex. In this process, the Met residues are partially oxidized to sulfoxide; this ability to scavenge superoxide may play a role in the proposed antioxidant properties of PrPC. This study provides further insight into the CuI coordination properties of His111 in human PrPC and the molecular mechanism of oxygen activation by this site. PMID:26930130

Soil Amendments to Reduce Bioavailability of Metals in Soils: Experimental Studies and Spectroscopic Verification

DTIC Science & Technology

2008-07-01

Leachate . ................................ 56 xi Table 24. Smelter Site Soil Lettuce Germination Percentage...sand soil (Table 22). This discovery was contrary to the hypothesized results. Archived samples of leachate from each treatment were examined...but after further investigation ,the pH and EC of the New Jersey leachate showed no remarkable differences between the unamended or sand unamended

Optimizing Restriction Site Placement for Synthetic Genomes

NASA Astrophysics Data System (ADS)

Montes, Pablo; Memelli, Heraldo; Ward, Charles; Kim, Joondong; Mitchell, Joseph S. B.; Skiena, Steven

Restriction enzymes are the workhorses of molecular biology. We introduce a new problem that arises in the course of our project to design virus variants to serve as potential vaccines: we wish to modify virus-length genomes to introduce large numbers of unique restriction enzyme recognition sites while preserving wild-type function by substitution of synonymous codons. We show that the resulting problem is NP-Complete, give an exponential-time algorithm, and propose effective heuristics, which we show give excellent results for five sample viral genomes. Our resulting modified genomes have several times more unique restriction sites and reduce the maximum gap between adjacent sites by three to nine-fold.

Binding of caffeine with caffeic acid and chlorogenic acid using fluorescence quenching, UV/vis and FTIR spectroscopic techniques.

PubMed

Belay, Abebe; Kim, Hyung Kook; Hwang, Yoon-Hwae

2016-03-01

The interactions of caffeine (CF) with chlorogenic acid (CGA) and caffeic acid (CFA) were investigated by fluorescence quenching, UV/vis and Fourier transform infrared (FTIR) spectroscopic techniques. The results of the study indicated that the fluorescence quenching between caffeine and hydroxycinnamic acids could be rationalized in terms of static quenching or the formation of non-fluorescent CF-CFA and CF-CGA complexes. From fluorescence quenching spectral analysis, the quenching constant (KSV), quenching rate constant (kq), number of binding sites (n), thermodynamic properties and conformational changes of the interaction were determined. The quenching constants (KSV) between CF and CGA, CFA are 1.84 × 10(4) and 1.04 × 10(4) L/mol at 298 K and their binding site n is ~ 1. Thermodynamic parameters determined using the Van't Hoff equation indicated that hydrogen bonds and van der Waal's forces have a major role in the reaction of caffeine with caffeic acid and chlorogenic acid. The 3D fluorescence, UV/vis and FTIR spectra also showed that the binding of CF with CFA and CGA induces conformational changes in CFA and CGA. Copyright © 2015 John Wiley & Sons, Ltd.

Multi-spectroscopic and voltammetric evidences for binding, conformational changes of bovine serum albumin with thiamine.

PubMed

Bagoji, Atmanand M; Gowda, Jayant I; Gokavi, Naveen M; Nandibewoor, Sharanappa T

2017-08-01

The interaction between thiamine hydrochloride (TA) and bovine serum albumin (BSA) was investigated by fluorescence, FTIR, UV-vis spectroscopic and cyclic voltammetric techniques under optimised physiological condition. The fluorescence intensity of BSA is gradually decreased upon addition of TA due to the formation of a BSA-TA complex. The binding parameters were evaluated and their behaviour at different temperatures was analysed. The quenching constants (K sv ) obtained were 2.6 × 10 4 , 2.2 × 10 4 and 2.0 × 10 4  L mol -1 at 288, 298 and 308 K, respectively. The binding mechanism was static-type quenching. The values of ΔH° and ΔS° were found to be 26.87 kJ mol -1 and 21.3 J K -1  mol -1 , and indicated that electrostatic interaction was the principal intermolecular force. The changes in the secondary structure of BSA upon interaction with TA were confirmed by synchronous and 3-D spectral results. Site probe studies reveal that TA is located in site I of BSA. The effects of some common metal ions on binding of BSA-TA complex were also investigated.

Spectroscopic analysis of soil metal contamination around a derelict mine site in the Blue Mountains, Australia

NASA Astrophysics Data System (ADS)

Shamsoddini, A.; Raval, S.; Taplin, R.

2014-09-01

Abandoned mine sites pose the potential threat of the heavy metal pollution spread through streams and via runoff leading to contamination of soil and water in their surrounding areas. Regular monitoring of these areas is critical to minimise impacts on water resources, flora and fauna. Conventional ground based monitoring is expensive and sometimes impractical; spectroscopic methods have been emerged as a reliable alternative for this purpose. In this study, the capabilities of the spectroscopy method were examined for modelling soil contamination from around the abandoned silver-zinc mine located at Yerranderie, NSW Australia. The diagnostic characteristics of the original reflectance data were compared with models derived from first and second derivatives of the reflectance data. The results indicate that the models derived from the first derivative of the reflectance data estimate heavy metals significantly more accurately than model derived from the original reflectance. It was also found in this study that there is no need to use second derivative for modelling heavy metal soil contamination. Finally, the results indicate that estimates were of greater accuracy for arsenic and lead compared to other heavy metals, while the estimation for silver was found to be the most erroneous.

Directing reaction pathways by catalyst active-site selection using self-assembled monolayers.

PubMed

Pang, Simon H; Schoenbaum, Carolyn A; Schwartz, Daniel K; Medlin, J Will

2013-01-01

One key route for controlling reaction selectivity in heterogeneous catalysis is to prepare catalysts that exhibit only specific types of sites required for desired product formation. Here we show that alkanethiolate self-assembled monolayers with varying surface densities can be used to tune selectivity to desired hydrogenation and hydrodeoxygenation products during the reaction of furfural on supported palladium catalysts. Vibrational spectroscopic studies demonstrate that the selectivity improvement is achieved by controlling the availability of specific sites for the hydrogenation of furfural on supported palladium catalysts through the selection of an appropriate alkanethiolate. Increasing self-assembled monolayer density by controlling the steric bulk of the organic tail ligand restricts adsorption on terrace sites and dramatically increases selectivity to desired products furfuryl alcohol and methylfuran. This technique of active-site selection simultaneously serves both to enhance selectivity and provide insight into the reaction mechanism.

An evaluation of traditional and emerging remote sensing technologies for the detection of fugitive contamination at selected Superfund hazardous waste sites

USGS Publications Warehouse

Slonecker, E. Terrence; Fisher, Gary B.

2011-01-01

This report represents a remote sensing research effort conducted by the U.S. Geological Survey in cooperation with the U.S. Environmental Protection Agency (EPA) for the EPA Office of Inspector General. The objective of this investigation was to explore the efficacy of remote sensing as a technology for postclosure monitoring of hazardous waste sites as defined under the Comprehensive Environmental Response Compensation and Liability Act of 1980 (Public Law 96-510, 42 U.S.C. §9601 et seq.), also known as \\"Superfund.\\" Five delisted Superfund sites in Maryland and Virginia were imaged with a hyperspectral sensor and visited for collection of soil, water, and spectral samples and inspection of general site conditions. This report evaluates traditional and hyperspectral imagery and field spectroscopic measurement techniques in the characterization and analysis of fugitive (anthropogenic, uncontrolled) contamination at previously remediated hazardous waste disposal sites.

STD-NMR-Based Protein Engineering of the Unique Arylpropionate-Racemase AMDase G74C.

PubMed

Gaßmeyer, Sarah Katharina; Yoshikawa, Hiroyuki; Enoki, Junichi; Hülsemann, Nadine; Stoll, Raphael; Miyamoto, Kenji; Kourist, Robert

2015-06-23

Structure-guided protein engineering achieved a variant of the unique racemase AMDase G74C, with 40-fold increased activity in the racemisation of several arylaliphatic carboxylic acids. Substrate binding during catalysis was investigated by saturation-transfer-difference NMR (STD-NMR) spectroscopy. All atoms of the substrate showed interactions with the enzyme. STD-NMR measurements revealed distinct nuclear Overhauser effects in experiments with and without molecular conversion. The spectroscopic analysis led to the identification of several amino acid residues whose substitutions increased the activity of G74C. Single amino acid exchanges increased the activity moderately; structure-guided saturation mutagenesis yielded a quadruple mutant with a 40 times higher reaction rate. This study presents STD-NMR as versatile tool for the analysis of enzyme-substrate interactions in catalytically competent systems and for the guidance of protein engineering. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

O2 reduction to H2O by the multicopper oxidases.

PubMed

Solomon, Edward I; Augustine, Anthony J; Yoon, Jungjoo

2008-08-14

In nature the four electron reduction of O2 to H2O is carried out by Cytochrome c oxidase (CcO) and the multicopper oxidases (MCOs). In the former, Cytochrome c provides electrons for pumping protons to produce a gradient for ATP synthesis, while in the MCOs the function is the oxidation of substrates, either organic or metal ions. In the MCOs the reduction of O2 is carried out at a trinuclear Cu cluster (TNC). Oxygen intermediates have been trapped which exhibit unique spectroscopic features that reflect novel geometric and electronic structures. These intermediates have both intact and cleaved O-O bonds, allowing the reductive cleavage of the O-O bond to be studied in detail both experimentally and computationally. These studies show that the topology of the TNC provides a unique geometric and electronic structure particularly suited to carry out this key reaction in nature.

O2 Reduction to H2O by the Multicopper Oxidases

PubMed Central

Solomon, Edward I.; Augustine, Anthony J.; Yoon, Jungjoo

2010-01-01

In nature the four electron reduction of O2 to H2O is carried out by Cytochrome c Oxidase (CcO) and the multicopper oxidases (MCOs). In the former, Cytochrome c provides electrons for pumping protons to produce a gradient for ATP synthesis, while in the MCOs the function is the oxidation of substrates, either organic or metal ions. In the MCOs the reduction of O2 is carried out at a trinuclear Cu cluster (TNC). Oxygen intermediates have been trapped which exhibit unique spectroscopic features that reflect novel geometric and electronic structures. These intermediates have both intact and cleaved O-O bonds, allowing the reductive cleavage of the O-O bond to be studied in detail both experimentally and computationally. These studies show that the topology of the TNC provides a unique geometric and electronic structure particularly suited to carry out this key reaction in Nature. PMID:18648693

Efficient design and verification of diagnostics for impurity transport experiments.

PubMed

Chilenski, M A; Greenwald, M J; Marzouk, Y M; Rice, J E; White, A E

2018-01-01

Recent attempts to measure impurity transport in Alcator C-Mod using an x-ray imaging crystal spectrometer and laser blow-off impurity injector have failed to yield unique reconstructions of the transport coefficient profiles. This paper presents a fast, linearized model which was constructed to estimate diagnostic requirements for impurity transport experiments. The analysis shows that the spectroscopic diagnostics on Alcator C-Mod should be capable of inferring simple profiles of impurity diffusion D Z and convection V Z accurate to better than ±10% uncertainty, suggesting that the failure to infer unique D Z and V Z from experimental data is attributable to an inadequate analysis procedure rather than the result of insufficient diagnostics. Furthermore, the analysis reveals that even a modest spatial resolution can overcome a low time resolution. This approach can be adapted to design and verify diagnostics for transport experiments on any magnetic confinement device.

Detection of Papaverine for the Possible Identification of Illicit Opium Cultivation.

PubMed

Mirsafavi, Rustin Y; Lai, Kristine; Kline, Neal D; Fountain, Augustus W; Meinhart, Carl D; Moskovits, Martin

2017-02-07

Papaverine is a non-narcotic alkaloid found endemically and uniquely in the latex of the opium poppy. It is normally refined out of the opioids that the latex is typically collected for, hence its presence in a sample is strong prima facie evidence that the carrier from whom the sample was collected is implicated in the mass cultivation of poppies or the collection and handling of their latex. We describe an analysis technique combining surface-enhanced Raman spectroscopy (SERS) with microfluidics for detecting papaverine at low concentrations and show that its SERS spectrum has unique spectroscopic features that allows its detection at low concentrations among typical opioids. The analysis requires approximately 2.5 min from sample loading to results, which is compatible with field use. The weak acid properties of papaverine hydrochloride were investigated, and Raman bands belonging to the protonated and unprotonated forms of the isoquinoline ring of papaverine were identified.

Surface complexation modeling of zinc sorption onto ferrihydrite.

PubMed

Dyer, James A; Trivedi, Paras; Scrivner, Noel C; Sparks, Donald L

2004-02-01

A previous study involving lead(II) [Pb(II)] sorption onto ferrihydrite over a wide range of conditions highlighted the advantages of combining molecular- and macroscopic-scale investigations with surface complexation modeling to predict Pb(II) speciation and partitioning in aqueous systems. In this work, an extensive collection of new macroscopic and spectroscopic data was used to assess the ability of the modified triple-layer model (TLM) to predict single-solute zinc(II) [Zn(II)] sorption onto 2-line ferrihydrite in NaNO(3) solutions as a function of pH, ionic strength, and concentration. Regression of constant-pH isotherm data, together with potentiometric titration and pH edge data, was a much more rigorous test of the modified TLM than fitting pH edge data alone. When coupled with valuable input from spectroscopic analyses, good fits of the isotherm data were obtained with a one-species, one-Zn-sorption-site model using the bidentate-mononuclear surface complex, (triple bond FeO)(2)Zn; however, surprisingly, both the density of Zn(II) sorption sites and the value of the best-fit equilibrium "constant" for the bidentate-mononuclear complex had to be adjusted with pH to adequately fit the isotherm data. Although spectroscopy provided some evidence for multinuclear surface complex formation at surface loadings approaching site saturation at pH >/=6.5, the assumption of a bidentate-mononuclear surface complex provided acceptable fits of the sorption data over the entire range of conditions studied. Regressing edge data in the absence of isotherm and spectroscopic data resulted in a fair number of surface-species/site-type combinations that provided acceptable fits of the edge data, but unacceptable fits of the isotherm data. A linear relationship between logK((triple bond FeO)2Zn) and pH was found, given by logK((triple bond FeO)2Znat1g/l)=2.058 (pH)-6.131. In addition, a surface activity coefficient term was introduced to the model to reduce the ionic strength dependence of sorption. The results of this research and previous work with Pb(II) indicate that the existing thermodynamic framework for the modified TLM is able to reproduce the metal sorption data only over a limited range of conditions. For this reason, much work still needs to be done in fine-tuning the thermodynamic framework and databases for the TLM.

Accelerated Evolution and Functional Divergence of the Dim Light Visual Pigment Accompanies Cichlid Colonization of Central America.

PubMed

Hauser, Frances E; Ilves, Katriina L; Schott, Ryan K; Castiglione, Gianni M; López-Fernández, Hernán; Chang, Belinda S W

2017-10-01

Cichlids encompass one of the most diverse groups of fishes in South and Central America, and show extensive variation in life history, morphology, and colouration. While studies of visual system evolution in cichlids have focussed largely on the African rift lake species flocks, Neotropical cichlids offer a unique opportunity to investigate visual system evolution at broader temporal and geographic scales. South American cichlid colonization of Central America has likely promoted accelerated rates of morphological evolution in Central American lineages as they encountered reduced competition, renewed ecological opportunity, and novel aquatic habitats. To investigate whether such transitions have influenced molecular evolution of vision in Central American cichlids, we sequenced the dim-light rhodopsin gene in 101 Neotropical cichlid species, spanning the diversity of the clade. We find strong evidence for increased rates of evolution in Central American cichlid rhodopsin relative to South American lineages, and identify several sites under positive selection in rhodopsin that likely contribute to adaptation to different photic environments. We expressed a Neotropical cichlid rhodopsin protein invitro for the first time, and found that while its spectral tuning properties were characteristic of typical vertebrate rhodopsin pigments, the rate of decay of its active signalling form was much slower, consistent with dim light adaptation in other vertebrate rhodopsins. Using site-directed mutagenesis combined with spectroscopic assays, we found that a key amino acid substitution present in some Central American cichlids accelerates the rate of decay of active rhodopsin, which may mediate adaptation to clear water habitats. © The Author 2017. Published by Oxford University Press on behalf of the Society for Molecular Biology and Evolution. All rights reserved. For permissions, please e-mail: journals.permissions@oup.com.

Quantum cascade laser-based analyzer for hydrogen sulfide detection at sub-parts-per-million levels

NASA Astrophysics Data System (ADS)

Nikodem, Michal; Krzempek, Karol; Stachowiak, Dorota; Wysocki, Gerard

2018-01-01

Due to its high toxicity, monitoring of hydrogen sulfide (H2S) concentration is essential in many industrial sites (such as natural gas extraction sites, petroleum refineries, geothermal power plants, or waste water treatment facilities), which require sub-parts-per-million sensitivities. We report on a quantum cascade laser-based spectroscopic system for detection of H2S in the midinfrared at ˜7.2 μm. We present a sensor design utilizing Herriott multipass cell and a wavelength modulation spectroscopy to achieve a detection limit of 140 parts per billion for 1-s integration time.

The VANDELS ESO public spectroscopic survey

NASA Astrophysics Data System (ADS)

McLure, R. J.; Pentericci, L.; Cimatti, A.; Dunlop, J. S.; Elbaz, D.; Fontana, A.; Nandra, K.; Amorin, R.; Bolzonella, M.; Bongiorno, A.; Carnall, A. C.; Castellano, M.; Cirasuolo, M.; Cucciati, O.; Cullen, F.; De Barros, S.; Finkelstein, S. L.; Fontanot, F.; Franzetti, P.; Fumana, M.; Gargiulo, A.; Garilli, B.; Guaita, L.; Hartley, W. G.; Iovino, A.; Jarvis, M. J.; Juneau, S.; Karman, W.; Maccagni, D.; Marchi, F.; Mármol-Queraltó, E.; Pompei, E.; Pozzetti, L.; Scodeggio, M.; Sommariva, V.; Talia, M.; Almaini, O.; Balestra, I.; Bardelli, S.; Bell, E. F.; Bourne, N.; Bowler, R. A. A.; Brusa, M.; Buitrago, F.; Caputi, K. I.; Cassata, P.; Charlot, S.; Citro, A.; Cresci, G.; Cristiani, S.; Curtis-Lake, E.; Dickinson, M.; Fazio, G. G.; Ferguson, H. C.; Fiore, F.; Franco, M.; Fynbo, J. P. U.; Galametz, A.; Georgakakis, A.; Giavalisco, M.; Grazian, A.; Hathi, N. P.; Jung, I.; Kim, S.; Koekemoer, A. M.; Khusanova, Y.; Fèvre, O. Le; Lotz, J. M.; Mannucci, F.; Maltby, D. T.; Matsuoka, K.; McLeod, D. J.; Mendez-Hernandez, H.; Mendez-Abreu, J.; Mignoli, M.; Moresco, M.; Mortlock, A.; Nonino, M.; Pannella, M.; Papovich, C.; Popesso, P.; Rosario, D. P.; Salvato, M.; Santini, P.; Schaerer, D.; Schreiber, C.; Stark, D. P.; Tasca, L. A. M.; Thomas, R.; Treu, T.; Vanzella, E.; Wild, V.; Williams, C. C.; Zamorani, G.; Zucca, E.

2018-05-01

VANDELS is a uniquely-deep spectroscopic survey of high-redshift galaxies with the VIMOS spectrograph on ESO's Very Large Telescope (VLT). The survey has obtained ultra-deep optical (0.48 < λ < 1.0 μm) spectroscopy of ≃2100 galaxies within the redshift interval 1.0 ≤ z ≤ 7.0, over a total area of ≃ 0.2 deg2 centred on the CANDELS UDS and CDFS fields. Based on accurate photometric redshift pre-selection, 85% of the galaxies targeted by VANDELS were selected to be at z ≥ 3. Exploiting the red sensitivity of the refurbished VIMOS spectrograph, the fundamental aim of the survey is to provide the high signal-to-noise ratio spectra necessary to measure key physical properties such as stellar population ages, masses, metallicities and outflow velocities from detailed absorption-line studies. Using integration times calculated to produce an approximately constant signal-to-noise ratio (20 < tint < 80 hours), the VANDELS survey targeted: a) bright star-forming galaxies at 2.4 ≤ z ≤ 5.5, b) massive quiescent galaxies at 1.0 ≤ z ≤ 2.5, c) fainter star-forming galaxies at 3.0 ≤ z ≤ 7.0 and d) X-ray/Spitzer-selected active galactic nuclei and Herschel-detected galaxies. By targeting two extragalactic survey fields with superb multi-wavelength imaging data, VANDELS will produce a unique legacy data set for exploring the physics underpinning high-redshift galaxy evolution. In this paper we provide an overview of the VANDELS survey designed to support the science exploitation of the first ESO public data release, focusing on the scientific motivation, survey design and target selection.

The VANDELS ESO spectroscopic survey

NASA Astrophysics Data System (ADS)

McLure, R. J.; Pentericci, L.; Cimatti, A.; Dunlop, J. S.; Elbaz, D.; Fontana, A.; Nandra, K.; Amorin, R.; Bolzonella, M.; Bongiorno, A.; Carnall, A. C.; Castellano, M.; Cirasuolo, M.; Cucciati, O.; Cullen, F.; De Barros, S.; Finkelstein, S. L.; Fontanot, F.; Franzetti, P.; Fumana, M.; Gargiulo, A.; Garilli, B.; Guaita, L.; Hartley, W. G.; Iovino, A.; Jarvis, M. J.; Juneau, S.; Karman, W.; Maccagni, D.; Marchi, F.; Mármol-Queraltó, E.; Pompei, E.; Pozzetti, L.; Scodeggio, M.; Sommariva, V.; Talia, M.; Almaini, O.; Balestra, I.; Bardelli, S.; Bell, E. F.; Bourne, N.; Bowler, R. A. A.; Brusa, M.; Buitrago, F.; Caputi, K. I.; Cassata, P.; Charlot, S.; Citro, A.; Cresci, G.; Cristiani, S.; Curtis-Lake, E.; Dickinson, M.; Fazio, G. G.; Ferguson, H. C.; Fiore, F.; Franco, M.; Fynbo, J. P. U.; Galametz, A.; Georgakakis, A.; Giavalisco, M.; Grazian, A.; Hathi, N. P.; Jung, I.; Kim, S.; Koekemoer, A. M.; Khusanova, Y.; Le Fèvre, O.; Lotz, J. M.; Mannucci, F.; Maltby, D. T.; Matsuoka, K.; McLeod, D. J.; Mendez-Hernandez, H.; Mendez-Abreu, J.; Mignoli, M.; Moresco, M.; Mortlock, A.; Nonino, M.; Pannella, M.; Papovich, C.; Popesso, P.; Rosario, D. P.; Salvato, M.; Santini, P.; Schaerer, D.; Schreiber, C.; Stark, D. P.; Tasca, L. A. M.; Thomas, R.; Treu, T.; Vanzella, E.; Wild, V.; Williams, C. C.; Zamorani, G.; Zucca, E.

2018-05-01

VANDELS is a uniquely-deep spectroscopic survey of high-redshift galaxies with the VIMOS spectrograph on ESO's Very Large Telescope (VLT). The survey has obtained ultra-deep optical (0.48 < λ < 1.0 μm) spectroscopy of ≃2100 galaxies within the redshift interval 1.0 ≤ z ≤ 7.0, over a total area of ≃ 0.2 deg2 centred on the CANDELS UDS and CDFS fields. Based on accurate photometric redshift pre-selection, 85% of the galaxies targeted by VANDELS were selected to be at z ≥ 3. Exploiting the red sensitivity of the refurbished VIMOS spectrograph, the fundamental aim of the survey is to provide the high signal-to-noise ratio spectra necessary to measure key physical properties such as stellar population ages, masses, metallicities and outflow velocities from detailed absorption-line studies. Using integration times calculated to produce an approximately constant signal-to-noise ratio (20 < tint < 80 hours), the VANDELS survey targeted: a) bright star-forming galaxies at 2.4 ≤ z ≤ 5.5, b) massive quiescent galaxies at 1.0 ≤ z ≤ 2.5, c) fainter star-forming galaxies at 3.0 ≤ z ≤ 7.0 and d) X-ray/Spitzer-selected active galactic nuclei and Herschel-detected galaxies. By targeting two extragalactic survey fields with superb multi-wavelength imaging data, VANDELS will produce a unique legacy data set for exploring the physics underpinning high-redshift galaxy evolution. In this paper we provide an overview of the VANDELS survey designed to support the science exploitation of the first ESO public data release, focusing on the scientific motivation, survey design and target selection.

Long-Term Trends of Carbon Monoxide Total Columnar Amount in Urban Areas and Background Regions: Ground- and Satellite-based Spectroscopic Measurements

NASA Astrophysics Data System (ADS)

Wang, Pucai; Elansky, N. F.; Timofeev, Yu. M.; Wang, Gengchen; Golitsyn, G. S.; Makarova, M. V.; Rakitin, V. S.; Shtabkin, Yu.; Skorokhod, A. I.; Grechko, E. I.; Fokeeva, E. V.; Safronov, A. N.; Ran, Liang; Wang, Ting

2018-07-01

A comparative study was carried out to explore carbon monoxide total columnar amount (CO TC) in background and polluted atmosphere, including the stations of ZSS (Zvenigorod), ZOTTO (Central Siberia), Peterhof, Beijing, and Moscow, during 1998-2014, on the basis of ground- and satellite-based spectroscopic measurements. Interannual variations of CO TC in different regions of Eurasia were obtained from ground-based spectroscopic observations, combined with satellite data from the sensors MOPITT (2001-14), AIRS (2003-14), and IASI MetOp-A (2010-13). A decreasing trend in CO TC (1998-2014) was found at the urban site of Beijing, where CO TC decreased by 1.14%±0.87% yr-1. Meanwhile, at the Moscow site, CO TC decreased remarkably by 3.73%±0.39% yr-1. In the background regions (ZSS, ZOTTO, Peterhof), the reduction was 0.9%-1.7% yr-1 during the same period. Based on the AIRSv6 satellite data for the period 2003-14, a slight decrease (0.4%-0.6% yr-1) of CO TC was detected over the midlatitudes of Eurasia, while a reduction of 0.9%-1.2% yr-1 was found in Southeast Asia. The degree of correlation between the CO TC derived from satellite products (MOPITTv6 Joint, AIRSv6 and IASI MetOp-A) and ground-based measurements was calculated, revealing significant correlation in unpolluted regions. While in polluted areas, IASI MetOp-A and AIRSv6 data underestimated CO TC by a factor of 1.5-2.8. On average, the correlation coefficient between ground- and satellite-based data increased significantly for cases with PBL heights greater than 500 m.

A Quantitative Raman Spectroscopic Signal for Metal–Phosphodiester Interactions in Solution†

PubMed Central

Christian, Eric L.; Anderson, Vernon E.; Carey, Paul R.; Harris, Michael E.

2011-01-01

Accurate identification and quantification of metal ion–phosphodiester interactions are essential for understanding the role of metal ions as determinants of three-dimensional folding of large RNAs and as cofactors in the active sites of both RNA and protein phosphodiesterases. Accomplishing this goal is difficult due to the dynamic and complex mixture of direct and indirect interactions formed with nucleic acids and other phosphodiesters in solution. To address this issue, Raman spectroscopy has been used to measure changes in bond vibrational energies due to metal interactions. However, the contributions of inner-sphere, H-bonding, and electrostatic interactions to the Raman spectrum of phosphoryl oxygens have not been analyzed quantitatively. Here, we report that all three forms of metal ion interaction result in attenuation of the Raman signal for the symmetric vibration of the nonbridging phosphate oxygens (νsPO2−), while only inner-sphere coordination gives rise to an apparent shift of νsPO2− to higher wavenumbers (νsPO2−M) in solution. Formation of νsPO2−M is shown to be both dependent on metal ion identity and an accurate measure of site-specific metal ion binding. In addition, the spectroscopic parameter reflecting the energetic difference between νsPO2− and νsPO2−M (ΔνM) is largely insensitive to changes in phosphodiester structure but strongly dependent on the absolute electronegativity and hardness of the interacting metal ion. Together, these studies provide strong experimental support for the use of νsPO2−M and ΔνM as general spectroscopic features for the quantitative analysis of metal binding affinity and the identification of metal ions associated with phosphodiesters in solution. PMID:20180599

Spectroscopic analysis of a novel Nd3+-activated barium borate glass for broadband laser amplification

NASA Astrophysics Data System (ADS)

Vázquez, G. V.; Muñoz H., G.; Camarillo, I.; Falcony, C.; Caldiño, U.; Lira, A.

2015-08-01

Spectroscopic parameters of a novel Nd3+-activated barium borate (BBONd) glass have been analyzed for broadband laser amplification. The Judd-Ofelt (JO) intensity parameters were determined through a systematic analysis of the absorption spectrum of Nd3+ ions in the BBONd glass. High values of the JO intensity parameters reveal a great centro-symmetrical loss of the Nd3+ sites and high covalency degree of the ligand field. The very high Ω6 intensity parameter value makes evident both a great structural distortion of the Nd3+ sites and a strong electron-phonon coupling between Nd3+ and free OH- ions, which is consistent with the phonon energy maximum (3442.1 cm-1) recorded by Raman spectroscopy. This strong electron-phonon coupling favors high effective bandwidth and gain bandwidth values of the laser emission (4F3/2 → 4I11/2) of Nd3+ ions. The electric-dipole oscillator strengths of all the Nd3+ absorption transitions, and in particular that of the hypersensitive transition (4I9/2 → 4G5/2), are enhanced by this great structural distortion of the host. Broadband laser amplification of the 4F3/2 → 4I11/2 emission (1062 nm) of Nd3+ ions in the BBONd glass pumped at 805 nm (4I9/2 → 4F5/2 + 2H9/2) is evaluated through the main fluorescent parameters in competition with non-radiative processes. In general, the BBONd glass exhibits spectroscopic parameters comparable with those reported in the literature for broadband laser amplification into the IR region.

Spectroscopic infrared extinction mapping as a probe of grain growth in IRDCs

NASA Astrophysics Data System (ADS)

Lim, Wanggi; Carey, Sean J.

2014-07-01

We present photometric and spectroscopic tests of MIR to FIR extinction laws toward IRDC G028.36+00.07, a potential site of massive star formation. Lim & Tan (2014, hereafter LT14) developed methods of FIR extinction mapping of this source using Spitzer-MIPS 24 micron and Herschel-PACS 70 micron images, and extending the MIR 8 micron mapping methods of (Butler & Tan 2012, hereafter BT12), finding evidence for grain growth in the highest mass surface density regions. Here we present initial results of spectroscopic infrared extinction (SIREX) mapping using Spitzer-IRS (14 to 38 micron) data of the same IRDC. These methods allow us to measure the SED of the diffuse Galactic ISM, which we compare to theoretical models of Draine & Li (2007), as well as to search for opacity law variations with mass surface density within the IRDC. By comparison with theoretical dust models, e.g., Ossenkopf & Henning (1994) and Ormel et al. (2011), we are able to search for compositional signatures of the grain ices, such as water and methanol. We find evidence for generally flatter MIR to FIR extinction laws as mass surface density increases, strengthening the evidence for grain and ice mantle growth in higher density regions.

In situ detection of warfarin using time-correlated single-photon counting

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

Rosengren, Annika M.; Karlsson, Bjoern C.G.; Naeslund, Inga

Highlights: {yields} Direct in situ measurement of specific isomeric forms of the anticoagulant warfarin. {yields} TCSPC spectroscopy in conjunction with synthetic Sudlow I binding site receptors. {yields} Development of sensor principle for use in clinical and environmental monitoring. -- Abstract: Here we report on a novel method for the direct in situ measurement of specific isomeric forms of the anticoagulant warfarin using time correlated single-photon counting (TCSPC) spectroscopy in conjunction with synthetic Sudlow I binding site receptors. The method is highly robust over the clinically significant concentration range, and demonstrates the potential of the binding site mimics in conjunction withmore » the spectroscopic strategy employed here for the determination of this important pharmaceutical in clinical or even environmental samples.« less

The GEISA Spectroscopic Database System in its latest Edition

NASA Astrophysics Data System (ADS)

Jacquinet-Husson, N.; Crépeau, L.; Capelle, V.; Scott, N. A.; Armante, R.; Chédin, A.

2009-04-01

GEISA (Gestion et Etude des Informations Spectroscopiques Atmosphériques: Management and Study of Spectroscopic Information)[1] is a computer-accessible spectroscopic database system, designed to facilitate accurate forward planetary radiative transfer calculations using a line-by-line and layer-by-layer approach. It was initiated in 1976. Currently, GEISA is involved in activities related to the assessment of the capabilities of IASI (Infrared Atmospheric Sounding Interferometer on board the METOP European satellite -http://earth-sciences.cnes.fr/IASI/)) through the GEISA/IASI database[2] derived from GEISA. Since the Metop (http://www.eumetsat.int) launch (October 19th 2006), GEISA/IASI is the reference spectroscopic database for the validation of the level-1 IASI data, using the 4A radiative transfer model[3] (4A/LMD http://ara.lmd.polytechnique.fr; 4A/OP co-developed by LMD and Noveltis with the support of CNES). Also, GEISA is involved in planetary research, i.e.: modelling of Titan's atmosphere, in the comparison with observations performed by Voyager: http://voyager.jpl.nasa.gov/, or by ground-based telescopes, and by the instruments on board the Cassini-Huygens mission: http://www.esa.int/SPECIALS/Cassini-Huygens/index.html. The updated 2008 edition of GEISA (GEISA-08), a system comprising three independent sub-databases devoted, respectively, to line transition parameters, infrared and ultraviolet/visible absorption cross-sections, microphysical and optical properties of atmospheric aerosols, will be described. Spectroscopic parameters quality requirement will be discussed in the context of comparisons between observed or simulated Earth's and other planetary atmosphere spectra. GEISA is implemented on the CNES/CNRS Ether Products and Services Centre WEB site (http://ether.ipsl.jussieu.fr), where all archived spectroscopic data can be handled through general and user friendly associated management software facilities. More than 350 researchers are registered for on line use of GEISA. Refs: 1. Jacquinet-Husson N., N.A. Scott, A. Chédin,L. Crépeau, R. Armante, V. Capelle, J. Orphal, A. Coustenis, C. Boonne, N. Poulet-Crovisier, et al. THE GEISA SPECTROSCOPIC DATABASE: Current and future archive for Earth and planetary atmosphere studies. JQSRT, 109, 1043-1059, 2008 2. Jacquinet-Husson N., N.A. Scott, A. Chédin, K. Garceran, R. Armante, et al. The 2003 edition of the GEISA/IASI spectroscopic database. JQSRT, 95, 429-67, 2005. 3. Scott, N.A. and A. Chedin, 1981: A fast line-by-line method for atmospheric absorption computations: The Automatized Atmospheric Absorption Atlas. J. Appl. Meteor., 20,556-564.

Electrochemical and spectroscopic characterization of surface sol-gel processes.

PubMed

Chen, Xiaohong; Wilson, George S

2004-09-28

(3-Mercaptopropyl)trimethoxysilane (MTS) forms a unique film on a platinum substrate by self-assembly and sol-gel cross-linking. The gelating and drying states of the self-assembled MTS sol-gel films were probed by use of electrochemical and spectroscopic methods. The thiol moiety was the only active group within the sol-gel network. Gold nanoparticles were employed to detect the availability of the thiol group and their interaction further indicated the physicochemical states of the sol-gel inner structure. It was found that the thiol groups in the open porous MTS aerogel matrix were accessible to the gold nanoparticles while thiol groups in the compact MTS xerogel network were not accessible to the gold nanoparticles. The characteristics of the sol-gel matrix change with time because of its own irreversible gelating and drying process. The present work provides direct evidence of gold nanoparticle binding with thiol groups within the sol-gel structures and explains the different permeability of "aerogel" and "xerogel" films of MTS on the basis of electrochemical and spectroscopic results. Two endogenous species, hydrogen peroxide and ascorbic acid, were used to test the permeability of the self-assembled sol-gel film in different states. The MTS xerogel film on the platinum electrode was extremely selective against ascorbic acid while maintaining high sensitivity to hydrogen peroxide in contrast to the relatively high permeability of ascorbic acid in the MTS aerogel film. This study showed the potential of the MTS sol-gel film as a nanoporous material in biosensor development.

Lasers for Frontier Spectroscopy

NASA Astrophysics Data System (ADS)

Baldacchini, Giuseppe

The first laser has been invented in 1960 by using the red light from a ruby crystal, and since then the laser field exploded almost exponentially, and thousands of different materials, in the state of solids, liquids, vapors, gases, plasmas, and elementary particles have lased up to now from less than I Å to more than 1 mm. Many of them have been used with outstanding results both in basic science, and in industrial and commercial applications, by changing for ever the same lifestyle of humankind. As far as spectroscopy is concerned, the laser light has started an unprecedented revolution because of its unique properties as monochromaticity, coherence, power, brightness and short-pulse regime, unrivaled by any other natural and artificial light source. Spectroscopy applications increased qualitatively and quantitatively with the laser sources themselves, and they are still proceeding in parallel with the moving of the laser field towards new territories. Apart the opening up of new regions of the electromagnetic spectrum, like the terahertz gap, and the outstanding increase of the output power which is giving rise to completely new spectroscopic effects, the improvement of laser sources and auxiliary equipment is producing a growth of traditional laser spectroscopy with superior resolution and sensitivity. Moreover, spectroscopic techniques and laser light contributed to the development of new chemical and physical processes which have been used to fabricate photonic materials with new spectroscopic properties enriching the laser field itself, in a virtuous cycle spectroscopy→aser→material and back to spectroscopy with no end in sight.

Development status of the mid-infrared two-field camera and spectrograph MIMIZUKU for the TAO 6.5-m Telescope

NASA Astrophysics Data System (ADS)

Kamizuka, Takafumi; Miyata, Takashi; Sako, Shigeyuki; Ohsawa, Ryou; Okada, Kazushi; Uchiyama, Masahito S.; Mori, Kiyoshi; Yamaguchi, Jumpei; Asano, Kentaro; Uchiyama, Mizuho; Sakon, Itsuki; Onaka, Takashi; Kataza, Hirokazu; Hasegawa, Sunao; Usui, Fumihiko; Takato, Naruhisa; Aoki, Tsutomu; Doi, Mamoru; Kato, Natsuko M.; Kitagawa, Yutaro; Kobayakawa, Yutaka; Kohno, Kotaro; Konishi, Masahiro; Minezaki, Takeo; Morokuma, Tomoki; Motohara, Kentaro; Ohashi, Hirofumi; Soyano, Takao; Takahashi, Hidenori; Tamura, Yoichi; Tanabé, Toshihiko; Tanaka, Masuo; Tarusawa, Ken'ichi; Terao, Yasunori; Yoshii, Yuzuru

2016-08-01

MIMIZUKU is the first-generation mid-infrared instrument for the university of Tokyo Atacama Observatory (TAO) 6.5-m telescope. MIMIZUKU provides imaging and spectroscopic monitoring capabilities in a wide wavelength range from 2 to 38 μm, including unique bands like 2.7-μm and 30-μm band. Recently, we decided to add spectroscopic functions, KL-band mode (λ= 2.1-4.0 μm R =λ/Δλ 210) and 2.7-μm band mode ( λ= 2.4-2.95 μm R 620), and continuous spectroscopic coverage from 2.1 to 26 μm is realized by this update. Their optical designing is completed, and fabrications of optical elements are ongoing. As recent progress, we also report the completion of the cryogenic system and optics. The cryogenic system has been updated by changing materials and structures of thermal links, and the temperatures of the optical bench and detector mounting stages finally achieved required temperatures. Their stability against instrument attitude is also confirmed through an inclination test. As for the optics, its gold-plated mirrors have been recovered from galvanic corrosion by refabrication and reconstruction. Enough image quality and stability are confirmed by room-temperature tests. MIMIZUKU is intended to be completed in this autumn, and commissioning at the Subaru telescope and scientific operations on the TAO telescope are planned in 2017 and around 2019, respectively. In this paper, these development activities and future prospects of MIMIZUKU are reported.

Explosives detection and identification using surface plasmon-coupled emission

NASA Astrophysics Data System (ADS)

Ja, Shiou-Jyh

2012-06-01

To fight against the explosives-related threats in defense and homeland security applications, a smarter sensing device that not only detects but differentiates multiple true threats from false positives caused by environmental interferents is essential. A new optical detection system is proposed to address these issues by using the temporal and spectroscopic information generated by the surface plasmon coupling emission (SPCE) effect. Innovative SPCE optics have been designed using Zemax software to project the fluorescence signal into clear "rainbow rings" on a CCD with subnanometer wavelength resolution. The spectroscopic change of the fluorescence signal and the time history of such changes due to the presence of a certain explosive analyte are unique and can be used to identify explosives. Thanks to high optical efficiency, reporter depositions as small as 160-μm in diameter can generate a sufficient signal, allowing a dense array of different reporters to be interrogated with wavelength multiplexing and detect a wide range of explosives. We have demonstrated detection and classification of explosives, such as TNT, NT, NM, RDX, PETN, and AN, with two sensing materials in a prototype.

[Spectral Analysis about the Pharmaceutical Cocrystal Formation of Piracetam and 3-Hydroxybenzoic Acid].

PubMed

Zhang, Hui-li; Xia, Yi; Hong, Zhi; Du, Yong

2015-07-01

Pharmaceutical cocrystal can improve physical and chemical properties of active pharmaceutical ingredient (API), meanwhile this feature has shown great potential in improving the pharmaceutical's properties and characteristics. In this study, cocrystal formation between piracetam and 3-hydroxybenzoic acid (3HBA) using grinding method has been characterized by Fourier transform infrared (FTIR), Raman and terahertz (THz) spectroscopical techniques. The vibrational modes of different motions are obtained by the assignment of the peaks in the spectra of the starting materials and the cocrystal components. FTIR, Raman and THz spectroscopical results show that the vibrational modes of the cocrystal are different from those of the starting materials. In addition, the dynamic process of the above cocrystal formation is investigated in-depth with Raman and THz spec- tra. Piracetam-3HBA cocrystal is formed pretty fast in first several minutes, and then the formation rate becomes slow. After 35 minutes, such formation process has been completed. The results offer the theoretical benchmark and unique means for real-time monitoring pharmaceutical cocrystal formation and also the corresponding quantitative analysis in the pharmaceutical field.

In vivo detection of SERS-encoded plasmonic nanostars in human skin grafts and live animal models.

PubMed

Register, Janna K; Fales, Andrew M; Wang, Hsin-Neng; Norton, Stephen J; Cho, Eugenia H; Boico, Alina; Pradhan, Sulolit; Kim, Jason; Schroeder, Thies; Wisniewski, Natalie A; Klitzman, Bruce; Vo-Dinh, Tuan

2015-11-01

Surface-enhanced Raman scattering (SERS)-active plasmonic nanomaterials have become a promising agent for molecular imaging and multiplex detection. Among the wide variety of plasmonics-active nanoparticles, gold nanostars offer unique plasmon properties that efficiently induce strong SERS signals. Furthermore, nanostars, with their small core size and multiple long thin branches, exhibit high absorption cross sections that are tunable in the near-infrared region of the tissue optical window, rendering them efficient for in vivo spectroscopic detection. This study investigated the use of SERS-encoded gold nanostars for in vivo detection. Ex vivo measurements were performed using human skin grafts to investigate the detection of SERS-encoded nanostars through tissue. We also integrated gold nanostars into a biocompatible scaffold to aid in performing in vivo spectroscopic analyses. In this study, for the first time, we demonstrate in vivo SERS detection of gold nanostars using small animal (rat) as well as large animal (pig) models. The results of this study establish the usefulness and potential of SERS-encoded gold nanostars for future use in long-term in vivo analyte sensing.

Determination of spectroscopic properties of atmospheric molecules from high resolution vacuum ultraviolet cross section and wavelength measurements

NASA Technical Reports Server (NTRS)

Parkinson, W. H.; Yoshino, K.; Freeman, D. E.

1993-01-01

An account is given of progress during the six-month period 1 Nov. 1992 to 30 Apr. 1993 on work on (1) cross section measurements of the Schumann-Runge continuum; (2) the determination of the predissociation linewidths of the Schumann-Runge bands of O2; (3) the determination of the molecular constants of the ground state of O2; (4) cross section measurements of CO2 in wavelength region 120-170 nm; and (4) determination of dissociation energy of O2. The experimental investigations are effected at high resolution with a 6.65 m scanning spectrometer which is, by virtue of its small instrumental width (FWHM = 0.0013 nm), uniquely suitable for cross section measurements of molecular bands with discrete rotational structure. Below 175 nm and in the region of the S-R continuum, synchrotron radiation is suitable for cross section measurements. All of these spectroscopic measurements are needed for accurate calculations of the production of atomic oxygen and penetration of solar radiation into the Earth's atmosphere.

Photoacoustic spectroscopic studies of polycyclic aromatic hydrocarbons

NASA Astrophysics Data System (ADS)

Zaidi, Zahid H.; Kumar, Pardeep; Garg, R. K.

1999-02-01

Because of their involvement in environmental pollutants, in carcinogenic activity, plastics, pharmaceuticals, synthesis of some laser dyes and presence in interstellar space etc., Polycyclic aromatic hydrocarbons (PAHs) are important. As their structure and properties can be varied systematically, they form a beautiful class of molecules for experimental and quantum chemical investigations. These molecules are being studied for last several years by using conventional spectroscopy. In recent years, Photoacoustic (PA) spectroscopy has emerged as a new non-destructive technique with unique capability and sensitivity. The PA effect is the process of generation of acoustic waves in a sample resulting from the absorption of photons. This technique not only reveals non- radiative transitions but also provides information about forbidden singlet-triplet transitions which are not observed normally by the conventional spectroscopy. The present paper deals with the spectroscopic studies of some PAH molecules by PA spectroscopy in the region 250 - 400 nm. The CNDO/S-CI method is used to calculate the electronic transitions with the optimized geometries. A good agreement is found between the experimental and calculated results.

Wind Variability in Intermediate Luminosity B Supergiants

NASA Technical Reports Server (NTRS)

Massa, Derck

1996-01-01

This study used the unique spectroscopic diagnostics of intermediate luminosity B supergiants to determine the ubiquity and nature of wind variability. Specifically, (1) A detailed analysis of HD 64760 demonstrated massive ejections into its wind, provided the first clear demonstration of a 'photospheric connection' and ionization shifts in a stellar wind; (2) The international 'IUE MEGA campaign' obtained unprecedented temporal coverage of wind variability in rapidly rotating stars and demonstrated regularly repeating wind features originating in the photosphere; (3) A detailed analysis of wind variability in the rapidly rotating B1 Ib, gamma Ara demonstrated a two component wind with distinctly different mean states at different epochs; (4) A follow-on campaign to the MEGA project to study slowly rotating stars was organized and deemed a key project by ESA/NASA, and will obtain 30 days of IUE observations in May-June 1996; and (5) A global survey of archival IUE time series identified recurring spectroscopic signatures, identified with different physical phenomena. Items 4 and 5 above are still in progress and will be completed this summer in collaboration with Raman Prinja at University College, London.

Spectroscopic and calorimetric studies on the interaction between PAMAM G4-OH and 5-fluorouracil in aqueous solutions

NASA Astrophysics Data System (ADS)

Buczkowski, Adam; Urbaniak, Pawel; Piekarski, Henryk; Palecz, Bartlomiej

2017-01-01

The results of spectroscopic measurements (an increase in solubility, equilibrium dialysis, 1H NMR titration) and calorimetric measurements (isothermal titration ITC) indicate spontaneous (ΔG < 0) binding of 5-fluorouracil molecules by PAMAM G4-OH dendrimer with terminal hydroxyl groups in an aqueous solution. PAMAM G4-OH dendrimer bonds about n = 8 ± 1 molecules of the drug with an equilibrium constant of K = 70 ± 10. The process of saturating the dendrimer active sites by the drug molecules is exothermal (ΔH < 0) and is accompanied by an advantageous change in entropy (ΔS > 0). The parameters of binding 5-fluorouracil by PAMAM G4-OH dendrimer were compared with those of binding this drug by the macromolecules of PAMAM G3-OH and G5-OH.

A detailed spectroscopic study on the interaction of Rhodamine 6G with human hemoglobin.

PubMed

Mandal, Paulami; Bardhan, Munmun; Ganguly, Tapan

2010-05-03

UV-vis, time-resolved fluorescence and circular dichroism spectroscopic investigations have been made to reveal the nature of the interactions between xanthene dye Rhodamine 6G and the well known protein hemoglobin. From the analysis of the steady-state and time-resolved fluorescence quenching of Rhodamine 6G in aqueous solutions in presence of hemoglobin, it is revealed that the quenching is static in nature. The primary binding pattern between Rhodamine and hemoglobin has been interpreted as combined effect of hydrophobic association and electrostatic interaction. The binding constants, number of binding sites and thermodynamic parameters at various pH of the environment have been computed. The binding average distance between the energy donor Rhodamine and acceptor hemoglobin has been determined from the Forster's theory. Copyright 2010 Elsevier B.V. All rights reserved.

THE NASA AMES POLYCYCLIC AROMATIC HYDROCARBON INFRARED SPECTROSCOPIC DATABASE: THE COMPUTED SPECTRA

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

Bauschlicher, C. W.; Ricca, A.; Boersma, C.

The astronomical emission features, formerly known as the unidentified infrared bands, are now commonly ascribed to polycyclic aromatic hydrocarbons (PAHs). The laboratory experiments and computational modeling done at the NASA Ames Research Center to create a collection of PAH IR spectra relevant to test and refine the PAH hypothesis have been assembled into a spectroscopic database. This database now contains over 800 PAH spectra spanning 2-2000 {mu}m (5000-5 cm{sup -1}). These data are now available on the World Wide Web at www.astrochem.org/pahdb. This paper presents an overview of the computational spectra in the database and the tools developed to analyzemore » and interpret astronomical spectra using the database. A description of the online and offline user tools available on the Web site is also presented.« less

A spectroscopic and photometric study of the unique pre- main sequence system KH 15D

NASA Astrophysics Data System (ADS)

Hamilton, Catrina Marie

2004-09-01

As a class, T Tauri stars are YSOs, some which are surrounded by circumstellar disks, and are recognized as the final stage of low-mass star formation. They also represent the earliest stage of stellar evolution that is optically visible, and, therefore, can be easily studied in detail. Understanding the processes through which these young stars interact with and eventually disperse their circumstellar disks is critical for understanding how they evolve from the T Tauri phase to the zero age main sequence (ZAMS), and how this affects the formation of planets, as well as their rotational evolution. KH 15D is a unique eclipsing system that could provide invaluable insight into the evolution of circumstellar disk material, as well as clues to the close stellar environment. Discovered in 1997, this star system has been observed to undergo an eclipse every 48 days in which the star's light is diminished by 3.5 magnitudes. What is so unusual about the eclipse is that the length of the eclipse has evolved over time, growing in length from 16 days initially, to ˜25 days in 2002/2003. Evolution of disk material on these timescales has never been observed before, and therefore provides us with a unique opportunity to refine our theories about remnant disks around young stars, how they transition, possibly into planets, and what role they play as the star matures and arrives on the zero age main sequence. Additionally, high resolution spectra obtained at specific phases during the December 2001 eclipse showed that as the obscuring matter cut across the star, dramatic spectral changes in the Hα and Hβ lines were seen. Its unique eclipse produces a “natural coronographic” effect in which the stellar photosphere is occulted, revealing details of its magnetosphere and surroundings during eclipse. There is evidence that the weak-lined T Tauri star (WTTS) central to the system is actively accreting gas, although probably not at the rate of a typical classical T Tauri star, calling into question the common practice of associating WTTS characteristics with the absence of an accretion disk. Here I present an investigation of the photometric and spectroscopic properties of the KH 15D eclipsing system, and discuss the implications that this system holds for the future research of T Tauri stars.

Geomorphological and Spectrophotometric Study of Philae Landing Site A

NASA Astrophysics Data System (ADS)

Pajola, M.; La Forgia, F.; Giacomini, L.; Oklay, N.; Massironi, M.; Bertini, I.; Simioni, E.; Marzari, F.; Barbieri, C.; Naletto, G.; Groussin, O.; Lazzarin, M.; Scholten, F.; Preusker, F.; Fornasier, S.; Vincent, J. B.; Sierks, H.

2015-10-01

On August 6, 2014, the European Space Agency's Rosetta spacecraft started orbiting the Jupiter family comet 67P/Churyumov-Gerasimenko (hereafter 67P). Afterwards, the OSIRIS instrument (Optical, Spectroscopic and Infrared Remote Imaging System [1]), got the highest-resolution-ever images of a cometary nucleus, reaching the unprecedented scale of 50 cm/px. A brief description of OSIRIS early analysis on the nucleus structure and activity of 67P is available in [2]. Despite its small dimensions, #4 km diameter, 67P shows a morphological diversity that is still puzzling the cometary community: boulders [3], highreflectivity particle clusters [4], local fracturing [5], pits [6], as well as dust covered terrains [7], are only few examples that can be found on 67P. Since the Rosetta arrival, an extremely detailed analysis of 67P surface has been performed to select five different landing sites candidates for the lander Philae. By using the OSIRIS images the comet shape model [8] has been produced to study the slope constraints, as well as the identification and measurements of boulders and production of hazard maps of the landing spots [3]. A final landing site, called Agilkia and located on the smaller lobe of the comet, was announced on October 15, 2014. Here, Philae, on November 12, 2014, made its historic comet touchdown [9]. Despite its unique scientific potential, one of the five finalists, called "site A", was avoided due to higher risks with respect to Agilkia, during both the landing phase and the surface operations. This area is located on the bigger lobe of the comet, on the Seth region [10] facing the Hathor cliff. Site A (Fig. 1) is close to the 'neck' region, i.e. the connecting bridge between the two lobes, where the main dust jet activity has been observed since the Rosetta arrival. This area is the biggest terrace of Seth region, delimited in the upper part by a steep wall showing multiple niches, strata heads and smaller terraces. Moreover, between the 5 finalists, this site has the unique value to provide detailed analysis of the multiple fractures present on its cliff and on the neighboring Hathor. Figure 1: Site A as imaged by the OSIRIS NAC camera on 6 August 2014 at 02:20:12 UT. The distance from the comet center is 117.24 km, the scale is 2.17 m/px. EPSC Abstracts Vol. 10, EPSC2015-526, 2015 European Planetary Science Congress 2015 c Author(s) 2015 EPSC European Planetary Science Congress We here present the geomorphological map coupled with the size-frequency distributions of boulders # 2 m located on the different types of terrains here identified, such as outcropping layered terrains, gravitational accumulation deposits, taluses and fine particle deposits. Gravitational slopes, derived through the 67P shape model by assuming uniform density, have been used to characterize and better interpret the various terrains. Moreover, we show the spectrophotometric properties of the area, studied through images taken by OSIRIS NAC with a scale of 50 cm/px. Albedo maps, as well as surface reflectance spectra have been obtained by taking advantage of the shape model and DTM in order to correct for the illumination and observing conditions of the terrain. This multidisciplinary analysis highlights that different types of deposits show different photometric properties.

Biophysical influence of isocarbophos on bovine serum albumin: Spectroscopic probing

NASA Astrophysics Data System (ADS)

Zhang, Hua-xin; Zhou, Ying; Liu, E.

Isocarbophos (ICP) is a phosphorous pesticide with high toxicity. It has been detected in several kinds of food and therefore can enter human body. In this paper, spectroscopic approaches including three-dimensional fluorescence (3D-FL) spectroscopy, UV-visible absorption spectroscopy and circular dichroism (CD) spectroscopy were employed to explore the binding of ICP to bovine serum albumin (BSA) at simulated physiological conditions. It was found that the fluorescence quenching of BSA was caused by the formation of ICP-BSA complex at ground state and belonged to static quenching mechanism. The binding constants, the number of binding sites, enthalpy change (ΔHθ), Gibbs free energy change (ΔGθ) and entropy change (ΔSθ) were calculated at four different temperatures according to Scatchard model and thermodynamic equations. To identify the binding location, fluorescence probe techniques were used. The results showed that warfarin, an acknowledged site marker for BSA, could be partially replaced by ICP when ICP was added to warfarin-BSA systems, which demonstrated that ICP primarily bound on Sudlow's site I in domain IIA of BSA molecule. The distance r (3.06 nm) between donor (Trp-212) and acceptor (ICP) was obtained based on Förster's non-radiation fluorescence resonance energy transfer (FRET) theory. Furthermore, the CD spectral results indicated that the secondary structure of BSA was changed in presence of ICP. The study is helpful to evaluating the toxicology of ICP and understanding its effects on the function of protein during the blood transportation process.

Detection of cervical intraepithelial neoplasias and cancers in cervical tissue by in vivo light scattering

PubMed Central

Mourant, Judith R.; Bocklage, Thérese J.; Powers, Tamara M.; Greene, Heather M.; Dorin, Maxine H.; Waxman, Alan G.; Zsemlye, Meggan M.; Smith, Harriet O.

2009-01-01

Objective To examine the utility of in vivo elastic light scattering measurements to identify cervical intraepithelial neoplasias (CIN) 2/3 and cancers in women undergoing colposcopy and to determine the effects of patient characteristics such as menstrual status on the elastic light scattering spectroscopic measurements. Materials and Methods A fiber optic probe was used to measure light transport in the cervical epithelium of patients undergoing colposcopy. Spectroscopic results from 151 patients were compared with histopathology of the measured and biopsied sites. A method of classifying the measured sites into two clinically relevant categories was developed and tested using five-fold cross-validation. Results Statistically significant effects by age at diagnosis, menopausal status, timing of the menstrual cycle, and oral contraceptive use were identified, and adjustments based upon these measurements were incorporated in the classification algorithm. A sensitivity of 77±5% and a specificity of 62±2% were obtained for separating CIN 2/3 and cancer from other pathologies and normal tissue. Conclusions The effects of both menstrual status and age should be taken into account in the algorithm for classifying tissue sites based on elastic light scattering spectroscopy. When this is done, elastic light scattering spectroscopy shows good potential for real-time diagnosis of cervical tissue at colposcopy. Guiding biopsy location is one potential near-term clinical application area, while facilitating ”see and treat” protocols is a longer term goal. Improvements in accuracy are essential. PMID:20694193

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

NASA Astrophysics Data System (ADS)

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

2015-03-01

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

Spectroscopic Biomarkers for Monitoring Wound Healing and Infection in Combat Wounds

DTIC Science & Technology

2013-10-01

disruption, blastwave-associated pressure injuries, air, thrombotic, and fat embolism , and compartment syndrome. In the treatment of such complex...often associated with overt vascular injury. These injuries include traumatic amputations, open fractures , crush injuries, burns, acute vascular...patients. While Task 1c was initiated, Raman spectra of different anatomical sites of volunteers looked very similar to skin and fat . The Raman

Photoelectron Diffraction and Holography Studies of 2D Materials and Interfaces

NASA Astrophysics Data System (ADS)

Kuznetsov, Mikhail V.; Ogorodnikov, Ilya I.; Usachov, Dmitry Yu.; Laubschat, Clemens; Vyalikh, Denis V.; Matsui, Fumihiko; Yashina, Lada V.

2018-06-01

Photoelectron diffraction (XPD) and holography (XPH) are powerful spectroscopic methods that allow comprehensive exploration and characterization of certain structural properties of materials, in particular those of 2D systems and interfaces. Recent developments in XPD and XPH are especially impressive when they are applied to partially disordered systems such as intercalation compounds, doped graphene, buffer layers or adsorbates and imperfectly ordered germanene and phoshporene. In our brief review, we sum up the advances in XPD and XPH studies of 2D materials and discuss the unique opportunities granted by these two interrelated methods.

Electron anions and the glass transition temperature.

PubMed

Johnson, Lewis E; Sushko, Peter V; Tomota, Yudai; Hosono, Hideo

2016-09-06

Properties of glasses are typically controlled by judicious selection of the glass-forming and glass-modifying constituents. Through an experimental and computational study of the crystalline, molten, and amorphous [Ca12Al14O32](2+) ⋅ (e(-))2, we demonstrate that electron anions in this system behave as glass modifiers that strongly affect solidification dynamics, the glass transition temperature, and spectroscopic properties of the resultant amorphous material. The concentration of such electron anions is a consequential control parameter: It invokes materials evolution pathways and properties not available in conventional glasses, which opens a unique avenue in rational materials design.

Facile Route to Rare Heterobimetallic Aluminum-Copper and Aluminum-Zinc Selenide Clusters.

PubMed

Li, Bin; Li, Jiancheng; Liu, Rui; Zhu, Hongping; Roesky, Herbert W

2017-03-20

Heterobimetallic aluminum-copper and aluminum-zinc clusters were prepared from the reaction of LAl(SeH) 2 [1; L = HC(CMeNAr) 2 and Ar = 2,6-iPr 2 C 6 H 3 ] with (MesCu) 4 and ZnEt 2 , respectively. The resulting clusters with the core structures of Al 2 Se 4 Cu 4 and Al 2 Se 4 Zn 3 exhibit unique metal-organic frameworks. This is a novel pathway for the synthesis of aluminum-copper and aluminum-zinc selenides. The products have been characterized by spectroscopic methods and single-crystal X-ray structural characterization.

A New Star-shaped Carbazole Derivative with Polyhedral Oligomeric Silsesquioxane Core: Crystal Structure and Unique Photoluminescence Property.

PubMed

Xu, Zixuan; Yu, Tianzhi; Zhao, Yuling; Zhang, Hui; Zhao, Guoyun; Li, Jianfeng; Chai, Lanqin

2016-01-01

A new inorganic–organic hybrid material based on polyhedral oligomeric silsesquioxane (POSS) capped with carbazolyl substituents, octakis[3-(carbazol-9-yl)propyldimethylsiloxy]-silsesquioxane (POSS-8Cz), was successfully synthesized and characterized. The X-ray crystal structure of POSS-8Cz were described. The photophysical properties of POSS-8Cz were investigated by using UV–vis,photoluminescence spectroscopic analysis. The hybrid material exhibits blue emission in the solution and the solid film.The morphology and thermal stablity properties were measured by X-ray diffraction (XRD) and TG-DTA analysis.

Enteridinines A and B from slime mold Enteridium lycoperdon.

PubMed

Rezanka, Tomás; Dvoráková, Radmila; Hanus, Lumír O; Dembitsky, Valery M

2004-02-01

Two novel deoxysugar esters, named enteridinines A and B, were isolated from the slime mold Enteridium lycoperdon. Their structures, including the absolute configurations of the hydroxyl and methyl groups, were determined by means of extensive spectroscopic data such as UV, IR, MS, 1D and 2D NMR spectra. Enteridinines A and B have unique structures containing 1,7-dioxaspiro[5.5]undecanes with an O-beta-D-mycarosyl-(1-->4)-beta-D-olivosyl and an O-beta-L-olivomycosyl-(1-->4)-beta-D-amicetosyl-(1-->4)-beta-L-digitoxosyl unit, respectively, and showed growth inhibitory activities against Gram positive bacteria.

H2 Emission Nebulosity Associated with KH 15D

NASA Astrophysics Data System (ADS)

Tokunaga, A. T.; Dahm, S.; Gässler, W.; Hayano, Yutaka; Hayashi, Masahiko; Iye, Masanori; Kanzawa, Tomio; Kobayashi, Naoto; Kamata, Yukiko; Minowa, Yosuke; Nedachi, Ko; Oya, Shin; Pyo, Tae-Soo; Saint-Jacques, D.; Terada, Hiroshi; Takami, Hideki; Takato, Naruhisa

2004-01-01

An H2 emission filament is found in close proximity to the unique object KH 15D using the adaptive optics system of the Subaru Telescope. The morphology of the filament, the presence of spectroscopic outflow signatures observed by Hamilton et al., and the detection of extended H2 emission from KH 15D by Deming, Charbonneau, & Harrington suggest that this filament arises from shocked H2 in an outflow. The filament extends about 15" to the north of KH 15D. Based on data collected at Subaru Telescope, which is operated by the National AstronomiObservatory of Japan.

AK Sco: a tidally induced atmospheric dynamo in a pre-main sequence binary?

NASA Astrophysics Data System (ADS)

Gómez de Castro, A. I.

2009-02-01

AK Sco is a unique source: a 10-30 Myrs old pre-main sequence spectroscopic binary composed by two nearly equal F5 stars that at periastron are separated by barely eleven stellar radii so, the stellar magnetospheres fill the Roche lobe at periastron. The orbit is not yet circularized (e = 0.47) and very strong tides are expected. This makes of AK Sco, the ideal laboratory to study the effect of gravitational tides in the stellar magnetic field building up during pre-main sequence evolution. Evidence of this effect is reported in this contribution.

VizieR Online Data Catalog: Hot subdwarf stars in LAMOST DR1 (Luo+, 2016)

NASA Astrophysics Data System (ADS)

Luo, Y.-P.; Nemeth, P.; Liu, C.; Deng, L.-C.; Han, Z.-W.

2018-01-01

We present a catalog of 166 spectroscopically identified hot subdwarf stars from LAMOST DR1, 44 of which show the characteristics of cool companions in their optical spectra. Atmospheric parameters of 122 subdwarf stars with non-composite spectra were measured by fitting the profiles of hydrogen (H) and helium (He) lines with synthetic spectra from non-LTE model atmospheres. A unique property of our sample is that it covers a large range in apparent magnitude and galactic latitude, therefore it contains a mix of stars from different populations and galactic environments. (3 data files).

Computational Evaluation of Mg–Salen Compounds as Subsurface Fluid Tracers: Molecular Dynamics Simulations in Toluene–Water Mixtures and Clay Mineral Nanopores

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

Greathouse, Jeffery A.; Boyle, Timothy J.; Kemp, Richard A.

Molecular tracers that can be selectively placed underground and uniquely identified at the surface using simple on-site spectroscopic methods would significantly enhance subsurface fluid monitoring capabilities. To ensure their widespread utility, the solubility of these tracers must be easily tuned to oil- or water-wet conditions as well as reducing or eliminating their propensity to adsorb onto subsurface rock and/or mineral phases. In this work, molecular dynamics simulations were used to investigate the relative solubilities and mineral surface adsorption properties of three candidate tracer compounds comprising Mg–salen derivatives of varying degrees of hydrophilic character. Simulations in water–toluene liquid mixtures indicate thatmore » the partitioning of each Mg–salen compound relative to the interface is strongly influenced by the degree of hydrophobicity of the compound. Simulations of these complexes in fluid-filled mineral nanopores containing neutral (kaolinite) and negatively charged (montmorillonite) mineral surfaces reveal that adsorption tendencies depend upon a variety of parameters, including tracer chemical properties, mineral surface type, and solvent type (water or toluene). Simulation snapshots and averaged density profiles reveal insight into the solvation and adsorption mechanisms that control the partitioning of these complexes in mixed liquid phases and nanopore environments. As a result, this work demonstrates the utility of molecular simulation in the design and screening of molecular tracers for use in subsurface applications.« less

Computational Evaluation of Mg–Salen Compounds as Subsurface Fluid Tracers: Molecular Dynamics Simulations in Toluene–Water Mixtures and Clay Mineral Nanopores

DOE PAGES

Greathouse, Jeffery A.; Boyle, Timothy J.; Kemp, Richard A.

2018-04-11

Molecular tracers that can be selectively placed underground and uniquely identified at the surface using simple on-site spectroscopic methods would significantly enhance subsurface fluid monitoring capabilities. To ensure their widespread utility, the solubility of these tracers must be easily tuned to oil- or water-wet conditions as well as reducing or eliminating their propensity to adsorb onto subsurface rock and/or mineral phases. In this work, molecular dynamics simulations were used to investigate the relative solubilities and mineral surface adsorption properties of three candidate tracer compounds comprising Mg–salen derivatives of varying degrees of hydrophilic character. Simulations in water–toluene liquid mixtures indicate thatmore » the partitioning of each Mg–salen compound relative to the interface is strongly influenced by the degree of hydrophobicity of the compound. Simulations of these complexes in fluid-filled mineral nanopores containing neutral (kaolinite) and negatively charged (montmorillonite) mineral surfaces reveal that adsorption tendencies depend upon a variety of parameters, including tracer chemical properties, mineral surface type, and solvent type (water or toluene). Simulation snapshots and averaged density profiles reveal insight into the solvation and adsorption mechanisms that control the partitioning of these complexes in mixed liquid phases and nanopore environments. As a result, this work demonstrates the utility of molecular simulation in the design and screening of molecular tracers for use in subsurface applications.« less

Berkeley Supernova Ia Program - I. Observations, data reduction and spectroscopic sample of 582 low-redshift Type Ia supernovae

NASA Astrophysics Data System (ADS)

Silverman, Jeffrey M.; Foley, Ryan J.; Filippenko, Alexei V.; Ganeshalingam, Mohan; Barth, Aaron J.; Chornock, Ryan; Griffith, Christopher V.; Kong, Jason J.; Lee, Nicholas; Leonard, Douglas C.; Matheson, Thomas; Miller, Emily G.; Steele, Thea N.; Barris, Brian J.; Bloom, Joshua S.; Cobb, Bethany E.; Coil, Alison L.; Desroches, Louis-Benoit; Gates, Elinor L.; Ho, Luis C.; Jha, Saurabh W.; Kandrashoff, Michael T.; Li, Weidong; Mandel, Kaisey S.; Modjaz, Maryam; Moore, Matthew R.; Mostardi, Robin E.; Papenkova, Marina S.; Park, Sung; Perley, Daniel A.; Poznanski, Dovi; Reuter, Cassie A.; Scala, James; Serduke, Franklin J. D.; Shields, Joseph C.; Swift, Brandon J.; Tonry, John L.; Van Dyk, Schuyler D.; Wang, Xiaofeng; Wong, Diane S.

2012-09-01

In this first paper in a series, we present 1298 low-redshift (z ≲ 0.2) optical spectra of 582 Type Ia supernovae (SNe Ia) observed from 1989 to 2008 as part of the Berkeley Supernova Ia Program (BSNIP). 584 spectra of 199 SNe Ia have well-calibrated light curves with measured distance moduli, and many of the spectra have been corrected for host-galaxy contamination. Most of the data were obtained using the Kast double spectrograph mounted on the Shane 3 m telescope at Lick Observatory and have a typical wavelength range of 3300-10 400 Å, roughly twice as wide as spectra from most previously published data sets. We present our observing and reduction procedures, and we describe the resulting SN Database, which will be an online, public, searchable data base containing all of our fully reduced spectra and companion photometry. In addition, we discuss our spectral classification scheme (using the SuperNova IDentification code, SNID; Blondin & Tonry), utilizing our newly constructed set of SNID spectral templates. These templates allow us to accurately classify our entire data set, and by doing so we are able to reclassify a handful of objects as bona fide SNe Ia and a few other objects as members of some of the peculiar SN Ia subtypes. In fact, our data set includes spectra of nearly 90 spectroscopically peculiar SNe Ia. We also present spectroscopic host-galaxy redshifts of some SNe Ia where these values were previously unknown. The sheer size of the BSNIP data set and the consistency of our observation and reduction methods make this sample unique among all other published SN Ia data sets and complementary in many ways to the large, low-redshift SN Ia spectra presented by Matheson et al. and Blondin et al. In other BSNIP papers in this series, we use these data to examine the relationships between spectroscopic characteristics and various observables such as photometric and host-galaxy properties.

Framework for Site Characterization for Monitored Natural Attenuation of Volatile Organic Compounds in Ground Water

EPA Science Inventory

Monitored Natural Attenuation (MNA) is unique among remedial technologies in relying entirely on natural processes to achieve site-specific objectives. Site characterization is essential to provide site-specific data and interpretations for the decision-making process (i.e., to ...

Catalytic surface radical in dye-decolorizing peroxidase: a computational, spectroscopic and site-directed mutagenesis study

PubMed Central

Linde, Dolores; Pogni, Rebecca; Cañellas, Marina; Lucas, Fátima; Guallar, Victor; Baratto, Maria Camilla; Sinicropi, Adalgisa; Sáez-Jiménez, Verónica; Coscolín, Cristina; Romero, Antonio; Medrano, Francisco Javier; Ruiz-Dueñas, Francisco J.; Martínez, Angel T.

2014-01-01

Dye-decolorizing peroxidase (DyP) of Auricularia auricula-judae has been expressed in Escherichia coli as a representative of a new DyP family, and subjected to mutagenic, spectroscopic, crystallographic and computational studies. The crystal structure of DyP shows a buried haem cofactor, and surface tryptophan and tyrosine residues potentially involved in long-range electron transfer from bulky dyes. Simulations using PELE (Protein Energy Landscape Exploration) software provided several binding-energy optima for the anthraquinone-type RB19 (Reactive Blue 19) near the above aromatic residues and the haem access-channel. Subsequent QM/MM (quantum mechanics/molecular mechanics) calculations showed a higher tendency of Trp-377 than other exposed haem-neighbouring residues to harbour a catalytic protein radical, and identified the electron-transfer pathway. The existence of such a radical in H2O2-activated DyP was shown by low-temperature EPR, being identified as a mixed tryptophanyl/tyrosyl radical in multifrequency experiments. The signal was dominated by the Trp-377 neutral radical contribution, which disappeared in the W377S variant, and included a tyrosyl contribution assigned to Tyr-337 after analysing the W377S spectra. Kinetics of substrate oxidation by DyP suggests the existence of high- and low-turnover sites. The high-turnover site for oxidation of RB19 (kcat> 200 s−1) and other DyP substrates was assigned to Trp-377 since it was absent from the W377S variant. The low-turnover site/s (RB19 kcat ~20 s−1) could correspond to the haem access-channel, since activity was decreased when the haem channel was occluded by the G169L mutation. If a tyrosine residue is also involved, it will be different from Tyr-337 since all activities are largely unaffected in the Y337S variant. PMID:25495127

Co2+-doped diopside: crystal structure and optical properties

NASA Astrophysics Data System (ADS)

Gori, C.; Tribaudino, M.; Mezzadri, F.; Skogby, H.; Hålenius, U.

2018-05-01

Synthetic clinopyroxenes along the CaMgSi2O6-CaCoSi2O6 join were investigated by a combined chemical-structural-spectroscopic approach. Single crystals were synthesized by flux growth methods, both from Ca-saturated and Ca-deficient starting compositions. Single crystal structure refinements show that the incorporation of Co2+ at the octahedrally coordinated cation sites of diopside, increases the unit-cell as well as the M1 and the M2 polyhedral volumes. Spectroscopic investigations (UV-VIS-NIR) of the Ca-rich samples reveal three main optical absorption bands, i.e. 4 T 1g → 4 T 2g( F), 4 T 1g → 4 A 2g( F) and 4 T 1g → 4 T 1g( P) as expected for Co2+ at a six-coordinated site. The bands arising from the 4 T 1g → 4 T 2g( F) and the 4 T 1g → 4 T 1g( P) electronic transitions, are each split into two components, due to the distortions of the M1 polyhedron from ideal Oh-symmetry. In spectra of both types, a band in the NIR range at ca 5000 cm-1 is caused by the 4 A 2g → 4 T 1g( F) electronic transition in Co2+ in a cubic field in the M2 site. Furthermore, an additional component to a band system at 14,000 cm-1, due to electronic transitions in Co2+ at the M2 site, is recorded in absorption spectra of Ca-deficient samples. No variations in Dq and Racah B parameters for Co2+ at the M1 site in response to compositional changes, were demonstrated, suggesting complete relaxation of the M1 polyhedron within the CaMgSi2O6-CaCoSi2O6 solid solution.

Co2+-doped diopside: crystal structure and optical properties

NASA Astrophysics Data System (ADS)

Gori, C.; Tribaudino, M.; Mezzadri, F.; Skogby, H.; Hålenius, U.

2017-12-01

Synthetic clinopyroxenes along the CaMgSi2O6-CaCoSi2O6 join were investigated by a combined chemical-structural-spectroscopic approach. Single crystals were synthesized by flux growth methods, both from Ca-saturated and Ca-deficient starting compositions. Single crystal structure refinements show that the incorporation of Co2+ at the octahedrally coordinated cation sites of diopside, increases the unit-cell as well as the M1 and the M2 polyhedral volumes. Spectroscopic investigations (UV-VIS-NIR) of the Ca-rich samples reveal three main optical absorption bands, i.e. 4 T 1g → 4 T 2g(F), 4 T 1g → 4 A 2g(F) and 4 T 1g → 4 T 1g(P) as expected for Co2+ at a six-coordinated site. The bands arising from the 4 T 1g → 4 T 2g(F) and the 4 T 1g → 4 T 1g(P) electronic transitions, are each split into two components, due to the distortions of the M1 polyhedron from ideal Oh-symmetry. In spectra of both types, a band in the NIR range at ca 5000 cm-1 is caused by the 4 A 2g → 4 T 1g(F) electronic transition in Co2+ in a cubic field in the M2 site. Furthermore, an additional component to a band system at 14,000 cm-1, due to electronic transitions in Co2+ at the M2 site, is recorded in absorption spectra of Ca-deficient samples. No variations in Dq and Racah B parameters for Co2+ at the M1 site in response to compositional changes, were demonstrated, suggesting complete relaxation of the M1 polyhedron within the CaMgSi2O6-CaCoSi2O6 solid solution.

Catalytic surface radical in dye-decolorizing peroxidase: a computational, spectroscopic and site-directed mutagenesis study.

PubMed

Linde, Dolores; Pogni, Rebecca; Cañellas, Marina; Lucas, Fátima; Guallar, Victor; Baratto, Maria Camilla; Sinicropi, Adalgisa; Sáez-Jiménez, Verónica; Coscolín, Cristina; Romero, Antonio; Medrano, Francisco Javier; Ruiz-Dueñas, Francisco J; Martínez, Angel T

2015-03-01

Dye-decolorizing peroxidase (DyP) of Auricularia auricula-judae has been expressed in Escherichia coli as a representative of a new DyP family, and subjected to mutagenic, spectroscopic, crystallographic and computational studies. The crystal structure of DyP shows a buried haem cofactor, and surface tryptophan and tyrosine residues potentially involved in long-range electron transfer from bulky dyes. Simulations using PELE (Protein Energy Landscape Exploration) software provided several binding-energy optima for the anthraquinone-type RB19 (Reactive Blue 19) near the above aromatic residues and the haem access-channel. Subsequent QM/MM (quantum mechanics/molecular mechanics) calculations showed a higher tendency of Trp-377 than other exposed haem-neighbouring residues to harbour a catalytic protein radical, and identified the electron-transfer pathway. The existence of such a radical in H₂O₂-activated DyP was shown by low-temperature EPR, being identified as a mixed tryptophanyl/tyrosyl radical in multifrequency experiments. The signal was dominated by the Trp-377 neutral radical contribution, which disappeared in the W377S variant, and included a tyrosyl contribution assigned to Tyr-337 after analysing the W377S spectra. Kinetics of substrate oxidation by DyP suggests the existence of high- and low-turnover sites. The high-turnover site for oxidation of RB19 (k(cat) > 200 s⁻¹) and other DyP substrates was assigned to Trp-377 since it was absent from the W377S variant. The low-turnover site/s (RB19 k(cat) ~20 s⁻¹) could correspond to the haem access-channel, since activity was decreased when the haem channel was occluded by the G169L mutation. If a tyrosine residue is also involved, it will be different from Tyr-337 since all activities are largely unaffected in the Y337S variant.

Mineralogy, Abundance, and Hydration State of Sulfates and Chlorides at the Mars Pathfinder Landing Site

NASA Technical Reports Server (NTRS)

Zolotov, M. Y.; Kuzmin, R. O.; Shock, E. L.

2004-01-01

Detection of elevated concentrations of S and Cl at the landing sites of Viking 1 and 2 [1], and Mars Pathfinder (MP) [2-5] reveals the presence of sulfates and chlorides in soil and rock samples [1-10]. These data are consistent with the findings of Ca sulfates and NaCl in Martian meteorites [11,12], and with Earth-based spectroscopic observations [13,14] tentatively indicating the presence of sulfates on Mars. Although the correlation of S and Mg in Viking and MP samples could reveal the occurrence of Mg sulfate [1-10], the mineralogy of sulfates and chlorides remains unclear.

Laser Controlled Tunneling in a Vertical Optical Lattice

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

Beaufils, Q.; Tackmann, G.; Wang, X.

2011-05-27

Raman laser pulses are used to induce coherent tunneling between neighboring sites of a vertical 1D optical lattice. Such tunneling occurs when the detuning of a probe laser from the atomic transition frequency matches multiples of the Bloch frequency, allowing for a spectroscopic control of the coupling between Wannier-Stark (WS) states. In particular, we prepare coherent superpositions of WS states of adjacent sites, and investigate the coherence time of these superpositions by realizing a spatial interferometer. This scheme provides a powerful tool for coherent manipulation of external degrees of freedom of cold atoms, which is a key issue for quantummore » information processing.« less

Characterization of the binding of 2-mercaptobenzimidazole to bovine serum albumin.

PubMed

Teng, Yue; Zou, Luyi; Huang, Ming; Zong, Wansong

2015-04-01

2-Mercaptobenzimidazole (MBI) is widely utilized as a corrosion inhibitor, copper-plating brightener and rubber accelerator. The residue of MBI in the environment is potentially harmful to human health. In this article, the interaction of MBI with bovine serum albumin (BSA) was explored using spectroscopic and molecular docking methods under physiological conditions. The positively charged MBI can spontaneously bind with the negatively charged BSA through electrostatic forces with one binding site. The site marker competition experiments and the molecular docking study revealed that MBI bound into site II (subdomain IIIA) of BSA, which further led to some secondary structure and microenvironmental changes of BSA. This work provides useful information on understanding the toxicological actions of MBI at the molecular level. Copyright © 2015 John Wiley & Sons, Ltd.

Spectroscopic evidence for origins of size and support effects on selectivity of Cu nanoparticle dehydrogenation catalysts.

PubMed

Witzke, M E; Dietrich, P J; Ibrahim, M Y S; Al-Bardan, K; Triezenberg, M D; Flaherty, D W

2017-01-03

Selective dehydrogenation catalysts that produce acetaldehyde from bio-derived ethanol can increase the efficiency of subsequent processes such as C-C coupling over metal oxides to produce 1-butanol or 1,3-butadiene or oxidation to acetic acid. Here, we use in situ X-ray absorption spectroscopy and steady state kinetics experiments to identify Cu δ+ at the perimeter of supported Cu clusters as the active site for esterification and Cu 0 surface sites as sites for dehydrogenation. Correlation of dehydrogenation and esterification selectivities to in situ measures of Cu oxidation states show that this relationship holds for Cu clusters over a wide-range of diameters (2-35 nm) and catalyst supports and reveals that dehydrogenation selectivities may be controlled by manipulating either.

A Study of Ziegler–Natta Propylene Polymerization Catalysts by Spectroscopic Methods

PubMed Central

Tkachenko, Olga P.; Kucherov, Alexey V.; Kustov, Leonid M.; Virkkunen, Ville; Leinonen, Timo; Denifl, Peter

2017-01-01

Ziegler–Natta polymerization catalysts were characterized by a complex of surface- and bulk-sensitive methods (DRIFTS, XPS, ESR, and XAS = XANES + EXAFS). A diffuse-reflectance Fourier-transform IR spectroscopy (DRIFTS) study showed the presence of strong Lewis acid sites in different concentrations and absence of strong basic sites in the polymerization catalysts. X-ray photoelectron spectroscopy (XPS), electron-spin resonance (ESR), and (X-ray absorption near-edge structure (XANES) analysis revealed the presence of Ti4+, Ti3+, Ti2+, and Ti1+ species in the surface layers and in the bulk of catalysts. The samples under study differ drastically in terms of the number of ESR-visible paramagnetic sites. The EXAFS study shows the presence of a Cl atom as a nearest neighbor of the absorbing Ti atom. PMID:28772850

Probing Gas Adsorption in Zeolites by Variable-Temperature IR Spectroscopy: An Overview of Current Research.

PubMed

Garrone, Edoardo; Delgado, Montserrat R; Bonelli, Barbara; Arean, Carlos O

2017-09-15

The current state of the art in the application of variable-temperature IR (VTIR) spectroscopy to the study of (i) adsorption sites in zeolites, including dual cation sites; (ii) the structure of adsorption complexes and (iii) gas-solid interaction energy is reviewed. The main focus is placed on the potential use of zeolites for gas separation, purification and transport, but possible extension to the field of heterogeneous catalysis is also envisaged. A critical comparison with classical IR spectroscopy and adsorption calorimetry shows that the main merits of VTIR spectroscopy are (i) its ability to provide simultaneously the spectroscopic signature of the adsorption complex and the standard enthalpy change involved in the adsorption process; and (ii) the enhanced potential of VTIR to be site specific in favorable cases.

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

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

Westre, Tami E.

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

SUMMARY OF TECHNIQUES AND UNIQUE USES FOR DIRECT PUSH METHODS IN SITE CHARACTERIZATION ON CONTAMINATED FIELD SITES

EPA Science Inventory

Site characterization of subsurface contaminant transport is often hampered by a lack of knowledge of site heterogeneity and temporal variations in hydrogeochemistry. Two case studies are reviewed to illustrate the utility of macro-scale mapping information along with spatially-...

Ub-ISAP: a streamlined UNIX pipeline for mining unique viral vector integration sites from next generation sequencing data.

PubMed

Kamboj, Atul; Hallwirth, Claus V; Alexander, Ian E; McCowage, Geoffrey B; Kramer, Belinda

2017-06-17

The analysis of viral vector genomic integration sites is an important component in assessing the safety and efficiency of patient treatment using gene therapy. Alongside this clinical application, integration site identification is a key step in the genetic mapping of viral elements in mutagenesis screens that aim to elucidate gene function. We have developed a UNIX-based vector integration site analysis pipeline (Ub-ISAP) that utilises a UNIX-based workflow for automated integration site identification and annotation of both single and paired-end sequencing reads. Reads that contain viral sequences of interest are selected and aligned to the host genome, and unique integration sites are then classified as transcription start site-proximal, intragenic or intergenic. Ub-ISAP provides a reliable and efficient pipeline to generate large datasets for assessing the safety and efficiency of integrating vectors in clinical settings, with broader applications in cancer research. Ub-ISAP is available as an open source software package at https://sourceforge.net/projects/ub-isap/ .

Low temperature Mössbauer spectroscopic studies on Sm3+ doped Zn-Mn ferrites

NASA Astrophysics Data System (ADS)

Jagadeesha Angadi, V.; Kubrin, S. P.; Sarychev, D. A.; Matteppanavar, Shidaling; Rudraswamy, B.; Liu, Hsiang-Lin; Praveena, K.

2017-11-01

For the first time, we report on the low temperature Mössbauer spectroscopic study of Zn2+0.5Mn2+0.5Sm3+xFe3+2-xO4 (where x = 0.01-0.05) prepared by the modified solution combustion method using a mixture of urea and glucose as a fuel. The Mössbauer spectroscopy at room and low temperatures was applied to understand the magnetic properties of the samples. The room temperature Mössbauer spectroscopy results suggest that the occupation of the octahedral sites by Sm3+ ions leads to the distortion enhancement of 57Fe nuclei environments, which leads to an increase in quadrupole splitting Δ values of D2 and D3 doublets. The low temperature Mössbauer spectroscopy results indicate that the presence of Sm3+ ions in the octahedron sites causes the decrease in the number of Fe-O-Fe chains. The transformation of Mössbauer spectra doublets into Zeeman sextets is accompanied by a significant decrease in the magnitude IM of Mössbauer spectra intensity within the 0-1.2 mm/s velocity range normalized to its value at 300 K. This drop in the temperature dependence of IM allows one to obtain the magnetic phase transition temperature TM from the Mössbauer experiment.

A Study on the Interaction of Rhodamine B with Methylthioadenosine Phosphorylase Protein Sourced from an Antarctic Soil Metagenomic Library

PubMed Central

Bujacz, Anna; Wierzbicka-Woś, Anna; Kur, Józef

2013-01-01

The presented study examines the phenomenon of the fluorescence under UV light excitation (312 nm) of E. coli cells expressing a novel metagenomic-derived putative methylthioadenosine phosphorylase gene, called rsfp, grown on LB agar supplemented with a fluorescent dye rhodamine B. For this purpose, an rsfp gene was cloned and expressed in an LMG194 E. coli strain using an arabinose promoter. The resulting RSFP protein was purified and its UV-VIS absorbance spectrum and emission spectrum were assayed. Simultaneously, the same spectroscopic studies were carried out for rhodamine B in the absence or presence of RSFP protein or native E. coli proteins, respectively. The results of the spectroscopic studies suggested that the fluorescence of E. coli cells expressing rsfp gene under UV illumination is due to the interaction of rhodamine B molecules with the RSFP protein. Finally, this interaction was proved by a crystallographic study and then by site-directed mutagenesis of rsfp gene sequence. The crystal structures of RSFP apo form (1.98 Å) and complex RSFP/RB (1.90 Å) show a trimer of RSFP molecules located on the crystallographic six fold screw axis. The RSFP complex with rhodamine B revealed the binding site for RB, in the pocket located on the interface between symmetry related monomers. PMID:23383268

In vivo Diagnosis of Cervical Intraepithelial Neoplasia Using 337-nm- Excited Laser-Induced Fluorescence

NASA Astrophysics Data System (ADS)

Ramanujam, N.; Mitchell, M. F.; Mahadevan, A.; Warren, S.; Thomsen, S.; Silva, E.; Richards-Kortum, R.

1994-10-01

Laser-induced fluorescence at 337-nm excitation was used in vivo to differentiate neoplastic [cervical intraepithelial neoplasia (CIN)], nonneoplastic abnormal (inflammation and human papilloma viral infection), and normal cervical tissues. A colposcope (low-magnification microscope used to view the cervix with reflected light) was used to identify 66 normal and 49 abnormal (5 inflammation, 21 human papilloma virus infection, and 23 CIN) sites on the cervix in 28 patients. These sites were then interrogated spectroscopically. A two-stage algorithm was developed to diagnose CIN. The first stage differentiated histologically abnormal tissues from colposcopically normal tissues with a sensitivity, specificity, and positive predictive value of 92%, 90%, and 88%, respectively. The second stage differentiated preneoplastic and neoplastic tissues from nonneoplastic abnormal tissues with a sensitivity, specificity, and positive predictive value of 87%, 73%, and 74%, respectively. Spectroscopic differences were consistent with a decrease in the absolute contribution of collagen fluorescence, an increase in the absolute contribution of oxyhemoglobin attenuation, and an increase in the relative contribution of reduced nicotinamide dinucleotide phosphate [NAD(P)H] fluorescence as tissue progresses from normal to abnormal in the same patient. These results suggest that in vivo fluorescence spectroscopy of the cervix can be used to diagnose CIN at colposcopy.

Interactions of oxytetracycline with a smectite clay: a spectroscopic study with molecular simulations.

PubMed

Aristilde, Ludmilla; Marichal, Claire; Miéhé-Brendlé, Jocelyne; Lanson, Bruno; Charlet, Laurent

2010-10-15

Binding of antibiotics to clay minerals can decrease both their physical and biological availability in soils. To elucidate the binding mechanisms of tetracycline antibiotics on smectite clays as a function of pH, we probed the interactions of oxytetracycline (OTC) with Na-montmorillonite (MONT) using X-ray diffraction (XRD), infrared (IR), and solid-state nuclear magnetic resonance (NMR) spectroscopies, and Monte Carlo molecular simulations. The XRD patterns demonstrate the presence of OTC in the MONT interlayer space at acidic pH whereas complexation of OTC by external basal and edge sites seems to prevail at pH 8. At both pH, the (1)H-(13)C NMR profile indicates restricted mobility of the adsorbed OTC species; and, -CH(3) deformation and C-N stretching IR vibration bands confirm a binding mechanism involving the protonated dimethylamino group of OTC. Changes in the (23)Na NMR environments are consistent with cation-exchange and cation complexation reactions at the different sites of adsorption. Molecular simulations indicate that MONT interlayer spacing and structural charge localization dictate favorable binding conformations of the intercalated OTC, facilitating multiple interactions in agreement with the spectroscopic data. Our results present complementary insights into the mechanisms of adsorption of TETs on smectites important for their retention in natural and engineered soil environments.

Mechanical Design of NESSI: New Mexico Tech Extrasolar Spectroscopic Survey Instrument

NASA Technical Reports Server (NTRS)

Santoro, Fernando G.; Olivares, Andres M.; Salcido, Christopher D.; Jimenez, Stephen R.; Jurgenson, Colby A.; Hrynevych, Michael A.; Creech-Eakman, Michelle J.; Boston, Penny J.; Schmidt, Luke M.; Bloemhard, Heather;

Laser spectroscopic probing of coexisting superfluid and insulating states of an atomic Bose–Hubbard system

PubMed Central

Kato, Shinya; Inaba, Kensuke; Sugawa, Seiji; Shibata, Kosuke; Yamamoto, Ryuta; Yamashita, Makoto; Takahashi, Yoshiro

2016-01-01

A system of ultracold atoms in an optical lattice has been regarded as an ideal quantum simulator for a Hubbard model with extremely high controllability of the system parameters. While making use of the controllability, a comprehensive measurement across the weakly to strongly interacting regimes in the Hubbard model to discuss the quantum many-body state is still limited. Here we observe a great change in the excitation energy spectra across the two regimes in an atomic Bose–Hubbard system by using a spectroscopic technique, which can resolve the site occupancy in the lattice. By quantitatively comparing the observed spectra and numerical simulations based on sum rule relations and a binary fluid treatment under a finite temperature Gutzwiller approximation, we show that the spectra reflect the coexistence of a delocalized superfluid state and a localized insulating state across the two regimes. PMID:27094083

Ground-based multi-station spectroscopic imaging with ALIS. - Scientific highlights, project status and future prospects

NASA Astrophysics Data System (ADS)

Brändström; Gustavsson, Björn; Pellinen-Wannberg, Asta; Sandahl, Ingrid; Sergienko, Tima; Steen, Ake

2005-08-01

The Auroral Large Imaging System (ALIS) was first proposed at the ESA-PAC meeting in Lahnstein 1989. The first spectroscopic imaging station was operational in 1994, and since then up to six stations have been in simultaneous operation. Each station has a scientific-grade CCD-detector and a filter-wheel for narrow-band interference-filters with six positions. The field-of-view is around 70°. Each imager is mounted in a positioning system, enabling imaging of a common volume from several sites. This enables triangulation and tomography. Raw data from ALIS is freely available at ("http://alis.irf.se") and ALIS is open for scientific colaboration. ALIS made the first unambiguous observations of Radio-induced optical emissions at high latitudes, and the detection of water in a Leonid meteor-trail. Both rockets and satellite coordination are considered for future observations with ALIS.

Study of the interaction of deoxynivalenol with human serum albumin by spectroscopic technique and molecular modelling.

PubMed

Li, Yuqin; Wang, Hao; Jia, Baoxiu; Liu, Caihong; Liu, Ke; Qi, Yongxiu; Hu, Zhide

2013-01-01

The mechanism of interaction between deoxynivalenol (DON) and human serum albumin (HSA) was studied using spectroscopic methods including fluorescence spectra, UV-VIS, Fourier transform infrared (FT-IR) and circular dichroism (CD). The quenching mechanism was investigated in terms of the association constants, number of binding sites and basic thermodynamic parameters. The distance between the HSA donor and the acceptor DON was 2.80 nm as derived from fluorescence resonance energy transfer. The secondary structure compositions of free HSA and its DON complexes were estimated by the FT-IR spectra. Alteration of the secondary protein structure in the presence of DON was confirmed by UV-VIS and CD spectroscopy. Molecular modelling revealed that a DON-protein complex was stabilised by hydrophobic forces and hydrogen bonding. It was potentially useful for elucidating the toxigenicity of DON when combined with biomolecular function effect, transmembrane transport, toxicological testing and the other experiments.

Molecular spectroscopic study for suggested mechanism of chrome tanned leather

NASA Astrophysics Data System (ADS)

Nashy, Elshahat H. A.; Osman, Osama; Mahmoud, Abdel Aziz; Ibrahim, Medhat

2012-03-01

Collagen represents the structural protein of the extracellular matrix, which gives strength of hides and/or skin under tanning process. Chrome tan is the most important tanning agent all over the world. The methods for production of leather evolved over several centuries as art and engineering with little understanding of the underlying science. The present work is devoted to suggest the most probable mechanistic action of chrome tan on hide proteins. First the affect of Cr upon hide protein is indicated by the studied mechanical properties. Then the spectroscopic characterization of the hide protein as well as chrome tanned leather was carried out with Horizontal Attenuated Total Reflection (HATR) FT-IR. The obtained results indicate how the chromium can attached with the active sites of collagen. Molecular modeling confirms that chromium can react with amino as well as carboxylate groups. Four schemes were obtained to describe the possible interactions of chrome tan with hide proteins.

Forbidden atomic transitions driven by an intensity-modulated laser trap.

PubMed

Moore, Kaitlin R; Anderson, Sarah E; Raithel, Georg

2015-01-20

Spectroscopy is an essential tool in understanding and manipulating quantum systems, such as atoms and molecules. The model describing spectroscopy includes the multipole-field interaction, which leads to established spectroscopic selection rules, and an interaction that is quadratic in the field, which is not often employed. However, spectroscopy using the quadratic (ponderomotive) interaction promises two significant advantages over spectroscopy using the multipole-field interaction: flexible transition rules and vastly improved spatial addressability of the quantum system. Here we demonstrate ponderomotive spectroscopy by using optical-lattice-trapped Rydberg atoms, pulsating the lattice light and driving a microwave atomic transition that would otherwise be forbidden by established spectroscopic selection rules. This ability to measure frequencies of previously inaccessible transitions makes possible improved determinations of atomic characteristics and constants underlying physics. The spatial resolution of ponderomotive spectroscopy is orders of magnitude better than the transition frequency would suggest, promising single-site addressability in dense particle arrays for quantum computing applications.

Exploring the mechanism of interaction between 5-(ethoxycarbonyl)-6-methyl-4-(4-methoxyphenyl)-3,4-dihydropyrimidin-2(1H)-one and human serum albumin: Spectroscopic, calorimetric and molecular modeling studies.

PubMed

Wang, Gongke; Li, Xiang; Ding, Xuelian; Wang, Dongchao; Yan, Changling; Lu, Yan

2011-07-15

In this paper, binding interaction of 5-(ethoxycarbonyl)-6-methyl-4-(4-methoxyphenyl)-3,4-dihydropyrimidin-2(1H)-one (EMMD) with human serum albumin (HSA) under physiological conditions was investigated by using spectroscopy, isothermal titration calorimetry (ITC) and molecular modeling techniques. The results of spectroscopic studies suggested that EMMD have a strong ability to quench the intrinsic fluorescence of HSA through static quenching procedure. ITC investigations indicated that drug-protein complex was stabilized by hydrophobic forces and hydrogen bonds, which was consistent with the results of molecular modeling studies. Competitive experiments indicated the displacement of warfarin by EMMD, which revealed that the binding site of EMMD to HSA was located at subdomain IIA. Copyright © 2011 Elsevier B.V. All rights reserved.

Imaging open-path Fourier transform infrared spectrometer for 3D cloud profiling

NASA Astrophysics Data System (ADS)

Rentz Dupuis, Julia; Mansur, David J.; Vaillancourt, Robert; Carlson, David; Evans, Thomas; Schundler, Elizabeth; Todd, Lori; Mottus, Kathleen

2010-04-01

OPTRA has developed an imaging open-path Fourier transform infrared (I-OP-FTIR) spectrometer for 3D profiling of chemical and biological agent simulant plumes released into test ranges and chambers. An array of I-OP-FTIR instruments positioned around the perimeter of the test site, in concert with advanced spectroscopic algorithms, enables real time tomographic reconstruction of the plume. The approach is intended as a referee measurement for test ranges and chambers. This Small Business Technology Transfer (STTR) effort combines the instrumentation and spectroscopic capabilities of OPTRA, Inc. with the computed tomographic expertise of the University of North Carolina, Chapel Hill. In this paper, we summarize the design and build and detail system characterization and test of a prototype I-OP-FTIR instrument. System characterization includes radiometric performance and spectral resolution. Results from a series of tomographic reconstructions of sulfur hexafluoride plumes in a laboratory setting are also presented.

Imaging open-path Fourier transform infrared spectrometer for 3D cloud profiling

NASA Astrophysics Data System (ADS)

Rentz Dupuis, Julia; Mansur, David J.; Engel, James R.; Vaillancourt, Robert; Todd, Lori; Mottus, Kathleen

2008-04-01

OPTRA and University of North Carolina are developing an imaging open-path Fourier transform infrared (I-OP-FTIR) spectrometer for 3D profiling of chemical and biological agent simulant plumes released into test ranges and chambers. An array of I-OP-FTIR instruments positioned around the perimeter of the test site, in concert with advanced spectroscopic algorithms, enables real time tomographic reconstruction of the plume. The approach will be considered as a candidate referee measurement for test ranges and chambers. This Small Business Technology Transfer (STTR) effort combines the instrumentation and spectroscopic capabilities of OPTRA, Inc. with the computed tomographic expertise of the University of North Carolina, Chapel Hill. In this paper, we summarize progress to date and overall system performance projections based on the instrument, spectroscopy, and tomographic reconstruction accuracy. We then present a preliminary optical design of the I-OP-FTIR.

An extensive analysis of the triple W UMa type binary FI BOO

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

Christopoulou, P.-E.; Papageorgiou, A.

We present a detailed analysis of the interesting W UMa binary FI Boo in view of the spectroscopic signature of a third body through photometry, period variation, and a thorough investigation of solution uniqueness. We obtained new BVR{sub c}I{sub c} photometric data that, when combined with spectroscopic data, enable us to analyze the system FI Boo and determine its basic orbital and physical properties through PHOEBE, as well as the period variation by studying the times of the minima. This combined approach allows us to study the long-term period changes in the system for the first time in order tomore » investigate the presence of a third body and to check extensively the solution uniqueness and the uncertainties of derived parameters. Our modeling indicates that FI Boo is a W-type moderate (f = 50.15% ± 8.10%) overcontact binary with component masses of M {sub h} = 0.40 ± 0.05 M {sub ☉} and M {sub c} = 1.07 ± 0.05 M {sub ☉}, temperatures of T {sub h} = 5746 ± 33 K and T {sub c} = 5420 ± 56 K, and a third body, which may play an important role in the formation and evolution. The results were tested by heuristic scanning and parameter kicking to provide the consistent and reliable set of parameters that was used to obtain the initial masses of the progenitors (1.71 ± 0.10 M {sub ☉} and 0.63 ± 0.01 M {sub ☉}, respectively). We also investigated the evolutionary status of massive components with several sets of widely used isochrones.« less

HIV integration sites in latently infected cell lines: evidence of ongoing replication.

PubMed

Symons, Jori; Chopra, Abha; Malatinkova, Eva; De Spiegelaere, Ward; Leary, Shay; Cooper, Don; Abana, Chike O; Rhodes, Ajantha; Rezaei, Simin D; Vandekerckhove, Linos; Mallal, Simon; Lewin, Sharon R; Cameron, Paul U

2017-01-13

Assessing the location and frequency of HIV integration sites in latently infected cells can potentially inform our understanding of how HIV persists during combination antiretroviral therapy. We developed a novel high throughput sequencing method to evaluate HIV integration sites in latently infected cell lines to determine whether there was virus replication or clonal expansion in these cell lines observed as multiple integration events at the same position. We modified a previously reported method using random DNA shearing and PCR to allow for high throughput robotic processing to identify the site and frequency of HIV integration in latently infected cell lines. Latently infected cell lines infected with intact virus demonstrated multiple distinct HIV integration sites (28 different sites in U1, 110 in ACH-2 and 117 in J1.1 per 150,000 cells). In contrast, cell lines infected with replication-incompetent viruses (J-Lat cells) demonstrated single integration sites. Following in vitro passaging of the ACH-2 cell line, we observed a significant increase in the frequency of unique HIV integration sites and there were multiple mutations and large deletions in the proviral DNA. When the ACH-2 cell line was cultured with the integrase inhibitor raltegravir, there was a significant decrease in the number of unique HIV integration sites and a transient increase in the frequency of 2-LTR circles consistent with virus replication in these cells. Cell lines latently infected with intact HIV demonstrated multiple unique HIV integration sites indicating that these cell lines are not clonal and in the ACH-2 cell line there was evidence of low level virus replication. These findings have implications for the use of latently infected cell lines as models of HIV latency and for the use of these cells as standards.

Asymmetric Volcano Trend in Oxygen Reduction Activity of Pt and Non-Pt Catalysts: In Situ Identification of the Site-Blocking Effect.

PubMed

Li, Jingkun; Alsudairi, Amell; Ma, Zi-Feng; Mukerjee, Sanjeev; Jia, Qingying

2017-02-01

Proper understanding of the major limitations of current catalysts for oxygen reduction reaction (ORR) is essential for further advancement. Herein by studying representative Pt and non-Pt ORR catalysts with a wide range of redox potential (E redox ) via combined electrochemical, theoretical, and in situ spectroscopic methods, we demonstrate that the role of the site-blocking effect in limiting the ORR varies drastically depending on the E redox of active sites; and the intrinsic activity of active sites with low E redox have been markedly underestimated owing to the overlook of this effect. Accordingly, we establish a general asymmetric volcano trend in the ORR activity: the ORR of the catalysts on the overly high E redox side of the volcano is limited by the intrinsic activity; whereas the ORR of the catalysts on the low E redox side is limited by either the site-blocking effect and/or intrinsic activity depending on the E redox .

Concentration and mindfulness meditations: unique forms of consciousness?

PubMed

Dunn, B R; Hartigan, J A; Mikulas, W L

1999-09-01

Electroencephalographic (EEG) recordings from 19 scalp recording sites were used to differentiate among two posited unique forms of mediation, concentration and mindfulness, and a normal relaxation control condition. Analyzes of all traditional frequency bandwidth data (i.e., delta 1-3 Hz; theta, 4-7 Hz; alpha, 8-12 Hz; beta 1, 13-25 Hz; beta 2, 26-32 Hz) showed strong mean amplitude frequency differences between the two meditation conditions and relaxation over numerous cortical sites. Furthermore, significant differences were obtained between concentration and mindfulness states at all bandwidths. Taken together, our results suggest that concentration and mindfulness "meditations" may be unique forms of consciousness and are not merely degrees of a state of relaxation.

Evaluation of soil contamination by explosives and metals at the Land Force Central Area Training Centre (LFCA TC) Meaford, Ontario (Phase I)

DTIC Science & Technology

2009-05-01

found in ammunition. The site characterization allowed the development of a unique expertise and positioned our departments to better understand the...environnementaux des composés énergétiques que l’on retrouve dans les munitions. La caractérisation des sites a permis de développer une expertise unique et a...éventualités pour prendre des mesures correctives, si nécessaire. Les premiers sites d’entraînement à être évalués ont été des bases de l’armée, telles que

On the quantitative inventory of the riverscape

USGS Publications Warehouse

Leopold, Luna Bergere; O'Brien Marchand, Maura

1968-01-01

In the vicinity of Berkeley, California, 24 minor valleys were described in terms of factors chosen to represent aspects of the river landscape. A total of 28 factors were evaluated at each site. Some were directly measurable, others were estimated, but each observation was assigned to one of five categories for that factor. Each factor for each site was then expressed as a uniqueness ratio, which depended on the number of sites being in the same category. The uniqueness ratio is believed to represent one way the scarcity of a given riverscape can be ranked quantitatively without bias based on notions of good or bad, and without assigning monetary value.

Chitin-induced activation of immune signaling by the rice receptor CEBiP relies on a unique sandwich-type dimerization

PubMed Central

Hayafune, Masahiro; Berisio, Rita; Marchetti, Roberta; Silipo, Alba; Kayama, Miyu; Desaki, Yoshitake; Arima, Sakiko; Squeglia, Flavia; Ruggiero, Alessia; Tokuyasu, Ken; Molinaro, Antonio; Kaku, Hanae; Shibuya, Naoto

2014-01-01

Perception of microbe-associated molecular patterns (MAMPs) through pattern recognition receptors (PRRs) triggers various defense responses in plants. This MAMP-triggered immunity plays a major role in the plant resistance against various pathogens. To clarify the molecular basis of the specific recognition of chitin oligosaccharides by the rice PRR, CEBiP (chitin-elicitor binding protein), as well as the formation and activation of the receptor complex, biochemical, NMR spectroscopic, and computational studies were performed. Deletion and domain-swapping experiments showed that the central lysine motif in the ectodomain of CEBiP is essential for the binding of chitin oligosaccharides. Epitope mapping by NMR spectroscopy indicated the preferential binding of longer-chain chitin oligosaccharides, such as heptamer-octamer, to CEBiP, and also the importance of N-acetyl groups for the binding. Molecular modeling/docking studies clarified the molecular interaction between CEBiP and chitin oligosaccharides and indicated the importance of Ile122 in the central lysine motif region for ligand binding, a notion supported by site-directed mutagenesis. Based on these results, it was indicated that two CEBiP molecules simultaneously bind to one chitin oligosaccharide from the opposite side, resulting in the dimerization of CEBiP. The model was further supported by the observations that the addition of (GlcNAc)8 induced dimerization of the ectodomain of CEBiP in vitro, and the dimerization and (GlcNAc)8-induced reactive oxygen generation were also inhibited by a unique oligosaccharide, (GlcNβ1,4GlcNAc)4, which is supposed to have N-acetyl groups only on one side of the molecule. Based on these observations, we proposed a hypothetical model for the ligand-induced activation of a receptor complex, involving both CEBiP and Oryza sativa chitin-elicitor receptor kinase-1. PMID:24395781

3 Tesla (1) H MR spectroscopy of hip bone marrow in a healthy population, assessment of normal fat content values and influence of age and sex.

PubMed

Pansini, Vittorio; Monnet, Aurélien; Salleron, Julia; Hardouin, Pierre; Cortet, Bernard; Cotten, Anne

2014-02-01

To evaluate in a healthy population normal spectroscopic fat content (FC) values of the hip bone marrow and to assess the influence of age and sex on bone marrow conversion. Eighty volunteers (40 men; 40 women; ages: 20-60 years; divided into four consecutive groups) underwent acetabulum, femoral head, femoral neck, greater trochanter, and diaphysis localized (1) H MR spectroscopy. FC values of each anatomical site were obtained according to the following formula: Fat content = CH2 /(CH2  + Water)*100. To assess bone marrow conversion, a spectroscopic conversion index (SCI) was calculated as FC neck/FC greater trochanter. FC values showed a gradient as follows: greater trochanter > femoral head > femoral neck > diaphysis > acetabulum in every age group both in men and in women. SCI increased with age both in men and women, showing lower values in women for every age group. We obtained normal spectroscopic FC values from different areas of the hip, according to age and sex. These values may be used as reference values to evaluate, by the means of (1) H MR spectroscopy, pathological conditions affecting hip bone marrow. Copyright © 2013 Wiley Periodicals, Inc.

Spectroscopic and Kinetic Characterization of Peroxidase-Like π-Cation Radical Pinch-Porphyrin-Iron(III) Reaction Intermediate Models of Peroxidase Enzymes.

PubMed

Hernández Anzaldo, Samuel; Arroyo Abad, Uriel; León García, Armando; Ramírez Rosales, Daniel; Zamorano Ulloa, Rafael; Reyes Ortega, Yasmi

2016-06-27

The spectroscopic and kinetic characterization of two intermediates from the H₂O₂ oxidation of three dimethyl ester [(proto), (meso), (deuteroporphyrinato) (picdien)]Fe(III) complexes ([FePPPic], [FeMPPic] and [FeDPPic], respectively) pinch-porphyrin peroxidase enzyme models, with s = 5/2 and 3/2 Fe(III) quantum mixed spin (qms) ground states is described herein. The kinetic study by UV/Vis at λmax = 465 nm showed two different types of kinetics during the oxidation process in the guaiacol test for peroxidases (1-3 + guaiacol + H₂O₂ → oxidation guaiacol products). The first intermediate was observed during the first 24 s of the reaction. When the reaction conditions were changed to higher concentration of pinch-porphyrins and hydrogen peroxide only one type of kinetics was observed. Next, the reaction was performed only between pinch-porphyrins-Fe(III) and H₂O₂, resulting in only two types of kinetics that were developed during the first 0-4 s. After this time a self-oxidation process was observed. Our hypotheses state that the formation of the π-cation radicals, reaction intermediates of the pinch-porphyrin-Fe(III) family with the ligand picdien [N,N'-bis-pyridin-2-ylmethyl-propane-1,3-diamine], occurred with unique kinetics that are different from the overall process and was involved in the oxidation pathway. UV-Vis, ¹H-NMR and ESR spectra confirmed the formation of such intermediates. The results in this paper highlight the link between different spectroscopic techniques that positively depict the kinetic traits of artificial compounds with enzyme-like activity.

Characterization of interactions of simvastatin, pravastatin, fluvastatin, and pitavastatin with bovine serum albumin: multiple spectroscopic and molecular docking.

PubMed

Shi, Jie-Hua; Wang, Qi; Pan, Dong-Qi; Liu, Ting-Ting; Jiang, Min

2017-05-01

The binding interactions of simvastatin (SIM), pravastatin (PRA), fluvastatin (FLU), and pitavastatin (PIT) with bovine serum albumin (BSA) were investigated for determining the affinity of four statins with BSA through multiple spectroscopic and molecular docking methods. The experimental results showed that SIM, PRA, FLU, and PIT statins quenched the intrinsic fluorescence of BSA through a static quenching process and the stable stains-BSA complexes with the binding constants in the order of 10 4  M -1 at 298 K were formed through intermolecular nonbond interaction. The values of ΔH 0 , ΔS 0 and ΔG 0 in the binding process of SIM, PRA, FLU, and PIT with BSA were negative at the studied temperature range, suggesting that the binding process of four statins and BSA was spontaneous and the main interaction forces were van der Waals force and hydrogen-bonding interactions. Moreover, the binding of four statins with BSA was enthalpy-driven process due to |ΔH°|>|TΔS°| under the studied temperature range. From the results of site marker competitive experiments and molecular docking, subdomain IIIA (site II) was the primary binding site for SIM, PRA, FLU, and PIT on BSA. The results of UV-vis absorption, synchronous fluorescence, 3D fluorescence and FT-IR spectra proved that the slight change in the conformation of BSA, while the significant changes in the conformation of SIM, PRA, FLU, and PIT drug in statin-BSA complexes, indicating that the flexibility of statin molecules plays an important role in increasing the stability of statin-BSA complexes.

[3Fe-4S] to [4Fe-4S] cluster conversion in Desulfovibrio fructosovorans [NiFe] hydrogenase by site-directed mutagenesis.

PubMed

Rousset, M; Montet, Y; Guigliarelli, B; Forget, N; Asso, M; Bertrand, P; Fontecilla-Camps, J C; Hatchikian, E C

1998-09-29

The role of the high potential [3Fe-4S]1+,0 cluster of [NiFe] hydrogenase from Desulfovibrio species located halfway between the proximal and distal low potential [4Fe-4S]2+,1+ clusters has been investigated by using site-directed mutagenesis. Proline 238 of Desulfovibrio fructosovorans [NiFe] hydrogenase, which occupies the position of a potential ligand of the lacking fourth Fe-site of the [3Fe-4S] cluster, was replaced by a cysteine residue. The properties of the mutant enzyme were investigated in terms of enzymatic activity, EPR, and redox properties of the iron-sulfur centers and crystallographic structure. We have shown on the basis of both spectroscopic and x-ray crystallographic studies that the [3Fe-4S] cluster of D. fructosovorans hydrogenase was converted into a [4Fe-4S] center in the P238 mutant. The [3Fe-4S] to [4Fe-4S] cluster conversion resulted in a lowering of approximately 300 mV of the midpoint potential of the modified cluster, whereas no significant alteration of the spectroscopic and redox properties of the two native [4Fe-4S] clusters and the NiFe center occurred. The significant decrease of the midpoint potential of the intermediate Fe-S cluster had only a slight effect on the catalytic activity of the P238C mutant as compared with the wild-type enzyme. The implications of the results for the role of the high-potential [3Fe-4S] cluster in the intramolecular electron transfer pathway are discussed.

Biophysical influence of isocarbophos on bovine serum albumin: spectroscopic probing.

PubMed

Zhang, Hua-xin; Zhou, Ying; Liu, E

2012-06-15

Isocarbophos (ICP) is a phosphorous pesticide with high toxicity. It has been detected in several kinds of food and therefore can enter human body. In this paper, spectroscopic approaches including three-dimensional fluorescence (3D-FL) spectroscopy, UV-visible absorption spectroscopy and circular dichroism (CD) spectroscopy were employed to explore the binding of ICP to bovine serum albumin (BSA) at simulated physiological conditions. It was found that the fluorescence quenching of BSA was caused by the formation of ICP-BSA complex at ground state and belonged to static quenching mechanism. The binding constants, the number of binding sites, enthalpy change (ΔH(θ)), Gibbs free energy change (ΔG(θ)) and entropy change (ΔS(θ)) were calculated at four different temperatures according to Scatchard model and thermodynamic equations. To identify the binding location, fluorescence probe techniques were used. The results showed that warfarin, an acknowledged site marker for BSA, could be partially replaced by ICP when ICP was added to warfarin-BSA systems, which demonstrated that ICP primarily bound on Sudlow's site I in domain IIA of BSA molecule. The distance r (3.06 nm) between donor (Trp-212) and acceptor (ICP) was obtained based on Förster's non-radiation fluorescence resonance energy transfer (FRET) theory. Furthermore, the CD spectral results indicated that the secondary structure of BSA was changed in presence of ICP. The study is helpful to evaluating the toxicology of ICP and understanding its effects on the function of protein during the blood transportation process. Copyright © 2012 Elsevier B.V. All rights reserved.

Synthesis, spectroscopic characterization and in vitro cytotoxicities of new organometallic palladium complexes with biologically active β-diketones; Biological evaluation probing of the interaction mechanism with DNA/Protein and molecular docking

NASA Astrophysics Data System (ADS)

Karami, Kazem; Rafiee, Mina; Lighvan, Zohreh Mehri; Zakariazadeh, Mostafa; Faal, Ali Yeganeh; Esmaeili, Seyed-Alireza; Momtazi-Borojeni, Amir Abbas

2018-02-01

[Pd{(C,N)sbnd C6H4CH (CH3)NH}(CUR)] (3) and [Pd2{(C,N)sbnd C6H4CH(CH3)NH2}2(μ-N3CS2)] (4) [cur = 1,7-bis(4-hydroxy-3-methoxyphenyl)-1,6-heptadiene-3,5-dion] novel organometallic complexes with biologically active ligands have been prepared and characterized via elemental analysis, multinuclear spectroscopic techniques (1H, and 13C NMR and IR) and their biological activities, including antitumoral activity and DNA-protein interactions have been investigated. Fluorescence spectroscopy used to study the interaction of the complexes with BSA have shown the affinity of the complexes for these proteins with relatively high binding constant values and the changed secondary structure of BSA in the presence of the complexes. In the meantime, spectroscopy and competitive titration have been applied to investigate the interaction of complexes with Warfarin and Ibuprofen site markers for sites I and II, respectively, with BSA. The results have suggested that the locations of complexes 3 and 4 are sites II and I, respectively. UV-Vis spectroscopy, emission titration and helix melting methods have been used to study the interaction of these complexes with CT-DNA, indicating that complexes are bound to CT-DNA by intercalation binding mode. In addition, good cytotoxic activity against MCF-7 (human breast cancer) and JURKAT (human leukemia) cell line has been shown by both complexes whereas low cytotoxicity was exerted on normal peripheral blood mononuclear cells.

Kinemage of action - Proposed reaction mechanism of glutamate-1-semialdehyde aminomutase at an atomic level

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

Sorensen, John L., E-mail: John_Sorensen@umanitoba.ca; Stetefeld, Joerg, E-mail: stetefel@cc.umanitoba.ca

2011-10-07

Highlights: {yields} Inhibitors of tetrapyrrole cofactor biosynthesis may be useful antibiotics. {yields} Mechanism of critical enzyme, glutamate-1-semialdehyde aminomutase, is presented. {yields} Unique vitamin B6-dependant enzyme traps intermediate in active site. {yields} Molecular dynamics show that a re-orientation of the substrate is required. -- Abstract: Glutamate-1-semialdehyde aminomutase (GSAM), a key enzyme in tetrapyrrole cofactor biosynthesis, performs a unique transamination on a single substrate. The substrate, glutamate-1-semialdehyde (GSA), undergoes a reaction that exchanges the position of an amine and a carbonyl group to produce 5-aminolevulinic acid (ALA). This transamination reaction is unique in the fact that is does not require an externalmore » cofactor to act as a nitrogen donor or acceptor in this transamination reaction. One of the other remarkable features of the catalytic mechanism is the release free in the enzyme active site of the intermediate 4,5-diaminovaleric acid (DAVA). The action of a gating loop prevents the escape of DAVA from the active site. In a MD simulation approach, using snapshots provided by X-ray crystallography and protein crystal absorption spectrometry data, the individual catalytic steps in this unique intramolecular transamination have been elucidated.« less

CLIP-seq analysis of multi-mapped reads discovers novel functional RNA regulatory sites in the human transcriptome.

PubMed

Zhang, Zijun; Xing, Yi

2017-09-19

Crosslinking or RNA immunoprecipitation followed by sequencing (CLIP-seq or RIP-seq) allows transcriptome-wide discovery of RNA regulatory sites. As CLIP-seq/RIP-seq reads are short, existing computational tools focus on uniquely mapped reads, while reads mapped to multiple loci are discarded. We present CLAM (CLIP-seq Analysis of Multi-mapped reads). CLAM uses an expectation-maximization algorithm to assign multi-mapped reads and calls peaks combining uniquely and multi-mapped reads. To demonstrate the utility of CLAM, we applied it to a wide range of public CLIP-seq/RIP-seq datasets involving numerous splicing factors, microRNAs and m6A RNA methylation. CLAM recovered a large number of novel RNA regulatory sites inaccessible by uniquely mapped reads. The functional significance of these sites was demonstrated by consensus motif patterns and association with alternative splicing (splicing factors), transcript abundance (AGO2) and mRNA half-life (m6A). CLAM provides a useful tool to discover novel protein-RNA interactions and RNA modification sites from CLIP-seq and RIP-seq data, and reveals the significant contribution of repetitive elements to the RNA regulatory landscape of the human transcriptome. © The Author(s) 2017. Published by Oxford University Press on behalf of Nucleic Acids Research.

Transition Metal Ions in Zeolites: Coordination and activation of O2

PubMed Central

Smeets, Pieter J.; Woertink, Julia S.; Sels, Bert F.; Solomon, Edward I.; Schoonheydt, Robert A.

2010-01-01

Zeolites containing transition metal ions (TMI) often show promising activity as heterogeneous catalysts in pollution abatement and selective oxidation reactions. In this paper, two aspects of research on the TMI Cu, Co and Fe in zeolites are discussed: (i) coordination to the lattice and (ii) activated oxygen species. At low loading, TMI preferably occupy exchange sites in six-membered oxygen rings (6MR) where the TMI preferentially coordinate with the oxygen atoms of Al tetrahedra. High TMI loadings result in a variety of TMI species formed at the zeolite surface. Removal of the extra-lattice oxygens during high temperature pretreatments can result in auto-reduction. Oxidation of reduced TMI sites often results in the formation of highly reactive oxygen species. In Cu-ZSM-5, calcination with O2 results in the formation of a species, which was found to be a crucial intermediate in both the direct decomposition of NO and N2O and the selective oxidation of methane into methanol. An activated oxygen species, called α-oxygen, is formed in Fe-ZSM5 and reported to be the active site in the partial oxidation of methane and benzene into methanol and phenol, respectively. However, this reactive α-oxygen can only be formed with N2O, not with O2. O2 activated Co intermediates in Faujasite (FAU) zeolites can selectively oxidize α-pinene and epoxidize styrene. In Co-FAU, CoIII superoxo and peroxo complexes are suggested to be the active cores, whereas in Cu and Fe-ZSM-5 various monomeric and dimeric sites have been proposed, but no consensus has been obtained. Very recently, the active site in Cu-ZSM-5 was identified as a bent [Cu-O-Cu]2+ core (Proc. Natl. Acad. Sci. USA 2009, 106, 18908-18913). Overall, O2 activation depends on the interplay of structural factors such as type of zeolite, size of the channels and cages and chemical factors such as Si/Al ratio and the nature, charge and distribution of the charge balancing cations. The presence of several different TMI sites hinders the direct study of the spectroscopic features of the active site. Spectroscopic techniques capable of selectively probing these sites, even if they only constitute a minor fraction of the total amount of TMI sites, are thus required. Fundamental knowledge of the geometric and electronic structure of the reactive active site can help in the design of novel selective oxidation catalysts. PMID:20380459

Identifying the Source of Large-Scale Atmospheric Variability in Jupiter

NASA Astrophysics Data System (ADS)

Orton, Glenn

2011-01-01

We propose to use the unique mid-infrared filtered imaging and spectroscopic capabilities of the Subaru COMICS instrument to determine the mechanisms associated with recent unusual rapid albedo and color transformations of several of Jupiter's bands, particularly its South Equatorial Belt (SEB), as a means to understand the coupling between its dynamics and chemistry. These observations will characterize the temperature, degree of cloud cover, and distribution of minor gases that serve as indirect tracers of vertical motions in regions that will be undergoing unusual large-scale changes in dynamics and chemistry: the SEB, as well as regions near the equator and Jupiter's North Temperate Belt. COMICS is ideal for this investigation because of its efficiency in doing both imaging and spectroscopy, its 24.5-mum filter that is unique to 8-meter-class telescopes, its wide field of view that allows imaging of nearly all of Jupiter's disk, coupled with a high diffraction-limited angular resolution and optimal mid-infrared atmospheric transparency.

Signature of nonadiabatic coupling in excited-state vibrational modes.

PubMed

Soler, Miguel A; Nelson, Tammie; Roitberg, Adrian E; Tretiak, Sergei; Fernandez-Alberti, Sebastian

2014-11-13

Using analytical excited-state gradients, vibrational normal modes have been calculated at the minimum of the electronic excited-state potential energy surfaces for a set of extended conjugated molecules with different coupling between them. Molecular model systems composed of units of polyphenylene ethynylene (PPE), polyphenylenevinylene (PPV), and naphthacene/pentacene (NP) have been considered. In all cases except the NP model, the influence of the nonadiabatic coupling on the excited-state equilibrium normal modes is revealed as a unique highest frequency adiabatic vibrational mode that overlaps with the coupling vector. This feature is removed by using a locally diabatic representation in which the effect of NA interaction is removed. Comparison of the original adiabatic modes with a set of vibrational modes computed in the locally diabatic representation demonstrates that the effect of nonadiabaticity is confined to only a few modes. This suggests that the nonadiabatic character of a molecular system may be detected spectroscopically by identifying these unique state-specific high frequency vibrational modes.

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

NASA Astrophysics Data System (ADS)

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

2013-01-01

Magnetoelectric materials have potential for being introduced into next generation technologies, especially memory devices. The AFeO3 (Pna21; A=Al, Ga) system has received attention to better understand the origins of magnetoelectric coupling. The magnetoelectric properties this system exhibits depend on the amount of anti-site disorder present, which is affected by the composition and the method of synthesis. In this study, Al1-xGaxFeO3 was synthesized by the ceramic method and studied by X-ray absorption spectroscopy. Al L2,3-, Ga K-, and Fe K-edge spectra were collected to examine how the average metal coordination number changes with composition. Examination of XANES spectra from Al1-xGaxFeO3 indicate that with increasing Ga content, Al increasingly occupies octahedral sites while Ga displays a preference for occupying the tetrahedral site. The Fe K-edge spectra indicate that more Fe is present in the tetrahedral site in AlFeO3 than in GaFeO3, implying more anti-site disorder is present in AlFeO3.

Semiconductor Nanomaterials-Based Fluorescence Spectroscopic and Matrix-Assisted Laser Desorption/Ionization (MALDI) Mass Spectrometric Approaches to Proteome Analysis

PubMed Central

Kailasa, Suresh Kumar; Cheng, Kuang-Hung; Wu, Hui-Fen

2013-01-01

Semiconductor quantum dots (QDs) or nanoparticles (NPs) exhibit very unusual physico-chemcial and optical properties. This review article introduces the applications of semiconductor nanomaterials (NMs) in fluorescence spectroscopy and matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS) for biomolecule analysis. Due to their unique physico-chemical and optical properties, semiconductors NMs have created many new platforms for investigating biomolecular structures and information in modern biology. These semiconductor NMs served as effective fluorescent probes for sensing proteins and cells and acted as affinity or concentrating probes for enriching peptides, proteins and bacteria proteins prior to MALDI-MS analysis. PMID:28788422

Dimacrolide Sesquiterpene Pyridine Alkaloids from the Stems of Tripterygium regelii.

PubMed

Fan, Dongsheng; Zhu, Guo-Yuan; Li, Ting; Jiang, Zhi-Hong; Bai, Li-Ping

2016-08-29

Two new dimacrolide sesquiterpene pyridine alkaloids (DMSPAs), dimacroregelines A (1) and B (2), were isolated from the stems of Tripterygium regelii. The structures of both compounds were characterized by extensive 1D and 2D NMR spectroscopic analyses, as well as HRESIMS data. Compounds 1 and 2 are two rare DMSPAs possessing unique 2-(3'-carboxybutyl)-3-furanoic acid units forming the second macrocyclic ring, representing the first example of DMSPAs bearing an extra furan ring in their second macrocyclic ring system. Compound 2 showed inhibitory effects on the proliferation of human rheumatoid arthritis synovial fibroblast cell (MH7A) at a concentration of 20 μM.

Spectroscopic studies of micelle-enhanced ligand exchange of gallium (III)/4-(2-pyridylazo) resorcinol complex by calf thymus DNA.

PubMed

Romeika, Jennifer M; Spurgeon, Charina L; Yan, Fei

2014-01-03

The effect of cationic micelles of cetyltrimethylammonium bromide (CTAB) on the interaction of gallium (III) with 4-(2-pyridylazo) resorcinol (PAR) under varying conditions has been studied spectrophotometrically. At pH 6.0, CTAB (0.05% w/v) markedly enhanced the absorption intensity of gallium (III)-PAR complex. Furthermore, the introduction of CTAB provided unique selectivity for the ligand exchange of Ga(III)-PAR by calf thymus dsDNA over calf thymus ssDNA. This phenomenon offers a novel spectrophotometric sensing strategy for direct detection of dsDNA. Copyright © 2013 Elsevier B.V. All rights reserved.

Photoacoustic resonance spectroscopy for biological tissue characterization

NASA Astrophysics Data System (ADS)

Gao, Fei; Feng, Xiaohua; Zheng, Yuanjin; Ohl, Claus-Dieter

2014-06-01

By "listening to photons," photoacoustics allows the probing of chromosomes in depth beyond the optical diffusion limit. Here we report the photoacoustic resonance effect induced by multiburst modulated laser illumination, which is theoretically modeled as a damped mass-string oscillator and a resistor-inductor-capacitor (RLC) circuit. Through sweeping the frequency of multiburst modulated laser, the photoacoustic resonance effect is observed experimentally on phantoms and porcine tissues. Experimental results demonstrate different spectra for each phantom and tissue sample to show significant potential for spectroscopic analysis, fusing optical absorption and mechanical vibration properties. Unique RLC circuit parameters are extracted to quantitatively characterize phantom and biological tissues.

SOFIA: On the Pathway toward Habitable Worlds

NASA Astrophysics Data System (ADS)

Gehrz, R. D.; Angerhausen, D.; Becklin, E. E.; Greenhouse, M. A.; Horner, S.; Krabbe, A.; Swain, M. R.; Young, E. T.

2010-10-01

The U.S./German Stratospheric Observatory for Infrared Astronomy (SOFIA), a 2.5-meter infrared airborne telescope in a Boeing 747-SP, will conduct 0.3 - 1,600 μm photometric, spectroscopic, and imaging observations from altitudes as high as 45,000 ft., where the average atmospheric transmission is greater than 80 percent. SOFIA’s first light cameras and spectrometers, as well as future generations of instruments, will enable SOFIA to make unique contributions to the characterization of the physical properties of proto-planetary disks around young stellar objects and of the atmospheres of exoplanets that transit their parent stars. We describe several types of experiments that are being contemplated.

A critical review of inductively coupled plasma-mass spectrometry for geoanalysis, geochemistry and hydrology, Part 1. Analytical performance

USGS Publications Warehouse

Brenner, I.B.; Taylor, Howard E.

1992-01-01

Present-day inductively coupled plasma-mass spectrometry (ICP-MS) instrumentation is described briefly. Emphasis is placed on performance characteristics for geoanalysis, geochemistry, and hydrology. Applications where ICP-MS would be indispensable are indicated. Determination of geochemically diagnostic trace elements (such as the rare earth elements [REE], U and Th), of isotope ratios for fingerprinting, tracer and other geo-isotope applications, and benchmark isotope dilution determinations are considered to be typical priority applications for ICP-MS. It is concluded that ICP-MS furnishes unique geoanalytical and environmental data that are not readily provided by conventional spectroscopic (emission and absorption) techniques.

Tuning topological phases in the XMnSb2 system via chemical substitution from first principles

NASA Astrophysics Data System (ADS)

Griffin, Sinead M.; Neaton, Jeffrey B.

New Dirac materials are sought for their interesting fundamental physics and for their potential technological applications. Protected symmetries offer a route to potential zero mass Dirac and Weyl fermions, and can lead unique transport properties and spectroscopic signatures. In this work, we use first-principles calculations to study the XMnSb2 family of materials and show how varying X changes the nature of bulk protected topological features in their electronic structure. We further discuss new design rules for predicting new topological materials suggested by our calculations. SG is supported by the Early Postdoc Mobility Fellowship of the SNF.

The spectroscopic, chemical, and photophysical properties of Martian soils and their analogs (MERC, phase 2)

NASA Technical Reports Server (NTRS)

Banin, Amos; Orenberg, James

1990-01-01

A series of variably proportioned iron/calcium smectite clays and iron loaded smectite clays containing iron up to the level found in the Martian soil were prepared from a typical montomorillonite clay using the Banin method. Evidence was obtained which supports the premise that these materials provide a unique and appropriate model soil system for the Martian surface in that they are consistent with the constraints imposed by the Viking surface elemental analysis, the reflectance data obtained by various spacecraft instruments and ground based telescopes, and the chemical reactivity measured by one of the Viking biology experiments, the Labeled Release (LR) experiment.

Rhodomollanol A, a Highly Oxygenated Diterpenoid with a 5/7/5/5 Tetracyclic Carbon Skeleton from the Leaves of Rhododendron molle.

PubMed

Zhou, Junfei; Zhan, Guanqun; Zhang, Hanqi; Zhang, Qihua; Li, Ying; Xue, Yongbo; Yao, Guangmin

2017-07-21

A novel diterpenoid with an unprecedented carbon skeleton, rhodomollanol A (1), and a new grayanane diterpenoid, rhodomollein XXXI (2), were isolated from the leaves of Rhododendron molle. Their structures were elucidated using comprehensive spectroscopic methods and single-crystal X-ray diffraction. Compound 1 possesses a unique cis/trans/trans/cis/cis-fused 3/5/7/5/5/5 hexacyclic ring system featuring a rare 7-oxabicyclo[4.2.1]nonane core decorated with three cyclopentane units. The plausible biosynthetic pathway for 1 was proposed. Compound 1 exhibited moderate PTP1B inhibitory activity.

Design and Synthesis of Semisynthetic Enzymes.

DTIC Science & Technology

1987-07-28

residues in proteins to be site- specifically replaced with synthetic amino acid analogues . Amino acids with novel steric, electronic, or spectroscopic...aminoacylated pCpA we have begun to develop new aminoacylation chemistry as outlined below. 13 The exocyclic amine of cytidine will be protected by the...I M acSe, PH 5 We have carried out preliminary experiments with 5’ dimethoxytrityl cytidine in which the exocyclic amino group is protected with the o

Development of sensing techniques for weaponry health monitoring

NASA Astrophysics Data System (ADS)

Edwards, Eugene; Ruffin, Paul B.; Walker, Ebonee A.; Brantley, Christina L.

2013-04-01

Due to the costliness of destructive evaluation methods for assessing the aging and shelf-life of missile and rocket components, the identification of nondestructive evaluation methods has become increasingly important to the Army. Verifying that there is a sufficient concentration of stabilizer is a dependable indicator that the missile's double-based solid propellant is viable. The research outlined in this paper summarizes the Army Aviation and Missile Research, Development, and Engineering Center's (AMRDEC's) comparative use of nanoporous membranes, carbon nanotubes, and optical spectroscopic configured sensing techniques for detecting degradation in rocket motor propellant. The first sensing technique utilizes a gas collecting chamber consisting of nanoporous structures that trap the smaller solid propellant particles for measurement by a gas analysis device. In collaboration with NASA-Ames, sensing methods are developed that utilize functionalized single-walled carbon nanotubes as the key sensing element. The optical spectroscopic sensing method is based on a unique light collecting optical fiber system designed to detect the concentration of the propellant stabilizer. Experimental setups, laboratory results, and overall effectiveness of each technique are presented in this paper. Expectations are for the three sensing mechanisms to provide nondestructive evaluation methods that will offer cost-savings and improved weaponry health monitoring.

Spectroscopic and Computational Investigations of Ligand Binding to IspH: Discovery of Non-diphosphate Inhibitors

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

O'Dowd, Bing; Williams, Sarah; Wang, Hongxin

Isoprenoid biosynthesis is an important area for anti-infective drug development. One isoprenoid target described is (E)-1-hydroxy-2-methyl-but-2-enyl 4-diphosphate (HMBPP) reductase (IspH), which forms isopentenyl diphosphate and dimethylallyl diphosphate from HMBPP in a 2H + /2e - reduction. IspH contains a 4 Fe-4 S cluster, and in this work, we first investigated how small molecules bound to the cluster by using HYSCORE and NRVS spectroscopies. The results of these, as well as other structural and spectroscopic investigations, led to the conclusion that, in most cases, ligands bound to IspH 4 Fe-4 S clusters by η 1 coordination, forming tetrahedral geometries at themore » unique fourth Fe, ligand side chains preventing further ligand (e.g., H 2 O, O 2 ) binding. Based on these ideas, we used in silico methods to find drug-like inhibitors that might occupy the HMBPP substrate binding pocket and bind to Fe, leading to the discovery of a barbituric acid analogue with a K i value of ≈500 nm against Pseudomonas aeruginosa IspH.« less

NEW INSIGHTS INTO THE PROBLEM OF THE SURFACE GRAVITY DISTRIBUTION OF COOL DA WHITE DWARFS

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

Tremblay, P.-E.; Bergeron, P.; Gianninas, A.

2010-04-01

We review at length the longstanding problem in the spectroscopic analysis of cool hydrogen-line (DA) white dwarfs (T{sub eff}< 13,000 K) where gravities are significantly higher than those found in hotter DA stars. The first solution that has been proposed for this problem is a mild and systematic helium contamination from convective mixing that would mimic the high gravities. We constrain this scenario by determining the helium abundances in six cool DA white dwarfs using high-resolution spectra from the Keck I 10 m telescope. We obtain no detections, with upper limits as low as He/H = 0.04 in some cases.more » This allows us to put this scenario to rest for good. We also extend our model grid to lower temperatures using improved Stark profiles with non-ideal gas effects from Tremblay and Bergeron and find that the gravity distribution of cool objects remains suspiciously high. Finally, we find that photometric masses are, on average, in agreement with expected values, and that the high-log g problem is so far unique to the spectroscopic approach.« less

Microburger Biochemistry: Extraction and Spectral Characterization of Myoglyobin from Hamburger

NASA Astrophysics Data System (ADS)

Bylkas, Sheri A.; Andersson, Laura A.

1997-04-01

This experiment provides a demonstration of useful biochemical methods at a Basic or Advanced Level, depending upon the available spectrophotometric equipment. The protocol combines protein extraction, ox-i-dation and reduction, and simple spectroscopic analysis, as well as gel filtration chromatography and generation/analysis of spectral scans. Mammalian myoglobin (Mb) is a monomeric O2-binding protein that functions in muscle to store oxygen. The single iron protoporphyrin IX (heme) group is bound to protein by the amino acid Histidine93. The common, stable forms, Met-Mb and Oxy-Mb are studied because in a non-living system, red Oxy-Mb is converted to brown Met-Mb as bound O2 molecule is released. Mb is easily extracted from steak, to illustrate and address why fresh meat is red and aged meat is brown; the protein has unique spectral properties that are diagnostic for characterization of sample identity. After application of heme redox chemical methods, the MetMb or OxyMb samples can be studied spectroscopically. The color change between Oxy-Mb and Met-Mb is dramatic (illustrating bright red fresh meat vs. brown older meat), and method(s) used in this laboratory are simple, inexpensive, and non-harmful to the student.

SPACE: the SPectroscopic, All-Sky Cosmic Explorer

NASA Technical Reports Server (NTRS)

Cimatti, A.; Robberto, M.; Baugh, C.; Beckwith, S. W. V.; Content, R.; Daddi, E.; deLucia, G.; Garilli, B.; Guzzo, L.; Kauffmann, G.;

Morphological biosignatures and the search for life on Mars.

PubMed

Cady, Sherry L; Farmer, Jack D; Grotzinger, John P; Schopf, J William; Steele, Andrew

2003-01-01

This report provides a rationale for the advances in instrumentation and understanding needed to assess claims of ancient and extraterrestrial life made on the basis of morphological biosignatures. Morphological biosignatures consist of bona fide microbial fossils as well as microbially influenced sedimentary structures. To be recognized as evidence of life, microbial fossils must contain chemical and structural attributes uniquely indicative of microbial cells or cellular or extracellular processes. When combined with various research strategies, high-resolution instruments can reveal such attributes and elucidate how morphological fossils form and become altered, thereby improving the ability to recognize them in the geological record on Earth or other planets. Also, before fossilized microbially influenced sedimentary structures can provide evidence of life, criteria to distinguish their biogenic from non-biogenic attributes must be established. This topic can be advanced by developing process-based models. A database of images and spectroscopic data that distinguish the suite of bona fide morphological biosignatures from their abiotic mimics will avoid detection of false-positives for life. The use of high-resolution imaging and spectroscopic instruments, in conjunction with an improved knowledge base of the attributes that demonstrate life, will maximize our ability to recognize and assess the biogenicity of extraterrestrial and ancient terrestrial life.

4MOST: the 4-metre Multi-Object Spectroscopic Telescope project at preliminary design review

NASA Astrophysics Data System (ADS)

de Jong, Roelof S.; Barden, Samuel C.; Bellido-Tirado, Olga; Brynnel, Joar G.; Frey, Steffen; Giannone, Domenico; Haynes, Roger; Johl, Diana; Phillips, Daniel; Schnurr, Olivier; Walcher, Jakob C.; Winkler, Roland; Ansorge, Wolfgang R.; Feltzing, Sofia; McMahon, Richard G.; Baker, Gabriella; Caillier, Patrick; Dwelly, Tom; Gaessler, Wolfgang; Iwert, Olaf; Mandel, Holger G.; Piskunov, Nikolai A.; Pragt, Johan H.; Walton, Nicholas A.; Bensby, Thomas; Bergemann, Maria; Chiappini, Cristina; Christlieb, Norbert; Cioni, Maria-Rosa L.; Driver, Simon; Finoguenov, Alexis; Helmi, Amina; Irwin, Michael J.; Kitaura, Francisco-Shu; Kneib, Jean-Paul; Liske, Jochen; Merloni, Andrea; Minchev, Ivan; Richard, Johan; Starkenburg, Else

2016-08-01

We present an overview of the 4MOST project at the Preliminary Design Review. 4MOST is a major new wide-field, high-multiplex spectroscopic survey facility under development for the VISTA telescope of ESO. 4MOST has a broad range of science goals ranging from Galactic Archaeology and stellar physics to the high-energy physics, galaxy evolution, and cosmology. Starting in 2021, 4MOST will deploy 2436 fibres in a 4.1 square degree field-of-view using a positioner based on the tilting spine principle. The fibres will feed one high-resolution (R 20,000) and two medium resolution (R 5000) spectrographs with fixed 3-channel designs and identical 6k x 6k CCD detectors. 4MOST will have a unique operations concept in which 5-year public surveys from both the consortium and the ESO community will be combined and observed in parallel during each exposure. The 4MOST Facility Simulator (4FS) was developed to demonstrate the feasibility of this observing concept, showing that we can expect to observe more than 25 million objects in each 5-year survey period and will eventually be used to plan and conduct the actual survey.

Solving complex photocycle kinetics. Theory and direct method.

PubMed Central

Nagle, J F

1991-01-01

A direct nonlinear least squares method is described that obtains the true kinetic rate constants and the temperature-independent spectra of n intermediates from spectroscopic data taken in the visible at three or more temperatures. A theoretical analysis, which is independent of implementation of the direct method, proves that well determined local solutions are not possible for fewer than three temperatures. This analysis also proves that measurements at more than n wavelengths are redundant, although the direct method indicates that convergence is faster if n + m wavelengths are measured, where m is of order one. This suggests that measurements should concentrate on high precision for a few measuring wavelengths, rather than lower precision for many wavelengths. Globally, false solutions occur, and the ability to reject these depends upon the precision of the data, as shown by explicit example. An optimized way to analyze vibrational spectroscopic data is also presented. Such data yield unique results, which are comparably accurate to those obtained from data taken in the visible with comparable noise. It is discussed how use of both kinds of data is advantageous if the data taken in the visible are significantly less noisy. PMID:2009362

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

NASA Astrophysics Data System (ADS)

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

2014-09-01

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

Spectroscopic evidence for origins of size and support effects on selectivity of Cu nanoparticle dehydrogenation catalysts

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

Witzke, M. E.; Dietrich, P. J.; Ibrahim, M. Y. S.

2016-12-12

Selective dehydrogenation catalysts that produce acetaldehyde from bio-derived ethanol can increase the efficiency of subsequent processes such as C–C coupling over metal oxides to produce 1-butanol or 1,3-butadiene or oxidation to acetic acid. Here, we use in situ X-ray absorption spectroscopy and steady state kinetics experiments to identify Cuδ+ at the perimeter of supported Cu clusters as the active site for esterification and Cu0 surface sites as sites for dehydrogenation. Correlation of dehydrogenation and esterification selectivities to in situ measures of Cu oxidation states show that this relationship holds for Cu clusters over a wide-range of diameters (2–35 nm) andmore » catalyst supports and reveals that dehydrogenation selectivities may be controlled by manipulating either.« less

Technological advances in site-directed spin labeling of proteins.

PubMed

Hubbell, Wayne L; López, Carlos J; Altenbach, Christian; Yang, Zhongyu

2013-10-01

Molecular flexibility over a wide time range is of central importance to the function of many proteins, both soluble and membrane. Revealing the modes of flexibility, their amplitudes, and time scales under physiological conditions is the challenge for spectroscopic methods, one of which is site-directed spin labeling EPR (SDSL-EPR). Here we provide an overview of some recent technological advances in SDSL-EPR related to investigation of structure, structural heterogeneity, and dynamics of proteins. These include new classes of spin labels, advances in measurement of long range distances and distance distributions, methods for identifying backbone and conformational fluctuations, and new strategies for determining the kinetics of protein motion. Copyright © 2013 Elsevier Ltd. All rights reserved.

Electrochemical insights into the mechanism of NiFe membrane-bound hydrogenases

PubMed Central

Flanagan, Lindsey A.; Parkin, Alison

2016-01-01

Hydrogenases are enzymes of great biotechnological relevance because they catalyse the interconversion of H2, water (protons) and electricity using non-precious metal catalytic active sites. Electrochemical studies into the reactivity of NiFe membrane-bound hydrogenases (MBH) have provided a particularly detailed insight into the reactivity and mechanism of this group of enzymes. Significantly, the control centre for enabling O2 tolerance has been revealed as the electron-transfer relay of FeS clusters, rather than the NiFe bimetallic active site. The present review paper will discuss how electrochemistry results have complemented those obtained from structural and spectroscopic studies, to present a complete picture of our current understanding of NiFe MBH. PMID:26862221

Synthesis of new visible light active photocatalysts of Ba(In(1/3)Pb(1/3)M'(1/3))O3 (M' = Nb, Ta): a band gap engineering strategy based on electronegativity of a metal component.

PubMed

Hur, Su Gil; Kim, Tae Woo; Hwang, Seong-Ju; Park, Hyunwoong; Choi, Wonyong; Kim, Sung Jin; Kim, Sun Jin; Choy, Jin-Ho

2005-08-11

We have synthesized new, efficient, visible light active photocatalysts through the incorporation of highly electronegative non-transition metal Pb or Sn ions into the perovskite lattice of Ba(In(1/3)Pb(1/3)M'(1/3))O3 (M = Sn, Pb; M' = Nb, Ta). X-ray diffraction, X-ray absorption spectroscopic, and energy dispersive spectroscopic microprobe analyses reveal that tetravalent Pb or Sn ions exist in the B-site of the perovskite lattice, along with In and Nb/Ta ions. According to diffuse UV-vis spectroscopic analysis, the Pb-containing quaternary metal oxides Ba(In(1/3)Pb(1/3)M'(1/3))O3 possess a much narrower band gap (E(g) approximately 1.48-1.50 eV) when compared to the ternary oxides Ba(In(1/2)M'(1/2))O3 (E(g) approximately 2.97-3.30 eV) and the Sn-containing Ba(In(1/3)Sn(1/3)M'(1/3))O3 derivatives (E(g) approximately 2.85-3.00 eV). Such a variation of band gap energy upon the substitution is attributable to the broadening of the conduction band caused by the dissimilar electronegativities of the B-site cations. In contrast to the ternary or the Sn-substituted quaternary compounds showing photocatalytic activity under UV-vis irradiation, the Ba(In(1/3)Pb(1/3)M'(1/3))O3 compounds induce an efficient photodegradation of 4-chlorophenol under visible light irradiation (lambda > 420 nm). The present results highlight that the substitution of electronegative non-transition metal cations can provide a very powerful way of developing efficient visible light harvesting photocatalysts through tuning of the band structure of a semiconductive metal oxide.

Towards optical spectroscopic anatomical mapping (OSAM) for lesion validation in cardiac tissue (Conference Presentation)

NASA Astrophysics Data System (ADS)

Singh-Moon, Rajinder P.; Zaryab, Mohammad; Hendon, Christine P.

2017-02-01

Electroanatomical mapping (EAM) is an invaluable tool for guiding cardiac radiofrequency ablation (RFA) therapy. The principle roles of EAM is the identification of candidate ablation sites by detecting regions of abnormal electrogram activity and lesion validation subsequent to RF energy delivery. However, incomplete lesions may present interim electrical inactivity similar to effective treatment in the acute setting, despite efforts to reveal them with pacing or drugs, such as adenosine. Studies report that the misidentification and recovery of such lesions is a leading cause of arrhythmia recurrence and repeat procedures. In previous work, we demonstrated spectroscopic characterization of cardiac tissues using a fiber optic-integrated RF ablation catheter. In this work, we introduce OSAM (optical spectroscopic anatomical mapping), the application of this spectroscopic technique to obtain 2-dimensional biodistribution maps. We demonstrate its diagnostic potential as an auxiliary method for lesion validation in treated swine preparations. Endocardial lesion sets were created on fresh swine cardiac samples using a commercial RFA system. An optically-integrated catheter console fabricated in-house was used for measurement of tissue optical spectra between 600-1000nm. Three dimensional, Spatio-spectral datasets were generated by raster scanning of the optical catheter across the treated sample surface in the presence of whole blood. Tissue optical parameters were recovered at each spatial position using an inverse Monte Carlo method. OSAM biodistribution maps showed stark correspondence with gross examination of tetrazolium chloride stained tissue specimens. Specifically, we demonstrate the ability of OSAM to readily distinguish between shallow and deeper lesions, a limitation faced by current EAM techniques. These results showcase the OSAMs potential for lesion validation strategies for the treatment of cardiac arrhythmias.

The 13th Data Release of the Sloan Digital Sky Survey: First Spectroscopic Data from the SDSS-IV Survey Mapping Nearby Galaxies at Apache Point Observatory

NASA Astrophysics Data System (ADS)

Albareti, Franco D.; Allende Prieto, Carlos; Almeida, Andres; Anders, Friedrich; Anderson, Scott; Andrews, Brett H.; Aragón-Salamanca, Alfonso; Argudo-Fernández, Maria; Armengaud, Eric; Aubourg, Eric; Avila-Reese, Vladimir; Badenes, Carles; Bailey, Stephen; Barbuy, Beatriz; Barger, Kat; Barrera-Ballesteros, Jorge; Bartosz, Curtis; Basu, Sarbani; Bates, Dominic; Battaglia, Giuseppina; Baumgarten, Falk; Baur, Julien; Bautista, Julian; Beers, Timothy C.; Belfiore, Francesco; Bershady, Matthew; Bertran de Lis, Sara; Bird, Jonathan C.; Bizyaev, Dmitry; Blanc, Guillermo A.; Blanton, Michael; Blomqvist, Michael; Bolton, Adam S.; Borissova, J.; Bovy, Jo; Nielsen Brandt, William; Brinkmann, Jonathan; Brownstein, Joel R.; Bundy, Kevin; Burtin, Etienne; Busca, Nicolás G.; Orlando Camacho Chavez, Hugo; Cano Díaz, M.; Cappellari, Michele; Carrera, Ricardo; Chen, Yanping; Cherinka, Brian; Cheung, Edmond; Chiappini, Cristina; Chojnowski, Drew; Chuang, Chia-Hsun; Chung, Haeun; Cirolini, Rafael Fernando; Clerc, Nicolas; Cohen, Roger E.; Comerford, Julia M.; Comparat, Johan; Correa do Nascimento, Janaina; Cousinou, Marie-Claude; Covey, Kevin; Crane, Jeffrey D.; Croft, Rupert; Cunha, Katia; Darling, Jeremy; Davidson, James W., Jr.; Dawson, Kyle; Da Costa, Luiz; Da Silva Ilha, Gabriele; Deconto Machado, Alice; Delubac, Timothée; De Lee, Nathan; De la Macorra, Axel; De la Torre, Sylvain; Diamond-Stanic, Aleksandar M.; Donor, John; Downes, Juan Jose; Drory, Niv; Du, Cheng; Du Mas des Bourboux, Hélion; Dwelly, Tom; Ebelke, Garrett; Eigenbrot, Arthur; Eisenstein, Daniel J.; Elsworth, Yvonne P.; Emsellem, Eric; Eracleous, Michael; Escoffier, Stephanie; Evans, Michael L.; Falcón-Barroso, Jesús; Fan, Xiaohui; Favole, Ginevra; Fernandez-Alvar, Emma; Fernandez-Trincado, J. G.; Feuillet, Diane; Fleming, Scott W.; Font-Ribera, Andreu; Freischlad, Gordon; Frinchaboy, Peter; Fu, Hai; Gao, Yang; Garcia, Rafael A.; Garcia-Dias, R.; Garcia-Hernández, D. A.; Garcia Pérez, Ana E.; Gaulme, Patrick; Ge, Junqiang; Geisler, Douglas; Gillespie, Bruce; Gil Marin, Hector; Girardi, Léo; Goddard, Daniel; Gomez Maqueo Chew, Yilen; Gonzalez-Perez, Violeta; Grabowski, Kathleen; Green, Paul; Grier, Catherine J.; Grier, Thomas; Guo, Hong; Guy, Julien; Hagen, Alex; Hall, Matt; Harding, Paul; Harley, R. E.; Hasselquist, Sten; Hawley, Suzanne; Hayes, Christian R.; Hearty, Fred; Hekker, Saskia; Hernandez Toledo, Hector; Ho, Shirley; Hogg, David W.; Holley-Bockelmann, Kelly; Holtzman, Jon A.; Holzer, Parker H.; Hu, Jian; Huber, Daniel; Hutchinson, Timothy Alan; Hwang, Ho Seong; Ibarra-Medel, Héctor J.; Ivans, Inese I.; Ivory, KeShawn; Jaehnig, Kurt; Jensen, Trey W.; Johnson, Jennifer A.; Jones, Amy; Jullo, Eric; Kallinger, T.; Kinemuchi, Karen; Kirkby, David; Klaene, Mark; Kneib, Jean-Paul; Kollmeier, Juna A.; Lacerna, Ivan; Lane, Richard R.; Lang, Dustin; Laurent, Pierre; Law, David R.; Leauthaud, Alexie; Le Goff, Jean-Marc; Li, Chen; Li, Cheng; Li, Niu; Li, Ran; Liang, Fu-Heng; Liang, Yu; Lima, Marcos; Lin, Lihwai; Lin, Lin; Lin, Yen-Ting; Liu, Chao; Long, Dan; Lucatello, Sara; MacDonald, Nicholas; MacLeod, Chelsea L.; Mackereth, J. Ted; Mahadevan, Suvrath; Geimba Maia, Marcio Antonio; Maiolino, Roberto; Majewski, Steven R.; Malanushenko, Olena; Malanushenko, Viktor; Dullius Mallmann, Nícolas; Manchado, Arturo; Maraston, Claudia; Marques-Chaves, Rui; Martinez Valpuesta, Inma; Masters, Karen L.; Mathur, Savita; McGreer, Ian D.; Merloni, Andrea; Merrifield, Michael R.; Meszáros, Szabolcs; Meza, Andres; Miglio, Andrea; Minchev, Ivan; Molaverdikhani, Karan; Montero-Dorta, Antonio D.; Mosser, Benoit; Muna, Demitri; Myers, Adam; Nair, Preethi; Nandra, Kirpal; Ness, Melissa; Newman, Jeffrey A.; Nichol, Robert C.; Nidever, David L.; Nitschelm, Christian; O’Connell, Julia; Oravetz, Audrey; Oravetz, Daniel J.; Pace, Zachary; Padilla, Nelson; Palanque-Delabrouille, Nathalie; Pan, Kaike; Parejko, John; Paris, Isabelle; Park, Changbom; Peacock, John A.; Peirani, Sebastien; Pellejero-Ibanez, Marcos; Penny, Samantha; Percival, Will J.; Percival, Jeffrey W.; Perez-Fournon, Ismael; Petitjean, Patrick; Pieri, Matthew; Pinsonneault, Marc H.; Pisani, Alice; Prada, Francisco; Prakash, Abhishek; Price-Jones, Natalie; Raddick, M. Jordan; Rahman, Mubdi; Raichoor, Anand; Barboza Rembold, Sandro; Reyna, A. M.; Rich, James; Richstein, Hannah; Ridl, Jethro; Riffel, Rogemar A.; Riffel, Rogério; Rix, Hans-Walter; Robin, Annie C.; Rockosi, Constance M.; Rodríguez-Torres, Sergio; Rodrigues, Thaíse S.; Roe, Natalie; Lopes, A. Roman; Román-Zúñiga, Carlos; Ross, Ashley J.; Rossi, Graziano; Ruan, John; Ruggeri, Rossana; Runnoe, Jessie C.; Salazar-Albornoz, Salvador; Salvato, Mara; Sanchez, Sebastian F.; Sanchez, Ariel G.; Sanchez-Gallego, José R.; Santiago, Basílio Xavier; Schiavon, Ricardo; Schimoia, Jaderson S.; Schlafly, Eddie; Schlegel, David J.; Schneider, Donald P.; Schönrich, Ralph; Schultheis, Mathias; Schwope, Axel; Seo, Hee-Jong; Serenelli, Aldo; Sesar, Branimir; Shao, Zhengyi; Shetrone, Matthew; Shull, Michael; Silva Aguirre, Victor; Skrutskie, M. F.; Slosar, Anže; Smith, Michael; Smith, Verne V.; Sobeck, Jennifer; Somers, Garrett; Souto, Diogo; Stark, David V.; Stassun, Keivan G.; Steinmetz, Matthias; Stello, Dennis; Storchi Bergmann, Thaisa; Strauss, Michael A.; Streblyanska, Alina; Stringfellow, Guy S.; Suarez, Genaro; Sun, Jing; Taghizadeh-Popp, Manuchehr; Tang, Baitian; Tao, Charling; Tayar, Jamie; Tembe, Mita; Thomas, Daniel; Tinker, Jeremy; Tojeiro, Rita; Tremonti, Christy; Troup, Nicholas; Trump, Jonathan R.; Unda-Sanzana, Eduardo; Valenzuela, O.; Van den Bosch, Remco; Vargas-Magaña, Mariana; Vazquez, Jose Alberto; Villanova, Sandro; Vivek, M.; Vogt, Nicole; Wake, David; Walterbos, Rene; Wang, Yuting; Wang, Enci; Weaver, Benjamin Alan; Weijmans, Anne-Marie; Weinberg, David H.; Westfall, Kyle B.; Whelan, David G.; Wilcots, Eric; Wild, Vivienne; Williams, Rob A.; Wilson, John; Wood-Vasey, W. M.; Wylezalek, Dominika; Xiao, Ting; Yan, Renbin; Yang, Meng; Ybarra, Jason E.; Yeche, Christophe; Yuan, Fang-Ting; Zakamska, Nadia; Zamora, Olga; Zasowski, Gail; Zhang, Kai; Zhao, Cheng; Zhao, Gong-Bo; Zheng, Zheng; Zheng, Zheng; Zhou, Zhi-Min; Zhu, Guangtun; Zinn, Joel C.; Zou, Hu

2017-12-01

The fourth generation of the Sloan Digital Sky Survey (SDSS-IV) began observations in 2014 July. It pursues three core programs: the Apache Point Observatory Galactic Evolution Experiment 2 (APOGEE-2), Mapping Nearby Galaxies at APO (MaNGA), and the Extended Baryon Oscillation Spectroscopic Survey (eBOSS). As well as its core program, eBOSS contains two major subprograms: the Time Domain Spectroscopic Survey (TDSS) and the SPectroscopic IDentification of ERosita Sources (SPIDERS). This paper describes the first data release from SDSS-IV, Data Release 13 (DR13). DR13 makes publicly available the first 1390 spatially resolved integral field unit observations of nearby galaxies from MaNGA. It includes new observations from eBOSS, completing the Sloan Extended QUasar, Emission-line galaxy, Luminous red galaxy Survey (SEQUELS), which also targeted variability-selected objects and X-ray-selected objects. DR13 includes new reductions of the SDSS-III BOSS data, improving the spectrophotometric calibration and redshift classification, and new reductions of the SDSS-III APOGEE-1 data, improving stellar parameters for dwarf stars and cooler stars. DR13 provides more robust and precise photometric calibrations. Value-added target catalogs relevant for eBOSS, TDSS, and SPIDERS and an updated red-clump catalog for APOGEE are also available. This paper describes the location and format of the data and provides references to important technical papers. The SDSS web site, http://www.sdss.org, provides links to the data, tutorials, examples of data access, and extensive documentation of the reduction and analysis procedures. DR13 is the first of a scheduled set that will contain new data and analyses from the planned ∼6 yr operations of SDSS-IV.

Is the Sudlow site I of human serum albumin more generous to adopt prospective anti-cancer bioorganic compound than that of bovine: A combined spectroscopic and docking simulation approach.

PubMed

Joshi, Ritika; Jadhao, Manojkumar; Kumar, Himank; Ghosh, Sujit Kumar

2017-12-01

A comparative biophysical study on the individual conformational adaptation embraced by two homologous serum albumins (SA) (bovine and human) towards a potential anticancer bioorganic compound 2-(6-chlorobenzo[d] thiazol-2-yl)-1H-benzo[de] isoquinoline-1,3(2H)- dione (CBIQD) is apparent from the discrimination in binding behavior and the ensuing consequences accomplished by combined in vitro optical spectroscopy, in silico molecular docking and molecular dynamics (MD) simulation. The Sudlow site I of HSA although anion receptive, harbors neutral CBIQD in Sudlow site I (subdomain IIA, close to Trp) of HSA, while in BSA its prefers to snugly fit into Sudlow site II (subdomain IIIA, close to Tyr). Based on discernable diminution of HSA mean fluorescence lifetime as a function of biluminophore concentration, facile occurrence of fluorescence resonance energy transfer (FRET) is substantiated as the probable quenching mechanism accompanied by structural deformations in the protein ensemble. CBIQD establishes itself within HSA close to Trp214, and consequently reduces the micropolarity of the cybotactic environment that is predominantly constituted by hydrophobic amino acid residues. The stronger association of CBIQD with HSA encourages an allosteric modulation leading to slight deformation in its secondary structure whereas for BSA the association is comparatively weaker. Sudlow site I of HSA is capable to embrace a favorable conformation like malleable gold to provide room for incoming CBIQD, whereas for BSA it behaves more like rigid cast-iron which does not admit any change thus forcing CBIQD to occupy an altogether different binding location i.e. the Sudlow site II. The anticancer CBIQD is found to be stable within the HSA scaffold as vindicated by root mean square deviation (RMSD) and root mean square fluctuation (RMSF) obtained by MD simulation. A competitively inhibited esterase-like activity of HSA upon CBIQD binding to Lys199 and Arg257 residues, plausibly envisions that similar naphthalimide based prodrugs, bearing ester functionality, can be particularly activated by Sudlow site I of HSA. The consolidated spectroscopic research described herein may encourage design of naphthalimide based pro-drugs for effective in vivo biodistribution using HSA-based drug delivery systems. Copyright © 2017 Elsevier Inc. All rights reserved.

Performance Art at the Campusphere: Pedagogical Experiments On-Site

ERIC Educational Resources Information Center

Ben-Shaul, Daphna

2018-01-01

Following a unique practice and research laboratory entitled "Performance: Site/Self" that took place in 2013-2015, this article discusses the implementation of performance art at an academic site--the Tel Aviv University campus. This pedagogical and artistic initiative, characterised by the transgressive pedagogy of performance art…

Anatomy-Based Algorithms for Detecting Oral Cancer Using Reflectance and Fluorescence Spectroscopy

PubMed Central

McGee, Sasha; Mardirossian, Vartan; Elackattu, Alphi; Mirkovic, Jelena; Pistey, Robert; Gallagher, George; Kabani, Sadru; Yu, Chung-Chieh; Wang, Zimmern; Badizadegan, Kamran; Grillone, Gregory; Feld, Michael S.

2010-01-01

Objectives We used reflectance and fluorescence spectroscopy to noninvasively and quantitatively distinguish benign from dysplastic/malignant oral lesions. We designed diagnostic algorithms to account for differences in the spectral properties among anatomic sites (gingiva, buccal mucosa, etc). Methods In vivo reflectance and fluorescence spectra were collected from 71 patients with oral lesions. The tissue was then biopsied and the specimen evaluated by histopathology. Quantitative parameters related to tissue morphology and biochemistry were extracted from the spectra. Diagnostic algorithms specific for combinations of sites with similar spectral properties were developed. Results Discrimination of benign from dysplastic/malignant lesions was most successful when algorithms were designed for individual sites (area under the receiver operator characteristic curve [ROC-AUC], 0.75 for the lateral surface of the tongue) and was least accurate when all sites were combined (ROC-AUC, 0.60). The combination of sites with similar spectral properties (floor of mouth and lateral surface of the tongue) yielded an ROC-AUC of 0.71. Conclusions Accurate spectroscopic detection of oral disease must account for spectral variations among anatomic sites. Anatomy-based algorithms for single sites or combinations of sites demonstrated good diagnostic performance in distinguishing benign lesions from dysplastic/malignant lesions and consistently performed better than algorithms developed for all sites combined. PMID:19999369

A Threonine Stabilizes the NiC and NiR Catalytic Intermediates of [NiFe]-hydrogenase*

PubMed Central

Abou-Hamdan, Abbas; Ceccaldi, Pierre; Lebrette, Hugo; Gutiérrez-Sanz, Oscar; Richaud, Pierre; Cournac, Laurent; Guigliarelli, Bruno; De Lacey, Antonio L.; Léger, Christophe; Volbeda, Anne; Burlat, Bénédicte; Dementin, Sébastien

2015-01-01

The heterodimeric [NiFe] hydrogenase from Desulfovibrio fructosovorans catalyzes the reversible oxidation of H2 into protons and electrons. The catalytic intermediates have been attributed to forms of the active site (NiSI, NiR, and NiC) detected using spectroscopic methods under potentiometric but non-catalytic conditions. Here, we produced variants by replacing the conserved Thr-18 residue in the small subunit with Ser, Val, Gln, Gly, or Asp, and we analyzed the effects of these mutations on the kinetic (H2 oxidation, H2 production, and H/D exchange), spectroscopic (IR, EPR), and structural properties of the enzyme. The mutations disrupt the H-bond network in the crystals and have a strong effect on H2 oxidation and H2 production turnover rates. However, the absence of correlation between activity and rate of H/D exchange in the series of variants suggests that the alcoholic group of Thr-18 is not necessarily a proton relay. Instead, the correlation between H2 oxidation and production activity and the detection of the NiC species in reduced samples confirms that NiC is a catalytic intermediate and suggests that Thr-18 is important to stabilize the local protein structure of the active site ensuring fast NiSI-NiC-NiR interconversions during H2 oxidation/production. PMID:25666617

A threonine stabilizes the NiC and NiR catalytic intermediates of [NiFe]-hydrogenase.

PubMed

Abou-Hamdan, Abbas; Ceccaldi, Pierre; Lebrette, Hugo; Gutiérrez-Sanz, Oscar; Richaud, Pierre; Cournac, Laurent; Guigliarelli, Bruno; De Lacey, Antonio L; Léger, Christophe; Volbeda, Anne; Burlat, Bénédicte; Dementin, Sébastien

2015-03-27

The heterodimeric [NiFe] hydrogenase from Desulfovibrio fructosovorans catalyzes the reversible oxidation of H2 into protons and electrons. The catalytic intermediates have been attributed to forms of the active site (NiSI, NiR, and NiC) detected using spectroscopic methods under potentiometric but non-catalytic conditions. Here, we produced variants by replacing the conserved Thr-18 residue in the small subunit with Ser, Val, Gln, Gly, or Asp, and we analyzed the effects of these mutations on the kinetic (H2 oxidation, H2 production, and H/D exchange), spectroscopic (IR, EPR), and structural properties of the enzyme. The mutations disrupt the H-bond network in the crystals and have a strong effect on H2 oxidation and H2 production turnover rates. However, the absence of correlation between activity and rate of H/D exchange in the series of variants suggests that the alcoholic group of Thr-18 is not necessarily a proton relay. Instead, the correlation between H2 oxidation and production activity and the detection of the NiC species in reduced samples confirms that NiC is a catalytic intermediate and suggests that Thr-18 is important to stabilize the local protein structure of the active site ensuring fast NiSI-NiC-NiR interconversions during H2 oxidation/production. © 2015 by The American Society for Biochemistry and Molecular Biology, Inc.

Fatty acid modulated human serum albumin binding of the β-carboline alkaloids norharmane and harmane.

PubMed

Domonkos, Celesztina; Fitos, Ilona; Visy, Júlia; Zsila, Ferenc

2013-12-02

Harmane and norharmane are representative members of the large group of natural β-carboline alkaloids featured with diverse pharmacological activities. In blood, these agents are transported by human serum albumin (HSA) which has a profound impact on the pharmacokinetic and pharmacodynamic properties of many therapeutic drugs and xenobiotics. By combination of various spectroscopic methods, the present contribution is aimed to elucidate how nonesterified fatty acids (FAs), the primary endogenous ligands of HSA, affect the binding properties of harmane and norharmane. Analysis of induced circular dichroism (CD) and fluorescence spectroscopic data indicates the inclusion of the neutral form of both molecules into the binding pocket of subdomain IIIA, which hosts two FA binding sites, too. The induced CD and UV absorption spectra of harmane and norharmane exhibit peculiar changes upon addition of FAs, suggesting the formation of ternary complexes in which the lipid ligands significantly alter the binding mode of the alkaloids via cooperative allosteric mechanism. To our knowledge, it is the first instance of the demonstration of drug-FA cobinding at site IIIA. In line with these results, molecular docking calculations showed two distinct binding positions of norharmane within subdomain IIIA. The profound increase in the affinity constants of β-carbolines estimated in the presence of FAs predicts that the unbound, pharmacologically active serum fraction of these compounds strongly depends on the actual lipid binding profile of HSA.

Superoxide reduction by a superoxide reductase lacking the highly conserved lysine residue

DOE PAGES

Teixeira, Miguel; Cabelli, Diane; Pinto, Ana F.; ...

2014-12-05

Superoxide reductases (SORs) are the most recently identified superoxide detoxification systems, being found in microorganisms from the three domains of life. These enzymes are characterized by a catalytic mononuclear iron site, with one cysteine and four histidine ligands of the ferrous active form. A lysine residue in the –EKHVP– motif, located close to the active site, has been considered to be essential for the enzyme function, by contributing to the positive surface patch that attracts the superoxide anion and by controlling the chemistry of the catalytic mechanism through a hydrogen bond network. However, we show here that this residue ismore » substituted by non-equivalent amino acids in several putative SORs from Archaea and unicellular Eukarya. In this work, we focus on mechanistic and spectroscopic studies of one of these less common enzymes, the SOR from the hyperthermophilic crenarchaeon Ignicoccus hospitalis. We employ pulse radiolysis fast kinetics and spectroscopic approaches to study the wild-type enzyme (₋E₂₃T₂₄HVP₋), and two mutants, T24K and E23A, the later mimicking enzymes lacking both the lysine and glutamate (a ferric ion ligand) of the motif. The efficiency of the wild type protein and mutants in reducing superoxide is comparable to other SORs, revealing the robustness of these enzymes to single mutations.« less

Spectroscopic and Computational Investigation of Iron(III) Cysteine Dioxygenase: Implications for the Nature of the Putative Superoxo-Fe(III) Intermediate

PubMed Central

2015-01-01

Cysteine dioxygenase (CDO) is a mononuclear, non-heme iron-dependent enzyme that converts exogenous cysteine (Cys) to cysteine sulfinic acid using molecular oxygen. Although the complete catalytic mechanism is not yet known, several recent reports presented evidence for an Fe(III)-superoxo reaction intermediate. In this work, we have utilized spectroscopic and computational methods to investigate the as-isolated forms of CDO, as well as Cys-bound Fe(III)CDO, both in the absence and presence of azide (a mimic of superoxide). An analysis of our electronic absorption, magnetic circular dichroism, and electron paramagnetic resonance data of the azide-treated as-isolated forms of CDO within the framework of density functional theory (DFT) computations reveals that azide coordinates directly to the Fe(III), but not the Fe(II) center. An analogous analysis carried out for Cys-Fe(III)CDO provides compelling evidence that at physiological pH, the iron center is six coordinate, with hydroxide occupying the sixth coordination site. Upon incubation of this species with azide, the majority of the active sites retain hydroxide at the iron center. Nonetheless, a modest perturbation of the electronic structure of the Fe(III) center is observed, indicating that azide ions bind near the active site. Additionally, for a small fraction of active sites, azide displaces hydroxide and coordinates directly to the Cys-bound Fe(III) center to generate a low-spin (S = 1/2) Fe(III) complex. In the DFT-optimized structure of this complex, the central nitrogen atom of the azide moiety lies within 3.12 Å of the cysteine sulfur. A similar orientation of the superoxide ligand in the putative Fe(III)-superoxo reaction intermediate would promote the attack of the distal oxygen atom on the sulfur of substrate Cys. PMID:25093959

Evaluating Protein Structure and Dynamics Using Co-Solvents, Photochemical Triggers, and Site-Specific Spectroscopic Probes

NASA Astrophysics Data System (ADS)

Abaskharon, Rachel M.

As ubiquitous and diverse biopolymers, proteins are dynamic molecules that are constantly engaging in inter- and intramolecular interactions responsible for their structure, fold, and function. Because of this, gaining a comprehensive understanding of the factors that control protein conformation and dynamics remains elusive as current experimental techniques often lack the ability to initiate and probe a specific interaction or conformational transition. For this reason, this thesis aims to develop methods to control and monitor protein conformations, conformational transitions, and dynamics in a site-specific manner, as well as to understand how specific and non-specific interactions affect the protein folding energy landscape. First, by using the co-solvent, trifluoroethanol (TFE), we show that the rate at which a peptide folds can be greatly impacted and thus controlled by the excluded volume effect. Secondly, we demonstrate the utility of several light-responsive molecules and reactions as methods to manipulate and investigate protein-folding processes. Using an azobenzene linker as a photo-initiator, we are able to increase the folding rate of a protein system by an order of magnitude by channeling a sub-population through a parallel, faster folding pathway. Additionally, we utilize a tryptophan-mediated electron transfer process to a nearby disulfide bond to strategically unfold a protein molecule with ultraviolet light. We also demonstrate the potential of two ruthenium polypyridyl complexes as ultrafast phototriggers of protein reactions. Finally, we develop several site-specific spectroscopic probes of protein structure and environment. Specifically, we demonstrate that a 13C-labeled aspartic acid residue constitutes a useful site-specific infrared probe for investigating salt-bridges and hydration dynamics of proteins, particularly in proteins containing several acidic amino acids. We also show that a proline-derivative, 4-oxoproline, possesses novel infrared properties that can be exploited to monitor the cis-trans isomerization process of individual proline residues in proteins.

QM/MM structural and spectroscopic analysis of the di-iron(II) and di-iron(III) ferroxidase site in M ferritin.

PubMed

Harris, Travis V; Morokuma, Keiji

2013-08-05

Ferritins are cage-like proteins composed of 24 subunits that take up iron(II) and store it as an iron(III) oxide mineral core. A critical step is the ferroxidase reaction, in which oxygen reacts with a di-iron(II) site, proceeding through a peroxo intermediate, to form μ-oxo/hydroxo-bridged di-iron(III) products. The recent crystal structures of copper(II)- and iron(III)-bound frog M ferritin at 2.8 Å resolution [Bertini; et al. J. Am. Chem. Soc. 2012, 134, 6169-6176] provided an opportunity to theoretically investigate the detailed structures of the reactant state and products. In this study, the quantum mechanical/molecular mechanical ONIOM method is used to structurally optimize a series of single-subunit models with various hydration, protonation, and coordination states of the ferroxidase site. Calculated exchange coupling constants (J), Mössbauer parameters, and time-dependent density functional theoretical (TD-DFT) circular dichroism spectra with electronic embedding are compared with the available experimental data. The di-iron(II) model with the most experimentally consistent structural and spectroscopic parameters has 5-coordinate iron centers with Glu23, Glu58, His61, and two waters completing one coordination sphere, and His54, Glu58, Glu103, and Asp140 completing the other. In contrast to a previously proposed structure, Gln137 is not directly coordinated, but it is involved in hydrogen bonding with several iron ligands. For the di-iron(III) products, we find that a μ-oxo-bridged and two doubly bridged (μ-hydroxo and μ-oxo/hydroxo) species are likely coproduced. Although four quadrupole doublets were observed experimentally, we find that two doublets may arise from a single asymmetrically coordinated ferroxidase site. These proposed key structures will help to explore the pathway connecting the di-Fe(II) state to the peroxo intermediate and the branching mechanisms leading to the multiple products.

The lost micro-deserts of the Patuxent River using landscape history, insect and plant specimens, and field work to detect and define a unique community

USGS Publications Warehouse

Droege, S.; Davis, C.A.; Steiner, W.E.; =Mawdsley, J.

2009-01-01

Historical and recent records of both plants and insects are synthesized for uplands along the eastern edge of Maryland?s Patuxent River from the edge of the Piedmont south to Jug Bay. This strip is characterized by deep sandy soils found in the Evesboro and Galestown sandy loams soil series. Within this narrow strip there exists a unique flora and fauna adapted to open dry sandy soils and occurring in small remnant patches associated with old sand mining operations and scattered protected areas. We illustrate the uniqueness of these sites using four groups, vascular plants, tenebrionid beetles (Coleoptera: Tenebrionidae), tiger beetles (Coleoptera: Cicindelidae), and bees (Hymenoptera: Apoidea: Anthophila). Within each of these groups, rare species were detected whose populations were locally restricted to this soil type and whose nearest known populations were often hundreds of kilometers away. In addition to documenting the direct conservation importance of these small sandy openings along the Patuxent, we contrast the lack of any indication from vertebrate inventories that this region is unique. The combination of plant and insect inventories appears to be a better means of clarifying a site?s importance than does any survey of a single taxonomic group.

Hydrologic Source Term Processes and Models for the Clearwater and Wineskin Tests, Rainier Mesa, Nevada National Security Site

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

Carle, Steven F.

2011-05-04

This report describes the development, processes, and results of a hydrologic source term (HST) model for the CLEARWATER (U12q) and WINESKIN (U12r) tests located on Rainier Mesa, Nevada National Security Site, Nevada (Figure 1.1). Of the 61 underground tests (involving 62 unique detonations) conducted on Rainier Mesa (Area 12) between 1957 and 1992 (USDOE, 2015), the CLEARWATER and WINESKIN tests present many unique features that warrant a separate HST modeling effort from other Rainier Mesa tests.

16 CFR 1031.18 - Method of review and comment.

Code of Federal Regulations, 2010 CFR

2010-01-01

... Commission staff is involved shall have a unique Web link on the Commission Web site with relevant... forwarded to appropriate staff for consideration and/or response. (c) On the voluntary standards Web site...

16 CFR 1031.18 - Method of review and comment.

Code of Federal Regulations, 2012 CFR

2012-01-01

... Commission staff is involved shall have a unique Web link on the Commission Web site with relevant... forwarded to appropriate staff for consideration and/or response. (c) On the voluntary standards Web site...

16 CFR 1031.18 - Method of review and comment.

Code of Federal Regulations, 2011 CFR

2011-01-01

... Commission staff is involved shall have a unique Web link on the Commission Web site with relevant... forwarded to appropriate staff for consideration and/or response. (c) On the voluntary standards Web site...

Chemoselective single-site Earth-abundant metal catalysts at metal–organic framework nodes

PubMed Central

Manna, Kuntal; Ji, Pengfei; Lin, Zekai; Greene, Francis X.; Urban, Ania; Thacker, Nathan C.; Lin, Wenbin

2016-01-01

Earth-abundant metal catalysts are critically needed for sustainable chemical synthesis. Here we report a simple, cheap and effective strategy of producing novel earth-abundant metal catalysts at metal–organic framework (MOF) nodes for broad-scope organic transformations. The straightforward metalation of MOF secondary building units (SBUs) with cobalt and iron salts affords highly active and reusable single-site solid catalysts for a range of organic reactions, including chemoselective borylation, silylation and amination of benzylic C–H bonds, as well as hydrogenation and hydroboration of alkenes and ketones. Our structural, spectroscopic and kinetic studies suggest that chemoselective organic transformations occur on site-isolated, electron-deficient and coordinatively unsaturated metal centres at the SBUs via σ-bond metathesis pathways and as a result of the steric environment around the catalytic site. MOFs thus provide a novel platform for the development of highly active and affordable base metal catalysts for the sustainable synthesis of fine chemicals. PMID:27574182

Chemoselective single-site Earth-abundant metal catalysts at metal–organic framework nodes

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

Manna, Kuntal; Ji, Pengfei; Lin, Zekai

2016-08-30

Earth-abundant metal catalysts are critically needed for sustainable chemical synthesis. Here we report a simple, cheap and effective strategy of producing novel earth-abundant metal catalysts at metal–organic framework (MOF) nodes for broad-scope organic transformations. The straightforward metalation of MOF secondary building units (SBUs) with cobalt and iron salts affords highly active and reusable single-site solid catalysts for a range of organic reactions, including chemoselective borylation, silylation and amination of benzylic C–H bonds, as well as hydrogenation and hydroboration of alkenes and ketones. Our structural, spectroscopic and kinetic studies suggest that chemoselective organic transformations occur on site-isolated, electron-deficient and coordinatively unsaturatedmore » metal centres at the SBUs via σ-bond metathesis pathways and as a result of the steric environment around the catalytic site. MOFs thus provide a novel platform for the development of highly active and affordable base metal catalysts for the sustainable synthesis of fine chemicals.« less

FT-Raman spectroscopic analysis of enhanced activity of supercritical carbon dioxide treated bacterial alpha-amylase.

PubMed

Paul, Kaninika; Dutta, Sayantani; Bhattacharjee, Paramita

2017-09-01

Our previous investigation on high pressure supercritical carbon dioxide treatment of a bacterial α-amylase had revealed enhanced activity of the same. 1 H NMR analysis of the activity enhanced enzyme led the authors to hypothesize that the enhancement was possibly owing to alterations in the active site of the enzyme. In the present study, the changes in the active site of the treated enzyme was analysed by Fourier-transform Raman (FT-Raman) spectroscopy. The spectra obtained revealed shifting of bands in the active site of α-amylase indicating a nudging effect of the bonds in this region consequent to high pressure treatment. Also, shifts in bands in the OH stretching vibration of water were observed in the enzyme spectra. These variations in the spectra confirmed changes in the active site as well as in the water associated with the same that perhaps had a concerted effect on the increased activity of α-amylase. Copyright © 2017 Elsevier Inc. All rights reserved.

MUSE spectroscopy and deep observations of a unique compact JWST target, lensing cluster CLIO

NASA Astrophysics Data System (ADS)

Griffiths, Alex; Conselice, Christopher J.; Alpaslan, Mehmet; Frye, Brenda L.; Diego, Jose M.; Zitrin, Adi; Yan, Haojing; Ma, Zhiyuan; Barone-Nugent, Robert; Bhatawdekar, Rachana; Driver, Simon P.; Robotham, Aaron S. G.; Windhorst, Rogier A.; Wyithe, J. Stuart B.

2018-04-01

We present the results of a VLT MUSE/FORS2 and Spitzer survey of a unique compact lensing cluster CLIO at z = 0.42, discovered through the GAMA survey using spectroscopic redshifts. Compact and massive clusters such as this are understudied, but provide a unique prospective on dark matter distributions and for finding background lensed high-z galaxies. The CLIO cluster was identified for follow-up observations due to its almost unique combination of high-mass and dark matter halo concentration, as well as having observed lensing arcs from ground-based images. Using dual band optical and infra-red imaging from FORS2 and Spitzer, in combination with MUSE optical spectroscopy we identify 89 cluster members and find background sources out to z = 6.49. We describe the physical state of this cluster, finding a strong correlation between environment and galaxy spectral type. Under the assumption of an NFW profile, we measure the total mass of CLIO to be M200 = (4.49 ± 0.25) × 1014 M⊙. We build and present an initial strong-lensing model for this cluster, and measure a relatively low intracluster light (ICL) fraction of 7.21 ± 1.53 per cent through galaxy profile fitting. Due to its strong potential for lensing background galaxies and its low ICL, the CLIO cluster will be a target for our 110 h James Webb Space Telescope `Webb Medium-Deep Field' (WMDF) GTO program.

A comparative study of CO adsorption on tetrahexahedral Pt nanocrystals and interrelated Pt single crystal electrodes by using cyclic voltammetry and in situ FTIR spectroscopy.

PubMed

Liu, Hai-Xia; Tian, Na; Ye, Jin-Yu; Lu, Bang-An; Ren, Jie; Huangfu, Zhi-Chao; Zhou, Zhi-You; Sun, Shi-Gang

2014-01-01

This study focuses on CO adsorption at tetrahexahedral Pt nanocrystals (THH Pt NCs) by using cyclic voltammetry and in situ FTIR spectroscopy. Since the electrochemically prepared THH Pt NCs in this study are enclosed by {730} facets which could be considered by a subfacet configuration of 2{210} + {310}, we have also studied CO adsorption on the interrelated Pt(310) and Pt(210) single crystal electrodes as a comparison. Cyclic voltammetry results demonstrated that CO adsorbs dominantly on the (100) sites of THH Pt NCs at low CO coverage (θ(CO)≤ 0.135), while on both (100) and (110) sites at higher CO coverage. On ordered Pt(310) and Pt(210), i.e. they were flame annealed and then cooled in H(2) + Ar, CO adsorption also illustrates relative priority on (100) sites at low CO coverage; while at high CO coverage or on oxygen-disordered Pt(310) and Pt(210) when they were cooled in air after flame annealing, the adsorption of CO presents a weak preference on (100) sites of Pt(310) and even no preference at all on (100) sites of Pt(210). In situ FTIR spectroscopic studies illustrated that CO adsorption on THH Pt NCs yields anomalous infrared effects (AIREs), which are depicted by the Fano-like IR feature on a dense distribution (60 μm(-2)) and the enhancement of abnormal IR absorption on a sparse distribution (22 μm(-2)) of THH Pt NCs on glassy carbon substrate. Systematic investigation of CO coverage dependence of IR features revealed that, on THH Pt NCs, the IR band center (ν(COL)) of linearly bonded CO (COL) is rapidly shifted to higher wavenumbers along with the increase of CO coverage to 0.184, yielding a fast linear increase rate with a high slope (dν(COL)/dθ(IR)(CO) = 219 cm(-1)); when θ > 0.184, the increase of ν(COL) with θCO slows down and deviates drastically from linearity. In contrast, the ν(COL) on the ordered Pt(310) electrode maintains a linear increase with θ(IR)(CO) for the whole range of θ(IR)(CO) variation, and gives a much smaller increase rate of slope 74.3 cm(-1). The significant differences in CO adsorption behavior on THH Pt NCs and on interrelated Pt single crystal planes demonstrated clearly the unique properties of nanoparticles enclosed by high-index facets.

Spectral Study of Water Tracks as an Analog for Recurring Slope Lineae

NASA Technical Reports Server (NTRS)

Ojha, L.; Wilhelm, M. B.; Wray, J. J.

2013-01-01

Liquid water is a key requirement for life on Earth, and serves as an important constraint on present day habitability on Mars. Recurring Slope Lineae (RSL) are a unique phenomenon on Mars that may be formed by brine seeps. Their morphological, seasonal and temporal characteristics support this hypothesis; however, spectral evidence has been lacking. Ojha et al., 2013 recently analyzed CRISM images from all confirmed RSL in the southern mid-latitudes and equatorial regions and found no spectro-scopic evidence for water. Instead, enhanced abun-dances or distinct grain sizes of both ferric and ferrous minerals are observed at most sites. The strength of these spectral signatures changes as a function of sea-son, possibly indicating removal of a fine-grained sur-face component during RSL flow, precipitation of fer-ric oxides, and/or wetting of the substrate. Water tracks (WT) have been suggested as a terrestrial analog for RSL by Levy et al., 2011. WT are defined as dark surface features that extend downslope in a linear or branching fashion, usually oriented along the steepest local gradient, in the Dry Valleys of Antarctica. They can be 1-3 m in width and can have lengths up to 2 km. They share many morphological and seasonal characteristics with RSL including active growth during summer seasons and fading during winter. Snowmelt, ground ice melt and deliquescence by hygroscopic salts have been suggested as possible formation mechanisms for water tracks. No spectral work to date has been reported for water tracks.

Resolved Star Formation in Galaxies Using Slitless Spectroscopy

NASA Astrophysics Data System (ADS)

Pirzkal, Norbert; Finkelstein, Steven L.; Larson, Rebecca L.; Malhotra, Sangeeta; Rhoads, James E.; Ryan, Russell E.; Tilvi, Vithal; FIGS Team

2018-06-01

The ability to spatially resolve individual star-formation regions in distant galaxies and simultaneously extract their physical properties via emission lines is a critical step forward in studying the evolution of galaxies. While efficient, deep slitless spectroscopic observations offer a blurry view of the summed properties of galaxies. We present our studies of resolved star formation over a wide range of redshifts, including high redshift Ly-a sources. The unique capabilities of the WFC3 IR Grism and our two-dimensional emission line method (EM2D) allows us to accurately identify the specific spatial origin of emission lines in galaxies, thus creating a spatial map of star-formation sites in any given galaxy. This method requires the use of multiple position angles on the sky to accurately derive both the location and the observed wavelengths of these emission lines. This has the added benefit of producing better defined redshifts for these sources. Building on our success in applying the EM2D method towards galaxies with [OII]. [OIII], and Ha emission lines, we have also applied EM2D to high redshift (z>6) Ly-a emitting galaxies. We are also able to produce accurate 2D emission line maps (MAP2D) of the Ly-a emission in WFC3 IR grism observations, looking for evidence that a significant amount of resonant scattering is taking place in high redshift galaxies such as in a newly identified z=7.5 Faint Infrared Galaxy Survey (FIGS) Ly-a galaxy.

THE SDSS-IV EXTENDED BARYON OSCILLATION SPECTROSCOPIC SURVEY: QUASAR TARGET SELECTION

DOE PAGES

Myers, Adam D.; Palanque-Delabrouille, Nathalie; Prakash, Abhishek; ...

2015-12-01

As part of the Sloan Digital Sky Survey (SDSS) IV the extended Baryon Oscillation Spectroscopic Survey (eBOSS) will improve measurements of the cosmological distance scale by applying the Baryon Acoustic Oscillation (BAO) method to quasar samples. eBOSS will adopt two approaches to target quasars over 7500 deg 2 . First, a "CORE" quasar sample will combine the optical selection in ugriz using a likelihood-based routine called XDQSOz, with a mid-IR-optical color cut. eBOSS CORE selection (to g < 22 or r < 22) should return ~70 deg -2 quasars at redshifts 0.9 < z < 2.2 and ~7 deg -2more » z > 2.1 quasars. Second, a selection based on variability in multi-epoch imaging from the Palomar Transient Factory should recover an additional ~3-4 deg -2 z > 2.1 quasars to g < 22.5. A linear model of how imaging systematics affect target density recovers the angular distribution of eBOSS CORE quasars over 96.7% (76.7%) of the SDSS north (south) Galactic Cap area. The eBOSS CORE quasar sample should thus be sufficiently dense and homogeneous over 0.9 < z < 2.2 to yield the first few-percent-level BAO constraint near eBOSS quasars at z > 2.1 will be used to improve BAO measurements in the Lyα Forest. Beyond its key cosmological goals, eBOSS should be the next-generation quasar survey, comprising > 500,000 new quasars and > 500,000 uniformly selected spectroscopically confirmed 0.9 < z < 2.2 quasars. At the conclusion of eBOSS, the SDSS will have provided unique spectra for more than 800,000 quasars.« less

AEGIS: The Diversity of Bright Near-IR-selected Distant Red Galaxies

NASA Astrophysics Data System (ADS)

Conselice, C. J.; Newman, J. A.; Georgakakis, A.; Almaini, O.; Coil, A. L.; Cooper, M. C.; Eisenhardt, P.; Foucaud, S.; Koekemoer, A.; Lotz, J.; Noeske, K.; Weiner, B.; Willmer, C. N. A.

2007-05-01

We use deep and wide near-infrared (NIR) imaging from the Palomar telescope combined with DEEP2 spectroscopy and HST and Chandra imaging to investigate the nature of galaxies that are red in NIR colors. We locate these ``distant red galaxies'' (DRGs) through the color cut (J-K)Vega>2.3 over 0.7 deg2, where we find 1010 DRG candidates down to Ks=20.5. We combine 95 high-quality spectroscopic redshifts with photometric redshifts from BRIJK photometry to determine the redshift and stellar mass distributions for these systems, and the morphological/structural and X-ray properties for 107 DRGs in the Extended Groth Strip. We find that many bright (J-K)Vega>2.3 galaxies with Ks<20.5 are at redshifts z<2, with 64% in the range 12 systems being massive with M*>1011 Msolar. HST imaging shows that the structural properties and morphologies of DRGs are also diverse, with the majority elliptical/compact (57%) and the remainder edge-on spiral (7%) and peculiar (29%). The DRGs at z<1.4 with high-quality spectroscopic redshifts are generally compact, with small half-light radii, and span a range in rest-frame optical properties. The spectral energy distribution for the DRGs at z<1.4 differs from higher redshift DRGs: they are bluer by 1 mag in observed (I-J) color. A pure IR color selection of high-redshift populations is not sufficient to identify unique populations, and other colors or spectroscopic redshifts are needed to produce homogeneous samples.

Spectroscopic confirmation of the rich z = 1.80 galaxy cluster JKCS 041 using the WFC3 grism: Environmental trends in the ages and structure of quiescent galaxies

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

Newman, Andrew B.; Ellis, Richard S.; Andreon, Stefano

2014-06-10

We present Hubble Space Telescope imaging and grism spectroscopy in the field of the distant galaxy cluster JKCS 041 using the Wide Field Camera 3. We confirm that JKCS 041 is a rich cluster and derive a redshift z = 1.80 via the spectroscopic identification of 19 member galaxies, of which 15 are quiescent. These are centered upon diffuse X-ray emission seen by the Chandra observatory. As JKCS 041 is the most distant known cluster with such a large, spectroscopically confirmed quiescent population, it provides a unique opportunity to study the effect of the environment on galaxy properties at earlymore » epochs. We construct high-quality composite spectra of the quiescent cluster members that reveal prominent Balmer and metallic absorption lines. Using these, we measure the mean stellar ages in two bins of stellar mass. The quiescent cluster members' ages agree remarkably closely with that inferred by Whitaker et al. for similarly selected samples in the field, supporting the idea that the cluster environment is more efficient at truncating star formation while not having a strong effect on the mean epoch of quenching. We find some evidence (90% confidence) for a lower fraction of disk-like quiescent systems in JKCS 041 compared to a sample of coeval field galaxies drawn from the CANDELS survey. Taking this into account, we do not detect a significant difference between the mass-radius relations of the quiescent JKCS 041 members and our z ∼ 1.8 field sample. Finally, we demonstrate how differences in the morphological mixture of quenched systems can complicate measures of the environmental dependence of size growth.« less

Probing the mechanism of interaction of metoprolol succinate with human serum albumin by spectroscopic and molecular docking analysis.

PubMed

Pawar, Suma K; Jaldappagari, Seetharamappa

2017-09-01

In the present work, the mechanism of the interaction between a β1 receptor blocker, metoprolol succinate (MS) and human serum albumin (HSA) under physiological conditions was investigated by spectroscopic techniques, namely fluorescence, Fourier transform infra-red spectroscopy (FT-IR), fluorescence lifetime decay and circular dichroism (CD) as well as molecular docking and cyclic voltammetric methods. The fluorescence and lifetime decay results indicated that MS quenched the intrinsic intensity of HSA through a static quenching mechanism. The Stern-Volmer quenching constants and binding constants for the MS-HSA system at 293, 298 and 303 K were obtained from the Stern-Volmer plot. Thermodynamic parameters for the interaction of MS with HSA were evaluated; negative values of entropy change (ΔG°) indicated the spontaneity of the MS and HSA interaction. Thermodynamic parameters such as negative ΔH° and positive ΔS° values revealed that hydrogen bonding and hydrophobic forces played a major role in MS-HSA interaction and stabilized the complex. The binding site for MS in HSA was identified by competitive site probe experiments and molecular docking studies. These results indicated that MS was bound to HSA at Sudlow's site I. The efficiency of energy transfer and the distance between the donor (HSA) and acceptor (MS) was calculated based on the theory of Fosters' resonance energy transfer (FRET). Three-dimensional fluorescence spectra and CD results revealed that the binding of MS to HSA resulted in an obvious change in the conformation of HSA. Cyclic voltammograms of the MS-HSA system also confirmed the interaction between MS and HSA. Furthermore, the effects of metal ions on the binding of MS to HSA were also studied. Copyright © 2017 John Wiley & Sons, Ltd.

Does Local Recurrence of Prostate Cancer After Radiation Therapy Occur at the Site of Primary Tumor? Results of a Longitudinal MRI and MRSI Study

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

Arrayeh, Elnasif; Westphalen, Antonio C.; Kurhanewicz, John

2012-04-01

Purpose: To determine if local recurrence of prostate cancer after radiation therapy occurs at the same site as the primary tumor before treatment, using longitudinal magnetic resonance (MR) imaging and MR spectroscopic imaging to assess dominant tumor location. Methods and Materials: This retrospective study was HIPAA compliant and approved by our Committee on Human Research. We identified all patients in our institutional prostate cancer database (1996 onward) who underwent endorectal MR imaging and MR spectroscopic imaging before radiotherapy for biopsy-proven prostate cancer and again at least 2 years after radiotherapy (n = 124). Two radiologists recorded the presence, location, andmore » size of unequivocal dominant tumor on pre- and postradiotherapy scans. Recurrent tumor was considered to be at the same location as the baseline tumor if at least 50% of the tumor location overlapped. Clinical and biopsy data were collected from all patients. Results: Nine patients had unequivocal dominant tumor on both pre- and postradiotherapy imaging, with mean pre- and postradiotherapy dominant tumor diameters of 1.8 cm (range, 1-2.2) and 1.9 cm (range, 1.4-2.6), respectively. The median follow-up interval was 7.3 years (range, 2.7-10.8). Dominant recurrent tumor was at the same location as dominant baseline tumor in 8 of 9 patients (89%). Conclusions: Local recurrence of prostate cancer after radiation usually occurs at the same site as the dominant primary tumor at baseline, suggesting supplementary focal therapy aimed at enhancing local tumor control would be a rational addition to management.« less

Biochemical analyses are instrumental in identifying the impact of mutations on holo and/or apo-forms and on the region(s) of alanine:glyoxylate aminotransferase variants associated with Primary Hyperoxaluria Type I☆

PubMed Central

Oppici, Elisa; Montioli, Riccardo; Lorenzetto, Antonio; Bianconi, Silvia; Borri Voltattorni, Carla; Cellini, Barbara

2012-01-01

Primary Hyperoxaluria Type I (PH1) is a disorder of glyoxylate metabolism caused by mutations in the human AGXT gene encoding liver peroxisomal alanine:glyoxylate aminotransferase (AGT), a pyridoxal 5′-phosphate (PLP) dependent enzyme. Previous investigations highlighted that, although PH1 is characterized by a significant variability in terms of enzymatic phenotype, the majority of the pathogenic variants are believed to share both structural and functional defects, as mainly revealed by data on AGT activity and expression level in crude cellular extracts. However, the knowledge of the defects of the AGT variants at a protein level is still poor. We therefore performed a side-by-side comparison between normal AGT and nine purified recombinant pathogenic variants in terms of catalytic activity, coenzyme binding mode and affinity, spectroscopic features, oligomerization, and thermal stability of both the holo- and apo-forms. Notably, we chose four variants in which the mutated residues are located in the large domain of AGT either within the active site and interacting with the coenzyme or in its proximity, and five variants in which the mutated residues are distant from the active site either in the large or in the small domain. Overall, this integrated analysis of enzymatic activity, spectroscopic and stability information is used to (i) reassess previous data obtained with crude cellular extracts, (ii) establish which form(s) (i.e. holoenzyme and/or apoenzyme) and region(s) (i.e. active site microenvironment, large and/or small domain) of the protein are affected by each mutation, and (iii) suggest the possible therapeutic approach for patients bearing the examined mutations. PMID:22018727

Biochemical analyses are instrumental in identifying the impact of mutations on holo and/or apo-forms and on the region(s) of alanine:glyoxylate aminotransferase variants associated with primary hyperoxaluria type I.

PubMed

Oppici, Elisa; Montioli, Riccardo; Lorenzetto, Antonio; Bianconi, Silvia; Borri Voltattorni, Carla; Cellini, Barbara

2012-01-01

Primary Hyperoxaluria Type I (PH1) is a disorder of glyoxylate metabolism caused by mutations in the human AGXT gene encoding liver peroxisomal alanine:glyoxylate aminotransferase (AGT), a pyridoxal 5'-phosphate (PLP) dependent enzyme. Previous investigations highlighted that, although PH1 is characterized by a significant variability in terms of enzymatic phenotype, the majority of the pathogenic variants are believed to share both structural and functional defects, as mainly revealed by data on AGT activity and expression level in crude cellular extracts. However, the knowledge of the defects of the AGT variants at a protein level is still poor. We therefore performed a side-by-side comparison between normal AGT and nine purified recombinant pathogenic variants in terms of catalytic activity, coenzyme binding mode and affinity, spectroscopic features, oligomerization, and thermal stability of both the holo- and apo-forms. Notably, we chose four variants in which the mutated residues are located in the large domain of AGT either within the active site and interacting with the coenzyme or in its proximity, and five variants in which the mutated residues are distant from the active site either in the large or in the small domain. Overall, this integrated analysis of enzymatic activity, spectroscopic and stability information is used to (i) reassess previous data obtained with crude cellular extracts, (ii) establish which form(s) (i.e. holoenzyme and/or apoenzyme) and region(s) (i.e. active site microenvironment, large and/or small domain) of the protein are affected by each mutation, and (iii) suggest the possible therapeutic approach for patients bearing the examined mutations. Copyright © 2011 Elsevier Inc. All rights reserved.

[3Fe-4S] to [4Fe-4S] cluster conversion in Desulfovibrio fructosovorans [NiFe] hydrogenase by site-directed mutagenesis

PubMed Central

Rousset, Marc; Montet, Yael; Guigliarelli, Bruno; Forget, Nicole; Asso, Marcel; Bertrand, Patrick; Fontecilla-Camps, Juan C.; Hatchikian, E. Claude

1998-01-01

The role of the high potential [3Fe-4S]1+,0 cluster of [NiFe] hydrogenase from Desulfovibrio species located halfway between the proximal and distal low potential [4Fe-4S]2+,1+ clusters has been investigated by using site-directed mutagenesis. Proline 238 of Desulfovibrio fructosovorans [NiFe] hydrogenase, which occupies the position of a potential ligand of the lacking fourth Fe-site of the [3Fe-4S] cluster, was replaced by a cysteine residue. The properties of the mutant enzyme were investigated in terms of enzymatic activity, EPR, and redox properties of the iron-sulfur centers and crystallographic structure. We have shown on the basis of both spectroscopic and x-ray crystallographic studies that the [3Fe-4S] cluster of D. fructosovorans hydrogenase was converted into a [4Fe-4S] center in the P238 mutant. The [3Fe-4S] to [4Fe-4S] cluster conversion resulted in a lowering of approximately 300 mV of the midpoint potential of the modified cluster, whereas no significant alteration of the spectroscopic and redox properties of the two native [4Fe-4S] clusters and the NiFe center occurred. The significant decrease of the midpoint potential of the intermediate Fe-S cluster had only a slight effect on the catalytic activity of the P238C mutant as compared with the wild-type enzyme. The implications of the results for the role of the high-potential [3Fe-4S] cluster in the intramolecular electron transfer pathway are discussed. PMID:9751716

Ensemble predictive model for more accurate soil organic carbon spectroscopic estimation

NASA Astrophysics Data System (ADS)

Vašát, Radim; Kodešová, Radka; Borůvka, Luboš

2017-07-01

A myriad of signal pre-processing strategies and multivariate calibration techniques has been explored in attempt to improve the spectroscopic prediction of soil organic carbon (SOC) over the last few decades. Therefore, to come up with a novel, more powerful, and accurate predictive approach to beat the rank becomes a challenging task. However, there may be a way, so that combine several individual predictions into a single final one (according to ensemble learning theory). As this approach performs best when combining in nature different predictive algorithms that are calibrated with structurally different predictor variables, we tested predictors of two different kinds: 1) reflectance values (or transforms) at each wavelength and 2) absorption feature parameters. Consequently we applied four different calibration techniques, two per each type of predictors: a) partial least squares regression and support vector machines for type 1, and b) multiple linear regression and random forest for type 2. The weights to be assigned to individual predictions within the ensemble model (constructed as a weighted average) were determined by an automated procedure that ensured the best solution among all possible was selected. The approach was tested at soil samples taken from surface horizon of four sites differing in the prevailing soil units. By employing the ensemble predictive model the prediction accuracy of SOC improved at all four sites. The coefficient of determination in cross-validation (R2cv) increased from 0.849, 0.611, 0.811 and 0.644 (the best individual predictions) to 0.864, 0.650, 0.824 and 0.698 for Site 1, 2, 3 and 4, respectively. Generally, the ensemble model affected the final prediction so that the maximal deviations of predicted vs. observed values of the individual predictions were reduced, and thus the correlation cloud became thinner as desired.

Binding of fluorescent acridine dyes acridine orange and 9-aminoacridine to hemoglobin: Elucidation of their molecular recognition by spectroscopy, calorimetry and molecular modeling techniques.

PubMed

Chatterjee, Sabyasachi; Kumar, Gopinatha Suresh

2016-06-01

The molecular interaction between hemoglobin (HHb), the major human heme protein, and the acridine dyes acridine orange (AO) and 9-aminoacridine (9AA) was studied by various spectroscopic, calorimetric and molecular modeling techniques. The dyes formed stable ground state complex with HHb as revealed from spectroscopic data. Temperature dependent fluorescence data showed the strength of the dye-protein complexation to be inversely proportional to temperature and the fluorescence quenching was static in nature. The binding-induced conformational change in the protein was investigated using circular dichroism, synchronous fluorescence, 3D fluorescence and FTIR spectroscopy results. Circular dichroism data also quantified the α-helicity change in hemoglobin due to the binding of acridine dyes. Calorimetric studies revealed the binding to be endothermic in nature for both AO and 9AA, though the latter had higher affinity, and this was also observed from spectroscopic data. The binding of both dyes was entropy driven. pH dependent fluorescence studies revealed the existence of electrostatic interaction between the protein and dye molecules. Molecular modeling studies specified the binding site and the non-covalent interactions involved in the association. Overall, the results revealed that a small change in the acridine chromophore leads to remarkable alteration in the structural and thermodynamic aspects of binding to HHb. Copyright © 2016 Elsevier B.V. All rights reserved.

New detection targets for amyloid-reactive probes: spectroscopic recognition of bacterial spores

NASA Astrophysics Data System (ADS)

Jones, Guilford, II; Landsman, Pavel

2005-05-01

We report characteristic changes in fluorescence of amyloid-binding dyes Thioflavin T (TfT), pinacyanol (PIN) and related dyes, caused by their interaction with suspended Bacillus spore cultures (B. subtilis, B thuringiensis). The gain in TfT emission in the presence of spores allowed their immediate detection in aqueous suspensions, with a sensitivity limit of < 105 spores per ml. The spectroscopic signatures are consistent with a large number of binding sites for the two dyes on spore coats. The possible structural relationship of these dye binding loci with characteristic motifs (β-stacks) of amyloid deposits and other misfolded protein formations suggests new designs for probing biocontamination and also for clinical studies of non-microbial human pathogens (e.g., amyloid-related protein aggregates in prion-related transmissible encephalopathies or in Alzheimer's disease). Also reported is a special screening technique that was designed and used herein for calibration of new detection probes and assays for spore detection. It employed spectroscopic interactions between the candidate amyloid stains and poly(vinylpyrrolidone)-coated colloid silica (Percoll) nanoparticles that also display remarkable parallelism with the corresponding dye-amyloid and dye-spore reactivities. Percoll may thus find new applications as a convenient non-biological structural model mimicking the putative probe-targeted motifs in both classes of bioanalytes. These findings are important in the design of new probes and assays for important human pathogens (i.e. bacterial spores and amyloidogenic protein aggregates).

MICRONERVA: A Novel Approach to Large Aperture Astronomical Spectroscopy

NASA Astrophysics Data System (ADS)

Hall, Ryan; Plavchan, Peter; Geneser, Claire; Giddens, Frank; Spangler, Sophia

2016-06-01

MICRONERVA (MICRO Novel Exoplanet Radial Velocity Array) is a project to measure precise spectroscopic radial velocities. The cost of telescopes are a strong function of diameter, and light gathering power as opposed to angular resolution is the fundamental driver for telescope design for many spectroscopic science applications. By sacrificing angular resolution, many multiple smaller fiber-fed telescopes can be combined to synthesize the light gathering power of a larger diameter telescope at a lower effective cost. For our MICRONERVA prototype, based upon the larger MINERVA project, we will attempt to demonstrate that an array of four 8-inch CPC Celestron telescopes can be automated with sufficient active guiding precision for robust nightly robotic operations. The light from each telescope is coupled into single mode fibers, which are conveniently matched to the point spread function of 8-inch telescopes, which can be diffraction limited at red wavelengths in typical seeing at good observing sites. Additionally, the output from an array of single mode fibers provides stable output illumination of a spectrograph, which is a critical requirement of future precise radial velocity instrumentation. All of the hardware from the system is automated using Python programs and ASCOM and MaxIm DL software drivers. We will present an overview of the current status of the project and plans for future work. The detection of exoplanets using the techniques of MICRONERVA could potentially enable cost reductions for many types of spectroscopic research.

Multivendor implementation and comparison of volumetric whole-brain echo-planar MR spectroscopic imaging.

PubMed

Sabati, Mohammad; Sheriff, Sulaiman; Gu, Meng; Wei, Juan; Zhu, Henry; Barker, Peter B; Spielman, Daniel M; Alger, Jeffry R; Maudsley, Andrew A

2015-11-01

To assess volumetric proton MR spectroscopic imaging (MRSI) of the human brain on multivendor MRI instruments. Echo-planar spectroscopic imaging was developed on instruments from three manufacturers, with matched specifications and acquisition protocols that accounted for differences in sampling performance, radiofrequency (RF) power, and data formats. Intersite reproducibility was evaluated for signal-normalized maps of N-acetylaspartate (NAA), creatine (Cre), and choline using phantom and human subject measurements. Comparative analyses included metrics for spectral quality, spatial coverage, and mean values in atlas-registered brain regions. Intersite differences for phantom measurements were less than 1.7% for individual metabolites and less than 0.2% for ratio measurements. Spatial uniformity ranged from 79% to 91%. The human studies found differences of mean values in the temporal lobe, but good agreement in other white matter regions, with maximum differences relative to their mean of under 3.2%. For NAA/Cre, the maximum difference was 1.8%. In gray matter, a significant difference was observed for frontal lobe NAA. Primary causes of intersite differences were attributed to shim quality, B0 drift, and accuracy of RF excitation. Correlation coefficients for measurements at each site were over 0.60, indicating good reliability. A volumetric intensity-normalized MRSI acquisition can be implemented in a comparable manner across multivendor MR instruments. © 2014 Wiley Periodicals, Inc.

Assessment and correction of turbidity effects on Raman observations of chemicals in aqueous solutions.

PubMed

Sinfield, Joseph V; Monwuba, Chike K

2014-01-01

Improvements in diode laser, fiber optic, and data acquisition technologies are enabling increased use of Raman spectroscopic techniques for both in lab and in situ water analysis. Aqueous media encountered in the natural environment often contain suspended solids that can interfere with spectroscopic measurements, yet removal of these solids, for example, via filtration, can have even greater adverse effects on the extent to which subsequent measurements are representative of actual field conditions. In this context, this study focuses on evaluation of turbidity effects on Raman spectroscopic measurements of two common environmental pollutants in aqueous solution: ammonium nitrate and trichloroethylene. The former is typically encountered in the runoff from agricultural operations and is a strong scatterer that has no significant influence on the Raman spectrum of water. The latter is a commonly encountered pollutant at contaminated sites associated with degreasing and cleaning operations and is a weak scatterer that has a significant influence on the Raman spectrum of water. Raman observations of each compound in aqueous solutions of varying turbidity created by doping samples with silica flour with grain sizes ranging from 1.6 to 5.0 μm were employed to develop relationships between observed Raman signal strength and turbidity level. Shared characteristics of these relationships were then employed to define generalized correction methods for the effect of turbidity on Raman observations of compounds in aqueous solution.

Volcanic glass signatures in spectroscopic survey of newly proposed lunar pyroclastic deposits

USGS Publications Warehouse

Besse, S.; Sunshine, J.M.; Gaddis, L.R.

2014-01-01

Moon Mineralogy Mapper spectroscopic observations are used to assess the mineralogy of five sites that have recently been proposed to include lunar dark mantle deposits (DMDs). Volcanic glasses have, for the first time, clearly been identified at the location of three of the proposed pyroclastic deposits. This is the first time that volcanic glasses have been identified at such a small scale on the lunar surface from remote sensing observations. Deposits at Birt E, Schluter, and Walther A appear to be glassy DMDs. Deposits at Birt E and Schluter show (1) morphological evidence suggesting a likely vent and (2) mineralogical evidence indicative of the presence of volcanic glasses. The Walther A deposits, although they show no morphological evidence of vents, have the spectroscopic characteristics diagnostic of volcanic glasses. The deposits of the Freundlich-Sharonov basin are separated in two areas: (1) the Buys-Ballot deposits lack mineralogical and morphological evidence and thus are found to be associated with mare volcanism not with DMDs and (2) the Anderson crater deposits, which do not exhibit glassy DMD signatures, but they appear to be associated with possible vent structures and so may be classifiable as DMDs. Finally, dark deposits near the crater Kopff are found to be associated with likely mare volcanism and not associated with DMDs. The spectral identification of volcanic glass seen in many of the potential DMDs is a strong indicator of their pyroclastic origin.

Identification of a unique Ca2+-binding site in rat acid-sensing ion channel 3.

PubMed

Zuo, Zhicheng; Smith, Rachel N; Chen, Zhenglan; Agharkar, Amruta S; Snell, Heather D; Huang, Renqi; Liu, Jin; Gonzales, Eric B

2018-05-25

Acid-sensing ion channels (ASICs) evolved to sense changes in extracellular acidity with the divalent cation calcium (Ca 2+ ) as an allosteric modulator and channel blocker. The channel-blocking activity is most apparent in ASIC3, as removing Ca 2+ results in channel opening, with the site's location remaining unresolved. Here we show that a ring of rat ASIC3 (rASIC3) glutamates (Glu435), located above the channel gate, modulates proton sensitivity and contributes to the formation of the elusive Ca 2+ block site. Mutation of this residue to glycine, the equivalent residue in chicken ASIC1, diminished the rASIC3 Ca 2+ block effect. Atomistic molecular dynamic simulations corroborate the involvement of this acidic residue in forming a high-affinity Ca 2+ site atop the channel pore. Furthermore, the reported observations provide clarity for past controversies regarding ASIC channel gating. Our findings enhance understanding of ASIC gating mechanisms and provide structural and energetic insights into this unique calcium-binding site.

Manganese Binding Properties of Human Calprotectin Under Conditions of High and Low Calcium: X-ray Crystallographic and Advanced EPR Spectroscopic Analysis

PubMed Central

Gagnon, Derek M.; Brophy, Megan Brunjes; Bowman, Sarah E. J.; Stich, Troy A.; Drennan, Catherine L.; Britt, R. David; Nolan, Elizabeth M.

2015-01-01

The antimicrobial protein calprotectin (CP), a hetero-oligomer of the S100 family members S100A8 and S100A9, is the only identified mammalian Mn(II)-sequestering protein. Human CP uses Ca(II) ions to tune its Mn(II) affinity at a biologically unprecedented hexahistidine site that forms at the S100A8/S100A9 interface, and the molecular basis for this phenomenon requires elucidation. Herein, we investigate the remarkable Mn(II) coordination chemistry of human CP using X-ray crystallography as well as continuous wave (CW) and pulse electron paramagnetic resonance (EPR) spectroscopies. An X-ray crystallographic structure of Mn(II)-CP containing one Mn(II), two Ca(II), and two Na(I) ions per CP heterodimer is reported. The CW EPR spectrum of Ca(II)- and Mn(II)-bound CP prepared with a 10:0.9:1 Ca(II):Mn(II):CP ratio is characterized by an unusually low zero-field splitting of 485 MHz (E/D = 0.30) for the S = 5/2 Mn(II) ion, consistent with the high symmetry of the His6 binding site observed crystallographically. Results from electron spin-echo envelope modulation and electron nuclear double resonance experiments reveal that the six Mn(II)-coordinating histidine residues of Ca(II)- and Mn(II)-bound CP are spectroscopically equivalent. The observed 15N (I = 1/2) hyperfine couplings (A) arise from two distinct classes of nitrogen atoms: the coordinating ε-nitrogen of the imidazole ring of each histidine ligand (A = [3.45, 3.71, 5.91] MHz) and the distal δ-nitrogen (A = [0.11, 0.18, 0.42] MHz). In the absence of Ca(II), the binding affinity of CP for Mn(II) drops by ca. two orders of magnitude and coincides with Mn(II) binding at the His6 site as well as other sites. This study demonstrates the role of Ca(II) in enabling high-affinity and specific binding of Mn(II) to the His6 site of human calprotectin. PMID:25597447

Manganese binding properties of human calprotectin under conditions of high and low calcium: X-ray crystallographic and advanced electron paramagnetic resonance spectroscopic analysis.

PubMed

Gagnon, Derek M; Brophy, Megan Brunjes; Bowman, Sarah E J; Stich, Troy A; Drennan, Catherine L; Britt, R David; Nolan, Elizabeth M

2015-03-04

The antimicrobial protein calprotectin (CP), a hetero-oligomer of the S100 family members S100A8 and S100A9, is the only identified mammalian Mn(II)-sequestering protein. Human CP uses Ca(II) ions to tune its Mn(II) affinity at a biologically unprecedented hexahistidine site that forms at the S100A8/S100A9 interface, and the molecular basis for this phenomenon requires elucidation. Herein, we investigate the remarkable Mn(II) coordination chemistry of human CP using X-ray crystallography as well as continuous-wave (CW) and pulse electron paramagnetic resonance (EPR) spectroscopies. An X-ray crystallographic structure of Mn(II)-CP containing one Mn(II), two Ca(II), and two Na(I) ions per CP heterodimer is reported. The CW EPR spectrum of Ca(II)- and Mn(II)-bound CP prepared with a 10:0.9:1 Ca(II):Mn(II):CP ratio is characterized by an unusually low zero-field splitting of 485 MHz (E/D = 0.30) for the S = 5/2 Mn(II) ion, consistent with the high symmetry of the His6 binding site observed crystallographically. Results from electron spin-echo envelope modulation and electron-nuclear double resonance experiments reveal that the six Mn(II)-coordinating histidine residues of Ca(II)- and Mn(II)-bound CP are spectroscopically equivalent. The observed (15)N (I = 1/2) hyperfine couplings (A) arise from two distinct classes of nitrogen atoms: the coordinating ε-nitrogen of the imidazole ring of each histidine ligand (A = [3.45, 3.71, 5.91] MHz) and the distal δ-nitrogen (A = [0.11, 0.18, 0.42] MHz). In the absence of Ca(II), the binding affinity of CP for Mn(II) drops by two to three orders of magnitude and coincides with Mn(II) binding at the His6 site as well as other sites. This study demonstrates the role of Ca(II) in enabling high-affinity and specific binding of Mn(II) to the His6 site of human calprotectin.

Manganese Binding Properties of Human Calprotectin under Conditions of High and Low Calcium: X-ray Crystallographic and Advanced Electron Paramagnetic Resonance Spectroscopic Analysis

DOE PAGES

Gagnon, Derek M.; Brophy, Megan Brunjes; Bowman, Sarah E. J.; ...

2015-01-18

The antimicrobial protein calprotectin (CP), a hetero-oligomer of the S100 family members S100A8 and S100A9, is the only identified mammalian Mn(II)-sequestering protein. Human CP uses Ca(II) ions to tune its Mn(II) affinity at a biologically unprecedented hexahistidine site that forms at the S100A8/S100A9 interface, and the molecular basis for this phenomenon requires elucidation. Here in this paper, we investigate the remarkable Mn(II) coordination chemistry of human CP using X-ray crystallography as well as continuous-wave (CW) and pulse electron paramagnetic resonance (EPR) spectroscopies. An X-ray crystallographic structure of Mn(II)-CP containing one Mn(II), two Ca(II), and two Na(I) ions per CP heterodimermore » is reported. The CW EPR spectrum of Ca(II)- and Mn(II)-bound CP prepared with a 10:0.9:1 Ca(II):Mn(II):CP ratio is characterized by an unusually low zero-field splitting of 485 MHz (E/D = 0.30) for the S = 5/2 Mn(II) ion, consistent with the high symmetry of the His6 binding site observed crystallographically. Results from electron spin–echo envelope modulation and electron–nuclear double resonance experiments reveal that the six Mn(II)-coordinating histidine residues of Ca(II)- and Mn(II)-bound CP are spectroscopically equivalent. The observed 15N (I = 1/2) hyperfine couplings (A) arise from two distinct classes of nitrogen atoms: the coordinating ε-nitrogen of the imidazole ring of each histidine ligand (A = [3.45, 3.71, 5.91] MHz) and the distal δ-nitrogen (A = [0.11, 0.18, 0.42] MHz). In the absence of Ca(II), the binding affinity of CP for Mn(II) drops by two to three orders of magnitude and coincides with Mn(II) binding at the His6 site as well as other sites. This study demonstrates the role of Ca(II) in enabling high-affinity and specific binding of Mn(II) to the His 6 site of human calprotectin.« less

Manganese Binding Properties of Human Calprotectin under Conditions of High and Low Calcium: X-ray Crystallographic and Advanced Electron Paramagnetic Resonance Spectroscopic Analysis

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

Gagnon, Derek M.; Brophy, Megan Brunjes; Bowman, Sarah E. J.

The antimicrobial protein calprotectin (CP), a hetero-oligomer of the S100 family members S100A8 and S100A9, is the only identified mammalian Mn(II)-sequestering protein. Human CP uses Ca(II) ions to tune its Mn(II) affinity at a biologically unprecedented hexahistidine site that forms at the S100A8/S100A9 interface, and the molecular basis for this phenomenon requires elucidation. Here in this paper, we investigate the remarkable Mn(II) coordination chemistry of human CP using X-ray crystallography as well as continuous-wave (CW) and pulse electron paramagnetic resonance (EPR) spectroscopies. An X-ray crystallographic structure of Mn(II)-CP containing one Mn(II), two Ca(II), and two Na(I) ions per CP heterodimermore » is reported. The CW EPR spectrum of Ca(II)- and Mn(II)-bound CP prepared with a 10:0.9:1 Ca(II):Mn(II):CP ratio is characterized by an unusually low zero-field splitting of 485 MHz (E/D = 0.30) for the S = 5/2 Mn(II) ion, consistent with the high symmetry of the His6 binding site observed crystallographically. Results from electron spin–echo envelope modulation and electron–nuclear double resonance experiments reveal that the six Mn(II)-coordinating histidine residues of Ca(II)- and Mn(II)-bound CP are spectroscopically equivalent. The observed 15N (I = 1/2) hyperfine couplings (A) arise from two distinct classes of nitrogen atoms: the coordinating ε-nitrogen of the imidazole ring of each histidine ligand (A = [3.45, 3.71, 5.91] MHz) and the distal δ-nitrogen (A = [0.11, 0.18, 0.42] MHz). In the absence of Ca(II), the binding affinity of CP for Mn(II) drops by two to three orders of magnitude and coincides with Mn(II) binding at the His6 site as well as other sites. This study demonstrates the role of Ca(II) in enabling high-affinity and specific binding of Mn(II) to the His 6 site of human calprotectin.« less

Isolation of anticancer drug TAXOL from Pestalotiopsis breviseta with apoptosis and B-Cell lymphoma protein docking studies.

PubMed

Kathiravan, G; Sureban, Sripathi M; Sree, Harsha N; Bhuvaneshwari, V; Kramony, Evelin

2012-12-01

Extraction and investigation of TAXOL from Pestalotiopsis breviseta (Sacc.) using protein docking, which is a computational technique that samples conformations of small molecules in protein-binding sites. Scoring functions are used to assess which of these conformations best complements the protein binding site and active site prediction. Coelomycetous fungi P. breviseta (Sacc.) Steyaert was screened for the production of TAXOL, an anticancer drug. TAXOL PRODUCTION WAS CONFIRMED BY THE FOLLOWING METHODS: Ultraviolet (UV) spectroscopic analysis, Infrared analysis, High performance liquid chromatography analysis (HPLC), and Liquid chromatography mass spectrum (LC-MASS). TAXOL produced by the fungi was compared with authentic TAXOL, and protein docking studies were performed. The BCL2 protein of human origin showed a higher affinity toward the compound paclitaxel. It has the binding energy value of -13.0061 (KJ/Mol) with four hydrogen bonds.

Isolation of anticancer drug TAXOL from Pestalotiopsis breviseta with apoptosis and B-Cell lymphoma protein docking studies

PubMed Central

Kathiravan, G.; Sureban, Sripathi M.; Sree, Harsha N.; Bhuvaneshwari, V.; Kramony, Evelin

2012-01-01

Background: Extraction and investigation of TAXOL from Pestalotiopsis breviseta (Sacc.) using protein docking, which is a computational technique that samples conformations of small molecules in protein-binding sites. Scoring functions are used to assess which of these conformations best complements the protein binding site and active site prediction. Materials and Methods: Coelomycetous fungi P. breviseta (Sacc.) Steyaert was screened for the production of TAXOL, an anticancer drug. Results: TAXOL production was confirmed by the following methods: Ultraviolet (UV) spectroscopic analysis, Infrared analysis, High performance liquid chromatography analysis (HPLC), and Liquid chromatography mass spectrum (LC-MASS). TAXOL produced by the fungi was compared with authentic TAXOL, and protein docking studies were performed. Conclusion: The BCL2 protein of human origin showed a higher affinity toward the compound paclitaxel. It has the binding energy value of −13.0061 (KJ/Mol) with four hydrogen bonds. PMID:24808664

Octahedral cation partitioning in Mg,Fe2+-olivine. Mössbauer spectroscopic study of synthetic (Mg0.5 Fe2+ 0.5)2SiO4 (Fa50)

NASA Astrophysics Data System (ADS)

Morozov, Mikhail; Brinkmann, Christian; Grodzicki, Michael; Lottermoser, Werner; Tippelt, Gerold; Amthauer, Georg; Kroll, Herbert

2005-11-01

The high-temperature partitioning of Fe2+ and Mg between the two non-equivalent octahedral M1 and M2 sites in synthetic olivine (Fa50) was studied by Mössbauer spectroscopy. Powder samples have been equilibrated in annealing experiments performed under reducing oxygen fugacity at temperatures between 500 and 800°C followed by rapid quenching in order to prevent redistribution of cations. M-site ordering with Fe2+ preferring M1, Mg preferring M2 sites increases continuously with rising equilibrium temperature. K D values increase from 1.21 at 500°C to 1.48 at 750°C. The results are consistent with both room temperature as well as in situ high temperature single crystal X-ray diffraction experiments of Heinemann et al. [8, 9].

Raman Spectroscopic Analysis of Fingernail Clippings Can Help Differentiate Between Postmenopausal Women Who Have and Have Not Suffered a Fracture

PubMed Central

Beattie, James R.; Cummins, Niamh M.; Caraher, Clare; O’Driscoll, Olive M.; Bansal, Aruna T.; Eastell, Richard; Ralston, Stuart H.; Stone, Michael D.; Pearson, Gill; Towler, Mark R.

2016-01-01

Raman spectroscopy was applied to nail clippings from 633 postmenopausal British and Irish women, from six clinical sites, of whom 42% had experienced a fragility fracture. The objective was to build a prediction algorithm for fracture using data from four sites (known as the calibration set) and test its performance using data from the other two sites (known as the validation set). Results from the validation set showed that a novel algorithm, combining spectroscopy data with clinical data, provided area under the curve (AUC) of 74% compared to an AUC of 60% from a reduced QFracture score (a clinically accepted risk calculator) and 61% from the dual-energy X-ray absorptiometry T-score, which is in current use for the diagnosis of osteoporosis. Raman spectroscopy should be investigated further as a noninvasive tool for the early detection of enhanced risk of fragility fracture. PMID:27429561

4d Electronic structure analysis of ruthenium in the perovskite oxides by Ru K- and L-edge XAS.

PubMed

Kim, J Y; Hwang, S H; Kim, S J; Demazeau, G; Choy, J H; Shimada, H

2001-03-01

The 4d electronic structure of ruthenium in the perovskite oxides, La2MRuIVO6 (M = Zn, Mg, and Li) and Ba2YRuVO6, has been investigated by the Ru K-and L-edge XANES and EXAFS analyses. Such X-ray absorption spectroscopic results clarify that the RuIV (d4) and RuV (d3) ions are stabilized in nearly regular Oh site. Comparing the Ru L-edge XANES spectra of perovskites containing isovalent ruthenium, it has been found that the t2g state is mainly influenced by A site cation, whereas the eg is mainly affected by neighboring B site cation. The experimental EXAFS spectra in the range of R < or = approximately 4.5 A are well reproduced by ab-initio calculation based on crystallographic data, which supports the long-range structure presented by Rietveld refinement.

Spontaneous and stimulated emission spectroscopy of a Nd(3+)-doped phosphate glass under wavelength selective pumping.

PubMed

Iparraguirre, I; Azkargorta, J; Balda, R; Venkata Krishnaiah, K; Jayasankar, C K; Al-Saleh, M; Fernández, J

2011-09-26

The influence of the host matrix on the spectroscopic and laser properties of Nd(3+) in a K-Ba-Al phosphate glass has been investigated as a function of rare-earth concentration. Site-selective time resolved laser spectroscopy and stimulated emission experiments under selective wavelength laser pumping show the existence of a very complex crystal field site distribution of Nd(3+) ions in this glass. The peak of the broad stimulated (4)F(3/2)→(4)I(11/2) emission shifts in a non monotonous way up to 3 nm as a function of the excitation wavelength. This behavior can be explained by the relatively moderate inter-site energy transfer among Nd(3+) ions found in this system and measured by using fluorescence line narrowing spectroscopy. The best slope efficiency obtained for the laser emission was 40%. © 2011 Optical Society of America

Spectroscopic pulsational frequency identification and mode determination of γ Doradus star HD 12901

NASA Astrophysics Data System (ADS)

Brunsden, E.; Pollard, K. R.; Cottrell, P. L.; Wright, D. J.; De Cat, P.

2012-12-01

Using multisite spectroscopic data collected from three sites, the frequencies and pulsational modes of the γ Doradus star HD 12901 were identified. A total of six frequencies in the range 1-2 d-1 were observed, their identifications supported by multiple line-profile measurement techniques and previously published photometry. Five frequencies were of sufficient signal-to-noise ratio for mode identification, and all five displayed similar three-bump standard deviation profiles which were fitted well with (l,m) = (1,1) modes. These fits had reduced χ2 values of less than 18. We propose that this star is an excellent candidate to test models of non-radially pulsating γ Doradus stars as a result of the presence of multiple (1,1) modes. This paper includes data taken at the Mount John University Observatory of the University of Canterbury (New Zealand), the McDonald Observatory of the University of Texas at Austin (Texas, USA) and the European Southern Observatory at La Silla (Chile).

Electron spin echo envelope modulation studies of the Cu(II)-substituted derivative of isopenicillin N synthase: A structural and spectroscopic model

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

Feng Jiang; Peisach, J.; Lijune Ming

Electron spin echo envelope modulation spectroscopy (ESEEM) was used to study the active site structure of isopenicillin N synthase (IPNS) from Cephalosporium acremonium with Cu(II) as a spectroscopic probe. Fourier transform of the simulated electron spin-echo envelope for the Cu(II)-substituted enzyme, Cu(II)IPNS, revealed two nearly magnetically equivalent, equatorially coordinated His imidazoles. The superhyperfine coupling constant, A{sub iso}, for the remote {sup 14}N of each imidazole was 1.65 MHz. The binding of substrate to the enzyme altered the magnetic coupling so that A{sub iso} is 1.30 MHz for one nitrogen and 2.16 MHz for the other. From a comparison of themore » ESSEM of Cu(II)IPNS in D{sub 2}O and H{sub 2}O, it is suggested that water is a ligand of Cu(II) and this is displaced upon the addition of substrate.« less

Vibrational spectroscopy reveals the initial steps of biological hydrogen evolution† †Electronic supplementary information (ESI) available: Complementary resonance Raman and infrared spectroscopic data. See DOI: 10.1039/c6sc01098a Click here for additional data file.

PubMed Central

Katz, S.; Noth, J.; Shafaat, H. S.; Happe, T.; Hildebrandt, P.

2016-01-01

[FeFe] hydrogenases are biocatalytic model systems for the exploitation and investigation of catalytic hydrogen evolution. Here, we used vibrational spectroscopic techniques to characterize, in detail, redox transformations of the [FeFe] and [4Fe4S] sub-sites of the catalytic centre (H-cluster) in a monomeric [FeFe] hydrogenase. Through the application of low-temperature resonance Raman spectroscopy, we discovered a novel metastable intermediate that is characterized by an oxidized [FeIFeII] centre and a reduced [4Fe4S]1+ cluster. Based on this unusual configuration, this species is assigned to the first, deprotonated H-cluster intermediate of the [FeFe] hydrogenase catalytic cycle. Providing insights into the sequence of initial reaction steps, the identification of this species represents a key finding towards the mechanistic understanding of biological hydrogen evolution. PMID:28451119

Steady-state fluorescence and phosphorescence spectroscopic studies of bacterial luciferase tryptophan mutants.

PubMed

Li, Z; Meighen, E A

1994-09-01

Bacterial luciferase, which catalyzes the bioluminescence reaction in luminous bacteria, consists of two nonidentical polypeptides, α and β. Eight mutants of luciferase with each of the tryptophans replaced by tyrosine were generated by site-directed mutagenesis and purified to homogeneity. The steady-state tryptophan fluorescence and low-temperature phosphorescence spectroscopic properties of these mutants were characterized. In some instances, mutation of only a single tryptophan residue resulted in large spectral changes. The tryptophan residues conserved in both the α and the β subunits exhibited distinct fluorescence emission properties, suggesting that these tryptophans have different local enviroments. The low-temperature phosphorescence data suggest that the tryptophans conserved in bot the α and the β subunits are not located at the subunit interface and/or involved in subunit interactions. The differences in the spectral properties of the mutants have provided useful information on the local environment of the individual tryptophan residues as well as on the quaternary structure of the protein.

Influence of silver nanoparticles on the spectroscopic properties of Sm{sup 3+} doped boro-phosphate glasses

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

Suthanthirakumar, P.; Marimuthu, K., E-mail: emari-ram2000@yahoo.com

The Sm{sup 3+} doped novel boro-phosphate glasses containing silver nanoparticles (NPs) (SmBPxA) have been prepared following the melt quenching technique and their structural and spectroscopic behavior were studied through HR-TEM, optical absorption and photoluminescence spectral measurements. The TEM analysis validates the existence of Ag NPs with an average diameter of ~8 nm. The Surface plasmon resonance (SPR) band of silver NPs was found at around 600 nm from the absorption spectrum of the Sm{sup 3+} ions free glass sample. The optical band gap energy (E{sub opt}) corresponding to the direct and indirect allowed transitions and the Urbach energy (ΔE) valuesmore » were determined from the absorption spectral measurements. The luminescence intensity is found to get enhance when the Ag NPs were embedded along with the Sm{sup 3+} ions in the prepared glasses due to the local electric field effect around the rare earth (RE) ion site produced by the SPR of Ag NPs.« less

A Novel Schiff Base of 3-acetyl-4-hydroxy-6-methyl-(2H)pyran-2-one and 2,2'-(ethylenedioxy)diethylamine as Potential Corrosion Inhibitor for Mild Steel in Acidic Medium

PubMed Central

Asegbeloyin, Jonnie N.; Ejikeme, Paul M.; Olasunkanmi, Lukman O.; Adekunle, Abolanle S.; Ebenso, Eno E.

2015-01-01

The corrosion inhibition activity of a newly synthesized Schiff base (SB) from 3-acetyl-4-hydroxy-6-methyl-(2H)-pyran-2-one and 2,2'-(ethylenedioxy)diethylamine was investigated on the corrosion of mild steel in 1 M HCl solution using potentiodynamic polarization and electrochemical impedance spectroscopic techniques. Ultraviolet-visible (UV-vis) and Raman spectroscopic techniques were used to study the chemical interactions between SB and mild steel surface. SB was found to be a relatively good inhibitor of mild steel corrosion in 1 M HCl. The inhibition efficiency increases with increase in concentration of SB. The inhibition activity of SB was ascribed to its adsorption onto mild steel surface, through physisorption and chemisorption, and described by the Langmuir adsorption model. Quantum chemical calculations indicated the presence of atomic sites with potential nucleophilic and electrophilic characteristics with which SB can establish electronic interactions with the charged mild steel surface.

Spectroscopic diagnostics of organic chemistry in the protostellar environment

NASA Technical Reports Server (NTRS)

Charnley, S. B.; Ehrenfreund, P.; Kuan, Y. J.

2001-01-01

A combination of astronomical observations, laboratory studies, and theoretical modelling is necessary to determine the organic chemistry of dense molecular clouds. We present spectroscopic evidence for the composition and evolution of organic molecules in protostellar environments. The principal reaction pathways to complex molecule formation by catalysis on dust grains and by reactions in the interstellar gas are described. Protostellar cores, where warming of dust has induced evaporation of icy grain mantles, are excellent sites in which to study the interaction between gas phase and grain-surface chemistries. We investigate the link between organics that are observed as direct products of grain surface reactions and those which are formed by secondary gas phase reactions of evaporated surface products. Theory predicts observable correlations between specific interstellar molecules, and also which new organics are viable for detection. We discuss recent infrared observations obtained with the Infrared Space Observatory, laboratory studies of organic molecules, theories of molecule formation, and summarise recent radioastronomical searches for various complex molecules such as ethers, azaheterocyclic compounds, and amino acids.

Molecular spectroscopic study for suggested mechanism of chrome tanned leather.

PubMed

Nashy, Elshahat H A; Osman, Osama; Mahmoud, Abdel Aziz; Ibrahim, Medhat

2012-03-01

Collagen represents the structural protein of the extracellular matrix, which gives strength of hides and/or skin under tanning process. Chrome tan is the most important tanning agent all over the world. The methods for production of leather evolved over several centuries as art and engineering with little understanding of the underlying science. The present work is devoted to suggest the most probable mechanistic action of chrome tan on hide proteins. First the affect of Cr upon hide protein is indicated by the studied mechanical properties. Then the spectroscopic characterization of the hide protein as well as chrome tanned leather was carried out with Horizontal Attenuated Total Reflection (HATR) FT-IR. The obtained results indicate how the chromium can attached with the active sites of collagen. Molecular modeling confirms that chromium can react with amino as well as carboxylate groups. Four schemes were obtained to describe the possible interactions of chrome tan with hide proteins. Copyright © 2011 Elsevier B.V. All rights reserved.

Dielectrophoresis-Assisted Raman Spectroscopy of Intravesicular Analytes on Metallic Pyramids.

PubMed

Barik, Avijit; Cherukulappurath, Sudhir; Wittenberg, Nathan J; Johnson, Timothy W; Oh, Sang-Hyun

2016-02-02

Chemical analysis of membrane-bound containers such as secretory vesicles, organelles, and exosomes can provide insights into subcellular biology. These containers are loaded with a range of important biomolecules, which further underscores the need for sensitive and selective analysis methods. Here we present a metallic pyramid array for intravesicular analysis by combining site-selective dielectrophoresis (DEP) and Raman spectroscopy. Sharp pyramidal tips act as a gradient force generator to trap nanoparticles or vesicles from the solution, and the tips are illuminated by a monochromatic light source for concurrent spectroscopic detection of trapped analytes. The parameters suitable for DEP trapping were optimized by fluorescence microscopy, and the Raman spectroscopy setup was characterized by a nanoparticle based model system. Finally, vesicles loaded with 4-mercaptopyridine were concentrated at the tips and their Raman spectra were detected in real time. These pyramidal tips can perform large-area array-based trapping and spectroscopic analysis, opening up possibilities to detect molecules inside cells or cell-derived vesicles.

In vivo Raman spectral pathology of human atherosclerosis and vulnerable plaque

NASA Astrophysics Data System (ADS)

Motz, Jason T.; Fitzmaurice, Maryann; Miller, Arnold; Gandhi, Saumil J.; Haka, Abigail S.; Galindo, Luis; Dasari, Ramachandra R.; Kramer, John R., Jr.; Feld, Michael S.

2006-03-01

The rupture of vulnerable atherosclerotic plaque accounts for the majority of clinically significant acute cardiovascular events. Because stability of these culprit lesions is directly related to chemical and morphological composition, Raman spectroscopy may be a useful technique for their study. Recent developments in optical fiber probe technology have allowed for the real-time in vivo Raman spectroscopic characterization of human atherosclerotic plaque demonstrated in this work. We spectroscopically examine 74 sites during carotid endarterectomy and femoral artery bypass surgeries. Of these, 34 are surgically biopsied and examined histologically. Excellent signal-to-noise ratio spectra are obtained in only 1 s and fit with an established model, demonstrating accurate tissue characterization. We also report the first evidence that Raman spectroscopy has the potential to identify vulnerable plaque, achieving a sensitivity and specificity of 79 and 85%, respectively. These initial findings indicate that Raman spectroscopy has the potential to be a clinically relevant diagnostic tool for studying cardiovascular disease.

Epsilon Aurigae Eclipse 2009 - Ingress

NASA Astrophysics Data System (ADS)

Hopkins, Jeffrey L.; Stencel, Robert E.; Leadbeater, Robin; Beckmann, Paul J.; Buil, Christian; Collins, Donald; Colombo, Tiziano; Garrel, Thierry; Gorodenski, Stanley; Gudmundsson, Snaevarr; Karlsson, Mukund Kurtadikar; Lindberg, Hans-Goran; Loughney, Des; Mauclaire, Benji; McCandless, Brian E.; Melillo, Frank J.; Miles, Richard; Pearson, Robert T.; Samolyk, Gerard; Schanne, Lothar; Strikis, Iakovos Marios; Teyssier, François; Thizy, Olivier

The mysterious star system epsilon Aurigae undergoes an eclipse every 27.1 years that lasts nearly two years. The most recent eclipse started during the late summer of 2009. An international campaign for observing this eclipse was created in 2006, with a web site for information and, to-date, 17 periodic newsletters for details, as well as a Yahoo forum List for immediate announcements and comments. Photometric data in the UBVRIJH bands have been submitted. Ingress occurred with first contact in the V band estimated at the second week of 2009 August and second contact estimated at 2010 mid-January. Spectroscopic data were also obtained during ingress. Spectroscopic data have been provided in the potassium I region, hydrogen alpha and beta regions and sodium D line region of the star system's spectrum. In this paper we describe details of observations and preliminary analysis during ingress and second contact. We introduce the observers and discuss plans for observing throughout totality and the end of the eclipse in 2011.

Molecular anions.

PubMed

Simons, Jack

2008-07-24

The experimental and theoretical study of molecular anions has undergone explosive growth over the past 40 years. Advances in techniques used to generate anions in appreciable numbers as well as new ion-storage, ion-optics, and laser spectroscopic tools have been key on the experimental front. Theoretical developments on the electronic structure and molecular dynamics fronts now allow one to achieve higher accuracy and to study electronically metastable states, thus bringing theory in close collaboration with experiment in this field. In this article, many of the experimental and theoretical challenges specific to studying molecular anions are discussed. Results from many research groups on several classes of molecular anions are overviewed, and both literature citations and active (in online html and pdf versions) links to numerous contributing scientists' Web sites are provided. Specific focus is made on the following families of anions: dipole-bound, zwitterion-bound, double-Rydberg, multiply charged, metastable, cluster-based, and biological anions. In discussing each kind of anion, emphasis is placed on the structural, energetic, spectroscopic, and chemical-reactivity characteristics that make these anions novel, interesting, and important.

Raising Awareness of Individual Creative Potential in Bioscientists Using a Web-Site Based Approach

ERIC Educational Resources Information Center

Adams, David J.; Hugh-Jones, Siobhan; Sutherland, Ed

2010-01-01

We report the preliminary results of work with a unique, web-site-based approach designed to help individual bioscientists identify and develop their individual creative capacity. The site includes a number of features that encourage individuals to interact with creativity techniques, communicate with colleagues remotely using an electronic notice…

Blue Ribbon Web Sites Contest Winners.

ERIC Educational Resources Information Center

Southworth, Samuel A.

2001-01-01

Presents a collection of prize-winning Web sites created by K-8 teachers nationwide. Some of the unique features of the Web sites include an online student-written newspaper; a sing-along section; a chronicle of the past 3 years of classes to see how the classes have evolved; and student art and writing projects. (SM)

Catalysis by metal-organic frameworks: fundamentals and opportunities.

PubMed

Ranocchiari, Marco; van Bokhoven, Jeroen Anton

2011-04-14

Crystalline porous materials are extremely important for developing catalytic systems with high scientific and industrial impact. Metal-organic frameworks (MOFs) show unique potential that still has to be fully exploited. This perspective summarizes the properties of MOFs with the aim to understand what are possible approaches to catalysis with these materials. We categorize three classes of MOF catalysts: (1) those with active site on the framework, (2) those with encapsulated active species, and (3) those with active sites attached through post-synthetic modification. We identify the tunable porosity, the ability to fine tune the structure of the active site and its environment, the presence of multiple active sites, and the opportunity to synthesize structures in which key-lock bonding of substrates occurs as the characteristics that distinguish MOFs from other materials. We experience a unique opportunity to imagine and design heterogeneous catalysts, which might catalyze reactions previously thought impossible.

Spectroscopic insights into the nature of active sites in iron–nitrogen–carbon electrocatalysts for oxygen reduction in acid

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

Jia, Qingying; Ramaswamy, Nagappan; Tylus, Urszula

Developing efficient and inexpensive catalysts for the sluggish oxygen reduction reaction (ORR) constitutes one of the grand challenges in the fabrication of commercially viable fuel cell devices and metal–air batteries for future energy applications. Despite recent achievements in designing advanced Pt-based and Pt-free catalysts, current progress primarily involves an empirical approach of trial-and-error combination of precursors and synthesis conditions, which limits further progress. Rational design of catalyst materials requires proper understanding of the mechanistic origin of the ORR and the underlying surface properties under operating conditions that govern catalytic activity. Herein, several different groups of iron-based catalysts synthesized via differentmore » methods and/or precursors were systematically studied by combining multiple spectroscopic techniques under ex situ and in situ conditions in an effort to obtain a comprehensive understanding of the synthesis-products correlations, nature of active sites, and the reaction mechanisms. These catalysts include original macrocycles, macrocycle-pyrolyzed catalysts, and Fe-N–C catalysts synthesized from individual Fe, N, and C precursors including polymer-based catalysts, metal organic framework (MOF)-based catalysts, and sacrificial support method (SSM)-based catalysts. The latter group of catalysts is most promising as not only they exhibit exceptional ORR activity and/or durability, but also the final products are controllable. We show that the high activity observed for most pyrolyzed Fe-based catalysts can mainly be attributed to a single active site: non-planar Fe–N 4 moiety embedded in distorted carbon matrix characterized by a high potential for the Fe 2+/3+ redox transition in acidic electrolyte/environment. The high intrinsic ORR activity, or turnover frequency (TOF), of this site is shown to be accounted for by redox catalysis mechanism that highlights the dominant role of the site-blocking effect. Moreover, a highly active MOF-based catalyst without Fe–N moieties was developed, and the active sites were identified as nitrogen-doped carbon fibers with embedded iron particles that are not directly involved in the oxygen reduction pathway. The high ORR activity and durability of catalysts involving this second site, as demonstrated in fuel cell, are attributed to the high density of active sites and the elimination or reduction of Fenton-type processes. The latter are initiated by hydrogen peroxide but are known to be accelerated by iron ions exposed to the surface, resulting in the formation of damaging free-radicals.« less

Live-cell stimulated Raman scattering imaging of alkyne-tagged biomolecules.

PubMed

Hong, Senlian; Chen, Tao; Zhu, Yuntao; Li, Ang; Huang, Yanyi; Chen, Xing

2014-06-02

Alkynes can be metabolically incorporated into biomolecules including nucleic acids, proteins, lipids, and glycans. In addition to the clickable chemical reactivity, alkynes possess a unique Raman scattering within the Raman-silent region of a cell. Coupling this spectroscopic signature with Raman microscopy yields a new imaging modality beyond fluorescence and label-free microscopies. The bioorthogonal Raman imaging of various biomolecules tagged with an alkyne by a state-of-the-art Raman imaging technique, stimulated Raman scattering (SRS) microscopy, is reported. This imaging method affords non-invasiveness, high sensitivity, and molecular specificity and therefore should find broad applications in live-cell imaging. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Chlorotheolides A and B, Spiroketals Generated via Diels-Alder Reactions in the Endophytic Fungus Pestalotiopsis theae.

PubMed

Liu, Ling; Han, Yu; Xiao, Junhai; Li, Li; Guo, Liangdong; Jiang, Xuejun; Kong, Lingyi; Che, Yongsheng

2016-10-28

Chlorotheolides A (1) and B (2), two new spiroketals possessing the unique [4,7]methanochromene and dispiro-trione skeletons, respectively, and their putative biosynthetic precursors, 1-undecen-2,3-dicarboxylic acid (3) and maldoxin (4), were isolated from the solid substrate fermentation of the plant endophytic fungus Pestalotiopsis theae (N635). Their structures were elucidated based on NMR spectroscopic data and electronic circular dichroism calculations. Biogenetically, compounds 1 and 2 could be generated from the co-isolated 3 and 4 via Diels-Alder reactions. Chlorotheolide (2) showed an antiproliferative effect against the human tumor cell line HeLa and induced an autophagic process in the cells.

Small interstellar molecules and what they tell us

NASA Astrophysics Data System (ADS)

Neufeld, David A.

2018-06-01

Observations at ultraviolet, visible, infrared and radio wavelengths provide a wealth of information about the molecular inventory of the interstellar medium (ISM). Because of the different chemical pathways responsible for their formation and destruction, different molecules probe specific aspects of the interstellar environment. Carefully interpreted with the use of astrochemical models, they provide unique information of general astrophysical importance, yielding estimates of the cosmic ray density, the molecular fraction, the ultraviolet radiation field, and the dissipation of energy within the turbulent ISM. Laboratory experiments and quantum-mechanical calculations are essential both in providing the spectroscopic data needed to identify interstellar molecules and for elucidating the fundamental physical and chemical processes that must be included in astrochemical models.

Three new fatty acid esters from the mushroom Boletus pseudocalopus.

PubMed

Kim, Ki Hyun; Choi, Sang Un; Lee, Kang Ro

2012-06-01

A bioassay-guided fractionation and chemical investigation of a MeOH extract of the Korean wild mushroom Boletus pseudocalopus resulted in the identification of three new fatty acid esters, named calopusins A-C (1-3), along with two known fatty acid methyl esters (4-5). These new compounds are structurally unique fatty acid esters with a 2,3-butanediol moiety. Their structures were elucidated through 1D- and 2D-NMR spectroscopic data and GC-MS analysis as well as a modified Mosher's method. The new compounds 1-3 showed significant inhibitory activity against the proliferation of the tested cancer cell lines with IC(50) values in the range 2.77-12.51 μM.

Exoplanet Observations in SOFIA's Cycle 1

NASA Astrophysics Data System (ADS)

Angerhausen, Daniel

2013-06-01

The NASA/DLR Stratospheric Observatory for Infrared Astronomy (SOFIA), a 2.5-meter infrared telescope on board a Boeing 747-SP, will conduct 0.3 - 1,600 micron photometric, spectroscopic, and imaging observations from altitudes as high as 45,000 ft. The airborne-based platform has unique advantages in comparison to ground- and space-based observatories in the field of characterization of the physical properties of exoplanets: parallel optical and near-infrared photometric and spectrophotometric follow-up observations during planetary transits and eclipses will be feasible with SOFIA's instrumentation, in particular the HIPO-FLITECAM optical/NIR instruments and possible future dedicated instrumentation. Here we present spectrophotometric exoplanet observations that were or will be conducted in SOFIA's cycle 1.

Contraction of π-Conjugated Rings upon Oxidation from Cyclooctatetraene to Benzene via the Tropylium Cation.

PubMed

Tamoto, Akira; Aratani, Naoki; Yamada, Hiroko

2017-11-16

We have serendipitously discovered a unique transformation of a cyclooctatetraene derivative 1 into a cycloheptatriene spirolactone 3 upon oxidation, which is the first such transformation reported in 60 years. Product 3 could be reversibly interconverted into the aromatic tropylium cation 3H + by acid/base treatment, which was accompanied by drastic spectroscopic changes. The resultant cycloheptatriene could be further converted into benzene upon oxidation. We characterized all the key structures by X-ray studies. Eventually, the π-conjugated ring size shrinks from 8 to 7, then finally to 6 upon oxidation, in the direction of the stronger aromatization. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Integrated approach to ischemic heart disease. The one-stop shop.

PubMed

Kramer, C M

1998-05-01

Magnetic resonance imaging is unique in its variety of applications for imaging the cardiovascular system. A thorough assessment of myocardial structure, function, and perfusion; assessment of coronary artery anatomy and flow; and spectroscopic evaluation of cardiac energetics can be readily performed by magnetic resonance imaging. One key to the advancement of cardiac magnetic resonance imaging as a clinical tool in the evaluation, the so called one stop shop. Improvements in magnetic resonance hardware, software, and imaging speed now permit this integrated examination. Cardiac magnetic resonance is a powerful technique with the potential to replace or complement other commonly used techniques in the diagnostic armamentarium of physicians caring for patients with ischemic heart disease.

High-energy cryo x-ray nano-imaging at the ID16A beamline of ESRF

NASA Astrophysics Data System (ADS)

da Silva, Julio C.; Pacureanu, Alexandra; Yang, Yang; Fus, Florin; Hubert, Maxime; Bloch, Leonid; Salome, Murielle; Bohic, Sylvain; Cloetens, Peter

2017-09-01

The ID16A beamline at ESRF offers unique capabilities for X-ray nano-imaging, and currently produces the worlds brightest high energy diffraction-limited nanofocus. Such a nanoprobe was designed for quantitative characterization of the morphology and the elemental composition of specimens at both room and cryogenic temperatures. Billions of photons per second can be delivered in a diffraction-limited focus spot size down to 13 nm. Coherent X-ray imaging techniques, as magnified holographic-tomography and ptychographic-tomography, are implemented as well as X-ray fluorescence nanoscopy. We will show the latest developments in coherent and spectroscopic X-ray nanoimaging implemented at the ID16A beamline

Real-Time Time-Frequency Two-Dimensional Imaging of Ultrafast Transient Signals in Solid-State Organic Materials

PubMed Central

Takeda, Jun; Ishida, Akihiro; Makishima, Yoshinori; Katayama, Ikufumi

2010-01-01

In this review, we demonstrate a real-time time-frequency two-dimensional (2D) pump-probe imaging spectroscopy implemented on a single shot basis applicable to excited-state dynamics in solid-state organic and biological materials. Using this technique, we could successfully map ultrafast time-frequency 2D transient absorption signals of β-carotene in solid films with wide temporal and spectral ranges having very short accumulation time of 20 ms per unit frame. The results obtained indicate the high potential of this technique as a powerful and unique spectroscopic tool to observe ultrafast excited-state dynamics of organic and biological materials in solid-state, which undergo rapid photodegradation. PMID:22399879

Electrochemical sensing of modified ABO3 perovskite: LaFe0.8 R0.2O3(R= Cr, Co, Al)

NASA Astrophysics Data System (ADS)

Vidya Rajan, N.; Alexander, L. K.

2017-06-01

Perovskite LaFeO3 with orthorhombic structure has been synthesized by citric acid mediated solution method. The effectiveness of ionic radii and Oxidation state of the doping material on ionic conductivity of the host matrix was evaluated by B-site (Fe) doping on LaFeO3 with Cr, Co and Al, resulting LaFe0.8 R0.2O3 (R = Cr, Co, Al). XRD with Rietveld refinement and Raman spectroscopic analysis demonstrate successful synthesis. The effect of the 20% B site doping on electrochemical activity is reported. The doped materials exhibit a decrease in sensing activity towards the non enzymatic detection of H2O2.

The function of prehistoric lithic tools: a combined study of use-wear analysis and FTIR microspectroscopy.

PubMed

Nunziante Cesaro, Stella; Lemorini, Cristina

2012-02-01

The application of combined use-wear analysis and FTIR micro spectroscopy for the investigation of the flint and obsidian tools from the archaeological sites of Masseria Candelaro (Foggia, Italy) and Sant'Anna di Oria (Brindisi, Italy) aiming to clarify their functional use is described. The tools excavated in the former site showed in a very high percentage spectroscopically detectable residues on their working edges. The identification of micro deposits is based on comparison with a great number of replicas studied in the same experimental conditions. FTIR data confirmed in almost all cases the use-wear analysis suggestions and added details about the material processed and about the working procedures. Copyright © 2011 Elsevier B.V. All rights reserved.

Development of selective laser treatment techniques using mid-infrared tunable nanosecond pulsed laser.

PubMed

Ishii, Katsunori; Saiki, Masayuki; Hazama, Hisanao; Awazu, Kunio

2010-01-01

Mid-infrared (MIR) laser with a specific wavelength can excite the corresponding biomolecular site to regulate chemical, thermal and mechanical interactions to biological molecules and tissues. In laser surgery and medicine, tunable MIR laser irradiation can realize the selective and less-invasive treatments and the special diagnosis by vibrational spectroscopic information. This paper showed a novel selective therapeutic technique for a laser angioplasty of atherosclerotic plaques and a laser dental surgery of a carious dentin using a MIR tunable nanosecond pulsed laser.

Influence of dopant substitution mechanism on catalytic properties within hierarchical architectures

PubMed Central

Newland, Stephanie H.; Sinkler, Wharton; Mezza, Thomas; Bare, Simon R.

2016-01-01

A range of hierarchically porous (HP) AlPO-5 catalysts, with isomorphously substituted transition metal ions, have been synthesized using an organosilane as a soft template. By employing a range of structural and spectroscopic characterization protocols, the properties of the dopant-substituted species within the HP architectures have been carefully evaluated. The resulting nature of the active site is shown to have a direct impact on the ensuing catalytic properties in the liquid-phase Beckmann rearrangement of cyclic ketones. PMID:27493563

Spectroscopy of γ Doradus stars

NASA Astrophysics Data System (ADS)

Brunsden, E.; Pollard, K. R.; Cottrell, P. L.; Wright, D. J.; De Cat, P.; Kilmartin, P. M.

2014-02-01

The musician programme at the University of Canterbury has been successfully identifying pulsation modes in many γ Doradus stars using hundreds of ground-based spectroscopic observations. This paper describes some of the successful mode identifications and emerging patterns of the programme. The hybrid γ Doradus/δ Scuti star HD 49434 remains an enigma, despite the analysis of more than 1700 multi-site high-resolution spectra. A new result for this star is apparently distinct line-profile variations for the γ Doradus and δ Scuti frequencies.

Influence of dopant substitution mechanism on catalytic properties within hierarchical architectures

NASA Astrophysics Data System (ADS)

Newland, Stephanie H.; Sinkler, Wharton; Mezza, Thomas; Bare, Simon R.; Raja, Robert

2016-07-01

A range of hierarchically porous (HP) AlPO-5 catalysts, with isomorphously substituted transition metal ions, have been synthesized using an organosilane as a soft template. By employing a range of structural and spectroscopic characterization protocols, the properties of the dopant-substituted species within the HP architectures have been carefully evaluated. The resulting nature of the active site is shown to have a direct impact on the ensuing catalytic properties in the liquid-phase Beckmann rearrangement of cyclic ketones.

Accumulation of slightly deleterious mutations in the mitochondrial genome: a hallmark of animal domestication.

PubMed

Hughes, Austin L

2013-02-15

The hypothesis that domestication leads to a relaxation of purifying selection on mitochondrial (mt) genomes was tested by comparative analysis of mt genes from dog, pig, chicken, and silkworm. The three vertebrate species showed mt genome phylogenies in which domestic and wild isolates were intermingled, whereas the domestic silkworm (Bombyx mori) formed a distinct cluster nested within its closest wild relative (Bombyx mandarina). In spite of these differences in phylogenetic pattern, significantly greater proportions of nonsynonymous SNPs than of synonymous SNPs were unique to the domestic populations of all four species. Likewise, in all four species, significantly greater proportions of RNA-encoding SNPs than of synonymous SNPs were unique to the domestic populations. Thus, domestic populations were characterized by an excess of unique polymorphisms in two categories generally subject to purifying selection: nonsynonymous sites and RNA-encoding sites. Many of these unique polymorphisms thus seem likely to be slightly deleterious; the latter hypothesis was supported by the generally lower gene diversities of polymorphisms unique to domestic populations in comparison to those of polymorphisms shared by domestic and wild populations. Copyright © 2012 Elsevier B.V. All rights reserved.

High-pressure structural behavior of hydrogarnet, katoite Ca3Al2(O4H4)3

NASA Astrophysics Data System (ADS)

Kyono, A.; Kato, M.; Sano-Furukawa, A.; Machida, S. I.; Hattori, T.

2016-12-01

High-pressure structural behavior of hydrogarnet, katoite Ca3Al2(O4H4)3, was investigated using single-crystal synchrotron x-ray diffraction, Raman spectroscopic, and neutron diffraction analyses. The high-pressure single-crystal synchrotron x-ray diffraction was performed at BL10A, Photon Factory, KEK, Japan. With compression, the a lattice parameter decreased continuously from 12.565 (1) Å to 12.226 (3) Å up to 7.1 GPa. A fit to the Birch-Murnaghan equation of state (EoS) based on the P-V data gives K0 = 56.0 (6) GPa, K' = 4.3 (1), and V0 = 1984.2 (5) Å3, which were consistent with the previous study by Lager et al. (2002). Weak reflections forbidden by the systematic absence of hk0 with k, l = 2n were observed at 5.5 GPa and their intensities became stronger as increasing pressure. The pattern change of systematic absence implies phase transformation from space group Ia-3d to its non-centrosymmetric space group I-43d. High-pressure Raman spectroscopic study was performed up to 8.3 GPa at room temperature. The pressure dependence of lattice modes showed a positive pressure shifts, whereas that of OH stretching vibration mode was changed negative above 5.1 GPa. The change indicates that the strength of hydrogen bonding turns to increase above 5.1 GPa. High-pressure and high-temperature neutron diffraction study was performed with six-axis large volume press, ATSUHIME, at BL11 (PLANET), J-PARC, Japan. At a pressure of approximately 8 GPa, the a lattice parameter increased with temperature, but neither thermal decomposition nor dehydroxylation process occurred up to 1123 K. The crystal structure of katoite was determined by Rietveld method using neutron diffraction data with the space group I-43d. The volume of dodecahedral site containing Ca cations and that of octahedral site occupied by Al cations remained almost constant with temperature, but two crystallographically inequivalent tetrahedral sites which were caused by phase transformation behaved differently from each other. The volume of T2 site was continuously increased, but that of T1 site was constantly decreased, resulting from anisotropic expansion of the dodecahedral site. Consequently, these anisotropic modifications of coordination polyhedra seem to induce the thermal decomposition of katoite at 1123 K and 8 GPa.

One Course, One Web Site--Of Course? Maybe Not!

ERIC Educational Resources Information Center

Cohn, Ellen R.

2004-01-01

Colleges and universities increasingly employ commercial Web-based course management systems (such as Blackboard and WebCT). How is it, then, that these institutions unquestioningly allocate a unique Web site to each class? Why establish one Web site for one course when other options provide so many benefits? Why isn't there a clamor for…

Examining the Presence of Social Media on University Web Sites

ERIC Educational Resources Information Center

Greenwood, Grant

2012-01-01

Over the past few years, social networking has exploded into a massive medium that has captured the attention of a large portion of the American population. The ever-growing social networking site(s) (SNS) movement has filled a networking gap and thus, has presented higher education institutions with unique opportunities (Reid 2009) to further…

Multifocal multi-site Warthin tumour.

PubMed

Hilton, Jennifer M; Phillips, John S; Hellquist, Henrik B; Premachandra, Don J

2008-12-01

The unique case of a 55-year-old man with multifocal adenolymphoma (Warthin's tumour) of both parotid glands, the neck and post-nasal space is presented. Warthin tumour is almost exclusively a parotid tumour but is known to be bilateral in 7-10% of cases and multifocal in 2% of cases. Most extraglandular Warthin tumours have been located in neck lymph nodes and only a few cases have been reported from other sites. The presented case is unique in having synchronous and metachronous Warthin tumours, as well as one of the tumours being neither truly parotid, nor within a lymph node.

Newberry EGS Seismic Velocity Model

DOE Data Explorer

Templeton, Dennise

2013-10-01

We use ambient noise correlation (ANC) to create a detailed image of the subsurface seismic velocity at the Newberry EGS site down to 5 km. We collected continuous data for the 22 stations in the Newberry network, together with 12 additional stations from the nearby CC, UO and UW networks. The data were instrument corrected, whitened and converted to single bit traces before cross correlation according to the methodology in Benson (2007). There are 231 unique paths connecting the 22 stations of the Newberry network. The additional networks extended that to 402 unique paths crossing beneath the Newberry site.

Onco-Regulon: an integrated database and software suite for site specific targeting of transcription factors of cancer genes

PubMed Central

Tomar, Navneet; Mishra, Akhilesh; Mrinal, Nirotpal; Jayaram, B.

2016-01-01

Transcription factors (TFs) bind at multiple sites in the genome and regulate expression of many genes. Regulating TF binding in a gene specific manner remains a formidable challenge in drug discovery because the same binding motif may be present at multiple locations in the genome. Here, we present Onco-Regulon (http://www.scfbio-iitd.res.in/software/onco/NavSite/index.htm), an integrated database of regulatory motifs of cancer genes clubbed with Unique Sequence-Predictor (USP) a software suite that identifies unique sequences for each of these regulatory DNA motifs at the specified position in the genome. USP works by extending a given DNA motif, in 5′→3′, 3′ →5′ or both directions by adding one nucleotide at each step, and calculates the frequency of each extended motif in the genome by Frequency Counter programme. This step is iterated till the frequency of the extended motif becomes unity in the genome. Thus, for each given motif, we get three possible unique sequences. Closest Sequence Finder program predicts off-target drug binding in the genome. Inclusion of DNA-Protein structural information further makes Onco-Regulon a highly informative repository for gene specific drug development. We believe that Onco-Regulon will help researchers to design drugs which will bind to an exclusive site in the genome with no off-target effects, theoretically. Database URL: http://www.scfbio-iitd.res.in/software/onco/NavSite/index.htm PMID:27515825

Design manual for low water stream crossings.

DOT National Transportation Integrated Search

1983-10-01

The purpose of this manual is to provide design guidelines for : low water stream crossings (LWSCs). Rigid criteria for determining the : applicability of a LWSC to a given site are not established since each : site is unique in terms of physical, so...

Constraining the Mass of the Spectacular Pandora's Cluster, Abell 2744

NASA Astrophysics Data System (ADS)

Carrasco, Rodrigo; Frye, Brenda; Coe, Dan; Dupke, Renato; Merten, Julian; Sodre, Laerte; Massey, Richard; Braglia, Filberto; Cypriano, Eduardo; Zitrin, Adi; Krick, Jessica; Benitez, Narciso

2011-08-01

Violent cluster mergers provide a unique opportunity to study the interplay between dark matter (DM) and ICM and to set constraints on the nature of DM. In particular, cluster mergers near first core passage allow us to ``see'' DM by comparing the spatial distribution of the intra-cluster gas (baryonic) to that of DM. We have recently finished a lensing analysis of the particularly interesting merging system, A2744, the Pandora cluster. We found that it is the result of a spectacular merging event, significantly more complex than the "Bullet Cluster", that produced a wide variety of new phenomenologies, among them, a Bullet, a Dark sub-cluster (no gas), a Ghost sub-cluster (no DM), which can provide fundamental insights to the physics of the ICM, and begs further observations. Our analyses revealed 34 arcs produced by strong gravitational lensing, none of which had been published to date. Spectroscopic redshifts of these arcs are essential to determine precise masses of the main merging system providing crucial information for further numerical simulations and to set stronger constraints on the DM self-interaction cross-section. Therefore we are requesting 17.2 hours on Gemini+GMOS-S, primarily to obtain spectroscopic redshifts of multiply strongly lensed arcs produced by this impressive cluster.

Total synthesis and antibacterial testing of the A54556 cyclic acyldepsipeptides isolated from Streptomyces hawaiiensis.

PubMed

Goodreid, Jordan D; Wong, Keith; Leung, Elisa; McCaw, Shannon E; Gray-Owen, Scott D; Lough, Alan; Houry, Walid A; Batey, Robert A

2014-10-24

The first total synthesis of all six known A54556 acyldepsipeptide (ADEP) antibiotics from Streptomyces hawaiiensis is reported. This family of compounds has a unique mechanism of antibacterial action, acting as activators of caseinolytic protease (ClpP). Assembly of the 16-membered depsipeptide core was accomplished via a pentafluorophenyl ester-based macrolactamization strategy. Late stage amine deprotection was carried out under neutral conditions by employing a mild hydrogenolysis strategy, which avoids the formation of undesired ring-opened depsipeptide side products encountered during deprotection of acid-labile protecting groups. The free amines were found to be significantly more reactive toward late stage amide bond formation as compared to the corresponding ammonium salts, giving final products in excellent yields. A thorough NMR spectroscopic analysis of these compounds was carried out to formally assign the structures and to aid with the spectroscopic assignment of ADEP analogues. The identity of two of the structures was confirmed by comparison with biologically produced samples from S. hawaiiensis. An X-ray crystallographic analysis of an ADEP analogue reveals a conformation similar to that found in cocrystal structures of ADEPs with ClpP protease. The degree of antibacterial activity of the different compounds was evaluated in vitro using MIC assays employing both Gram-positive and Gram-negative strains and a fluorescence-based biochemical assay.

Oxidative precipitation of ruthenium oxide for supercapacitors: Enhanced capacitive performances by adding cetyltrimethylammonium bromide

NASA Astrophysics Data System (ADS)

Chen, I.-Li; Wei, Yu-Chen; Chen, Tsan-Yao; Hu, Chi-Chang; Lin, Tsang-Lang

2014-12-01

Thermally stable and porous RuO2·xH2O with superior rate-retention capability is prepared by the H2O2-oxidative precipitation method modified with the cetyltrimethylammonium bromide (CTAB) template. The specific capacitance and rate-retention of RuO2·xH2O are considerably enhanced by the CTAB modification and annealing at 200 °C because of extremely localized crystallization and pore opening of slightly sintered RuO2·xH2O nanoparticles trapped with CTAB. This unique structure, confirmed by the X-ray absorption spectroscopic (XAS), Raman spectroscopic, and transmission electron microscopic (TEM) analyses, favors the utilization of RuO2·xH2O nanocrystals and increases the electrolyte accessibility in comparing with RuO2·xH2O without CTAB modification. The preferential orientation growth along the {101} facet of RuO2 nanocrystals in some local regions is acquired by the CTAB modification and annealing in air at temperatures ≥350 °C. Such preferential orientation growth of RuO2 crystallites is attributable to the oxidation of trapped surfactants during the thermal annealing process, which adsorb on the high surface energy planes of RuO2.

Pentacyclic antibiotics from a tidal mud flat-derived actinomycete.

PubMed

Moon, Kyuho; Chung, Beomkoo; Shin, Yoonho; Rheingold, Arnold L; Moore, Curtis E; Park, Sung Jean; Park, Sunghyouk; Lee, Sang Kook; Oh, Ki-Bong; Shin, Jongheon; Oh, Dong-Chan

2015-03-27

The combination of investigating a unique source of chemically prolific bacterium with an LC/MS-based bacterial strain selection approach resulted in the discovery of two new secondary metabolites, buanmycin (1) and buanquinone (2), from the culture of a marine Streptomyces strain, which was isolated from a tidal mudflat in Buan, Republic of Korea. The carbon backbone of buanmycin (1), comprising 20 quaternary carbons out of 30 total carbons, was determined via (13)C-(13)C COSY NMR analysis after labeling 1 with (13)C by culturing the bacterium with (13)C-glucose. The complete structure of 1 was confidently elucidated, primarily based on 1D and 2D NMR spectroscopic and X-ray crystallographic analysis, as that of a new pentacyclic xanthone. The absolute configuration of the α-methyl serine unit in 1 was established by applying the advanced Marfey's method. The structure of buanquinone (2) was determined to be a new pentacyclic quinone based on NMR and MS spectroscopic data. Buanmycin exhibited potent cytotoxicity against colorectal carcinoma cells (HCT-116) and gastric carcinoma cells (SNU-638) with submicromolar IC50 values and strongly inhibited the pathogenic Gram-negative bacterium Salmonella enterica (MIC = 0.7 μM). In particular, buanmycin demonstrated inhibition of sortase A, which is a promising target for antibiotic discovery.