WorldWideScience

Sample records for rich structural chemistry

  1. Phosphorus Chemistry in Oxygen Rich Stars

    Science.gov (United States)

    Bernal, Jacob; Schmidt, Deborah; Anderson, Julie; Ziurys, Lucy M.

    2017-06-01

    Observations of PO and PN have been carried out at the Arizona Radio Observatory at 1, 2, and 3 mm. Multiple transitions of PO and PN have been detected towards the O-rich AGB stars TX Cam and RCas. Data obtained toward supergiant stars VY Canis Majoris and NML Cyg have also been analyzed. Abundances were obtained for these molecules in all four objects using the radiative transfer code ESCAPADE, which is suitable for symmetric and asymmetric stellar outflows. The abundances of PN and PO were found to be in the range 10^{-8} - 10^{-7} relative to H_{2}. While PN appears to be a parent molecule formed by LTE chemistry near the stellar photosphere, PO appears to be created further out from the star at r > 400 R_*.

  2. Properties of neutron-rich nuclei studied by fission product nuclear chemistry

    International Nuclear Information System (INIS)

    Meyer, R.A.; Henry, E.A.; Griffin, H.C.; Lien, O.G. III; Lane, S.M.; Stevenson, P.C.; Yaffe, R.P.; Skarnemark, G.

    1979-09-01

    A review is given of the properties of neutron-rich nuclei studied by fission product nuclear chemistry and includes the techniques used in elemental isolation and current research on the structure of nuclei near 132 Sn, particle emission, and coexisting structure in both neutron-poor and neutron-rich nuclei. 35 references

  3. The leucine-rich repeat structure.

    Science.gov (United States)

    Bella, J; Hindle, K L; McEwan, P A; Lovell, S C

    2008-08-01

    The leucine-rich repeat is a widespread structural motif of 20-30 amino acids with a characteristic repetitive sequence pattern rich in leucines. Leucine-rich repeat domains are built from tandems of two or more repeats and form curved solenoid structures that are particularly suitable for protein-protein interactions. Thousands of protein sequences containing leucine-rich repeats have been identified by automatic annotation methods. Three-dimensional structures of leucine-rich repeat domains determined to date reveal a degree of structural variability that translates into the considerable functional versatility of this protein superfamily. As the essential structural principles become well established, the leucine-rich repeat architecture is emerging as an attractive framework for structural prediction and protein engineering. This review presents an update of the current understanding of leucine-rich repeat structure at the primary, secondary, tertiary and quaternary levels and discusses specific examples from recently determined three-dimensional structures.

  4. Structure correlation and chemistry

    International Nuclear Information System (INIS)

    Buergi, H.B.

    1998-01-01

    The main goal of crystal and molecular structure determination is to provide a starting point for understanding the physical, chemical and biological properties of matter. At present, results from nearly 300000 crystal structure studies are available in computer-readable form. Structure correlation attempts to extract knowledge and understanding from this body of information, which is not available from its parts. This article reviews some typical examples: libraries of prototypal molecular dimensions, mappings of chemical reaction pathways, correlations between structure on one hand and energy, reaction rate, catalytic activity or magnetism on the other. The knowledge gained from structure-correlation studies, together with quantum-chemical and other modeling techniques, provides conceptual and practical tools for designing molecules and materials with tailor-made properties. (orig.)

  5. Crystal chemistry of nephelines from ijolites and nepheline-rich pegmatites: influence of composition and genesis on the crystal structure investigated by X-ray diffraction

    DEFF Research Database (Denmark)

    Vulić, Predrag; Balić-Žunić, Tonči; Belmonte, Louise Josefine

    2011-01-01

    Ten nepheline single crystals from five different localities representing rocks from nepheline-syenite pegmatites to urtite, ijolite and cancrinite-ijolite were investigated chemically and structurally. The chemical compositions were determined by electron microprobe, whereas the crystal structur...

  6. Structural Chemistry of Human RNA Methyltransferases.

    Science.gov (United States)

    Schapira, Matthieu

    2016-03-18

    RNA methyltransferases (RNMTs) play important roles in RNA stability, splicing, and epigenetic mechanisms. They constitute a promising target class that is underexplored by the medicinal chemistry community. Information of relevance to drug design can be extracted from the rich structural coverage of human RNMTs. In this work, the structural chemistry of this protein family is analyzed in depth. Unlike most methyltransferases, RNMTs generally feature a substrate-binding site that is largely open on the cofactor-binding pocket, favoring the design of bisubstrate inhibitors. Substrate purine or pyrimidines are often sandwiched between hydrophobic walls that can accommodate planar ring systems. When the substrate base is laying on a shallow surface, a 5' flanking base is sometimes anchored in a druggable cavity. The cofactor-binding site is structurally more diverse than in protein methyltransferases and more druggable in SPOUT than in Rossman-fold enzymes. Finally, conformational plasticity observed both at the substrate and cofactor binding sites may be a challenge for structure-based drug design. The landscape drawn here may inform ongoing efforts toward the discovery of the first human RNMT inhibitors.

  7. Organoactinide chemistry: synthesis, structure, and solution dynamics

    International Nuclear Information System (INIS)

    Brennan, J.G.

    1985-12-01

    This thesis considers three aspects of organoactinide chemistry. In chapter one, a bidentate phosphine ligand was used to kinetically stabilize complexes of the type Cp 2 MX 2 . Ligand redistribution processes are present throughout the synthetic work, as has often been observed in uranium cyclopentadienyl chemistry. The effects of covalent M-L bonding on the solution and solid state properties of U(III) coordination complexes are considered. In particular, the nature of the more subtle interaction between the metal and the neutral ligand are examined. Using relative basicity data obtained in solution, and solid state structural data (and supplemented by gas phase photoelectron measurements), it is demonstrated that the more electron rich U(III) centers engage in significant U → L π-donation. Trivalent uranium is shown to be capable of acting either as a one- or two-electron reducing agent toward a wide variety of unsaturated organic and inorganic molecules, generating molecular classes unobtainable via traditional synthetic approaches, as well as offering an alternative synthetic approach to molecules accessible via metathesis reactions. Ligand redistribution processes are again observed, but given the information concerning ligand lability, this reactivity pattern is applied to the synthesis of pure materials inaccessible from redox chemistry. 214 refs., 33 figs., 10 tabs

  8. Beyond "Inert" Ideas to Teaching General Chemistry from Rich Contexts: Visualizing the Chemistry of Climate Change (VC3)

    Science.gov (United States)

    Mahaffy, Peter G.; Holme, Thomas A.; Martin-Visscher, Leah; Martin, Brian E.; Versprille, Ashley; Kirchhoff, Mary; McKenzie, Lallie; Town, Marcy

    2017-01-01

    As one approach to moving beyond transmitting "inert" ideas to chemistry students, we use the term "teaching from rich contexts" to describe implementations of case studies or context-based learning based on systems thinking that provide deep and rich opportunities for learning crosscutting concepts through contexts. This…

  9. The 1 mm spectrum of VY Canis Majoris: Chemistry in an O-rich envelope

    Science.gov (United States)

    Tenenbaum, Emily D.; Milam, Stefanie N.; Apponi, Aldo J.; Woolf, Neville J.; Ziurys, Lucy M.; Schöier, Fredrik L.

    2008-10-01

    We present preliminary results of an unbiased spectral survey at 1 mm of the oxygen-rich supergiant, VY CMa. A number of exotic molecules have been detected, including NaCl and PO, and a relatively rich organic chemistry is observed. Results of the survey will be compared with carbon-rich stars.

  10. Transition metal chemistry of hydroxy(–OH)-rich molecules ...

    Indian Academy of Sciences (India)

    Administrator

    Appropriately designed hydroxy(–OH) containing Schiff's base and Mannich base molecules have been recently found to be important for development of the coordination chemistry of a number of metal ions in the biomimetic chemistry of metalloenzymes. In this context, our group has studied the coordination role of these ...

  11. Organic chemistry in a CO2 rich early Earth atmosphere

    Science.gov (United States)

    Fleury, Benjamin; Carrasco, Nathalie; Millan, Maëva; Vettier, Ludovic; Szopa, Cyril

    2017-12-01

    The emergence of life on the Earth has required a prior organic chemistry leading to the formation of prebiotic molecules. The origin and the evolution of the organic matter on the early Earth is not yet firmly understood. Several hypothesis, possibly complementary, are considered. They can be divided in two categories: endogenous and exogenous sources. In this work we investigate the contribution of a specific endogenous source: the organic chemistry occurring in the ionosphere of the early Earth where the significant VUV contribution of the young Sun involved an efficient formation of reactive species. We address the issue whether this chemistry can lead to the formation of complex organic compounds with CO2 as only source of carbon in an early atmosphere made of N2, CO2 and H2, by mimicking experimentally this type of chemistry using a low pressure plasma reactor. By analyzing the gaseous phase composition, we strictly identified the formation of H2O, NH3, N2O and C2N2. The formation of a solid organic phase is also observed, confirming the possibility to trigger organic chemistry in the upper atmosphere of the early Earth. The identification of Nitrogen-bearing chemical functions in the solid highlights the possibility for an efficient ionospheric chemistry to provide prebiotic material on the early Earth.

  12. Chemistry and structure of technetium complexes

    International Nuclear Information System (INIS)

    Baldas, J.; Boas, J.F.; Bonnyman, J.; Williams, G.A.

    1983-01-01

    The structures of tris(2-aminobenzenethiolato) technetium(VI) and dichlorobis(diethyldithiocarbamato) thionitrosyltechnetium(V) have been determined by single crystal x-ray diffraction analysis. The preparation and chemistry of thiocyanato complexes of technetium have been investigated

  13. Non-Equilibrium Chemistry of O-Rich AGB Stars as Revealed by ALMA

    Science.gov (United States)

    Wong, Ka Tat

    2018-04-01

    Chemical models suggest that pulsation driven shocks propagating from the stellar surfaces of oxygen-rich evolved stars to the dust formation zone trigger non-equilibrium chemistry in the shocked gas near the star, including the formation of carbon-bearing molecules in the stellar winds dominated by oxygen-rich chemistry. Recent long-baseline ALMA observations are able to give us a detailed view of the molecular line emission and absorption at an angular resolution of a few stellar radii. I am going to present the latest results from the ALMA observations of IK Tau and o Cet in late 2017, with a particular focus on HCN.

  14. The atomic structure and chemistry of Fe-rich steps on antiphase boundaries in Ti-doped Bi0.9Nd0.15FeO3

    Directory of Open Access Journals (Sweden)

    Ian MacLaren

    2014-06-01

    Full Text Available Stepped antiphase boundaries are frequently observed in Ti-doped Bi0.85Nd0.15FeO3, related to the novel planar antiphase boundaries reported recently. The atomic structure and chemistry of these steps are determined by a combination of high angle annular dark field and bright field scanning transmission electron microscopy imaging, together with electron energy loss spectroscopy. The core of these steps is found to consist of 4 edge-sharing FeO6 octahedra. The structure is confirmed by image simulations using a frozen phonon multislice approach. The steps are also found to be negatively charged and, like the planar boundaries studied previously, result in polarisation of the surrounding perovskite matrix.

  15. The Physics and Chemistry of Oxygen-Rich Circumstellar Envelopes as Traced by Simple Molecules

    Science.gov (United States)

    Wong, Ka Tat

    2018-04-01

    multiple radio inversion lines of NH3. Furthermore, mid-infrared absorption of NH3 has been observed by the NASA Infrared Telescope Facility (IRTF) for IK Tau and VY CMa. Full radiative transfer modelling including mid-infrared pumping to the first vibrationally excited state (v2=1) has been carried out to reproduce the observed emission and absorption spectra and to retrieve the NH3 abundances in the targets. It is found that the NH3 emission in the CSEs of the targets arises from localised spatial-kinematic structures in which the gas density may be higher than in the surrounding gas. Circumstellar shocks may contribute to, but cannot fully account for, the formation of the molecule. Besides circumstellar chemistry, our understanding of the dust formation and wind-driving mechanisms of oxygen-rich evolved stars is still incomplete. One of the obstacles in the past was the difficulty in imaging the dust condensation and wind acceleration zones due to the lack of high-angular resolution instruments. Thanks to the Atacama Large Millimeter/submillimeter Array (ALMA), which has the longest baseline of about 15 km, we are now able to produce high-fidelity images at unprecedented angular resolutions of tens of milliarcseconds (mas) in the (sub)millimetre regime. Such angular resolutions, which are comparable to the stellar radii of nearby objects, are necessary to understand the gas dynamics and chemical evolution in the pulsating atmosphere and dust formation zone of nearby AGB stars. The eponymous Mira-type long-period variable, o Cet, was observed as a Science Verification target during the first ALMA Long Baseline Campaign that took place in 2014. The observations produced images of the stellar radio photosphere and the molecular transitions of SiO and H2O at an angular resolution of about 30 mas near 220 GHz (1.3 mm). The millimetre stellar disc of o Cet was resolved and modelled. More importantly, this is the first time that molecular line absorption against the

  16. Structure of neutron-rich nuclei

    International Nuclear Information System (INIS)

    Nazarewicz, W.; Oak Ridge National Lab., TN; Warsaw Univ.

    1997-11-01

    One of the frontiers of today's nuclear science is the ''journey to the limits'': of atomic charge and nuclear mass, of neutron-to-proton ratio, and of angular momentum. The new data on exotic nuclei are expected to bring qualitatively new information about the fundamental properties of the nucleonic many-body system, the nature of the nuclear interaction, and nucleonic correlations at various energy-distance scales. In this talk, current developments in nuclear structure of neutron-rich nuclei are discussed from a theoretical perspective

  17. Structure of neutron-rich nuclei

    International Nuclear Information System (INIS)

    Nazarewicz, W.

    2000-01-01

    Complete text of publication follows. The uncharted regions of the (N,Z) plane contain information that can answer many questions of fundamental importance for science: How many protons and neutrons can be clustered together by the strong interaction to form a bound nucleus? What are the proton and neutron magic numbers of the exotic nuclei? What are the properties of very short-lived exotic nuclei with extreme neutron-to-proton ratios? What is the effective nucleon-nucleon interaction in a nucleus that has a very large neutron excess? Nuclear life far from stability is different from that around the stability line; the promised access to completely new combinations of proton and neutron numbers offers prospects for new structural phenomena. The main objective of this talk is to discuss some of the challenges and opportunities of research with exotic nuclei. The covered topics will include: Theoretical challenges; Skins and halos in heavy nuclei; Shape coexistence in exotic nuclei; Beta-decays of neutron-rich nuclei. (author)

  18. Chalcone: A Privileged Structure in Medicinal Chemistry.

    Science.gov (United States)

    Zhuang, Chunlin; Zhang, Wen; Sheng, Chunquan; Zhang, Wannian; Xing, Chengguo; Miao, Zhenyuan

    2017-06-28

    Privileged structures have been widely used as an effective template in medicinal chemistry for drug discovery. Chalcone is a common simple scaffold found in many naturally occurring compounds. Many chalcone derivatives have also been prepared due to their convenient synthesis. These natural products and synthetic compounds have shown numerous interesting biological activities with clinical potentials against various diseases. This review aims to highlight the recent evidence of chalcone as a privileged scaffold in medicinal chemistry. Multiple aspects of chalcone will be summarized herein, including the isolation of novel chalcone derivatives, the development of new synthetic methodologies, the evaluation of their biological properties, and the exploration of the mechanisms of action as well as target identification. This review is expected to be a comprehensive, authoritative, and critical review of the chalcone template to the chemistry community.

  19. Structure of Light Neutron-rich Nuclei

    International Nuclear Information System (INIS)

    Dlouhy, Zdenek

    2007-01-01

    In this contribution we searched for irregularities in various separation energies in the frame of mass measurement of neutron-rich nuclei at GANIL. On this basis we can summarize that the new doubly magic nuclei are 8 He, 22 O and 24 O. They are characterized by extra stability and, except 24 O, they cannot accept and bind additional neutrons. However, if we add to these nuclei a proton we obtain 9 Li and 25 F which are the core for two-neutron halo nucleus 11 Li and enables that fluorine can bound even 6 more neutrons, respectively. In that aspect the doubly magic nuclei in the neutron-rich region can form the basis either for neutron halo or very neutron-rich nuclei. (Author)

  20. Investigating Students' Success in Solving and Attitudes towards Context-Rich Open-Ended Problems in Chemistry

    Science.gov (United States)

    Overton, Tina L.; Potter, Nicholas M.

    2011-01-01

    Much research has been carried out on how students solve algorithmic and structured problems in chemistry. This study is concerned with how students solve open-ended, ill-defined problems in chemistry. Over 200 undergraduate chemistry students solved a number of open-ended problem in groups and individually. The three cognitive variables of…

  1. Structure and stabilization of hydrogen-rich transverse.

    Energy Technology Data Exchange (ETDEWEB)

    Lyra, Sgouria [Sandia National Lab. (SNL-CA), Livermore, CA (United States); Wilde, B [Georgia Inst. of Technology, Atlanta, GA (United States); Kolla, Hemanth [Sandia National Lab. (SNL-CA), Livermore, CA (United States); Seitzman, J. [Georgia Inst. of Technology, Atlanta, GA (United States); Lieuwen, T. C. [Georgia Inst. of Technology, Atlanta, GA (United States); Chen, Jacqueline H. [Sandia National Lab. (SNL-CA), Livermore, CA (United States)

    2014-07-01

    This paper reports the results of a joint experimental and numerical study of the ow characteristics and flame stabilization of a hydrogen rich jet injected normal to a turbulent, vitiated cross ow of lean methane combustion products. Simultaneous high-speed stereoscopic PIV and OH PLIF measurements were obtained and analyzed alongside three-dimensional direct numerical simulations of inert and reacting JICF with detailed H2/CO chemistry. Both the experiment and the simulation reveal that, contrary to most previous studies of reacting JICF stabilized in low-to-moderate temperature air cross ow, the present conditions lead to an autoigniting, burner-attached flame that initiates uniformly around the burner edge. Significant asymmetry is observed, however, between the reaction zones located on the windward and leeward sides of the jet, due to the substantially different scalar dissipation rates. The windward reaction zone is much thinner in the near field, while also exhibiting significantly higher local and global heat release than the much broader reaction zone found on the leeward side of the jet. The unsteady dynamics of the windward shear layer, which largely control the important jet/cross flow mixing processes in that region, are explored in order to elucidate the important flow stability implications arising in the reacting JICF. Vorticity spectra extracted from the windward shear layer reveal that the reacting jet is globally unstable and features two high frequency peaks, including a fundamental mode whose Strouhal number of ~0.7 agrees well with previous non-reacting JICF stability studies. The paper concludes with an analysis of the ignition, ame stabilization, and global structure of the burner-attached flame. Chemical explosive mode analysis (CEMA) shows that the entire windward shear layer, and a large region on the leeward side of the jet, are highly explosive prior to ignition and are dominated by non-premixed flame structures after

  2. From simple to complex prebiotic chemistry in a carbon-rich universe

    Science.gov (United States)

    Lage, C.; Janot-Pacheco, E.; Domiciano de Souza, A.; Suárez, O.; Bendjoya, P.; Gadotti, D. A.

    2012-09-01

    It is well known that the main components of important biomolecules are quite common not only in the Solar System, but also in other planetary systems and in the Galactic ISM. The ubiquitous presence of C in the Universe and the unique carbon chemical properties and carbon bonding thermodynamics supports the spontaneous self-replication of monomers into larger polymers, yielding the formation of large molecules. The detection of an ever increasing number of organic molecules in the interstellar medium (ISM) by radio-telescopes and chemical analysis of meteorites boosted astrochemical theories on radiation-induced chemistry, supported by laboratory experiments. In this scenario of exogenous origin of carbon compounds, polyaromatic hydrocarbons (PAHs) may represent a resilient way of accumulating carbon as a robust cosmic reservoir. Consisting of a family of compounds with fused aromatic rings, the abundances of its larger members (50-100 carbon atoms) were estimated to be on top scores just after H2 and CO. PAHs have been detected in the ISM, in star-forming regions, ~14% of low-mass premainsequence stars, and, remarkably, in some 54% of intermediate mass stars. They have also been detected by SPITZER in distant galaxies up to z = 3. PAHs were promptly photolysed into a family of radicals if exposed to UV and oxygen-bearing molecules in laboratory. The presence of oxygenbearing molecules was shown in the laboratory to bring aromatic rings into an unstable chemistry leading to the production of e.g. alcohols, ketones and ether radicals. It has already been observed that carbon-and oxygen-rich stellar envelopes give rise to richer carbon chemistry. It appears very tempting to think that key prebiotic fragments should appear along planetary formation as C-O reaction byproducts such as methanol (CH3OH), formaldehyde (H2CO) and also simpler hydrocarbons as methyl acetylene (CH3CCH). Under an Astrobiology perspective it is plausible to map PAHs and oxygen compounds

  3. CARBON-RICH GIANT PLANETS: ATMOSPHERIC CHEMISTRY, THERMAL INVERSIONS, SPECTRA, AND FORMATION CONDITIONS

    Energy Technology Data Exchange (ETDEWEB)

    Madhusudhan, Nikku [Department of Astrophysical Sciences, Princeton University, Princeton, NJ 08544 (United States); Mousis, Olivier [Institut UTINAM, CNRS-UMR 6213, Observatoire de Besancon, BP 1615, F-25010 Besancon Cedex (France); Johnson, Torrence V. [Jet Propulsion Laboratory, California Institute of Technology, Pasadena, CA 91109 (United States); Lunine, Jonathan I., E-mail: nmadhu@astro.princeton.edu [Department of Astronomy, Cornell University, Ithaca, NY 14853 (United States)

    2011-12-20

    The recent inference of a carbon-rich atmosphere, with C/O {>=} 1, in the hot Jupiter WASP-12b motivates the exotic new class of carbon-rich planets (CRPs). We report a detailed study of the atmospheric chemistry and spectroscopic signatures of carbon-rich giant (CRG) planets, the possibility of thermal inversions in their atmospheres, the compositions of icy planetesimals required for their formation via core accretion, and the apportionment of ices, rock, and volatiles in their envelopes. Our results show that CRG atmospheres probe a unique region in composition space, especially at high temperature (T). For atmospheres with C/O {>=} 1, and T {approx}> 1400 K in the observable atmosphere, most of the oxygen is bound up in CO, while H{sub 2}O is depleted and CH{sub 4} is enhanced by up to two or three orders of magnitude each, compared to equilibrium compositions with solar abundances (C/O = 0.54). These differences in the spectroscopically dominant species for the different C/O ratios cause equally distinct observable signatures in the spectra. As such, highly irradiated transiting giant exoplanets form ideal candidates to estimate atmospheric C/O ratios and to search for CRPs. We also find that the C/O ratio strongly affects the abundances of TiO and VO, which have been suggested to cause thermal inversions in highly irradiated hot Jupiter atmospheres. A C/O = 1 yields TiO and VO abundances of {approx}100 times lower than those obtained with equilibrium chemistry assuming solar abundances, at P {approx} 1 bar. Such a depletion is adequate to rule out thermal inversions due to TiO/VO even in the most highly irradiated hot Jupiters, such as WASP-12b. We estimate the compositions of the protoplanetary disk, the planetesimals, and the envelope of WASP-12b, and the mass of ices dissolved in the envelope, based on the observed atmospheric abundances. Adopting stellar abundances (C/O = 0.44) for the primordial disk composition and low-temperature formation conditions

  4. Teaching Beginning Chemistry Students Simple Lewis Dot Structures

    Science.gov (United States)

    Nassiff, Peter; Czerwinski, Wendy A.

    2015-01-01

    Students beginning their initial study of chemistry often have a difficult time mastering simple Lewis dot structures. Textbooks show students how to manipulate Lewis structures by moving valence electron dots around the chemical structure so each atom has an octet or duet. However, an easier method of teaching Lewis structures for simple…

  5. Organizational Information Requirements, Media Richness and Structural Design

    OpenAIRE

    Richard L. Daft; Robert H. Lengel

    1986-01-01

    This paper answers the question, "Why do organizations process information?" Uncertainty and equivocality are defined as two forces that influence information processing in organizations. Organization structure and internal systems determine both the amount and richness of information provided to managers. Models are proposed that show how organizations can be designed to meet the information needs of technology, interdepartmental relations, and the environment. One implication for managers i...

  6. Natural Proline-Rich Cyclopolypeptides from Marine Organisms: Chemistry, Synthetic Methodologies and Biological Status.

    Science.gov (United States)

    Fang, Wan-Yin; Dahiya, Rajiv; Qin, Hua-Li; Mourya, Rita; Maharaj, Sandeep

    2016-10-26

    Peptides have gained increased interest as therapeutics during recent years. More than 60 peptide drugs have reached the market for the benefit of patients and several hundreds of novel therapeutic peptides are in preclinical and clinical development. The key contributor to this success is the potent and specific, yet safe, mode of action of peptides. Among the wide range of biologically-active peptides, naturally-occurring marine-derived cyclopolypeptides exhibit a broad range of unusual and potent pharmacological activities. Because of their size and complexity, proline-rich cyclic peptides (PRCPs) occupy a crucial chemical space in drug discovery that may provide useful scaffolds for modulating more challenging biological targets, such as protein-protein interactions and allosteric binding sites. Diverse pharmacological activities of natural cyclic peptides from marine sponges, tunicates and cyanobacteria have encouraged efforts to develop cyclic peptides with well-known synthetic methods, including solid-phase and solution-phase techniques of peptide synthesis. The present review highlights the natural resources, unique structural features and the most relevant biological properties of proline-rich peptides of marine-origin, focusing on the potential therapeutic role that the PRCPs may play as a promising source of new peptide-based novel drugs.

  7. Bonding, structure and solid-state chemistry

    CERN Document Server

    Ladd, Mark

    2016-01-01

    This book is aimed at undergraduate students in both chemistry and those degree subjects in which chemistry forms a significant part. It does not reflect any particular academic year, and so finds a place during the normal span of degree studies in the physical sciences. An A-level standard in science and mathematics is presumed; additional mathematical treatments are discussed in Appendices. An introductory first chapter leads into the main subject matter, which is treated through four chapters in terms of the principle bonding forces of cohesion in the solid state; a further chapter discusses nanosize materials. Important applications of the study topics are interspersed at appropriate points within the text. Each chapter is provided with a set of problems of varying degrees of difficulty, so as to assist the reader in gaining a facility with the subject matter and its applications. The problems are supplemented by detailed tutorial solutions, some of which present additional relevant material that indicate...

  8. Enhancing prospective chemistry teachers cognitive structures in the topics of bonding and hybridization by internet-assisted chemistry applications

    OpenAIRE

    Özge Özyalçın Oskay, Sinem Dinçol

    2011-01-01

    The purpose of this study is to determine the effects of internet-assisted chemistry applications on prospective chemistry teachers’ cognitive structures in the topics of bonding and hybridization. The sample of the study consisted of 36 prospective chemistry teachers attending Hacettepe University, Faculty of Education, the Department of Chemistry Education in 2010-2011 academic year and taking Basic Chemistry I lesson. In the study, students were separated into experimental and control gr...

  9. Biradical character of D-rich carriers in the insoluble organic matter of carbonaceous chondrites: A relic of the protoplanetary disk chemistry

    Science.gov (United States)

    Delpoux, Olivier; Gourier, Didier; Vezin, Hervé; Binet, Laurent; Derenne, Sylvie; Robert, François

    2011-01-01

    The insoluble organic matter (IOM) of the Orgueil meteorite contains deuterium-rich radicals detectable by Electron Paramagnetic Resonance (EPR) techniques ( Gourier et al., 2008). However the structure of these deuterium carriers remains poorly constrained. In this work, their electronic structure is deduced from the measurement of the spin states S by transient nutation in pulsed-EPR. It is shown that these deuterium-rich radicals are dominated by biradicaloids (species with S = 0 ground state and thermally accessible S = 1 state) and biradicals (species with S = 1 ground state) representing ˜61% and ˜31% of the radicals in the IOM of Orgueil, respectively, while single radicals ( S = 1/2) contribute only to ˜8%. This is definitely different from mature terrestrial IOMs, which are known to contain almost exclusively S = 1/2 radicals. A structural model is proposed, whereby the occurrence of dominant biradicaloids and biradicals is the direct consequence of the structure of the IOM, made of a network of small aromatic moieties linked by branched and short aliphatic units. This implies that the formation of stable biradicaloids and biradicals by C-H breaking and their deuterium enrichment are produced after the formation of the IOM in the primitive solar system. These results reinforce the idea that the formation of the IOM and the deuterium-rich hotspots are the product of ion chemistry in the solar disk.

  10. Chemistry

    International Nuclear Information System (INIS)

    Ferris, L.M.

    1975-01-01

    The chemical research and development efforts related to the design and ultimate operation of molten-salt breeder reactor systems are concentrated on fuel- and coolant-salt chemistry, including the development of analytical methods for use in these systems. The chemistry of tellurium in fuel salt is being studied to help elucidate the role of this element in the intergranular cracking of Hastelloy N. Studies were continued of the effect of oxygen-containing species on the equilibrium between dissolved UF 3 and dissolved UF 4 , and, in some cases, between the dissolved uranium fluorides and graphite, and the UC 2 . Several aspects of coolant-salt chemistry are under investigation. Hydroxy and oxy compounds that could be formed in molten NaBF 4 are being synthesized and characterized. Studies of the chemistry of chromium (III) compounds in fluoroborate melts were continued as part of a systematic investigation of the corrosion of structural alloys by coolant salt. An in-line voltammetric method for determining U 4+ /U 3+ ratios in fuel salt was tested in a forced-convection loop over a six-month period. (LK)

  11. Natural Cr3+-rich ettringite: occurrence, properties, and crystal structure

    Science.gov (United States)

    Seryotkin, Yurii V.; Sokol, Ella V.; Kokh, Svetlana N.; Murashko, Mikhail N.

    2017-08-01

    Cr3+-rich ettringite with Cr3+→Al substitution and Cr/(Cr + Al) ratios up to 0.40-0.50 was found in mineral assemblages of the Ma'aleh Adumim area of Mottled Zone (Judean Desert). The Cr3+-rich compositions were the latest in the thaumasite → ettringite-thaumasite solid solution → ettringite → ettringite-bentorite solid solution series. The mineral-forming solution was enriched in Cr3+ and had a pH buffered by afwillite at 11-12. Chromium was inherited from larnite rocks produced by high-temperature combustion metamorphic alteration of bioproductive calcareous sediments. The Cr/(Cr + Al) ratios are within 0.10-0.15 in most of the analysed crystals. This degree of substitution imparts pink colouration to the crystals, but does not affect their habit (a combination of monohedra and a prism). The habit changes to pyramid faces in coarse and later Cr3+-bearing crystals as Cr/(Cr + Al) ratios increase abruptly to 0.40-0.50. Single-crystal XRD analysis of one Cr-free and two Cr3+-rich samples and their structure determination and refinement indicate that the Cr-rich crystals (with Cr/(Cr + Al) to 0.3) preserve the symmetry and metrics of ettringite. The Ca-O bonding network undergoes differentiation with increase of Cr3+ concentration at octahedral M sites. The compression of Ca2 and expansion of Ca1 polyhedra sub-networks correlates with the degree of Cr3+→Al substitution.

  12. Level structures of neutron-rich Xe isotopes

    Energy Technology Data Exchange (ETDEWEB)

    Ahmad, I.; Lister, C.J.; Morss, L.R. [and others

    1995-08-01

    The level structures of neutron-rich Xe isotopes were determined by observing prompt gamma-ray coincidences in {sup 248}Cm fission fragments. A 5-mg {sup 248}Cm, in the form of {sup 248}Cm-KCl pellet, was placed inside Eurogam array which consisted of 45 Compton-suppressed Ge detectors and 5 Low-Energy Photon Spectrometers. Transitions in Xe isotopes were identified by the appearance of new peaks in the {gamma}-ray spectra obtained by gating on the gamma peaks of the complementary Mo fragments.

  13. Pharmaceutical process chemistry: evolution of a contemporary data-rich laboratory environment.

    Science.gov (United States)

    Caron, Stéphane; Thomson, Nicholas M

    2015-03-20

    Over the past 20 years, the industrial laboratory environment has gone through a major transformation in the industrial process chemistry setting. In order to discover and develop robust and efficient syntheses and processes for a pharmaceutical portfolio with growing synthetic complexity and increased regulatory expectations, the round-bottom flask and other conventional equipment familiar to a traditional organic chemistry laboratory are being replaced. The new process chemistry laboratory fosters multidisciplinary collaborations by providing a suite of tools capable of delivering deeper process understanding through mechanistic insights and detailed kinetics translating to greater predictability at scale. This transformation is essential to the field of organic synthesis in order to promote excellence in quality, safety, speed, and cost efficiency in synthesis.

  14. High Energy Radical Chemistry Formation of HCN- rich Atmospheres on early Earth

    Czech Academy of Sciences Publication Activity Database

    Ferus, Martin; Kubelík, Petr; Knížek, Antonín; Pastorek, Adam; Sutherland, J.D.; Civiš, Svatopluk

    2017-01-01

    Roč. 7, č. 1 (2017), č. článku 6275. ISSN 2045-2322 R&D Projects: GA ČR GA17-05076S; GA MŠk(CZ) LM2015083; GA MŠk LG15013 Grant - others:Akademie věd - GA AV ČR(CZ) R200401521 Institutional support: RVO:61388955 Keywords : high-power laser * transform emission-spectroscopy * induced dielectric-breakdown * prebiotic organic-synthesis * nucleobase formation Subject RIV: CF - Physical ; Theoretical Chemistry OBOR OECD: Physical chemistry Impact factor: 4.259, year: 2016

  15. Weakly bound structures in neutron rich Si isotopes

    International Nuclear Information System (INIS)

    Singh, D.; Saxena, G.; Yadav, H.L.

    2009-01-01

    Production of radioactive beams have facilitated the nuclear structure studies away from the line of β-stability, especially for the neutron rich drip line nuclei. Theoretical investigations of these nuclei have been carried out by using various approaches viz. few body model or clusters, shell model and mean field theories, both nonrelativistic as well as relativistic mean field (RMF). The advantage of the RMF approach, however, is that in this treatment the spin-orbit interaction is included in a natural way. This is especially advantageous for the description of drip-line nuclei for which the spin-orbit interaction plays an important role. In this communication we report briefly the results of our calculations for the Si isotopes carried out within the framework of RMF + BCS approach

  16. A General Chemistry Experiment Incorporating Synthesis and Structural Determination

    Science.gov (United States)

    van Ryswyk, Hal

    1997-07-01

    An experiment for the general chemistry laboratory is described wherein gas chromatography-mass spectroscopy (GC-MS) and diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) are used to characterize the products of a series of microscale reactions on vanillin. A single sophisticated instrument can be incorporated into the laboratory given sufficient attention to the use of sampling accessories and software macros. Synthetic experiments coupled with modern instrumental techniques can be used in the general chemistry laboratory to illustrate the concepts of synthesis, structure, bonding, and spectroscopy.

  17. Ionization probes of molecular structure and chemistry

    Energy Technology Data Exchange (ETDEWEB)

    Johnson, P.M. [State Univ. of New York, Stony Brook (United States)

    1993-12-01

    Various photoionization processes provide very sensitive probes for the detection and understanding of the spectra of molecules relevant to combustion processes. The detection of ionization can be selective by using resonant multiphoton ionization or by exploiting the fact that different molecules have different sets of ionization potentials. Therefore, the structure and dynamics of individual molecules can be studied even in a mixed sample. The authors are continuing to develop methods for the selective spectroscopic detection of molecules by ionization, and to use these methods for the study of some molecules of combustion interest.

  18. Constraining Phosphorus Chemistry in Carbon- and Oxygen-Rich Circumstellar Envelopes: Observations of PN, HCP, and CP

    Science.gov (United States)

    Milam, S. N.; Halfen, D. T.; Tenenbaum, E. D.; Apponi, A. J.; Woolf, N. J.; Ziurys, L. M.

    2008-09-01

    Millimeter-wave observations of PN, CP, and HCP have been carried out toward circumstellar envelopes of evolved stars using the Arizona Radio Observatory (ARO). HCP and PN have been identified in the carbon-rich source CRL 2688 via observations at 1 mm using the Submillimeter Telescope (SMT) and 2-3 mm with the Kitt Peak 12 m. An identical set of measurements were carried out toward IRC +10216, as well as observations of CP at 1 mm. PN was also observed toward VY Canis Majoris (VY CMa), an oxygen-rich supergiant star. The PN and HCP line profiles in CRL 2688 and IRC +10216 are roughly flat topped, indicating unresolved, optically thin emission; CP, in contrast, has a distinct "U" shape in IRC +10216. Modeling of the line profiles suggests abundances, relative to H2, of f(PN) ~ (3-5) × 10-9 and f(HCP) ~ 2 × 10-7 in CRL 2688, about an order of magnitude higher than in IRC +10216. In VY CMa, f(PN) is ~4 × 10-8. The data in CRL 2688 and IRC +10216 are consistent with LTE formation of HCP and PN in the inner envelope, as predicted by theoretical calculations, with CP a photodissociation product at larger radii. The observed abundance of PN in VY CMa is a factor of 100 higher than LTE predictions. In IRC +10216, the chemistry of HCP/CP mimics that of HCN/CN and suggests an N2 abundance of f ~ 1 × 10-7. The chemistry of phosphorus appears active in both carbon- and oxygen-rich envelopes of evolved stars.

  19. Studies of coal structure using carbene chemistry

    Energy Technology Data Exchange (ETDEWEB)

    1990-01-01

    The object of this grant was to react coal, derivatized forms of coal, and solvent swelled coal with carbenes (divalent carbon species) under mild conditions. These carbenes were to be prepared by treating the coal with several diazo compounds and then thermally decomposing them at relatively low temperatures (80--130{degree}C). The carbenes were to be chosen to show varying selectively toward aromatic rings containing heteroatom functionalities and toward polynuclear aromatic systems. In some instances, where selectivities toward aromatic and heteroaromatic ring systems were not known, model studies were to be carried out. Because of the generally mild conditions employed and the good selectivity anticipated, and actually observed with one particular system, it was expected that this methodology would provide structural information about the coal, along with data on the extent of occurrence and type of aromatic systems. After carbene reactions, treatment of the coal samples was to include extractions and thermolysis. Physical studies included thermogravimetric analysis, diffuse reflectance FT-IR spectroscopy, NMR ({sup 1}H and {sup 13}C) spectroscopy, gas chromatography, GC/MS and GC/FT-IR. 7 figs., 10 tabs.

  20. The complex metal-rich boride Ti{sub 1+x}Rh{sub 2-x+y}Ir{sub 3-y}B{sub 3} (x=0.68, y=1.06) with a new structure type containing B{sub 4} zigzag fragments: Synthesis, crystal chemistry and theoretical calculations

    Energy Technology Data Exchange (ETDEWEB)

    Goerens, Christian [Institute of Inorganic Chemistry, RWTH Aachen University, Landoltweg 1, 52064 Aachen (Germany); Fokwa, Boniface P.T., E-mail: boniface.fokwa@ac.rwth-aachen.de [Institute of Inorganic Chemistry, RWTH Aachen University, Landoltweg 1, 52064 Aachen (Germany)

    2012-08-15

    Polycrystalline samples and single crystals of the new complex boride Ti{sub 1+x}Rh{sub 2-x+y}Ir{sub 3-y}B{sub 3} (x=0.68; y=1.06) were synthesized by arc-melting the elements in a water-cooled copper crucible under an argon atmosphere and characterized by X-Ray diffraction as well as EDX measurements. The crystal structure was refined on the basis of single crystal data. The new phase, which represents a new structure type containing trans zigzag B{sub 4} fragments as well as isolated boron atoms crystallizes in the orthorhombic space group Pbam (Nr. 55) with the lattice parameters a=8.620(1) A, b=14.995(2) A and c=3.234(1) A. First-principles density functional theory calculations using the Vienna ab-initio simulation package (VASP) were performed on an appropriate structural model (using a supercell approach) and the experimental crystallographic data could be reproduced accurately. Based on this model, the density of states and crystal orbital Hamilton population (for bonding analysis) were calculated, using the linear muffin-tin orbital atomic sphere approximation (LMTO-ASA) method. According to these calculations, this metal-rich compound should be metallic, as expected. Furthermore, very strong boron-boron interactions are observed in the trans zigzag B{sub 4} fragment, which induce a clear differentiation of two types of metal-boron contacts with different strength. The observed three-dimensional metal-metal interaction is in good agreement with the predicted metallic behavior. - graphical abstract: The structure of Ti{sub 1.68(2)}Rh{sub 2.38(6)}Ir{sub 1.94(4)} B{sub 3}, a new structure type containing planar trans zigzag B{sub 4} units, is another example which illustrates the tendency of metal-rich borides to form B-B bonds with increasing boron content. Beside the B{sub 4} fragment it exhibits one-dimensional chains of titanium atoms and hold one-dimensional strings of face-sharing empty tetrahedral and square pyramidal clusters (see figure). Highlights

  1. Progress in organic and physical chemistry structures and mechanisms

    CERN Document Server

    Zaikov, Gennady E; Lobanov, Anton V

    2013-01-01

    Progress in Organic and Physical Chemistry: Structures and Mechanisms provides a collection of new research in the field of organic and physical properties, including new research on: The physical principles of the conductivity of electrical conducting polymer compounds The dependence on constants of electromagnetic interactions upon electron spacial-energy characteristics Effects of chitosan molecultural weight on rehological behavior of chitosan modified nanoclay at hight hydrated state Bio-structural energy criteria of functional states in normal and pathological conditions Potentiometric study on the international between devalent cations and sodium carboxylates in aqueous solutions Structural characteristic changes in erythrocyte membranes of mice bearing Alzheimer's-like disease caused by the olfactory bulbetomy This volume is intended to provide an overview of new studies and research for engineers, faculty, researchers, and upper-level students in the field of organic and physical chemistry.

  2. Structure-based classification and ontology in chemistry

    Directory of Open Access Journals (Sweden)

    Hastings Janna

    2012-04-01

    Full Text Available Abstract Background Recent years have seen an explosion in the availability of data in the chemistry domain. With this information explosion, however, retrieving relevant results from the available information, and organising those results, become even harder problems. Computational processing is essential to filter and organise the available resources so as to better facilitate the work of scientists. Ontologies encode expert domain knowledge in a hierarchically organised machine-processable format. One such ontology for the chemical domain is ChEBI. ChEBI provides a classification of chemicals based on their structural features and a role or activity-based classification. An example of a structure-based class is 'pentacyclic compound' (compounds containing five-ring structures, while an example of a role-based class is 'analgesic', since many different chemicals can act as analgesics without sharing structural features. Structure-based classification in chemistry exploits elegant regularities and symmetries in the underlying chemical domain. As yet, there has been neither a systematic analysis of the types of structural classification in use in chemistry nor a comparison to the capabilities of available technologies. Results We analyze the different categories of structural classes in chemistry, presenting a list of patterns for features found in class definitions. We compare these patterns of class definition to tools which allow for automation of hierarchy construction within cheminformatics and within logic-based ontology technology, going into detail in the latter case with respect to the expressive capabilities of the Web Ontology Language and recent extensions for modelling structured objects. Finally we discuss the relationships and interactions between cheminformatics approaches and logic-based approaches. Conclusion Systems that perform intelligent reasoning tasks on chemistry data require a diverse set of underlying computational

  3. Structural manifestations of aging in Se-rich glasses

    Science.gov (United States)

    Dash, S.; Ravindren, S.; Chen, P.; Boolchand, P.

    2015-03-01

    We examine weakly cross-linked GexSe100-x (0%modulated DSC and Raman scattering experiments. Homogeneity of melts was carefully verified using FT-Raman line profiling. Upon aging at RT for 4 months, we find the width of the glass transition W(x) steadily decreasing from 10C at 7% Ge to 2C for pure Se. The 5-fold reduction of W(x) with a decrease of Ge content is accompanied by a 2-fold increase in the non-reversing enthalpy. Rejuvenation of the aged glasses changes W(x) from 15C at 7% Ge to 7C for pure Se. Tg is found to decrease upon rejuvenation with the difference (Tg(aged)-Tg(rejuv)) showing a maximum near 3% Ge and vanishing for pure Se and 6% of Ge, which are topological thresholds. These results in Se-rich glasses are consistent with aging induced decoupling of Se8 crowns and growth of extended range structural correlations between polymeric Sen chains due to lone pair interactions. At higher x, near 8-10% of Ge, eutectic effects are manifested. Work supported by NSF Grant DMR 08-53957.

  4. Structural elucidation, molecular representation and solvent interactions of vitrinite-rich and inertinite-rich South African coals

    Science.gov (United States)

    van Niekerk, Daniel

    The structural differences and similarities of two Permian-aged South African coals, vitrinite-rich Waterberg and inertinite-rich Highveld coals (similar rank, carbon content and Permian age), were evaluated. With South African coals the opportunity presented itself to study not only Permian-aged Gondwana vitrinite but also inertinite. It was expected that these coals would differ from Northern hemisphere Carboniferous coals. It was concluded from various structural data that both coals, although different in maceral composition and depositional basins, are similar in their base structural composition. The main differences were that the inertinite-rich Highveld coal was more ordered, more aromatic, and had less hydrogen than the vitrinite-rich Waterberg coal. Analytical data were used to construct large-scale advanced molecular representations for vitrinite-rich Waterberg and inertinite-rich Highveld coals. The three-dimensional models were structurally diverse with a molecular weight range of 78 to 1900 amu. The vitrinite-rich coal model consisted of 18,572 atoms and 191 individual molecules and the inertinite-rich coal model consisted of 14,242 atoms and 158 individual molecules. This largescale modeling effort was enabled by the development of various PERL scripts to automate various visualization and analytical aspects. Coal swelling studies were conducted using the traditional pack-bed swelling method and a new novel single-particle stop-motion videography swelling method with NMP and CS2/NMP solvents. The pack-bed swelling showed that vitrinite-rich coal had a greater swelling extent and that swelling extent for both coals was greater in CS2/NMP binary solvent than for NMP. Single-particle swelling experiments showed that both coals, for both solvents, exhibit overshoot-type and climbing-type swelling behaviors. Inertinite-coal had a faster swelling rate, in both solvents, than the vitrinite-rich coal. The single-particle swelling data was used to calculate

  5. PROTO-PLANETARY DISK CHEMISTRY RECORDED BY D-RICH ORGANIC RADICALS IN CARBONACEOUS CHONDRITES

    International Nuclear Information System (INIS)

    Remusat, Laurent; Robert, Francois; Meibom, Anders; Mostefaoui, Smail; Delpoux, Olivier; Binet, Laurent; Gourier, Didier; Derenne, Sylvie

    2009-01-01

    Insoluble organic matter (IOM) in primitive carbonaceous meteorites has preserved its chemical composition and isotopic heterogeneity since the solar system formed ∼4.567 billion years ago. We have identified the carrier moieties of isotopically anomalous hydrogen in IOM isolated from the Orgueil carbonaceous chondrite. Data from high spatial resolution, quantitative isotopic NanoSIMS mapping of Orgueil IOM combined with data from electron paramagnetic resonance spectroscopy reveals that organic radicals hold all the deuterium excess (relative to the bulk IOM) in distinct, micrometer-sized, D-rich hotspots. Taken together with previous work, the results indicate that an isotopic exchange reaction took place between pre-existing organic compounds characterized by low D/H ratios and D-rich gaseous molecules, such as H 2 D + or HD 2 + . This exchange reaction most likely took place in the diffuse outer regions of the proto-planetary disk around the young Sun, offering a model that reconciles meteoritic and cometary isotopic compositions of organic molecules.

  6. Proto-Planetary Disk Chemistry Recorded by D-Rich Organic Radicals in Carbonaceous Chondrites

    Science.gov (United States)

    Remusat, Laurent; Robert, François; Meibom, Anders; Mostefaoui, Smail; Delpoux, Olivier; Binet, Laurent; Gourier, Didier; Derenne, Sylvie

    2009-06-01

    Insoluble organic matter (IOM) in primitive carbonaceous meteorites has preserved its chemical composition and isotopic heterogeneity since the solar system formed ~4.567 billion years ago. We have identified the carrier moieties of isotopically anomalous hydrogen in IOM isolated from the Orgueil carbonaceous chondrite. Data from high spatial resolution, quantitative isotopic NanoSIMS mapping of Orgueil IOM combined with data from electron paramagnetic resonance spectroscopy reveals that organic radicals hold all the deuterium excess (relative to the bulk IOM) in distinct, micrometer-sized, D-rich hotspots. Taken together with previous work, the results indicate that an isotopic exchange reaction took place between pre-existing organic compounds characterized by low D/H ratios and D-rich gaseous molecules, such as H2D+ or HD2 +. This exchange reaction most likely took place in the diffuse outer regions of the proto-planetary disk around the young Sun, offering a model that reconciles meteoritic and cometary isotopic compositions of organic molecules.

  7. From energy-rich phosphate compounds to warfare agents: A review on the chemistry of organic phosphate compounds

    Directory of Open Access Journals (Sweden)

    Luciano Albino Giusti

    2008-12-01

    Full Text Available The chemistry of the phosphorus-oxygen bond is widely used in biological systems in many processes, such as energy transduction and the storage, transmission and expression of genetic information, which are essential to living beings in relation to a wide variety of functions. Compounds containing this bond have been designed for many purposes, ranging from agricultural defense systems, in order to increase food production, to nerve agents, for complaining use in warfare. In this review, features related to the chemistry of organic phosphate compounds are discussed, with particular emphasis on the role of phosphate compounds in biochemical events and in nerve agents. To this aim, the energy-rich phosphate compounds are focused, particularly the mode of their use as energy currency in cells. Historical and recent studies carried out by research groups have tried to elucidate the mechanism of action of enzymes responsible for energy transduction through the use of biochemical studies, enzyme models, and artificial enzymes. Finally, recent studies on the detoxification of nerve agents based on phosphorous esters are presented, and on the utilization of chromogenic and fluorogenic chemosensors for the detection of these phosphate species.

  8. Structure of proton-rich nuclei of astrophysical interest

    Energy Technology Data Exchange (ETDEWEB)

    Roeckl, E [Gesellschaft fuer Schwerionenforschung (GSI), Darmstadt (Germany)

    1998-06-01

    Recent experimental data concerning proton-rich nuclei between A=20 and A=100 are presented and discussed with respect to their relevance to the astrophysical rp process and to the calibration of solar neutrino detectors. (orig.)

  9. CARBON CHEMISTRY IN THE ENVELOPE OF VY CANIS MAJORIS: IMPLICATIONS FOR OXYGEN-RICH EVOLVED STARS

    International Nuclear Information System (INIS)

    Ziurys, L. M.; Tenenbaum, E. D.; Pulliam, R. L.; Woolf, N. J.; Milam, S. N.

    2009-01-01

    Observations of the carbon-bearing molecules CO, HCN, CS, HNC, CN, and HCO + have been conducted toward the circumstellar envelope of the oxygen-rich red supergiant star, VY Canis Majoris (VY CMa), using the Arizona Radio Observatory (ARO). CO and HCN were also observed toward the O-rich shells of NML Cyg, TX Cam, IK Tau, and W Hya. Rotational transitions of these species at 1 mm, 0.8 mm, and 0.4 mm were measured with the ARO Submillimeter Telescope, including the J = 6 → 5 line of CO at 691 GHz toward TX Cam and W Hya. The ARO 12 m was used for 2 mm and 3 mm observations. Four transitions were observed for HCO + in VY CMa, the first definitive identification of this ion in a circumstellar envelope. Molecular line profiles from VY CMa are complex, indicating three separate outflows: a roughly spherical flow and separate red- and blueshifted winds, as suggested by earlier observations. Spectra from the other sources appear to trace a single outflow component. The line data were modeled with a radiative transfer code to establish molecular abundances relative to H 2 and source distributions. Abundances for CO derived for these objects vary over an order of magnitude, f ∼ 0.4-5 x 10 -4 , with the lower values corresponding to the supergiants. For HCN, a similar range in abundance is found (f ∼ 0.9-9 x 10 -6 ), with no obvious dependence on the mass-loss rate. In VY CMa, HCO + is present in all three outflows with f ∼ 0.4-1.6 x 10 -8 and a spatial extent similar to that of CO. HNC is found only in the red- and blueshifted components with [HCN]/[HNC] ∼ 150-190, while [CN]/[HCN] ∼ 0.01 in the spherical flow. All three velocity components are traced in CS, which has a confined spatial distribution and f ∼ 2-6 x 10 -7 . These observations suggest that carbon-bearing molecules in O-rich shells are produced by a combination of photospheric shocks and photochemistry. Shocks may play a more prominent role in the supergiants because of their macroturbulent

  10. Carbon Chemistry in the Envelope of VY Canis Majoris: Implications for Oxygen-Rich Evolved Stars

    Science.gov (United States)

    Ziurys, L. M.; Tenenbaum, E. D.; Pulliam, R. L.; Woolf, N. J.; Milam, S. N.

    2009-04-01

    Observations of the carbon-bearing molecules CO, HCN, CS, HNC, CN, and HCO+ have been conducted toward the circumstellar envelope of the oxygen-rich red supergiant star, VY Canis Majoris (VY CMa), using the Arizona Radio Observatory (ARO). CO and HCN were also observed toward the O-rich shells of NML Cyg, TX Cam, IK Tau, and W Hya. Rotational transitions of these species at 1 mm, 0.8 mm, and 0.4 mm were measured with the ARO Submillimeter Telescope, including the J = 6 → 5 line of CO at 691 GHz toward TX Cam and W Hya. The ARO 12 m was used for 2 mm and 3 mm observations. Four transitions were observed for HCO+ in VY CMa, the first definitive identification of this ion in a circumstellar envelope. Molecular line profiles from VY CMa are complex, indicating three separate outflows: a roughly spherical flow and separate red- and blueshifted winds, as suggested by earlier observations. Spectra from the other sources appear to trace a single outflow component. The line data were modeled with a radiative transfer code to establish molecular abundances relative to H2 and source distributions. Abundances for CO derived for these objects vary over an order of magnitude, f ~ 0.4-5 × 10-4, with the lower values corresponding to the supergiants. For HCN, a similar range in abundance is found (f ~ 0.9-9 × 10-6), with no obvious dependence on the mass-loss rate. In VY CMa, HCO+ is present in all three outflows with f ~ 0.4-1.6 × 10-8 and a spatial extent similar to that of CO. HNC is found only in the red- and blueshifted components with [HCN]/[HNC] ~ 150-190, while [CN]/[HCN] ~ 0.01 in the spherical flow. All three velocity components are traced in CS, which has a confined spatial distribution and f ~ 2-6 × 10-7. These observations suggest that carbon-bearing molecules in O-rich shells are produced by a combination of photospheric shocks and photochemistry. Shocks may play a more prominent role in the supergiants because of their macroturbulent velocities.

  11. Chemistry of the organic-rich hot core G327.3-0.6

    Science.gov (United States)

    Gibb, E.; Nummelin, A.; Irvine, W. M.; Whittet, D. C.; Bergman, P.; Ferris, J. P. (Principal Investigator)

    2000-01-01

    We present gas-phase abundances of species found in the organic-rich hot core G327.3-0.6. The data were taken with the Swedish-ESO Submillimetre Telescope (SEST). The 1-3 mm spectrum of this source is dominated by emission features of nitrile species and saturated organics, with abundances greater than those found in many other hot cores, including Sgr B2 and OMC-1. Population diagram analysis indicates that many species (CH3CN, C2H3CN, C2H5CN, CH3OH, etc.) have hot components that originate in a compact (2") region. Gas-phase chemical models cannot reproduce the high abundances of these molecules found in hot cores, and we suggest that they originate from processing and evaporation of icy grain mantle material. In addition, we report the first detection of vibrationally excited ethyl cyanide and the first detection of methyl mercaptan (CH3SH) outside the Galactic center.

  12. High-spin structure of neutron-rich Dy isotopes

    Indian Academy of Sciences (India)

    Neutron-rich Dy isotopes; high-spin states; g-factors; cranked HFB theory. ... for 164Dy marking a clear separation in the behaviour as a function of neutron ... cipal x-axis as the cranking axis) in this mass region we have planned to make a sys-.

  13. Enhancing prospective chemistry teachers cognitive structures in the topics of bonding and hybridization by internet-assisted chemistry applications

    Directory of Open Access Journals (Sweden)

    Özge Özyalçın Oskay, Sinem Dinçol

    2011-08-01

    Full Text Available The purpose of this study is to determine the effects of internet-assisted chemistry applications on prospective chemistry teachers’ cognitive structures in the topics of bonding and hybridization. The sample of the study consisted of 36 prospective chemistry teachers attending Hacettepe University, Faculty of Education, the Department of Chemistry Education in 2010-2011 academic year and taking Basic Chemistry I lesson. In the study, students were separated into experimental and control groups according to their pre-cognitive structures. Students were requested to answer two open ended questions. Answers by each student were gathered and evaluated by flow map method. “Bonding and hybridization” topics were taught to control group with traditional teaching method and to experimental group besides traditional method internet-assisted applications were conducted. The same open-ended questions were given to both groups and their cognitive structures were examined once more. The differences between control and experimental groups’ cognitive structures were examined. A significant difference was identified in favour of experimental group (p<0, 05. The mean score of the Experimental group was X=19.94, and the mean score of the Control group was X=13.88. In addition, subsequent to internet assisted chemistry applications differences in terms of concepts and descriptions in prospective chemistry teachers’ in experimental and control group cognitive structure have been determined. When post flow maps of prospective chemistry teachers in experimental group, on whom internet assisted chemistry applications were made, are formed, it has been determined that there are more statements about hybridization, hybridization types, molecule geometry and bond angles compared to control grou

  14. Modern electronic structure theory and applications in organic chemistry

    CERN Document Server

    Davidson, ER

    1997-01-01

    This volume focuses on the use of quantum theory to understand and explain experiments in organic chemistry. High level ab initio calculations, when properly performed, are useful in making quantitative distinctions between various possible interpretations of structures, reactions and spectra. Chemical reasoning based on simpler quantum models is, however, essential to enumerating the likely possibilities. The simpler models also often suggest the type of wave function likely to be involved in ground and excited states at various points along reaction paths. This preliminary understanding is n

  15. Effects of Chemistry on Blunt-Body Wake Structure

    Science.gov (United States)

    Dogra, Virendra K.; Moss, James N.; Wilmoth, Richard G.; Taylor, Jeff C.; Hassan, H. A.

    1995-01-01

    Results of a numerical study are presented for hypersonic low-density flow about a 70-deg blunt cone using direct simulation Monte Carlo (DSMC) and Navier-Stokes calculations. Particular emphasis is given to the effects of chemistry on the near-wake structure and on the surface quantities and the comparison of the DSMC results with the Navier-Stokes calculations. The flow conditions simulated are those experienced by a space vehicle at an altitude of 85 km and a velocity of 7 km/s during Earth entry. A steady vortex forms in the near wake for these freestream conditions for both chemically reactive and nonreactive air gas models. The size (axial length) of the vortex for the reactive air calculations is 25% larger than that of the nonreactive air calculations. The forebody surface quantities are less sensitive to the chemistry than the base surface quantities. The presence of the afterbody has no effect on the forebody flow structure or the surface quantities. The comparisons of DSMC and Navier-Stokes calculations show good agreement for the wake structure and the forebody surface quantities.

  16. The complex metal-rich boride Ti1+xRh2-x+yIr3-yB3 (x=0.68, y=1.06) with a new structure type containing B4 zigzag fragments: Synthesis, crystal chemistry and theoretical calculations

    Science.gov (United States)

    Goerens, Christian; Fokwa, Boniface P. T.

    2012-08-01

    Polycrystalline samples and single crystals of the new complex boride Ti1+xRh2-x+yIr3-yB3 (x=0.68; y=1.06) were synthesized by arc-melting the elements in a water-cooled copper crucible under an argon atmosphere and characterized by X-Ray diffraction as well as EDX measurements. The crystal structure was refined on the basis of single crystal data. The new phase, which represents a new structure type containing trans zigzag B4 fragments as well as isolated boron atoms crystallizes in the orthorhombic space group Pbam (Nr. 55) with the lattice parameters a=8.620(1) Å, b=14.995(2) Å and c=3.234(1) Å. First-principles density functional theory calculations using the Vienna ab-initio simulation package (VASP) were performed on an appropriate structural model (using a supercell approach) and the experimental crystallographic data could be reproduced accurately. Based on this model, the density of states and crystal orbital Hamilton population (for bonding analysis) were calculated, using the linear muffin-tin orbital atomic sphere approximation (LMTO-ASA) method. According to these calculations, this metal-rich compound should be metallic, as expected. Furthermore, very strong boron-boron interactions are observed in the trans zigzag B4 fragment, which induce a clear differentiation of two types of metal-boron contacts with different strength. The observed three-dimensional metal-metal interaction is in good agreement with the predicted metallic behavior.

  17. Nuclear chemistry on the Czech Technical University in Prague after introduction of structured study and foundation of the Centre for Radiochemistry and Radiation Chemistry

    International Nuclear Information System (INIS)

    John, J.

    2007-01-01

    In this presentation the author (head of the Centre for Radiochemistry and Radiation Chemistry) give a short review of history of the Department of Nuclear Chemistry and of the Centre for Radiochemistry and Radiation Chemistry of the Czech Technical University in Prague. Education in structured study in specialisation of nuclear chemistry in bachelor level, master level, as well as post-graduate study in nuclear chemistry with academic degree PhD. are realised. Some scientific results are presented

  18. Understanding surface structure and chemistry of single crystal lanthanum aluminate

    KAUST Repository

    Pramana, Stevin S.

    2017-03-02

    The surface crystallography and chemistry of a LaAlO3 single crystal, a material mainly used as a substrate to deposit technologically important thin films (e.g. for superconducting and magnetic devices), was analysed using surface X-ray diffraction and low energy ion scattering spectroscopy. The surface was determined to be terminated by Al-O species, and was significantly different from the idealised bulk structure. Termination reversal was not observed at higher temperature (600 °C) and chamber pressure of 10−10 Torr, but rather an increased Al-O occupancy occurred, which was accompanied by a larger outwards relaxation of Al from the bulk positions. Changing the oxygen pressure to 10−6 Torr enriched the Al site occupancy fraction at the outermost surface from 0.245(10) to 0.325(9). In contrast the LaO, which is located at the next sub-surface atomic layer, showed no chemical enrichment and the structural relaxation was lower than for the top AlO2 layer. Knowledge of the surface structure will aid the understanding of how and which type of interface will be formed when LaAlO3 is used as a substrate as a function of temperature and pressure, and so lead to improved design of device structures.

  19. A Structural View on Medicinal Chemistry Strategies against Drug Resistance.

    Science.gov (United States)

    Agnello, Stefano; Brand, Michael; Chellat, Mathieu F; Gazzola, Silvia; Riedl, Rainer

    2018-05-30

    The natural phenomenon of drug resistance represents a generic impairment that hampers the benefits of drugs in all major clinical indications. Antibacterials and antifungals are affected as well as compounds for the treatment of cancer, viral infections or parasitic diseases. Despite the very diverse set of biological targets and organisms involved in the development of drug resistance, underlying molecular processes have been identified to understand the emergence of resistance and to overcome this detrimental mechanism. Detailed structural information of the root causes for drug resistance is nowadays frequently available to design next generation drugs anticipated to suffer less from resistance. This knowledge-based approach is a prerequisite in the fight against the inevitable occurrence of drug resistance to secure the achievements of medicinal chemistry in the future. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. Structure of the neutron-rich lithium isotopes in heavy-ion reactions

    International Nuclear Information System (INIS)

    Bespalova, O.V.; Galakhmatova, B.S.; Romanovskij, E.A.; Shitikova, K.V.; Burov, V.V.; Rzyanin, M.V.; Miller, H.G.; Yen, G.D.

    1993-01-01

    The structure properties, for factors, angular distributions and interaction cross sections of Li neutron-rich isotopes have been analyzed in the unified way. A good qualitative agreement with the experiment data was obtained. 20 refs.; 11 figs.; 1 tab

  1. Structural chemistry of superconducting pnictides and pnictide oxides with layered structures

    Energy Technology Data Exchange (ETDEWEB)

    Johrendt, Dirk [Ludwig-Maximilians-Univ. Muenchen (Germany). Dept. Chemie und Biochemie; Hosono, Hideo [Tokyo Institute of Technology, Yokohama (Japan). Frontier Research Center; Hoffmann, Rolf-Dieter; Poettgen, Rainer [Muenster Univ. (Germany). Inst. fuer Anorganische und Analytische Chemie

    2011-07-01

    The basic structural chemistry of superconducting pnictides and pnictide oxides is reviewed. Crystal chemical details of selected compounds and group subgroup schemes are discussed with respect to phase transitions upon charge-density formation, the ordering of vacancies, or the ordered displacements of oxygen atoms. Furthermore, the influences of doping and solid solutions on the valence electron concentration are discussed in order to highlight the structural and electronic flexibility of these materials. (orig.)

  2. Chemistry

    International Nuclear Information System (INIS)

    Ferris, L.M.

    1976-01-01

    Research progress is reported in programs on fuel-salt chemistry, properties of compounds in the Li--Te system, Te spectroscopy UF 4 --H equilibria, porous electrode studies of molten salts, fuel salt-coolant salt reactions, thermodynamic properties of transition-metal fluorides, and properties of sodium fluoroborate. Developmental work on analytical methods is summarized including in-line analysis of molten MSBR fuel, analysis of coolant-salts for tritium, analysis of molten LiF--BeF 2 --ThF 4 for Fe and analysis of LiF--BeF--ThF 4 for Te

  3. Chemistry and structure of giant molecular clouds in energetic environments

    Science.gov (United States)

    Anderson, Crystal Nicole

    2016-09-01

    Throughout the years many studies on Galactic star formation have been conducted. This resulted in the idea that giant molecular clouds (GMCs) are hierarchical in nature with substructures spanning a large range of sizes. The physical processes that determine how molecular clouds fragment, form clumps/cores and then stars depends strongly on both recent radiative and mechanical feed- back from massive stars and, on longer term, from enhanced cooling due to the buildup of metals. Radiative and mechanical energy input from stellar populations can alter subsequent star formation over a large part of a galaxy and hence is relevant to the evolution of galaxies. Much of our knowledge of star formation on galaxy wide scales is based on scaling laws and other parametric descriptions. But to understand the overall evolution of star formation in galaxies we need to watch the feedback processes at work on giant molecular cloud (GMC) scales. By doing this we can begin to answer how strong feedback environments change the properties of the substructure in GMCs. Tests of Galactic star formation theory to other galaxies has been a challenging process due to the lack of resolution with current instruments. Thus, only the nearest galaxies allow us to resolve GMCs and their substructures. The Large Magellanic Cloud (LMC), is one of the closest low metallicity dwarf galaxies (D˜ 50 kpc) and is close enough that current instruments can resolve the sub- structure of its GMCs to molecular gas tracers (e.g. HCO+, HCN, HNC, CS, C2H, N2H+) detected in the LMC at 1.5-40 pc scales and in NGC 5253 at 40 pc scales. I then compare the molecular gas detections to the Central Molecular Zone in our Galaxy. Dense molecular gas was detected in all of the sources. For the regions in the LMC, molecular lines of CS, N2H+, C 2H, HNC, HCO+ and HCN were all detected in N159W and N113 while only HCN, HCO+, HNC, and C2H were detected in 30Dor-10. Toward NGC 5253 only HCO+, HCN, C2H and CS were detected. I

  4. The Logical and Psychological Structure of Physical Chemistry and Its Relevance to the Organization/Sequencing of the Major Areas Covered in Physical Chemistry Textbooks

    Science.gov (United States)

    Tsaparlis, Georgios

    2014-01-01

    Jensen's scheme for the logical structure of chemistry is taken as reference to study the logical structure of physical chemistry. The scheme distinguishes three dimensions (composition and structure, energy, and time), with each dimension treated at one of the three levels (molar, molecular, and electrical). Such a structure places the outer…

  5. Structural and functional rich club organization of the brain in children and adults.

    Directory of Open Access Journals (Sweden)

    David S Grayson

    Full Text Available Recent studies using Magnetic Resonance Imaging (MRI have proposed that the brain's white matter is organized as a rich club, whereby the most highly connected regions of the brain are also highly connected to each other. Here we use both functional and diffusion-weighted MRI in the human brain to investigate whether the rich club phenomena is present with functional connectivity, and how this organization relates to the structural phenomena. We also examine whether rich club regions serve to integrate information between distinct brain systems, and conclude with a brief investigation of the developmental trajectory of rich-club phenomena. In agreement with prior work, both adults and children showed robust structural rich club organization, comprising regions of the superior medial frontal/dACC, medial parietal/PCC, insula, and inferior temporal cortex. We also show that these regions were highly integrated across the brain's major networks. Functional brain networks were found to have rich club phenomena in a similar spatial layout, but a high level of segregation between systems. While no significant differences between adults and children were found structurally, adults showed significantly greater functional rich club organization. This difference appeared to be driven by a specific set of connections between superior parietal, insula, and supramarginal cortex. In sum, this work highlights the existence of both a structural and functional rich club in adult and child populations with some functional changes over development. It also offers a potential target in examining atypical network organization in common developmental brain disorders, such as ADHD and Autism.

  6. Species richness and soil properties in Pinus ponderosa forests: A structural equation modeling analysis

    Science.gov (United States)

    Laughlin, D.C.; Abella, S.R.; Covington, W.W.; Grace, J.B.

    2007-01-01

    Question: How are the effects of mineral soil properties on understory plant species richness propagated through a network of processes involving the forest overstory, soil organic matter, soil nitrogen, and understory plant abundance? Location: North-central Arizona, USA. Methods: We sampled 75 0.05-ha plots across a broad soil gradient in a Pinus ponderosa (ponderosa pine) forest ecosystem. We evaluated multivariate models of plant species richness using structural equation modeling. Results: Richness was highest at intermediate levels of understory plant cover, suggesting that both colonization success and competitive exclusion can limit richness in this system. We did not detect a reciprocal positive effect of richness on plant cover. Richness was strongly related to soil nitrogen in the model, with evidence for both a direct negative effect and an indirect non-linear relationship mediated through understory plant cover. Soil organic matter appeared to have a positive influence on understory richness that was independent of soil nitrogen. Richness was lowest where the forest overstory was densest, which can be explained through indirect effects on soil organic matter, soil nitrogen and understory cover. Finally, model results suggest a variety of direct and indirect processes whereby mineral soil properties can influence richness. Conclusions: Understory plant species richness and plant cover in P. ponderosa forests appear to be significantly influenced by soil organic matter and nitrogen, which are, in turn, related to overstory density and composition and mineral soil properties. Thus, soil properties can impose direct and indirect constraints on local species diversity in ponderosa pine forests. ?? IAVS; Opulus Press.

  7. Structure, richness and composition of arboreal plants in a cloud thinning forest of Tolima (Colombia)

    International Nuclear Information System (INIS)

    Campo Kurmen, Juan Manuel

    2010-01-01

    Structure, richness, and floristic composition of the woody elements of the selective logging forest of the Vereda Dantas, (Ibague, Tolima, Colombia), where studied in a 0.1 ha plot sampled for all individuals ≥2.5 cm dbh. the forest is characterized by scarcity of lianas and hemiepiphytic, absence of typical families of the Colombian cloud forests between 2000 and 2500 m (Araceae, Ericaceae, Myrtaceae, Meliaceae and Aquifoliaceae), and richness increment of the Sabiaceae and Euphorbiaceae. Compared to others cloud forest from the Colombian Andes and the Neotropic, it has, fewer individuals (237 individuals ≥2.5 cm dbh per 0.1 ha) and more large trees (39.7% of individuals ≥10 cm dbh per 0.1 ha). The forest has a lower woody species richness (75 species ≥2.5 cm dbh per 0.1 ha). Apparently, the effects of selective timber extraction on structure, richness, and floristic composition are decrease floristic richness and density of individuals, decrease of lianas density and richness, and more individuals of secondary species, likes: Hedyosmum goudotianum Slms-Laubach var. goudatianum, Miconia resima Naud, and Palicourea calophlebia Standl.

  8. The Role of Cesium Cation in Controlling Interphasial Chemistry on Graphite Anode in Propylene Carbonate-Rich Electrolytes

    Energy Technology Data Exchange (ETDEWEB)

    Xiang, Hongfa; Mei, Donghai; Yan, Pengfei; Bhattacharya, Priyanka; Burton, Sarah D.; Cresce, Arthur V.; Cao, Ruiguo; Engelhard, Mark H.; Bowden, Mark E.; Zhu, Zihua; Polzin, Bryant; Wang, Chong M.; Xu, Kang; Zhang, Jiguang; Xu, Wu

    2015-09-10

    Propylene carbonate (PC) is seldom used in lithium-ion batteries (LIBs) due to its sustained co-intercalation into graphene structure and the eventual graphite exfoliation, despite potential advantages it brings, such as wider liquid range and lower cost. Here we discover that cesium cation (Cs+), originally used to suppress dendrite growth of Li metal anode, directs the formation of solid electrolyte interphase (SEI) on graphitic anode in PC-rich electrolytes through preferential solvation. Effective suppression of PC-decomposition and graphite-exfoliation was achieved when the ratio of ethylene carbonate (EC)/PC in electrolytes was so adjusted that the reductive decomposition of Cs+-(EC)m (1≤m≤2) complex precedes that of Li+-(PC)n (3≤n≤5). The interphase directed by Cs+ is stable, ultrathin and compact, leading to significant improvements in LIB performances. In a broader context, the accurate tailoring of SEI chemical composition by introducing a new solvation center represents a fundamental breakthrough in manipulating interfacial reactions processes that once were elusive.

  9. Chemistry

    International Nuclear Information System (INIS)

    Ferris, L.M.

    1975-01-01

    Research and development activities dealing with the chemical problems related to design and ultimate operation of molten-salt reactor systems are described. An experimental test stand was constructed to expose metallurgical test specimens to Te 2 vapor at defined temperatures and deposition rates. To better define the chemistry of fluoroborate coolant, several aspects are being investigated. The behavior of hydroxy and oxy compounds in molten NaBF 4 is being investigated to define reactions and compounds that may be involved in corrosion and/or could be involved in methods for trapping tritium. Two corrosion products of Hastelloy N, Na 3 CrF 6 and Na 5 Cr 3 F 14 , were identified from fluoroborate systems. The evaluation of fluoroborate and alternate coolants continued. Research on the behavior of hydrogen and its isotopes is summarized. The solubilities of hydrogen, deuterium, and helium in Li 2 BeF 4 are very low. The sorption of tritium on graphite was found to be significant (a few milligrams of tritium per kilogram of graphite), possibly providing a means of sequestering a portion of the tritium produced. Development of analytical methods continued with emphasis on voltammetric and spectrophotometric techniques for the in-line analysis of corrosion products such as Fe 2+ and Cr 3+ and the determination of the U 3+ /U 4+ ratio in MSBR fuel salt. Similar studies were conducted with the NaBF 4 --NaF coolant salt. Information developed during the previous operation of the CSTF has been assessed and used to formulate plans for evaluation of in-line analytical methods in future CSTF operations. Electroanalytical and spectrophotometric research suggests that an electroactive protonic species is present in molten NaBF 4 --NaF, and that this species rapidly equilibrates with a volatile proton-containing species. Data obtained from the CSTF indicated that tritium was concentrated in the volatile species. (JGB)

  10. Using Structure-Based Organic Chemistry Online Tutorials with Automated Correction for Student Practice and Review

    Science.gov (United States)

    O'Sullivan, Timothy P.; Hargaden, Gra´inne C.

    2014-01-01

    This article describes the development and implementation of an open-access organic chemistry question bank for online tutorials and assessments at University College Cork and Dublin Institute of Technology. SOCOT (structure-based organic chemistry online tutorials) may be used to supplement traditional small-group tutorials, thereby allowing…

  11. An Analysis of Prospective Chemistry Teachers' Cognitive Structures through Flow Map Method: The Subject of Oxidation and Reduction

    Science.gov (United States)

    Temel, Senar

    2016-01-01

    This study aims to analyse prospective chemistry teachers' cognitive structures related to the subject of oxidation and reduction through a flow map method. Purposeful sampling method was employed in this study, and 8 prospective chemistry teachers from a group of students who had taken general chemistry and analytical chemistry courses were…

  12. Structural material anomaly detection system using water chemistry data

    International Nuclear Information System (INIS)

    Asakura, Yamato; Nagase, Makoto; Uchida, Shunsuke; Ohsumi, Katsumi.

    1992-01-01

    The concept of an advanced water chemistry diagnosis system for detection of anomalies and preventive maintenance of system components is proposed and put into a concrete form. Using the analogy to a medical inspection system, analyses of water chemistry change will make it possible to detect symptoms of anomalies in system components. Then, correlations between water chemistry change and anomaly occurrence in the components of the BWR primary cooling system are analyzed theoretically. These fragmentary correlations are organized and reduced to an algorithm for the on-line diagnosis system using on-line monitoring data, pH and conductivity. By using actual plant data, the on-line diagnosis model system is verified to be applicable for early and automatic finding of the anomaly cause and for timely supply of much diagnostic information to plant operators. (author)

  13. Flame chemistry of alkane-rich gasoline fuels and a surrogate using photoionization mass spectrometry: I. Primary reference fuel

    KAUST Repository

    Selim, H.

    2015-03-30

    Improving the gasoline engines performance requires thorough understanding of their fundamental chemistry of combustion. Since the actual gasoline fuels are difficult to examine, due to the lack of knowledge about their exact composition as well as their numerous fuel components, the approach of using simpler gasoline fuels with limited number of components or using surrogate fuels has become more common. In this study, the combustion chemistry of laminar premixed flame of different gasoline fuels/surrogate has been examined. In this particular paper, the primary reference fuel, PRF84, has been examined at equivalence ratio of 1 and pressure of 20 Torr. The gas analysis was conducted using vacuum ultraviolet photoionization mass spectrometry.

  14. Flame chemistry of alkane-rich gasoline fuels and a surrogate using photoionization mass spectrometry: I. Primary reference fuel

    KAUST Repository

    Selim, H.; Lucassen, A.; Hansen, N.; Sarathy, Mani

    2015-01-01

    Improving the gasoline engines performance requires thorough understanding of their fundamental chemistry of combustion. Since the actual gasoline fuels are difficult to examine, due to the lack of knowledge about their exact composition as well as their numerous fuel components, the approach of using simpler gasoline fuels with limited number of components or using surrogate fuels has become more common. In this study, the combustion chemistry of laminar premixed flame of different gasoline fuels/surrogate has been examined. In this particular paper, the primary reference fuel, PRF84, has been examined at equivalence ratio of 1 and pressure of 20 Torr. The gas analysis was conducted using vacuum ultraviolet photoionization mass spectrometry.

  15. Heavy metals pollution influence the community structure of Cyanobacteria in nutrient rich tropical estuary

    Digital Repository Service at National Institute of Oceanography (India)

    Anas, A.; Jasmin, C.; Sheeba V.A.; Gireeshkumar, T.R; Nair, S.

    , Mn, Fe, Ni, Cu and Zn) on community structure of cyanobacteria in a nutrient rich tropical estuary, Cochin Estuary (CE), across the southwest coast of India. Dissolved heavy metals were higher in CE during dry season, with Zn as major pollutant...

  16. Managed forest landscape structure and avian species richness in the southeastern US

    Science.gov (United States)

    Craig Loehle; T. Bently Wigley; Scott Rutzmoser; John A. Gerwin; Patrick D. Keyser; Richard A. Lancia; Christopher J. Reynolds; Ronald E. Thill; Robert Weih; Don White; Petra Bohall Wood

    2005-01-01

    Forest structural features at the stand scale (e.g., snags, stem density, species composition) and habitat attributes at larger spatial scales (e.g., landscape pattern, road density) can influence biological diversity and have been proposed as indicators in sustainable forestry programs. This study investigated relationships between such factors and total richness of...

  17. Abnormal rich club organization and impaired correlation between structural and functional connectivity in migraine sufferers.

    Science.gov (United States)

    Li, Kang; Liu, Lijun; Yin, Qin; Dun, Wanghuan; Xu, Xiaolin; Liu, Jixin; Zhang, Ming

    2017-04-01

    Because of the unique position of the topologically central role of densely interconnected brain hubs, our study aimed to investigate whether these regions and their related connections would be particularly vulnerable to migraine. In our study, we explored the rich club structure and its role in global functional dynamics in 30 patients with migraine without aura and 30 healthy controls. DTI and resting fMRI were used to construct structural connectivity (SC) and functional connectivity (FC) networks. An independent replication data set of 26 patients and 26 controls was included to replicate and validate significant findings. As compared with the controls, the structural networks of patients exhibited altered rich club organization with higher level of feeder connection density, abnormal small-world organization with increased global efficiency and decreased strength of SC-FC coupling. As these abnormal topological properties and headache attack duration exhibited a significant association with increased density of feeder connections, our results indicated that migraine may be characterized by a selective alteration of the structural connectivity of the rich club regions, tending to have higher 'bridgeness' with non-rich club regions, which may increase the integration among pain-related brain circuits with more excitability but less inhibition for the modulation of migraine.

  18. Direct Atomic Scale Observation of the Structure and Chemistry of Order/Disorder Interfaces

    National Research Council Canada - National Science Library

    Srinivasan, R; Banerjee, R; Hwang, J. Y; Viswanathan, G. B; Tiley, J; Fraser, H. L

    2008-01-01

    ... distributed ordered intermetallic precipitates within a disordered matrix. The structure and chemistry at the precipitate/matrix interface plays a critical role in determining the effectiveness of the strengthening mechanism...

  19. Structure of metal-rich (001) surfaces of III-V compound semiconductors

    DEFF Research Database (Denmark)

    Kumpf, C.; Smilgies, D.; Landemark, E.

    2001-01-01

    The atomic structure of the group-III-rich surface of III-V semiconductor compounds has been under intense debate for many years, yet none of the models agrees with the experimental data available. Here we present a model for the three-dimensional structure of the (001)-c(8x2) reconstruction on In......(8 x 2) reconstructions of III-V semiconductor surfaces contain the same essential building blocks....

  20. Laser-spectroscopy studies of the nuclear structure of neutron-rich radium

    Science.gov (United States)

    Lynch, K. M.; Wilkins, S. G.; Billowes, J.; Binnersley, C. L.; Bissell, M. L.; Chrysalidis, K.; Cocolios, T. E.; Goodacre, T. Day; de Groote, R. P.; Farooq-Smith, G. J.; Fedorov, D. V.; Fedosseev, V. N.; Flanagan, K. T.; Franchoo, S.; Garcia Ruiz, R. F.; Gins, W.; Heinke, R.; Koszorús, Á.; Marsh, B. A.; Molkanov, P. L.; Naubereit, P.; Neyens, G.; Ricketts, C. M.; Rothe, S.; Seiffert, C.; Seliverstov, M. D.; Stroke, H. H.; Studer, D.; Vernon, A. R.; Wendt, K. D. A.; Yang, X. F.

    2018-02-01

    The neutron-rich radium isotopes, Ra-233222, were measured with Collinear Resonance Ionization Spectroscopy (CRIS) at the ISOLDE facility, CERN. The hyperfine structure of the 7 s2S10→7 s 7 p P31 transition was probed, allowing measurement of the magnetic moments, quadrupole moments, and changes in mean-square charge radii. These results are compared to existing literature values, and the new moments and change in mean-square charge radii of 231Ra are presented. Low-resolution laser spectroscopy of the very neutron-rich 233Ra has allowed the isotope shift and relative charge radius to be determined for the first time.

  1. Complex chemistry

    International Nuclear Information System (INIS)

    Kim, Bong Gon; Kim, Jae Sang; Kim, Jin Eun; Lee, Boo Yeon

    2006-06-01

    This book introduces complex chemistry with ten chapters, which include development of complex chemistry on history coordination theory and Warner's coordination theory and new development of complex chemistry, nomenclature on complex with conception and define, chemical formula on coordination compound, symbol of stereochemistry, stereo structure and isomerism, electron structure and bond theory on complex, structure of complex like NMR and XAFS, balance and reaction on solution, an organo-metallic chemistry, biology inorganic chemistry, material chemistry of complex, design of complex and calculation chemistry.

  2. Chemistry and possible resource potential of cobalt rich ferromanganese crust from Afanasiy-Nikitin seamount in the Indian Ocean

    Digital Repository Service at National Institute of Oceanography (India)

    Parthiban, G.; Banakar, V.K.

    , Ni, Co, Zn and V and found to be rich in Co (upto 0.88%) mineralogically, the studied Fe-Mn crust samples contain poorly crystalline d-MnO sub(2) and minor amount of Carbonate Fluorapatite (CFA) and feldspars. The low Mn/Fe ratios (less than 2), d...

  3. Rich club analysis in the Alzheimer's disease connectome reveals a relatively undisturbed structural core network.

    Science.gov (United States)

    Daianu, Madelaine; Jahanshad, Neda; Nir, Talia M; Jack, Clifford R; Weiner, Michael W; Bernstein, Matt A; Thompson, Paul M

    2015-08-01

    Diffusion imaging can assess the white matter connections within the brain, revealing how neural pathways break down in Alzheimer's disease (AD). We analyzed 3-Tesla whole-brain diffusion-weighted images from 202 participants scanned by the Alzheimer's Disease Neuroimaging Initiative-50 healthy controls, 110 with mild cognitive impairment (MCI) and 42 AD patients. From whole-brain tractography, we reconstructed structural brain connectivity networks to map connections between cortical regions. We tested whether AD disrupts the "rich club" - a network property where high-degree network nodes are more interconnected than expected by chance. We calculated the rich club properties at a range of degree thresholds, as well as other network topology measures including global degree, clustering coefficient, path length, and efficiency. Network disruptions predominated in the low-degree regions of the connectome in patients, relative to controls. The other metrics also showed alterations, suggesting a distinctive pattern of disruption in AD, less pronounced in MCI, targeting global brain connectivity, and focusing on more remotely connected nodes rather than the central core of the network. AD involves severely reduced structural connectivity; our step-wise rich club coefficients analyze points to disruptions predominantly in the peripheral network components; other modalities of data are needed to know if this indicates impaired communication among non rich club regions. The highly connected core was relatively preserved, offering new evidence on the neural basis of progressive risk for cognitive decline. © 2015 Wiley Periodicals, Inc.

  4. Chemistry and the development of research into the structure of matter

    International Nuclear Information System (INIS)

    Coldanskij, V.

    1977-01-01

    Efforts have been made recently to explain the structure of the atomic nucleus and the structure of the electron shell of the atom using a unified quantum mechanics description. The applications are surveyed of the knowledge of the nucleus and electron shell structure in chemistry. Electron paramagnetic resonance, nuclear magnetic resonance and gamma resonance spectrometry are presented as examples. (J.B.)

  5. Chemistry and the development of research into the structure of matter

    Energy Technology Data Exchange (ETDEWEB)

    Coldanskii, V

    1977-06-01

    Efforts have been made recently to explain the structure of the atomic nucleus and the structure of the electron shell of the atom using a unified quantum mechanics description. The applications are surveyed of the knowledge of the nucleus and electron shell structure in chemistry. Electron paramagnetic resonance, nuclear magnetic resonance and gamma resonance spectrometry are presented as examples.

  6. Structure Determination of Unknown Organic Liquids Using NMR and IR Spectroscopy: A General Chemistry Laboratory

    Science.gov (United States)

    Pavel, John T.; Hyde, Erin C.; Bruch, Martha D.

    2012-01-01

    This experiment introduced general chemistry students to the basic concepts of organic structures and to the power of spectroscopic methods for structure determination. Students employed a combination of IR and NMR spectroscopy to perform de novo structure determination of unknown alcohols, without being provided with a list of possible…

  7. Contrasting roles of water chemistry, lake morphology, land-use, climate and spatial processes in driving phytoplankton richness in the Danish landscape

    DEFF Research Database (Denmark)

    Özkan, Korhan; Jeppesen, Erik; Søndergaard, Martin

    2013-01-01

    Understanding of the forces driving the structure of biotic communities has long been an important focus for ecology, with implications for applied and conservation science. To elucidate the factors driving phytoplankton genus richness in the Danish landscape, we analyzed data derived from late-s...

  8. Natural analogue study of CO2 storage monitoring using probability statistics of CO2-rich groundwater chemistry

    Science.gov (United States)

    Kim, K. K.; Hamm, S. Y.; Kim, S. O.; Yun, S. T.

    2016-12-01

    For confronting global climate change, carbon capture and storage (CCS) is one of several very useful strategies as using capture of greenhouse gases like CO2 spewed from stacks and then isolation of the gases in underground geologic storage. CO2-rich groundwater could be produced by CO2 dissolution into fresh groundwater around a CO2 storage site. As consequence, natural analogue studies related to geologic storage provide insights into future geologic CO2 storage sites as well as can provide crucial information on the safety and security of geologic sequestration, the long-term impact of CO2 storage on the environment, and field operation and monitoring that could be implemented for geologic sequestration. In this study, we developed CO2 leakage monitoring method using probability density function (PDF) by characterizing naturally occurring CO2-rich groundwater. For the study, we used existing data of CO2-rich groundwaters in different geological regions (Gangwondo, Gyeongsangdo, and Choongchungdo provinces) in South Korea. Using PDF method and QI (quantitative index), we executed qualitative and quantitative comparisons among local areas and chemical constituents. Geochemical properties of groundwater with/without CO2 as the PDF forms proved that pH, EC, TDS, HCO3-, Ca2+, Mg2+, and SiO2 were effective monitoring parameters for carbonated groundwater in the case of CO2leakage from an underground storage site. KEY WORDS: CO2-rich groundwater, CO2 storage site, monitoring parameter, natural analogue, probability density function (PDF), QI_quantitative index Acknowledgement This study was supported by the "Basic Science Research Program through the National Research Foundation of Korea (NRF), which is funded by the Ministry of Education (NRF-2013R1A1A2058186)" and the "R&D Project on Environmental Management of Geologic CO2 Storage" from KEITI (Project number: 2014001810003).

  9. Structure of neutron-rich nuclei around the N = 50 shell-gap closure

    Science.gov (United States)

    Faul, T.; Duchêne, G.; Thomas, J.-C.; Nowacki, F.; Huyse, M.; Van Duppen, P.

    2010-04-01

    The structure of neutron-rich nuclei in the vicinity of 78Ni have been investigated via the β-decay of 71,73,75Cu isotopes (ISOLDE, CERN). Experimental results have been compared with shell-model calculations performed with the ANTOINE code using a large (2p3/21f5/22p1/21g9/2) valence space and a 56/28Ni28 core.

  10. Of the crystal chemistry of Ruddlesden-Porter type structures in high Tc ceramic superconductors

    International Nuclear Information System (INIS)

    Dwivedi, A.; Cormack, A.N.

    1990-01-01

    This paper reports on atomistic computer simulation employed to examine the energetics and crystal chemistry of some Ruddlesden-Popper type oxide superconductors. Similar structural patterns have been noticed in the superconducting oxides. The formation of Ruddlesden-Popper type layers (alternating slabs of rocksalt and perovskite structures) is similar in many respects to that seen in the system Sr-Ti-O. However, there are some significant differences, for example, the rocksalt and perovskite blocks in the new superconducting compounds are not necessarily electrically neutral unlike in the Sr-Ti-O system and this may well lead to significant differences in their structural chemistry

  11. Structure and chemistry of model catalysts in ultrahigh vacuum

    Science.gov (United States)

    Walker, Joshua D.

    The study of catalysis is a key area of focus not only in the industrial sector but also in the nature and biological systems. The market for catalysis is a multi-billion dollar industry. Many of the materials and products we use on a daily basis are formed through a catalytic process. The quest to understanding and improving catalytic mechanisms is ongoing. Many model catalysts use transition metals as a support for chemical reactions to take place due to their selectivity and activity. Palladium, gold, and copper metals are studied in this work and show the ability to be catalytically reactive. It is important to understand the characteristics and properties of these surfaces. A well-known example of catalysis is the conversion of carbon monoxide (CO), a very harmful gas to carbon dioxide (CO2) which is less harmful. This reaction is mainly seen in the automotive industry. This reaction is investigated in this work on a Au(111) single crystal, which is normally inert but becomes reactivity with the adsorption of oxygen on the surface. Temperature Programmed Desorption (TPD) is used to understand some of the chemistry and effects with and without the addition of H2O. The oxidation of CO is shown to be enhanced by the addition of water, but warrants further analysis too fully understand the different mechanisms and reaction pathways existing. The field of nano-electronics is rapidly growing as technology continues to challenge scientists to create innovative ideas. The trend to produce smaller electronic products is increasing as consumer demands persist. It has been shown previously that 1,4-phenlyene diisocyanobenzene (1,4-PDI) on Au(111) react to form one-dimensional oligomer chains comprising alternating gold and 1,4-PDI units on the Au(111) surface. A similar compound 1,3-phenlyene diisocyanobenzene (1,3-PDI) was studied in order to investigate whether the oligomerization found for 1,4-PDI is a general phenomenon and to ultimately explore the effect of

  12. Petrography and chemistry of tungsten-rich oxycalciobetafite in hydrothermal veins of the Adamello contact aureole, northern Italy

    Science.gov (United States)

    Lumpkin, Gregory R.; Gieré, Reto; Williams, C. Terry; McGlinn, Peter J.; Payne, Timothy E.

    2017-09-01

    Tungsten-rich oxycalciobetafite occurs in complex Ti-rich hydrothermal veins emplaced within dolomite marble in the contact aureole of the Adamello batholith, northern Italy, where it occurs as overgrowths on zirconolite. The betafite is weakly zoned and contains 29-34 wt% UO2. In terms of end-members, the betafite contains approximately 50 mol% CaUTi2O7 and is one of the closest known natural compositions to the pyrochlore phase proposed for use in titanate nuclear waste forms. Amorphization and volume expansion of the betafite caused cracks to form in the enclosing silicate mineral grains. Backscattered electron images reveal that betafite was subsequently altered along crystal rims, particularly near the cracks. Electron probe microanalyses reveal little difference in composition between altered and unaltered areas, except for lower totals, suggesting that alteration is primarily due to hydration. Zirconolite contains up to 18 wt% ThO2 and 24 wt% UO2, and exhibits strong compositional zoning, but no internal cracking due to differential (and anisotropic) volume expansion and no visible alteration. The available evidence demonstrates that both oxycalciobetafite and zirconolite retained actinides for approximately 40 million years after the final stage of vein formation. During this time, oxycalciobetafite and zirconolite accumulated a total alpha-decay dose of 3.0-3.6 × 1016 and 0.2-2.0 × 1016 α/mg, respectively.

  13. Structurally Based Therapeutic Evaluation: A Therapeutic and Practical Approach to Teaching Medicinal Chemistry.

    Science.gov (United States)

    Alsharif, Naser Z.; And Others

    1997-01-01

    Explains structurally based therapeutic evaluation of drugs, which uses seven therapeutic criteria in translating chemical and structural knowledge into therapeutic decision making in pharmaceutical care. In a Creighton University (Nebraska) medicinal chemistry course, students apply the approach to solve patient-related therapeutic problems in…

  14. Chemical Structure and Properties: A Modified Atoms-First, One-Semester Introductory Chemistry Course

    Science.gov (United States)

    Schaller, Chris P.; Graham, Kate J.; Johnson, Brian J.; Jakubowski, Henry V.; McKenna, Anna G.; McIntee, Edward J.; Jones, T. Nicholas; Fazal, M. A.; Peterson, Alicia A.

    2015-01-01

    A one-semester, introductory chemistry course is described that develops a primarily qualitative understanding of structure-property relationships. Starting from an atoms-first approach, the course examines the properties and three-dimensional structure of metallic and ionic solids before expanding into a thorough investigation of molecules. In…

  15. Compositional and structural variabilities of Mg-rich iron oxide spinels from tuffite

    Directory of Open Access Journals (Sweden)

    W. N. Mussel

    1999-12-01

    Full Text Available Maghemite (γFe2O3 from tuffite is exceptionally rich in Mg, relatively to most of those reportedly found in other mafic lithosystems. To investigate in detail the compositional and structural variabilities of this natural magnetic iron oxide, sets of crystals were isolated from samples collected at different positions in a tuffite weathering mantle. These sets of crystal were individually powdered and studied by X-ray diffractometry, Mössbauer spectroscopy, magnetization measurements and chemical analysis. Lattice parameter of the cubic cell (a0 was found to vary from 0.834(1 to 0.8412(1 nm. Lower a0-values are characteristic of maghemite whereas higher ones are related to a magnetite precursor. FeO content ranges up to 17 mass % and spontaneous magnetization ranges from 8 to 32 J T-1 kg-1. Zero-field room temperature Mössbauer spectra are rather complex, indicating that the hyperfine field distributions due to Fe3+ and mixed valence Fe3+/2+ overlap. The structural variabilities of the (Mg, Ti-rich iron oxide spinels is essentially related to the range of chemical composition of its precursor (Mg, Ti-rich magnetite, and probably to the extent to which it has been oxidized during transformation in soil.

  16. Connecting Structure-Property and Structure-Function Relationships across the Disciplines of Chemistry and Biology: Exploring Student Perceptions

    Science.gov (United States)

    Kohn, Kathryn P.; Underwood, Sonia M.; Cooper, Melanie M.

    2018-01-01

    While many university students take science courses in multiple disciplines, little is known about how they perceive common concepts from different disciplinary perspectives. Structure-property and structure-function relationships have long been considered important explanatory concepts in the disciplines of chemistry and biology, respectively.…

  17. Solution structure of the twelfth cysteine-rich ligand-binding repeat in rat megalin

    International Nuclear Information System (INIS)

    Wolf, Christian A.; Dancea, Felician; Shi Meichen; Bade-Noskova, Veronika; Rueterjans, Heinz; Kerjaschki, Dontscho; Luecke, Christian

    2007-01-01

    Megalin, an approx. 600 kDa transmembrane glycoprotein that acts as multi-ligand transporter, is a member of the low density lipoprotein receptor gene family. Several cysteine-rich repeats, each consisting of about 40 residues, are responsible for the multispecific binding of ligands. The solution structure of the twelfth cysteine-rich ligand-binding repeat with class A motif found in megalin features two short β-strands and two helical turns, yielding the typical fold with a I-III, II-V and IV-VI disulfide bridge connectivity pattern and a calcium coordination site at the C-terminal end. The resulting differences in electrostatic surface potential compared to other ligand-binding modules of this gene family, however, may be responsible for the functional divergence

  18. Mirror energy difference and the structure of loosely bound proton-rich nuclei around A =20

    Science.gov (United States)

    Yuan, Cenxi; Qi, Chong; Xu, Furong; Suzuki, Toshio; Otsuka, Takaharu

    2014-04-01

    The properties of loosely bound proton-rich nuclei around A =20 are investigated within the framework of the nuclear shell model. In these nuclei, the strength of the effective interactions involving the loosely bound proton s1/2 orbit is significantly reduced in comparison with that of those in their mirror nuclei. We evaluate the reduction of the effective interaction by calculating the monopole-based-universal interaction (VMU) in the Woods-Saxon basis. The shell-model Hamiltonian in the sd shell, such as USD, can thus be modified to reproduce the binding energies and energy levels of the weakly bound proton-rich nuclei around A =20. The effect of the reduction of the effective interaction on the structure and decay properties of these nuclei is also discussed.

  19. Nuclear structure far from stability: the neutron-rich 69-79Cu isotopes

    International Nuclear Information System (INIS)

    Franchoo, Serge

    2015-01-01

    Far from stability, the nuclear structure that is predicted by the shell model is evolving. Old magic numbers disappear, while new ones appear. Our understanding of the underlying nuclear force that drives these changes is still incomplete. After a short overview across the nuclear chart, we discuss the strength functions of the shell-model orbitals in the neutron-rich copper isotopes towards the 78 Ni doubly-magic nucleus. These were measured in a 72 Zn(d, 3 He) 71 Cu proton pick-up reaction in inverse kinematics with a radioactive beam at the Ganil laboratory in France. We also present the latest results from a 80 Zn(p,2p) 79 Cu knockout experiment at Riken in Japan, leading to selective population of hole states in 79 Cu. Our findings show that the Z=28 shell gap in the neutron-rich copper isotopes is surprisingly steady against the addition of neutrons beyond N=40. (author)

  20. New Circumstellar Sources of PO and PN: The Increasing Role of Phosphorus Chemistry in Oxygen-rich Stars

    Science.gov (United States)

    Ziurys, L. M.; Schmidt, D. R.; Bernal, J. J.

    2018-04-01

    PO and PN have been newly identified in several oxygen-rich circumstellar envelopes, using the Submillimeter Telescope of the Arizona Radio Observatory. The J = 5 → 4 and J = 6 → 5 transitions of PN near 235 and 282 GHz, and the lambda doublets originating in the J = 5.5 → 4.5 and J = 6.5 → 5.5 lines of PO at 240 and 284 GHz, have been detected toward the shells of asymptotic giant branch (AGB) stars TX Cam and R Cas. A similar set of lines has been observed toward the supergiant NML Cyg, and new transitions of these two molecules were also measured toward the AGB star IK Tau. Along with the previous data from VY Canis Majoris (VY CMa), these spectral lines were analyzed using the non-local thermodynamic equilibrium (non-LTE) circumstellar modeling code, ESCAPADE. For the AGB stars, peak abundances found for PN and PO were f ∼ (1–2) × 10‑8 and (0.5–1) × 10‑7, respectively, while those for the supergiants were f(PN) ∼ (0.3–0.7) × 10‑8 and f(PO) ∼ (5–7) × 10‑8. PN was well modeled with a spherical radial distribution, suggesting formation near the stellar photosphere, perhaps enhanced by shocks. PO was best reproduced by a shell model, indicating a photochemical origin, except for VY CMa. Overall, the abundance of PO is a factor of 5–20 greater than that of PN. This study suggests that phosphorus-bearing molecules are common in O-rich envelopes, and that a significant amount of phosphorus (>20%) remains in the gas phase.

  1. EGCG Inhibited Lipofuscin Formation Based on Intercepting Amyloidogenic β-Sheet-Rich Structure Conversion.

    Directory of Open Access Journals (Sweden)

    Shuxian Cai

    Full Text Available Lipofuscin (LF is formed during lipid peroxidation and sugar glycosylation by carbonyl-amino crosslinks with biomacrolecules, and accumulates slowly within postmitotic cells. The environmental pollution, modern dietary culture and lifestyle changes have been found to be the major sources of reactive carbonyl compounds in vivo. Irreversible carbonyl-amino crosslinks induced by carbonyl stress are essentially toxiferous for aging-related functional losses in modern society. Results show that (--epigallocatechin gallate (EGCG, the main polyphenol in green tea, can neutralize the carbonyl-amino cross-linking reaction and inhibit LF formation, but the underlying mechanism is unknown.We explored the mechanism of the neutralization process from protein, cell, and animal levels using spectrofluorometry, infrared spectroscopy, conformation antibodies, and electron microscopy. LF demonstrated an amyloidogenic β-sheet-rich with antiparallel structure, which accelerated the carbonyl-amino crosslinks formation and disrupted proteolysis in both PC12 cells and D-galactose (D-gal-induced brain aging mice models. Additionally, EGCG effectively inhibited the formation of the amyloidogenic β-sheet-rich structure of LF, and prevented its conversion into toxic and on-pathway aggregation intermediates, thereby cutting off the carbonyl-amino crosslinks.Our study indicated that the amyloidogenic β-sheet structure of LF may be the core driving force for carbonyl-amino crosslinks further formation, which mediates the formation of amyloid fibrils from native state of biomacrolecules. That EGCG exhibits anti-amyloidogenic β-sheet-rich structure properties to prevent the LF formation represents a novel strategy to impede the development of degenerative processes caused by ageing or stress-induced premature senescence in modern environments.

  2. Advancing viral RNA structure prediction: measuring the thermodynamics of pyrimidine-rich internal loops.

    Science.gov (United States)

    Phan, Andy; Mailey, Katherine; Saeki, Jessica; Gu, Xiaobo; Schroeder, Susan J

    2017-05-01

    Accurate thermodynamic parameters improve RNA structure predictions and thus accelerate understanding of RNA function and the identification of RNA drug binding sites. Many viral RNA structures, such as internal ribosome entry sites, have internal loops and bulges that are potential drug target sites. Current models used to predict internal loops are biased toward small, symmetric purine loops, and thus poorly predict asymmetric, pyrimidine-rich loops with >6 nucleotides (nt) that occur frequently in viral RNA. This article presents new thermodynamic data for 40 pyrimidine loops, many of which can form UU or protonated CC base pairs. Uracil and protonated cytosine base pairs stabilize asymmetric internal loops. Accurate prediction rules are presented that account for all thermodynamic measurements of RNA asymmetric internal loops. New loop initiation terms for loops with >6 nt are presented that do not follow previous assumptions that increasing asymmetry destabilizes loops. Since the last 2004 update, 126 new loops with asymmetry or sizes greater than 2 × 2 have been measured. These new measurements significantly deepen and diversify the thermodynamic database for RNA. These results will help better predict internal loops that are larger, pyrimidine-rich, and occur within viral structures such as internal ribosome entry sites. © 2017 Phan et al.; Published by Cold Spring Harbor Laboratory Press for the RNA Society.

  3. Structure of Ni-rich Ni--Cr--B--Si coating alloys

    International Nuclear Information System (INIS)

    Knotek, O.; Lugscheider, E.; Reimann, H.

    1975-01-01

    The structures of quaternary, nickel-rich Ni--Cr--B--Si alloys were analyzed at a constant boron content of 10 at. percent and a temperature of 850 0 C. The composition range for silicide formation was determined. In these quaternary alloys, known binary nickel silicides, nickel and chromium borides, and the ternary silico-boride Ni 6 Si 2 B were confirmed. A new composition for the W 5 Si 3 -type phase in the Ni--B--Si system was proposed. (U.S.)

  4. Chemistry and structure of lunar and synthetic armalcolite

    International Nuclear Information System (INIS)

    Wechsler, B.A.; Prewitt, C.T.; Papike, J.J.

    1976-01-01

    A study of the chemical trends displayed by lunar armalcolites has been made in conjunction with single-crystal X-ray structure refinements of lunar and synthetic armalcolite in order to assess the possible importance of Ti 3+ in lunar armalcolite and to characterize the effects of cation substitutions on the structure. The apparent cation deficiences found in lunar armalcolites analyzed with the electron microprobe most likely reflect the presence of Ti 3+ , although the existence of vacancies cannot be ruled out. Structure refinements of an Apollo 17 armalcolite are consistent with either interpretation. These results support experimental evidence suggesting the presence of Ti 3+ in armalcolite and indicate that virtually all lunar armalcolites probably contain approximately 4-11 mol.% Ti 2 3+ Ti 4+ 0 5 component in solid solution. The cation distribution in lunar armalcolite is essentially completely ordered. However, synthetic crystals quenched from near 1200 0 C have been found to retain significant cation disorder. (Auth.)

  5. Isotope chemistry and molecular structure. The WINIMAX weighting factor

    International Nuclear Information System (INIS)

    Lee, M.W.; Bigeleisen, J.

    1979-01-01

    The modulating coefficients for the finite polynomial expansion of the logarithm of the reduced partition function, lnb (u), of a harmonic oscillator have been obtained for the range of 0 6 . It is shown that this weighting function is near optimum to insure minimum amplitudes of oscillation in the expansion of lnb (u) as a function of the order of the expansion and to include most of the important molecular structure information contained in the moments of the eigenvalues. Beyond Σu/sub i/ 6 , there is little new structural information

  6. Structural and Chemical Evolution of Li- and Mn-rich Layered Cathode Material

    Energy Technology Data Exchange (ETDEWEB)

    Zheng, Jianming; Xu, Pinghong; Gu, Meng; Xiao, Jie; Browning, Nigel D.; Yan, Pengfei; Wang, Chong M.; Zhang, Jiguang

    2015-02-24

    Lithium (Li)- and manganese-rich (LMR) layered-structure materials are very promising cathodes for high energy density lithium-ion batteries. However, their voltage fading mechanism and its relationships with fundamental structural changes are far from being sufficiently understood. Here we report the detailed phase transformation pathway in the LMR cathode (Li[Li0.2Ni0.2Mn0.6]O2) during cycling for the samples prepared by hydro-thermal assistant method. It is found the transformation pathway of LMR cathode is closely correlated to its initial structure and preparation conditions. The results reveal that LMR cathode prepared by HA approach experiences a phase transformation from the layered structure to a LT-LiCoO2 type defect spinel-like structure (Fd-3m space group) and then to a disordered rock-salt structure (Fm-3m space group). The voltage fade can be well correlated with the Li ion insertion into octahedral sites, rather than tetrahedral sites, in both defect spinel-like structure and disordered rock-salt structure. The reversible Li insertion/removal into/from the disordered rock-salt structure is ascribed to the Li excess environment that can satisfy the Li percolating in the disordered rock-salt structure despite the increased kinetic barrier. Meanwhile, because of the presence of a great amount of oxygen vacancies, a significant decrease of Mn valence is detected in the cycled particle, which is below that anticipated for a potentially damaging Jahn-Teller distortion (+3.5). Clarification of the phase transformation pathway, cation redistribution, oxygen vacancy and Mn valence change undoubtedly provides insights into a profound understanding on the voltage fade, and capacity degradation of LMR cathode. The results also inspire us to further enhance the reversibility of LMR cathode via improving its surface structural stability.

  7. Click chemistry for the conservation of cellular structures and fluorescent proteins: ClickOx.

    Science.gov (United States)

    Löschberger, Anna; Niehörster, Thomas; Sauer, Markus

    2014-05-01

    Reactive oxygen species (ROS), including hydrogen peroxide, are known to cause structural damage not only in living, but also in fixed, cells. Copper-catalyzed azide-alkyne cycloaddition (click chemistry) is known to produce ROS. Therefore, fluorescence imaging of cellular structures, such as the actin cytoskeleton, remains challenging when combined with click chemistry protocols. In addition, the production of ROS substantially weakens the fluorescence signal of fluorescent proteins. This led us to develop ClickOx, which is a new click chemistry protocol for improved conservation of the actin structure and better conservation of the fluorescence signal of green fluorescent protein (GFP)-fusion proteins. Herein we demonstrate that efficient oxygen removal by addition of an enzymatic oxygen scavenger system (ClickOx) considerably reduces ROS-associated damage during labeling of nascent DNA with ATTO 488 azide by Cu(I)-catalyzed click chemistry. Standard confocal and super-resolution fluorescence images of phalloidin-labeled actin filaments and GFP/yellow fluorescent protein-labeled cells verify the conservation of the cytoskeleton microstructure and fluorescence intensity, respectively. Thus, ClickOx can be used advantageously for structure preservation in conventional and most notably in super-resolution microscopy methods. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Structure activity study on the quinone/quinone methide chemistry of flavonoids

    NARCIS (Netherlands)

    Awad, H.M.; Boersma, M.G.; Boeren, S.; Bladeren, van P.J.; Vervoort, J.; Rietjens, I.M.C.M.

    2001-01-01

    A structure-activity study on the quinone/quinone methide chemistry of a series of 3',4'-dihydroxyflavonoids was performed. Using the glutathione trapping method followed by HPLC, 1H NMR, MALDI-TOF, and LC/MS analysis to identify the glutathionyl adducts, the chemical behavior of the

  9. The role of supramolecular chemistry in stimuli responsive and hierarchically structured functional organic materials

    NARCIS (Netherlands)

    Schenning, A.P.H.J.; Bastiaansen, C.W.M.; Broer, D.J.; Debije, M.G.

    2014-01-01

    ABSTRACT: In this review, we show the important role of supramolecular chemistry in the fabrication of stimuli responsive and hierarchically structured liquid crystalline polymer networks. Supramolecular interactions can be used to create three dimensional order or as molecular triggers in materials

  10. A contribution to the study of the structure, reactivity and bioinorganic chemistry of iron

    International Nuclear Information System (INIS)

    Toma, H.E.

    1984-01-01

    The research work on inorganic and biological chemistry of iron developed at the University of Sao Paulo (SP, Brazil) is reviewed. Considerations are made about: π interactions, electronic structure and spectroscopy of cyanoferrates; solvation studies and kinetics of substitution reactions involving iron complexes; reactivity of coordinating ligands and iron interactions with biomolecules. (C.L.B.) [pt

  11. Structure, Bonding and Surface Chemistry of Metal Oxide Nanoclusters

    Science.gov (United States)

    2015-06-23

    an electrospray ionization time-of-flight (ESI-TOF) mass spectrometer to the lab (PerSeptive Biosystems Mariner), which provides a different...with this Project Faculty: Professor Michael A. Duncan (one month summer salary) Prof. Heather Abbott -Lyons, summer visiting faculty and...Distribution approved for public release. 4. H. L. Abbott , A. D. Brathwaite and M. A. Duncan, "Infrared spectroscopy and structures of mass-selected

  12. GPCR crystal structures: Medicinal chemistry in the pocket.

    Science.gov (United States)

    Shonberg, Jeremy; Kling, Ralf C; Gmeiner, Peter; Löber, Stefan

    2015-07-15

    Recent breakthroughs in GPCR structural biology have significantly increased our understanding of drug action at these therapeutically relevant receptors, and this will undoubtedly lead to the design of better therapeutics. In recent years, crystal structures of GPCRs from classes A, B, C and F have been solved, unveiling a precise snapshot of ligand-receptor interactions. Furthermore, some receptors have been crystallized in different functional states in complex with antagonists, partial agonists, full agonists, biased agonists and allosteric modulators, providing further insight into the mechanisms of ligand-induced GPCR activation. It is now obvious that there is enormous diversity in the size, shape and position of the ligand binding pockets in GPCRs. In this review, we summarise the current state of solved GPCR structures, with a particular focus on ligand-receptor interactions in the binding pocket, and how this can contribute to the design of GPCR ligands with better affinity, subtype selectivity or efficacy. Copyright © 2015 Elsevier Ltd. All rights reserved.

  13. Enzymatic synthesis of capric acid-rich structured lipids (MUM type) using Candida antarctica lipase.

    Science.gov (United States)

    SilRoy, Sumita; Ghosh, Mahua

    2011-01-01

    The objective of the work was to produce capric acid rich structured lipids starting from various Indian indigenous vegetable oils, such as rice bran, ground nut and mustard oils. Acidolysis reaction between individual vegetable oils and capric acid in one is to three molar ratios at 45 degree centigrade temperature was carried out using position specific Candida antarctica lipase so as to protect the Sn-2 position of the oils which are rich in unsaturated fatty acids. The incorporation of capric acid depended on the reaction time showing 6 % within 6 h and 30.8 % in 72 h with rice bran oil. Similarly, in ground nut oil incorporation of capric acid was 34.2 % in 72 h compared to 5.3 % in 6 h. Thus mustard oil showed much lower incorporation than the other two oils, with 3.3 % and 19.5 % in 6 and 72 h respectively. The incorporation of capric acid was influenced by the nature of the fatty acids present in the original oil. The fatty acid composition of Sn-2 position of the structured triacylglycerols of the three oils revealed that capric acid was mainly replacing the fatty acids occupying the Sn-1 and 3 positions of the triglyceride molecule.

  14. Li-rich layer-structured cathode materials for high energy Li-ion batteries

    Science.gov (United States)

    Li, Liu; Lee, Kim Seng; Lu, Li

    2014-08-01

    Li-rich layer-structured xLi2MnO3 ṡ (1 - x)LiMO2 (M = Mn, Ni, Co, etc.) materials have attracted much attention due to their extraordinarily high reversible capacity as the cathode material in Li-ion batteries. To better understand the nature of this type of materials, this paper reviews history of development of the Li-rich cathode materials, and provides in-depth study on complicated crystal structures and reaction mechanisms during electrochemical charge/discharge cycling. Despite the fabulous capability at low rate, several drawbacks still gap this type of high-capacity cathode materials from practical applications, for instance the large irreversible capacity loss at first cycle, poor rate capability, severe voltage decay and capacity fade during electrochemical charge/discharge cycling. This review will also address mechanisms for these inferior properties and propose various possible solutions to solve above issues for future utilization of these cathode materials in commercial Li-ion batteries.

  15. Crystal structure of modular sodium-rich and low-iron eudialyte from Lovozero alkaline massif

    Energy Technology Data Exchange (ETDEWEB)

    Rozenberg, K. A.; Rastsvetaeva, R. K., E-mail: rast@ns.crys.ras.ru; Aksenov, S. M. [Federal Scientific Research Center “Crystallography and Photonics”, Russian Academy of Sciences, Shubnikov Institute of Crystallography (Russian Federation)

    2016-09-15

    The structure of the sodium-rich representative of the eudialyte group found by A.P. Khomyakov at the Lovozero massif (Kola Peninsula) is studied by X-ray diffraction. The trigonal cell parameters are: a = 14.2032(1) and c = 60.612(1) Å, V = 10589.13 Å3, space group R3m. The structure is refined to the final R = 5.0% in the anisotropic approximation of atomic displacement parameters using 3742|F| > 3σ(F). The idealized formula (Z = 3) is Na{sub 37}Ca{sub 10}Mn{sub 2}FeZr{sub 6}Si{sub 50}(Ti, Nb){sub 2}O{sub 144}(OH){sub 5}Cl{sub 3} · H{sub 2}O. Like other 24-layer minerals of the eudialyte group, this mineral has a modular structure. Its structure contains two modules, namely, “alluaivite” (with an admixture of “eudialyte”) and “kentbrooksite,” called according to the main structural fragments of alluaivite, eudialyte, and kentbrooksite. The mineral found at the Lovozero alkaline massif shows some chemical and symmetry-structural distinctions from the close-in-composition labyrinthite modular mineral from the Khibiny massif. The difference between the minerals stems from different geochemical conditions of mineral formation in the two regions.

  16. Rich structure in the correlation matrix spectra in non-equilibrium steady states.

    Science.gov (United States)

    Biswas, Soham; Leyvraz, Francois; Monroy Castillero, Paulino; Seligman, Thomas H

    2017-01-17

    It has been shown that, if a model displays long-range (power-law) spatial correlations, its equal-time correlation matrix will also have a power law tail in the distribution of its high-lying eigenvalues. The purpose of this paper is to show that the converse is generally incorrect: a power-law tail in the high-lying eigenvalues of the correlation matrix may exist even in the absence of equal-time power law correlations in the initial model. We may therefore view the study of the eigenvalue distribution of the correlation matrix as a more powerful tool than the study of spatial Correlations, one which may in fact uncover structure, that would otherwise not be apparent. Specifically, we show that in the Totally Asymmetric Simple Exclusion Process, whereas there are no clearly visible correlations in the steady state, the eigenvalues of its correlation matrix exhibit a rich structure which we describe in detail.

  17. Modern quantum chemistry introduction to advanced electronic structure theory

    CERN Document Server

    Szabo, Attila

    1996-01-01

    The aim of this graduate-level textbook is to present and explain, at other than a superficial level, modem ab initio approaches to the calculation of the electronic structure and properties of molecules. The first three chapters contain introductory material culminating in a thorough discussion of the Hartree-Fock approximation.The remaining four chapters describe a variety of more sophisticated approaches, which improve upon this approximation.Among the highlights of the seven chapters are (1) a review of the mathematics (mostly matrix algebra) required for the rest of the book, (2) an intr

  18. Chemistry and Structure-Activity Relationships of Psychedelics.

    Science.gov (United States)

    Nichols, David E

    2018-01-01

    This chapter will summarize structure-activity relationships (SAR) that are known for the classic serotonergic hallucinogens (aka psychedelics), focusing on the three chemical types: tryptamines, ergolines, and phenethylamines. In the brain, the serotonin 5-HT 2A receptor plays a key role in regulation of cortical function and cognition, and also appears to be the principal target for hallucinogenic/psychedelic drugs such as LSD. It is one of the most extensively studied of the 14 known types of serotonin receptors. Important structural features will be identified for activity and, where possible, those that the psychedelics have in common will be discussed. Because activation of the 5-HT 2A receptor is the principal mechanism of action for psychedelics, compounds with 5-HT 2A agonist activity generally are quickly discarded by the pharmaceutical industry. Thus, most of the research on psychedelics can be related to activation of 5-HT 2A receptors. Therefore, much of the discussion will include not only clinical or anecdotal studies, but also will consider data from animal models as well as a certain amount of molecular pharmacology where it is known.

  19. Physics and Chemistry of Creating New Titanates with Perovskite Structure

    Science.gov (United States)

    Politova, E. D.; Kaleva, G. M.; Golubko, N. V.; Mosunov, A. V.; Sadovskaya, N. V.; Bel'kova, D. A.; Strebkov, D. A.; Stefanovich, S. Yu.; Kiselev, D. A.; Kislyuk, A. M.

    2018-06-01

    The phase formation, structural features, and dielectric, ferroelectric, and piezoelectric properties of ceramics with compositions from the region of the morphotropic phase boundary in the (Na0.5Bi0.5)TiO3-BaTiO3-Bi(Mg0.5Ti0.5)O3 system modified by different low-melting additives (Bi2O3, V2O5, KCl, NaCl-LiF, LiF, CuO, and MnO2) are studied. First-order phase transitions are detected near 700-800 and 400 K that display relaxor behavior and are indicative of the presence of polar regions in a nonpolar matrix. Prospects for improving the piezoelectric properties of the modified ceramic samples are confirmed.

  20. An ezrin-rich, rigid uropod-like structure directs movement of amoeboid blebbing cells.

    Science.gov (United States)

    Lorentzen, Anna; Bamber, Jeffrey; Sadok, Amine; Elson-Schwab, Ilan; Marshall, Christopher J

    2011-04-15

    Melanoma cells can switch between an elongated mesenchymal-type and a rounded amoeboid-type migration mode. The rounded 'amoeboid' form of cell movement is driven by actomyosin contractility resulting in membrane blebbing. Unlike elongated A375 melanoma cells, rounded A375 cells do not display any obvious morphological front-back polarisation, although polarisation is thought to be a prerequisite for cell movement. We show that blebbing A375 cells are polarised, with ezrin (a linker between the plasma membrane and actin cytoskeleton), F-actin, myosin light chain, plasma membrane, phosphatidylinositol (4,5)-bisphosphate and β1-integrin accumulating at the cell rear in a uropod-like structure. This structure does not have the typical protruding shape of classical leukocyte uropods, but, as for those structures, it is regulated by protein kinase C. We show that the ezrin-rich uropod-like structure (ERULS) is an inherent feature of polarised A375 cells and not a consequence of cell migration, and is necessary for cell invasion. Furthermore, we demonstrate that membrane blebbing is reduced at this site, leading to a model in which the rigid ezrin-containing structure determines the direction of a moving cell through localised inhibition of membrane blebbing.

  1. Combustion chemistry of alcohols: Experimental and modeled structure of a premixed 2-methylbutanol flame

    KAUST Repository

    Lucassen, Arnas; Park, Sungwoo; Hansen, Nils; Sarathy, Mani

    2014-01-01

    This paper presents a detailed investigation of 2-methylbutanol combustion chemistry in low-pressure premixed flames. This chemistry is of particular interest to study because this compound is potentially a lignocellulosic-based, next-generation biofuel. The detailed chemical structure of a stoichiometric low-pressure (25 Torr) flame was determined using flame-sampling molecular-beam mass spectrometry. A total of 55 species were identified and subsequently quantitative mole fraction profiles as function of distance from the burner surface were determined. In an independent effort, a detailed flame chemistry model for 2-methylbutanol was assembled based on recent knowledge gained from combustion chemistry studies for butanol isomers ([Sarathy et al. Combust. Flame 159 (6) (2012) 2028-2055]) and iso-pentanol (3-methylbutanol) [Sarathy et al. Combust. Flame 160 (12) (2013) 2712-2728]. Experimentally determined and modeled mole fraction profiles were compared to demonstrate the model's capabilities. Examples of individual mole fraction profiles are discussed together with the most significant fuel consumption pathways to highlight the combustion chemistry of 2-methylbutanol. Discrepancies between experimental and modeling results are used to suggest areas where improvement of the kinetic model would be needed. © 2014.

  2. Combustion chemistry of alcohols: Experimental and modeled structure of a premixed 2-methylbutanol flame

    KAUST Repository

    Lucassen, Arnas

    2014-06-14

    This paper presents a detailed investigation of 2-methylbutanol combustion chemistry in low-pressure premixed flames. This chemistry is of particular interest to study because this compound is potentially a lignocellulosic-based, next-generation biofuel. The detailed chemical structure of a stoichiometric low-pressure (25 Torr) flame was determined using flame-sampling molecular-beam mass spectrometry. A total of 55 species were identified and subsequently quantitative mole fraction profiles as function of distance from the burner surface were determined. In an independent effort, a detailed flame chemistry model for 2-methylbutanol was assembled based on recent knowledge gained from combustion chemistry studies for butanol isomers ([Sarathy et al. Combust. Flame 159 (6) (2012) 2028-2055]) and iso-pentanol (3-methylbutanol) [Sarathy et al. Combust. Flame 160 (12) (2013) 2712-2728]. Experimentally determined and modeled mole fraction profiles were compared to demonstrate the model\\'s capabilities. Examples of individual mole fraction profiles are discussed together with the most significant fuel consumption pathways to highlight the combustion chemistry of 2-methylbutanol. Discrepancies between experimental and modeling results are used to suggest areas where improvement of the kinetic model would be needed. © 2014.

  3. Benthic megafaunal community structure of cobalt-rich manganese crusts on Necker Ridge

    Science.gov (United States)

    Morgan, Nicole B.; Cairns, Stephen; Reiswig, Henry; Baco, Amy R.

    2015-10-01

    In the North Pacific Ocean, the seamounts of the Hawaiian Archipelago and the Mid-Pacific Mountains are connected by Necker Ridge, a 600 km-long feature spanning a depth range of 1400-4000 m. The Necker Ridge is a part of a large area of the central and western Pacific under consideration for cobalt-rich manganese crust mining. We describe the fauna and community structure of the previously unsampled Necker Ridge based on explorations with the submersible Pisces IV. On five pinnacles and a portion of the Ridge ranging from 1400 to 2000 m deep, 27 transects were recorded using HD video, and voucher specimens were collected to aid in species identification. The video was analyzed to identify and count the megafauna found on each transect and to characterize the substrate. Diversity increased from south to north along the feature. There was a significant difference in community structure between southern and northern pinnacles, with southern pinnacles dominated by crinoids of the Family Charitometridae and northern pinnacles dominated by octocorals, especially the Families Isididae and Chrysogorgiidae. DistLM demonstrated a correlation between community structure on the pinnacles and at least six environmental variables, including latitude, sediment cover, and oxygen concentration, but not including depth. The discontinuous and patchy nature of these distinct megafaunal communities highlights growing evidence that cobalt-rich seamounts are highly heterogeneous habitats, and that managing seamounts may require more complex regulations than treating them as a single ecological unit. These results suggest that extensive community analysis should occur at a given site to determine management priority areas, prior to consideration of that site for exploitation of natural resources.

  4. Electronic structure and chemistry of the heaviest elements

    International Nuclear Information System (INIS)

    Pershina, V.; Fricke, B.

    1998-04-01

    Progress in the development of relativistic molecular codes has allowed for an adequate description of the electronic structure of the very heavy element compounds, and for the interpretation and prediction of their molecular properties. Most of the theoretical investigations for compounds, interesting from the experimental point of view, have been carried out using the LDF methods. The studied species were group 4, 5 and 6 gas-phase compounds of the transactinides along with their lighter homologs, and their complexes in aqueous solutions. As a result of these calculations, trends within the transition-element groups and within the beginning of the transactinide series for molecular properties such as ionicity, covalence, stability towards oxidation or reduction, crystal-field and spin-orbit effects, bonding, and the influence of relativistic effects on them have been established. In combination with some other models, these calculations allowed for predicting properties measured experimentally: volatility of compounds, redox potentials in solutions and complex formation. Especially promising were predictions of equilibria of reaction using the DS-DV method. Agreement between results of the calculations and experiment confirmed the necessity of doing relativistic MO calculations and the unreliability of the straightforward extrapolations of properties within the chemical groups. (orig.)

  5. Developing and Implementing a Reorganized Undergraduate Chemistry Curriculum Based on the Foundational Chemistry Topics of Structure, Reactivity, and Quantitation

    Science.gov (United States)

    Schaller, Chris P.; Graham, Kate J.; Johnson, Brian J.; Fazal, M. A.; Jones, T. Nicholas; McIntee, Edward J.; Jakubowski, Henry V.

    2014-01-01

    The recent revision of undergraduate curricular guidelines from the American Chemical Society Committee on Professional Training (ACS-CPT) has generated interest in examining new ways of organizing course sequences both for chemistry majors and for nonmajors. A radical reconstruction of the foundation-level chemistry curriculum is presented in…

  6. Structure of light proton-rich nuclei on the drip-line

    International Nuclear Information System (INIS)

    Guimaraes, V.; Toyokawa, H.; Yun, C.C.; Niizeki, T.; Ito, K.; Kishida, T.; Kubo, T.; Pu, Y.; Ohura, M.; Orihara, H.; Terakawa, T.; Hamada, S.; Hirai, M.; Miyatake, H.

    1995-01-01

    Among proton-rich unstable nuclei on the light proton drip-line, nuclear structure of 21 Mg, 17 Ne, 13 O, 11 N and 9 C have been investigated by the three-neutron pick-up reaction ( 3 He, 6 He). The angular distributions measured for this reaction have shown a characteristic feature of a transferred angular-momentum (L) dependence, which provides spin-parity assignments for the new levels in these nuclei. Here, the results on the nuclear structure of 17 Ne and 11 N are reported. The nucleus 17 Ne we almost unknown before, except that the mass excess had been determined and a few states had been suggested. Many T = 3/2 states were known in the other three members ( 17 N, 17 O and 17 F). Thus, the inclusion of the data on 17 Ne levels has enabled an extensive analysis in terms of the Isobaric Multiplet Mass Equation (IMME) for several excited state quartets. This is the first report on such an extensive analysis in the same mass ststem for a wide range in excitation energy. The 11 N nucleus was investigated to learn about the structure of A 11 system. This mass has been intensively studied, specially because of the halo structure observed in 11 Li and the spin parity-inversion of the 11 Be ground-state. The 11 N nucleus was totally unknown before except for the possible ground state

  7. Structure dependent electrochemical performance of Li-rich layered oxides in lithium-ion batteries

    Energy Technology Data Exchange (ETDEWEB)

    Fu, Fang; Yao, Yuze; Wang, Haiyan; Xu, Gui-Liang; Amine, Khalil; Sun, Shi-Gang; Shao, Minhua

    2017-04-08

    Rational and precise control of the structure and dimension of electrode materials is an efficient way to improve their electrochemical performance. In this work, solvothermal or co-precipitation method is used to synthesize lithium-rich layered oxide materials of Li1.2Mn0.56Co0.12Ni0.12O2 (LLO) with various morphologies and structures, including microspheres, microrods, nanoplates, and irregular nanoparticles. These materials exhibit strong structure- dependent electrochemical properties. The porous hierarchical structured LLO microrods exhibit the best performance, delivering a discharge capacity of 264.6 mAh g(-1) at 0.5 C with over 91% retention after 100 cycles. At a high rate of 5 C, a high discharge capacity of 173.6 mAh g(-1) can be achieved. This work reveals the relationship between the morphologies and electrochemical properties of LLO cathode materials, and provides a feasible approach to fabricating robust and high-performance electrode materials for lithium-ion batteries.

  8. Multiscale pore structure and its effect on gas transport in organic-rich shale

    Science.gov (United States)

    Wu, Tianhao; Li, Xiang; Zhao, Junliang; Zhang, Dongxiao

    2017-07-01

    A systematic investigation of multiscale pore structure in organic-rich shale by means of the combination of various imaging techniques is presented, including the state-of-the-art Helium-Ion-Microscope (HIM). The study achieves insight into the major features at each scale and suggests the affordable techniques for specific objectives from the aspects of resolution, dimension, and cost. The pores, which appear to be isolated, are connected by smaller pores resolved by higher-resolution imaging. This observation provides valuable information, from the microscopic perspective of pore structure, for understanding how gas accumulates and transports from where it is generated. A comprehensive workflow is proposed based on the characteristics acquired from the multiscale pore structure analysis to simulate the gas transport process. The simulations are completed with three levels: the microscopic mechanisms should be taken into consideration at level I; the spatial distribution features of organic matter, inorganic matter, and macropores constitute the major issue at level II; and the microfracture orientation and topological structure are dominant factors at level III. The results of apparent permeability from simulations agree well with the values acquired from experiments. By means of the workflow, the impact of various gas transport mechanisms at different scales can be investigated more individually and precisely than conventional experiments.

  9. The structural chemistry of metallocorroles: combined X-ray crystallography and quantum chemistry studies afford unique insights.

    Science.gov (United States)

    Thomas, Kolle E; Alemayehu, Abraham B; Conradie, Jeanet; Beavers, Christine M; Ghosh, Abhik

    2012-08-21

    Although they share some superficial structural similarities with porphyrins, corroles, trianionic ligands with contracted cores, give rise to fundamentally different transition metal complexes in comparison with the dianionic porphyrins. Many metallocorroles are formally high-valent, although a good fraction of them are also noninnocent, with significant corrole radical character. These electronic-structural characteristics result in a variety of fascinating spectroscopic behavior, including highly characteristic, paramagnetically shifted NMR spectra and textbook cases of charge-transfer spectra. Although our early research on corroles focused on spectroscopy, we soon learned that the geometric structures of metallocorroles provide a fascinating window into their electronic-structural characteristics. Thus, we used X-ray structure determinations and quantum chemical studies, chiefly using DFT, to obtain a comprehensive understanding of metallocorrole geometric and electronic structures. This Account describes our studies of the structural chemistry of metallocorroles. At first blush, the planar or mildly domed structure of metallocorroles might appear somewhat uninteresting particularly when compared to metalloporphyrins. Metalloporphyrins, especially sterically hindered ones, are routinely ruffled or saddled, but the missing meso carbon apparently makes the corrole skeleton much more resistant to nonplanar distortions. Ruffling, where the pyrrole rings are alternately twisted about the M-N bonds, is energetically impossible for metallocorroles. Saddling is also uncommon; thus, a number of sterically hindered, fully substituted metallocorroles exhibit almost perfectly planar macrocycle cores. Against this backdrop, copper corroles stand out as an important exception. As a result of an energetically favorable Cu(d(x2-y2))-corrole(π) orbital interaction, copper corroles, even sterically unhindered ones, are inherently saddled. Sterically hindered substituents

  10. Bryophyte species richness on retention aspens recovers in time but community structure does not.

    Science.gov (United States)

    Oldén, Anna; Ovaskainen, Otso; Kotiaho, Janne S; Laaka-Lindberg, Sanna; Halme, Panu

    2014-01-01

    Green-tree retention is a forest management method in which some living trees are left on a logged area. The aim is to offer 'lifeboats' to support species immediately after logging and to provide microhabitats during and after forest re-establishment. Several studies have shown immediate decline in bryophyte diversity after retention logging and thus questioned the effectiveness of this method, but longer term studies are lacking. Here we studied the epiphytic bryophytes on European aspen (Populus tremula L.) retention trees along a 30-year chronosequence. We compared the bryophyte flora of 102 'retention aspens' on 14 differently aged retention sites with 102 'conservation aspens' on 14 differently aged conservation sites. We used a Bayesian community-level modelling approach to estimate the changes in bryophyte species richness, abundance (area covered) and community structure during 30 years after logging. Using the fitted model, we estimated that two years after logging both species richness and abundance of bryophytes declined, but during the following 20-30 years both recovered to the level of conservation aspens. However, logging-induced changes in bryophyte community structure did not fully recover over the same time period. Liverwort species showed some or low potential to benefit from lifeboating and high potential to re-colonise as time since logging increases. Most moss species responded similarly, but two cushion-forming mosses benefited from the logging disturbance while several weft- or mat-forming mosses declined and did not re-colonise in 20-30 years. We conclude that retention trees do not function as equally effective lifeboats for all bryophyte species but are successful in providing suitable habitats for many species in the long-term. To be most effective, retention cuts should be located adjacent to conservation sites, which may function as sources of re-colonisation and support the populations of species that require old-growth forests.

  11. Bryophyte species richness on retention aspens recovers in time but community structure does not.

    Directory of Open Access Journals (Sweden)

    Anna Oldén

    Full Text Available Green-tree retention is a forest management method in which some living trees are left on a logged area. The aim is to offer 'lifeboats' to support species immediately after logging and to provide microhabitats during and after forest re-establishment. Several studies have shown immediate decline in bryophyte diversity after retention logging and thus questioned the effectiveness of this method, but longer term studies are lacking. Here we studied the epiphytic bryophytes on European aspen (Populus tremula L. retention trees along a 30-year chronosequence. We compared the bryophyte flora of 102 'retention aspens' on 14 differently aged retention sites with 102 'conservation aspens' on 14 differently aged conservation sites. We used a Bayesian community-level modelling approach to estimate the changes in bryophyte species richness, abundance (area covered and community structure during 30 years after logging. Using the fitted model, we estimated that two years after logging both species richness and abundance of bryophytes declined, but during the following 20-30 years both recovered to the level of conservation aspens. However, logging-induced changes in bryophyte community structure did not fully recover over the same time period. Liverwort species showed some or low potential to benefit from lifeboating and high potential to re-colonise as time since logging increases. Most moss species responded similarly, but two cushion-forming mosses benefited from the logging disturbance while several weft- or mat-forming mosses declined and did not re-colonise in 20-30 years. We conclude that retention trees do not function as equally effective lifeboats for all bryophyte species but are successful in providing suitable habitats for many species in the long-term. To be most effective, retention cuts should be located adjacent to conservation sites, which may function as sources of re-colonisation and support the populations of species that require old

  12. Mapping RNA Structure In Vitro with SHAPE Chemistry and Next-Generation Sequencing (SHAPE-Seq).

    Science.gov (United States)

    Watters, Kyle E; Lucks, Julius B

    2016-01-01

    Mapping RNA structure with selective 2'-hydroxyl acylation analyzed by primer extension (SHAPE) chemistry has proven to be a versatile method for characterizing RNA structure in a variety of contexts. SHAPE reagents covalently modify RNAs in a structure-dependent manner to create adducts at the 2'-OH group of the ribose backbone at nucleotides that are structurally flexible. The positions of these adducts are detected using reverse transcriptase (RT) primer extension, which stops one nucleotide before the modification, to create a pool of cDNAs whose lengths reflect the location of SHAPE modification. Quantification of the cDNA pools is used to estimate the "reactivity" of each nucleotide in an RNA molecule to the SHAPE reagent. High reactivities indicate nucleotides that are structurally flexible, while low reactivities indicate nucleotides that are inflexible. These SHAPE reactivities can then be used to infer RNA structures by restraining RNA structure prediction algorithms. Here, we provide a state-of-the-art protocol describing how to perform in vitro RNA structure probing with SHAPE chemistry using next-generation sequencing to quantify cDNA pools and estimate reactivities (SHAPE-Seq). The use of next-generation sequencing allows for higher throughput, more consistent data analysis, and multiplexing capabilities. The technique described herein, SHAPE-Seq v2.0, uses a universal reverse transcription priming site that is ligated to the RNA after SHAPE modification. The introduced priming site allows for the structural analysis of an RNA independent of its sequence.

  13. Rich RNA Structure Landscapes Revealed by Mutate-and-Map Analysis.

    Directory of Open Access Journals (Sweden)

    Pablo Cordero

    2015-11-01

    Full Text Available Landscapes exhibiting multiple secondary structures arise in natural RNA molecules that modulate gene expression, protein synthesis, and viral infection [corrected]. We report herein that high-throughput chemical experiments can isolate an RNA's multiple alternative secondary structures as they are stabilized by systematic mutagenesis (mutate-and-map, M2 and that a computational algorithm, REEFFIT, enables unbiased reconstruction of these states' structures and populations. In an in silico benchmark on non-coding RNAs with complex landscapes, M2-REEFFIT recovers 95% of RNA helices present with at least 25% population while maintaining a low false discovery rate (10% and conservative error estimates. In experimental benchmarks, M2-REEFFIT recovers the structure landscapes of a 35-nt MedLoop hairpin, a 110-nt 16S rRNA four-way junction with an excited state, a 25-nt bistable hairpin, and a 112-nt three-state adenine riboswitch with its expression platform, molecules whose characterization previously required expert mutational analysis and specialized NMR or chemical mapping experiments. With this validation, M2-REEFFIT enabled tests of whether artificial RNA sequences might exhibit complex landscapes in the absence of explicit design. An artificial flavin mononucleotide riboswitch and a randomly generated RNA sequence are found to interconvert between three or more states, including structures for which there was no design, but that could be stabilized through mutations. These results highlight the likely pervasiveness of rich landscapes with multiple secondary structures in both natural and artificial RNAs and demonstrate an automated chemical/computational route for their empirical characterization.

  14. Nano-phase separation and structural ordering in silica-rich mixed network former glasses.

    Science.gov (United States)

    Liu, Hao; Youngman, Randall E; Kapoor, Saurabh; Jensen, Lars R; Smedskjaer, Morten M; Yue, Yuanzheng

    2018-06-13

    We investigate the structure, phase separation, glass transition, and crystallization in a mixed network former glass series, i.e., B2O3-Al2O3-SiO2-P2O5 glasses with varying SiO2/B2O3 molar ratio. All the studied glasses exhibit two separate glassy phases: droplet phase (G1) with the size of 50-100 nm and matrix phase (G2), corresponding to a lower calorimetric glass transition temperature (Tg1) and a higher one (Tg2), respectively. Both Tg values decrease linearly with the substitution of B2O3 for SiO2, but the magnitude of the decrease is larger for Tg1. Based on nuclear magnetic resonance and Raman spectroscopy results, we infer that the G1 phase is rich in boroxol rings, while the G2 phase mainly involves the B-O-Si network. Both phases contain BPO4- and AlPO4-like units. Ordered domains occur in G2 upon isothermal and dynamic heating, driven by the structural heterogeneity in the as-prepared glasses. The structural ordering lowers the activation energy of crystal growth, thus promoting partial crystallization of G2. These findings are useful for understanding glass formation and phase separation in mixed network former oxide systems, and for tailoring their properties.

  15. Tetrahelical structural family adopted by AGCGA-rich regulatory DNA regions

    Science.gov (United States)

    Kocman, Vojč; Plavec, Janez

    2017-05-01

    Here we describe AGCGA-quadruplexes, an unexpected addition to the well-known tetrahelical families, G-quadruplexes and i-motifs, that have been a focus of intense research due to their potential biological impact in G- and C-rich DNA regions, respectively. High-resolution structures determined by solution-state nuclear magnetic resonance (NMR) spectroscopy demonstrate that AGCGA-quadruplexes comprise four 5'-AGCGA-3' tracts and are stabilized by G-A and G-C base pairs forming GAGA- and GCGC-quartets, respectively. Residues in the core of the structure are connected with edge-type loops. Sequences of alternating 5'-AGCGA-3' and 5'-GGG-3' repeats could be expected to form G-quadruplexes, but are shown herein to form AGCGA-quadruplexes instead. Unique structural features of AGCGA-quadruplexes together with lower sensitivity to cation and pH variation imply their potential biological relevance in regulatory regions of genes responsible for basic cellular processes that are related to neurological disorders, cancer and abnormalities in bone and cartilage development.

  16. Rule of five in 2015 and beyond: Target and ligand structural limitations, ligand chemistry structure and drug discovery project decisions.

    Science.gov (United States)

    Lipinski, Christopher A

    2016-06-01

    The rule of five (Ro5), based on physicochemical profiles of phase II drugs, is consistent with structural limitations in protein targets and the drug target ligands. Three of four parameters in Ro5 are fundamental to the structure of both target and drug binding sites. The chemical structure of the drug ligand depends on the ligand chemistry and design philosophy. Two extremes of chemical structure and design philosophy exist; ligands constructed in the medicinal chemistry synthesis laboratory without input from natural selection and natural product (NP) metabolites biosynthesized based on evolutionary selection. Exceptions to Ro5 are found mostly among NPs. Chemistry chameleon-like behavior of some NPs due to intra-molecular hydrogen bonding as exemplified by cyclosporine A is a strong contributor to NP Ro5 outliers. The fragment derived, drug Navitoclax is an example of the extensive expertise, resources, time and key decisions required for the rare discovery of a non-NP Ro5 outlier. Copyright © 2016 Elsevier B.V. All rights reserved.

  17. Structure and function of ABCG2-rich extracellular vesicles mediating multidrug resistance.

    Directory of Open Access Journals (Sweden)

    Vicky Goler-Baron

    2011-01-01

    Full Text Available Multidrug resistance (MDR is a major impediment to curative cancer chemotherapy. The ATP-Binding Cassette transporters ABCG2, ABCB1 and ABCC2 form a unique defense network against multiple structurally and functionally distinct chemotherapeutics, thereby resulting in MDR. Thus, deciphering novel mechanisms of MDR and their overcoming is a major goal of cancer research. Recently we have shown that overexpression of ABCG2 in the membrane of novel extracellular vesicles (EVs in breast cancer cells results in mitoxantrone resistance due to its dramatic sequestration in EVs. However, nothing is known about EVs structure, biogenesis and their ability to concentrate multiple antitumor agents. To this end, we here found that EVs are structural and functional homologues of bile canaliculi, are apically localized, sealed structures reinforced by an actin-based cytoskeleton and secluded from the extracellular milieu by the tight junction proteins occludin and ZO-1. Apart from ABCG2, ABCB1 and ABCC2 were also selectively targeted to the membrane of EVs. Moreover, Ezrin-Radixin-Moesin protein complex selectively localized to the border of the EVs membrane, suggesting a key role for the tethering of MDR pumps to the actin cytoskeleton. The ability of EVs to concentrate and sequester different antitumor drugs was also explored. Taking advantage of the endogenous fluorescence of anticancer drugs, we found that EVs-forming breast cancer cells display high level resistance to topotecan, imidazoacridinones and methotrexate via efficient intravesicular drug concentration hence sequestering them away from their cellular targets. Thus, we identified a new modality of anticancer drug compartmentalization and resistance in which multiple chemotherapeutics are actively pumped from the cytoplasm and highly concentrated within the lumen of EVs via a network of MDR transporters differentially targeted to the EVs membrane. We propose a composite model for the structure and

  18. Geometric structure of chemistry-relevant graphs zigzags and central circuits

    CERN Document Server

    Deza, Michel-Marie; Shtogrin, Mikhail Ivanovitch

    2015-01-01

    The central theme of the present book is zigzags and central-circuits of three- or four-regular plane graphs, which allow a double covering or covering of the edgeset to be obtained. The book presents zigzag and central circuit structures of geometric fullerenes and several other classes of graph of interest in the fields of chemistry and mathematics. It also discusses the symmetries, parameterization and the Goldberg–Coxeter construction for those graphs. It is the first book on this subject, presenting full structure theory of such graphs. While many previous publications only addressed particular questions about selected graphs, this book is based on numerous computations and presents extensive data (tables and figures), as well as algorithmic and computational information. It will be of interest to researchers and students of discrete geometry, mathematical chemistry and combinatorics, as well as to lay mathematicians.

  19. Relative influence of soil chemistry and topography on soil available micronutrients by structural equation modeling

    OpenAIRE

    Zhu, Hongfen; Zhao, Ying; Nan, Feng; Duan, Yonghong; Bi, Rutian

    2016-01-01

    Soil chemical and topographic properties are two important factors influencing available micronutrient distribution of soil in the horizontal dimension. The objective of this study was to explore the relative influence of soil chemistry (including soil pH, soil organic matter, total nitrogen, available phosphorus, and available potassium) and topography (including elevation, slope, aspect, and wetness index) on the availability of micronutrients (Fe, Mn, Cu, Zn, and B) using structural equati...

  20. Ocean-Continent Transition Structure of the Pelotas Magma-Rich Continental Margin, South Atlantic

    Science.gov (United States)

    Harkin, Caroline; Kusznir, Nick; Roberts, Alan; Manatschal, Gianreto; McDermott, Ken

    2017-04-01

    Rifted continental margins in the southern South Atlantic are magma-rich showing well developed volcanic extrusives known as seaward dipping reflectors (SDRs). Here we examine the magma-rich continental rifted margin of the Pelotas Basin, offshore Brazil. Deep seismic reflection data displays a large package of seaward dipping reflectors with an approximate width of 200 km and a varying thickness of 10 km to 17 km that have previously been interpreted as volcanic SDRs. We examine these SDRs to explore if they are composed predominantly of basaltic or sedimentary-volcaniclastic material. We also study the thickness of the crustal basement beneath the SDRs. Additionally we investigate if these SDRs are underlain by thin 'hyper-extended' continental crust or if they have been deposited on new magmatic basement. The answers to these questions are important in understanding the structure and formation processes of magma-rich continental margins. We use gravity inversion to investigate SDR composition by varying the proportion of basalt to sediments-volcaniclastics (basalt fraction) which determines the SDR densities in the gravity inversion. By matching the Moho depth and two-way travel time from gravity inversion and deep seismic reflection data, we determine the lateral variation in basalt fraction of the SDRs. Our analysis suggests: 1) There is an overall pattern of SDR basalt fraction and bulk density decreasing oceanward. This could be due to increasing sediment content oceanward or it could result from the change in basalt flows to hyaloclastites as water depth increases. 2) The SDR package can be split into two distinct sub packages based on the basalt fraction results, where the proximal side of each package has a higher basalt fraction and density. 3) The inner SDR package contains reflectors that bear a resemblance to the SDRs described by Hinz (1981) corresponding to syn-tectonic volcanic eruptions into an extensional basin, while the outer SDR package has

  1. Comparison of the associative structure of two different types of rich coals and their coking properties

    Energy Technology Data Exchange (ETDEWEB)

    Hengfu Shui; Changhui Lin; Meng Zhang; Zhicai Wang; Mingdong Zheng [Anhui University of Technology, Maanshan (China). School of Chemistry and Chemical Engineering

    2010-07-15

    Solvent extractions of two different types of Chinese rich coals i.e. Aiweiergou coal (AG) and Zaozhuang coal (ZZ) using the mixed solvent of carbon disulfide/N-methyl-2-pyrrolidinone (CS{sub 2}/NMP) with different mixing ratios were carried out and the caking indexes of the extracted residues were measured. It was found that the extracted residues from the two types of coals showed different changing tendencies of the caking indexes with the extraction yield. When the extraction yield attained about 50% for ZZ coal, the extracted residue had no caking property. However for AG coal, when the extraction yield reached the maximum of 63.5%, the corresponding extracted residue still had considerable caking property with the caking index of 25. This difference indicated the different associative structure of the two coals although they are of the same coalification. Hydro-thermal treatment of the two rich coals gave different extract fractionation distributions for the treated coals compared to those of raw coals respectively. The coking property evaluations of the two coals and their hydro-thermally treated ones were carried out in a crucible coking determination. The results showed that the hydro-thermal treatment could greatly improve the micro-strengths of the resulting coke from the two coals, and the improvement was more significant for the more aggregated AG coal. The reactivities of hydro-thermally treated AG coal blends were almost the same as those of raw coal blends. The higher coke reactivities of AG raw coal and its hydro-thermally treated ones than those of ZZ coal might be attributed to its special ash composition. 20 refs.,4 figs., 5 tabs.

  2. Species Richness and Community Structure on a High Latitude Reef: Implications for Conservation and Management

    Directory of Open Access Journals (Sweden)

    Wayne Houston

    2011-07-01

    Full Text Available In spite of the wealth of research on the Great Barrier Reef, few detailed biodiversity assessments of its inshore coral communities have been conducted. Effective conservation and management of marine ecosystems begins with fine-scale biophysical assessments focused on diversity and the architectural species that build the structural framework of the reef. In this study, we investigate key coral diversity and environmental attributes of an inshore reef system surrounding the Keppel Bay Islands near Rockhampton in Central Queensland, Australia, and assess their implications for conservation and management. The Keppels has much higher coral diversity than previously found. The average species richness for the 19 study sites was ~40 with representatives from 68% of the ~244 species previously described for the southern Great Barrier Reef. Using scleractinian coral species richness, taxonomic distinctiveness and coral cover as the main criteria, we found that five out of 19 sites had particularly high conservation value. A further site was also considered to be of relatively high value. Corals at this site were taxonomically distinct from the others (representatives of two families were found here but not at other sites and a wide range of functionally diverse taxa were present. This site was associated with more stressful conditions such as high temperatures and turbidity. Highly diverse coral communities or biodiversity ‘hotspots’ and taxonomically distinct reefs may act as insurance policies for climatic disturbance, much like Noah’s Arks for reefs. While improving water quality and limiting anthropogenic impacts are clearly important management initiatives to improve the long-term outlook for inshore reefs, identifying, mapping and protecting these coastal ‘refugia’ may be the key for ensuring their regeneration against catastrophic climatic disturbance in the meantime.

  3. Variance in water chemistry parameters in isolated wetlands of Florida, USA, and relationships with macroinvertebrate and diatom community structure

    Science.gov (United States)

    Eighty small isolated wetlands throughout Florida were sampled in 2005 to explore within-site variability of water chemistry parameters and relate water chemistry to macroinvertebrate and diatom community structure. Three samples or measures of water were collected within each si...

  4. Electronic structure and fine structural features of the air-grown UNxOy on nitrogen-rich uranium nitride

    Science.gov (United States)

    Long, Zhong; Zeng, Rongguang; Hu, Yin; Liu, Jing; Wang, Wenyuan; Zhao, Yawen; Luo, Zhipeng; Bai, Bin; Wang, Xiaofang; Liu, Kezhao

    2018-06-01

    Oxide formation on surface of nitrogen-rich uranium nitride film/particles was investigated using X-ray photoelectron spectroscopy (XPS), auger electron spectroscopy (AES), aberration-corrected transmission electron microscopy (TEM), and high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) coupled with electron energy-loss spectroscopy (EELS). XPS and AES studies indicated that the oxidized layer on UN2-x film is ternary compound uranium oxynitride (UNxOy) in 5-10 nm thickness. TEM/HAADF-STEM and EELS studies revealed the UNxOy crystallizes in the FCC CaF2-type structure with the lattice parameter close to the CaF2-type UN2-x matrix. The work can provide further information to the oxidation mechanism of uranium nitride.

  5. New experimental investigation of cluster structures in 10 Be and 16 C neutron-rich nuclei

    Science.gov (United States)

    Dell'Aquila, L.; Acosta, D.; Auditore, L.; Cardella, G.; De Filippo, E.; De Luca, S.; Francalanza, L.; Gnoffo, B.; Lanzalone, G.; Lombardo, I.; Martorana, N. S.; Norella, S.; Pagano, A.; Pagano, E. V.; Papa, M.; Pirrone, S.; Politi, G.; Quattrocchi, L.; Rizzo, F.; Russotto, P.; Trifirò, A.; Trimarchi, M.; Verde, G.; Vigilante, M.

    2017-11-01

    The existence of cluster structures in ^{10} Be and ^{16} C neutron-rich isotopes is investigated via projectile break-up reactions induced on polyethylene (CH _2 target. We used a fragmentation beam constituted by 55MeV/u ^{10} Be and 49MeV/u ^{16} C beams provided by the FRIBs facility at INFN-LNS. Invariant mass spectra of 4{He}+ 6 He and 6{He} + ^{10} Be breakup fragments are reconstructed by means of the CHIMERA 4π detector to investigate the presence of excited states of projectile nuclei characterized by cluster structure. In the first case, we suggest the presence of a new state in ^{10} Be at 13.5MeV. A non-vanishing yield corresponding to 20.6MeV excitation energy of ^{16} C was observed in the 6{He} + ^{10} Be cluster decay channel. To improve the results of the present analysis, a new experiment has been performed recently, taking advantage of the coupling of CHIMERA and FARCOS. In the paper we describe the data reduction process of the new experiment together with preliminary results.

  6. Correlation between reflectance and photoluminescent properties of al-rich ZnO nano-structures

    Science.gov (United States)

    Khan, Firoz; Baek, Seong-Ho; Ahmad, Nafis; Lee, Gun Hee; Seo, Tae Hoon; Suh, Eun-kyung; Kim, Jae Hyun

    2015-05-01

    Al rich zinc oxide nano-structured films were synthesized using spin coating sol-gel technique. The films were annealed in oxygen ambient in the temperature range of 200-700 °C. The structural, optical, and photoluminescence (PL) properties of the films were studied at various annealing temperatures using X-ray diffraction spectroscopy, field emission scanning electron microscopy, photoluminescence emission spectra measurement, and Raman and UV-Vis spectroscopy. The optical band gap was found to decrease with the increase of the annealing temperature following the Gauss Amp function due to the confinement of the exciton. The PL peak intensity in the near band region (INBE) was found to increase with the increase of the annealing temperature up to 600 °C, then to decrease fast to a lower value for the annealing temperature of 700 °C due to crystalline quality. The Raman peak of E2 (low) was red shifted from 118 cm-1 to 126 cm-1 with the increase of the annealing temperature. The intensity of the second order phonon (TA+LO) at 674 cm-1 was found to decrease with the increase of the annealing temperature. The normalized values of the reflectance and the PL intensity in the NBE region were highest for the annealing temperature of 600 °C. A special correlation was found between the reflectance at λ = 1000 nm and the normalized PL intensity in the green region due to scattering due to presence of grains.

  7. Structure of neutron rich nuclei of Germanium and Gallium beyond N equals 50 at Alto

    International Nuclear Information System (INIS)

    Lebois, M.

    2008-09-01

    The gamma rays following the beta decay of the following very neutron-rich isotopes: 82,83,84 Ga produced by photo-fission, have been studied at the newly built ISOL facility in Orsay: ALTO. In ALTO the interaction of an electron beam with U 238 target generates a continuous spectra of Bremsstrahlung gamma radiation that triggers U 238 fission. The fission fragments are then ionized, extracted and mass-separated. The analysis of the data has shown the existence of an isomer in 31 84 Ga 53 and has enabled us to confirm known results on 32 83 Ge 51 energy levels including the gamma transition between the 1/2+ state at 247,7 KeV and the fundamental state. We have also proposed the first energy level scheme for 33 84 As 51 . In order to understand the structure of the nucleus we have used the Thankappan and True model that gives a description of the coupling between the pair-pair core (half-magical) and the single nucleon. This model applied to the N=51 chain ( 38 89 Sr 51 , 36 87 Kr 51 , 34 85 Se 51 , 32 83 Ge 51 and 30 81 Zn 51 ) has allowed us to see the main features of odd isotope structure. We have also confirmed previous results concerning the nature of the states in the following decay 31 83 Ga 52 → 32 83 Ge 51

  8. Structural landscape of the proline-rich domain of Sos1 nucleotide exchange factor.

    Science.gov (United States)

    McDonald, Caleb B; Bhat, Vikas; Kurouski, Dmitry; Mikles, David C; Deegan, Brian J; Seldeen, Kenneth L; Lednev, Igor K; Farooq, Amjad

    2013-01-01

    Despite its key role in mediating a plethora of cellular signaling cascades pertinent to health and disease, little is known about the structural landscape of the proline-rich (PR) domain of Sos1 guanine nucleotide exchange factor. Herein, using a battery of biophysical tools, we provide evidence that the PR domain of Sos1 is structurally disordered and adopts an extended random coil-like conformation in solution. Of particular interest is the observation that while chemical denaturation of PR domain results in the formation of a significant amount of polyproline II (PPII) helices, it has little or negligible effect on its overall size as measured by its hydrodynamic radius. Our data also show that the PR domain displays a highly dynamic conformational basin in agreement with the knowledge that the intrinsically unstructured proteins rapidly interconvert between an ensemble of conformations. Collectively, our study provides new insights into the conformational equilibrium of a key signaling molecule with important consequences on its physiological function. Copyright © 2013 Elsevier B.V. All rights reserved.

  9. Protein Phosphorylation and Mineral Binding Affect the Secondary Structure of the Leucine-Rich Amelogenin Peptide

    Directory of Open Access Journals (Sweden)

    Hajime Yamazaki

    2017-06-01

    Full Text Available Previously, we have shown that serine-16 phosphorylation in native full-length porcine amelogenin (P173 and the Leucine-Rich Amelogenin Peptide (LRAP(+P, an alternative amelogenin splice product, affects protein assembly and mineralization in vitro. Notably, P173 and LRAP(+P stabilize amorphous calcium phosphate (ACP and inhibit hydroxyapatite (HA formation, while non-phosphorylated counterparts (rP172, LRAP(−P guide the growth of ordered bundles of HA crystals. Based on these findings, we hypothesize that the phosphorylation of full-length amelogenin and LRAP induces conformational changes that critically affect its capacity to interact with forming calcium phosphate mineral phases. To test this hypothesis, we have utilized Fourier transform infrared spectroscopy (FTIR to determine the secondary structure of LRAP(−P and LRAP(+P in the absence/presence of calcium and selected mineral phases relevant to amelogenesis; i.e., hydroxyapatite (HA: an enamel crystal prototype and (ACP: an enamel crystal precursor phase. Aqueous solutions of LRAP(−P or LRAP(+P were prepared with or without 7.5 mM of CaCl2 at pH 7.4. FTIR spectra of each solution were obtained using attenuated total reflectance, and amide-I peaks were analyzed to provide secondary structure information. Secondary structures of LRAP(+P and LRAP(−P were similarly assessed following incubation with suspensions of HA and pyrophosphate-stabilized ACP. Amide I spectra of LRAP(−P and LRAP(+P were found to be distinct from each other in all cases. Spectra analyses showed that LRAP(−P is comprised mostly of random coil and β-sheet, while LRAP(+P exhibits more β-sheet and α-helix with little random coil. With added Ca, the random coil content increased in LRAP(−P, while LRAP(+P exhibited a decrease in α-helix components. Incubation of LRAP(−P with HA or ACP resulted in comparable increases in β-sheet structure. Notably, however, LRAP(+P secondary structure was more affected by

  10. Consequences of buffelgrass pasture development for primary productivity, perennial plant richness, and vegetation structure in the drylands of Sonora, Mexico.

    Science.gov (United States)

    Franklin, Kimberly; Molina-Freaner, Francisco

    2010-12-01

    In large parts of northern Mexico native plant communities are being converted to non-native buffelgrass (Pennisetum ciliare) pastures, and this conversion could fundamentally alter primary productivity and species richness. In Sonora, Mexico land conversion is occurring at a regional scale along a rainfall-driven gradient of primary productivity, across which native plant communities transition from desert scrub to thorn scrub. We used a paired sampling design to compare a satellite-derived index of primary productivity, richness of perennial plant species, and canopy-height profiles of native plant communities with buffelgrass pastures. We sampled species richness across a gradient of primary productivity in desert scrub and thorn scrub vegetation to examine the influence of site productivity on the outcomes of land conversion. We also examined the influence of pasture age on species richness of perennial plants. Index values of primary productivity were lower in buffelgrass pastures than in native vegetation, which suggests a reduction in primary productivity. Land conversion reduced species richness by approximately 50% at local and regional scales, reduced tree and shrub cover by 78%, and reduced canopy height. Land conversion disproportionately reduced shrub species richness, which reflects the common practice among Sonoran ranchers of conserving certain tree and cactus species. Site productivity did not affect the outcomes of land conversion. The age of a buffelgrass pasture was unrelated to species richness within the pasture, which suggests that passive recovery of species richness to preconversion levels is unlikely. Our findings demonstrate that land conversion can result in large losses of plant species richness at local and regional scales and in substantial changes to primary productivity and vegetation structure, which casts doubt on the feasibility of restoring native plant communities without active intervention on the part of land managers.

  11. Investigation of the single Particle Structure of the neutron-rich Sodium Isotopes $^{27-31}\\!$Na

    CERN Document Server

    2002-01-01

    We propose to study the single particle structure of the neutron-rich isotopes $^{27-31}\\!$Na. These isotopes will be investigated via neutron pickup reactions in inverse kinematics on a deuterium and a beryllium target. Scattered beam particles and transfer products are detected in a position sensitive detector located around 0$^\\circ$. De-excitation $\\gamma$-rays emitted after an excited state has been populated will be registered by the MINIBALL Germanium array. The results will shed new light on the structure of the neutron-rich sodium isotopes and especially on the region of strong deformation around the N=20 nucleus $^{31}\\!$Na.

  12. Enzymatic preparation of "functional oil" rich in feruloylated structured lipids with solvent-free ultrasound pretreatment.

    Science.gov (United States)

    Zhang, Haiping; Zheng, Mingming; Shi, Jie; Tang, Hu; Deng, Qianchun; Huang, Fenghong; Luo, Dan

    2018-05-15

    In this study, a series of functional oils rich in feruloylated structured lipids (FSLs) was prepared by enzymatic transesterification of ethyl ferulate (EF) with triglycerides under ultrasound pretreatment. A conversion of more than 92.7% and controllable FSLs (3.1%-26.3%) can be obtained under the following conditions: 16% enzyme, substrate ratio 1:5 (oil/EF, mol/mol), 85 °C, ultrasound 1 h, pulse mode 3 s/3s (working/waiting), and 17.0 W/mL. Compared to conventional mechanical stirring, the activation energy decreased from 50.0 kJ/mol to 40.7 kJ/mol. The apparent kinetic constant increased by more than 13 times, and the time required for the maximum conversion reduced sharply from 20-60 h to 4-6h, which was the fastest rate for enzymatic synthesis of FSLs. The antioxidant activities of the functional oil significantly increased 1.0- to 8.1-fold more than that of the raw oil. The functional oil could be widely applied in various fields of functional foods. Copyright © 2017 Elsevier Ltd. All rights reserved.

  13. Structure study and properties of rare earth-rich glassed for the conditioning of nuclear waste

    International Nuclear Information System (INIS)

    Bardez, I.

    2004-11-01

    A new nuclear glass composition, able to immobilize highly radioactive liquid wastes from high burn-up UO 2 fuel, was established and its structure studied. The composition of the selected rare earth-rich glass is (molar %): 61.79 SiO 2 - 8.94 B 2 O 3 - 3.05 Al 2 O 3 - 14.41 Na 2 O - 6.32 CaO - 1.89 ZrO 2 - 3.60 RE 2 O 3 (with RE = La, Ce, Pr and Nd) The aim of this study was to determine the local environment of the rare earth in this glass and also to glean information about the effect of glass composition on the rare earth neighbouring (influence of Si, B, Al, Na and Ca contents). To this end, several series of glasses, prepared from the baseline glass, were studied by different characterisation methods such as EXAFS spectroscopy at the neodymium L III -edge, optical absorption spectroscopy, Raman spectroscopy and 29 Si, 27 Al and 11 B MAS-NMR. By coupling all the results obtained, several hypotheses about the nature of the rare earth neighbouring in the glass were proposed. (author)

  14. Structure and properties of rare earth-rich glassed for nuclear waste immobilisation

    International Nuclear Information System (INIS)

    Bardez, I.

    2004-11-01

    A new nuclear glass composition, able to immobilize highly radioactive liquid wastes from high burn-up UO 2 fuel, was established and its structure studied. The composition of the selected rare earth-rich glass is (molar %): 61.79 SiO 2 - 8.94 B 2 O 3 - 3.05 Al 2 O 3 - 14.41 Na 2 O - 6.32 CaO - 1.89 ZrO 2 - 3.60 RE 2 O 3 (with RE = La, Ce, Pr and Nd). The aim of this study was to determine the local environment of the rare earth in this glass and also to glean information about the effect of glass composition on the rare earth neighbouring (influence of Si, B, Al, Na and Ca contents). To this end, several series of glasses, prepared from the baseline glass, were studied by different characterisation methods such as EXAFS spectroscopy at the neodymium LIII-edge, optical absorption spectroscopy, Raman spectroscopy and 29 Si, 27 Al and 11 B MAS-NMR. By coupling all the results obtained, several hypotheses about the nature of the rare earth neighbouring in the glass were proposed. (author)

  15. Synthesis, electronic structure, elastic properties, and interfacial behavior of icosahedral boron-rich solids

    Energy Technology Data Exchange (ETDEWEB)

    Hunold, Oliver

    2017-08-01

    Boron-rich solids are commonly characterized by icosahedral clusters, where 12 B atoms form an icosahedron, giving rise to outstanding mechanical and transport properties. However, broader applications are limited due to the high synthesis temperature required to obtain the icosahedra-based crystalline structure. Utilizing high power pulsed magnetron sputtering (HPPMS), the deposition temperature may be lowered as compared to direct current magnetron sputtering by enhanced surface diffusion. Therefore, HPPMS was utilized to investigate the influence of the substrate temperature on the structural evolution of B-rich Al-Y-B thin films. The formation of the intended AlYB{sub 14} phase together with the (Y,Al)B{sub 6} impurity phase, containing 1.8 at.% less B than AlYB{sub 14}, was observed at a growth temperature of 800 C and hence 600 C below the bulk synthesis temperature. Based on density functional theory (DFT) calculations it is inferred that minute compositional variations may lead to formation of competing phases, such as (Y,Al)B{sub 6}. Furthermore, 800 C still limits the usage significantly. Therefore, quantum mechanical material design was applied to identify phases with even higher phase stabilities compared to AlYB{sub 14}. Phase stability of T{sub 0.75}Y{sub 0.75}B{sub 14} (T= Sc, Ti, V, Y, Zr, Nb, Si) critically depends on the exact magnitude of charge transferred by T and Y to the B icosahedra. The highest phase stabilities have been identified for Sc{sub 0.75}Y{sub 0.75}B{sub 14}, Ti{sub 0.75}Y{sub 0.75}B{sub 14}, and Zr{sub 0.75}Y{sub 0.75}B{sub 14}. ln combination with Young's modulus values up to 517 GPa these phases are very interesting from a wear-resistance point of view. Still high synthesis temperatures limit the use of such systems onto technologically relevant substrate materials. However, amorphous B-rich solids, which can be synthesized without additional heating, exhibit attractive mechanical and electrical properties. Within these

  16. Study of the structure of yrast bands of neutron-rich 114-124Pd isotopes

    Science.gov (United States)

    Chaudhary, Ritu; Devi, Rani; Khosa, S. K.

    2018-02-01

    The projected shell model calculations have been carried out in the neutron-rich 114-124Pd isotopic mass chain. The results have been obtained for the deformation systematics of E(2+1) and E(4+1)/E({2}+1) values, BCS subshell occupation numbers, yrast spectra, backbending phenomena, B( E2) transition probabilities and g-factors in these nuclei. The observed systematics of E(2+1) values and R_{42} ratios in the 114-124Pd isotopic mass chain indicate that there is a decrease of collectivity as the neutron number increases from 68 to 78. The occurrence of backbending in these nuclei as well as the changes in the calculated B( E2) transition probabilities and g -factors predict that there are changes in the structure of yrast bands in these nuclei. These changes occur at the spin where there is crossing of g-band by 2-qp bands. The predicted backbendings and predicted values of B( E2)s and g-factors in some of the isotopes need to be confirmed experimentally.

  17. Atomic Scale Structure-Chemistry Relationships at Oxide Catalyst Surfaces and Interfaces

    Science.gov (United States)

    McBriarty, Martin E.

    Oxide catalysts are integral to chemical production, fuel refining, and the removal of environmental pollutants. However, the atomic-scale phenomena which lead to the useful reactive properties of catalyst materials are not sufficiently understood. In this work, the tools of surface and interface science and electronic structure theory are applied to investigate the structure and chemical properties of catalytically active particles and ultrathin films supported on oxide single crystals. These studies focus on structure-property relationships in vanadium oxide, tungsten oxide, and mixed V-W oxides on the surfaces of alpha-Al2O3 and alpha-Fe2O 3 (0001)-oriented single crystal substrates, two materials with nearly identical crystal structures but drastically different chemical properties. In situ synchrotron X-ray standing wave (XSW) measurements are sensitive to changes in the atomic-scale geometry of single crystal model catalyst surfaces through chemical reaction cycles, while X-ray photoelectron spectroscopy (XPS) reveals corresponding chemical changes. Experimental results agree with theoretical calculations of surface structures, allowing for detailed electronic structure investigations and predictions of surface chemical phenomena. The surface configurations and oxidation states of V and W are found to depend on the coverage of each, and reversible structural shifts accompany chemical state changes through reduction-oxidation cycles. Substrate-dependent effects suggest how the choice of oxide support material may affect catalytic behavior. Additionally, the structure and chemistry of W deposited on alpha-Fe 2O3 nanopowders is studied using X-ray absorption fine structure (XAFS) measurements in an attempt to bridge single crystal surface studies with real catalysts. These investigations of catalytically active material surfaces can inform the rational design of new catalysts for more efficient and sustainable chemistry.

  18. Structures of plutonium coordination compounds: A review of past work, recent single crystal x-ray diffraction results, and what we're learning about plutonium coordination chemistry

    Science.gov (United States)

    Neu, M. P.; Matonic, J. H.; Smith, D. M.; Scott, B. L.

    2000-07-01

    The compounds we have isolated and characterized include plutonium(III) and plutonium(IV) bound by ligands with a range of donor types and denticity (halide, phosphine oxide, hydroxamate, amine, sulfide) in a variety of coordination geometries. For example, we have obtained the first X-ray structure of Pu(III) complexed by a soft donor ligand. Using a "one pot" synthesis beginning with Pu metal strips and iodine in acetonitrile and adding trithiacyclononane we isolated the complex, PuI3(9S3)(MeCN)2 (Figure 1). On the other end of the coordination chemistry spectrum, we have obtained the first single crystal structure of the Pu(IV) hexachloro anion (Figure 2). Although this species has been used in plutonium purification via anion exchange chromatography for decades, the bond distances and exact structure were not known. We have also characterized the first plutonium-biomolecule complex, Pu(IV) bound by the siderophore desferrioxamine E.In this presentation we will review the preparation, structures, and importance of previously known coordination compounds and of those we have recently isolated. We will show the coordination chemistry of plutonium is rich and varied, well worth additional exploration.

  19. Impacts of operating conditions and solution chemistry on osmotic membrane structure and performance

    KAUST Repository

    Wong, Mavis C.Y.; Martinez, Kristina; Ramon, Guy Z.; Hoek, Eric M.V.

    2012-01-01

    Herein, we report on changes in the performance of a commercial cellulose triacetate (CTA) membrane, imparted by varied operating conditions and solution chemistries. Changes to feed and draw solution flow rate did not significantly alter the CTA membrane's water permeability, salt permeability, or membrane structural parameter when operated with the membrane skin layer facing the draw solution (PRO-mode). However, water and salt permeability increased with increasing feed or draw solution temperature, while the membrane structural parameter decreased with increasing draw solution, possibly due to changes in polymer intermolecular interactions. High ionic strength draw solutions may de-swell the CTA membrane via charge neutralization, which resulted in lower water permeability, higher salt permeability, and lower structural parameter. This observed trend was further exacerbated by the presence of divalent cations which tends to swell the polymer to a greater extent. Finally, the calculated CTA membrane's structural parameter was lower and less sensitive to external factors when operated in PRO-mode, but highly sensitive to the same factors when the skin layer faced the feed solution (FO-mode), presumably due to swelling/de-swelling of the saturated porous substructure by the draw solution. This is a first attempt aimed at systematically evaluating the changes in performance of the CTA membrane due to operating conditions and solution chemistry, shedding new insight into the possible advantages and disadvantages of this material in certain applications. © 2011 Elsevier B.V.

  20. Some aspects of the chemistry of fast reactor fuel, structural material and decontamination

    International Nuclear Information System (INIS)

    Ganesan, V.

    2012-01-01

    The chemistry of materials pertaining to fast reactors is both fascinating and challenging considering the nature of materials involved such as the fuel, coolant, control and shielding materials in addition to the interactions between the structural materials and the fuel/coolant depending on the nature and conditions involved. The different chemical forms of fuel materials, the need to operate up to high burnups with consequent interactions of the fuel with clad materials, the need to close the fuel cycle by recovery of the fuel materials from spent fuels for refabrication and the necessity to manage the waste, throw a host of challenges which make their study scientifically interesting and technologically important. The use of liquid sodium as coolant in fast reactor heat transport systems combined with its inherent chemical reactivity opens up an interesting branch of chemistry involving liquid sodium especially in contact with structural materials during normal operation of the reactor and with fuels in the event of fuel pin failure. The phenomenon of sodium wetting and the associated corrosion of structural materials in contact with it combined with the need to carryout decontamination of such materials make it interesting to examine and evaluate their suitability for reuse without compromising on their structural integrity. Boron being the material of choice for control and shielding applications in fast reactors with varying isotopic enrichment and the technological challenge to produce large quantities of boron carbide makes it unique. Some of these aspects are addressed in this paper. (author)

  1. Impacts of operating conditions and solution chemistry on osmotic membrane structure and performance

    KAUST Repository

    Wong, Mavis C.Y.

    2012-02-01

    Herein, we report on changes in the performance of a commercial cellulose triacetate (CTA) membrane, imparted by varied operating conditions and solution chemistries. Changes to feed and draw solution flow rate did not significantly alter the CTA membrane\\'s water permeability, salt permeability, or membrane structural parameter when operated with the membrane skin layer facing the draw solution (PRO-mode). However, water and salt permeability increased with increasing feed or draw solution temperature, while the membrane structural parameter decreased with increasing draw solution, possibly due to changes in polymer intermolecular interactions. High ionic strength draw solutions may de-swell the CTA membrane via charge neutralization, which resulted in lower water permeability, higher salt permeability, and lower structural parameter. This observed trend was further exacerbated by the presence of divalent cations which tends to swell the polymer to a greater extent. Finally, the calculated CTA membrane\\'s structural parameter was lower and less sensitive to external factors when operated in PRO-mode, but highly sensitive to the same factors when the skin layer faced the feed solution (FO-mode), presumably due to swelling/de-swelling of the saturated porous substructure by the draw solution. This is a first attempt aimed at systematically evaluating the changes in performance of the CTA membrane due to operating conditions and solution chemistry, shedding new insight into the possible advantages and disadvantages of this material in certain applications. © 2011 Elsevier B.V.

  2. Vanadium-rich tourmaline from graphitic rocks at Bítovánky, Czech republic; compositional variation, crystal structure

    Czech Academy of Sciences Publication Activity Database

    Cempírek, J.; Houzar, S.; Novák, M.; Selway, J.B.; Šrein, Vladimír

    2006-01-01

    Roč. 28, Spec. pap. (2006), s. 39-41 ISSN 1896-2203. [Central European Mineralogical Conference /1./. Vyšná Boca, 11.09.2006-15.09.2006] Institutional research plan: CEZ:AV0Z30460519 Keywords : V-rich tourmaline * compositional variation * crystal structure Subject RIV: DB - Geology ; Mineralogy

  3. Impact of the Fused Deposition (FDM Printing Process on Polylactic Acid (PLA Chemistry and Structure

    Directory of Open Access Journals (Sweden)

    Michael Arthur Cuiffo

    2017-06-01

    Full Text Available Polylactic acid (PLA is an organic polymer commonly used in fused deposition (FDM printing and biomedical scaffolding that is biocompatible and immunologically inert. However, variations in source material quality and chemistry make it necessary to characterize the filament and determine potential changes in chemistry occurring as a result of the FDM process. We used several spectroscopic techniques, including laser confocal microscopy, Fourier transform infrared (FTIR spectroscopy and photoacousitc FTIR spectroscopy, Raman spectroscopy, and X-ray photoelectron spectroscopy (XPS in order to characterize both the bulk and surface chemistry of the source material and printed samples. Scanning electron microscopy (SEM and differential scanning calorimetry (DSC were used to characterize morphology, cold crystallinity, and the glass transition and melting temperatures following printing. Analysis revealed calcium carbonate-based additives which were reacted with organic ligands and potentially trace metal impurities, both before and following printing. These additives became concentrated in voids in the printed structure. This finding is important for biomedical applications as carbonate will impact subsequent cell growth on printed tissue scaffolds. Results of chemical analysis also provided evidence of the hygroscopic nature of the source material and oxidation of the printed surface, and SEM imaging revealed micro- and submicron-scale roughness that will also impact potential applications.

  4. The chemistry and structure of nickel–tungsten coatings obtained by pulse galvanostatic electrodeposition

    International Nuclear Information System (INIS)

    Argañaraz, M.P. Quiroga; Ribotta, S.B.; Folquer, M.E.; Zelaya, E.; Llorente, C.; Ramallo-López, J.M.; Benítez, G.; Rubert, A.; Gassa, L.M.; Vela, M.E.; Salvarezza, R.C.

    2012-01-01

    A detailed characterization of electrodeposited Ni-W coatings prepared by pulse electrodeposition on steel and copper substrates is presented. The coatings were obtained at high current pulse frequency and show high microhardness and absence of brittleness. The surface of the coating consists of nanometer sized crystals forming a cauliflower-like structure protected by a mixture of nickel and tungsten oxides. The cauliflower structure is preserved into the bulk coating that exhibits an average composition ≈70 at% Ni-30 at% W. Different phases are observed in the bulk structure: a W-rich amorphous phase (≈40%) and Ni-rich crystalline phases (≈60%). The crystalline phases consist of crystalline domains ≈7 nm in size of Ni(W) (fcc) solid solution (12 at% W content) and a minor Ni 4 W component (less than 10%). The amorphous phase exhibits a less compact Ni-W structure where some amount of C could also be present. Oxidized W species cannot be detected in the bulk coating, thus discarding the presence of significant amounts of tungsten carbide, tungstates or citrate–tungsten complexes. Our results shed light on controversial points related to the chemical composition and demonstrate the complex structure of this system.

  5. Organic chemistry

    International Nuclear Information System (INIS)

    2003-08-01

    This book with sixteen chapter explains organic chemistry on linkage isomerism such as alkane, cycloalkane, alkene, aromatic compounds, stereo selective isomerization, aromatic compounds, stereo selective isomerization, organic compounds, stereo selective isomerization, organic halogen compound, alcohol, ether, aldehyde and ketone, carboxylic acid, dicarboxylic acid, fat and detergent, amino, carbohydrate, amino acid and protein, nucleotide and nucleic acid and spectroscopy, a polymer and medical chemistry. Each chapter has introduction structure and characteristic and using of organic chemistry.

  6. Diffusion tractography and graph theory analysis reveal the disrupted rich-club organization of white matter structural networks in early Tourette Syndrome children

    Science.gov (United States)

    Wen, Hongwei; Liu, Yue; Wang, Shengpei; Zhang, Jishui; Peng, Yun; He, Huiguang

    2017-03-01

    Tourette syndrome (TS) is a childhood-onset neurobehavioral disorder. At present, the topological disruptions of the whole brain white matter (WM) structural networks remain poorly understood in TS children. Considering the unique position of the topologically central role of densely interconnected brain hubs, namely the rich club regions, therefore, we aimed to investigate whether the rich club regions and their related connections would be particularly vulnerable in early TS children. In our study, we used diffusion tractography and graph theoretical analyses to explore the rich club structures in 44 TS children and 48 healthy children. The structural networks of TS children exhibited significantly increased normalized rich club coefficient, suggesting that TS is characterized by increased structural integrity of this centrally embedded rich club backbone, potentially resulting in increased global communication capacity. In addition, TS children showed a reorganization of rich club regions, as well as significantly increased density and decreased number in feeder connections. Furthermore, the increased rich club coefficients and feeder connections density of TS children were significantly positively correlated to tic severity, indicating that TS may be characterized by a selective alteration of the structural connectivity of the rich club regions, tending to have higher bridging with non-rich club regions, which may increase the integration among tic-related brain circuits with more excitability but less inhibition for information exchanges between highly centered brain regions and peripheral areas. In all, our results suggest the disrupted rich club organization in early TS children and provide structural insights into the brain networks.

  7. Three-dimensional structure and cytokine distribution of platelet-rich fibrin.

    Science.gov (United States)

    Bai, Meng-Yi; Wang, Ching-Wei; Wang, Jyun-Yi; Lin, Ming-Fang; Chan, Wing P

    2017-02-01

    Previous reports have revealed that several cytokines (including platelet-derived growth factor-BB, transforming growth factors-β1 and insulin-like growth factor-1) can enhance the rate of bone formation and synthesis of extracellular matrix in orthopaedics or periodontology. This study aimed to determine the concentration of cytokines within platelet-rich fibrin microstructures and investigate whether there are differences in the different portions of platelet-rich fibrin, which has implications for proper clinical use of platelet-rich fibrin gel. Whole blood was obtained from six New Zealand rabbits (male, 7 to 39 weeks old, weight 2.7-4 kg); it was then centrifuged for preparation of platelet-rich fibrin gels and harvest of plasma. The resultant platelet-rich fibrin gels were used for cytokine determination, histological analyses and scanning electron microscopy. All plasmas obtained were subject to the same cytokine determination assays for the purpose of comparison. Cytokines platelet-derived growth factor-BB and transforming growth factor-β1 formed concentration gradients from high at the red blood cell end of the platelet-rich fibrin gel (p=1.88×10-5) to low at the plasma end (p=0.19). Insulin-like growth factor-1 concentrations were similar at the red blood cell and plasma ends. The porosities of the platelet-rich fibrin samples taken in sequence from the red blood cell end to the plasma end were 6.5% ± 4.9%, 24.8% ± 7.5%, 30.3% ± 8.5%, 41.4% ± 12.3%, and 40.3% ± 11.7%, respectively, showing a gradual decrease in the compactness of the platelet-rich fibrin network. Cytokine concentrations are positively associated with platelet-rich fibrin microstructure and portion in a rabbit model. As platelet-rich fibrin is the main entity currently used in regenerative medicine, assessing cytokine concentration and the most valuable portion of PRF gels is essential and recommended to all physicians.

  8. Three-dimensional structure and cytokine distribution of platelet-rich fibrin

    Directory of Open Access Journals (Sweden)

    Meng-Yi Bai

    Full Text Available OBJECTIVES: Previous reports have revealed that several cytokines (including platelet-derived growth factor-BB, transforming growth factors-β1 and insulin-like growth factor-1 can enhance the rate of bone formation and synthesis of extracellular matrix in orthopaedics or periodontology. This study aimed to determine the concentration of cytokines within platelet-rich fibrin microstructures and investigate whether there are differences in the different portions of platelet-rich fibrin, which has implications for proper clinical use of platelet-rich fibrin gel. METHODS: Whole blood was obtained from six New Zealand rabbits (male, 7 to 39 weeks old, weight 2.7-4 kg; it was then centrifuged for preparation of platelet-rich fibrin gels and harvest of plasma. The resultant platelet-rich fibrin gels were used for cytokine determination, histological analyses and scanning electron microscopy. All plasmas obtained were subject to the same cytokine determination assays for the purpose of comparison. RESULTS: Cytokines platelet-derived growth factor-BB and transforming growth factor-β1 formed concentration gradients from high at the red blood cell end of the platelet-rich fibrin gel (p=1.88×10-5 to low at the plasma end (p=0.19. Insulin-like growth factor-1 concentrations were similar at the red blood cell and plasma ends. The porosities of the platelet-rich fibrin samples taken in sequence from the red blood cell end to the plasma end were 6.5% ± 4.9%, 24.8% ± 7.5%, 30.3% ± 8.5%, 41.4% ± 12.3%, and 40.3% ± 11.7%, respectively, showing a gradual decrease in the compactness of the platelet-rich fibrin network. CONCLUSION: Cytokine concentrations are positively associated with platelet-rich fibrin microstructure and portion in a rabbit model. As platelet-rich fibrin is the main entity currently used in regenerative medicine, assessing cytokine concentration and the most valuable portion of PRF gels is essential and recommended to all physicians.

  9. Expression, purification and preliminary biochemical and structural characterization of the leucine rich repeat namesake domain of leucine rich repeat kinase 2.

    Science.gov (United States)

    Vancraenenbroeck, Renée; Lobbestael, Evy; Weeks, Stephen D; Strelkov, Sergei V; Baekelandt, Veerle; Taymans, Jean-Marc; De Maeyer, Marc

    2012-03-01

    Mutations in leucine-rich repeat kinase 2 (LRRK2) are the most common cause of familial Parkinson's disease. Much research effort has been directed towards the catalytic core region of LRRK2 composed of GTPase (ROC, Ras of complex proteins) and kinase domains and a connecting COR (C-terminus of ROC) domain. In contrast, the precise functions of the protein-protein interaction domains, such as the leucine-rich repeat (LRR) domain, are not known. In the present study, we modeled the LRRK2 LRR domain (LRR(LRRK2)) using a template assembly approach, revealing the presence of 14 LRRs. Next, we focused on the expression and purification of LRR(LRRK2) in Escherichia coli. Buffer optimization revealed that the protein requires the presence of a zwitterionic detergent, namely Empigen BB, during solubilization and the subsequent purification and characterization steps. This indicates that the detergent captures the hydrophobic surface patches of LRR(LRRK2) thereby suppressing its aggregation. Circular dichroism (CD) spectroscopy measured 18% α-helices and 21% β-sheets, consistent with predictions from the homology model. Size exclusion chromatography (SEC) and dynamic light scattering measurements showed the presence of a single species, with a Stokes radius corresponding to the model dimensions of a protein monomer. Furthermore, no obvious LRR(LRRK2) multimerization was detected via cross-linking studies. Finally, the LRR(LRRK2) clinical mutations did not influence LRR(LRRK2) secondary, tertiary or quaternary structure as determined via SEC and CD spectroscopy. We therefore conclude that these mutations are likely to affect putative LRR(LRRK2) inter- and intramolecular interactions. Copyright © 2011 Elsevier B.V. All rights reserved.

  10. Two genetic loci produce distinct carbohydrate-rich structural components of the Pseudomonas aeruginosa biofilm matrix.

    Science.gov (United States)

    Friedman, Lisa; Kolter, Roberto

    2004-07-01

    Pseudomonas aeruginosa forms biofilms, which are cellular aggregates encased in an extracellular matrix. Molecular genetics studies of three common autoaggregative phenotypes, namely wrinkled colonies, pellicles, and solid-surface-associated biofilms, led to the identification of two loci, pel and psl, that are involved in the production of carbohydrate-rich components of the biofilm matrix. The pel gene cluster is involved in the production of a glucose-rich matrix material in P. aeruginosa strain PA14 (L. Friedman and R. Kolter, Mol. Microbiol. 51:675-690, 2004). Here we investigate the role of the pel gene cluster in P. aeruginosa strain ZK2870 and identify a second genetic locus, termed psl, involved in the production of a mannose-rich matrix material. The 11 predicted protein products of the psl genes are homologous to proteins involved in carbohydrate processing. P. aeruginosa is thus able to produce two distinct carbohydrate-rich matrix materials. Either carbohydrate-rich matrix component appears to be sufficient for mature biofilm formation, and at least one of them is required for mature biofilm formation in P. aeruginosa strains PA14 and ZK2870. Copyright 2004 American Society for Microbiology

  11. A new titanium-bearing calcium aluminosilicate phase. 2: Crystallography and crystal chemistry of grains formed in slowly cooled melts with bulk compositions of calcium-aluminium-rich inclusions

    Science.gov (United States)

    Barber, David J.; Beckett, John R.; Paque, Julie M.; Stolper, Edward

    1994-01-01

    The crystallography and crystal chemistry of a new calcium- titanium-aluminosilicate mineral (UNK) observed in synthetic analogs to calcium-aluminum-rich inclusions (CAIs) from carbonaceous chondrites was studied by electron diffraction techniques. The unit cell is primitive hexagonal or trigonal, with a = 0.790 +/- 0.02 nm and c = 0.492 +/- 0.002 nm, similar to the lattice parameters of melilite and consistent with cell dimensions for crystals in a mixer furnace slag described by Barber and Agrell (1994). The phase frequently displays an epitactic relationship in which melilite acts as the host, with (0001)(sub UNK) parallel (001)(sub mel) and zone axis group 1 0 -1 0(sub UNK) parallel zone axis group 1 0 0(sub mel). If one of the two space groups determined by Barber and Agrell (1994) for their sample of UNK is applicable (P3m1 or P31m), then the structure is probably characterized by puckered sheets of octahedra and tetrahedra perpendicular to the c-axis with successive sheets coordinated by planar arrays of Ca. In this likely structure, each unit cell contains three Ca sites located in mirror planes, one octahedrally coordinated cation located along a three-fold axis and five tetrahedrally coordinated cations, three in mirrors and two along triads. The octahedron contains Ti but, because there are 1.3-1.9 cations of Ti/formula unit, some of the Ti must also be in tetrahedral coordination, an unusual but not unprecedented situation for a silicate. Tetrahedral sites in mirror planes would contain mostly Si, with lesser amounts of Al while those along the triads correspondingly contain mostly Al with subordinate Ti. The structural formula, therefore, can be expressed as Ca(sub 3)(sup VIII)(Ti,Al)(sup VI)(Al,Ti,Si)(sub 2)(sup IV)(Si,Al)(sub 3)(sup IV)O14 with Si + Ti = 4. Compositions of meteoritic and synthetic Ti-bearing samples of the phase can be described in terms of a binary solid solution between the end-members Ca3TiAl2Si3O14 and Ca3Ti(AlTi)(AlSi2)O14. A Ti

  12. Managing expectations: assessment of chemistry databases generated by automated extraction of chemical structures from patents.

    Science.gov (United States)

    Senger, Stefan; Bartek, Luca; Papadatos, George; Gaulton, Anna

    2015-12-01

    First public disclosure of new chemical entities often takes place in patents, which makes them an important source of information. However, with an ever increasing number of patent applications, manual processing and curation on such a large scale becomes even more challenging. An alternative approach better suited for this large corpus of documents is the automated extraction of chemical structures. A number of patent chemistry databases generated by using the latter approach are now available but little is known that can help to manage expectations when using them. This study aims to address this by comparing two such freely available sources, SureChEMBL and IBM SIIP (IBM Strategic Intellectual Property Insight Platform), with manually curated commercial databases. When looking at the percentage of chemical structures successfully extracted from a set of patents, using SciFinder as our reference, 59 and 51 % were also found in our comparison in SureChEMBL and IBM SIIP, respectively. When performing this comparison with compounds as starting point, i.e. establishing if for a list of compounds the databases provide the links between chemical structures and patents they appear in, we obtained similar results. SureChEMBL and IBM SIIP found 62 and 59 %, respectively, of the compound-patent pairs obtained from Reaxys. In our comparison of automatically generated vs. manually curated patent chemistry databases, the former successfully provided approximately 60 % of links between chemical structure and patents. It needs to be stressed that only a very limited number of patents and compound-patent pairs were used for our comparison. Nevertheless, our results will hopefully help to manage expectations of users of patent chemistry databases of this type and provide a useful framework for more studies like ours as well as guide future developments of the workflows used for the automated extraction of chemical structures from patents. The challenges we have encountered

  13. Guangxi crustal structural evolution and the formation and distribution regularities of U-rich strata

    International Nuclear Information System (INIS)

    Kang Zili.

    1989-01-01

    Based on summing up Guangxi geotectonic features and evolutionary regularities, this paper discusses the occurrence features, formation conditions and time-space distribution regularities of various U-rich strata during the development of geosyncline, platform and diwa stages, Especially, during diwa stage all those U-rich strata might be reworked to a certain degree and resulted in the mobilization of uranium, then enriching to form polygenetic composite uranium ore deposits with stratabound features. This study will be helpful for prospecting in the region

  14. Molecular cloning and construction of the coding region for human acetylcholinesterase reveals a G + C-rich attenuating structure

    International Nuclear Information System (INIS)

    Soreq, H.; Ben-Aziz, R.; Prody, C.A.; Seidman, S.; Gnatt, A.; Neville, L.; Lieman-Hurwitz, J.; Lev-Lehman, E.; Ginzberg, D.; Lapidot-Lifson, Y.; Zakut, H.

    1990-01-01

    To study the primary structure of human acetylcholinesterase and its gene expression and amplification, cDNA libraries from human tissues expressing oocyte-translatable AcChoEase mRNA were constructed and screened with labeled oligodeoxynucleotide probes. Several cDNA clones were isolated that encoded a polypeptide with ≥50% identically aligned amino acids to Torpedo AcChoEase and human butyrylcholinesterase. However, these cDNA clones were all truncated within a 300-nucleotide-long G + C-rich region with a predicted pattern of secondary structure having a high Gibbs free energy downstream from the expected 5' end of the coding region. Screening of a genomic DNA library revealed the missing 5' domain. When ligated to the cDNA and constructed into a transcription vector, this sequence encoded a synthetic mRNA translated in microinjected oocytes into catalytically active AcChoEase with marked preference for acetylthiocholine over butyrylthiocholine as a substrate, susceptibility to inhibition by the AcChoEase inhibitor BW284C51, and resistance to the AcChoEase inhibitor tetraisopropylpyrophosphoramide. Blot hybridization of genomic DNA from different individuals carrying amplified AcChoEase genes revealed variable intensities and restriction patterns with probes from the regions upstream and downstream from the predicted G + C-rich structure. Thus, the human AcChoEase gene includes a putative G + C-rich attenuator domain and is subject to structural alterations in cases of AcChoEase gene amplification

  15. Crystal structure refinements of tetragonal (OH,F)-rich spessartine and henritermierite garnets

    Energy Technology Data Exchange (ETDEWEB)

    Antao, Sytle M.; Cruickshank, Laura A.

    2018-01-30

    Cubic garnet (space group Ia\\overline 3 d) has the general formulaX3Y2Z3O12, whereX,YandZare cation sites. In the tetragonal garnet (space groupI41/acd), the corresponding cation sites areX1 andX2,Y, andZ1 andZ2. In both space groups only theYsite is the same. The crystal chemistry of a tetragonal (OH,F)-rich spessartine sample from Tongbei, near Yunxiao, Fujian Province, China, with compositionX(Mn2.82Fe^{2+}_{0.14}Ca0.04)Σ3Y{Al1.95Fe^{3+}_{0.05}}Σ2Z[(SiO4)2.61(O4H4)0.28(F4)0.11]Σ3(Sps94Alm5Grs1) was studied with single-crystal X-ray diffraction and space groupI41/acd. The deviation of the unit-cell parameters from cubic symmetry is small [a= 11.64463(1),c= 11.65481 (2) Å,c/a= 1.0009]. Point analyses and back-scattered electron images, obtained by electron-probe microanalysis, indicate a homogeneous composition. TheZ2 site is fully occupied, but theZ1 site contains vacancies. The occupiedZ1 andZ2 sites with Si atoms are surrounded by four O atoms, as in anhydrous cubic garnets. Pairs of split sites are O1 with F11 and O2 with O22. When theZ1 site is vacant, a larger [(O2H2)F2] tetrahedron is formed by two OH and two F anions in the O22 and F11 sites, respectively. This [(O2

  16. Organic chemistry as a language and the implications of chemical linguistics for structural and retrosynthetic analyses.

    Science.gov (United States)

    Cadeddu, Andrea; Wylie, Elizabeth K; Jurczak, Janusz; Wampler-Doty, Matthew; Grzybowski, Bartosz A

    2014-07-28

    Methods of computational linguistics are used to demonstrate that a natural language such as English and organic chemistry have the same structure in terms of the frequency of, respectively, text fragments and molecular fragments. This quantitative correspondence suggests that it is possible to extend the methods of computational corpus linguistics to the analysis of organic molecules. It is shown that within organic molecules bonds that have highest information content are the ones that 1) define repeat/symmetry subunits and 2) in asymmetric molecules, define the loci of potential retrosynthetic disconnections. Linguistics-based analysis appears well-suited to the analysis of complex structural and reactivity patterns within organic molecules. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Structure and chemistry of the Si(111)/AlN interface

    Science.gov (United States)

    Radtke, G.; Couillard, M.; Botton, G. A.; Zhu, D.; Humphreys, C. J.

    2012-01-01

    We investigate the atomic structure and the chemistry of the Si(111)/AlN interface for an AlN film grown at low-temperature (735 °C) by metalorganic vapor phase epitaxy. A heterogeneous interface is formed from the alternation of crystallographically abrupt and partly amorphous regions. The polarity of the AlN film, along with the projected atomic structure of the crystalline interface, is retrieved using high-angle annular dark field imaging, and a model, based on these experimental observations, is proposed for the bonding at the interface. Electron energy-loss spectrum-imaging, however, also reveals a chemical intermixing, placing our growth conditions at the onset of SiNx interlayer formation.

  18. Probing chemistry within the membrane structure of wood with soft X-ray spectral microscopy

    International Nuclear Information System (INIS)

    Cody, George D.

    2000-01-01

    Scanning Transmission Soft X-ray spectral microscopy on Carbon's 1s absorption edge reveals the distribution of structural biopolymers within cell membrane regions of modern cedar and oak. Cellulose is extremely susceptible to beam damage. Spectroscopic studies of beam damage reveals that the chemical changes resulting from secondary electron impact may be highly selective and is consistent with hydroxyl eliminations and structural rearrangement of pyranose rings in alpha-cellulose to hydroxyl substituted γ pyrones. A study of acetylated cellulose demonstrates significantly different chemistry; principally massive decarboxylation. Defocusing the beam to a 2 μm spot size allows for the acquisition of 'pristine' cellulose spectra. Spectral deconvolution is used to assess the distribution of lignin and cellulose in the different regions of the cell membrane. Using the intensity of the hydroxylated aromatic carbons 1s-π * transition, the ratio of coniferyl and syringyl based lignin within the middle lamellae and secondary cell wall of oak, an angiosperm can be determined

  19. Structure and chemistry of passivated SiC/SiO{sub 2} interfaces

    Energy Technology Data Exchange (ETDEWEB)

    Houston Dycus, J.; Xu, Weizong; LeBeau, James M. [Department of Materials Science and Engineering, North Carolina State University, Raleigh, North Carolina 27695-7907 (United States); Lichtenwalner, Daniel J.; Hull, Brett; Palmour, John W. [Power Devices R& D, Wolfspeed, A Cree Company, Research Triangle Park, North Carolina 27709 (United States)

    2016-05-16

    Here, we report on the chemistry and structure of 4H-SiC/SiO{sub 2} interfaces passivated either by nitric oxide annealing or Ba deposition. Using aberration corrected scanning transmission electron microscopy and spectroscopy, we find that Ba and N remain localized at SiC/SiO{sub 2} interface after processing. Further, we find that the passivating species can introduce significant changes to the near-interface atomic structure of SiC. Specifically, we quantify significant strain for nitric oxide annealed sample where Si dangling bonds are capped by N. In contrast, strain is not observed at the interface of the Ba treated samples. Finally, we place these results in the context of field effect mobility.

  20. New directions towards structure formation and stability of protein-rich foods from globular proteins

    NARCIS (Netherlands)

    Purwanti, N.; Goot, van der A.J.; Boom, R.M.; Vereijken, J.M.

    2010-01-01

    Concentrated protein-rich foods have strong potential to be developed in terms of health and well-being roles. Unfortunately, limitations in creating products with the rights texture and stability hinder the use of those products by consumers. Main reason is that the formation of micro- and

  1. Structural and isotopic analysis of kerogens in sediments rich in free sulfurised Botryococcus braunii biomarkers

    NARCIS (Netherlands)

    Sinninghe Damsté, J.S.; Grice, K.; Schouten, S.; Blokker, P.; Derenne, S.; Largeau, C.; Nissenbaum, A.

    2003-01-01

    Type I kerogens of two relatively immature, unusual hypersaline sediments [with extracts rich in sulfurised Botryococcus braunii (B. braunii) biomarkers] of Miocene/Pliocene age from the Sdom Formation (Dead Sea, Israel), have been investigated using a variety of organic geochemical techniques. Py

  2. Terrain and vegetation structural influences on local avian species richness in two mixed-conifer forests

    Science.gov (United States)

    Jody C. Vogeler; Andrew T. Hudak; Lee A. Vierling; Jeffrey Evans; Patricia Green; Kerri T. Vierling

    2014-01-01

    Using remotely-sensed metrics to identify regions containing high animal diversity and/or specific animal species or guilds can help prioritize forest management and conservation objectives across actively managed landscapes. We predicted avian species richness in two mixed conifer forests, Moscow Mountain and Slate Creek, containing different management contexts and...

  3. Chemistry in protoplanetary disks

    Science.gov (United States)

    Semenov, D. A.

    2012-01-01

    In this lecture I discuss recent progress in the understanding of the chemical evolution of protoplanetary disks that resemble our Solar system during the first ten million years. At the verge of planet formation, strong variations of temperature, density, and radiation intensities in these disks lead to a layered chemical structure. In hot, dilute and heavily irradiated atmosphere only simple radicals, atoms, and atomic ions can survive, formed and destroyed by gas-phase processes. Beneath the atmosphere a partly UV-shielded, warm molecular layer is located, where high-energy radiation drives rich chemistry, both in the gas phase and on dust surfaces. In a cold, dense, dark disk midplane many molecules are frozen out, forming thick icy mantles where surface chemistry is active and where complex (organic) species are synthesized.

  4. The 2009 Nobel Prize in Chemistry: Thomas A. Steitz and the structure of the ribosome.

    Science.gov (United States)

    Zhao, Peter

    2011-06-01

    Over the past 200 years, there have been countless groundbreaking discoveries in biology and medicine at Yale University. However, one particularly noteworthy discovery with profoundly important and broad consequences happened here in just the past two decades. In 2009, Thomas Steitz, the Sterling Professor of Molecular Biophysics & Biochemistry, was awarded the Nobel Prize in Chemistry for "studies of the structure and function of the ribosome," along with Venkatraman Ramakrishnan of the MRC Laboratory of Molecular Biology and Ada E. Yonath of the Weizmann Institute of Science. This article covers the historical context of Steitz's important discovery, the techniques his laboratory used to study the ribosome, and the impact that this research has had, and will have, on the future of biological and medical research.

  5. Probing the chemistry, electronic structure and redox energetics in pentavalent organometallic actinide complexes

    Energy Technology Data Exchange (ETDEWEB)

    Graves, Christopher R [Los Alamos National Laboratory; Vaughn, Anthony E [Los Alamos National Laboratory; Morris, David E [Los Alamos National Laboratory; Kiplinger, Jaqueline L [Los Alamos National Laboratory

    2008-01-01

    Complexes of the early actinides (Th-Pu) have gained considerable prominence in organometallic chemistry as they have been shown to undergo chemistries not observed with their transition- or lanthanide metal counterparts. Further, while bonding in f-element complexes has historically been considered to be ionic, the issue of covalence remains a subject of debate in the area of actinide science, and studies aimed at elucidating key bonding interactions with 5f-orbitals continue to garner attention. Towards this end, our interests have focused on the role that metal oxidation state plays in the structure, reactivity and spectral properties of organouranium complexes. We report our progress in the synthesis of substituted U{sup V}-imido complexes using various routes: (1) Direct oxidation of U{sup IV}-imido complexes with copper(I) salts; (2) Salt metathesis with U{sup V}-imido halides; (3) Protonolysis and insertion of an U{sup V}-imido alkyl or aryl complex with H-N{double_bond}CPh{sub 2} or N{triple_bond}C-Ph, respectively, to form a U{sup V}-imido ketimide complex. Further, we report and compare the crystallographic, electrochemical, spectroscopic and magnetic characterization of the pentavalent uranium (C{sub 5}Me{sub 5}){sub 2}U({double_bond}N-Ar)(Y) series (Y = OTf, SPh, C{triple_bond}C-Ph, NPh{sub 2}, OPh, N{double_bond}CPh{sub 2}) to further interrogate the molecular, electronic, and magnetic structures of this new class of uranium complexes.

  6. Medicinal Chemistry Projects Requiring Imaginative Structure-Based Drug Design Methods.

    Science.gov (United States)

    Moitessier, Nicolas; Pottel, Joshua; Therrien, Eric; Englebienne, Pablo; Liu, Zhaomin; Tomberg, Anna; Corbeil, Christopher R

    2016-09-20

    Computational methods for docking small molecules to proteins are prominent in drug discovery. There are hundreds, if not thousands, of documented examples-and several pertinent cases within our research program. Fifteen years ago, our first docking-guided drug design project yielded nanomolar metalloproteinase inhibitors and illustrated the potential of structure-based drug design. Subsequent applications of docking programs to the design of integrin antagonists, BACE-1 inhibitors, and aminoglycosides binding to bacterial RNA demonstrated that available docking programs needed significant improvement. At that time, docking programs primarily considered flexible ligands and rigid proteins. We demonstrated that accounting for protein flexibility, employing displaceable water molecules, and using ligand-based pharmacophores improved the docking accuracy of existing methods-enabling the design of bioactive molecules. The success prompted the development of our own program, Fitted, implementing all of these aspects. The primary motivation has always been to respond to the needs of drug design studies; the majority of the concepts behind the evolution of Fitted are rooted in medicinal chemistry projects and collaborations. Several examples follow: (1) Searching for HDAC inhibitors led us to develop methods considering drug-zinc coordination and its effect on the pKa of surrounding residues. (2) Targeting covalent prolyl oligopeptidase (POP) inhibitors prompted an update to Fitted to identify reactive groups and form bonds with a given residue (e.g., a catalytic residue) when the geometry allows it. Fitted-the first fully automated covalent docking program-was successfully applied to the discovery of four new classes of covalent POP inhibitors. As a result, efficient stereoselective syntheses of a few screening hits were prioritized rather than synthesizing large chemical libraries-yielding nanomolar inhibitors. (3) In order to study the metabolism of POP inhibitors by

  7. Nuclear structure studies of neutron-rich heavy nuclei by mass measurements of francium and radium isotopes

    Energy Technology Data Exchange (ETDEWEB)

    Rosenbusch, Marco [Ernst-Moritz-Arndt-Universitaet, Institut fuer Physik, 17487 Greifswald (Germany); Collaboration: ISOLTRAP-Collaboration

    2013-07-01

    The mass is a unique property of an atomic nucleus reflecting its binding energy and thus the sum of all interactions at work. Precise measurements of nuclear masses especially of short-lived exotic nuclides provide important input for nuclear structure, nuclear astrophysics, tests of the Standard Model, and weak interaction studies. The Penning-trap mass spectrometer ISOLTRAP at the on-line isotope separator ISOLDE/CERN has been set up for precision mass measurements and continuously improved for accessing more exotic nuclides. The mass uncertainty is typically δm / m=10{sup -8} and the accessible half-life has been reduced to about 50 ms. In this contribution, the results of a measurement campaign of neutron-rich francium and radium isotopes will be presented, i.e. the masses of the isotopic chain of {sup 224-233}Fr and {sup 233,234}Ra, one of the most neutron-rich ensemble obtainable at ISOL facilities. The mass {sup 234}Ra denotes the heaviest mass ever measured with ISOLTRAP. Experimental data in the neutron-rich, heavy mass region is of great interest for studies of structural evolution far from stability, especially because the knowledge from nuclear mass models is scarce. The impact of the new data on the physics in this mass region as well as recent technical developments of ISOLTRAP are discussed.

  8. Purification, structure and immunobiological activity of an arabinan-rich pectic polysaccharide from the cell walls of Prunus dulcis seeds.

    Science.gov (United States)

    Dourado, Fernando; Madureira, Pedro; Carvalho, Vera; Coelho, Ricardo; Coimbra, Manuel A; Vilanova, Manuel; Mota, Manuel; Gama, Francisco M

    2004-10-20

    The structure and bioactivity of a polysaccharide extracted and purified from a 4M KOH + H3BO3 solution from Prunus dulcis seed cell wall material was studied. Anion-exchange chromatography of the crude extract yielded two sugar-rich fractions: one neutral (A), the other acidic (E). These fractions contain a very similar monosaccharide composition: 5:2:1 for arabinose, uronic acids and xylose, respectively, rhamnose and galactose being present in smaller amounts. As estimated by size-exclusion chromatography, the acidic fraction had an apparent molecular mass of 762 kDa. Methylation analysis (from the crude and fractions A and E), suggests that the polysaccharide is an arabinan-rich pectin. In all cases, the polysaccharides bear the same type of structural Ara moieties with highly branched arabinan-rich pectic polysaccharides. The average relative proportions of the arabinosyl linkages is 3:2:1:1 for T-Araf:(1-->5)-Araf:(1-->3,5)-Araf:(1-->2,3,5)-Araf. The crude polysaccharide extract and fractions A and E induced a murine lymphocyte stimulatory effect, as evaluated by the in vitro and in vivo expression of lymphocyte activation markers and spleen mononuclear cells culture proliferation. The lymphocyte stimulatory effect was stronger on B- than on T-cells. No evidence of cytotoxic effects induced by the polysaccharide fractions was found.

  9. Crystal structure and dimerization equilibria of PcoC, a methionine-rich copper resistance protein from Escherichia coli

    Energy Technology Data Exchange (ETDEWEB)

    Wernimont, A.K.; Huffman, D.L.; Finney, L.A.; Demeler, B.; O' Halloran, T.V.; Rosenzweig, A.C.

    2010-03-08

    PcoC is a soluble periplasmic protein encoded by the plasmid-born pco copper resistance operon of Escherichia coli. Like PcoA, a multicopper oxidase encoded in the same locus and its chromosomal homolog CueO, PcoC contains unusual methionine rich sequences. Although essential for copper resistance, the functions of PcoC, PcoA, and their conserved methionine-rich sequences are not known. Similar methionine motifs observed in eukaryotic copper transporters have been proposed to bind copper, but there are no precedents for such metal binding sites in structurally characterized proteins. The high-resolution structures of apo PcoC, determined for both the native and selenomethionine-containing proteins, reveal a seven-stranded barrel with the methionines unexpectedly housed on a solvent-exposed loop. Several potential metal-binding sites can be discerned by comparing the structures to spectroscopic data reported for copper-loaded PcoC. In the native structure, the methionine loop interacts with the same loop on a second molecule in the asymmetric unit. In the selenomethionine structure, the methionine loops are more exposed, forming hydrophobic patches on the protein surface. These two arrangements suggest that the methionine motifs might function in protein-protein interactions between PcoC molecules or with other methionine-rich proteins such as PcoA. Analytical ultracentrifugation data indicate that a weak monomer-dimer equilibrium exists in solution for the apo protein. Dimerization is significantly enhanced upon binding Cu(I) with a measured {Delta}({Delta}G{sup o}) {le} -8.0 kJ/mole, suggesting that copper might bind at the dimer interface.

  10. The Materials Chemistry of Atomic Oxygen with Applications to Anisotropic Etching of Submicron Structures in Microelectronics and the Surface Chemistry Engineering of Porous Solids

    Science.gov (United States)

    Koontz, Steve L.; Leger, Lubert J.; Wu, Corina; Cross, Jon B.; Jurgensen, Charles W.

    1994-01-01

    Neutral atomic oxygen is the most abundant component of the ionospheric plasma in the low Earth orbit environment (LEO; 200 to 700 kilometers altitude) and can produce significant degradation of some spacecraft materials. In order to produce a more complete understanding of the materials chemistry of atomic oxygen, the chemistry and physics of O-atom interactions with materials were determined in three radically different environments: (1) The Space Shuttle cargo bay in low Earth orbit (the EOIM-3 space flight experiment), (2) a high-velocity neutral atom beam system (HVAB) at Los Alamos National Laboratory (LANL), and (3) a microwave-plasma flowing-discharge system at JSC. The Space Shuttle and the high velocity atom beam systems produce atom-surface collision energies ranging from 0.1 to 7 eV (hyperthermal atoms) under high-vacuum conditions, while the flowing discharge system produces a 0.065 eV surface collision energy at a total pressure of 2 Torr. Data obtained in the three different O-atom environments referred to above show that the rate of O-atom reaction with polymeric materials is strongly dependent on atom kinetic energy, obeying a reactive scattering law which suggests that atom kinetic energy is directly available for overcoming activation barriers in the reaction. General relationships between polymer reactivity with O atoms and polymer composition and molecular structure have been determined. In addition, vacuum ultraviolet photochemical effects have been shown to dominate the reaction of O atoms with fluorocarbon polymers. Finally, studies of the materials chemistry of O atoms have produced results which may be of interest to technologists outside the aerospace industry. Atomic oxygen 'spin-off' or 'dual use' technologies in the areas of anisotropic etching in microelectronic materials and device processing, as well as surface chemistry engineering of porous solid materials are described.

  11. Developmental programming of aortic and renal structure in offspring of rats fed fat-rich diets in pregnancy

    DEFF Research Database (Denmark)

    Armitage, James A.; Lakasing, Lorin; Taylor, Paul D.

    2005-01-01

    Evidence from human and animal studies suggests that maternal nutrition can induce developmental programming of adult hypertension in offspring. We have previously described a model of maternal dietary imbalance in Sprague-Dawley rats whereby administration of a maternal diet rich in animal lard......-Dawley rats fed a control diet (OC) or lard-rich diet (OHF) during pregnancy and suckling followed by a control diet post-weaning. To gain further insight, we assessed aortic reactivity and elasticity in an organ bath preparation and renal renin and Na+,K+-ATPase activity. Plasma aldosterone concentration...... weight, glomerular number or volume in OHF compared with OC, but renin and Na+,K+-ATPase activity were significantly reduced in OHF compared with controls. Programmed alterations to aortic structure and function are consistent with previous observations that exposure to maternal high fat diets produces...

  12. Summer Ephemeroptera, Plecoptera, and Trichoptera (EPT) species richness and community structure in the lower Illinois River basin of Illinois

    Science.gov (United States)

    DeWalt, R.E.; Webb, D.W.; Harris, M.A.

    1999-01-01

    Ephemeroptera, Plecoptera, and Trichoptera (EPT) species richness is useful for monitoring stream health, but no published studies in Illinois quantitatively document EPT richness or assemblage structure. The objectives of this study were to characterize adult EPT richness and structure and relate these to relative water quality at eight stream sites (160-69,300 km3 area) in the lower Illinois River basin. Adults were ultra-violet light trapped in June, July, and August 1997. Nutrient enrichment by nitrate and nitrite nitrogen was strongly evident, especially in smaller drainages, while critical loss of stable habitat was observed in larger water bodies. Seventy EPT species were identified from 17,889 specimens. Trichoptera were by far the most speciose (41 species), followed by Ephemeroptera (26), and Plecoptera (3). Caddisflies also dominated species richness across sites, contributing 18.0 of the average 28.9 total EPT species collected. Site EPT richness varied significantly (F = 5.51, p = 0.003, df = 7), with smaller drainages supporting greater richness, generally. Differences were also evident for months (F = 21.7, p = 0.0001, df = 2), with June being lower (11.8 average) than either July (20.6) or August (18.1) values. Hilsenhoff biotic index (HBI) scores did not vary significantly across sites (F = 0.7, p = 0.7, df = 7), but were different across months (F = 5.4, p = 0.02, df = 2). June (4.23) and July (4.53) means were not different, but both were lower (of better quality) than August (5.33) scores. The relationship of EPT to HBI scores was not investigated statistically due to problems of sample size and interdependence of monthly samples, but graphical analysis suggested no consistent relationship. This suggested a decoupling of the HBI from the EPT and implied that the gain in taxonomic resolution achieved by using adults outstripped the resolution of the HBI. Use of the HBI to characterize adult aquatic insect communities is discouraged. New state

  13. Structural Analysis of Lexical Bundles in University Lectures of Politics and Chemistry

    Directory of Open Access Journals (Sweden)

    Hadi Kashiha

    2014-01-01

    Full Text Available Referred to as extended collocations, lexical bundles are considered as a main factor in building fluency in academic discourse; helping to shape meaning and coherence in a text or speech. For decades, lexical bundles have attracted considerable amount of attention in corpus-based research in English for Academic Purposes (EAP. While, the focus of the most of the studies on lexical bundles was to explore the use of these multi-word expressions in academic written registers such as research articles, academic spoken registers such as university lectures have not received that amount of attention from the scholars. In this vein, there is still an open question of how they are structurally different across disciplines. With these concerns in mind, this study aimed to explore how lexical bundles are used structurally in a 50291 words corpus of 8 university lectures across two disciplines: chemistry and politics. To this aim, the most frequent four-word bundles in the corpus were classified according to their grammatical types to see the possible disciplinary variations in their frequency of use as well as the structure involved in their use. Results of the analysis revealed that noun phrase and prepositional phrase fragments were the most common structures in the lectures of the two disciplines, accounting for more than half of the bundles in politics. University lecturers appear to apply a variety of structures in the use of lexical bundles often peculiar to the discipline in order to convey their disciplinary messages.  This would lead to the need to emphasize the instruction of the most common structures in that discipline in a way for the lectures to be as comprehensive as possible for the intended audiences.

  14. Structural vs. intrinsic carriers: contrasting effects of cation chemistry and disorder on ionic conductivity in pyrochlores

    International Nuclear Information System (INIS)

    Perriot, Romain; Uberuaga, Blas P.

    2015-01-01

    We use molecular dynamics simulations to investigate the role of cation disorder on oxygen diffusion in Gd 2 Zr 2 O 7 (GZO) and Gd 2 Ti 2 O 7 (GTO) pyrochlores, a class of complex oxides which contain a structural vacancy relative to the basic fluorite structure. The introduction of disorder has distinct effects depending on the chemistry of the material, increasing the mobility of structural carriers by up to four orders of magnitude in GZO. In contrast, in GTO, there is no mobility at zero or low disorder on the ns timescale, but higher disorder liberates the otherwise immobile carriers, allowing diffusion with rates comparable to GZO for the fully disordered material. Here, we show that the cation disorder enhances the diffusivity by both increasing the concentration of mobile structural carriers and their individual mobility. The disorder also influences the diffusion in materials containing intrinsic carriers, such as additional vacancies VO or oxygen interstitials OI. And while in ordered GZO and GTO the contribution of the intrinsic carriers dominates the overall diffusion of oxygen, OI in GZO contributes along with structural carriers, and the total diffusion rate can be calculated by assuming simple additive contributions from the two sources. Although the disorder in the materials with intrinsic defects usually enhances the diffusivity as in the defect-free case, in low concentrations, cation antisites AB or BA, where A = Gd and B = Zr or Ti, can act as traps for fast intrinsic defects. The trapping results in a lowering of the diffusivity, and causes a non-monotonic behavior of the diffusivity with disorder. Conversely, in the case of slow intrinsic defects, the main effect of the disorder is to liberate the structural carriers, resulting in an increase of the diffusivity regardless of the defect trapping.

  15. Nuclear chemistry

    International Nuclear Information System (INIS)

    Vertes, A.; Kiss, I.

    1987-01-01

    This book is an introduction to the application of nuclear science in modern chemistry. The first group of chapters discuss the basic phenomena and concepts of nuclear physics with emphasis on their relation to chemical problems, including the main properties and the composition of atomic nuclei, nuclear reactions, radioactive decay and interactions of radiation with matter. These chapters provide the basis for understanding the following chapters which encompass the wide scope of nuclear chemistry. The methods of the investigation of chemical structure based on the interaction of nuclear radiation with matter including positronium chemistry and other exotic atoms is elaborated in particular detail. Separate chapters are devoted to the use of radioactive tracers, the chemical consequences of nuclear processes (i.e. hot atom chemistry), radiation chemistry, isotope effects and their applications, and the operation of nuclear reactors

  16. Nuclear chemistry

    International Nuclear Information System (INIS)

    Vertes, A.; Kiss, I.

    1987-01-01

    This book is an introduction to the application of nuclear science in modern chemistry. The first group of chapters discuss the basic phenomena and concepts of nuclear physics with emphasis on their relation to chemical problems, including the main properties and the composition of atomic nuclei, nuclear reactions, radioactive decay and interactions of radiation with matter. These chapters provide the basis for understanding the following chapters which encompass the wide scope of nuclear chemistry. The methods of the investigation of chemical structure based on the interaction of nuclear radiation with matter including positronium chemistry and other exotic atoms is elaborated in particular detail. Separate chapters are devoted to the use of radioactive tracers, the chemical consequences of nuclear processes (i.e. hot atom chemistry), radiation chemistry, isotope effects and their applications, and the operation of nuclear reactors. (Auth.)

  17. Crystal chemistry of Ruddlesden-Popper type structures in high Tc ceramic superconductors

    International Nuclear Information System (INIS)

    Dwivedi, Anurag; Cormack, A.N.

    1991-01-01

    Similar structural patterns have been noticed in the systems La-Cu-O, La-Ni-O and Bi and Tl-containing superconducting oxides. The formation of Ruddlesden-Popper type layers (alternating slabs of rocksalt and perovskite strucutres) is seen in these oxides which is similar in many respects to what is seen in the system Sr-Ti-O. However, there are some significant differences, for example the rocksalt and perovskite blocks in new superconducting compounds are not necessarily electrically neutral, unlike in the Sr-Ti-O system. It, thus, becomes necessary to create oxygen vacancies in the basic perovskite structure of Bi-containing compounds, when the width of the perovskite slab changes on addition of extra Cu-O planes. Results of atomistic simulations suggest that these missing oxygen ions allows the Cu-O planes to buckle in Bi-series of compounds. This is also supported by the absence of buckling in the Sr-Ti-O series of compounds and the first member of Bi-containing compounds in which there are no missing oxygen ions. Additional results on the phase stability of polytypoid structure in la-Cu-O system and defect chemistry of compounds of La N i-O system are presented. (author). 14 re fs., 7 figs., 4 tabs

  18. Introducing NMR to a General Chemistry Audience: A Structural-Based Instrumental Laboratory Relating Lewis Structures, Molecular Models, and [superscript 13]C NMR Data

    Science.gov (United States)

    Pulliam, Curtis R.; Pfeiffer, William F.; Thomas, Alyssa C.

    2015-01-01

    This paper describes a first-year general chemistry laboratory that uses NMR spectroscopy and model building to emphasize molecular shape and structure. It is appropriate for either a traditional or an atoms-first curriculum. Students learn the basis of structure and the use of NMR data through a cooperative learning hands-on laboratory…

  19. "Just as the Structural Formula Does": Names, Diagrams, and the Structure of Organic Chemistry at the 1892 Geneva Nomenclature Congress.

    Science.gov (United States)

    Hepler-Smith, Evan

    2015-02-01

    At the Geneva Nomenclature Congress of 1892, some of the foremost organic chemists of the late nineteenth century crafted a novel relationship between chemical substances, chemical diagrams, and chemical names that has shaped practices of chemical representation ever since. During the 1880s, the French chemist Charles Friedel organised the nomenclature reform effort that culminated in the Geneva Congress; in the disorderly nomenclature of German synthetic chemistry, Friedel saw an opportunity to advance French national interests and his own pedagogical goals. Friedel and a group of close colleagues reconceived nomenclature as a unified field, in which all chemical names ought to relate clearly to one another and to the structure of the compounds they represented. The German chemist Adolf von Baeyer went a step farther, arguing for names that precisely and uniquely corresponded to the structural formula of each compound, tailored for use in chemical dictionaries and handbooks. Baeyer's vision prevailed at the Geneva Congress, which consequently codified rules for rigorously mapping structural formulas into names, resulting in names that faithfully represented the features of these diagrams but not always the chemical behaviour of the compounds themselves. This approach ultimately limited both the number of chemical compounds that the Geneva rules were able to encompass and the breadth of their application. However, the relationship between diagram and name established at the Geneva Congress became the foundation not only of subsequent systems of chemical nomenclature but of methods of organising information that have supported the modern chemical sciences.

  20. Chemistry of Iron N -heterocyclic carbene complexes: Syntheses, structures, reactivities, and catalytic applications

    KAUST Repository

    Riener, Korbinian

    2014-05-28

    Iron is the most abundant transition metal in Earth\\'s crust. It is relatively inexpensive, not very toxic, and environmentally benign. Undoubtedly, due to the involvement in a multitude of biological processes, which heavily rely on the rich functionalities of iron-containing enzymes, iron is one of the most important elements in nature. Additionally, three-coordinate iron complexes have been reported during the past several years. In this review, the mentioned iron NHC complexes are categorized by their main structure and reactivity attributes. Thus, monocarbene and bis-monocarbene complexes are presented first. This class is subdivided into carbonyl, nitrosyl, and halide compounds followed by a brief section on other, more unconventional iron NHC motifs. Subsequently, donor-substituted complexes bearing bi-, tri-, tetra-, or even pentadentate ligands and further pincer as well as scorpionato motifs are described.

  1. Structural, mechanical and corrosion studies of Cr-rich inclusions in 152 cladding of dissimilar metal weld joint

    Science.gov (United States)

    Li, Yifeng; Wang, Jianqiu; Han, En-Hou; Yang, Chengdong

    2018-01-01

    Cr-rich inclusions were discovered in 152 cladding at the inner wall of domestic dissimilar metal weld joint, and their morphologies, microstructures, mechanical properties and corrosion behaviors were systematically characterized by SEM, TEM, nanoindentation and FIB. The results indicate that the Cr-rich inclusions originate from large-size Cr particles in 152 welding electrode flux, and they are 50-150 μm in size in most cases, and there is a continuous transition zone of 2-5 μm in width between the Cr inclusion core and 152 cladding matrix, and the transition zone consists of Ni & Fe-rich dendritic austenite and Cr23C6 and Cr matrix. The transition zone has the highest nanoindentation hardness (7.66 GPa), which is much harder than the inclusion core (5.14 GPa) and 152 cladding (3.71 GPa). In-situ microscopic tensile tests show that cracks initialize preferentially in transition zone, and then propagate into the inclusion core, and creep further into 152 cladding after penetrating the core area. The inclusion core and its transition zone both share similar oxide film structure with nickel-base 152 cladding matrix in simulated primary water, while those two parts present better general corrosion resistance than 152 cladding matrix due to higher Cr concentration.

  2. Adaptation of quantum chemistry software for the electronic structure calculations on GPU for solid-state systems

    International Nuclear Information System (INIS)

    Gusakov, V.E.; Bel'ko, V.I.; Dorozhkin, N.N.

    2015-01-01

    We report on adaptation of quantum chemistry software - Quantum Espresso and LASTO - for the electronic structure calculations for the complex solid-state systems on the GeForce series GPUs using the nVIDIA CUDA technology. Specifically, protective covering based on transition metal nitrides are considered. (authors)

  3. Incorporating Modeling and Simulations in Undergraduate Biophysical Chemistry Course to Promote Understanding of Structure-Dynamics-Function Relationships in Proteins

    Science.gov (United States)

    Hati, Sanchita; Bhattacharyya, Sudeep

    2016-01-01

    A project-based biophysical chemistry laboratory course, which is offered to the biochemistry and molecular biology majors in their senior year, is described. In this course, the classroom study of the structure-function of biomolecules is integrated with the discovery-guided laboratory study of these molecules using computer modeling and…

  4. Measurements of local chemistry and structure in Ni(O)-YSZ composites during reduction using energy-filtered environmental TEM

    DEFF Research Database (Denmark)

    Jeangros, Quentin; Hansen, Thomas Willum; Wagner, Jakob Birkedal

    2014-01-01

    Energy-filtered transmission electron microscopy images are acquired during the reduction of a NiO-YSZ composite in H-2 up to 600 degrees C. Temperature-resolved quantitative information about both chemistry and structure is extracted with nm spatial resolution from the data, paving the way...

  5. Microdiffraction and CBED crystal structure determination of the Si-rich phase in laser-clad Ni alloy FP-5

    International Nuclear Information System (INIS)

    Liu, Y.; Mazumder, J.

    1995-01-01

    This paper demonstrates an example of using kinematical microdiffraction to solve an unknown Si-rich phase of micrometer size in a laser-clad Ni alloy FP-5 on Al alloy AA333. The composition of the Si-rich phase obtained by energy-dispersice X-ray spectroscopy (EDX) analysis in a transmission electron microscope is approximately 0.7wt%Al, 71wt%Si, 3.3wt%Cr, 0.8wt%Fe, 21wt%Ni and 2.8wt%Cu. The point group was identified by the standard convergent-beam symmetry analysis to be P6 3 /mmc (No. 194). Structure analysies by microdiffraction (MD) indicates that the Si-rich phase is a close-packed structure.The intensity distribution in the microdiffraction pattern of the [1120] zone axis taken with a very thin area showed a close match with kinematical calculation. A close-packed-structure model specified as ABCACB was deduced from the [1120] zone axis MD pattern. The randomly distributed atoms of all the elements in the unit cell are at 2/3, 1/3-1/12; 1/3, 1/12; 0, 0, 3/12, 1/3, 2/3, 5/12, 2/3, 1/3, 7/12; 0,0, 9/12. The model was checked by comparison with a simulated diffraction pattern map and with a simulated [0001] zone-axis CBED pattern, which showed complete agreement with the proposed model. (orig.)

  6. Chemistry and cosmology.

    Science.gov (United States)

    Black, John H

    2006-01-01

    The simplest elements, hydrogen and helium, offer a remarkably rich chemistry, which has controlled crucial features of the early evolution of the universe. Theoretical models of the origin of structure (stars, galaxies, clusters of galaxies, etc.) now incorporate this chemistry in some detail. In addition to the origin of structure, cosmologists are concerned with observational tests of competing world models. Primordial chemistry may give rise to some of the earliest departures from thermodynamic equilibrium in the universe. These effects may be observable as broad-band spectroscopic distortions of the cosmic background radiation, which otherwise exhibits a nearly perfect blackbody spectrum. The chemical history of the expanding universe is followed through a detailed calculation of the evolution of the abundances of H, H+, H-, H2, H2+, H3+, and other minor species. It is shown that continuous absorption by the small concentration of H- can produce a distortion in the cosmic background spectrum with a maximum at a frequency near nu/c = 9 cm-1 (wavelength 1.1 mm). The predicted effect lies only a factor of 5 below current limits. Its detection would provide an important test of our understanding of the recombination epoch of the universe.

  7. Structure vs chemistry: friction and wear of Pt-based metallic surfaces.

    Science.gov (United States)

    Caron, A; Louzguine-Luzguin, D V; Bennewitz, R

    2013-11-13

    In comparison of a Pt57.5Cu14.7Ni5.3P22.5 metallic glass with a Pt(111) single crystal we find that wearless friction is determined by chemistry through bond formation alloying, while wear is determined by structure through plasticity mechanisms. In the wearless regime, friction is affected by the chemical composition of the counter body and involves the formation of a liquid-like neck and interfacial alloying. The wear behavior of Pt-based metallic surfaces is determined by their structural properties and corresponding mechanisms for plastic deformation. In the case of Pt(111) wear occurs by dislocation-mediated homogeneous plastic deformation. In contrast the wear of Pt57.5Cu14.7Ni5.3P22.5 metallic glass occurs through localized plastic deformation in shear bands that merge together in a single shear zone above a critical load and corresponds to the shear softening of metallic glasses. These results open a new route in the control of friction and wear of metals and are relevant for the development of self-lubricated and wear-resistant mechanical devices.

  8. Structure of Se-rich As-Se glasses by high-resolution x-ray photoelectron spectroscopy

    International Nuclear Information System (INIS)

    Golovchak, R.; Kovalskiy, A.; Miller, A. C.; Jain, H.; Shpotyuk, O.

    2007-01-01

    To establish the validity of various proposed structural models, we have investigated the structure of the binary As x Se 100-x chalcogenide glass family (x≤40) by high-resolution x-ray photoelectron spectroscopy. From the composition dependence of the valence band, the contributions to the density of states from the 4p lone pair electrons of Se and the 4p bonding states and 4s electrons of Se and As are identified in the top part of the band. The analysis of Se 3d and As 3d core-level spectra supports the so-called chain crossing model for the atomic structure of Se-rich As x Se 100-x bulk glasses. The results also indicate small deviations (∼3-8%) from this model, especially for glass compositions with short Se chains (25 40 Se 60 and of Se-Se-Se fragments in a glass with composition x=30 is established

  9. Structural evolution of Ge-rich Si1−xGex films deposited by jet-ICPCVD

    Directory of Open Access Journals (Sweden)

    Yu Wang

    2015-11-01

    Full Text Available Amorphous Ge-rich Si1−xGex films with local Ge-clustering were deposited by dual-source jet-type inductively coupled plasma chemical-vapor deposition (jet-ICPCVD. The structural evolution of the deposited films annealed at various temperatures (Ta is investigated. Experimental results indicate that the crystallization occurs to form Ge and Si clusters as Ta = 500 °C. With raising Ta up to 900 °C, Ge clusters percolate together and Si diffuses and redistributes to form a Ge/SiGe core/shell structure, and some Ge atoms partially diffuse to the surface as a result of segregation. The present work will be helpful in understanding the structural evolution process of a hybrid SiGe films and beneficial for further optimizing the microstructure and properties.

  10. Structural and functional characterization of EIAV gp45 fusion peptide proximal region and asparagine-rich layer

    Energy Technology Data Exchange (ETDEWEB)

    Duan, Liangwei; Du, Jiansen [State Key Laboratory of Medicinal Chemical Biology, College of Life Sciences, Nankai University, Tianjin 300071 (China); Wang, Xuefeng; Zhou, Jianhua; Wang, Xiaojun [State Key Laboratory of Veterinary Biotechnology, Harbin Veterinary Research Institute, Chinese Academy of Agricultural Sciences, Harbin 150001 (China); Liu, Xinqi, E-mail: liu2008@nankai.edu.cn [State Key Laboratory of Medicinal Chemical Biology, College of Life Sciences, Nankai University, Tianjin 300071 (China)

    2016-04-15

    Equine infectious anaemia virus (EIAV) and human immunodeficiency virus (HIV) are members of the lentiviral genus. Similar to HIV gp41, EIAV gp45 is a fusogenic protein that mediates fusion between the viral particle and the host cell membrane. The crystal structure of gp45 reported reveals a different conformation in the here that includes the fusion peptide proximal region (FPPR) and neighboring asparagine-rich layer compared with previous HIV-1 gp41 structures. A complicated hydrogen-bond network containing a cluster of solvent molecules appears to be critical for the stability of the gp45 helical bundle. Interestingly, viral replication was relatively unaffected by site-directed mutagenesis of EIAV, in striking contrast to that of HIV-1. Based on these observations, we speculate that EIAV is more adaptable to emergent mutations, which might be important for the evolution of EIAV as a quasi-species, and could potentially contribute to the success of the EIAV vaccine. - Highlights: • The crystal structure of EIAV gp45 was determined. • The fusion peptide proximal region adopts a novel conformation different to HIV-1. • The asparagine-rich layer includes an extensive hydrogen-bond network. • These regions of EIAV are highly tolerant to mutations. • The results provide insight into the mechanism of gp41/gp45-mediated membrane fusion.

  11. Experimental study of the structure of rich premixed 1,3-butadiene/CH4/O2/Ar flame.

    OpenAIRE

    Gueniche , Hadj-Ali; Glaude , Pierre-Alexandre; Fournet , René; Battin-Leclerc , Frédérique

    2006-01-01

    traduit de Fizika Goreniya I Vzryva, 2006, 42, 89-95.; The structure of a laminar rich premixed 1,3-C4H6/CH4/O2/Ar flame have been investigated. 1,3-Butadiene, methane, oxygen and argon mole fractions are 0.033; 0.2073; 0.3315, and 0.4280, respectively, for an equivalent ratio of 1.80. The flame has been stabilized on a burner at a pressure of 6.7 kPa (50 Torr). The concentration profiles of stable species were measured by gas chromatography after sampling with a quartz probe. Quantified spec...

  12. Experimental study of the structure of rich premixed 1,3-butadiene/CH4/O2/Ar flame

    OpenAIRE

    Gueniche, Hadj-Ali; Glaude, Pierre-Alexandre; Fournet, René; Battin-Leclerc, Frédérique

    2007-01-01

    The structure of a laminar rich premixed 1,3-C4H6/CH4/O2/Ar flame have been investigated. 1,3-Butadiene, methane, oxygen and argon mole fractions are 0.033; 0.2073; 0.3315, and 0.4280, respectively, for an equivalent ratio of 1.80. The flame has been stabilized on a burner at a pressure of 6.7 kPa (50 Torr). The concentration profiles of stable species were measured by gas chromatography after sampling with a quartz probe. Quantified species included carbon monoxide and dioxide, methane, oxyg...

  13. Structural and Chemical Properties of the Nitrogen-Rich Energetic Material Triaminoguanidinium 1-methyl-5-nitriminotetrazolate under Pressure

    Science.gov (United States)

    2012-08-01

    ABSTRACT 16. SECURITY CLASSIFICATION OF: The structural and chemical properties of the bi-molecular, hydrogen-bonded, nitrogen-rich ener- getic...School Apprenticeship Program (ARO-HSAP), and the Depart- ment of Energy National Nuclear Security Administration (Carnegie/DOE Alliance Center; DE-FC52...B. J. Baer, H. Cynn, W. J. Evans, V. Iota , and C. S. Yoo, Phys. Rev. B 76(1), 014113 (2007). 9T. M. Klapötke, J. Stierstorfer, and A. U. Wallek, Chem

  14. Hyperfine structure and isotope shift of the neutron-rich barium isotopes 139-146Ba and 148Ba

    International Nuclear Information System (INIS)

    Wendt, K.; Ahmad, S.A.; Klempt, W.; Neugart, R.; Otten, E.W.

    1988-01-01

    The hyperfine structure and isotope shift in the 6s 2 S 1/2 -6p 2 P 3/2 line of Ba II (455.4 nm) have been measured by collinear fast-beam laser spectroscopy for the neutron-rich isotopes 139-146 Ba and 148 Ba. Nuclear moments and mean square charge radii of these isotopes have been recalculated. The isotope shift of the isotope 148 Ba (T 1/2 = 0.64 s) could be studied for the first time, yielding δ 2 > 138,148 = 1.245(3) fm 2 . (orig.)

  15. Impact of triaxiality on the rotational structure of neutron-rich rhenium isotopes

    Directory of Open Access Journals (Sweden)

    M.W. Reed

    2016-01-01

    Full Text Available A number of 3-quasiparticle isomers have been found and characterised in the odd-mass, neutron-rich, 187Re, 189Re and 191Re nuclei, the latter being four neutrons beyond stability. The decay of the isomers populates states in the rotational bands built upon the 9/2−[514] Nilsson orbital. These bands exhibit a degree of signature splitting that increases with neutron number. This splitting taken together with measurements of the M1/E2 mixing ratios and with the changes observed in the energy of the gamma-vibrational band coupled to the 9/2−[514] state, suggests an increase in triaxiality, with γ values of 5°, 18° and 25° deduced in the framework of a particle-rotor model.

  16. Ni4Ti3 precipitate structures in Ni-rich NiTi shape memory alloys

    International Nuclear Information System (INIS)

    Holec, D.; Bojda, O.; Dlouhy, A.

    2008-01-01

    Non-uniform distributions of Ni 4 Ti 3 precipitate crystallographic variants are investigated in a Ni-rich NiTi shape memory alloy after aging, assisted by external stress. A finite-element method model is presented that considers the elastic anisotropy of the B2 parent phase and also mutual misorientations of grains in a polycrystalline sample. On loading by the external stress, the stress is redistributed in the microstructure and the precipitation of some Ni 4 Ti 3 crystallographic variants becomes distinctly favorable in grain boundary regions since these variant configurations minimize the elastic interaction energy. The volume fraction of the affected grain boundary regions is calculated and the numerical results are compared with the data obtained by differential scanning calorimetry and transmission electron microscopy

  17. The structure and species richness of the diatom assemblages of the Western Carpathian spring fens along the gradient of mineral richness

    Czech Academy of Sciences Publication Activity Database

    Fránková, Markéta; Bojková, J.; Poulíčková, A.; Hájek, Michal

    2009-01-01

    Roč. 9, č. 2 (2009), s. 355-368 ISSN 1802-5439 Institutional research plan: CEZ:AV0Z60050516 Keywords : diatoms * Western Carpathians * poor-rich gradient Subject RIV: EF - Botanics Impact factor: 1.762, year: 2009

  18. Relative Importance of Current and Past Landscape Structure and Local Habitat Conditions for Plant Species Richness in Dry Grassland-Like Forest Openings

    Czech Academy of Sciences Publication Activity Database

    Husáková, I.; Münzbergová, Zuzana

    2014-01-01

    Roč. 9, č. 5 (2014), s. 1-15 E-ISSN 1932-6203 Institutional support: RVO:67985939 Keywords : landscape structure * species richness * dry grassland Subject RIV: EF - Botanics Impact factor: 3.234, year: 2014

  19. Fine-Structure Measurements of Oxygen A Band Absorbance for Estimating the Thermodynamic Average Temperature of the Earth's Atmosphere: An Experiment in Physical and Environmental Chemistry

    Science.gov (United States)

    Myrick, M. L.; Greer, A. E.; Nieuwland, A.; Priore, R. J.; Scaffidi, J.; Andreatta, Daniele; Colavita, Paula

    2006-01-01

    The experiment describe the measures of the A band transitions of atmospheric oxygen, a rich series of rotation-electronic absorption lines falling in the deep red portion of the optical spectrum and clearly visible owing to attenuation of solar radiation. It combines pure physical chemistry with analytical and environmental science and provides a…

  20. Structure Identification Using High Resolution Mass Spectrometry Data and the EPAs Chemistry Dashboard (ACS Fall meeting)

    Science.gov (United States)

    The iCSS Chemistry Dashboard is a publicly accessible dashboard provided by the National Center for Computation Toxicology at the US-EPA. It serves a number of purposes, including providing a chemistry database underpinning many of our public-facing projects (e.g. ToxCast and Exp...

  1. C,N-Chelated Organotin(IV) Azides: Synthesis, Structure and Use within the Click Chemistry.

    Czech Academy of Sciences Publication Activity Database

    Švec, P.; Bartoš, K.; Růžičková, Z.; Cuřínová, Petra; Dušek, L.; Turek, J.; de Proft, F.; Růžička, A.

    2016-01-01

    Roč. 40, č. 7 (2016), s. 5808-5817 ISSN 1144-0546 Grant - others:FWO(BE) 12T6615N Institutional support: RVO:67985858 Keywords : organotin(IV)azides * click chemistry * chelation Subject RIV: CC - Organic Chemistry Impact factor: 3.269, year: 2016

  2. PubChemQC Project: A Large-Scale First-Principles Electronic Structure Database for Data-Driven Chemistry.

    Science.gov (United States)

    Nakata, Maho; Shimazaki, Tomomi

    2017-06-26

    Large-scale molecular databases play an essential role in the investigation of various subjects such as the development of organic materials, in silico drug design, and data-driven studies with machine learning. We have developed a large-scale quantum chemistry database based on first-principles methods. Our database currently contains the ground-state electronic structures of 3 million molecules based on density functional theory (DFT) at the B3LYP/6-31G* level, and we successively calculated 10 low-lying excited states of over 2 million molecules via time-dependent DFT with the B3LYP functional and the 6-31+G* basis set. To select the molecules calculated in our project, we referred to the PubChem Project, which was used as the source of the molecular structures in short strings using the InChI and SMILES representations. Accordingly, we have named our quantum chemistry database project "PubChemQC" ( http://pubchemqc.riken.jp/ ) and placed it in the public domain. In this paper, we show the fundamental features of the PubChemQC database and discuss the techniques used to construct the data set for large-scale quantum chemistry calculations. We also present a machine learning approach to predict the electronic structure of molecules as an example to demonstrate the suitability of the large-scale quantum chemistry database.

  3. Relationships between avian richness and landscape structure at multiple scales using multiple landscapes

    Science.gov (United States)

    Michael S. Mitchell; Scott H. Rutzmoser; T. Bently Wigley; Craig Loehle; John A. Gerwin; Patrick D. Keyser; Richard A. Lancia; Roger W. Perry; Christopher L. Reynolds; Ronald E. Thill; Robert Weih; Don White; Petra Bohall Wood

    2006-01-01

    Little is known about factors that structure biodiversity on landscape scales, yet current land management protocols, such as forest certification programs, place an increasing emphasis on managing for sustainable biodiversity at landscape scales. We used a replicated landscape study to evaluate relationships between forest structure and avian diversity at both stand...

  4. Evolving knowledge of sex differences in brain structure, function, and chemistry.

    Science.gov (United States)

    Cosgrove, Kelly P; Mazure, Carolyn M; Staley, Julie K

    2007-10-15

    Clinical and epidemiologic evidence demonstrates sex differences in the prevalence and course of various psychiatric disorders. Understanding sex-specific brain differences in healthy individuals is a critical first step toward understanding sex-specific expression of psychiatric disorders. Here, we evaluate evidence on sex differences in brain structure, chemistry, and function using imaging methodologies, including functional magnetic resonance imaging (fMRI), positron emission tomography (PET), single photon emission computed tomography (SPECT), and structural magnetic resonance imaging (MRI) in mentally healthy individuals. MEDLINE searches of English-language literature (1980-November 2006) using the terms sex, gender, PET, SPECT, MRI, fMRI, morphometry, neurochemistry, and neurotransmission were performed to extract relevant sources. The literature suggests that while there are many similarities in brain structure, function, and neurotransmission in healthy men and women, there are important differences that distinguish the male from the female brain. Overall, brain volume is greater in men than women; yet, when controlling for total volume, women have a higher percentage of gray matter and men a higher percentage of white matter. Regional volume differences are less consistent. Global cerebral blood flow is higher in women than in men. Sex-specific differences in dopaminergic, serotonergic, and gamma-aminobutyric acid (GABA)ergic markers indicate that male and female brains are neurochemically distinct. Insight into the etiology of sex differences in the normal living human brain provides an important foundation to delineate the pathophysiological mechanisms underlying sex differences in neuropsychiatric disorders and to guide the development of sex-specific treatments for these devastating brain disorders.

  5. Nuclear structure studies of the neutron-rich Rubidium isotopes using Coulomb excitation

    CERN Multimedia

    Reiter, P; Blazhev, A A; Voulot, D; Meot, V H; Simpson, G S; Georgiev, G P; Gaudefroy, L; Roig, O

    We propose to study the properties of odd-mass neutron-rich rubidium isotopes by the Coulomb-excitation technique, using the Miniball array coupled to the REX-ISOLDE facility. The results from similar measurements from the recent years (e.g. for the odd-mass and the odd-odd Cu isotopes, IS435) have shown the strong potential in such measurements for gaining information both for single-particle-like and collective states in exotic nuclei. Since there is practically no experimental information for excited states in the odd-mass Rb isotopes beyond $^{93}$Rb, the present study should be able to provide new data in a region of spherical ($^{93}$Rb and $^{95}$Rb) as well as well-deformed nuclei ($^{97}$Rb and $^{99}$Rb). Of particular interest is the rapid shape change that occurs when going from $^{95}$Rb (${\\varepsilon}_{2}$=0.06) to $^{97}$Rb (${\\varepsilon}_{2}$=0.3). These results should be of significant astrophysical interest as well, due to the close proximity of the r-process path.

  6. Evolution of nuclear structure in neutron-rich odd-Zn isotopes and isomers

    Directory of Open Access Journals (Sweden)

    C. Wraith

    2017-08-01

    Full Text Available Collinear laser spectroscopy was performed on Zn (Z=30 isotopes at ISOLDE, CERN. The study of hyperfine spectra of nuclei across the Zn isotopic chain, N=33–49, allowed the measurement of nuclear spins for the ground and isomeric states in odd-A neutron-rich nuclei up to N=50. Exactly one long-lived (>10 ms isomeric state has been established in each 69–79Zn isotope. The nuclear magnetic dipole moments and spectroscopic quadrupole moments are well reproduced by large-scale shell–model calculations in the f5pg9 and fpg9d5 model spaces, thus establishing the dominant term in their wave function. The magnetic moment of the intruder Iπ=1/2+ isomer in 79Zn is reproduced only if the νs1/2 orbital is added to the valence space, as realized in the recently developed PFSDG-U interaction. The spin and moments of the low-lying isomeric state in 73Zn suggest a strong onset of deformation at N=43, while the progression towards 79Zn points to the stability of the Z=28 and N=50 shell gaps, supporting the magicity of 78Ni.

  7. Species richness and structure of an anuran community in an Atlantic Forest site in southern Brazil

    Directory of Open Access Journals (Sweden)

    Adriele Karlokoski Cunha

    2010-06-01

    Full Text Available The species richness and spatial distribution of an anuran community were studied over 12 months in an Atlantic Forest area in São José dos Pinhais Municipality, Paraná State, southern Brazil. During field surveys, we registered 32 species from ten families: Brachycephalidae (2, Bufonidae (2, Centrolenidae (1, Cycloramphidae (1, Hemiphractidae (1, Hylidae (18, Hylodidae (1, Leiuperidae (2, Leptodactylidae (3, and Microhylidae (1. Sixteen species were registered in open areas, while seventeen species were found on forest borders and twenty species in forest areas. In relation to the microhabitat utilization, species were registered according to stratum of vocalization: 1 on the ground (eight; 2 in the water (two; 3 in the lower stratum (eleven; 4 in the intermediate stratum (five; 5 in the upper stratum (four. Five species were abundant (15.6%, while twelve were common (37.5%, and fifteen were considered rare (46.9%. The biological aspects of the majority of the species described in this work as related to forest areas are not well known. This fact reinforces the importance of Atlantic Forest conservation.

  8. Pressure-induced chemistry in a nitrogen-hydrogen host-guest structure

    Science.gov (United States)

    Spaulding, Dylan K.; Weck, Gunnar; Loubeyre, Paul; Datchi, Fréderic; Dumas, Paul; Hanfland, Michael

    2014-12-01

    New topochemistry in simple molecular systems can be explored at high pressure. Here we examine the binary nitrogen/hydrogen system using Raman spectroscopy, synchrotron X-ray diffraction, synchrotron infrared microspectroscopy and visual observation. We find a eutectic-type binary phase diagram with two stable high-pressure van der Waals compounds, which we identify as (N2)6(H2)7 and N2(H2)2. The former represents a new type of van der Waals host-guest compound in which hydrogen molecules are contained within channels in a nitrogen lattice. This compound shows evidence for a gradual, pressure-induced change in bonding from van der Waals to ionic interactions near 50 GPa, forming an amorphous dinitrogen network containing ionized ammonia in a room-temperature analogue of the Haber-Bosch process. Hydrazine is recovered on decompression. The nitrogen-hydrogen system demonstrates the potential for new pressure-driven chemistry in high-pressure structures and the promise of tailoring molecular interactions for materials synthesis.

  9. Groundwater Chemistry Regulated by Hydrochemical Processes and Geological Structures: A Case Study in Tongchuan, China

    Directory of Open Access Journals (Sweden)

    Xinyan Li

    2018-03-01

    Full Text Available Knowledge of hydrochemical processes in groundwater helps to identify the relationship between geochemical processes and groundwater quality as well as to understand the hydrochemical evaluation of groundwater, which is important for the sustainable management of groundwater resources. This study aims to identify the chemical characteristics of groundwater in the area of Tongchuan City, China. A total of 58 groundwater samples were collected. A hierarchical cluster analysis divided samples into three clusters and six sub-clusters (cluster 1a, 1b, 2a, 2b, 3a, 3b according to hydrochemical facies. Graphical plots of multiple ionic ratios, saturation indices, and ion exchange indices were employed to examine hydrochemical processes that result in different hydrochemical facies of each cluster. Results show the predominance of carbonate and silicate weathering in cluster 1, silicate weathering in cluster 2, and carbonate weathering in cluster 3. Ionic exchange is a ubiquitous process among all clusters. The distribution of clusters is related to the regional geology, which may result in different hydrochemical processes. Two stratigraphic sections identify the differences in hydrochemical processes resulting from complex stratum structures and varied aquifer media. Cluster 2a shows an interesting difference in water chemistry along the groundwater flow path. Further study by oxygen and hydrogen isotope indicated that mixing between Quaternary and the Permian aquifers resulting from faulting is the main reason for the distinctive characteristic of cluster 2a.

  10. Porous structure and surface chemistry of phosphoric acid activated carbon from corncob

    Science.gov (United States)

    Sych, N. V.; Trofymenko, S. I.; Poddubnaya, O. I.; Tsyba, M. M.; Sapsay, V. I.; Klymchuk, D. O.; Puziy, A. M.

    2012-11-01

    Active carbons have been prepared from corncob using chemical activation with phosphoric acid at 400 °C using varied ratio of impregnation (RI). Porous structure of carbons was characterized by nitrogen adsorption and scanning electron microscopy. Surface chemistry was studied by IR and potentiometric titration method. It has been shown that porosity development was peaked at RI = 1.0 (SBET = 2081 m2/g, Vtot = 1.1 cm3/g), while maximum amount of acid surface groups was observed at RI = 1.25. Acid surface groups of phosphoric acid activated carbons from corncob includes phosphate and strongly acidic carboxylic (pK = 2.0-2.6), weakly acidic carboxylic (pK = 4.7-5.0), enol/lactone (pK = 6.7-7.4; 8.8-9.4) and phenol (pK = 10.1-10.7). Corncob derived carbons showed high adsorption capacity to copper, especially at low pH. Maximum adsorption of methylene blue and iodine was observed for carbon with most developed porosity (RI = 1.0).

  11. The control of stoichiometry in Epitaxial semiconductor structures. Interfacial Chemistry: Property relations. A workshop review

    Science.gov (United States)

    Bachmann, Klaus J.

    1995-01-01

    A workshop on the control of stoichiometry in epitaxial semiconductor structures was held on August 21-26, 1995 in the hotel Stutenhaus at Vesser in Germany. The secluded location of the workshop in the forest of Thuringia and its informal style stimulated extensive private discussions among the participants and promoted new contacts between young scientists from Eastern and Western Europe and the USA. Topics addressed by the presentations were interactions of precursors to heteroepitaxy and doping with the substrate surface, the control of interfacial properties under the conditions of heteroepitaxy for selected materials systems, methods of characterization of interfaces and native point defects in semiconductor heterostructures and an in depth evaluation of the present status of the control and characterization of the point defect chemistry for one specific semiconductor (ZnGeP2), including studies of both heterostructures and bulk single crystals. The selected examples of presentations and comments given here represent individual choices - made by the author to highlight major points of the discussions.

  12. A qualitative inquiry into the effects of visualization on high school chemistry students' learning process of molecular structure

    Science.gov (United States)

    Deratzou, Susan

    This research studies the process of high school chemistry students visualizing chemical structures and its role in learning chemical bonding and molecular structure. Minimal research exists with high school chemistry students and more research is necessary (Gabel & Sherwood, 1980; Seddon & Moore, 1986; Seddon, Tariq, & Dos Santos Veiga, 1984). Using visualization tests (Ekstrom, French, Harman, & Dermen, 1990a), a learning style inventory (Brown & Cooper, 1999), and observations through a case study design, this study found visual learners performed better, but needed more practice and training. Statistically, all five pre- and post-test visualization test comparisons were highly significant in the two-tailed t-test (p > .01). The research findings are: (1) Students who tested high in the Visual (Language and/or Numerical) and Tactile Learning Styles (and Social Learning) had an advantage. Students who learned the chemistry concepts more effectively were better at visualizing structures and using molecular models to enhance their knowledge. (2) Students showed improvement in learning after visualization practice. Training in visualization would improve students' visualization abilities and provide them with a way to think about these concepts. (3) Conceptualization of concepts indicated that visualizing ability was critical and that it could be acquired. Support for this finding was provided by pre- and post-Visualization Test data with a highly significant t-test. (4) Various molecular animation programs and websites were found to be effective. (5) Visualization and modeling of structures encompassed both two- and three-dimensional space. The Visualization Test findings suggested that the students performed better with basic rotation of structures as compared to two- and three-dimensional objects. (6) Data from observations suggest that teaching style was an important factor in student learning of molecular structure. (7) Students did learn the chemistry concepts

  13. Materials Chemistry

    CERN Document Server

    Fahlman, Bradley D

    2011-01-01

    The 2nd edition of Materials Chemistry builds on the strengths that were recognized by a 2008 Textbook Excellence Award from the Text and Academic Authors Association (TAA). Materials Chemistry addresses inorganic-, organic-, and nano-based materials from a structure vs. property treatment, providing a suitable breadth and depth coverage of the rapidly evolving materials field. The 2nd edition continues to offer innovative coverage and practical perspective throughout. After briefly defining materials chemistry and its history, seven chapters discuss solid-state chemistry, metals, semiconducting materials, organic "soft" materials, nanomaterials, and materials characterization. All chapters have been thoroughly updated and expanded with, for example, new sections on ‘soft lithographic’ patterning, ‘click chemistry’ polymerization, nanotoxicity, graphene, as well as many biomaterials applications. The polymer and ‘soft’ materials chapter represents the largest expansion for the 2nd edition. Each ch...

  14. Electron spin interactions in chemistry and biology fundamentals, methods, reactions mechanisms, magnetic phenomena, structure investigation

    CERN Document Server

    Likhtenshtein, Gertz

    2016-01-01

    This book presents the versatile and pivotal role of electron spin interactions in nature. It provides the background, methodologies and tools for basic areas related to spin interactions, such as spin chemistry and biology, electron transfer, light energy conversion, photochemistry, radical reactions, magneto-chemistry and magneto-biology. The book also includes an overview of designing advanced magnetic materials, optical and spintronic devices and photo catalysts. This monograph appeals to scientists and graduate students working in the areas related to spin interactions physics, biophysics, chemistry and chemical engineering.

  15. Phenomenological study of nuclear structure of neutron-rich 88Rb isotope

    Science.gov (United States)

    Gupta, Surbhi; Gupta, Anuradha; Bharti, Arun

    2018-05-01

    A theoretical study of the nuclear structure of odd-odd 88Rb nucleus in the A ˜100 mass region is carried out by using the angular-momentum-projection technique implemented in the Projected Shell Model (PSM). The influence of the high-j orbitals, h11/2 for neutrons and g9/2 for protons on the structure of 88Rb isotope is investigated in the present case by assuming an axial symmetry in the deformed basis. For this isotope, PSM calculations are performed to obtain the yrast line and also the description of the formation of the yrast level structure from multi-quasi-particle configurations. The back-bending in moment of inertia and transition energies have also been calculated and compared with the experimental data.

  16. Mass measurement and structure studies of neutron-rich isotopes of Zn, Ni, Fe

    International Nuclear Information System (INIS)

    Dessagne, P.

    1982-01-01

    With the Orsay MP Tandem, the reaction ( 14 C, 16 O) on 58 - 60 - 62 - 64 Ni, 64 - 66 - 68 - 70 Zn, 74 - 76 Ge and 82 Se targets, and the reaction ( 14 C, 15 O) on 60 - 62 - 64 Ni, 68 - 70 Zn, 76 Ge targets, have been investigated at 72 MeV bombarding energy. The mass excess of neutron rich nuclei: 63 Fe (-55.19+-.06MeV), 69 Ni(-60.14+-.06 MeV), 75 Zn(.62.7+-08 MeV) have been measured for the first time, and those of 62 Fe, 68 Ni, 74 Zn, 80 Ge have been remeasured. A new equipment has been designed in order to perform measurements at zero degree. From the angular distribution around 0 0 for the 70 Zn( 14 C, 16 O) reaction, the first state of 68 Ni observed for the first time (1.77 MeV +- .04 MeV) has been shown to be a 0 + . This result establishes a new case of 2 1+ - 0 2+ inversion. The systematics of the ( 14 C, 16 O) measurements on the even Ni and Zn isotopes have shown a different behaviour with two series. For the Ni → Fe (g.s.) transitions, the ratio σsub(exp)/σsub(DWBA) increases by a factor of four when the neutron number varies from 30 to 36. Whereas for the Zn → Ni (gs) transitions this ratio remains constant for the first three isotopes and decrease by a factor of two when N=40. For the Ni → Fe transitions, axial and spherical symmetries have been used. In agreement with the shell model no change are found with the spherical symmetry. For the axial symmetry a variation is observed but strongly dapendant of the sub-shell. Hence no clear conclusion can be deduced for the cross section estimate. For the Zn → Ni transitions, the spherical symmetry has been used. One configuration prevails, leading to a qualitative agreement with the experimental results [fr

  17. Species Richness Responses to Structural or Compositional Habitat Diversity between and within Grassland Patches: A Multi-Taxon Approach

    Science.gov (United States)

    Lengyel, Szabolcs; Déri, Eszter; Magura, Tibor

    2016-01-01

    Habitat diversity (spatial heterogeneity within and between habitat patches in a landscape, HD) is often invoked as a driver of species diversity at small spatial scales. However, the effect of HD on species richness (SR) of multiple taxa is not well understood. We quantified HD and SR in a wet-dry gradient of open grassland habitats in Hortobágy National Park (E-Hungary) and tested the effect of compositional and structural factors of HD on SR of flowering plants, orthopterans, true bugs, spiders, ground beetles and birds. Our dataset on 434 grassland species (170 plants, 264 animals) showed that the wet-dry gradient (compositional HD at the between-patch scale) was primarily related to SR in orthopterans, ground-dwelling arthropods, and all animals combined. The patchiness, or plant association richness, of the vegetation (compositional HD at the within-patch scale) was related to SR of vegetation-dwelling arthropods, whereas vegetation height (structural HD at the within-patch scale) was related to SR of ground-dwelling arthropods and birds. Patch area was related to SR only in birds, whereas management (grazing, mowing, none) was related to SR of plants and true bugs. All relationships between HD and SR were positive, indicating increasing SR with increasing HD. However, total SR was not related to HD because different taxa showed similar positive responses to different HD variables. Our findings, therefore, show that even though HD positively influences SR in a wide range of grassland taxa, each taxon responds to different compositional or structural measures of HD, resulting in the lack of a consistent relationship between HD and SR when taxon responses are pooled. The idiosyncratic responses shown here exemplify the difficulties in detecting general HD-SR relationships over multiple taxa. Our results also suggest that management and restoration aimed specifically to sustain or increase the diversity of habitats are required to conserve biodiversity in

  18. Species Richness Responses to Structural or Compositional Habitat Diversity between and within Grassland Patches: A Multi-Taxon Approach.

    Directory of Open Access Journals (Sweden)

    Szabolcs Lengyel

    Full Text Available Habitat diversity (spatial heterogeneity within and between habitat patches in a landscape, HD is often invoked as a driver of species diversity at small spatial scales. However, the effect of HD on species richness (SR of multiple taxa is not well understood. We quantified HD and SR in a wet-dry gradient of open grassland habitats in Hortobágy National Park (E-Hungary and tested the effect of compositional and structural factors of HD on SR of flowering plants, orthopterans, true bugs, spiders, ground beetles and birds. Our dataset on 434 grassland species (170 plants, 264 animals showed that the wet-dry gradient (compositional HD at the between-patch scale was primarily related to SR in orthopterans, ground-dwelling arthropods, and all animals combined. The patchiness, or plant association richness, of the vegetation (compositional HD at the within-patch scale was related to SR of vegetation-dwelling arthropods, whereas vegetation height (structural HD at the within-patch scale was related to SR of ground-dwelling arthropods and birds. Patch area was related to SR only in birds, whereas management (grazing, mowing, none was related to SR of plants and true bugs. All relationships between HD and SR were positive, indicating increasing SR with increasing HD. However, total SR was not related to HD because different taxa showed similar positive responses to different HD variables. Our findings, therefore, show that even though HD positively influences SR in a wide range of grassland taxa, each taxon responds to different compositional or structural measures of HD, resulting in the lack of a consistent relationship between HD and SR when taxon responses are pooled. The idiosyncratic responses shown here exemplify the difficulties in detecting general HD-SR relationships over multiple taxa. Our results also suggest that management and restoration aimed specifically to sustain or increase the diversity of habitats are required to conserve

  19. Relative importance of current and past landscape structure and local habitat conditions for plant species richness in dry grassland-like forest openings.

    Science.gov (United States)

    Husáková, Iveta; Münzbergová, Zuzana

    2014-01-01

    In fragmented landscapes, plant species richness may depend not only on local habitat conditions but also on landscape structure. In addition, both present and past landscape structure may be important for species richness. There are, however, only a few studies that have investigated the relative importance of all of these factors. The aim of this study was to examine the effect of current and past landscape structures and habitat conditions on species richness at dry grassland-like forest openings in a forested landscape and to assess their relative importance for species richness. We analyzed information on past and present landscape structures using aerial photographs from 1938, 1973, 1988, 2000 and 2007. We calculated the area of each locality and its isolation in the present and in the past and the continuity of localities in GIS. At each locality, we recorded all vascular plant species (296 species in 110 forest openings) and information on abiotic conditions of the localities. We found that the current species richness of the forest openings was significantly determined by local habitat conditions as well as by landscape structure in the present and in the past. The highest species richness was observed on larger and more heterogeneous localities with rocks and shallow soils, which were already large and well connected to other localities in 1938. The changes in the landscape structure in the past can thus have strong effects on current species richness. Future studies attempting to understand determinants of species diversity in fragmented landscapes should also include data on past landscape structure, as it may in fact be more important than the present structure.

  20. General chemistry

    International Nuclear Information System (INIS)

    Kwon, Yeong Sik; Lee, Dong Seop; Ryu, Haung Ryong; Jang, Cheol Hyeon; Choi, Bong Jong; Choi, Sang Won

    1993-07-01

    The book concentrates on the latest general chemistry, which is divided int twenty-three chapters. It deals with basic conception and stoichiometry, nature of gas, structure of atoms, quantum mechanics, symbol and structure of an electron of ion and molecule, chemical thermodynamics, nature of solid, change of state and liquid, properties of solution, chemical equilibrium, solution and acid-base, equilibrium of aqueous solution, electrochemistry, chemical reaction speed, molecule spectroscopy, hydrogen, oxygen and water, metallic atom; 1A, IIA, IIIA, carbon and atom IVA, nonmetal atom and an inert gas, transition metals, lanthanons, and actinoids, nuclear properties and radioactivity, biochemistry and environment chemistry.

  1. Investigations of the Electronic Properties and Surface Structures of Aluminium-Rich Quasicrystalline Alloys

    Energy Technology Data Exchange (ETDEWEB)

    Barrow, Jason A. [Iowa State Univ., Ames, IA (United States)

    2003-01-01

    The work presented in this dissertation has investigated three distinct areas of interest in the field of quasicrystals: bulk structure, transport properties, and electronic structure. First, they have described the results of a study which explored the fundamental interactions between the atomic species of the icosahedral Al-Pd-Mn quasicrystal. The goal of this work was to determine whether the pseudo-MacKay or Bergman type clusters have a special stability or are merely a geometric coincidence. This was carried out by using laser vaporization to produce gas-phase metal clusters, which were analyzed using time-of-flight mass spectrometry. Both the kinetic and thermodynamic stabilities of the clusters were probed. The data indicated no special stability for either pseudo-MacKay or Bergman type clusters as isolated units. This, however, is not proof that these clusters are simply a geometric coincidence. It is possible that such clusters only have stability in the framework of the bulk matrix and do not exist as isolated units. Next, they have reported their investigations of the bulk thermal transport properties of a decagonal Al-Ni-Co two dimensional quasicrystal in the temperature range 373K-873K. The properties of a sample oriented along the periodic axis and another oriented along the aperiodic axis were measured. A high degree of anisotropy was observed between the aperiodic and periodic directions. Additionally, the properties were measured for a sample miscut to an orientation 45° off-axis. The properties of the miscut sample were shown to have good agreement with a theoretical model used to describe thermal transport in metallic single crystals. This model only considers thermal transport by a free-electron gas; therefore, agreement with experimental data suggests the validity of the Drude free-electron model for the decagonal Al-Ni-Co at these temperatures. Consequently, the observed anisotropy may be adequately described using classical transport

  2. Interstellar chemistry.

    Science.gov (United States)

    Klemperer, William

    2006-08-15

    In the past half century, radioastronomy has changed our perception and understanding of the universe. In this issue of PNAS, the molecular chemistry directly observed within the galaxy is discussed. For the most part, the description of the molecular transformations requires specific kinetic schemes rather than chemical thermodynamics. Ionization of the very abundant molecular hydrogen and atomic helium followed by their secondary reactions is discussed. The rich variety of organic species observed is a challenge for complete understanding. The role and nature of reactions involving grain surfaces as well as new spectroscopic observations of interstellar and circumstellar regions are topics presented in this special feature.

  3. Impact of the Fused Deposition (FDM) Printing Process on Polylactic Acid (PLA) Chemistry and Structure

    OpenAIRE

    Michael Arthur Cuiffo; Jeffrey Snyder; Alicia M. Elliott; Nicholas Romero; Sandhiya Kannan; Gary P. Halada

    2017-01-01

    Polylactic acid (PLA) is an organic polymer commonly used in fused deposition (FDM) printing and biomedical scaffolding that is biocompatible and immunologically inert. However, variations in source material quality and chemistry make it necessary to characterize the filament and determine potential changes in chemistry occurring as a result of the FDM process. We used several spectroscopic techniques, including laser confocal microscopy, Fourier transform infrared (FTIR) spectroscopy and pho...

  4. Effects of soil water table regime on tree community species richness and structure of alluvial forest fragments in Southeast Brazil.

    Science.gov (United States)

    Silva, A C; Higuchi, P; van den Berg, E

    2010-08-01

    In order to determine the influence of soil water table fluctuation on tree species richness and structure of alluvial forest fragments, 24 plots were allocated in a point bar forest and 30 plots in five forest fragments located in a floodplain, in the municipality of São Sebastião da Bela Vista, Southeast Brazil, totalizing 54, 10 X 20 m, plots. The information recorded in each plot were the soil water table level, diameter at breast height (dbh), total height and botanical identity off all trees with dbh > 5 cm. The water table fluctuation was assessed through 1 m deep observation wells in each plot. Correlations analysis indicated that sites with shallower water table in the flooding plains had a low number of tree species and high tree density. Although the water table in the point bar remained below the wells during the study period, low tree species richness was observed. There are other events taking place within the point bar forest that assume a high ecological importance, such as the intensive water velocity during flooding and sedimentation processes.

  5. Effects of soil water table regime on tree community species richness and structure of alluvial forest fragments in Southeast Brazil

    Directory of Open Access Journals (Sweden)

    AC. Silva

    Full Text Available In order to determine the influence of soil water table fluctuation on tree species richness and structure of alluvial forest fragments, 24 plots were allocated in a point bar forest and 30 plots in five forest fragments located in a floodplain, in the municipality of São Sebastião da Bela Vista, Southeast Brazil, totalizing 54, 10 X 20 m, plots. The information recorded in each plot were the soil water table level, diameter at breast height (dbh, total height and botanical identity off all trees with dbh > 5 cm. The water table fluctuation was assessed through 1 m deep observation wells in each plot. Correlations analysis indicated that sites with shallower water table in the flooding plains had a low number of tree species and high tree density. Although the water table in the point bar remained below the wells during the study period, low tree species richness was observed. There are other events taking place within the point bar forest that assume a high ecological importance, such as the intensive water velocity during flooding and sedimentation processes.

  6. Composition, structure, and properties of iron-rich nontronites of different origins

    Energy Technology Data Exchange (ETDEWEB)

    Palchik, N. A., E-mail: nadezhda@igm.nsc.ru; Grigorieva, T. N.; Moroz, T. N. [Russian Academy of Sciences, Sobolev Institute of Geology and Mineralogy, Siberian Branch (Russian Federation)

    2013-03-15

    The composition, structure, and properties of smectites of different origins have been studied by X-ray diffraction, IR spectroscopy, scanning electron microscopy, and microprobe analysis. The results showed that nontronites of different origins differ in composition, properties, morphology, and IR spectroscopic characteristics. Depending on the degree of structural order and the negative charge of iron-silicate layers in nontronites, the shift of the 001 reflection to smaller angles as a result of impregnation with ethylene glycol (this shift is characteristic of the smectite group) occurs differently. The calculated values of the parameter b (from 9.11 to 9.14A) are valid for the extreme terms of dioctahedral smectite representatives: nontronites.

  7. Nanoscale structural heterogeneity in Ni-rich half-Heusler TiNiSn

    International Nuclear Information System (INIS)

    Douglas, Jason E.; Pollock, Tresa M.; Chater, Philip A.; Brown, Craig M.; Seshadri, Ram

    2014-01-01

    The structural implications of excess Ni in the TiNiSn half-Heusler compound are examined through a combination of synchrotron x-ray and neutron scattering studies, in conjunction with first principles density functional theory calculations on supercells. Despite the phase diagram suggesting that TiNiSn is a line compound with no solid solution, for small x in TiNi 1+x Sn there is indeed an appearance—from careful analysis of the scattering—of some solubility, with the excess Ni occupying the interstitial tetrahedral site in the half-Heusler structure. The analysis performed here would point to the excess Ni not being statistically distributed, but rather occurring as coherent nanoclusters. First principles calculations of energetics, carried out using supercells, support a scenario of Ni interstitials clustering, rather than a statistical distribution.

  8. The latest general chemistry

    International Nuclear Information System (INIS)

    Ryu, Geun Bae; Choi, Se Yeong; Kim, Chin Yeong; Yoon, Gil Jung; Lee, Eun Seok; Seo, Moon Gyu

    1995-02-01

    This book deals with the latest general chemistry, which is comprised of twenty-three chapters, the contents of this book are introduction, theory of atoms and molecule, chemical formula and a chemical reaction formula, structure of atoms, nature of atoms and the periodic table, structure of molecule and spectrum, gas, solution, solid, chemical combination, chemical reaction speed, chemical equilibrium, thermal chemistry, oxidation-reduction, electrochemistry, acid-base, complex, aquatic chemistry, air chemistry, nuclear chemistry, metal and nonmetal, organic chemistry and biochemistry. It has exercise in the end of each chapter.

  9. Electrostatics in Chemistry

    Indian Academy of Sciences (India)

    fundamental concepts of electrostatics as applied to atoms and molecules. The electric ... chemistry, the chemistry of the covalent bond, deals with the structures ..... the position of an asteroid named Ceres ... World Scientific. Singapore, 1992.

  10. Structural and optical properties of silicon rich oxide films in graded-stoichiometric multilayers for optoelectronic devices

    Energy Technology Data Exchange (ETDEWEB)

    Palacios-Huerta, L.; Aceves-Mijares, M. [Electronics Department, INAOE, Apdo. 51, Puebla, Pue. 72000, México (Mexico); Cabañas-Tay, S. A.; Cardona-Castro, M. A.; Morales-Sánchez, A., E-mail: alfredo.morales@cimav.edu.mx [Centro de Investigación en Materiales Avanzados S.C., Unidad Monterrey-PIIT, Apodaca, NL 66628, México (Mexico); Domínguez-Horna, C. [Instituto de Microelectrónica de Barcelona, IMB-CNM (CSIC), Bellaterra 08193, Barcelona (Spain)

    2016-07-18

    Silicon nanocrystals (Si-ncs) are excellent candidates for the development of optoelectronic devices. Nevertheless, different strategies are still necessary to enhance their photo and electroluminescent properties by controlling their structural and compositional properties. In this work, the effect of the stoichiometry and structure on the optical properties of silicon rich oxide (SRO) films in a multilayered (ML) structure is studied. SRO MLs with silicon excess gradually increased towards the top and bottom and towards the center of the ML produced through the variation of the stoichiometry in each SRO layer were fabricated and confirmed by X-ray photoelectron spectroscopy. Si-ncs with three main sizes were observed by a transmission electron microscope, in agreement with the stoichiometric profile of each SRO layer. The presence of the three sized Si-ncs and some oxygen related defects enhances intense violet/blue and red photoluminescence (PL) bands. The SRO MLs were super-enriched with additional excess silicon by Si{sup +} implantation, which enhanced the PL intensity. Oxygen-related defects and small Si-ncs (<2 nm) are mostly generated during ion implantation enhancing the violet/blue band to become comparable to the red band. The structural, compositional, and luminescent characteristics of the multilayers are the result of the contribution of the individual characteristics of each layer.

  11. Surface chemistry and electronic structure of nonpolar and polar GaN films

    Energy Technology Data Exchange (ETDEWEB)

    Mishra, Monu; Krishna, T.C. Shibin; Aggarwal, Neha; Gupta, Govind, E-mail: govind@nplindia.org

    2015-08-01

    Highlights: • Surface chemistry and electronic structure of polar and nonpolar GaN is reported. • Influence of polarization on electron affinity of p & np GaN films is investigated. • Correlation between surface morphology and polarity has been deduced. - Abstract: Photoemission and microscopic analysis of nonpolar (a-GaN/r-Sapphire) and polar (c-GaN/c-Sapphire) epitaxial gallium nitride (GaN) films grown via RF-Molecular Beam Epitaxy is reported. The effect of polarization on surface properties like surface states, electronic structure, chemical bonding and morphology has been investigated and correlated. It was observed that polarization lead to shifts in core level (CL) as well as valence band (VB) spectra. Angle dependent X-ray Photoelectron Spectroscopic analysis revealed higher surface oxide in polar GaN film compared to nonpolar GaN film. On varying the take off angle (TOA) from 0° to 60°, the Ga−O/Ga−N ratio varied from 0.11–0.23 for nonpolar and 0.17–0.36 for polar GaN film. The nonpolar film exhibited N-face polarity while Ga-face polarity was perceived in polar GaN film due to the inherent polarization effect. Polarization charge compensated surface states were observed on the polar GaN film and resulted in downward band bending. Ultraviolet photoelectron spectroscopic measurements revealed electron affinity and ionization energy of 3.4 ± 0.1 eV and 6.8 ± 0.1 eV for nonpolar GaN film and 3.8 ± 0.1 eV and 7.2 ± 0.1 eV for polar GaN film respectively. Field Emission Scanning Electron Microscopy measurements divulged smooth morphology with pits on polar GaN film. The nonpolar film on the other hand showed pyramidal structures having facets all over the surface.

  12. Structural and functional characterization of a multifunctional alanine-rich peptide analogue from Pleuronectes americanus.

    Directory of Open Access Journals (Sweden)

    Ludovico Migliolo

    Full Text Available Recently, defense peptides that are able to act against several targets have been characterized. The present work focuses on structural and functional evaluation of the peptide analogue Pa-MAP, previously isolated as an antifreeze peptide from Pleuronectes americanus. Pa-MAP showed activities against different targets such as tumoral cells in culture (CACO-2, MCF-7 and HCT-116, bacteria (Escherichia coli ATCC 8739 and Staphylococcus aureus ATCC 25923, viruses (HSV-1 and HSV-2 and fungi (Candida parapsilosis ATCC 22019, Trichophyton mentagrophytes (28d&E and T. rubrum (327. This peptide did not show toxicity against mammalian cells such as erythrocytes, Vero and RAW 264.7 cells. Molecular mechanism of action was related to hydrophobic residues, since only the terminal amino group is charged at pH 7 as confirmed by potentiometric titration. In order to shed some light on its structure-function relations, in vitro and in silico assays were carried out using circular dichroism and molecular dynamics. Furthermore, Pa-MAP showed partial unfolding of the peptide changes in a wide pH (3 to 11 and temperature (25 to 95°C ranges, although it might not reach complete unfolding at 95°C, suggesting a high conformational stability. This peptide also showed a conformational transition with a partial α-helical fold in water and a full α-helical core in SDS and TFE environments. These results were corroborated by spectral data measured at 222 nm and by 50 ns dynamic simulation. In conclusion, data reported here show that Pa-MAP is a potential candidate for drug design against pathogenic microorganisms due to its structural stability and wide activity against a range of targets.

  13. Porous structure and surface chemistry of phosphoric acid activated carbon from corncob

    International Nuclear Information System (INIS)

    Sych, N.V.; Trofymenko, S.I.; Poddubnaya, O.I.; Tsyba, M.M.; Sapsay, V.I.; Klymchuk, D.O.; Puziy, A.M.

    2012-01-01

    Highlights: ► Phosphoric acid activation results in formation of carbons with acidic surface groups. ► Maximum amount of surface groups is introduced at impregnation ratio 1.25. ► Phosphoric acid activated carbons show high capacity to copper. ► Phosphoric acid activated carbons are predominantly microporous. ► Maximum surface area and pore volume achieved at impregnation ratio 1.0. - Abstract: Active carbons have been prepared from corncob using chemical activation with phosphoric acid at 400 °C using varied ratio of impregnation (RI). Porous structure of carbons was characterized by nitrogen adsorption and scanning electron microscopy. Surface chemistry was studied by IR and potentiometric titration method. It has been shown that porosity development was peaked at RI = 1.0 (S BET = 2081 m 2 /g, V tot = 1.1 cm 3 /g), while maximum amount of acid surface groups was observed at RI = 1.25. Acid surface groups of phosphoric acid activated carbons from corncob includes phosphate and strongly acidic carboxylic (pK = 2.0–2.6), weakly acidic carboxylic (pK = 4.7–5.0), enol/lactone (pK = 6.7–7.4; 8.8–9.4) and phenol (pK = 10.1–10.7). Corncob derived carbons showed high adsorption capacity to copper, especially at low pH. Maximum adsorption of methylene blue and iodine was observed for carbon with most developed porosity (RI = 1.0).

  14. Secondary Structures in Phe-Containing Isolated Dipeptide Chains: Laser Spectroscopy vs Quantum Chemistry.

    Science.gov (United States)

    Loquais, Yohan; Gloaguen, Eric; Habka, Sana; Vaquero-Vara, Vanesa; Brenner, Valérie; Tardivel, Benjamin; Mons, Michel

    2015-06-11

    The intrinsic conformational landscape of two phenylalanine-containing protein chain models (-Gly-Phe- and -Ala-Phe- sequences) has been investigated theoretically and experimentally in the gas phase. The near UV spectroscopy (first ππ* transition of the Phe ring) is obtained experimentally under jet conditions where the conformational features can be resolved. Single-conformation IR spectroscopy in the NH stretch region is then obtained by IR/UV double resonance in the ground state, leading to resolved vibrational spectra that are assigned in terms of conformation and H-bonding content from comparison with quantum chemistry calculations. For the main conformer, whose UV spectrum exhibits a significant Franck-Condon activity in low frequency modes involving peptide backbone motions relative to the Phe chromophore, excited state IR spectroscopy has also been recorded in a UV/IR/UV experiment. The NH stretch spectral changes observed in such a ππ* labeling experiment enable us to determine those NH bonds that are coupled to the phenyl ring; they are compared to CC2 excited state calculations to quantify the geometry change upon ππ* excitation. The complete and consistent series of data obtained enable us to propose an unambiguous assignment for the gallery of conformers observed and to demonstrate that, in these two sequences, three conceptually important local structural motifs of proteins (β-strands, 27 ribbons, and β-turns) are represented. The satisfactory agreement between the experimental conformational distribution and the predicted landscape anticipated from the DFT-D approach demonstrates the capabilities of a theoretical method that accounts for dispersive interactions. It also shows that the flaws, inherent to a resonant two-photon ionization detection scheme, often evoked for aromatic chromophores, do not seem to be significant in the case of Phe.

  15. Porous structure and surface chemistry of phosphoric acid activated carbon from corncob

    Energy Technology Data Exchange (ETDEWEB)

    Sych, N.V.; Trofymenko, S.I.; Poddubnaya, O.I.; Tsyba, M.M. [Institute for Sorption and Endoecology Problems, National Academy of Sciences of Ukraine, 13 General Naumov St., 03164 Kyiv (Ukraine); Sapsay, V.I.; Klymchuk, D.O. [M.G. Kholodny Institute of Botany, National Academy of Sciences of Ukraine, 2 Tereshchenkivska St., 01601 Kyiv (Ukraine); Puziy, A.M., E-mail: alexander.puziy@ispe.kiev.ua [Institute for Sorption and Endoecology Problems, National Academy of Sciences of Ukraine, 13 General Naumov St., 03164 Kyiv (Ukraine)

    2012-11-15

    Highlights: Black-Right-Pointing-Pointer Phosphoric acid activation results in formation of carbons with acidic surface groups. Black-Right-Pointing-Pointer Maximum amount of surface groups is introduced at impregnation ratio 1.25. Black-Right-Pointing-Pointer Phosphoric acid activated carbons show high capacity to copper. Black-Right-Pointing-Pointer Phosphoric acid activated carbons are predominantly microporous. Black-Right-Pointing-Pointer Maximum surface area and pore volume achieved at impregnation ratio 1.0. - Abstract: Active carbons have been prepared from corncob using chemical activation with phosphoric acid at 400 Degree-Sign C using varied ratio of impregnation (RI). Porous structure of carbons was characterized by nitrogen adsorption and scanning electron microscopy. Surface chemistry was studied by IR and potentiometric titration method. It has been shown that porosity development was peaked at RI = 1.0 (S{sub BET} = 2081 m{sup 2}/g, V{sub tot} = 1.1 cm{sup 3}/g), while maximum amount of acid surface groups was observed at RI = 1.25. Acid surface groups of phosphoric acid activated carbons from corncob includes phosphate and strongly acidic carboxylic (pK = 2.0-2.6), weakly acidic carboxylic (pK = 4.7-5.0), enol/lactone (pK = 6.7-7.4; 8.8-9.4) and phenol (pK = 10.1-10.7). Corncob derived carbons showed high adsorption capacity to copper, especially at low pH. Maximum adsorption of methylene blue and iodine was observed for carbon with most developed porosity (RI = 1.0).

  16. Large-scale micromagnetic simulation of Nd-Fe-B sintered magnets with Dy-rich shell structures

    Directory of Open Access Journals (Sweden)

    T. Oikawa

    2016-05-01

    Full Text Available Large-scale micromagnetic simulations have been performed using the energy minimization method on a model with structural features similar to those of Dy grain boundary diffusion (GBD-processed sintered magnets. Coercivity increases as a linear function of the anisotropy field of the Dy-rich shell, which is independent of Dy composition in the core as long as the shell thickness is greater than about 15 nm. This result shows that the Dy contained in the initial sintered magnets prior to the GBD process is not essential for enhancing coercivity. Magnetization reversal patterns indicate that coercivity is strongly influenced by domain wall pinning at the grain boundary. This observation is found to be consistent with the one-dimensional pinning theory.

  17. Spatial variability of microbial richness and diversity and relationships with soil organic carbon, texture and structure across an agricultural field

    DEFF Research Database (Denmark)

    Naveed, Muhammad; Herath, Lasantha; Møldrup, Per

    2016-01-01

    Highlights •Bacterial richness and Shannon diversity showed strong spatial autocorrelations. •Fungal richness and Shannon diversity did not show any clear spatial autocorrelations. •Ratio of clay to organic carbon was found a best predictor of bacterial richness and diversities. •Soil water...

  18. Petrography and mineral chemistry of carbonatites and mica-rich rocks from the Araxá complex (Alto Paranaíba Province, Brazil

    Directory of Open Access Journals (Sweden)

    GIANBOSCO TRAVERSA

    2001-03-01

    Full Text Available The Araxá complex (16 km² comprises carbonatites forming a central core and a complex network of concentric and radial dykes as well as small veins; additionally, it includes mica-rich rocks, phoscorites and lamprophyres. Fenites also occur and are represented by Proterozoic quartzites and schists of the Araxá Group. The petrographic study of 130 borehole samples indicates that the complex is basically made up by two rock-types, carbonatites and mica-rich rocks, and subordinately by a third unit of hybrid composition. Carbonatites range chemically in composition, the most abundant type being magnesiocarbonatites. Dolomite and calcite correspond to the chief constituents, but other carbonate phases, including the Ce-group RE minerals, are also recognized. Phosphates and oxides are widespread accessories whereas silicate minerals consist of olivine, clinopyroxene, mica and amphibole. Mica-rich rocks are represented by abundant glimmeritic rocks and scarce cumulitic phlogopite-, olivine- and diopside-bearing pyroxenites. Hybrid rocks mainly contain phlogopite and tetraferriphlogopite as cumulus and intercumulus phases, respectively; carbonate minerals may also be found. Chemical data indicate that the carbonatites are strongly enriched in REE and have lower contents of Nb, Zr, V, Cr, Ni and Rb compared to the mica-rich rocks. The higher K, Nb and Zr contents of the latter rocks are believed to be related to metasomatic processes (glimmeritization of the pyroxenites. Similar REE patterns for carbonatites and mica-rich rocks seem to suggest that they are related to a single parental magma, possibly of ijolitic composition. Steep LREE/HREE fractionation and high sigmaREE content of some carbonatite samples would be explained by hydrothermal and supergenic processes.O complexo de Araxá (16 km² é constituído por carbonatitos na forma de um núcleo central e de complexa rede de diques concêntricos e radiais, além de pequenos veios

  19. Structural characterization of guaiacyl-rich lignins in flax (Linum usitatissimum) fibers and shives.

    Science.gov (United States)

    del Río, José C; Rencoret, Jorge; Gutiérrez, Ana; Nieto, Lidia; Jiménez-Barbero, Jesús; Martínez, Ángel T

    2011-10-26

    The structural characteristics of the lignins from flax (Linum usitatissimum) fibers and shives were studied. Significant differences in the content and composition of the lignin from both parts were observed. The lignin contents were 3.8% in the fibers and 29.0% in the shives. Analysis by Py-GC/MS indicated a H:G:S molar ratio of 13:72:15 in the milled wood lignin (MWL) isolated from flax fibers and a molar ratio of 5:87:8 in the MWL isolated from flax shives. In addition, 2D-NMR showed a predominance of β-O-4' aryl ether linkages, followed by β-5' phenylcoumaran and β-β' resinol-type linkages in both MWLs, with a higher content of condensed linkages in flax shives. Thioacidolysis (followed by Raney nickel desulfurization) gave further information on the lignin units involved in the different linkages and confirmed the enrichment of G units. The thioacidolysis dimers released were similar from both lignins, with a predominance of the β-5' followed by β-1' and 5-5' structures.

  20. Studies of rotational structures in the neutron-rich niobium isotopes 101-103

    International Nuclear Information System (INIS)

    Paffrath, U.

    1989-08-01

    The aim of this thesis was to study rotational structures in the low-lying levels of the niobium isotopes 101, 102, and 103. This was performed at the recoil separator JOSEF of the Nuclear Research Facility Juelich by studies of the β-decays of the zirconium isotopes 101-103 into their niobium daughters. By γ-γ respectively X-γ coincidence measurements the already existing term schemes of the niobium isotopes should be verified respectively extended and by γ-γ angular-correlation measurements the rotational structures should be studied. The term schemes of the niobium isotopes 101 and 102 could be confirmed in the framework of the performed experiments while the level scheme of the 103 Nb could be essentially extended. From the X-γ coincidence measurement for a plurality of γ transitions the conversion coefficients and by this the dominant multipolarities could be determined. With these conversion coefficients then also the mixing parameters were calculated. These data together with the results from the γ-γ angular-correlation experiments led to a fixing concerning the spins and parities at a series of levels in all three niobium isotopes. (orig./HSI) [de

  1. Understanding of the structure activity relationship of PtPd bimetallic catalysts prepared by surface organometallic chemistry and ion exchange during the reaction of iso-butane with hydrogen

    KAUST Repository

    Al-Shareef, Reem A.; Harb, Moussab; Saih, Youssef; Ould-Chikh, Samy; Roldan, Manuel A.; Anjum, Dalaver H.; Guyonnet, Elodie Bile; Candy, Jean-Pierre; Jan, Deng-Yang; Abdo, Suheil F.; Aguilar-Tapia, Antonio; Proux, Olivier; Hazemann, Jean-Louis; Basset, Jean-Marie

    2018-01-01

    Well-defined silica supported bimetallic catalysts Pt100-x Pdx were prepared by Surface Organometallic Chemistry (SOMC) and Ionic-Exchange (IE) methods. For all investigated catalysts, iso-butane reaction with hydrogen under differential conditions led to the formation of methane and propane, n-butane, and traces of iso-butylene. The total reaction rate decreased with increasing the Pd loading for both catalysts series as a result of decreasing turnover rate of both isomerization and hydrogenolysis. In the case of Pt100-x Pdx(SOMC) catalysts, the experimental results in combination with DFT calculations suggested a selective coverage of Pt (1 0 0) surface by agglomerated Pd atoms like “islands”, assuming that each metal roughly keeps its intrinsic catalytic properties with relatively small electron transfer from Pt to Pd in the case of Pt-rich sample and from Pd to Pt in the case of Pd-rich sample. For the PtPd catalysts prepared by IE, the catalytic behavior could be explained by the formation of a surface alloy between Pt and Pd in the case of Pd-rich sample and by the segregation of a small amount of Pd on the surface in the case of Pt-rich sample, as demonstrated by TEM, EXAFS and DFT. The catalytic results were explained by a structure activity relationship based on the proposed mechanism of CH bond and CC bond activation and cleavage for iso-butane hydrogenolysis, isomerization, cracking and dehydrogenation.

  2. Understanding of the structure activity relationship of PtPd bimetallic catalysts prepared by surface organometallic chemistry and ion exchange during the reaction of iso-butane with hydrogen

    KAUST Repository

    Alshareef, Reem Abdul aziz Hamed

    2018-04-25

    Well-defined silica supported bimetallic catalysts Pt100-x Pdx were prepared by Surface Organometallic Chemistry (SOMC) and Ionic-Exchange (IE) methods. For all investigated catalysts, iso-butane reaction with hydrogen under differential conditions led to the formation of methane and propane, n-butane, and traces of iso-butylene. The total reaction rate decreased with increasing the Pd loading for both catalysts series as a result of decreasing turnover rate of both isomerization and hydrogenolysis. In the case of Pt100-x Pdx(SOMC) catalysts, the experimental results in combination with DFT calculations suggested a selective coverage of Pt (1 0 0) surface by agglomerated Pd atoms like “islands”, assuming that each metal roughly keeps its intrinsic catalytic properties with relatively small electron transfer from Pt to Pd in the case of Pt-rich sample and from Pd to Pt in the case of Pd-rich sample. For the PtPd catalysts prepared by IE, the catalytic behavior could be explained by the formation of a surface alloy between Pt and Pd in the case of Pd-rich sample and by the segregation of a small amount of Pd on the surface in the case of Pt-rich sample, as demonstrated by TEM, EXAFS and DFT. The catalytic results were explained by a structure activity relationship based on the proposed mechanism of CH bond and CC bond activation and cleavage for iso-butane hydrogenolysis, isomerization, cracking and dehydrogenation.

  3. Microbial diversity and community structure in an antimony-rich tailings dump.

    Science.gov (United States)

    Xiao, Enzong; Krumins, Valdis; Dong, Yiran; Xiao, Tangfu; Ning, Zengping; Xiao, Qingxiang; Sun, Weimin

    2016-09-01

    To assess the impact of antimony (Sb) on microbial community structure, 12 samples were taken from an Sb tailings pile in Guizhou Province, Southwest China. All 12 samples exhibited elevated Sb concentrations, but the mobile and bioaccessible fractions were small in comparison to total Sb concentrations. Besides the geochemical analyses, microbial communities inhabiting the tailing samples were characterized to investigate the interplay between the microorganisms and environmental factors in mine tailings. In all samples, Proteobacteria and Actinobacteria were the most dominant phyla. At the genus level, Thiobacillus, Limnobacter, Nocardioides, Lysobacter, Phormidium, and Kaistobacter demonstrated relatively high abundances. The two most abundant genera, Thiobacillus and Limnobacter, are characterized as sulfur-oxidizing bacteria and thiosulfate-oxidizing bacteria, respectively, while the genus Lysobacter contains arsenic (As)-resistant bacteria. Canonical correspondence analysis (CCA) indicates that TOC and the sulfate to sulfide ratio strongly shaped the microbial communities, suggesting the influence of the environmental factors in the indigenous microbial communities.

  4. Structural, thermal and optical absorption features of heavy metal oxides doped tellurite rich glasses

    Directory of Open Access Journals (Sweden)

    Kawa M. Kaky

    Full Text Available In order to improve tellurite glass stability to be applicable for optical fiber amplifier applications, glasses with the composition of (70 − xTeO2. (10ZnO. (10WO3. (5Na2O. (5TiO2. (xBi2O3 (x = 1, 2, 3, 4, and 5 mol% have been produced and characterized using the related methods. Structural properties were investigated using X-ray diffraction (XRD which confirms the non-crystalline structure and scanning electron microscopy (SEM micrographs also confirm the XRD results. The energy dispersive X-ray (EDX analysis profiles show that all the mentioned elements are present in the prepared glasses. Following the IR spectra, all the tellurium bonds such as stretching vibrations of TeO4 tbp and TeO3/TeO3+1 unit are revealed. Raman spectra confirm the presence of different functional groups, actually, it shows bands mainly in four spectral regions: R1 (65–150 cm−1, R2 (280–550 cm−1, R3 (880–950 cm−1 and R4 (916–926 cm−1 and the identified bands are assigned to respective molecular groups. The thermal study was carried out using Differential scanning calorimetry (DSC which indicates good thermal stability of the synthesized glasses with increasing Bi concentration. From the optical absorption spectra, we evaluated cut-off edge wavelengths and found increasing cutoff wavelength with an increase in Bi2O3 concentration. In the UV–Visible region, optical band gap energy and allowed transitions were investigated using three methods; direct, indirect, and absorption spectrum fitting (ASF, and band gaps from indirect and ASF were matched. Keywords: Tellurite glasses, XRD, FT-IR, Raman, TGA/DSC

  5. Structural, thermal and optical absorption features of heavy metal oxides doped tellurite rich glasses

    Science.gov (United States)

    Kaky, Kawa M.; Lakshminarayana, G.; Baki, S. O.; Kityk, I. V.; Taufiq-Yap, Y. H.; Mahdi, M. A.

    In order to improve tellurite glass stability to be applicable for optical fiber amplifier applications, glasses with the composition of (70 - x)TeO2. (10)ZnO. (10)WO3. (5)Na2O. (5)TiO2. (x)Bi2O3 (x = 1, 2, 3, 4, and 5 mol%) have been produced and characterized using the related methods. Structural properties were investigated using X-ray diffraction (XRD) which confirms the non-crystalline structure and scanning electron microscopy (SEM) micrographs also confirm the XRD results. The energy dispersive X-ray (EDX) analysis profiles show that all the mentioned elements are present in the prepared glasses. Following the IR spectra, all the tellurium bonds such as stretching vibrations of TeO4 tbp and TeO3/TeO3+1 unit are revealed. Raman spectra confirm the presence of different functional groups, actually, it shows bands mainly in four spectral regions: R1 (65-150) cm-1, R2 (280-550) cm-1, R3 (880-950) cm-1 and R4 (916-926) cm-1 and the identified bands are assigned to respective molecular groups. The thermal study was carried out using Differential scanning calorimetry (DSC) which indicates good thermal stability of the synthesized glasses with increasing Bi concentration. From the optical absorption spectra, we evaluated cut-off edge wavelengths and found increasing cutoff wavelength with an increase in Bi2O3 concentration. In the UV-Visible region, optical band gap energy and allowed transitions were investigated using three methods; direct, indirect, and absorption spectrum fitting (ASF), and band gaps from indirect and ASF were matched.

  6. Chemistry of Iron N -heterocyclic carbene complexes: Syntheses, structures, reactivities, and catalytic applications

    KAUST Repository

    Riener, Korbinian; Haslinger, Stefan; Raba, Andreas; Hogerl, Manuel Peter; Cokoja, Mirza; Herrmann, Wolfgang A.; Kü hn, Fritz

    2014-01-01

    Iron is the most abundant transition metal in Earth's crust. It is relatively inexpensive, not very toxic, and environmentally benign. Undoubtedly, due to the involvement in a multitude of biological processes, which heavily rely on the rich

  7. Synthesis of 2-monoacylglycerols and structured triacylglycerols rich in polyunsaturated fatty acids by enzyme catalyzed reactions.

    Science.gov (United States)

    Rodríguez, Alicia; Esteban, Luis; Martín, Lorena; Jiménez, María José; Hita, Estrella; Castillo, Beatriz; González, Pedro A; Robles, Alfonso

    2012-08-10

    This paper studies the synthesis of structured triacylglycerols (STAGs) by a four-step process: (i) obtaining 2-monoacylglycerols (2-MAGs) by alcoholysis of cod liver oil with several alcohols, catalyzed by lipases Novozym 435, from Candida antartica and DF, from Rhizopus oryzae, (ii) purification of 2-MAGs, (iii) formation of STAGs by esterification of 2-MAGs with caprylic acid catalyzed by lipase DF, from R. oryzae, and (iv) purification of these STAGs. For the alcoholysis of cod liver oil, absolute ethanol, ethanol 96% (v/v) and 1-butanol were compared; the conditions with ethanol 96% were then optimized and 2-MAG yields of around 54-57% were attained using Novozym 435. In these 2-MAGs, DHA accounted for 24-31% of total fatty acids. In the operational conditions this lipase maintained a stable level of activity over at least 11 uses. These results were compared with those obtained with lipase DF, which deactivated after only three uses. The alcoholysis of cod liver oil and ethanol 96% catalyzed by Novozym 435 was scaled up by multiplying the reactant amounts 100-fold and maintaining the intensity of treatment constant (IOT=3g lipase h/g oil). In these conditions, the 2-MAG yield attained was about 67%; these 2-MAGs contained 36.6% DHA. The synthesized 2-MAGs were separated and purified from the alcoholysis reaction products by solvent extraction using solvents of low toxicity (ethanol and hexane); 2-MAG recovery yield and purity of the target product were approximately 96.4% and 83.9%, respectively. These 2-MAGs were transformed to STAGs using the optimal conditions obtained in a previous work. After synthesis and purification, 93% pure STAGs were obtained, containing 38% DHA at sn-2 position and 60% caprylic acid (CA) at sn-1,3 positions (of total fatty acids at these positions), i.e. the major TAG is the STAG with the structure CA-DHA-CA. Copyright © 2012 Elsevier Inc. All rights reserved.

  8. Structural and magnetic study of mechanically deformed Fe rich FeAlSi ternary alloys

    International Nuclear Information System (INIS)

    Legarra, E.; Apiñaniz, E.; Plazaola, F.

    2012-01-01

    Highlights: ► Addition of Si to binary Fe–Al alloys makes the disordering more difficult. ► Si addition opposes the large volume increase found in FeAl alloys with deformation. ► Disordering induces a redistribution of non-ferrous atoms around Fe atoms in Fe 75 Al 25−x Si x and Fe 70 Al 30−x Si x . ► Addition of Si to binary Fe 75 Al 25 and Fe 70 Al 30 alloys opposes the magnetic behavior induced by Al in the magnetism of Fe. ► Si inhibits the para-ferro transition found in Fe 60 Al 40 alloy with disordering. - Abstract: In this work we study systematically the influence of different Al/Si ratios on the magnetic and structural properties of mechanically disordered powder Fe 75 Al 25−x Si x , Fe 70 Al 30−x Si x and Fe 60 Al 40−x Si x alloys by means of Mössbauer spectroscopy, X-ray diffraction and magnetic measurements. In order to obtain different stages of disorder the alloys were deformed by different methods: crushing induction melted alloys and ball milling annealed (ordered) alloys using different number of balls and speed. X-ray and Mössbauer data show that mechanical deformation induces the disordered A2 structure in these alloys. The results indicate that addition of Si to binary Fe–Al alloys makes the disordering more difficult. In addition, X-ray diffraction patterns show that the normalized lattice parameter variation of the disordered alloys of each composition decreases monotonically with Si content, indicating clearly that Si addition opposes the large volume increase found in FeAl alloys with deformation. The study of the hyperfine fields indicates that there is a redistribution of non-ferrous atoms around Fe atoms with the disordering; indeed, there is an inversion of the behavior of the hyperfine field of the Fe atoms. On the other hand, the magnetic measurements indicate that addition of Si to binary Fe 75 Al 25 and Fe 70 Al 30 alloys opposes the magnetic behavior induced by Al in the magnetism of Fe.

  9. Effect of the kind of alkaline and rare earth ions on the structure of a glass rich in earth; Effet de la nature des ions alcalins et alcalino-terreux sur la structure d un verre riche en terre

    Energy Technology Data Exchange (ETDEWEB)

    Quintas, Arnaud; Caurant, Daniel; Majerus, Odile [Laboratoire de Chimie Appliquee de l Etat Solide, UMR 7574, ENSCP, 11 rue Pierre et Marie Curie, 75231 Paris Cedex 05, (France); Lenoir, Marion; Dussossoy, Jean-Luc [Commissariat a l Energie Atomique, Centre d Etudes de la Vallee du Rhone, DIEC/SCDV/LEBM, 30207 Bagnols-sur-Ceze, (France); Charpentier, Thibault [Service de Chimie Moleculaire, DSM/DRECAM/CEA Saclay, 91191 Gif-sur-Yvette Cedex, (France); Neuville, Daniel R. [Laboratoire de Physique des Mineraux et des Magmas, UMR 7047-CNRS-IPGP, Universite Pierre et Marie Curie, 4 place Jussieu, 75252 Paris Cedex 05, (France); Gervais, C. [Laboratoire de Chimie de la matiere condensee, UMR7574, Universite Pierre et Marie Curie, 4 place Jussieu, F-75252 Paris Cedex 05, (France)

    2006-07-01

    In the framework of a structural study of a nuclear wastes containment glass of type alumino borosilicate and rich in rare earths, the influence of the kind of alkaline or rare earth ions is analyzed. For that, two glasses series have been prepared in which the Na{sup +} ion (respectively Ca{sup 2+} ions) present in the standard composition is totally substituted by another alkaline ion Li{sup +}, K{sup +}, Rb{sup +} or Cs{sup +} (respectively another rare earth ion Mg{sup 2+}, Sr{sup 2+} or Ba{sup 2+}). These glasses, analyzed by optical absorption, Raman and {sup 27}Al or {sup 11}B NMR spectroscopies have revealed the strong impact of the kind of the modifying ion as well as the structure of the vitreous lattice (variation of the ratio BO{sub 3}/BO{sub 4} and local variations of the polymerization degree) than the local surroundings of the rare earth (decrease of the covalency degree of the bond Nd-O with the increase of the field force of the modifying ion). (O.M.)

  10. Physical Chemistry '98: Fourth International Conference on Fundamental and Applied Aspects of Physical Chemistry - Papers

    International Nuclear Information System (INIS)

    Ribnikar, S.; Anic, S.

    1998-01-01

    The proceedings has following chapters: Plenary lectures; Chemical Thermodynamics; Spectroscopy, Molecular Structures, Physical Chemistry of Plasma; Kinetics, Catalysis, Nonlinear Dynamics; Electrochemistry; Biophysical Chemistry, Photochemistry, Radiation Chemistry; Radiochemistry, Nuclear Chemistry; Solid State Physical Chemistry, Material Science; Macromolecular Physical Chemistry; Environmental Protection; Phase Boundaries; Complex Compounds; General Physical Chemistry. A separated abstract was prepared for each of the 20 papers selected from the three chapters: Biophysical Chemistry, Photochemistry, Radiation Chemistry; Radiochemistry, Nuclear Chemistry. and Environmental Protection. Refs and figs

  11. Study of the structure of light neutron rich nucleus with the Tonnerre array

    International Nuclear Information System (INIS)

    Pietri, St.

    2003-06-01

    This work concern the technical development made on the multidetector TONNERRE and the study of the 34 Si nucleus by a complete beta-neutron-gamma spectroscopy. In the first part various tests performed on modules of the detector in the 'Centre d'Etude de Bruyere le Chatel' are presented. A modification of the embassies of the photomultipliers tubes allows to gain more than 50% in the neutron efficiency and to obtain a threshold lower than 300 keV for the neutron energy. A complete C++ simulation of the neutron propagation in the array was carried out. It explains that the slow component of the light output of the scintillator may be responsible of the shape of the time-of-flight spectrum. The second part of these report presents the experiment devoted to the study of the structure of the 34 Si from the beta decay of the 34 Al. It was performed at the GANIL facility using the TONNERRE array and germanium of ENOGAM. The 34 Al was produced by projectile fragmentation of a 36 S beam of 50 MeV/A in a target of 9 Be. A complete beta scheme of the 34 Al is proposed. Eight neutron lines following the 34 Al decay were observed for the first time. Finally we suggest that a monopolar transition could occur in the 34 Si nucleus signing a O + 2 state at 2133 keV. (author)

  12. Structure of neutron-rich isotopes of boron and carbon at the limits of stability

    International Nuclear Information System (INIS)

    Leblond, Sylvain

    2015-01-01

    The unbound nuclei 18 B and 21 C have been studied in an experiment undertaken at the RIBF-RIKEN using the recently commissioned SAMURAI spectrometer and NEBULA neutron array. The two systems were probed using single-neutron and single and two-proton knockout from secondary beams of 22 C, 22 N, et 23 O respectively in the case of 21 C and 19 B, 19 C and 20 N for 18 B. The invariant mass spectra were reconstructed from the momentum of the fragment ( 17 B, 20 C) and neutron. In order to interpret the results a complete simulation of the experimental setup was utilised. The analysis procedures as well as the calibrations were verified through a measurement of the well-known ground state of 16 B. In the case of 18 B three states were observed: an s-wave virtual state (as ≤ -50 fm), an l=2 resonance at E r =0.77 ± 0.09 MeV and an l=0 resonance at E r = 1.6 ± 0.6 MeV. These results suggest that the low-lying level structure of 18 B is governed by a competition between the neutron 2s 1/2 and 1d 5/2 configurations. In the case of 21 C resonances were observed at E r = 0.8 ± 0.15 MeV (l = 0) and E r = 1.5 ±0.1 MeV (l=2), a result which confirms predictions of an inversion of the 5/2 + and 1/2 + levels. Finally an analysis of the momentum distributions for 18 B and 21 C produced in single-neutron knockout was carried out. The results indicate that the valence neutrons 19 B and 22 C are in mixed (2s 1/2 ) 2 and (1d 5/2 ) 2 configurations. (author)

  13. Radiation chemistry

    International Nuclear Information System (INIS)

    Rodgers, F.; Rodgers, M.A.

    1987-01-01

    The contents of this book include: Interaction of ionizing radiation with matter; Primary products in radiation chemistry; Theoretical aspects of radiation chemistry; Theories of the solvated electron; The radiation chemistry of gases; Radiation chemistry of colloidal aggregates; Radiation chemistry of the alkali halides; Radiation chemistry of polymers; Radiation chemistry of biopolymers; Radiation processing and sterilization; and Compound index

  14. Impact of casein and egg white proteins on the structure of wheat gluten-based protein-rich food.

    Science.gov (United States)

    Wouters, Arno G B; Rombouts, Ine; Lagrain, Bert; Delcour, Jan A

    2016-02-01

    There is a growing interest in texturally and nutritionally satisfying vegetable alternatives to meat. Wheat gluten proteins have unique functional properties but a poor nutritional value in comparison to animal proteins. This study investigated the potential of egg white and bovine milk casein with well-balanced amino acid composition to increase the quality of wheat gluten-based protein-rich foods. Heating a wheat gluten (51.4 g)-water (100.0 mL) blend for 120 min at 100 °C increased its firmness less than heating a wheat gluten (33.0 g)-freeze-dried egg white (16.8 g)-water (100.0 mL) blend. In contrast, the addition of casein to the gluten-water blend negatively impacted firmness after heating. Firmness was correlated with loss of protein extractability in sodium dodecyl sulfate containing medium during heating, which was higher with egg white than with casein. Even more, heat-induced polymerization of the gluten-water blend with egg white but not with casein was greater than expected from the losses in extractability of gluten and egg white on their own. Structure formation was favored by mixing gluten with egg white but not with casein. These observations were linked to the intrinsic polymerization behavior of egg white and casein, but also to their interaction with gluten. Thus not all nutritionally suitable proteins can be used for enrichment of gluten-based protein-rich foods. © 2015 Society of Chemical Industry.

  15. Structure, thermal stability and resistance under external irradiation of rare earths and molybdenum-rich alumino-borosilicate glasses

    International Nuclear Information System (INIS)

    Chouard, N.

    2011-01-01

    In France, the highly radioactive nuclear liquid wastes arising from spent nuclear fuel reprocessing (fission products + minor actinides (FPA)) are currently immobilized in an alumino-borosilicate glass called 'R7T7'. In the future, the opportunity of using new alumino-borosilicate glass compositions (HTC glasses) is considered in order to increase the waste loading in glasses and thus significantly decrease the number of glass canisters. However, the increase of the concentration of FPA could lead to the crystallization of rare-earth-rich phases (Ca 2 RE 8 (SiO 4 ) 6 O 2 ) or molybdenum-rich phases (CaMoO 4 , Na 2 MoO 4 ) during melt cooling, which can modify the confinement properties of the glass (chemical durability, self-irradiation resistance..), particularly if they can incorporate radionuclides α or β in their structure. This thesis can be divided into two parts: The first part deals with studying the relationship that can occur between the composition, the structure and the crystallization tendency of simplified seven oxides glasses, belonging to the SiO 2 -B 2 O 3 -Al 2 O 3 -Na 2 O-CaO-MoO 3 -Nd 2 O 3 system and derived from the composition of the HTC glass at 22,5 wt. % in FPA. The impact of the presence of platinoid elements (RuO 2 in our case) on the crystallization of the different phases is also studied. The second part deals with the effect of actinides α decays and more particularly of nuclear interactions essentially coming from recoil nuclei (simulated here by heavy ions external irradiations) on the behaviour under irradiation of an alumino-borosilicate glass containing apatite Ca 2 Nd 8 (SiO 4 ) 6 O 2 crystals, that can incorporate actinides in their structure. Two samples containing apatite crystals with different size are studied, in order to understand the impact of microstructure on the irradiation resistance of this kind of material. (author) [fr

  16. Multistep continuous-flow synthesis in medicinal chemistry: discovery and preliminary structure-activity relationships of CCR8 ligands.

    Science.gov (United States)

    Petersen, Trine P; Mirsharghi, Sahar; Rummel, Pia C; Thiele, Stefanie; Rosenkilde, Mette M; Ritzén, Andreas; Ulven, Trond

    2013-07-08

    A three-step continuous-flow synthesis system and its application to the assembly of a new series of chemokine receptor ligands directly from commercial building blocks is reported. No scavenger columns or solvent switches are necessary to recover the desired test compounds, which were obtained in overall yields of 49-94%. The system is modular and flexible, and the individual steps of the sequence can be interchanged with similar outcome, extending the scope of the chemistry. Biological evaluation confirmed activity on the chemokine CCR8 receptor and provided initial structure-activity-relationship (SAR) information for this new ligand series, with the most potent member displaying full agonist activity with single-digit nanomolar potency. To the best of our knowledge, this represents the first published example of efficient use of multistep flow synthesis combined with biological testing and SAR studies in medicinal chemistry. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Study of Chemistry and Structure-Property Relationship on Tunable Plasmonic Nanostructures

    Science.gov (United States)

    Jing, Hao

    In this dissertation, the rational design and controllable fabrication of an array of novel plasmonic nanostructures with geometrically tunable optical properties are demonstrated, including metal-semiconductor hybrid hetero-nanoparticles, bimetallic noble metal nanoparticles and hollow nanostructures (nanobox and nanocage). Firstly, I have developed a robust wet chemistry approach to the geometry control of Ag-Cu2O core-shell nanoparticles through epitaxial growth of Cu2O nanoshells on the surfaces of various Ag nanostructures, such as quasi-spherical nanoparticles, nanocubes, and nanocuboids. Precise control over the core and the shell geometries enables me to develop detailed, quantitative understanding of how the Cu2O nanoshells introduce interesting modifications to the resonance frequencies and the extinction spectral line shapes of multiple plasmon modes of the Ag cores. Secondly, I present a detailed and systematic study of the controlled overgrowth of Pd on Au nanorods. The overgrowth of Pd nanoshells with fine-controlled dimensions and architectures on single-crystalline Au nanorods through seed-mediated growth protocol in the presence of various surfactants is investigated. Thirdly, I have demonstrated that creation of high-index facets on subwavelength metallic nanoparticles provides a unique approach to the integration of desired plasmonic and catalytic properties on the same nanoparticle. Through site-selective surface etching of metallic nanocuboids whose surfaces are dominated by low-index facets, I have controllably fabricated nanorice and nanodumbbell particles, which exhibit drastically enhanced catalytic activities arising from the catalytically active high index facets abundant on the particle surfaces. And the nanorice and nanodumbbell particles also possess appealing tunable plasmonic properties that allow us to gain quantitative insights into nanoparticle-catalyzed reactions with unprecedented sensitivity and detail through time

  18. Structure and electronic properties of InN and In-rich group III-nitride alloys

    International Nuclear Information System (INIS)

    Walukiewicz, W; III, J W Ager; Yu, K M; Liliental-Weber, Z; Wu, J; Li, S X; Jones, R E; Denlinger, J D

    2006-01-01

    The experimental study of InN and In-rich InGaN by a number of structural, optical and electrical methods is reviewed. Recent advances in thin film growth have produced single crystal epitaxial layers of InN which are similar in structural quality to GaN films made under similar conditions and which can have electron concentrations below 1 x 10 18 cm -3 and mobilities exceeding 2000 cm 2 (Vs) -1 . Optical absorption, photoluminescence, photo-modulated reflectance and soft x-ray spectroscopy measurements were used to establish that the room temperature band gap of InN is 0.67 ± 0.05 eV. Experimental measurements of the electron effective mass in InN are presented and interpreted in terms of a non-parabolic conduction band caused by the k · p interaction across the narrow gap. Energetic particle irradiation is shown to be an effective method to control the electron concentration, n, in undoped InN. Optical studies of irradiated InN reveal a large Burstein-Moss shift of the absorption edge with increasing n. Fundamental studies of the energy levels of defects in InN and of electron transport are also reviewed. Finally, the current experimental evidence for p-type activity in Mg-doped InN is evaluated. (topical review)

  19. The structure of neutron-rich nuclei explored via in-beam gamma-ray spectroscopy of fast beams

    International Nuclear Information System (INIS)

    Glasmacher, T.; Campbell, C.M.; Church, J.A.; Dinca, D.C.; Hansen, P.G.; Olliver, H.; Perry, B.C.; Sherrill, B.M.; Terry, J.R.; Bazin, D.; Enders, J.; Gade, A.; Hu, Z.; Mueller, W.F.

    2003-01-01

    In-beam gamma-ray spectroscopy with fast exotic beams provides an efficient tool to study bound states in exotic neutron-rich nuclei. Specialized experimental techniques have been developed and explore different aspects of nuclear structure. Inelastic scattering experiments with γ-ray detection can measure the response of exotic nuclei to electromagnetic (Coulomb excitation with a heavy target) or hadronic probes (proton scattering with hydrogen target). In-beam fragmentation populates higher-lying bound states to establish levels. Single- and two-nucleon knockout reactions allow for detailed wavefunction spectroscopy of individual levels and for the measurement of spectroscopic factors. Experimental programs employing these techniques are now underway at all projectile-fragmentation facilities around the world. Here we report on several successful in-beam gamma-ray spectroscopy experiments that have been performed at the Coupled Cyclotron Facility at Michigan State University with an emphasis on elucidating the evolution of nuclear structure around neutron numbers N=16, N=20, and N=28 in the π(sd) shell. (orig.)

  20. Effect of the kind of alkaline and rare earth ions on the structure of a glass rich in earth

    International Nuclear Information System (INIS)

    Quintas, Arnaud; Caurant, Daniel; Majerus, Odile; Lenoir, Marion; Dussossoy, Jean-Luc; Charpentier, Thibault; Neuville, Daniel R.; Gervais, C.

    2006-01-01

    In the framework of a structural study of a nuclear wastes containment glass of type alumino borosilicate and rich in rare earths, the influence of the kind of alkaline or rare earth ions is analyzed. For that, two glasses series have been prepared in which the Na + ion (respectively Ca 2+ ions) present in the standard composition is totally substituted by another alkaline ion Li + , K + , Rb + or Cs + (respectively another rare earth ion Mg 2+ , Sr 2+ or Ba 2+ ). These glasses, analyzed by optical absorption, Raman and 27 Al or 11 B NMR spectroscopies have revealed the strong impact of the kind of the modifying ion as well as the structure of the vitreous lattice (variation of the ratio BO 3 /BO 4 and local variations of the polymerization degree) than the local surroundings of the rare earth (decrease of the covalency degree of the bond Nd-O with the increase of the field force of the modifying ion). (O.M.)

  1. Synthesis and structure of bivalent ytterbocenes and their coordination chemistry with pi-acceptor ligands

    Energy Technology Data Exchange (ETDEWEB)

    Schultz, Madeleine [Univ. of California, Berkeley, CA (United States)

    2000-05-01

    The bivalent lanthanide metallocenes [1,3-(Me3C)2C5H3]2Yb and (Me4C5H)2Yb have been synthesized and their structures have been determined by X-ray crystallography. Comparison with the known structures of (Me5C5)2Yb and [1,3 -(Me3Si)2C5H3]2Yb leads to an understanding of the role of intermolecular contacts in stabilizing these coordinatively unsaturated molecules. The optical spectra of the base-free ytterbocenes and their Lewis-base adducts have been measured; the position of the HOMO - LUMO transition can be correlated with the degree of bending of the complexes in solution according to a molecular orbital model. Electron - electron repulsion, resulting from additional σ-donor ligands, also affects the HOMO - LUMO transition by increasing the energy of the filled f-orbitals. The base-free metallocene (Me5C5)2Yb coordinates carbon monoxide, resulting in a decrease in Vco relative to that of fi-ee carbon monoxide. This behavior is reminiscent of d-transition metallocene chemistry. Other base-free ytterbocenes also coordinate carbon monoxide and the degree of back-donation is related to the substituents on the cyclopentadienide rings. Isocyanides are coordinated in a 1:2 ratio by the ytterbocenes, giving complexes having vcN higher than those of the free isocyanides. An electrostatic bonding model has been used to explain the changes in CN stretching frequencies. The optical spectra of the carbonyl and isocyanide complexes are consistent with the molecular orbital model of the variation in the HOMO - LUMO gap upon bending, and the increase in electron - electron repulsion due to the additional ligands. The complex (Me5C5)2Yb(bipy) exhibits optical, infrared and NMIZ spectroscopy and an X-ray crystal

  2. The Effects of Cognitive Structure Variables on Achievement in College Chemistry

    Science.gov (United States)

    Ring, Donald G.; Novak, Joseph D.

    1971-01-01

    College freshmen chemistry students who performed best on the course examinations possessed both relevant facts and relevant subsuming concepts. This conclusion supports Ausubel's theory of learning. The presence of facts unorganized by subsumers had little facilitating effect on learning of new materials. (AL)

  3. Leg tendon glands in male bumblebees (Bombus terrestris): structure, secretion chemistry, and possible functions

    Czech Academy of Sciences Publication Activity Database

    Jarau, S.; Žáček, Petr; Šobotník, Jan; Vrkoslav, Vladimír; Hadravová, Romana; Coppée, Audrey; Vašíčková, Soňa; Jiroš, Pavel; Valterová, Irena

    2012-01-01

    Roč. 99, č. 12 (2012), s. 1039-1049 ISSN 0028-1042 R&D Projects: GA TA ČR TA01020969 Institutional support: RVO:61388963 Keywords : bumblebee * hydrocarbons * leg tendon glands * sex specific secretion * wax esters Subject RIV: CC - Organic Chemistry Impact factor: 2.144, year: 2012

  4. Re-Structuring of Marine Communities Exposed to Environmental Change: A Global Study on the Interactive Effects of Species and Functional Richness

    Science.gov (United States)

    Wahl, Martin; Link, Heike; Alexandridis, Nicolaos; Thomason, Jeremy C.; Cifuentes, Mauricio; Costello, Mark J.; da Gama, Bernardo A. P.; Hillock, Kristina; Hobday, Alistair J.; Kaufmann, Manfred J.; Keller, Stefanie; Kraufvelin, Patrik; Krüger, Ina; Lauterbach, Lars; Antunes, Bruno L.; Molis, Markus; Nakaoka, Masahiro; Nyström, Julia; bin Radzi, Zulkamal; Stockhausen, Björn; Thiel, Martin; Vance, Thomas; Weseloh, Annika; Whittle, Mark; Wiesmann, Lisa; Wunderer, Laura; Yamakita, Takehisa; Lenz, Mark

    2011-01-01

    Species richness is the most commonly used but controversial biodiversity metric in studies on aspects of community stability such as structural composition or productivity. The apparent ambiguity of theoretical and experimental findings may in part be due to experimental shortcomings and/or heterogeneity of scales and methods in earlier studies. This has led to an urgent call for improved and more realistic experiments. In a series of experiments replicated at a global scale we translocated several hundred marine hard bottom communities to new environments simulating a rapid but moderate environmental change. Subsequently, we measured their rate of compositional change (re-structuring) which in the great majority of cases represented a compositional convergence towards local communities. Re-structuring is driven by mortality of community components (original species) and establishment of new species in the changed environmental context. The rate of this re-structuring was then related to various system properties. We show that availability of free substratum relates negatively while taxon richness relates positively to structural persistence (i.e., no or slow re-structuring). Thus, when faced with environmental change, taxon-rich communities retain their original composition longer than taxon-poor communities. The effect of taxon richness, however, interacts with another aspect of diversity, functional richness. Indeed, taxon richness relates positively to persistence in functionally depauperate communities, but not in functionally diverse communities. The interaction between taxonomic and functional diversity with regard to the behaviour of communities exposed to environmental stress may help understand some of the seemingly contrasting findings of past research. PMID:21611170

  5. Deep-UV Raman spectroscopic analysis of structure and dissolution rates of silica-rich sodium borosilicate glasses

    Energy Technology Data Exchange (ETDEWEB)

    Windisch, Charles F.; Pierce, Eric M.; Burton, Sarah D.; Bovaird, Chase C.

    2011-03-24

    As part of ongoing studies to evaluate the relationships between structural variations in silicate glasses and rates of glass dissolution in aqueous media, molecular structures present in sodium borosilicate glasses of composition Na2O.xB2O3.(3-x)SiO2, with x 1 (Na2O/B2O3 ratio 1), were analyzed using deep-UV Raman spectroscopy. The results were quantified in terms of the fraction of SiO4 tetrahedra with one non-bridging oxygen (Q3) and then correlated with Na2O and B2O3 content. Increasing Na2O was found to raise the fraction of Q3 units in the glasses systematically, in agreement with studies on related glasses, and, as long as the value of x was not too high, contribute to higher rates of dissolution in single pass flow-through testing. The finding was obtained across more than one series of silica-rich glasses prepared for independent dissolution studies. In contrast, dissolution rates were less strongly determined by the Q3 fraction when the value of x was near unity and appeared to grow larger upon further reduction of the Q3 fraction. The results were interpreted to indicate the increasingly important role of network hydrolysis in the glass dissolution mechanism as the BO4 tetrahedron replaces the Q3 unit as the charge-compensating structure for Na+ ions. Finally, the use of deep-UV Raman spectroscopy was found to be advantageous in studying finely powdered glasses in cases where visible Raman spectroscopy suffered from weak Raman scattering and fluorescence interference.

  6. Structure and chemistry of epitaxial ceria thin films on yttria-stabilized zirconia substrates, studied by high resolution electron microscopy

    Energy Technology Data Exchange (ETDEWEB)

    Sinclair, Robert, E-mail: bobsinc@stanford.edu [Department of Materials Science and Engineering, Stanford University, Stanford, CA 94305 (United States); Lee, Sang Chul, E-mail: sclee99@stanford.edu [Department of Materials Science and Engineering, Stanford University, Stanford, CA 94305 (United States); Shi, Yezhou; Chueh, William C. [Department of Materials Science and Engineering, Stanford University, Stanford, CA 94305 (United States); Stanford Synchrotron Radiation Lightsource, SLAC National Accelerator Laboratory, Menlo Park, CA 94025 (United States); Stanford Institute for Materials and Energy Sciences, SLAC National Accelerator Laboratory, Menlo Park, CA 94025 (United States)

    2017-05-15

    We have applied aberration-corrected transmission electron microscopy (TEM) imaging and electron energy loss spectroscopy (EELS) to study the structure and chemistry of epitaxial ceria thin films, grown by pulsed laser deposition onto (001) yttria-stabilized zirconia (YSZ) substrates. There are few observable defects apart from the expected mismatch interfacial dislocations and so the films would be expected to have good potential for applications. Under high electron beam dose rate (above about 6000 e{sup -}/Å{sup 2}s) domains of an ordered structure appear and these are interpreted as being created by oxygen vacancy ordering. The ordered structure does not appear at lower lose rates (ca. 2600 e{sup -}/Å{sup 2}s) and can be removed by imaging under 1 mbar oxygen gas in an environmental TEM. EELS confirms that there is both oxygen deficiency and the associated increase in Ce{sup 3+} versus Ce{sup 4+} cations in the ordered domains. In situ high resolution TEM recordings show the formation of the ordered domains as well as atomic migration along the ceria thin film (001) surface. - Highlights: • The local structure and chemistry of ceria can be studied by TEM combined with EELS. • At lower electron, there are no observable changes in the ceria thin films. • At higher dose rates, an ordered phase is created due to oxygen vacancy ordering. • In situ HRTEM shows the oxygen vacancy ordering and the movement of surface atoms.

  7. Interaction of tantalum, chromium, and phosphorus at 1070 K: Phase diagram and structural chemistry

    Energy Technology Data Exchange (ETDEWEB)

    Lomnytska, Ya. [Ivan Franko National University of Lviv, Kyryla and Mefodiya Street 6, UA-79005 Lviv (Ukraine); Babizhetskyy, V., E-mail: v.babizhetskyy@googlemail.com [Ivan Franko National University of Lviv, Kyryla and Mefodiya Street 6, UA-79005 Lviv (Ukraine); Oliynyk, A. [Department of Chemistry, University of Alberta, Edmonton, Alberta, Canada T6G 2G2 (Canada); Toma, O. [Laboratory MOLTECH – Anjou, UMR-CNRS 6200, University of Angers, 49045 Angers (France); Dzevenko, M. [Ivan Franko National University of Lviv, Kyryla and Mefodiya Street 6, UA-79005 Lviv (Ukraine); Mar, A. [Department of Chemistry, University of Alberta, Edmonton, Alberta, Canada T6G 2G2 (Canada)

    2016-03-15

    Solid-state phase equilibria have been established in the Ta–Cr–P system in the region of 0–67 at% P at 1070 K through powder X-ray diffraction analysis. Mutual substitution of Ta and Cr in binary phosphides gives rise to significant homogeneity ranges in Ta{sub 1.00–0.66}Cr{sub 0–0.34}P (NbAs-type; a=3.332(3)–3.1366(3) Å, c=11.386(4)–11.364(2) Å), Ta{sub 3.0–2.1}Cr{sub 0–0.9}P (Ti{sub 3}P-type, a=10.156(2)–9.9992(2) Å, c=5.015(1)–4.956(2) Å), and Cr{sub 3.0–2.4}Ta{sub 0–0.6}P (Ni{sub 3}P-type, a=9.186(5)–9.217(4) Å, c=4.557(3)–4.5911(3) Å). A limited homogeneity range is found in the ternary phase Ta{sub 1.0–0.8}Cr{sub 1.0–1.2}P (TiNiSi-type, a=6.2344(5)–6.141(2) Å, b=3.5034(3)–3.3769(6) Å, c=7.3769(6)–7.357(2) Å). The OsGe{sub 2}-type structures (space group C2/m) of a new P-rich compound, Ta{sub 0.92(2)}Cr{sub 0.08(2)}P{sub 2} (a=8.8586(3) Å, b=3.2670(2) Å, c=7.4871(2) Å, β=119.315(2)°) as well as of the Ti-containing analogue Ta{sub 0.93(3)}Ti{sub 0.07(3)}P{sub 2} (a=8.8592(5) Å, b=3.2663(3) Å, c=7.4870(5) Å, β=119.309(2)°) were refined from powder X-ray diffraction data. - Graphical abstract: Solid-state phase equilibria have been established in the Ta–Cr–P system in the region of 0–67 at% P at 1070 K through powder X-ray diffraction analysis. Mutual substitution of Ta and Cr in binary phosphides gives rise to significant homogeneity ranges in Ta{sub 1.00–0.66}Cr{sub 0–0.34}P, Ta{sub 3.0–2.1}Cr{sub 0–0.9}P, and Cr{sub 3.0–2.4}Ta{sub 0–0.6}P. A limited homogeneity range is found in the ternary phase Ta{sub 1.0–0.8}Cr{sub 1.0–1.2}P. The OsGe{sub 2}-type structures of a new P-rich compound, Ta{sub 0.92(2)}Cr{sub 0.08(2)}P{sub 2} as well as of the Ti-containing analogue Ta{sub 0.93(3)}Ti{sub 0.07(3)}P{sub 2} were establish from powder X-ray diffraction data. No homogeneity ranges for binary compounds Cr{sub 12}P{sub 7}, Cr{sub 2}P, Ta{sub 5}P{sub 3} were detected. - Highlights:

  8. Seasonal Dynamics in the Chemistry and Structure of the Fat Bodies of Bumblebee Queens

    Czech Academy of Sciences Publication Activity Database

    Votavová, A.; Tomčala, Aleš; Kofroňová, Edita; Kudzejová, Michaela; Šobotník, J.; Jiroš, Pavel; Komzáková, O.; Valterová, Irena

    2015-01-01

    Roč. 10, č. 11 (2015), e0142261/1-e0142261/14 E-ISSN 1932-6203 R&D Projects: GA ČR(CZ) GA14-04291S Institutional support: RVO:61388963 Keywords : transmission electron microscopy * triacylglycerols * phospholipids * fat ty acid composition * glycogen Subject RIV: CB - Analytical Chemistry, Separation Impact factor: 3.057, year: 2015 http://journals.plos.org/plosone/article?id=10.1371/journal.pone.0142261

  9. Human platelet glycoprotein IX: An adhesive prototype of leucine-rich glycoproteins with flank-center-flank structures

    International Nuclear Information System (INIS)

    Hickey, M.J.; Williams, S.A.; Roth, G.J.

    1989-01-01

    The glycoprotein (GP) Ib-IX complex on the surface of human platelets functions as the von Willebrand factor receptor and mediates von Willebrand factor-dependent platelet adhesion to blood vessels. GPIX is a relatively small (M r , 17,000) protein that may provide for membrane insertion and orientation of the larger component of the complex. GPIb (M r , 165,000). Using antibody screening, the authors cloned a cDNA encoding GPIX from a human erythroleukemia cell cDNA library constructed in phage λgt11. Lacking a 5' untranslated region and start codon, the cDNA sequence includes 604 nucleotides, beginning with 495 bases at the 5' end coding for 165 amino acids, followed by a stop codon and 106 noncoding bases at the 3' end. By Northern blot analysis, the GPIX cDNA hybridizes with a single 1.0-kilobase species of platelet poly(A) + RNA. Translation of the cDNA sequence gives a predicted protein sequence beginning with a truncated putative signal sequence of 5 amino acids followed by a sequence of 17 amino acids matching that determined directly by Edman degradation of intact GPIX. GPIX contains a leucine-rich glycoprotein (LRG) sequence of 24 amino acids similar to conserved LRG sequences in GPIb and other proteins from humans, Drosophila, and yeast. The role of the flank-LRG center-flank structure in the evolution and function of the LRG proteins remains to be defined

  10. Structure analysis of molecular systems in the Institute of Macromolecular Chemistry of the Czech Academy of Sciences

    Czech Academy of Sciences Publication Activity Database

    Hašek, Jindřich

    2010-01-01

    Roč. 17, 2a (2010), k32-k34 ISSN 1211-5894. [Struktura 2010. Soláň, 14.06.2010-17.06.2010] R&D Projects: GA AV ČR IAA500500701; GA ČR GA305/07/1073 Institutional research plan: CEZ:AV0Z40500505 Keywords : Academy of Sciences of the Czech Republic * X-ray structure analysis * crystallography Subject RIV: CD - Macromolecular Chemistry http:// xray .cz/ms/bul2010-2a/hasek.pdf

  11. Are carnivore digestive separation mechanisms revealed on structure-rich diets?: Faecal inconsistency in dogs (Canis familiaris) fed day old chicks

    NARCIS (Netherlands)

    Cuyper, De Annelies; Clauss, M.; Hesta, Myriam; Cools, An; Bosch, G.; Hendriks, W.H.; Janssens, Geert P.J.

    2018-01-01

    Pronounced variations in faecal consistency have been described anecdotally for some carnivore species fed a structure-rich diet. Typically two faecal consistencies are distinguished, namely hard and firm versus liquid and viscous faeces. It is possible that a separation mechanism is operating in

  12. Machine learning of single molecule free energy surfaces and the impact of chemistry and environment upon structure and dynamics.

    Science.gov (United States)

    Mansbach, Rachael A; Ferguson, Andrew L

    2015-03-14

    The conformational states explored by polymers and proteins can be controlled by environmental conditions (e.g., temperature, pressure, and solvent) and molecular chemistry (e.g., molecular weight and side chain identity). We introduce an approach employing the diffusion map nonlinear machine learning technique to recover single molecule free energy landscapes from molecular simulations, quantify changes to the landscape as a function of external conditions and molecular chemistry, and relate these changes to modifications of molecular structure and dynamics. In an application to an n-eicosane chain, we quantify the thermally accessible chain configurations as a function of temperature and solvent conditions. In an application to a family of polyglutamate-derivative homopeptides, we quantify helical stability as a function of side chain length, resolve the critical side chain length for the helix-coil transition, and expose the molecular mechanisms underpinning side chain-mediated helix stability. By quantifying single molecule responses through perturbations to the underlying free energy surface, our approach provides a quantitative bridge between experimentally controllable variables and microscopic molecular behavior, guiding and informing rational engineering of desirable molecular structure and function.

  13. The environment, not space, dominantly structures the landscape patterns of the richness and composition of the tropical understory vegetation.

    Directory of Open Access Journals (Sweden)

    Yue-Hua Hu

    Full Text Available The mechanisms driving the spatial patterns of species richness and composition are essential to the understanding of biodiversity. Numerous studies separately identify the contributions of the environment (niche process and space (neutral process to the species richness or composition at different scales, but few studies have investigated the contributions of both types of processes in the two types of data at the landscape scale. In this study, we partitioned the spatial variations in all, exotic and native understory plant species richness and composition constrained by environmental variables and space in 134 plots that were spread across 10 counties in Hainan Island in southern China. The 134 plots included 70 rubber (Hevea brasiliensis plantation plots, 50 eucalyptus (Eucalyptus urophylla plantation plots, and 14 secondary forest plots. RDA based variation partitioning was run to assess the contribution of environment and space to species richness and composition. The results showed that the environmental variables alone explained a large proportion of the variations in both the species richness and composition of all, native, and exotic species. The RDA results indicated that overstory composition (forest type here plays a leading role in determining species richness and composition patterns. The alpha and beta diversities of the secondary forest plots were markedly higher than that of the two plantations. In conclusion, niche differentiation processes are the principal mechanisms that shape the alpha and beta diversities of understory plant species in Hainan Island.

  14. Hibiscus sabdariffa (Roselle) Polyphenol-rich Extract Averts Cardiac Functional and Structural Abnormalities in Type 1 Diabetic Rats.

    Science.gov (United States)

    Mohammed Yusof, Nur Liyana; Zainalabidin, Satirah; Mohd Fauzi, Norsyahida; Budin, Siti Balkis

    2018-05-04

    Diabetes mellitus is often associated with cardiac functional and structural alteration, an initial event leading to cardiovascular complications. Hibiscus sabdariffa or roselle has been widely proven as an antioxidant and recently has incited research interest for its potential in treating cardiovascular disease. Therefore, this study aimed to determine the cardioprotective effects of H. sabdariffa (roselle) polyphenol-rich extract (HPE) in type-1 induced diabetic rats. Twenty-four male Sprague-Dawley rats were randomized into four groups (n=6/group): non-diabetic (NDM), diabetic alone (DM), diabetic supplemented with HPE (DM+HPE) and metformin (DM+MET). Type-1 diabetes was induced with streptozotocin (55 mg/kg/i.p). Rats were forced-fed HPE (100 mg/kg) and metformin (150 mg/kg) daily for eight weeks. Results showed that HPE supplementation improved hyperglycemia and dyslipidemia significantly (p<0.05) in DM+HPE compared to DM group. HPE supplementation attenuated cardiac oxidative damage in DM group, indicated by low malondialdehyde and advanced oxidation protein product. As for the antioxidant status, HPE significantly (p<0.05) increased glutathione level, as well as catalase and superoxide dismutase 1 and 2 activities. These findings correlate with cardiac function, whereby HPE supplementation improved left ventricle developed pressure, coronary flow, cardiac contractility and relaxation rate significantly (p<0.05). Histological analysis showed a marked decrease in cardiomyocyte hypertrophy and fibrosis in DM+HPE compared to DM group. Ultrastructural changes and impairment of mitochondria induced by diabetes were minimized by HPE supplementation. Collectively, these findings suggest that HPE is a potential cardioprotective agent in a diabetic setting through its hypoglycemic, anti-hyperlipidemia and antioxidant properties.

  15. Variation in fish community structure, richness, and diversity in 56 Danish lakes with contrasting depth, size, and trophic state: does the method matter?

    DEFF Research Database (Denmark)

    Menezes, Rosemberg; Borchsenius, Finn; Svenning, J.-C.

    2013-01-01

    a better understanding of fish communities. We compare fish community composition, richness, and diversity in 56 Danish lakes using data obtained by gillnetting in different lake zones and near-shore electrofishing, respectively. On average, electrofishing captured more species than offshore gillnets......, but not more than littoral gillnets. Overall, the different fish sampling methods showed consistency as to fish community structure, but noticeable differences in community–environment relationships. Lake area was the best predictor for fish species richness in the littoral samplings, while it was poor...... community, as all methods miss some important species that other methods capture. However, electrofishing seems to be a fast alternative to gillnets for monitoring fish species richness and composition in littoral habitats of Danish lakes....

  16. Selectivity on-target of bromodomain chemical probes by structure-guided medicinal chemistry and chemical biology.

    Science.gov (United States)

    Galdeano, Carles; Ciulli, Alessio

    2016-09-01

    Targeting epigenetic proteins is a rapidly growing area for medicinal chemistry and drug discovery. Recent years have seen an explosion of interest in developing small molecules binding to bromodomains, the readers of acetyl-lysine modifications. A plethora of co-crystal structures has motivated focused fragment-based design and optimization programs within both industry and academia. These efforts have yielded several compounds entering the clinic, and many more are increasingly being used as chemical probes to interrogate bromodomain biology. High selectivity of chemical probes is necessary to ensure biological activity is due to an on-target effect. Here, we review the state-of-the-art of bromodomain-targeting compounds, focusing on the structural basis for their on-target selectivity or lack thereof. We also highlight chemical biology approaches to enhance on-target selectivity.

  17. Influence of surface chemistry on the structural organization of monomolecular protein layers adsorbed to functionalized aqueous interfaces

    DEFF Research Database (Denmark)

    Lösche, M.; Piepenstock, M.; Diederich, A.

    1993-01-01

    The molecular organization of streptavidin (SA) bound to aqueous surface monolayers of biotin-functionalized lipids and binary lipid mixtures has been investigated with neutron reflectivity and electron and fluorescence microscopy. The substitution of deuterons (2H) for protons (1H), both...... in subphase water molecules and in the alkyl chains of the lipid surface monolayer, was utilized to determine the interface structure on the molecular length scale. In all cases studied, the protein forms monomolecular layers underneath the interface with thickness values of apprx 40 ANG . A systematic...... dependence of the structural properties of such self-assembled SA monolayers on the surface chemistry was observed: the lateral protein density depends on the length of the spacer connecting the biotin moiety and its hydrophobic anchor. The hydration of the lipid head groups in the protein-bound state...

  18. Structures of pseudechetoxin and pseudecin, two snake-venom cysteine-rich secretory proteins that target cyclic nucleotide-gated ion channels: implications for movement of the C-terminal cysteine-rich domain

    Energy Technology Data Exchange (ETDEWEB)

    Suzuki, Nobuhiro [Department of Applied Biochemistry, University of Tsukuba, Tsukuba, Ibaraki 305-8572 (Japan); Department of Biochemistry, National Institute of Agrobiological Sciences, Tsukuba, Ibaraki 305-8602 (Japan); Yamazaki, Yasuo [Department of Biochemistry, Meiji Pharmaceutical University, Kiyose, Tokyo 204-8588 (Japan); Brown, R. Lane [Neurological Science Institute, Oregon Health and Science University, Beaverton, Oregon 97006 (United States); Fujimoto, Zui [Department of Biochemistry, National Institute of Agrobiological Sciences, Tsukuba, Ibaraki 305-8602 (Japan); Morita, Takashi, E-mail: tmorita@my-pharm.ac.jp [Department of Biochemistry, Meiji Pharmaceutical University, Kiyose, Tokyo 204-8588 (Japan); Mizuno, Hiroshi, E-mail: tmorita@my-pharm.ac.jp [Department of Biochemistry, National Institute of Agrobiological Sciences, Tsukuba, Ibaraki 305-8602 (Japan); VALWAY Technology Center, NEC Soft Ltd, Koto-ku, Tokyo 136-8627 (Japan); Institute for Biological Resources and Functions, National Institute of Advanced Industrial Science and Technology, Central 6, Tsukuba, Ibaraki 305-8566 (Japan); Department of Applied Biochemistry, University of Tsukuba, Tsukuba, Ibaraki 305-8572 (Japan)

    2008-10-01

    The structures of pseudechetoxin and pseudecin suggest that both proteins bind to cyclic nucleotide-gated ion channels in a manner in which the concave surface occludes the pore entrance. Cyclic nucleotide-gated (CNG) ion channels play pivotal roles in sensory transduction by retinal photoreceptors and olfactory neurons. The elapid snake toxins pseudechetoxin (PsTx) and pseudecin (Pdc) are the only known protein blockers of CNG channels. These toxins belong to a cysteine-rich secretory protein (CRISP) family containing an N-terminal pathogenesis-related proteins of group 1 (PR-1) domain and a C-terminal cysteine-rich domain (CRD). PsTx and Pdc are highly homologous proteins, but their blocking affinities on CNG channels are different: PsTx blocks both the olfactory and retinal channels with ∼15–30-fold higher affinity than Pdc. To gain further insights into their structure and function, the crystal structures of PsTx, Pdc and Zn{sup 2+}-bound Pdc were determined. The structures revealed that most of the amino-acid-residue differences between PsTx and Pdc are located around the concave surface formed between the PR-1 domain and the CRD, suggesting that the concave surface is functionally important for CNG-channel binding and inhibition. A structural comparison in the presence and absence of Zn{sup 2+} ion demonstrated that the concave surface can open and close owing to movement of the CRD upon Zn{sup 2+} binding. The data suggest that PsTx and Pdc occlude the pore entrance and that the dynamic motion of the concave surface facilitates interaction with the CNG channels.

  19. Structures of pseudechetoxin and pseudecin, two snake-venom cysteine-rich secretory proteins that target cyclic nucleotide-gated ion channels: implications for movement of the C-terminal cysteine-rich domain

    International Nuclear Information System (INIS)

    Suzuki, Nobuhiro; Yamazaki, Yasuo; Brown, R. Lane; Fujimoto, Zui; Morita, Takashi; Mizuno, Hiroshi

    2008-01-01

    The structures of pseudechetoxin and pseudecin suggest that both proteins bind to cyclic nucleotide-gated ion channels in a manner in which the concave surface occludes the pore entrance. Cyclic nucleotide-gated (CNG) ion channels play pivotal roles in sensory transduction by retinal photoreceptors and olfactory neurons. The elapid snake toxins pseudechetoxin (PsTx) and pseudecin (Pdc) are the only known protein blockers of CNG channels. These toxins belong to a cysteine-rich secretory protein (CRISP) family containing an N-terminal pathogenesis-related proteins of group 1 (PR-1) domain and a C-terminal cysteine-rich domain (CRD). PsTx and Pdc are highly homologous proteins, but their blocking affinities on CNG channels are different: PsTx blocks both the olfactory and retinal channels with ∼15–30-fold higher affinity than Pdc. To gain further insights into their structure and function, the crystal structures of PsTx, Pdc and Zn 2+ -bound Pdc were determined. The structures revealed that most of the amino-acid-residue differences between PsTx and Pdc are located around the concave surface formed between the PR-1 domain and the CRD, suggesting that the concave surface is functionally important for CNG-channel binding and inhibition. A structural comparison in the presence and absence of Zn 2+ ion demonstrated that the concave surface can open and close owing to movement of the CRD upon Zn 2+ binding. The data suggest that PsTx and Pdc occlude the pore entrance and that the dynamic motion of the concave surface facilitates interaction with the CNG channels

  20. Genetic structure, diversity, and allelic richness in composite collection and reference set in chickpea (Cicer arietinum L.

    Directory of Open Access Journals (Sweden)

    Gowda Cholenahalli LL

    2008-10-01

    Full Text Available Abstract Background Plant genetic resources (PGR are the basic raw materials for future genetic progress and an insurance against unforeseen threats to agricultural production. An extensive characterization of PGR provides an opportunity to dissect structure, mine allelic variations, and identify diverse accessions for crop improvement. The Generation Challenge Program http://www.generationcp.org conceptualized the development of "composite collections" and extraction of "reference sets" from these for more efficient tapping of global crop-related genetic resources. In this study, we report the genetic structure, diversity and allelic richness in a composite collection of chickpea using SSR markers, and formation of a reference set of 300 accessions. Results The 48 SSR markers detected 1683 alleles in 2915 accessions, of which, 935 were considered rare, 720 common and 28 most frequent. The alleles per locus ranged from 14 to 67, averaged 35, and the polymorphic information content was from 0.467 to 0.974, averaged 0.854. Marker polymorphism varied between groups of accessions in the composite collection and reference set. A number of group-specific alleles were detected: 104 in Kabuli, 297 in desi, and 69 in wild Cicer; 114 each in Mediterranean and West Asia (WA, 117 in South and South East Asia (SSEA, and 10 in African region accessions. Desi and kabuli shared 436 alleles, while wild Cicer shared 17 and 16 alleles with desi and kabuli, respectively. The accessions from SSEA and WA shared 74 alleles, while those from Mediterranean 38 and 33 alleles with WA and SSEA, respectively. Desi chickpea contained a higher proportion of rare alleles (53% than kabuli (46%, while wild Cicer accessions were devoid of rare alleles. A genotype-based reference set captured 1315 (78% of the 1683 composite collection alleles of which 463 were rare, 826 common, and 26 the most frequent alleles. The neighbour-joining tree diagram of this reference set represents

  1. A Structural Model for Binding of the Serine-Rich Repeat Adhesin GspB to Host Carbohydrate Receptors

    Energy Technology Data Exchange (ETDEWEB)

    Pyburn, Tasia M.; Bensing, Barbara A.; Xiong, Yan Q.; Melancon, Bruce J.; Tomasiak, Thomas M.; Ward, Nicholas J.; Yankovskaya, Victoria; Oliver, Kevin M.; Cecchini, Gary; Sulikowski, Gary A.; Tyska, Matthew J.; Sullam, Paul M.; Iverson, T.M. (VA); (UCLA); (Vanderbilt); (UCSF)

    2014-10-02

    GspB is a serine-rich repeat (SRR) adhesin of Streptococcus gordonii that mediates binding of this organism to human platelets via its interaction with sialyl-T antigen on the receptor GPIb{alpha}. This interaction appears to be a major virulence determinant in the pathogenesis of infective endocarditis. To address the mechanism by which GspB recognizes its carbohydrate ligand, we determined the high-resolution x-ray crystal structure of the GspB binding region (GspB{sub BR}), both alone and in complex with a disaccharide precursor to sialyl-T antigen. Analysis of the GspB{sub BR} structure revealed that it is comprised of three independently folded subdomains or modules: (1) an Ig-fold resembling a CnaA domain from prokaryotic pathogens; (2) a second Ig-fold resembling the binding region of mammalian Siglecs; (3) a subdomain of unique fold. The disaccharide was found to bind in a pocket within the Siglec subdomain, but at a site distinct from that observed in mammalian Siglecs. Confirming the biological relevance of this binding pocket, we produced three isogenic variants of S. gordonii, each containing a single point mutation of a residue lining this binding pocket. These variants have reduced binding to carbohydrates of GPIb{alpha}. Further examination of purified GspB{sub BR}-R484E showed reduced binding to sialyl-T antigen while S. gordonii harboring this mutation did not efficiently bind platelets and showed a significant reduction in virulence, as measured by an animal model of endocarditis. Analysis of other SRR proteins revealed that the predicted binding regions of these adhesins also had a modular organization, with those known to bind carbohydrate receptors having modules homologous to the Siglec and Unique subdomains of GspBBR. This suggests that the binding specificity of the SRR family of adhesins is determined by the type and organization of discrete modules within the binding domains, which may affect the tropism of organisms for different tissues.

  2. SnSe Nanocrystals: Synthesis, Structure, Optical Properties, and Surface Chemistry

    KAUST Repository

    Baumgardner, William J.; Choi, Joshua J.; Lim, Yee-Fun; Hanrath, Tobias

    2010-01-01

    The colloidal synthesis of SnSe nanoparticles is accomplished through the injection of bis[bis(trimethylsilyl)amino]tin(II) into hot trioctylphosphine: selenium in the presence of oleylamine. Through the manipulation of reaction temperature particles are grown with the average diameter reliably tuned to 4-10 nm. Quantum confinement is examined by establishing a relationship between particle size and band gap while the in depth growth dynamics are illuminated through UV-vis-NIR spectroscopy. Surface chemistry effects are explored, including the demonstration of useful ligand exchanges and the development of routes toward anisotropic particle growth. Finally, transient current-voltage properties of SnSe nanocrystal films in the dark and light are examined. © 2010 American Chemical Society.

  3. SnSe Nanocrystals: Synthesis, Structure, Optical Properties, and Surface Chemistry

    KAUST Repository

    Baumgardner, William J.

    2010-07-21

    The colloidal synthesis of SnSe nanoparticles is accomplished through the injection of bis[bis(trimethylsilyl)amino]tin(II) into hot trioctylphosphine: selenium in the presence of oleylamine. Through the manipulation of reaction temperature particles are grown with the average diameter reliably tuned to 4-10 nm. Quantum confinement is examined by establishing a relationship between particle size and band gap while the in depth growth dynamics are illuminated through UV-vis-NIR spectroscopy. Surface chemistry effects are explored, including the demonstration of useful ligand exchanges and the development of routes toward anisotropic particle growth. Finally, transient current-voltage properties of SnSe nanocrystal films in the dark and light are examined. © 2010 American Chemical Society.

  4. Interface of Chemistry and Biology

    OpenAIRE

    I. Kira Astakhova

    2013-01-01

    Many exciting research studies in Science today lie at the interface between various disciplines. The interface between Chemistry and Biology is particularly rich, since it closely reflects Nature and the origins of Life. Multiple research groups in the Chemistry Departments around the world have made substantial efforts to interweave ideas from Chemistry and Biology to solve important questions related to material science and healthcare, just to name a few. International Journal of Bioorgani...

  5. Fundamentals of nuclear chemistry

    International Nuclear Information System (INIS)

    Majer, V.

    1982-01-01

    The author of the book has had 25 years of experience at the Nuclear Chemistry of Prague Technical University. In consequence, the book is intended as a basic textbook for students of this field. Its main objectives are an easily understandable presentation of the complex subject and in spite of the uncertainty which still characterizes the definition and subjects of nuclear chemistry - a systematic classification and logical structure. Contents: 1. Introduction (history and definition); 2. General nuclear chemistry (physical fundamentals, hot atom chemistry, interaction of nuclear radiation with matter, radioactive elements, isotope effects, isotope exchange, chemistry of radioactive trace elements); 3. Methods of nuclear chemistry of nuclear chemistry (radiochemical methods, activation, separation and enrichment chemistry); 4. Preparative nuclear chemistry (isotope production, labelled compounds); 5. Analytival nuclear chemistry; 6. Applied nuclear chemistry (isotope applications in general physical and analytical chemistry). The book is supplemented by an annex with tables, a name catalogue and a subject index which will facilitate access to important information. (RB) [de

  6. Interconnection between the geometry and the structure of unit cells of substances in inorganic chemistry

    International Nuclear Information System (INIS)

    Eliseev, A.A.; Kuz'micheva, G.M.

    1979-01-01

    Regularity of interconnection between the geometry and the structure of elementary cells of inorganic compounds is investigated. Structural motives on the basis of NaCl structure for all phases of rare earth chalcogenides are built. It is shown that compounds (phases of variable content), detected on 23 (out of 48 possible) state diagrams of rare earths chalcogen binary systems are closely bound both from the viewpoint of geometric dimensions of elementary cells and structural motives. It is shown that using ion representations the number of formula units in the cell of a new rare earth chalcogenide can be calculated and its structural motif can be built

  7. Utilization of paramagnetic relaxation enhancements for high-resolution NMR structure determination of a soluble loop-rich protein with sparse NOE distance restraints

    International Nuclear Information System (INIS)

    Furuita, Kyoko; Kataoka, Saori; Sugiki, Toshihiko; Hattori, Yoshikazu; Kobayashi, Naohiro; Ikegami, Takahisa; Shiozaki, Kazuhiro; Fujiwara, Toshimichi; Kojima, Chojiro

    2015-01-01

    NMR structure determination of soluble proteins depends in large part on distance restraints derived from NOE. In this study, we examined the impact of paramagnetic relaxation enhancement (PRE)-derived distance restraints on protein structure determination. A high-resolution structure of the loop-rich soluble protein Sin1 could not be determined by conventional NOE-based procedures due to an insufficient number of NOE restraints. By using the 867 PRE-derived distance restraints obtained from the NOE-based structure determination procedure, a high-resolution structure of Sin1 could be successfully determined. The convergence and accuracy of the determined structure were improved by increasing the number of PRE-derived distance restraints. This study demonstrates that PRE-derived distance restraints are useful in the determination of a high-resolution structure of a soluble protein when the number of NOE constraints is insufficient

  8. Effects of Management on Lichen Species Richness, Ecological Traits and Community Structure in the Rodnei Mountains National Park (Romania).

    Science.gov (United States)

    Ardelean, Ioana Violeta; Keller, Christine; Scheidegger, Christoph

    2015-01-01

    Lichens are valuable bio-indicators for evaluating the consequences of human activities that are increasingly changing the earth's ecosystems. Since a major objective of national parks is the preservation of biodiversity, our aim is to analyse how natural resource management, the availability of lichen substrates and environmental parameters influence lichen diversity in Rodnei Mountains National Park situated in the Eastern Carpathians. Three main types of managed vegetation were investigated: the transhumance systems in alpine meadows, timber exploitation in mixed and pure spruce forests, and the corresponding conserved sites. The data were sampled following a replicated design. For the analysis, we considered not only all lichen species, but also species groups from different substrates such as soil, trees and deadwood. The lichen diversity was described according to species richness, red-list status and substrate-specialist species richness. The variation in species composition was related to the environmental variables. Habitat management was found to negatively influence species richness and alter the lichen community composition, particularly for threatened and substrate-specialist species. It reduced the mean level of threatened species richness by 59%, when all lichen species were considered, and by 81%, when only epiphytic lichens were considered. Management-induced disturbance significantly decreased lichen species richness in forest landscapes with long stand continuity. The diversity patterns of the lichens indicate a loss of species richness and change in species composition in areas where natural resources are still exploited inside the borders of the national park. It is thus imperative for protected areas, in particular old-growth forests and alpine meadows, to receive more protection than they have received in the past to ensure populations of the characteristic species remain viable in the future.

  9. Effects of Management on Lichen Species Richness, Ecological Traits and Community Structure in the Rodnei Mountains National Park (Romania.

    Directory of Open Access Journals (Sweden)

    Ioana Violeta Ardelean

    Full Text Available Lichens are valuable bio-indicators for evaluating the consequences of human activities that are increasingly changing the earth's ecosystems. Since a major objective of national parks is the preservation of biodiversity, our aim is to analyse how natural resource management, the availability of lichen substrates and environmental parameters influence lichen diversity in Rodnei Mountains National Park situated in the Eastern Carpathians. Three main types of managed vegetation were investigated: the transhumance systems in alpine meadows, timber exploitation in mixed and pure spruce forests, and the corresponding conserved sites. The data were sampled following a replicated design. For the analysis, we considered not only all lichen species, but also species groups from different substrates such as soil, trees and deadwood. The lichen diversity was described according to species richness, red-list status and substrate-specialist species richness. The variation in species composition was related to the environmental variables. Habitat management was found to negatively influence species richness and alter the lichen community composition, particularly for threatened and substrate-specialist species. It reduced the mean level of threatened species richness by 59%, when all lichen species were considered, and by 81%, when only epiphytic lichens were considered. Management-induced disturbance significantly decreased lichen species richness in forest landscapes with long stand continuity. The diversity patterns of the lichens indicate a loss of species richness and change in species composition in areas where natural resources are still exploited inside the borders of the national park. It is thus imperative for protected areas, in particular old-growth forests and alpine meadows, to receive more protection than they have received in the past to ensure populations of the characteristic species remain viable in the future.

  10. Bad chemistry

    OpenAIRE

    Petsko, Gregory A

    2004-01-01

    General chemistry courses haven't changed significantly in forty years. Because most basic chemistry students are premedical students, medical schools have enormous influence and could help us start all over again to create undergraduate chemistry education that works.

  11. Fundamentals of nuclear chemistry

    International Nuclear Information System (INIS)

    Matel, L.; Dulanska, S.

    2013-01-01

    This text-book is an introductory text in nuclear chemistry and radiochemistry, aimed on university undergraduate students in chemistry and related disciplines (physics, nuclear engineering). It covers the key aspects of modern nuclear chemistry. The text begins with basic theories in contemporary physics. It relates nuclear phenomena to key divisions of chemistry such as atomic structure, spectroscopy, equilibria and kinetics. It also gives an introduction to sources of ionizing radiation, detection of ionizing radiation, nuclear power industry and accident on nuclear installations as well as basic knowledge's of radiobiology. This book is essential reading for those taking a first course in nuclear chemistry and is a useful companion to other volumes in physical and analytical chemistry. It will also be of use to those new to working in nuclear chemistry or radiochemistry.

  12. The formation, structure, and ageing of As-rich hydrous ferric oxide at the abandoned Sb deposit Pezinok (Slovakia)

    Science.gov (United States)

    Majzlan, Juraj; Lalinská, Bronislava; Chovan, Martin; Jurkovič, L.'ubomír; Milovská, Stanislava; Göttlicher, Jörg

    2007-09-01

    The abandoned Sb deposit Pezinok in Slovakia is a significant source of As and Sb pollution that can be traced in the upper horizons of soils kilometers downstream. The source of the metalloids are two tailing impoundments which hold ˜380,000 m 3 of mining waste. The tailings and the discharged water have circumneutral pH values (7.0 ± 0.6) because the acidity generated by the decomposition of the primary sulfides (pyrite, FeS 2; arsenopyrite, FeAsS; berthierite, FeSb 2S 4) is rapidly neutralized by the abundant carbonates. The weathering rims on the primary sulfides are iron oxides which act as very efficient scavengers of As and Sb (with up to 19.2 wt% As and 23.7 wt% Sb). In-situ μ-XANES experiments indicate that As in the weathering rims is fully oxidized (As 5+). The pore solutions in the impoundment body contain up to 81 ppm As and 2.5 ppm Sb. Once these solutions are discharged from the impoundments, they precipitate or deposit masses of As-rich hydrous ferric oxide (As-HFO) with up to 28.3 wt% As 2O 5 and 2.7 wt% Sb. All As-HFO samples are amorphous to X-rays. They contain Fe and As in their highest oxidation state and in octahedral and tetrahedral coordination, respectively, as suggested by XANES and EXAFS studies on Fe K and As K edges. The iron octahedra in the As-HFO share edges to form short single chains and the chains polymerize by sharing edges or corners with the adjacent units. The arsenate ions attach to the chains in a bidentate-binuclear and monodentate fashion. In addition, hydrogen-bonded complexes may exist to satisfy the bonding requirements of all oxygen atoms in the first coordination sphere of As 5+. Structural changes in the As-HFO samples were traced by chemical analyses and Fe EXAFS spectroscopy during an ageing experiment. As the samples age, As becomes more easily leachable. EXAFS spectra show a discernible trend of increasing number of Fe-Fe pairs at a distance of 3.3-3.5 Å, that is, increasing polymerization of the iron

  13. The Learner Characteristics, Features of Desktop 3D Virtual Reality Environments, and College Chemistry Instruction: A Structural Equation Modeling Analysis

    Science.gov (United States)

    Merchant, Zahira; Goetz, Ernest T.; Keeney-Kennicutt, Wendy; Kwok, Oi-man; Cifuentes, Lauren; Davis, Trina J.

    2012-01-01

    We examined a model of the impact of a 3D desktop virtual reality environment on the learner characteristics (i.e. perceptual and psychological variables) that can enhance chemistry-related learning achievements in an introductory college chemistry class. The relationships between the 3D virtual reality features and the chemistry learning test as…

  14. High Structure Active Learning Pedagogy for the Teaching of Organic Chemistry: Assessing the Impact on Academic Outcomes

    Science.gov (United States)

    Crimmins, Michael T.; Midkiff, Brooke

    2017-01-01

    Organic Chemistry is a required course for programs in chemistry, biology, and many health science careers. It has historically been considered a highly challenging course with significant failure rates. As with many science disciplines, the teaching of Organic Chemistry has traditionally focused on unstructured exposition-centered delivery of…

  15. Bioactive Structure of Membrane Lipids and Natural Products Elucidated by a Chemistry-Based Approach.

    Science.gov (United States)

    Murata, Michio; Sugiyama, Shigeru; Matsuoka, Shigeru; Matsumori, Nobuaki

    2015-08-01

    Determining the bioactive structure of membrane lipids is a new concept, which aims to examine the functions of lipids with respect to their three-dimensional structures. As lipids are dynamic by nature, their "structure" does not refer solely to a static picture but also to the local and global motions of the lipid molecules. We consider that interactions with lipids, which are completely defined by their structures, are controlled by the chemical, functional, and conformational matching between lipids and between lipid and protein. In this review, we describe recent advances in understanding the bioactive structures of membrane lipids bound to proteins and related molecules, including some of our recent results. By examining recent works on lipid-raft-related molecules, lipid-protein interactions, and membrane-active natural products, we discuss current perspectives on membrane structural biology. © 2015 The Chemical Society of Japan & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Structure-Function Analysis of Cf-9, a Receptor-Like Protein with Extracytoplasmic Leucine-Rich Repeats

    NARCIS (Netherlands)

    Hoorn, van der R.A.L.; Wulff, B.B.H.; Rivas, S.; Durrant, M.C.; Ploeg, van der A.; Wit, de P.J.G.M.; Jones, J.D.G.

    2005-01-01

    The tomato (Lycopersicon pimpinellifolium) resistance protein Cf-9 belongs to a large class of plant proteins with extracytoplasmic Leu-rich repeats (eLRRs). eLRR proteins play key roles in plant defense and development, mainly as receptor-like proteins or receptor-like kinases, conferring

  17. Synthesis, crystal structure, vibrational spectra and theoretical calculations of quantum chemistry of a potential antimicrobial Meldrum's acid derivative

    Science.gov (United States)

    Campelo, M. J. M.; Freire, P. T. C.; Mendes Filho, J.; de Toledo, T. A.; Teixeira, A. M. R.; da Silva, L. E.; Bento, R. R. F.; Faria, J. L. B.; Pizani, P. S.; Gusmão, G. O. M.; Coutinho, H. D. M.; Oliveira, M. T. A.

    2017-10-01

    A new derivative of Meldrum's acid 5-((5-chloropyridin-2-ylamino)methylene)-2,2-dimethyl-1,3-dioxane-4,6-dione (CYMM) of molecular formula C12H11ClN2O4 was synthesized and structurally characterized using single crystal X-ray diffraction technique. The vibrational properties of the crystal were studied by Fourier Transform infrared (FT-IR), Fourier Transform Raman (FT-Raman) techniques and theoretical calculations of quantum chemistry using Density functional theory (DFT) and Density functional perturbation theory (DFPT). A comparison with experimental spectra allowed the assignment of all the normal modes. The descriptions of the normal modes were carried by means of potential energy distribution (PED). Additionally, analysis of the antimicrobial activity and antibiotic resistance modulatory activity was carried out to evaluate the antibacterial potential of the CYMM.

  18. Effects of habitat structure on the epifaunal community in Mussismilia corals: does coral morphology influence the richness and abundance of associated crustacean fauna?

    Science.gov (United States)

    Nogueira, Marcos M.; Neves, Elizabeth; Johnsson, Rodrigo

    2015-06-01

    Coral habitat structures increase abundance and richness of organisms by providing niches, easy access to resources and refuge from predators. Corals harbor a great variety of animals; the variation in coral species morphology contributes to the heterogeneity and complexity of habitat types. In this report, we studied the richness and abundance of crustaceans (Decapoda, Copepoda, Peracarida and Ostracoda) associated with three species of Mussismilia exhibiting different growth morphologies, in two different coral reefs of the Bahia state (Caramuanas and Boipeba-Moreré, Brazil). Mussismilia hispida is a massive coral; M. braziliensis also has a massive growth pattern, but forms a crevice in the basal area of the corallum; M. harttii has a meandroid pattern. PERMANOVA analysis suggests significant differences in associated fauna richness among Mussismilia species, with higher values for M. harttii, followed by M. braziliensis and later by M. hispida. The same trend was observed for density, except that the comparison of M. braziliensis and M. hispida did not show differences. Redundancy and canonical correspondence analysis indicated that almost all of the crustacean species were more associated with the M. harttii colonies that formed a group clearly separated from colonies of M. braziliensis and M. hispida. We also found that the internal volume of interpolyp space, only present in M. harttii, was the most important factor influencing richness and abundance of all analyzed orders of crustaceans.

  19. Polymer chemistry (revised edition)

    International Nuclear Information System (INIS)

    Kim, Jae Mum

    1987-02-01

    This book deals with polymer chemistry, which is divided into fourteen chapters. The contents of this book are development of polymer chemistry, conception of polymer, measurement of polymer chemistry, conception of polymer, measurement of polymer, molecule structure of polymer, thermal prosperities of solid polymer, basic theory of polymerization, radical polymerization, ion polymerization, radical polymerization, copolymerization, polymerization by step-reaction, polymer reaction, crown polymer and inorganic polymer on classification and process of creation such as polymeric sulfur and carbon fiber.

  20. A study of new rare-earth metal group-13 chalcohalides. Structures, chemistry, and optical properties

    International Nuclear Information System (INIS)

    Dorhout, P.K.; Van Calcar, P.M.

    1998-01-01

    Full text: Several new quaternary compounds from the rare-earth metal group-13 chalcohalide family have been prepared from alkaline earth halide flux reactions of binary and elemental starting materials. One compound, for example, Ca 2 La 6G a 2 S 1 4 , crystallizes as needles in an hexagonal cell while another, more disordered structure, La 11 Ga 19 Cl 6 S 42 , crystallizes as monoclinic plates. The former is a condensed structure with channels that contain the alkaline earth element while the latter forms a layered structure containing rare-earth halide clusters within interlayer galleries. These compounds are new members of a family of rare-earth metal main-group chalcogenides which show promise as electroluminescent materials. Structural and spectroscopic studies of these and related compounds will be discussed

  1. Crystal chemistry of germanates: Characteristic structural features of Li,Ge-germanates

    International Nuclear Information System (INIS)

    Ilyushin, G.D.; Dem'yanets, L.N.

    2000-01-01

    Crystallochemical classification of eleven compounds from the Li-germanate family is suggested. Depending on the set of the primary building units (PBU) (M-octahedra of the composition [GeO 6 ] and T-tetrahedra of the composition [GeO 4 ]) and the type of their 'condensation', these germanates are divided into three crystallochemical groups: framework MT-structures (four phases), condensed MT-structures (two phases), and tetrahedral T-condensed structures (five phases). The structural characteristics of the framework Li,Ge-germanates are considered, i.e., their symmetry, crystallographically independent sets of the primary building units, framework architecture, and the types of chains and layers of the (Ge,O)-radicals

  2. Free and Open Source Chemistry Software in Research of Quantitative Structure-Toxicity Relationship of Pesticides

    Directory of Open Access Journals (Sweden)

    Rastija Vesna

    2017-01-01

    Full Text Available Pesticides are toxic chemicals aimed for the destroying pest on crops. Numerous data evidence about toxicity of pesticides on aquatic organisms. Since pesticides with similar properties tend to have similar biological activities, toxicity may be predicted from structure. Their structure feature and properties are encoded my means of molecular descriptors. Molecular descriptors can capture quite simple two-dimensional (2D chemical structures to highly complex three-dimensional (3D chemical structures. Quantitative structure-toxicity relationship (QSTR method uses linear regression analyses for correlation toxicity of chemical with their structural feature using molecular descriptors. Molecular descriptors were calculated using open source software PaDEL and in-house built PyMOL plugin (PyDescriptor. PyDescriptor is a new script implemented with the commonly used visualization software PyMOL for calculation of a large and diverse set of easily interpretable molecular descriptors encoding pharmacophoric patterns and atomic fragments. PyDescriptor has several advantages like free and open source, can work on all major platforms (Windows, Linux, MacOS. QSTR method allows prediction of toxicity of pesticides without experimental assay. In the present work, QSTR analysis for toxicity of a dataset of mixtures of 5 classes of pesticides comprising has been performed.

  3. Short interspersed elements (SINEs) from insectivores. Two classes of mammalian SINEs distinguished by A-rich tail structure.

    Science.gov (United States)

    Borodulina, O R; Kramerov, D A

    2001-10-01

    Four tRNA-related SINE families were isolated from the genome of the shrew Sorex araneus (SOR element), mole Mogera robusta (TAL element), and hedgehog Mesechinus dauuricus (ERI-1 and ERI-2 elements). Each of these SINEs families is specific for a single Insectivora family: SOR, for Soricidae (shrews); TAL, for Talpidae (moles and desmans); ERI-1 and ERI-2, for Erinaceidae (hedgehogs). There is a long polypyrimidine region (TC-motif) in TAL, ERI-1, and ERI-2 elements located immediately upstream of an A-rich tail with polyadenylation signals (AATAAA) and an RNA polymerase III terminator (T(4-6)) or TCT(3-4)). Ten out of 14 analyzed mammalian tRNA-related SINE families have an A-rich tail similar to that of TAL, ERI-1, and ERI-2 elements. These elements were assigned to class T+. The other four SINEs including SOR element have no polyadenylation signal and transcription terminator in their A-rich tail and were assigned to class T-. Class T+ SINEs occur only in mammals, and most of them have a long polypyrimidine region. Possible models of retroposition of class T+ and T- SINEs are discussed.

  4. Quantum chemistry the development of ab initio methods in molecular electronic structure theory

    CERN Document Server

    Schaefer III, Henry F

    2004-01-01

    This guide is guaranteed to prove of keen interest to the broad spectrum of experimental chemists who use electronic structure theory to assist in the interpretation of their laboratory findings. A list of 150 landmark papers in ab initio molecular electronic structure methods, it features the first page of each paper (which usually encompasses the abstract and introduction). Its primary focus is methodology, rather than the examination of particular chemical problems, and the selected papers either present new and important methods or illustrate the effectiveness of existing methods in predi

  5. Substitution Structures of Large Molecules and Medium Range Correlations in Quantum Chemistry Calculations

    Science.gov (United States)

    Evangelisti, Luca; Pate, Brooks

    2017-06-01

    A study of the minimally exciting topic of agreement between experimental and measured rotational constants of molecules was performed on a set of large molecules with 16-18 heavy atoms (carbon and oxygen). The molecules are: nootkatone (C_{15}H_{22}O), cedrol (C_{15}H_{26}O), ambroxide (C_{16}H_{28}O), sclareolide (C_{16}H_{22}O_{2}), and dihydroartemisinic acid (C_{15}H_{24}O_{2}). For this set of molecules we obtained 13C-subsitution structures for six molecules (this includes two conformers of nootkatone). A comparison of theoretical structures and experimental substitution structures was performed in the spirit of the recent work of Grimme and Steinmetz.[1] Our analysis focused the center-of-mass distance of the carbon atoms in the molecules. Four different computational methods were studied: standard DFT (B3LYP), dispersion corrected DFT (B3LYP-D3BJ), hybrid DFT with dispersion correction (B2PLYP-D3), and MP2. A significant difference in these theories is how they handle medium range correlation of electrons that produce dispersion forces. For larger molecules, these dispersion forces produce an overall contraction of the molecule around the center-of-mass. DFT poorly treats this effect and produces structures that are too expanded. MP2 calculations overestimate the correction and produce structures that are too compact. Both dispersion corrected DFT methods produce structures in excellent agreement with experiment. The analysis shows that the difference in computational methods can be described by a linear error in the center-of-mass distance. This makes it possible to correct poorer performing calculations with a single scale factor. We also reexamine the issue of the "Costain error" in substitution structures and show that it is significantly larger in these systems than in the smaller molecules used by Costain to establish the error limits. [1] Stefan Grimme and Marc Steinmetz, "Effects of London dispersion correction in density functional theory on

  6. Energetics and crystal chemistry of Ruddlesden-Popper type structures in high T(sub c) ceramic superconductors

    Science.gov (United States)

    Dwivedi, Anurag; Cormack, A. N.

    1990-01-01

    The formation of Ruddlesden-Popper type layers (alternating slabs of rocksalt and perovskite structures) is seen in these oxides which is similar in many respects to what is seen in the system Sr-Ti-O. However, it was observed that there are some significant differences, for example the rocksalt and perovskite blocks in new superconducting compounds are not necessarily electrically, unlike in Sr-Ti-O systems. This will certainly render an additional coulombic bonding energy between two different types of blocks and may well lead to significant differences in their structural chemistry. In the higher order members of the various homologous series, additional Cu-O planes are inserted in the perovskite blocks. In order for the unit cell to electrically neutral the net positive charge on rocksalt block (which remains constant throughout the homologous series) should be balanced by an equal negative charge on perovskite block. It, thus becomes necessary to create oxygen vacancies in the basic perovskite structure, when width of the perovskite slab changes on addition of extra Cu-O planes. Results of atomistic simulations suggest that these missing oxygen ions allow the Cu-O planes to buckle in these compounds. This is also supported by the absence of buckling in the first member of Bi-containing compounds in which there are no missing oxygen ions and the Sr-Ti-O series of compounds. Additional results are presented on the phase stability of polytypoid structures in these crystal chemically complex systems. The studies will focus on the determination of the location of Cu(3+) in the structures of higher order members of the La-Cu-O system and whether Cu(3+) ions or oxygen vacancies are energetically more favorable charge compensating mechanism.

  7. Chemistry and structure of coal derived asphaltenes and preasphaltenes. Quarterly progress report, April-June 1980

    Energy Technology Data Exchange (ETDEWEB)

    Yen, T. F.

    1980-01-01

    It is the objective of this project to isolate the asphaltene and preasphaltene fractions from coal liquids from a number of liquefaction processes. These processes consist of in general: catalytic hydrogenation, staged pyrolysis and solvent refining. These asphaltene fractions may be further separated by both gradient elution through column chromatography, and molecular size distribution through gel permeation chromatography. Those coal-derived asphaltene and preasphaltene fractions will be investigated by various chemical and physical methods for characterization of their structures. After the parameters are obtained, these parameters will be correlated with the refining and conversion variables which control a given type of liquefaction process. The effects of asphaltene in catalysis, ash or metal removal, desulfurization and denitrification will also be correlated. It is anticipated that understanding the role of asphaltenes in liquefaction processes will enable engineers to both improve existing processes, and to make recommendations for operational changes in planned liquefaction units in the United States. The objective of Phase 1 was to complete the isolation and separation of coal liquid fractions and to initiate their characterization. The objective of Phase 2 is to continue the characterization of coal asphaltenes and other coal liquid fractions by use of physical and instrumental methods. The structural parameters obtained will be used to postulate hypothetical average structures for coal liquid fractions. The objective of Phase 3 is to concentrate on the characterization of the preasphaltene (benzene insoluble fraction) of coal liquid fraction by the available physical and chemical methods to obtain a number of structural parameters.

  8. Structural superlubricity of platinum on graphite under ambient conditions: The effects of chemistry and geometry

    Science.gov (United States)

    Özoǧul, Alper; Ipek, Semran; Durgun, Engin; Baykara, Mehmet Z.

    2017-11-01

    An investigation of the frictional behavior of platinum nanoparticles laterally manipulated on graphite has been conducted to answer the question of whether the recent observation of structural superlubricity under ambient conditions [E. Cihan, S. İpek, E. Durgun, and M. Z. Baykara, Nat. Commun. 7, 12055 (2016)] is exclusively limited to the gold-graphite interface. Platinum nanoparticles have been prepared by e-beam evaporation of a thin film of platinum on graphite, followed by post-deposition annealing. Morphological and structural characterization of the nanoparticles has been performed via scanning electron microscopy and transmission electron microscopy, revealing a crystalline structure with no evidence of oxidation under ambient conditions. Lateral manipulation experiments have been performed via atomic force microscopy under ambient conditions, whereby results indicate the occurrence of structural superlubricity at mesoscopic interfaces of 4000-75 000 nm2, with a noticeably higher magnitude of friction forces when compared with gold nanoparticles of similar contact areas situated on graphite. Ab initio simulations of sliding involving platinum and gold slabs on graphite confirm the experimental observations, whereby the higher magnitude of friction forces is attributed to stronger energy barriers encountered by platinum atoms sliding on graphite, when compared with gold. On the other hand, as predicted by theory, the scaling power between friction force and contact size is found to be independent of the chemical identity of the sliding atoms, but to be determined by the geometric qualities of the interface, as characterized by an average "sharpness score" assigned to the nanoparticles.

  9. Mathematical Chemistry

    OpenAIRE

    Trinajstić, Nenad; Gutman, Ivan

    2002-01-01

    A brief description is given of the historical development of mathematics and chemistry. A path leading to the meeting of these two sciences is described. An attempt is made to define mathematical chemistry, and journals containing the term mathematical chemistry in their titles are noted. In conclusion, the statement is made that although chemistry is an experimental science aimed at preparing new compounds and materials, mathematics is very useful in chemistry, among other things, to produc...

  10. Medicinal Chemistry and Molecular Modeling: An Integration to Teach Drug Structure-Activity Relationship and the Molecular Basis of Drug Action

    Science.gov (United States)

    Carvalho, Ivone; Borges, Aurea D. L.; Bernardes, Lilian S. C.

    2005-01-01

    The use of computational chemistry and the protein data bank (PDB) to understand and predict the chemical and molecular basis involved in the drug-receptor interactions is discussed. A geometrical and chemical overview of the great structural similarity in the substrate and inhibitor is provided.

  11. Band connectivity for topological quantum chemistry: Band structures as a graph theory problem

    Science.gov (United States)

    Bradlyn, Barry; Elcoro, L.; Vergniory, M. G.; Cano, Jennifer; Wang, Zhijun; Felser, C.; Aroyo, M. I.; Bernevig, B. Andrei

    2018-01-01

    The conventional theory of solids is well suited to describing band structures locally near isolated points in momentum space, but struggles to capture the full, global picture necessary for understanding topological phenomena. In part of a recent paper [B. Bradlyn et al., Nature (London) 547, 298 (2017), 10.1038/nature23268], we have introduced the way to overcome this difficulty by formulating the problem of sewing together many disconnected local k .p band structures across the Brillouin zone in terms of graph theory. In this paper, we give the details of our full theoretical construction. We show that crystal symmetries strongly constrain the allowed connectivities of energy bands, and we employ graph theoretic techniques such as graph connectivity to enumerate all the solutions to these constraints. The tools of graph theory allow us to identify disconnected groups of bands in these solutions, and so identify topologically distinct insulating phases.

  12. Soft chemistry routes for synthesis of rare earth oxide nanoparticles with well defined morphological and structural characteristics

    Science.gov (United States)

    Mancic, L.; Marinkovic, B. A.; Marinkovic, K.; Dramicanin, M.; Milosevic, O.

    2011-11-01

    Phosphors of (Y0.75Gd0.25)2O3:Eu3+ (5 at.%) have been prepared through soft chemistry routes. Conversion of the starting nitrates mixture into oxide is performed through two approaches: (a) hydrothermal treatment (HT) at 200 °C/3 h of an ammonium hydrogen carbonate precipitated mixture and (b) by thermally decomposition of pure nitrate precursor solution at 900 °C in dispersed phase (aerosol) within a tubular flow reactor by spray pyrolysis process (SP). The powders are additionally thermally treated at different temperatures: 600, 1000, and 1100 °C for either 3 or 12 h. HT—derived particles present exclusively one-dimensional morphology (nanorods) up to the temperatures of 600 °C, while the leaf-like particles start to grow afterward. SP—derived particles maintain their spherical shape up to the temperatures of 1100 °C. These submicron sized spheres were actually composed of randomly aggregated nanoparticles. All powders exhibits cubic Ia- 3 structure (Y0.75Gd0.25)2O3:Eu and have improved optical characteristics due to their nanocrystalline nature. The detailed study of the influence of structural and morphological powder characteristics on their emission properties is performed based on the results of X-ray powder diffractometry, scanning electron microscopy, X-ray energy dispersive spectroscopy, transmission electron microscopy, and photoluminescence measurements.

  13. NMR strategies to support medicinal chemistry workflows for primary structure determination.

    Science.gov (United States)

    Oguadinma, Paul; Bilodeau, Francois; LaPlante, Steven R

    2017-01-15

    Central to drug discovery is the correct characterization of the primary structures of compounds. In general, medicinal chemists make great synthetic and characterization efforts to deliver the intended compounds. However, there are occasions which incorrect compounds are presented, such as those reported for Bosutinib and TIC10. This may be due to a variety of reasons such as uncontrolled reaction schemes, reliance on limited characterization techniques (LC-MS and/or 1D 1H NMR spectra), or even the lack of availability or knowledge of characterization strategies. Here, we present practical NMR approaches that support medicinal chemist workflows for addressing compound characterization issues and allow for reliable primary structure determinations. These strategies serve to differentiate between regioisomers and geometric isomers, distinguish between N- versus O-alkyl analogues, and identify rotamers and atropisomers. Overall, awareness and application of these available NMR methods (e.g. HMBC/HSQC, ROESY and VT experiments, to name only a few) should help practicing chemists to reveal chemical phenomena and avoid mis-assignment of the primary structures of compounds. Copyright © 2016 Elsevier Ltd. All rights reserved.

  14. Oceanographic conditions structure forage fishes into lipid-rich and lipid-poor communities in lower Cook Inlet, Alaska, USA

    Science.gov (United States)

    Abookire, Alisa A.; Piatt, John F.

    2005-01-01

    Forage fishes were sampled with a mid-water trawl in lower Cook Inlet, Alaska, USA, from late July to early August 1996 to 1999. We sampled 3 oceanographically distinct areas of lower Cook Inlet: waters adjacent to Chisik Island, in Kachemak Bay, and near the Barren Islands. In 163 tows using a mid-water trawl, 229 437 fishes with fork length lipid-poor gadids (walleye pollock and Pacific cod), and significantly increased in lipid-rich species such as Pacific sand lance, Pacific herring, and capelin. ?? Inter-Research 2005.

  15. Structural Analyses of Phase Stability in Amorphous and Partially Crystallized Ge-Rich GeTe Films Prepared by Atomic Layer Deposition.

    Science.gov (United States)

    Gwon, Taehong; Mohamed, Ahmed Yousef; Yoo, Chanyoung; Park, Eui-Sang; Kim, Sanggyun; Yoo, Sijung; Lee, Han-Koo; Cho, Deok-Yong; Hwang, Cheol Seong

    2017-11-29

    The local bonding structures of Ge x Te 1-x (x = 0.5, 0.6, and 0.7) films prepared through atomic layer deposition (ALD) with Ge(N(Si(CH 3 ) 3 ) 2 ) 2 and ((CH 3 ) 3 Si) 2 Te precursors were investigated using Ge K-edge X-ray absorption spectroscopy (XAS). The results of the X-ray absorption fine structure analyses show that for all of the compositions, the as-grown films were amorphous with a tetrahedral Ge coordination of a mixture of Ge-Te and Ge-Ge bonds but without any signature of Ge-GeTe decomposition. The compositional evolution in the valence band electronic structures probed through X-ray photoelectron spectroscopy suggests a substantial chemical influence of additional Ge on the nonstoichiometric GeTe. This implies that the ALD process can stabilize Ge-abundant bonding networks like -Te-Ge-Ge-Te- in amorphous GeTe. Meanwhile, the XAS results on the Ge-rich films that had undergone post-deposition annealing at 350 °C show that the parts of the crystalline Ge-rich GeTe became separated into Ge crystallites and rhombohedral GeTe in accordance with the bulk phase diagram, whereas the disordered GeTe domains still remained, consistent with the observations of transmission electron microscopy and Raman spectroscopy. Therefore, amorphousness in GeTe may be essential for the nonsegregated Ge-rich phases and the low growth temperature of the ALD enables the achievement of the structurally metastable phases.

  16. Linking interfacial chemistry of CO2 to surface structures of hydrated metal oxide nanoparticles: hematite.

    Science.gov (United States)

    Chernyshova, Irina V; Ponnurangam, Sathish; Somasundaran, Ponisseril

    2013-05-14

    A better understanding of interaction with dissolved CO2 is required to rationally design and model the (photo)catalytic and sorption processes on metal (hydr)oxide nanoparticles (NPs) in aqueous media. Using in situ FTIR spectroscopy, we address this problem for rhombohedral 38 nm hematite (α-Fe2O3) nanoparticles as a model. We not only resolve the structures of the adsorbed carbonate species, but also specify their adsorption sites and their location on the nanoparticle surface. The spectral relationships obtained present a basis for a new method of characterizing the microscopic structural and acid-base properties (related to individual adsorption sites) of hydrated metal (hydr)oxide NPs using atmospherically derived CO2 as a probe. Specifically, we distinguish two carbonate species suggesting two principally different adsorption mechanisms. One species, which is more weakly adsorbed, has an inner-sphere mononuclear monodentate structure which is formed by a conventional ligand-exchange mechanism. At natural levels of dissolved carbonate and pH from 3 to 11, this species is attached to the most acidic/reactive surface cations (surface states) associated with ferrihydrite-like surface defects. The second species, which is more strongly adsorbed, presents a mixed C and O coordination of bent CO2. This species uniquely recognizes the stoichiometric rhombohedral {104} facets in the NP texture. Like in gas phase, it is formed through the surface coordination of molecular CO2. We address how the adsorption sites hosting these two carbonate species are affected by the annealing and acid etching of the NPs. These results support the nanosize-induced phase transformation of hematite towards ferrihydrite under hydrous conditions, and additionally show that the process starts from the roughened areas of the facet intersections.

  17. Constitutional dynamic chemistry: bridge from supramolecular chemistry to adaptive chemistry.

    Science.gov (United States)

    Lehn, Jean-Marie

    2012-01-01

    Supramolecular chemistry aims at implementing highly complex chemical systems from molecular components held together by non-covalent intermolecular forces and effecting molecular recognition, catalysis and transport processes. A further step consists in the investigation of chemical systems undergoing self-organization, i.e. systems capable of spontaneously generating well-defined functional supramolecular architectures by self-assembly from their components, thus behaving as programmed chemical systems. Supramolecular chemistry is intrinsically a dynamic chemistry in view of the lability of the interactions connecting the molecular components of a supramolecular entity and the resulting ability of supramolecular species to exchange their constituents. The same holds for molecular chemistry when the molecular entity contains covalent bonds that may form and break reversibility, so as to allow a continuous change in constitution by reorganization and exchange of building blocks. These features define a Constitutional Dynamic Chemistry (CDC) on both the molecular and supramolecular levels.CDC introduces a paradigm shift with respect to constitutionally static chemistry. The latter relies on design for the generation of a target entity, whereas CDC takes advantage of dynamic diversity to allow variation and selection. The implementation of selection in chemistry introduces a fundamental change in outlook. Whereas self-organization by design strives to achieve full control over the output molecular or supramolecular entity by explicit programming, self-organization with selection operates on dynamic constitutional diversity in response to either internal or external factors to achieve adaptation.The merging of the features: -information and programmability, -dynamics and reversibility, -constitution and structural diversity, points to the emergence of adaptive and evolutive chemistry, towards a chemistry of complex matter.

  18. Cyclodextrin chemistry

    International Nuclear Information System (INIS)

    Khan, M.Z.; Chuaqui, C.A.

    1990-05-01

    The chemistry of cyclodextrins was studied. This study included synthesising some cyclodextrin derivatives, preparing selected inclusion complexes with cyclodextrin and investigating the effects of gamma irradiation on cyclodextrins and certain linear oligosaccharides. This report presents a brief review of the structure and properties of cyclodextrins, the synthesis of cyclodextrin derivatives, their complexation and applications. This is followed by a description of the synthesis of some cyclodextrin derivatives and the preparation of inclusion complexes of cyclodextrin with some organic compounds. Finally, the effects of gamma irradiation on cyclodextrins, some of their derivatives and certain structurally related carbohydrates are discussed. The gamma irradiation studies were carried out for two reasons: to study the effects of gamma irradiation on cyclodextrins and their derivatives; and to investigate selectivity during the gamma irradiation of cyclodextrin derivatives

  19. Radical Chemistry and Structural Relationships of PPCP Degradation by UV/Chlorine Treatment in Simulated Drinking Water.

    Science.gov (United States)

    Guo, Kaiheng; Wu, Zihao; Shang, Chii; Yao, Bo; Hou, Shaodong; Yang, Xin; Song, Weihua; Fang, Jingyun

    2017-09-19

    The UV/chlorine process is an emerging advanced oxidation process (AOP) used for the degradation of micropollutants. However, the radical chemistry of this AOP is largely unknown for the degradation of numerous structurally diverse micropollutants in water matrices of varying quality. These issues were addressed by grouping 34 pharmaceuticals and personal care products (PPCPs) according to the radical chemistry of their degradation in the UV/chlorine process at practical PPCP concentrations (1 μg L -1 ) and in different water matrices. The contributions of HO • and reactive chlorine species (RCS), including Cl • , Cl 2 •- , and ClO • , to the degradation of different PPCPs were compound specific. RCS showed considerable reactivity with olefins and benzene derivatives, such as phenols, anilines, and alkyl-/alkoxybenzenes. A good linear relationship was found between the RCS reactivity and negative values of the Hammett ∑σ p + constant for aromatic PPCPs, indicating that electron-donating groups promote the attack of benzene derivatives by RCS. The contribution of HO • , but not necessarily RCS, to PPCP removal decreased with increasing pH. ClO • showed high reactivity with some PPCPs, such as carbamazepine, caffeine, and gemfibrozil, with second-order rate constants of 9.2 × 10 7 , 1.03 × 10 8 , and 4.16 × 10 8 M -1 s -1 , respectively, which contributed to their degradation. Natural organic matter (NOM) induced significant scavenging of ClO • and greatly decreased the degradation of PPCPs that was attributable to ClO • , with a second-order rate constant of 4.5 × 10 4 (mg L -1 ) -1 s -1 . Alkalinity inhibited the degradation of PPCPs that was primarily attacked by HO • and Cl • but had negligible effects on the degradation of PPCPs by ClO • . This is the first study on the reactivity of RCS, particularly ClO • , with structurally diverse PPCPs under simulated drinking water condition.

  20. Is Chemistry Attractive for Pupils? Czech Pupils' Perception of Chemistry

    Science.gov (United States)

    Kubiatko, Milan

    2015-01-01

    Chemistry is an important subject due to understanding the composition and structure of the things around us. The main aim of the study was to find out the perception of chemistry by lower secondary school pupils. The partial aims were to find out the influence of gender, year of study and favorite subject on the perception of chemistry. The…

  1. Perceived Autonomy-Support, Expectancy, Value, Metacognitive Strategies and Performance in Chemistry: A Structural Equation Model in Undergraduates

    Science.gov (United States)

    González, Antonio; Paoloni, Paola-Verónica

    2015-01-01

    Research in chemistry education has highlighted a number of variables that predict learning and performance, such as teacher-student interactions, academic motivation and metacognition. Most of this chemistry research has examined these variables by identifying dyadic relationships through bivariate correlations. The main purpose of this study was…

  2. Structural and Conformational Chemistry from Electrochemical Molecular Machines. Replicating Biological Functions. A Review.

    Science.gov (United States)

    Otero, Toribio F

    2017-12-14

    Each constitutive chain of a conducting polymer electrode acts as a reversible multi-step electrochemical molecular motor: reversible reactions drive reversible conformational movements of the chain. The reaction-driven cooperative actuation of those molecular machines generates, or destroys, inside the film the free volume required to lodge/expel balancing counterions and solvent: reactions drive reversible film volume variations, which basic structural components are here identified and quantified from electrochemical responses. The content of the reactive dense gel (chemical molecular machines, ions and water) mimics that of the intracellular matrix in living functional cells. Reaction-driven properties (composition-dependent properties) and devices replicate biological functions and organs. An emerging technological world of soft, wet, reaction-driven, multifunctional and biomimetic devices and the concomitant zoomorphic or anthropomorphic robots is presented. © 2017 The Chemical Society of Japan & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Production of recombinant disulfide-rich venom peptides for structural and functional analysis via expression in the periplasm of E. coli.

    Directory of Open Access Journals (Sweden)

    Julie K Klint

    Full Text Available Disulfide-rich peptides are the dominant component of most animal venoms. These peptides have received much attention as leads for the development of novel therapeutic agents and bioinsecticides because they target a wide range of neuronal receptors and ion channels with a high degree of potency and selectivity. In addition, their rigid disulfide framework makes them particularly well suited for addressing the crucial issue of in vivo stability. Structural and functional characterization of these peptides necessitates the development of a robust, reliable expression system that maintains their native disulfide framework. The bacterium Escherichia coli has long been used for economical production of recombinant proteins. However, the expression of functional disulfide-rich proteins in the reducing environment of the E. coli cytoplasm presents a significant challenge. Thus, we present here an optimised protocol for the expression of disulfide-rich venom peptides in the periplasm of E. coli, which is where the endogenous machinery for production of disulfide-bonds is located. The parameters that have been investigated include choice of media, induction conditions, lysis methods, methods of fusion protein and peptide purification, and sample preparation for NMR studies. After each section a recommendation is made for conditions to use. We demonstrate the use of this method for the production of venom peptides ranging in size from 2 to 8 kDa and containing 2-6 disulfide bonds.

  4. Using Gas-Phase Guest-Host Chemistry to Probe the Structures of b Ions of Peptides

    Science.gov (United States)

    Somogyi, Árpád; Harrison, Alex G.; Paizs, Béla

    2012-12-01

    Middle-sized b n ( n ≥ 5) fragments of protonated peptides undergo selective complex formation with ammonia under experimental conditions typically used to probe hydrogen-deuterium exchange in Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS). Other usual peptide fragments like y, a, a*, etc., and small b n ( n ≤ 4) fragments do not form stable ammonia adducts. We propose that complex formation of b n ions with ammonia is characteristic to macrocyclic isomers of these fragments. Experiments on a protonated cyclic peptide and N-terminal acetylated peptides fully support this hypothesis; the protonated cyclic peptide does form ammonia adducts while linear b n ions of acetylated peptides do not undergo complexation. Density functional theory (DFT) calculations on the proton-bound dimers of all-Ala b 4 , b 5 , and b 7 ions and ammonia indicate that the ionizing proton initially located on the peptide fragment transfers to ammonia upon adduct formation. The ammonium ion is then solvated by N+-H…O H-bonds; this stabilization is much stronger for macrocyclic b n isomers due to the stable cage-like structure formed and entropy effects. The present study demonstrates that gas-phase guest-host chemistry can be used to selectively probe structural features (i.e., macrocyclic or linear) of fragments of protonated peptides. Stable ammonia adducts of b 9 , b 9 -A, and b 9 -2A of A8YA, and b 13 of A20YVFL are observed indicating that even these large b-type ions form macrocyclic structures.

  5. A mineral-rich extract from the red marine algae Lithothamnion calcareum preserves bone structure and function in female mice on a Western-style diet.

    Science.gov (United States)

    Aslam, Muhammad Nadeem; Kreider, Jaclynn M; Paruchuri, Tejaswi; Bhagavathula, Narasimharao; DaSilva, Marissa; Zernicke, Ronald F; Goldstein, Steven A; Varani, James

    2010-04-01

    The purpose of this study was to determine whether a mineral-rich extract derived from the red marine algae Lithothamnion calcareum could be used as a dietary supplement for prevention of bone mineral loss. Sixty C57BL/6 mice were divided into three groups based on diet: the first group received a high-fat Western-style diet (HFWD), the second group was fed the same HFWD along with the mineral-rich extract included as a dietary supplement, and the third group was used as a control and was fed a low-fat rodent chow diet (AIN76A). Mice were maintained on the respective diets for 15 months. Then, long bones (femora and tibiae) from both males and females were analyzed by three-dimensional micro-computed tomography (micro-CT) and (bones from female mice) concomitantly assessed in bone strength studies. Tartrate-resistant acid phosphatase (TRAP), osteocalcin, and N-terminal peptide of type I procollagen (PINP) were assessed in plasma samples obtained from female mice at the time of sacrifice. To summarize, female mice on the HFWD had reduced bone mineralization and reduced bone strength relative to female mice on the low-fat chow diet. The bone defects in female mice on the HFWD were overcome in the presence of the mineral-rich supplement. In fact, female mice receiving the mineral-rich supplement in the HFWD had better bone structure/function than did female mice on the low-fat chow diet. Female mice on the mineral-supplemented HFWD had higher plasma levels of TRAP than mice of the other groups. There were no differences in the other two markers. Male mice showed little diet-specific differences by micro-CT.

  6. Comparison of osteointegration property between PEKK and PEEK: Effects of surface structure and chemistry.

    Science.gov (United States)

    Yuan, Bo; Cheng, Qinwen; Zhao, Rui; Zhu, Xiangdong; Yang, Xiao; Yang, Xi; Zhang, Kai; Song, Yueming; Zhang, Xingdong

    2018-07-01

    Weak osteointegration affects the long-term stability of polyaryletherketone (PAEK) implants. Surface modification provides a potential solution to improve the osteointegration property of PAEKs. Polyetheretherketone (PEEK) and polyetherketoneketone (PEKK) are two representative PAEK materials, but the latter has more ketone groups and better potential for surface chemical modification than the former. In this work, porous PEKK (PEKK-P) and PEEK (PEEK-P) were fabricated by a porogen leaching method. The samples were treated with 80% sulfuric acid (PEKK-SP and PEEK-SP) and then simulated body fluid (SBF) incubation (PEKK-BSP and PEEK-BSP). More micropores and higher hydrophilic SO 3 H groups were found on PEKK-SP than PEEK-SP. Likely, more bone-like apatite crystals deposited on PEKK-BSP than PEEK-BSP. To evaluate their osteointegration properties, the samples were implanted in femoral condyle defects (Φ3 × 4 mm 3 ) of rat models, and micro-computed tomography (μ-CT), histology and mechanical analyzes were performed on the retrieved specimens. For control groups, i.e. the dense samples (PEKK-D and PEEK-D), only a handful of bone creeping growth on the implant surface was seen on them. However, with the interconnected macropores, surface micro/nano topography and bone-like apatite, notable bone growth into the inner pores was observed on PEKK-BSP and PEEK-BSP. Furthermore, quantitative analyses confirmed that the newly formed bone in PEKK-BSP was nearly more than doubled than that in PEEK-BSP. The push-out force testing results (PEKK-D ≈ PEEK-D < PEKK-P ≈ PEEK-P < PEEK-BSP < PEKK-BSP) suggested that the surface chemical modification (sulfonation treatment followed by SBF incubation) along with build-in porous structure played more important role in enhancing the mechanical stability of both PAEK materials than just the physical structure change. Our results revealed that PEKK with more ketone groups allowed easier sulfonation and

  7. Nanofat-derived stem cells with platelet-rich fibrin improve facial contour remodeling and skin rejuvenation after autologous structural fat transplantation

    Science.gov (United States)

    Liang, Zhi-Jie; Chen, Hai; Zhu, Mao-Guang; Xu, Fang-Tian; He, Ning; Wei, Xiao-Juan; Li, Hong-Mian

    2017-01-01

    Traditional autologous fat transplantation is a common surgical procedure for treating facial soft tissue depression and skin aging. However, the transplanted fat is easily absorbed, reducing the long-term efficacy of the procedure. Here, we examined the efficacy of nanofat-assisted autologous fat structural transplantation. Nanofat-derived stem cells (NFSCs) were isolated, mechanically emulsified, cultured, and characterized. Platelet-rich fibrin (PRF) enhanced proliferation and adipogenic differentiation of NFSCs in vitro. We then compared 62 test group patients with soft tissue depression or signs of aging who underwent combined nanofat, PRF, and autologous fat structural transplantation to control patients (77 cases) who underwent traditional autologous fat transplantation. Facial soft tissue depression symptoms and skin texture were improved to a greater extent after nanofat transplants than after traditional transplants, and the nanofat group had an overall satisfaction rate above 90%. These data suggest that NFSCs function similarly to mesenchymal stem cells and share many of the biological characteristics of traditional fat stem cell cultures. Transplants that combine newly-isolated nanofat, which has a rich stromal vascular fraction (SVF), with PRF and autologous structural fat granules may therefore be a safe, highly-effective, and long-lasting method for remodeling facial contours and rejuvenating the skin. PMID:28978136

  8. Primary vesicles, vesicle-rich segregation structures and recognition of primary and secondary porosities in lava flows from the Paraná igneous province, southern Brazil

    Science.gov (United States)

    Barreto, Carla Joana S.; de Lima, Evandro F.; Goldberg, Karin

    2017-04-01

    This study focuses on a volcanic succession of pāhoehoe to rubbly lavas of the Paraná-Etendeka Province exposed in a single road profile in southernmost Brazil. This work provides an integrated approach for examining primary vesicles and vesicle-rich segregation structures at the mesoscopic scale. In addition, this study provides a quantitative analysis of pore types in thin section. We documented distinct distribution patterns of vesicle and vesicle-rich segregation structures according to lava thickness. In compound pāhoehoe lavas, the cooling allows only vesicles (pipe vesicles to be frozen into place. In inflated pāhoehoe lavas, vesicles of different sizes are common, including pipe vesicles, and also segregation structures such as proto-cylinders, cylinders, cylinder sheets, vesicle sheets, and pods. In rubbly lavas, only vesicles of varying sizes occur. Gas release from melt caused the formation of primary porosity, while hydrothermal alteration and tectonic fracturing are the main processes that generated secondary porosity. Although several forms of porosity were created in the basaltic lava flows, the precipitation of secondary minerals within the pores has tended to reduce the original porosities. Late-stage fractures could create efficient channel networks for possible hydrocarbon/groundwater migration and entrapment owing to their ability to connect single pores. Quantitative permeability data should be gathered in future studies to confirm the potential of these lavas for store hydrocarbons or groundwater.

  9. General Chemistry for Engineers.

    Science.gov (United States)

    Kybett, B. D.

    1982-01-01

    Discusses the relationship between molecular structure, intermolecular forces, and tensile strengths of a polymer and suggests that this is a logical way to introduce polymers into a general chemistry course. (Author/JN)

  10. From Chemistry to Behavior. Molecular Structure and Bioactivity of Repellents against Ixodes ricinus Ticks.

    Directory of Open Access Journals (Sweden)

    Simone Del Fabbro

    Full Text Available Tick-borne zoonoses are considered as emerging diseases. Tick repellents represent an effective tool for reducing the risk of tick bite and pathogens transmission. Previous work demonstrated the repellent activity of the phenylpropanoid eugenol against Ixodes ricinus; here we investigate the relationship between molecular structure and repellency in a group of substances related to that compound. We report the biological activity of 18 compounds varying for the presence/number of several moieties, including hydroxyl and methoxy groups and carbon side-chain. Each compound was tested at different doses with a bioassay designed to measure repellency against individual tick nymphs. Both vapor pressure and chemical features of the tested compounds appeared to be related to repellency. In particular, the hydroxyl and methoxy groups as well as the side-chain on the benzene ring seem to play a role. These results are discussed in light of available data on chemical perception in ticks. In the course of the study new repellent compounds were identified; the biological activity of some of them (at least as effective as the "gold standard" repellent DEET appears to be very promising from a practical point of view.

  11. Low-lying level structure of the neutron-rich nucleus {sup 109}Nb: A possible oblate-shape isomer

    Energy Technology Data Exchange (ETDEWEB)

    Watanabe, H., E-mail: hiroshi@ribf.riken.j [RIKEN Nishina Center, 2-1 Hirosawa, Wako, Saitama 351-0198 (Japan); Sumikama, T. [Department of Physics, Faculty of Science and Technology, Tokyo University of Science, 2641 Yamazaki, Noda, Chiba (Japan); Nishimura, S. [RIKEN Nishina Center, 2-1 Hirosawa, Wako, Saitama 351-0198 (Japan); Yoshinaga, K. [Department of Physics, Faculty of Science and Technology, Tokyo University of Science, 2641 Yamazaki, Noda, Chiba (Japan); Li, Z. [RIKEN Nishina Center, 2-1 Hirosawa, Wako, Saitama 351-0198 (Japan); Miyashita, Y. [Department of Physics, Faculty of Science and Technology, Tokyo University of Science, 2641 Yamazaki, Noda, Chiba (Japan); Yamaguchi, K. [Department of Physics, Osaka University, Machikaneyama-machi 1-1, Osaka 560-0043 Toyonaka (Japan); Baba, H. [RIKEN Nishina Center, 2-1 Hirosawa, Wako, Saitama 351-0198 (Japan); Berryman, J.S. [Nuclear Science Division, Lawrence Berkeley National Laboratory, Berkeley, CA 94720 (United States); Blasi, N. [INFN, Sezione di Milano, via Celoria 16, I-20133 Milano (Italy); Bracco, A.; Camera, F. [INFN, Sezione di Milano, via Celoria 16, I-20133 Milano (Italy); Dipartimento di Fisica, Universita di Milano, via Celoria 16, I-20133 Milano (Italy); Chiba, J. [Department of Physics, Faculty of Science and Technology, Tokyo University of Science, 2641 Yamazaki, Noda, Chiba (Japan); Doornenbal, P. [RIKEN Nishina Center, 2-1 Hirosawa, Wako, Saitama 351-0198 (Japan); Go, S.; Hashimoto, T.; Hayakawa, S. [Center for Nuclear Study, University of Tokyo, Hirosawa 2-1, Wako, Saitama 351-0198 (Japan); Hinke, C. [Physik Department, Technische Universitaet Muenchen, D-85748 Garching (Germany); Ideguchi, E. [Center for Nuclear Study, University of Tokyo, Hirosawa 2-1, Wako, Saitama 351-0198 (Japan); Isobe, T. [RIKEN Nishina Center, 2-1 Hirosawa, Wako, Saitama 351-0198 (Japan)

    2011-01-31

    The neutron-rich nuclei {sup 109}Nb and {sup 109}Zr have been populated using in-flight fission of a {sup 238}U beam at 345 MeV/nucleon at the RIBF facility. A T{sub 1/2}=150(30) ns isomer at 313 keV has been identified in {sup 109}Nb for the first time. The low-lying levels in {sup 109}Nb have been also populated following the {beta}-decay of {sup 109}Zr. Based on the difference in feeding pattern between the isomeric and {beta} decays, the decay scheme from the isomeric state in {sup 109}Nb was established. The observed hindrances of the electromagnetic transitions deexciting the isomeric state are discussed in terms of possible shape coexistence. Potential energy surface calculations for single-proton configurations predict the presence of low-lying oblate-deformed states in {sup 109}Nb.

  12. Insights into the Structure and Metabolic Function of Microbes That Shape Pelagic Iron-Rich Aggregates ( Iron Snow )

    Energy Technology Data Exchange (ETDEWEB)

    Lu, S [Friedrich Schiller University Jena, Jena Germany; Chourey, Karuna [ORNL; REICHE, M [Friedrich Schiller University Jena, Jena Germany; Nietzsche, S [Friedrich Schiller University Jena, Jena Germany; Shah, Manesh B [ORNL; Hettich, Robert {Bob} L [ORNL; Kusel, K [Friedrich Schiller University Jena, Jena Germany

    2013-01-01

    Metaproteomics combined with total nucleic acid-based methods aided in deciphering the roles of microorganisms in the formation and transformation of iron-rich macroscopic aggregates (iron snow) formed in the redoxcline of an acidic lignite mine lake. Iron snow had high total bacterial 16S rRNA gene copies, with 2 x 109 copies g (dry wt)-1 in the acidic (pH 3.5) central lake basin and 4 x 1010 copies g (dry wt)-1 in the less acidic (pH 5.5) northern lake basin. Active microbial communities in the central basin were dominated by Alphaproteobacteria (36.6%) and Actinobacteria (21.4%), and by Betaproteobacteria (36.2%) in the northern basin. Microbial Fe-cycling appeared to be the dominant metabolism in the schwertmannite-rich iron snow, because cloning and qPCR assigned up to 61% of active bacteria as Fe-cycling bacteria (FeB). Metaproteomics revealed 70 unique proteins from central basin iron snow and 283 unique proteins from 43 genera from northern basin. Protein identification provided a glimpse into in situ processes, such as primary production, motility, metabolism of acidophilic FeB, and survival strategies of neutrophilic FeB. Expression of carboxysome shell proteins and RubisCO indicated active CO2 fixation by Fe(II) oxidizers. Flagellar proteins from heterotrophs indicated their activity to reach and attach surfaces. Gas vesicle proteins related to CO2-fixing Chlorobium suggested that microbes could influence iron snow sinking. We suggest that iron snow formed by autotrophs in the redoxcline acts as a microbial parachute, since it is colonized by motile heterotrophs during sinking which start to dissolve schwertmannite.

  13. Chemistry Notes

    Science.gov (United States)

    School Science Review, 1976

    1976-01-01

    Described are eight chemistry experiments and demonstrations applicable to introductory chemistry courses. Activities include: measure of lattice enthalpy, Le Chatelier's principle, decarboxylation of soap, use of pocket calculators in pH measurement, and making nylon. (SL)

  14. Chemistry Dashboard

    Science.gov (United States)

    The Chemistry Dashboard is part of a suite of dashboards developed by EPA to help evaluate the safety of chemicals. The Chemistry Dashboard provides access to a variety of information on over 700,000 chemicals currently in use.

  15. Comparison of Different Biomass Pretreatment Techniques and Their Impact on Chemistry and Structure

    International Nuclear Information System (INIS)

    Singh, Seema; Cheng, Gang; Sathitsuksanoh, Noppadon; Wu, Dong; Varanasi, Patanjali; George, Anthe; Balan, Venkatesh; Gao, Xiadi; Kumar, Rajeev; Dale, Bruce E.; Wyman, Charles E.; Simmons, Blake A.

    2015-01-01

    Pretreatment of lignocellulosic biomass is a prerequisite to overcome recalcitrance and allow enzyme accessibility to cellulose and maximize product recovery for improved economics of second-generation lignocellulosic bio-refineries. Recently, the three US-DOE funded Bioenergy Research Centers [Joint Bioenergy Institute (JBEI), Great Lakes Bioenergy Research Center (GLBRC), and BioEnergy Science Center (BESC)] compared ionic liquid (IL), dilute sulfuric acid (DA), and ammonia fiber expansion (AFEX TM ) pretreatments and published comparative data on mass balance, total sugar yields, substrate accessibility, and microbial fermentation [Biotechnology for Biofuels 7: 71; 72 (2014)]. In this study, corn stover solids from IL, DA, and AFEX pretreatments were compared to gain comprehensive, in-depth understanding of induced morphological and chemical changes incorporated to corn stover, and how they overcome the biomass recalcitrance. These studies reveal that biomass recalcitrance is overcome by combination of structural and chemical changes to carbohydrates and lignin after pretreatment. Thermal analysis indicates that AFEX and IL pretreated corn stover showed a lower thermal stability while DA pretreated corn stover showed the opposite. The surface roughness variations measured by small-angle neutron scattering were correlated to the removal and redistribution of biomass components and was consistent with compositional analysis, atomic force microscopy (AFM) and confocal fluorescence imaging results. With AFM and confocal fluorescent microscopy, lignin was found to be re-deposited on cellulose surface with average cellulose fiber width significantly decreased for DA pretreated corn stover (one-third of IL and AFEX). HSQC NMR spectra revealed a ~17.9% reduction of β-aryl ether units after AFEX, ~59.8% reduction after DA, and >98% reduction after IL. Both NMR and size exclusion chromatography showed similar patterns of lignin de-polymerization with highest degree of de

  16. Comparison of Different Biomass Pretreatment Techniques and Their Impact on Chemistry and Structure

    Energy Technology Data Exchange (ETDEWEB)

    Singh, Seema, E-mail: seesing@sandia.gov; Cheng, Gang; Sathitsuksanoh, Noppadon; Wu, Dong; Varanasi, Patanjali; George, Anthe [Deconstruction Division, Joint BioEnergy Institute (JBEI), Emeryville, CA (United States); Sandia National Laboratories, Biological and Materials Sciences Center, Livermore, CA (United States); Balan, Venkatesh [Department of Chemical Engineering and Materials Science, DOE Great Lakes BioEnergy Research Center (GLBRC), Michigan State University, Lansing, MI (United States); Gao, Xiadi [Oak Ridge National Laboratory, BioEnergy Science Center (BESC), Oak Ridge, TN (United States); Department of Chemical and Environmental Engineering, Bourns College of Engineering, Riverside, CA (United States); Center for Environmental Research and Technology (CE-CERT), Bourns College of Engineering, University of California Riverside, Riverside, CA (United States); Kumar, Rajeev [Oak Ridge National Laboratory, BioEnergy Science Center (BESC), Oak Ridge, TN (United States); Center for Environmental Research and Technology (CE-CERT), Bourns College of Engineering, University of California Riverside, Riverside, CA (United States); Dale, Bruce E. [Department of Chemical Engineering and Materials Science, DOE Great Lakes BioEnergy Research Center (GLBRC), Michigan State University, Lansing, MI (United States); Wyman, Charles E. [Oak Ridge National Laboratory, BioEnergy Science Center (BESC), Oak Ridge, TN (United States); Department of Chemical and Environmental Engineering, Bourns College of Engineering, Riverside, CA (United States); Center for Environmental Research and Technology (CE-CERT), Bourns College of Engineering, University of California Riverside, Riverside, CA (United States); Simmons, Blake A. [Deconstruction Division, Joint BioEnergy Institute (JBEI), Emeryville, CA (United States); Sandia National Laboratories, Biological and Materials Sciences Center, Livermore, CA (United States)

    2015-02-06

    Pretreatment of lignocellulosic biomass is a prerequisite to overcome recalcitrance and allow enzyme accessibility to cellulose and maximize product recovery for improved economics of second-generation lignocellulosic bio-refineries. Recently, the three US-DOE funded Bioenergy Research Centers [Joint Bioenergy Institute (JBEI), Great Lakes Bioenergy Research Center (GLBRC), and BioEnergy Science Center (BESC)] compared ionic liquid (IL), dilute sulfuric acid (DA), and ammonia fiber expansion (AFEX{sup TM}) pretreatments and published comparative data on mass balance, total sugar yields, substrate accessibility, and microbial fermentation [Biotechnology for Biofuels 7: 71; 72 (2014)]. In this study, corn stover solids from IL, DA, and AFEX pretreatments were compared to gain comprehensive, in-depth understanding of induced morphological and chemical changes incorporated to corn stover, and how they overcome the biomass recalcitrance. These studies reveal that biomass recalcitrance is overcome by combination of structural and chemical changes to carbohydrates and lignin after pretreatment. Thermal analysis indicates that AFEX and IL pretreated corn stover showed a lower thermal stability while DA pretreated corn stover showed the opposite. The surface roughness variations measured by small-angle neutron scattering were correlated to the removal and redistribution of biomass components and was consistent with compositional analysis, atomic force microscopy (AFM) and confocal fluorescence imaging results. With AFM and confocal fluorescent microscopy, lignin was found to be re-deposited on cellulose surface with average cellulose fiber width significantly decreased for DA pretreated corn stover (one-third of IL and AFEX). HSQC NMR spectra revealed a ~17.9% reduction of β-aryl ether units after AFEX, ~59.8% reduction after DA, and >98% reduction after IL. Both NMR and size exclusion chromatography showed similar patterns of lignin de-polymerization with highest degree

  17. Seasonal Dynamics in the Chemistry and Structure of the Fat Bodies of Bumblebee Queens.

    Directory of Open Access Journals (Sweden)

    Alena Votavová

    Full Text Available Insects' fat bodies are responsible for nutrient storage and for a significant part of intermediary metabolism. Thus, it can be expected that the structure and content of the fat body will adaptively change, if an insect is going through different life stages. Bumblebee queens belong to such insects as they dramatically change their physiology several times over their lives in relation to their solitary overwintering, independent colony foundation stage, and during the colony life-cycle ending in the senescent stage. Here, we report on changes in the ultrastructure and lipid composition of the peripheral fat body of Bombus terrestris queens in relation to seasonal changes in the queens' activity. Six life stages are defined and evaluated in particular: pharate, callow, before and after hibernation, egg-laying, and senescence. Transmission electron microscopy revealed that the fat body contained two main cell types-adipocytes and oenocytes. Only adipocytes reveal important changes related to the life phase, and mostly the ration between inclusion and cytoplasm volume varies among particular stages. Both electron microscopy and chemical analyses of lipids highlighted seasonal variability in the quantity of the stored lipids, which peaked prior to hibernation. Triacylglycerols appeared to be the main energy source during hibernation, while the amount of glycogen before and after hibernation remained unchanged. In addition, we observed that the representation of some fatty acids within the triacylglycerols change during the queen's life. Last but not least, we show that fat body cell membranes do not undergo substantial changes concerning phospholipid composition in relation to overwintering. This finding supports the hypothesis that the cold-adaptation strategy of bumblebee queens is more likely to be based on polyol accumulation than on the restructuring of lipid membranes.

  18. Comparison of Different Biomass Pretreatment Techniques and their Impact on Chemistry and Structure

    Directory of Open Access Journals (Sweden)

    Seema eSingh

    2015-02-01

    Full Text Available Pretreatment of lignocellulosic biomass is a prerequisite to overcome recalcitrance and allow enzyme accessibility to cellulose and maximize product recovery for improved economics of second-generation lignocellulosic bio-refineries. Recently, the three US-DOE funded Bioenergy Research Centers (Joint Bioenergy Institute (JBEI, Great Lakes Bioenergy Research Center (GLBRC, and BioEnergy Science Center (BESC compared ionic liquid (IL, dilute sulfuric acid (DA, and ammonia fiber expansion (AFEXTM pretreatments and published comparative data on mass balance, total sugar yields, substrate accessibility, and microbial fermentation (Biotechnology for Biofuels 7: 71; 72 (2014. In this study, corn stover solids from IL, DA, and AFEX pretreatments were compared to gain comprehensive, in-depth understanding of induced morphological and chemical changes incorporated to corn stover, and how they overcome the biomass recalcitrance. These studies reveal that biomass recalcitrance is overcome by combination of structural and chemical changes to carbohydrates and lignin after pretreatment. Thermal analysis indicates that AFEX and IL pretreated corn stover showed a lower thermal stability while DA pretreated corn stover showed the opposite. The surface roughness variations measured by SANS were correlated to the removal and redistribution of biomass components and was consistent with compositional analysis, AFM and confocal fluorescence imaging results. With AFM and confocal fluorescent microscopy, lignin was found to be re-deposited on cellulose surface with average cellulose fiber width significantly decreased for DA pretreated corn stover (one third of IL and AFEX. HSQC NMR spectra revealed a ~17.9% reduction of β-aryl ether units after AFEX, ~59.8% reduction after DA and >98% reduction after IL. Both NMR and SEC showed similar patterns of lignin depolymerization with highest degree of depolymerization observed for IL followed with DA and AFEX.

  19. Impact of fluorine based reactive chemistry on structure and properties of high moment magnetic material

    Energy Technology Data Exchange (ETDEWEB)

    Yang, Xiaoyu, E-mail: xiaoyu.yang@wdc.com; Chen, Lifan; Han, Hongmei; Fu, Lianfeng; Sun, Ming; Liu, Feng; Zhang, Jinqiu [Western Digital Corporation, 44100 Osgood Road, Fremont, California 94539 (United States)

    2014-05-07

    The impact of the fluorine-based reactive ion etch (RIE) process on the structural, electrical, and magnetic properties of NiFe and CoNiFe-plated materials was investigated. Several techniques, including X-ray fluorescence, 4-point-probe, BH looper, transmission electron microscopy (TEM), and electron energy loss spectroscopy (EELS), were utilized to characterize both bulk film properties such as thickness, average composition, Rs, ρ, Bs, Ms, and surface magnetic “dead” layers' properties such as thickness and element concentration. Experimental data showed that the majority of Rs and Bs changes of these bulk films were due to thickness reduction during exposure to the RIE process. ρ and Ms change after taking thickness reduction into account were negligible. The composition of the bulk films, which were not sensitive to surface magnetic dead layers with nano-meter scale, showed minimum change as well. It was found by TEM and EELS analysis that although both before and after RIE there were magnetic dead layers on the top surface of these materials, the thickness and element concentration of the layers were quite different. Prior to RIE, dead layer was actually native oxidation layers (about 2 nm thick), while after RIE dead layer consisted of two sub-layers that were about 6 nm thick in total. Sub-layer on the top was native oxidation layer, while the bottom layer was RIE “damaged” layer with very high fluorine concentration. Two in-situ RIE approaches were also proposed and tested to remove such damaged sub-layers.

  20. Leg tendon glands in male bumblebees ( Bombus terrestris): structure, secretion chemistry, and possible functions

    Science.gov (United States)

    Jarau, Stefan; Žáček, Petr; Šobotník, Jan; Vrkoslav, Vladimír; Hadravová, Romana; Coppée, Audrey; Vašíčková, Soňa; Jiroš, Pavel; Valterová, Irena

    2012-12-01

    Among the large number of exocrine glands described in bees, the tarsal glands were thought to be the source of footprint scent marks. However, recent studies showed that the compounds used for marking by stingless bees are secreted by leg tendon instead of tarsal glands. Here, we report on the structure of leg tendon glands in males of Bombus terrestris, together with a description of the chemical composition of their secretions and respective changes of both during the males' lives. The ultrastructure of leg tendon glands shows that the secretory cells are located in three independent regions, separated from each other by unmodified epidermal cells: in the femur, tibia, and basitarsus. Due to the common site of secretion release, the organ is considered a single secretory gland. The secretion of the leg tendon glands of B. terrestris males differs in its composition from those of workers and queens, in particular by (1) having larger proportions of compounds with longer chain lengths, which we identified as wax esters; and (2) by the lack of certain hydrocarbons (especially long chain dienes). Other differences consist in the distribution of double bond positions in the unsaturated hydrocarbons that are predominantly located at position 9 in males but distributed at seven to nine different positions in the female castes. Double bond positions may change chemical and physical properties of a molecule, which can be recognized by the insects and, thus, may serve to convey specific information. The function of male-specific compounds identified from their tendon glands remains elusive, but several possibilities are discussed.

  1. Probing and tuning the size, morphology, chemistry and structure of nanoscale cerium oxide

    Science.gov (United States)

    Kuchibhatla, Satyanarayana Vnt

    Cerium oxide (ceria)-based materials in the nanoscale regime are of significant fundamental and technological interest. Nanoceria in pure and doped forms has current and potential use in solid oxide fuel cells, catalysis, UV-screening, chemical mechanical planarization, oxygen sensors, and bio-medical applications. The characteristic feature of Ce to switch between the +3 and +4 oxidation states renders oxygen buffering capability to ceria. The ease of this transformation was expected to be enhanced in the nanoceria. In most the practical scenarios, it is necessary to have a stable suspension of ceria nanoparticles (CNPs) over longer periods of time. However, the existing literature is confined to short term studies pertaining to synthesis and property evaluation. Having understood the need for a comprehensive understanding of the CNP suspensions, this dissertation is primarily aimed at understanding the behavior of CNPs in various chemical and physical environments. We have synthesized CNPs in the absence of any surfactants at room temperature and studied the aging characteristics. After gaining some understanding about the behavior of this functional oxide, the synthesis environment and aging temperature were varied, and their affects were carefully analyzed using various materials analysis techniques such as high resolution transmission electron microscopy (HRTEM), UV-Visible spectroscopy (UV-Vis), and X-ray photoelectron spectroscopy (XPS). When the CNPs were aged at room temperature in as-synthesized condition, they were observed to spontaneously assemble and evolve as fractal superoctahedral structures. The reasons for this unique polycrystalline morphology were attributed to the symmetry driven assembly of the individual truncated octahedral and octahedral seed of the ceria. HRTEM and Fast Fourier Transform (FFT) analyses were used to explain the agglomeration behavior and evolution of the octahedral morphology. Some of the observations were supported by

  2. Combinatorial chemistry

    DEFF Research Database (Denmark)

    Nielsen, John

    1994-01-01

    An overview of combinatorial chemistry is presented. Combinatorial chemistry, sometimes referred to as `irrational drug design,' involves the generation of molecular diversity. The resulting chemical library is then screened for biologically active compounds.......An overview of combinatorial chemistry is presented. Combinatorial chemistry, sometimes referred to as `irrational drug design,' involves the generation of molecular diversity. The resulting chemical library is then screened for biologically active compounds....

  3. Aquatic Chemistry

    International Nuclear Information System (INIS)

    Kim, Dong Yeun; Kim, Oh Sik; Kim, Chang Guk; Park, Cheong Gil; Lee, Gwi Hyeon; Lee, Cheol Hui

    1987-07-01

    This book deals aquatic chemistry, which treats water and environment, chemical kinetics, chemical balance like dynamical characteristic, and thermodynamics, acid-base chemistry such as summary, definition, kinetics, and PH design for mixture of acid-base chemistry, complex chemistry with definition, and kinetics, precipitation and dissolution on summary, kinetics of precipitation and dissolution, and balance design oxidation and resolution with summary, balance of oxidation and resolution.

  4. Positronium chemistry

    CERN Document Server

    Green, James

    1964-01-01

    Positronium Chemistry focuses on the methodologies, reactions, processes, and transformations involved in positronium chemistry. The publication first offers information on positrons and positronium and experimental methods, including mesonic atoms, angular correlation measurements, annihilation spectra, and statistical errors in delayed coincidence measurements. The text then ponders on positrons in gases and solids. The manuscript takes a look at the theoretical chemistry of positronium and positronium chemistry in gases. Topics include quenching, annihilation spectrum, delayed coincidence

  5. Structure and properties of rare earth-rich glassed for nuclear waste immobilisation; Etude des caracteristiques structurales et des proprietes de verres riches en terres rares destines au confinement des produits de fission et elements a vie longue

    Energy Technology Data Exchange (ETDEWEB)

    Bardez, I

    2004-11-15

    A new nuclear glass composition, able to immobilize highly radioactive liquid wastes from high burn-up UO{sub 2} fuel, was established and its structure studied. The composition of the selected rare earth-rich glass is (molar %): 61.79 SiO{sub 2} - 8.94 B{sub 2}O{sub 3} - 3.05 Al{sub 2}O{sub 3} - 14.41 Na{sub 2}O - 6.32 CaO - 1.89 ZrO{sub 2} - 3.60 RE{sub 2}O{sub 3} (with RE = La, Ce, Pr and Nd). The aim of this study was to determine the local environment of the rare earth in this glass and also to glean information about the effect of glass composition on the rare earth neighbouring (influence of Si, B, Al, Na and Ca contents). To this end, several series of glasses, prepared from the baseline glass, were studied by different characterisation methods such as EXAFS spectroscopy at the neodymium LIII-edge, optical absorption spectroscopy, Raman spectroscopy and {sup 29}Si, {sup 27}Al and {sup 11}B MAS-NMR. By coupling all the results obtained, several hypotheses about the nature of the rare earth neighbouring in the glass were proposed. (author)

  6. Conference 'Chemistry of hydrides' Proceedings

    International Nuclear Information System (INIS)

    1991-07-01

    This collection of thesis of conference of Chemistry hydrides presents the results of investigations concerning of base questions of chemistry of nonorganic hydrides, including synthesis questions, studying of physical and chemical properties, thermodynamics, analytical chemistry, investigation of structure, equilibriums in the systems of metal-hydrogen, behaviour of nonorganic hydrides in non-water mediums and applying investigations in the chemistry area and technology of nonorganic hydrides

  7. Phase equilibria, crystal chemistry, electronic structure and physical properties of Ag-Ba-Ge clathrates

    Energy Technology Data Exchange (ETDEWEB)

    Zeiringer, I.; Chen Mingxing [Institute of Physical Chemistry, University of Vienna, Waehringerstr. 42, 1090 Wien (Austria); Bednar, I.; Royanian, E.; Bauer, E. [Institute of Solid State Physics, Vienna University of Technology, Wiedner Hauptstr. 8-10, 1040 Wien (Austria); Podloucky, R.; Grytsiv, A. [Institute of Physical Chemistry, University of Vienna, Waehringerstr. 42, 1090 Wien (Austria); Rogl, P., E-mail: peter.franz.rogl@univie.ac.at [Institute of Physical Chemistry, University of Vienna, Waehringerstr. 42, 1090 Wien (Austria); Effenberger, H. [Institute of Mineralogy and Crystallography, University of Vienna, A-1090 Wien (Austria)

    2011-04-15

    In the Ag-Ba-Ge system the clathrate type-{Iota} solid solution, Ba{sub 8}Ag{sub x}Ge{sub 46-x-y{open_square}y}, extends at 800 deg. C from binary Ba{sub 8}Ge{sub 43{open_square}3} ({open_square} is a vacancy) to Ba{sub 8}Ag{sub 5.3}Ge{sub 40.7}. For the clathrate phase (1 {<=} x {<=} 5.3) the cubic space group Pm3-bar n was established by X-ray powder diffraction and confirmed by X-ray single-crystal analyses of the samples Ba{sub 8}Ag{sub 2.3}Ge{sub 41.9{open_square}1.8} and Ba{sub 8}Ag{sub 4.4}Ge{sub 41.3{open_square}0.3}. Increasing the concentration of Ag causes the lattice parameters of the solid solution to increase linearly from a value of a = 1.0656 (x = 0, y = 3) to a = 1.0842 (x = 4.8, y = 0) nm. Site preference determination using X-ray refinement reveals that Ag atoms preferentially occupy the 6d site randomly mixed with Ge and vacancies, which become filled in the compound Ba{sub 8}Ag{sub 4.8}Ge{sub 41.2} when the Ag content increases. At 600 {sup o}C the phase region of the clathrate solution Ba{sub 8}Ag{sub x}Ge{sub 46-x-y{open_square}y} becomes separated from the Ba-Ge boundary and extends from 6.6 to 9.8 at.% Ag. The compound Ba{sub 6}Ge{sub 25} (clathrate type-{Iota}X) dissolves at 800 {sup o}C a maximum of 1.5 at.% Ag. The homogeneity regions of the two ternary compounds BaAg{sub 2-x}Ge{sub 2+x} (ThCr{sub 2}Si{sub 2}-type, 0.2 {<=} x {<=} 0.7) and Ba(Ag{sub 1-x}Ge{sub x}){sub 2} (AlB{sub 2}-type, 0.65 {<=} x {<=} 0.75) were established at 800 deg. C. Studies of transport properties for the series of Ba{sub 8}Ag{sub x}Ge{sub 46-x-y{open_square}y} compounds evidenced that electrons are the predominant charge carriers with the Fermi energy close to a gap. Its position can be fine-tuned by the substitution of Ge by Ag atoms and by mechanical processing of the starting material, Ba{sub 8}Ge{sub 43}. The proximity of the electronic structure at Fermi energy of Ba{sub 8}Ag{sub x}Ge{sub 46-x-y{open_square}y} to a gap is also corroborated by density

  8. Crystal structure of LGR4-Rspo1 complex: insights into the divergent mechanisms of ligand recognition by leucine-rich repeat G-protein-coupled receptors (LGRs).

    Science.gov (United States)

    Xu, Jin-Gen; Huang, Chunfeng; Yang, Zhengfeng; Jin, Mengmeng; Fu, Panhan; Zhang, Ni; Luo, Jian; Li, Dali; Liu, Mingyao; Zhou, Yan; Zhu, Yongqun

    2015-01-23

    Leucine-rich repeat G-protein-coupled receptors (LGRs) are a unique class of G-protein-coupled receptors characterized by a large extracellular domain to recognize ligands and regulate many important developmental processes. Among the three groups of LGRs, group B members (LGR4-6) recognize R-spondin family proteins (Rspo1-4) to stimulate Wnt signaling. In this study, we successfully utilized the "hybrid leucine-rich repeat technique," which fused LGR4 with the hagfish VLR protein, to obtain two recombinant human LGR4 proteins, LGR415 and LGR49. We determined the crystal structures of ligand-free LGR415 and the LGR49-Rspo1 complex. LGR4 exhibits a twisted horseshoe-like structure. Rspo1 adopts a flat and β-fold architecture and is bound in the concave surface of LGR4 in the complex through electrostatic and hydrophobic interactions. All the Rspo1-binding residues are conserved in LGR4-6, suggesting that LGR4-6 bind R-spondins through an identical surface. Structural analysis of our LGR4-Rspo1 complex with the previously determined LGR4 and LGR5 structures revealed that the concave surface of LGR4 is the sole binding site for R-spondins, suggesting a one-site binding model of LGR4-6 in ligand recognition. The molecular mechanism of LGR4-6 is distinct from the two-step mechanism of group A receptors LGR1-3 and the multiple-interface binding model of group C receptors LGR7-8, suggesting LGRs utilize the divergent mechanisms for ligand recognition. Our structures, together with previous reports, provide a comprehensive understanding of the ligand recognition by LGRs. © 2015 by The American Society for Biochemistry and Molecular Biology, Inc.

  9. Industry-Government-University Cooperative Research Program for the Development of Structural Materials from Sulfate-Rich FGD Scrubber Sludge

    Energy Technology Data Exchange (ETDEWEB)

    V. M. Malhotra; Y. P. Chugh

    2003-08-31

    The main aim of our project was to develop technology, which converts flue gas desulfurization (FGD) sulfate-rich scrubber sludge into value-added decorative materials. Specifically, we were to establish technology for fabricating cost effective but marketable materials, like countertops and decorative tiles from the sludge. In addition, we were to explore the feasibility of forming siding material from the sludge. At the end of the project, we were to establish the potential of our products by generating 64 countertop pieces and 64 tiles of various colors. In pursuit of our above-mentioned goals, we conducted Fourier transform infrared (FTIR) and differential scanning calorimetry (DSC) measurements of the binders and co-processed binders to identify their curing behavior. Using our 6-inch x 6-inch and 4-inch x 4-inch high pressure and high temperature hardened stainless steel dies, we developed procedures to fabricate countertop and decorative tile materials. The composites, fabricated from sulfate-rich scrubber sludge, were subjected to mechanical tests using a three-point bending machine and a dynamic mechanical analyzer (DMA). We compared our material's mechanical performance against commercially obtained countertops. We successfully established the procedures for the development of countertop and tile composites from scrubber sludge by mounting our materials on commercial boards. We fabricated more than 64 pieces of countertop material in at least 11 different colors having different patterns. In addition, more than 100 tiles in six different colors were fabricated. We also developed procedures by which the fabrication waste, up to 30-weight %, could be recycled in the manufacturing of our countertops and decorative tiles. Our experimental results indicated that our countertops had mechanical strength, which was comparable to high-end commercial countertop materials and contained substantially larger inorganic content than the commercial products. Our

  10. Arbuscular Mycorrhizal Fungi Community Structure, Abundance and Species Richness Changes in Soil by Different Levels of Heavy Metal and Metalloid Concentration

    Science.gov (United States)

    Krishnamoorthy, Ramasamy; Kim, Chang-Gi; Subramanian, Parthiban; Kim, Ki-Yoon; Selvakumar, Gopal; Sa, Tong-Min

    2015-01-01

    Arbuscular Mycorrhizal Fungi (AMF) play major roles in ecosystem functioning such as carbon sequestration, nutrient cycling, and plant growth promotion. It is important to know how this ecologically important soil microbial player is affected by soil abiotic factors particularly heavy metal and metalloid (HMM). The objective of this study was to understand the impact of soil HMM concentration on AMF abundance and community structure in the contaminated sites of South Korea. Soil samples were collected from the vicinity of an abandoned smelter and the samples were subjected to three complementary methods such as spore morphology, terminal restriction fragment length polymorphism (T-RFLP) and denaturing gradient gel electrophoresis (DGGE) for diversity analysis. Spore density was found to be significantly higher in highly contaminated soil compared to less contaminated soil. Spore morphological study revealed that Glomeraceae family was more abundant followed by Acaulosporaceae and Gigasporaceae in the vicinity of the smelter. T-RFLP and DGGE analysis confirmed the dominance of Funneliformis mosseae and Rhizophagus intraradices in all the study sites. Claroideoglomus claroideum, Funneliformis caledonium, Rhizophagus clarus and Funneliformis constrictum were found to be sensitive to high concentration of soil HMM. Richness and diversity of Glomeraceae family increased with significant increase in soil arsenic, cadmium and zinc concentrations. Our results revealed that the soil HMM has a vital impact on AMF community structure, especially with Glomeraceae family abundance, richness and diversity. PMID:26035444

  11. Detection of G-Quadruplex Structures Formed by G-Rich Sequences from Rice Genome and Transcriptome Using Combined Probes.

    Science.gov (United States)

    Chang, Tianjun; Li, Weiguo; Ding, Zhan; Cheng, Shaofei; Liang, Kun; Liu, Xiangjun; Bing, Tao; Shangguan, Dihua

    2017-08-01

    Putative G-quadruplex (G4) forming sequences (PQS) are highly prevalent in the genome and transcriptome of various organisms and are considered as potential regulation elements in many biological processes by forming G4 structures. The formation of G4 structures highly depends on the sequences and the environment. In most cases, it is difficult to predict G4 formation by PQS, especially PQS containing G2 tracts. Therefore, the experimental identification of G4 formation is essential in the study of G4-related biological functions. Herein, we report a rapid and simple method for the detection of G4 structures by using a pair of complementary reporters, hemin and BMSP. This method was applied to detect G4 structures formed by PQS (DNA and RNA) searched in the genome and transcriptome of Oryza sativa. Unlike most of the reported G4 probes that only recognize part of G4 structures, the proposed method based on combined probes positively responded to almost all G4 conformations, including parallel, antiparallel, and mixed/hybrid G4, but did not respond to non-G4 sequences. This method shows potential for high-throughput identification of G4 structures in genome and transcriptome. Furthermore, BMSP was observed to drive some PQS to form more stable G4 structures or induce the G4 formation of some PQS that cannot form G4 in normal physiological conditions, which may provide a powerful molecular tool for gene regulation.

  12. Residue Modification and Mass Spectrometry for the Investigation of Structural and Metalation Properties of Metallothionein and Cysteine-Rich Proteins

    Directory of Open Access Journals (Sweden)

    Gordon W. Irvine

    2017-04-01

    Full Text Available Structural information regarding metallothioneins (MTs has been hard to come by due to its highly dynamic nature in the absence of metal-thiolate cluster formation and crystallization difficulties. Thus, typical spectroscopic methods for structural determination are limited in their usefulness when applied to MTs. Mass spectrometric methods have revolutionized our understanding of protein dynamics, structure, and folding. Recently, advances have been made in residue modification mass spectrometry in order to probe the hard-to-characterize structure of apo- and partially metalated MTs. By using different cysteine specific alkylation reagents, time dependent electrospray ionization mass spectrometry (ESI-MS, and step-wise “snapshot” ESI-MS, we are beginning to understand the dynamics of the conformers of apo-MT and related species. In this review we highlight recent papers that use these and similar techniques for structure elucidation and attempt to explain in a concise manner the data interpretations of these complex methods. We expect increasing resolution in our picture of the structural conformations of metal-free MTs as these techniques are more widely adopted and combined with other promising tools for structural elucidation.

  13. Implementation and Evaluation of Web-Based Learning Activities on Bonding and the Structure of Matter for 10-th Grade Chemistry

    Science.gov (United States)

    Frailich, Marcel

    This study deals with the development, implementation, and evaluation of web-based activities associated with the topic of chemical bonding , as taught in 10th grade chemistry. A website was developed entitled: "Chemistry and the Chemical Industry in the Service of Mankind", its URL is: http://stwww.weizmann.ac.il/g-chem/learnchem (Kesner, Frailich, & Hofstein, 2003). The main goal of this study was to assess the educational effectiveness of website activities dealing with the chemical bonding concept. These activities include visualization tools, as well as topics relevant to daily life and industrial applications. The study investigated the effectiveness of a web-based learning environment regarding the understanding of chemical bonding concepts, students' perceptions of the classroom learning environment, their attitudes regarding the relevance of learning chemistry to everyday life, and their interest in chemistry studies. As mentioned before, in the present study we focused on activities (from the website), all of which deal with chemical bonding concept. The following are the reasons for the decision to focus on this topic: (1) Chemical bonding is a key concept that is taught in 10th grade chemistry in high school. It provides the basis for many other chemistry topics that are taught later, and (2) Chemical bonding is a difficult for students using existing tools (e. g., static models in books, ball-and- stick models), which are insufficient to demonstrate the abstract nature phenomena associated with this topic. The four activities developed for this study are (1) models of the atomic structure, (2) metals -- structure and properties, (3) ionic substances in everyday life and in industry, and (4) molecular substances -- structure, properties, and uses. The study analyzed both quantitative and qualitative research. The quantitative tools of the study included: A Semantic Differential questionnaire and a Chemistry Classroom Web-Based Learning Environment

  14. Forensic Chemistry

    Science.gov (United States)

    Bell, Suzanne

    2009-07-01

    Forensic chemistry is unique among chemical sciences in that its research, practice, and presentation must meet the needs of both the scientific and the legal communities. As such, forensic chemistry research is applied and derivative by nature and design, and it emphasizes metrology (the science of measurement) and validation. Forensic chemistry has moved away from its analytical roots and is incorporating a broader spectrum of chemical sciences. Existing forensic practices are being revisited as the purview of forensic chemistry extends outward from drug analysis and toxicology into such diverse areas as combustion chemistry, materials science, and pattern evidence.

  15. Structural characterization of copper(II) binding to α-synuclein: Insights into the bioinorganic chemistry of Parkinson's disease

    Science.gov (United States)

    Rasia, Rodolfo M.; Bertoncini, Carlos W.; Marsh, Derek; Hoyer, Wolfgang; Cherny, Dmitry; Zweckstetter, Markus; Griesinger, Christian; Jovin, Thomas M.; Fernández, Claudio O.

    2005-01-01

    The aggregation of α-synuclein (AS) is characteristic of Parkinson's disease and other neurodegenerative synucleinopathies. We demonstrate here that Cu(II) ions are effective in accelerating AS aggregation at physiologically relevant concentrations without altering the resultant fibrillar structures. By using numerous spectroscopic techniques (absorption, CD, EPR, and NMR), we have located the primary binding for Cu(II) to a specific site in the N terminus, involving His-50 as the anchoring residue and other nitrogen/oxygen donor atoms in a square planar or distorted tetragonal geometry. The carboxylate-rich C terminus, originally thought to drive copper binding, is able to coordinate a second Cu(II) equivalent, albeit with a 300-fold reduced affinity. The NMR analysis of AS–Cu(II) complexes reveals the existence of conformational restrictions in the native state of the protein. The metallobiology of Cu(II) in Parkinson's disease is discussed by a comparative analysis with other Cu(II)-binding proteins involved in neurodegenerative disorders. PMID:15767574

  16. A systematic study of band structure and electromagnetic properties of neutron rich odd mass Eu isotopes in the projected shell model framework

    Energy Technology Data Exchange (ETDEWEB)

    Pandit, Rakesh K.; Devi, Rani [University of Jammu, Department of Physics and Electronics, Jammu (India); Khosa, S.K. [Central University of Jammu, Department of Physics and Astronomical Sciences, Jammu (India); Bhat, G.H.; Sheikh, J.A. [University of Kashmir, Department of Physics, Srinagar (India)

    2017-10-15

    The positive and negative parity rotational band structure of the neutron rich odd mass Eu isotopes with neutron numbers ranging from 90 to 96 are investigated up to the high angular momentum. In the theoretical analysis of energy spectra, transition energies and electromagnetic transition probabilities we employ the projected shell model. The calculations successfully describe the formation of the ground and excited band structures from the single particle and multi quasiparticle configurations. Calculated excitation energy spectra, transition energies, exact quantum mechanically calculated B(E2) and B(M1) transition probabilities are compared with experimental data wherever available and a reasonably good agreement is obtained with the observed data. The change in deformation in the ground state band with the increase in angular momentum and the increase in neutron number has also been established. (orig.)

  17. Towards Prediction Of Crystal Structure Of Al-Rich Intermetallides Formed In Al-T-A Systems

    International Nuclear Information System (INIS)

    Bram, Avraham I.; Meshic, Louisa; Ilse Katz institute for nanotechnology, Ben Gurion University of the Negev; Venkert, Arie

    2014-01-01

    Crystal structure of the material has a significant contribution on its properties. However, there is no universal model that can predict precisely the crystallographic structure of a stable material at specific composition and temperature. Since the 1950's, various prediction approaches were developed and yielded many different methods of computer simulation and innovative theories which are summarized in the review of Woodley et al. These methods are based on complicated calculations of quantum sizes

  18. High-resolution crystal structure of Streptococcus pyogenes β-NAD{sup +} glycohydrolase in complex with its endogenous inhibitor IFS reveals a highly water-rich interface

    Energy Technology Data Exchange (ETDEWEB)

    Yoon, Ji Young; An, Doo Ri; Yoon, Hye-Jin [Seoul National University, Seoul 151-747 (Korea, Republic of); Kim, Hyoun Sook [Seoul National University, Seoul 151-747 (Korea, Republic of); Seoul National University, Seoul 151-742 (Korea, Republic of); Lee, Sang Jae [Seoul National University, Seoul 151-742 (Korea, Republic of); Im, Ha Na; Jang, Jun Young [Seoul National University, Seoul 151-747 (Korea, Republic of); Suh, Se Won, E-mail: sewonsuh@snu.ac.kr [Seoul National University, Seoul 151-747 (Korea, Republic of); Seoul National University, Seoul 151-747 (Korea, Republic of)

    2013-11-01

    The crystal structure of the complex between the C-terminal domain of Streptococcus pyogenes β-NAD{sup +} glycohydrolase and an endogenous inhibitor for SPN was determined at 1.70 Å. It reveals that the interface between the two proteins is highly rich in water molecules. One of the virulence factors produced by Streptococcus pyogenes is β-NAD{sup +} glycohydrolase (SPN). S. pyogenes injects SPN into the cytosol of an infected host cell using the cytolysin-mediated translocation pathway. As SPN is toxic to bacterial cells themselves, S. pyogenes possesses the ifs gene that encodes an endogenous inhibitor for SPN (IFS). IFS is localized intracellularly and forms a complex with SPN. This intracellular complex must be dissociated during export through the cell envelope. To provide a structural basis for understanding the interactions between SPN and IFS, the complex was overexpressed between the mature SPN (residues 38–451) and the full-length IFS (residues 1–161), but it could not be crystallized. Therefore, limited proteolysis was used to isolate a crystallizable SPN{sub ct}–IFS complex, which consists of the SPN C-terminal domain (SPN{sub ct}; residues 193–451) and the full-length IFS. Its crystal structure has been determined by single anomalous diffraction and the model refined at 1.70 Å resolution. Interestingly, our high-resolution structure of the complex reveals that the interface between SPN{sub ct} and IFS is highly rich in water molecules and many of the interactions are water-mediated. The wet interface may facilitate the dissociation of the complex for translocation across the cell envelope.

  19. High-resolution crystal structure of Streptococcus pyogenes β-NAD+ glycohydrolase in complex with its endogenous inhibitor IFS reveals a highly water-rich interface

    International Nuclear Information System (INIS)

    Yoon, Ji Young; An, Doo Ri; Yoon, Hye-Jin; Kim, Hyoun Sook; Lee, Sang Jae; Im, Ha Na; Jang, Jun Young; Suh, Se Won

    2013-01-01

    The crystal structure of the complex between the C-terminal domain of Streptococcus pyogenes β-NAD + glycohydrolase and an endogenous inhibitor for SPN was determined at 1.70 Å. It reveals that the interface between the two proteins is highly rich in water molecules. One of the virulence factors produced by Streptococcus pyogenes is β-NAD + glycohydrolase (SPN). S. pyogenes injects SPN into the cytosol of an infected host cell using the cytolysin-mediated translocation pathway. As SPN is toxic to bacterial cells themselves, S. pyogenes possesses the ifs gene that encodes an endogenous inhibitor for SPN (IFS). IFS is localized intracellularly and forms a complex with SPN. This intracellular complex must be dissociated during export through the cell envelope. To provide a structural basis for understanding the interactions between SPN and IFS, the complex was overexpressed between the mature SPN (residues 38–451) and the full-length IFS (residues 1–161), but it could not be crystallized. Therefore, limited proteolysis was used to isolate a crystallizable SPN ct –IFS complex, which consists of the SPN C-terminal domain (SPN ct ; residues 193–451) and the full-length IFS. Its crystal structure has been determined by single anomalous diffraction and the model refined at 1.70 Å resolution. Interestingly, our high-resolution structure of the complex reveals that the interface between SPN ct and IFS is highly rich in water molecules and many of the interactions are water-mediated. The wet interface may facilitate the dissociation of the complex for translocation across the cell envelope

  20. Effect of the stoichiometry of Si-rich silicon nitride thin films on their photoluminescence and structural properties

    Energy Technology Data Exchange (ETDEWEB)

    Torchynska, T.V., E-mail: ttorch@esfm.ipn.mx [ESFM—Instituto Politecnico Nacional, Mexico DF 07738 (Mexico); Casas Espinola, J.L. [ESFM—Instituto Politecnico Nacional, Mexico DF 07738 (Mexico); Vergara Hernandez, E. [UPIITA—Instituto Politecnico Nacional, Mexico DF 07320 (Mexico); Khomenkova, L., E-mail: khomen@ukr.net [V. Lashkaryov Institute of Semiconductor Physics, 45 Pr. Nauky, 03028 Kyiv (Ukraine); Delachat, F.; Slaoui, A. [ICube, 23 rue du Loess, BP 20 CR, 67037 Strasbourg Cedex 2 (France)

    2015-04-30

    Si-rich Silicon nitride films were grown on silicon substrates by plasma enhanced chemical vapor deposition. The film stoichiometry was controlled via the variation of NH{sub 3}/SiH{sub 4} ratio from 0.45 up to 1.0. Thermal annealing at 1100 °C for 30 min in the nitrogen flow was applied to form the Si nanocrystals in the films that have been investigated by means of photoluminescence and Raman scattering methods, as well as transmission electron microscopy. Several emission bands have been detected with the peak positions at: 2.8–3.0 eV, 2.5–2.7 eV, 2.10–2.25 eV, and 1.75–1.98 eV. The temperature dependences of photoluminescence spectra were studied with the aim to confirm the types of optical transitions and the nature of light emitting defects in silicon nitride. The former three bands were assigned to the defects in silicon nitride, whereas the last one (1.75–1.98 eV) was attributed to the exciton recombination inside of Si nanocrystals. The photoluminescence mechanism is discussed. - Highlights: • Substoichiometric silicon nitride films were grown by PECVD technique. • The variation of the NH{sub 3}/SiH{sub 4} ratio controls excess Si content in the films. • Both Si nanocrystals and amorphous Si phase were observed in annealed films. • Temperature evolution of carrier recombination via Si nanocrystals and host defects.

  1. Chemistry Division annual progress report for period ending January 31, 1984

    Energy Technology Data Exchange (ETDEWEB)

    1984-05-01

    Progress is reported in the following fields: coal chemistry, aqueous chemistry at high temperatures and pressures, geochemistry, high-temperature chemistry and thermodynamics of structural materials, chemistry of transuranium elements and compounds, separations chemistry, elecrochemistry, catalysis, chemical physics, theoretical chemistry, nuclear waste chemistry, chemistry of hazardous chemicals, and thermal energy storage.

  2. Scandium Terminal Imido Chemistry.

    Science.gov (United States)

    Lu, Erli; Chu, Jiaxiang; Chen, Yaofeng

    2018-02-20

    Research into transition metal complexes bearing multiply bonded main-group ligands has developed into a thriving and fruitful field over the past half century. These complexes, featuring terminal M═E/M≡E (M = transition metal; E = main-group element) multiple bonds, exhibit unique structural properties as well as rich reactivity, which render them attractive targets for inorganic/organometallic chemists as well as indispensable tools for organic/catalytic chemists. This fact has been highlighted by their widespread applications in organic synthesis, for example, as olefin metathesis catalysts. In the ongoing renaissance of transition metal-ligand multiple-bonding chemistry, there have been reports of M═E/M≡E interactions for the majority of the metallic elements of the periodic table, even some actinide metals. In stark contrast, the largest subgroup of the periodic table, rare-earth metals (Ln = Sc, Y, and lanthanides), have been excluded from this upsurge. Indeed, the synthesis of terminal Ln═E/Ln≡E multiple-bonding species lagged behind that of the transition metal and actinide congeners for decades. Although these species had been pursued since the discovery of a rare-earth metal bridging imide in 1991, such a terminal (nonpincer/bridging hapticities) Ln═E/Ln≡E bond species was not obtained until 2010. The scarcity is mainly attributed to the energy mismatch between the frontier orbitals of the metal and the ligand atoms. This renders the putative terminal Ln═E/Ln≡E bonds extremely reactive, thus resulting in the formation of aggregates and/or reaction with the ligand/environment, quenching the multiple-bond character. In 2010, the stalemate was broken by the isolation and structural characterization of the first rare-earth metal terminal imide-a scandium terminal imide-by our group. The double-bond character of the Sc═N bond was unequivocally confirmed by single-crystal X-ray diffraction. Theoretical investigations revealed the presence

  3. Quadruplexes in 'Dicty': crystal structure of a four-quartet G-quadruplex formed by G-rich motif found in the Dictyostelium discoideum genome.

    Science.gov (United States)

    Guédin, Aurore; Lin, Linda Yingqi; Armane, Samir; Lacroix, Laurent; Mergny, Jean-Louis; Thore, Stéphane; Yatsunyk, Liliya A

    2018-06-01

    Guanine-rich DNA has the potential to fold into non-canonical G-quadruplex (G4) structures. Analysis of the genome of the social amoeba Dictyostelium discoideum indicates a low number of sequences with G4-forming potential (249-1055). Therefore, D. discoideum is a perfect model organism to investigate the relationship between the presence of G4s and their biological functions. As a first step in this investigation, we crystallized the dGGGGGAGGGGTACAGGGGTACAGGGG sequence from the putative promoter region of two divergent genes in D. discoideum. According to the crystal structure, this sequence folds into a four-quartet intramolecular antiparallel G4 with two lateral and one diagonal loops. The G-quadruplex core is further stabilized by a G-C Watson-Crick base pair and a A-T-A triad and displays high thermal stability (Tm > 90°C at 100 mM KCl). Biophysical characterization of the native sequence and loop mutants suggests that the DNA adopts the same structure in solution and in crystalline form, and that loop interactions are important for the G4 stability but not for its folding. Four-tetrad G4 structures are sparse. Thus, our work advances understanding of the structural diversity of G-quadruplexes and yields coordinates for in silico drug screening programs and G4 predictive tools.

  4. Vascular epiphytes of the Atlantic Forest in the Sinos River basin, state of Rio Grande do Sul, Brazil: richness, floristic composition and community structure.

    Science.gov (United States)

    Barbosa, M D; Becker, D F P; Cunha, S; Droste, A; Schmitt, J L

    2015-05-01

    The Atlantic Forest, which has a vast epiphytic richness, is a priority area for preservation, listed as one of the five most important world hotspots. Vascular epiphyte richness, composition and community structure were studied in two fragments, one of the ombrophilous (29º43'42"S and 50º22'00"W) and the other of the seasonal (29º40'54"S and 51º06'56"W) forest, both belonging to the Atlantic Forest biome in the Sinos River basin, Rio Grande do Sul, Brazil. In each fragment, 40 trees, divided into four ecological zones, were analyzed. In each zone, the occurrence of the species was recorded, and the importance value of each species was calculated according to the frequency of phorophytes and intervals, and cover scores. The Shannon index was calculated for the two communities. In the fragment of the ombrophilous forest (F1), 30 epiphytic species were recorded, and in the seasonal forest (F2), 25. The highest importance value was found for Microgramma squamulosa (Kaulf.) de la Sota in both fragments. The diversity indexes for F1 (H'=2.72) and F2 (H'=2.55) were similar and reflected the subtropical location of the areas. The decrease in mean richness in both fragments in zone 3 (internal crown) to zone 4 (external crown) may be associated with time and space availability for epiphyte occupation and microclimate variations. Exclusive species were found in the areas, which suggest that a greater number of preserved fragments may result in a greater number of preserved epiphytic species in the Sinos River basin.

  5. TEM study of structural and microstructural characteristics of a precipitate phase in Ni-rich Ni–Ti–Hf and Ni–Ti–Zr shape memory alloys

    International Nuclear Information System (INIS)

    Santamarta, R.; Arróyave, R.; Pons, J.; Evirgen, A.; Karaman, I.; Karaca, H.E.; Noebe, R.D.

    2013-01-01

    The precipitates formed after suitable thermal treatments in seven Ni-rich Ni–Ti–Hf and Ni–Ti–Zr high-temperature shape memory alloys have been investigated by conventional and high-resolution transmission electron microscopy. In both ternary systems, the precipitate coarsening kinetics become faster as the Ni and ternary element contents (Hf or Zr) of the bulk alloy are increased, in agreement with the precipitate composition measured by energy-dispersive X-ray microanalysis. The precipitate structure has been found to be the same in both Hf- and Zr-containing ternary alloys, and determined to be a superstructure of the B2 austenite phase, which arises from a recombination of the Hf/Zr and Ti atoms in their sublattice. Two different structural models for the precipitate phase were optimized using density functional theory methods. These calculations indicate that the energetics of the structure are not very sensitive to the atomic configuration of the Ti–Hf/Zr planes, thus significant configurational disorder due to entropic effects can be envisaged at high temperatures. The precipitates are fully coherent with the austenite B2 matrix; however, upon martensitic transformation, they lose some coherency with the B19′ matrix as a result of the transformation shear process in the surrounding matrix. The strain accommodation around the particles is much easier in the Ni–Ti–Zr-containing alloys than in the Ni–Ti–Hf system, which correlates well with the lower transformation strain and stiffness predicted for the Ni–Ti–Zr alloys. The B19′ martensite twinning modes observed in the studied Ni-rich ternary alloys are not changed by the new precipitated phase, being equivalent to those previously reported in Ni-poor ternary alloys

  6. Absolute band structure determination on naturally occurring rutile with complex chemistry: Implications for mineral photocatalysis on both Earth and Mars

    Science.gov (United States)

    Li, Yan; Xu, Xiaoming; Li, Yanzhang; Ding, Cong; Wu, Jing; Lu, Anhuai; Ding, Hongrui; Qin, Shan; Wang, Changqiu

    2018-05-01

    Rutile is the most common and stable form of TiO2 that ubiquitously existing on Earth and other terrestrial planets like Mars. Semiconducting mineral such as rutile-based photoredox reactions have been considered to play important roles in geological times. However, due to the inherent complexity in chemistry, the precision determination on band structure of natural rutile and the theoretical explanation on its solar-driven photochemistry have been hardly seen yet. Considering the multiple minor and trace elements in natural rutile, we firstly obtained the single-crystal crystallography, mineralogical composition and defects characteristic of the rutile sample by using both powder and single crystal X-ray diffraction, electron microprobe analysis and X-ray photoelectron spectroscopy. Then, the band gap was accurately determined by synchrotron-based O K-edge X-ray absorption and emission spectra, which was firstly applied to natural rutile due to its robustness on compositions and defects. The absolute band edges of the rutile sample was calculated by considering the electronegativity of the atoms, band gap and point of zero charge. Besides, after detecting the defect energy levels by photoluminescence spectra, we drew the schematic band structure of natural rutile. The band gap (2.7 eV) of natural rutile was narrower than that of synthetic rutile (3.0 eV), and the conduction and valence band edges of natural rutile at pH = pHPZC were determined to be -0.04 V and 2.66 V (vs. NHE), respectively. The defect energy levels located at nearly the middle position of the forbidden band. Further, we used theoretical calculations to verify the isomorphous substitution of Fe and V for Ti gave rise to the distortion of TiO6 octahedron and created vacancy defects in natural rutile. Based on density functional theory, the narrowed band gap was interpreted to the contribution of Fe-3d and V-3d orbits, and the defect energy state was formed by hybridization of O-2p and Fe/V/Ti-3d

  7. Structure-activity relationships of the antimicrobial peptide arasin 1 - and mode of action studies of the N-terminal, proline-rich region.

    Directory of Open Access Journals (Sweden)

    Victoria S Paulsen

    Full Text Available Arasin 1 is a 37 amino acid long proline-rich antimicrobial peptide isolated from the spider crab, Hyas araneus. In this work the active region of arasin 1 was identified through structure-activity studies using different peptide fragments derived from the arasin 1 sequence. The pharmacophore was found to be located in the proline/arginine-rich NH(2 terminus of the peptide and the fragment arasin 1(1-23 was almost equally active to the full length peptide. Arasin 1 and its active fragment arasin 1(1-23 were shown to be non-toxic to human red blood cells and arasin 1(1-23 was able to bind chitin, a component of fungal cell walls and the crustacean shell. The mode of action of the fully active N-terminal arasin 1(1-23 was explored through killing kinetic and membrane permeabilization studies. At the minimal inhibitory concentration (MIC, arasin 1(1-23 was not bactericidal and had no membrane disruptive effect. In contrast, at concentrations of 5×MIC and above it was bactericidal and interfered with membrane integrity. We conclude that arasin 1(1-23 has a different mode of action than lytic peptides, like cecropin P1. Thus, we suggest a dual mode of action for arasin 1(1-23 involving membrane disruption at peptide concentrations above MIC, and an alternative mechanism of action, possibly involving intracellular targets, at MIC.

  8. Spatially Resolved Artificial Chemistry

    DEFF Research Database (Denmark)

    Fellermann, Harold

    2009-01-01

    Although spatial structures can play a crucial role in chemical systems and can drastically alter the outcome of reactions, the traditional framework of artificial chemistry is a well-stirred tank reactor with no spatial representation in mind. Advanced method development in physical chemistry has...... made a class of models accessible to the realms of artificial chemistry that represent reacting molecules in a coarse-grained fashion in continuous space. This chapter introduces the mathematical models of Brownian dynamics (BD) and dissipative particle dynamics (DPD) for molecular motion and reaction...

  9. Computational quantum chemistry website

    International Nuclear Information System (INIS)

    1997-01-01

    This report contains the contents of a web page related to research on the development of quantum chemistry methods for computational thermochemistry and the application of quantum chemistry methods to problems in material chemistry and chemical sciences. Research programs highlighted include: Gaussian-2 theory; Density functional theory; Molecular sieve materials; Diamond thin-film growth from buckyball precursors; Electronic structure calculations on lithium polymer electrolytes; Long-distance electronic coupling in donor/acceptor molecules; and Computational studies of NOx reactions in radioactive waste storage

  10. Spatially Resolved Artificial Chemistry

    DEFF Research Database (Denmark)

    Fellermann, Harold

    2009-01-01

    made a class of models accessible to the realms of artificial chemistry that represent reacting molecules in a coarse-grained fashion in continuous space. This chapter introduces the mathematical models of Brownian dynamics (BD) and dissipative particle dynamics (DPD) for molecular motion and reaction......Although spatial structures can play a crucial role in chemical systems and can drastically alter the outcome of reactions, the traditional framework of artificial chemistry is a well-stirred tank reactor with no spatial representation in mind. Advanced method development in physical chemistry has...

  11. DOE fundamentals handbook: Chemistry

    International Nuclear Information System (INIS)

    1993-01-01

    The Chemistry Handbook was developed to assist nuclear facility operating contractors in providing operators, maintenance personnel, and the technical staff with the necessary fundamentals training to ensure a basic understanding of chemistry. The handbook includes information on the atomic structure of matter; chemical bonding; chemical equations; chemical interactions involved with corrosion processes; water chemistry control, including the principles of water treatment; the hazards of chemicals and gases, and basic gaseous diffusion processes. This information will provide personnel with a foundation for understanding the chemical properties of materials and the way these properties can impose limitations on the operation of equipment and systems

  12. Observation of structure transition as a function of temperature in depositing hydrogenated sp2-rich carbon films

    Science.gov (United States)

    Wang, Yongfu; Gao, Kaixiong; Zhang, Junyan

    2018-05-01

    In this study, we carried out the transition experiments of graphite-like (GL) to fullerene-like (FL) structures by placing high temperature steel substrates in the depositing environment which can form FL hydrogenated carbon films. We investigated the changes of bond mixtures, H content, aromatic clusters and internal stress at the transition process, and proposed the transformation mechanism inferred from Raman, TEM cross-section, FTIR and XPS results. It was found that the size of aromatic clusters and accordingly graphene planes and the formation of edge dangling bonds were the key steps. H+ bombardment leaded to the splitting of large graphene planes (at GL stage) into more and smaller planes (at FL stage) and the formation of edge dangling bonds; Some of these dangling bonds were reduced by the formation of pentagons and subsequent curving of the smaller planes, which were an indicator of FL structures.

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

    Science.gov (United States)

    Mackenzie, Ruari

    2017-08-01

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

  14. RPA prevents G-rich structure formation at lagging-strand telomeres to allow maintenance of chromosome ends.

    Science.gov (United States)

    Audry, Julien; Maestroni, Laetitia; Delagoutte, Emmanuelle; Gauthier, Tiphaine; Nakamura, Toru M; Gachet, Yannick; Saintomé, Carole; Géli, Vincent; Coulon, Stéphane

    2015-07-14

    Replication protein A (RPA) is a highly conserved heterotrimeric single-stranded DNA-binding protein involved in DNA replication, recombination, and repair. In fission yeast, the Rpa1-D223Y mutation provokes telomere shortening. Here, we show that this mutation impairs lagging-strand telomere replication and leads to the accumulation of secondary structures and recruitment of the homologous recombination factor Rad52. The presence of these secondary DNA structures correlates with reduced association of shelterin subunits Pot1 and Ccq1 at telomeres. Strikingly, heterologous expression of the budding yeast Pif1 known to efficiently unwind G-quadruplex rescues all the telomeric defects of the D223Y cells. Furthermore, in vitro data show that the identical D to Y mutation in human RPA specifically affects its ability to bind G-quadruplex. We propose that RPA prevents the formation of G-quadruplex structures at lagging-strand telomeres to promote shelterin association and facilitate telomerase action at telomeres. © 2015 The Authors.

  15. Radiation chemistry

    Energy Technology Data Exchange (ETDEWEB)

    None

    1973-07-01

    Research progress is reported on radiation chemistry of heavy elements that includes the following topics: radiation chemistry of plutonium in nitric acid solutions (spectrophotometric analysis and gamma radiolysis of Pu(IV) and Pu(VI) in nitric acid solution); EPR studies of intermediates formed in radiolytic reactions with aqueous medium; two-phase radiolysis and its effect on the distribution coefficient of plutonium; and radiation chemistry of nitric acid. (DHM)

  16. Fundamentals of quantum chemistry

    CERN Document Server

    House, J E

    2004-01-01

    An introduction to the principles of quantum mechanics needed in physical chemistry. Mathematical tools are presented and developed as needed and only basic calculus, chemistry, and physics is assumed. Applications include atomic and molecular structure, spectroscopy, alpha decay, tunneling, and superconductivity. New edition includes sections on perturbation theory, orbital symmetry of diatomic molecules, the Huckel MO method and Woodward/Hoffman rules as well as a new chapter on SCF and Hartree-Fock methods. * This revised text clearly presents basic q

  17. Technetium chemistry

    International Nuclear Information System (INIS)

    Burns, C.; Bryan, J.; Cotton, F.; Ott, K.; Kubas, G.; Haefner, S.; Barrera, J.; Hall, K.; Burrell, A.

    1996-01-01

    Technetium chemistry is a young and developing field. Despite the limited knowledge of its chemistry, technetium is the workhorse for nuclear medicine. Technetium is also a significant environmental concern because it is formed as a byproduct of nuclear weapons production and fission-power generators. Development of new technetium radio-pharmaceuticals and effective environmental control depends strongly upon knowledge of basic technetium chemistry. The authors performed research into the basic coordination and organometallic chemistry of technetium and used this knowledge to address nuclear medicine and environmental applications. This is the final report of a three-year Laboratory-Directed Research and Development (LDRD) project at the Los Alamos National Laboratory (LANL)

  18. Chemistry Technology

    Data.gov (United States)

    Federal Laboratory Consortium — Chemistry technology experts at NCATS engage in a variety of innovative translational research activities, including:Design of bioactive small molecules.Development...

  19. Coordination chemistry of technetium as related to nuclear medicine

    International Nuclear Information System (INIS)

    Srivastava, S.C.; Richards, P.

    1982-01-01

    Significant advances have been made in the area of technetium coordination chemistry during the last five years. The main driving force behind this recent surge of interest in the field has been due to the practical application of technetium-99m in the rapidly growing speciality of nuclear medicine. Technetium-99 is one of the products of nuclear fission reactions, but it was the development of the molybdenum-99-technetium-99m generator about two decades ago that provided the basis for the development of radiopharmaceuticals routinely used in modern diagnostic applications. The chemistry of this element has proven to be quite rich owing to its multiple oxidation states and variable geometry. This can be attributed to its position in the middle of the periodic table. Diagnostic radiopharmaceuticals comprise predominantly III, IV and V oxidation states of Tc and involve a variety of coordination complexes. Even though the chemistry of Tc has been slow to evolve, recent synthetic advances have provided a more scientific basis for the study of a number of compounds with diverse coordination geometries and structures. Ligands with oxygen, nitrogen and sulfur donor atoms have been utilized to elucidate various aspects of the coordination chemistry of Tc. Single crystal X-ray structural analysis has been extensively used to characterize Tc complexes and thus construct a firm foundation for the study of synthetic and mechanistic aspects of the chemistry of this element. (author)

  20. Magnetic properties of Fe-rich rare-earth intermetallic compounds with a ThMn12 structure

    International Nuclear Information System (INIS)

    Ohashi, K.; Tawara, Y.; Osugi, R.; Shimao, M.

    1988-01-01

    Sm(Fe/sub 1-//sub x/M/sub x/) 12 ternary compounds based on the tetragonal ThMn 12 structure where M is Ti, Si, V, Cr, and Mo were investigated. M atoms have a preference for site occupation. Ti atoms occupy the 8i or 8j site and Cr atoms occupy the 8i site. Curie temperatures on Sm(M,Fe) 12 compounds are around 590 K except for the SmMo 2 Fe 10 compound (T/sub c/ = 483 K). The SmTiFe 11 and SmSi 2 Fe 10 compounds have a high saturation magnetization and magnetic anisotropy

  1. Regeneration performance of CO2-rich solvents by using membrane vacuum regeneration technology: Relationships between absorbent structure and regeneration efficiency

    International Nuclear Information System (INIS)

    Yan, Shuiping; Fang, Mengxiang; Wang, Zhen; Luo, Zhongyang

    2012-01-01

    Highlights: ► MVR may be viable to successfully use less valuable heat to replace high grade steam. ► Increasing OH and amine groups will increase the regeneration efficiency. ► Absorbents with a four carbon chain length will be more attractive to MVR. ► Amino acid salts will be more appropriate for MVR. ► HRM conducted at ambient pressure and low temperature is inferior to MVR. -- Abstract: In order to give a better understanding for the selection of suitable absorbents for the novel membrane vacuum regeneration technology (MVR) which has the potential to reduce CO 2 energy requirement by utilizing the waste heat or low-grade energy, an experimental study to determine the relationships between chemical structure and vacuum regeneration behavior of CO 2 absorbents at 70 °C and 10 kPa was performed. Eleven typical absorbents with different functional groups in their chemical structures were investigated in terms of vacuum regeneration efficiencies. Results showed that the regeneration efficiency decreased with an increase of number of activated hydrogen atom in amine group and decreased with the number of hydroxyl group. Especially, more attention should be paid to these alkanolamines with one hydrogen atom in amine group and two or more hydroxyl groups in the structures due to their better comprehensive performance in regeneration, absorbent loss and CO 2 absorption aspects. Increasing the carbon chain length and amine groups in the absorbent structure contributed to the improvement of regeneration performance and reduction of absorbent volatile loss. These absorbents with a four carbon chain length bonded at amine group might be more attractive to MVR. Furthermore, polyamines were superior to monoamines in terms of higher regeneration efficiencies and lower absorbent losses. Additionally, the individual effects of the potassium carboxylate group and hydroxymethylene group were also compared in this study. Results showed that amino acid salts were more

  2. Deep-UV Raman spectroscopic analysis of structure and dissolution rates of silica-rich sodium borosilicate glasses

    Energy Technology Data Exchange (ETDEWEB)

    Pierce, Eric M [ORNL; WindischJr., Charles F. [Pacific Northwest National Laboratory (PNNL); Burton, Sarah D. [Pacific Northwest National Laboratory (PNNL); Bovaird, Chase C. [Pacific Northwest National Laboratory (PNNL)

    2010-01-01

    As part of ongoing studies to evaluate relationships between structure and rates of dissolution of silicate glasses in aqueous media, sodium borosilicate glasses of composition Na2O xB2O3 (3 x)SiO2, with x 1 (Na2O/B2O3 ratio 1), were analyzed using deep-UV Raman spectroscopy. Results were quantified in terms of the fraction of SiO4 tetrahedra with one non-bridging oxygen (Q3) and then correlated with Na2O and B2O3 content. The Q3 fractionwas found to increase with increasing Na2O content, in agreement with studies on related glasses, and, as long as the value of x was not too high, this contributed to higher rates of dissolution in single pass flow-through testing. In contrast, dissolution rates were less strongly determined by the Q3 fraction when the value of x was near unity, and appeared to grow larger upon further reduction of the Q3 fraction. Results were interpreted to indicate the increasingly important role of network hydrolysis in the glass dissolution mechanism as the BO4 tetrahedron replaces the Q3 unit as the charge-compensating structure for Na+ ions. Finally, the use of deep-UV Raman spectroscopy was found to be advantageous in studying finely powdered glasses in cases where visible Raman spectroscopy suffered from weak Raman scattering and fluorescence interference.

  3. CsAg{sub 5}Te{sub 3}: a new metal-rich telluride with a unique tunnel structure

    Energy Technology Data Exchange (ETDEWEB)

    Jing, Li [Rutgers Univ., Camden, NJ (United States). Dept. of Chem.; Hongyou, Guo [Rutgers Univ., Camden, NJ (United States). Dept. of Chem.; Xiang, Zhang [Michigan State Univ., East Lansing, MI (United States). Dept. of Chemistry; Kanatzidis, M G [Michigan State Univ., East Lansing, MI (United States). Dept. of Chemistry

    1995-02-15

    The synthesis and structure of a new ternary silver telluride, CsAg{sub 5}Te{sub 3}, is described. The compound was prepared from a Cs{sub 2}Te-CaTe-Te flux but it can also be prepared from a direct combination of Cs{sub 2}Te and Ag{sub 2}Te under vacuum at 600 C. The crystal data for CsAg{sub 5}Te{sub 3} at 20 C (Mo K{alpha} radiation) are as follows: a=14.672(2) A and c=4.601(3) A; V=990.5(8) A{sup 3}; Z=4; D{sub calc}=7.075 g cm{sup -3}; space group, P4{sub 2} /mnm (No. 136); 2{theta}{sub max}=50 ; number of independent data collected, 572; number of data observed with I>3{sigma}(I), 267; number of variables, 32; {mu}=218.51 cm{sup -1}; extinction coefficient, 0.585x10{sup -7}; final R=0.040; R{sub w}=0.046; goodness of fit, 1.42. The compound features a new structure type with Cs{sup +}-filled, relatively large tunnels running through the lattice. The material is a semiconductor with a band gap of about 0.65 eV. ((orig.))

  4. Study of the structure of light neutron rich nucleus with the Tonnerre array; Etude de la structure de noyaux legers riches en neutrons a l'aide du multidetecteur Tonnerre

    Energy Technology Data Exchange (ETDEWEB)

    Pietri, St

    2003-06-01

    This work concern the technical development made on the multidetector TONNERRE and the study of the {sup 34}Si nucleus by a complete beta-neutron-gamma spectroscopy. In the first part various tests performed on modules of the detector in the 'Centre d'Etude de Bruyere le Chatel' are presented. A modification of the embassies of the photomultipliers tubes allows to gain more than 50% in the neutron efficiency and to obtain a threshold lower than 300 keV for the neutron energy. A complete C++ simulation of the neutron propagation in the array was carried out. It explains that the slow component of the light output of the scintillator may be responsible of the shape of the time-of-flight spectrum. The second part of these report presents the experiment devoted to the study of the structure of the {sup 34}Si from the beta decay of the {sup 34}Al. It was performed at the GANIL facility using the TONNERRE array and germanium of ENOGAM. The {sup 34}Al was produced by projectile fragmentation of a {sup 36}S beam of 50 MeV/A in a target of {sup 9}Be. A complete beta scheme of the {sup 34}Al is proposed. Eight neutron lines following the {sup 34}Al decay were observed for the first time. Finally we suggest that a monopolar transition could occur in the {sup 34}Si nucleus signing a O{sup +}{sub 2} state at 2133 keV. (author)

  5. Level structure of 68149Er81 and high-spin isomerism in proton-rich N=81, 82, 83 nuclei

    International Nuclear Information System (INIS)

    Broda, R.; Daly, P.J.; McNeill, J.; Janssens, R.V.F.; Radford, D.C.

    1987-01-01

    The level structure of the N=81 nucleus 149 Er has been studied by γ-ray spectroscopy following the reaction 92 Mo+255 MeV 60 Ni. Yrast levels in 149 Er are established up to ≅ 3.3 MeV, including 0.61 and 4.8 μs isometric states. Most of the observed levels are interpreted as seniority-three states arising from the coupling of s 1/2 , d 3/2 and h 11/2 neutron holes with πh n 11/2 . Isomers identified in the reaction 96 Ru+255 MeV 58 Ni are tentatively assigned to 151 Yb. The B(E2) values of high-spin isomers in Z=66-70, N=81-83 nuclei are surveyed. (orig.)

  6. Principles of Chemistry (by Michael Munowitz)

    Science.gov (United States)

    Kovac, Reviewed By Jeffrey

    2000-05-01

    At a time when almost all general chemistry textbooks seem to have become commodities designed by marketing departments to offend no one, it is refreshing to find a book with a unique perspective. Michael Munowitz has written what I can only describe as a delightful chemistry book, full of conceptual insight, that uses a novel and interesting pedagogic strategy. This is a book that has much to recommend it. This is the best-written general chemistry book I have ever read. An editor with whom I have worked recently remarked that he felt his job was to help authors make their writing sing. Well, the writing in Principles of Chemistry sings with the full, rich harmonies and creative inventiveness of the King's Singers or Chanticleer. Here is the first sentence of the introduction: "Central to any understanding of the physical world is one discovery of paramount importance, a truth disarmingly simple yet profound in its implications: matter is not continuous." This is prose to be savored and celebrated. Principles of Chemistry has a distinct perspective on chemistry: the perspective of the physical chemist. The focus is on simplicity, what is common about molecules and reactions; begin with the microscopic and build bridges to the macroscopic. The author's perspective is clear from the organization of the book. After three rather broad introductory chapters, there are four chapters that develop the quantum mechanical theory of atoms and molecules, including a strong treatment of molecular orbital theory. Unlike many books, Principles of Chemistry presents the molecular orbital approach first and introduces valence bond theory later only as an approximation for dealing with more complicated molecules. The usual chapters on descriptive inorganic chemistry are absent (though there is an excellent chapter on organic and biological molecules and reactions as well as one on transition metal complexes). Instead, descriptive chemistry is integrated into the development of

  7. Relations between water physico-chemistry and benthic algal communities in a northern Canadian watershed: defining reference conditions using multiple descriptors of community structure.

    Science.gov (United States)

    Thomas, Kathryn E; Hall, Roland I; Scrimgeour, Garry J

    2015-09-01

    Defining reference conditions is central to identifying environmental effects of anthropogenic activities. Using a watershed approach, we quantified reference conditions for benthic algal communities and their relations to physico-chemical conditions in rivers in the South Nahanni River watershed, NWT, Canada, in 2008 and 2009. We also compared the ability of three descriptors that vary in terms of analytical costs to define algal community structure based on relative abundances of (i) all algal taxa, (ii) only diatom taxa, and (iii) photosynthetic pigments. Ordination analyses showed that variance in algal community structure was strongly related to gradients in environmental variables describing water physico-chemistry, stream habitats, and sub-watershed structure. Water physico-chemistry and local watershed-scale descriptors differed significantly between algal communities from sites in the Selwyn Mountain ecoregion compared to sites in the Nahanni-Hyland ecoregions. Distinct differences in algal community types between ecoregions were apparent irrespective of whether algal community structure was defined using all algal taxa, diatom taxa, or photosynthetic pigments. Two algal community types were highly predictable using environmental variables, a core consideration in the development of Reference Condition Approach (RCA) models. These results suggest that assessments of environmental impacts could be completed using RCA models for each ecoregion. We suggest that use of algal pigments, a high through-put analysis, is a promising alternative compared to more labor-intensive and costly taxonomic approaches for defining algal community structure.

  8. Comparative Geometrical Analysis of Leucine-Rich Repeat Structures in the Nod-Like and Toll-Like Receptors in Vertebrate Innate Immunity

    Directory of Open Access Journals (Sweden)

    Norio Matsushima

    2015-08-01

    Full Text Available The NOD-like receptors (NLRs and Toll-like receptors (TLRs are pattern recognition receptors that are involved in the innate, pathogen pattern recognition system. The TLR and NLR receptors contain leucine-rich repeats (LRRs that are responsible for ligand interactions. In LRRs short β-strands stack parallel and then the LRRs form a super helical arrangement of repeating structural units (called a coil of solenoids. The structures of the LRR domains of NLRC4, NLRP1, and NLRX1 in NLRs and of TLR1-5, TLR6, TLR8, TLR9 in TLRs have been determined. Here we report nine geometrical parameters that characterize the LRR domains; these include four helical parameters from HELFIT analysis. These nine parameters characterize well the LRR structures in NLRs and TLRs; the LRRs of NLR adopts a right-handed helix. In contrast, the TLR LRRs adopt either a left-handed helix or are nearly flat; RP105 and CD14 also adopt a left-handed helix. This geometrical analysis subdivides TLRs into four groups consisting of TLR3/TLR8/TLR9, TLR1/TLR2/TRR6, TLR4, and TLR5; these correspond to the phylogenetic tree based on amino acid sequences. In the TLRs an ascending lateral surface that consists of loops connecting the β-strand at the C-terminal side is involved in protein, protein/ligand interactions, but not the descending lateral surface on the opposite side.

  9. Ultrahigh and High Resolution Structures and Mutational Analysis of Monomeric Streptococcus pyogenes SpeB Reveal a Functional Role for the Glycine-rich C-terminal Loop

    Energy Technology Data Exchange (ETDEWEB)

    González-Páez, Gonzalo E.; Wolan, Dennis W. (Scripps)

    2012-09-05

    Cysteine protease SpeB is secreted from Streptococcus pyogenes and has been studied as a potential virulence factor since its identification almost 70 years ago. Here, we report the crystal structures of apo mature SpeB to 1.06 {angstrom} resolution as well as complexes with the general cysteine protease inhibitor trans-epoxysuccinyl-L-leucylamido(4-guanidino)butane and a novel substrate mimetic peptide inhibitor. These structures uncover conformational changes associated with maturation of SpeB from the inactive zymogen to its active form and identify the residues required for substrate binding. With the use of a newly developed fluorogenic tripeptide substrate to measure SpeB activity, we determined IC{sub 50} values for trans-epoxysuccinyl-L-leucylamido(4-guanidino)butane and our new peptide inhibitor and the effects of mutations within the C-terminal active site loop. The structures and mutational analysis suggest that the conformational movements of the glycine-rich C-terminal loop are important for the recognition and recruitment of biological substrates and release of hydrolyzed products.

  10. Structure Identification Using High Resolution Mass Spectrometry Data and the EPA’s CompTox Chemistry Dashboard (EAS)

    Science.gov (United States)

    The iCSS CompTox Dashboard is a publicly accessible dashboard provided by the National Center for Computation Toxicology at the US-EPA. It serves a number of purposes, including providing a chemistry database underpinning many of our public-facing projects (e.g. ToxCast and ExpoC...

  11. Modeling Human Serum Albumin Tertiary Structure to Teach Upper-Division Chemistry Students Bioinformatics and Homology Modeling Basics

    Science.gov (United States)

    Petrovic, Dus?an; Zlatovic´, Mario

    2015-01-01

    A homology modeling laboratory experiment has been developed for an introductory molecular modeling course for upper-division undergraduate chemistry students. With this experiment, students gain practical experience in homology model preparation and assessment as well as in protein visualization using the educational version of PyMOL…

  12. Molecular Structure of Salt Solutions: A New View of the Interface with Implications for Heterogeneous Atmospheric Chemistry

    Czech Academy of Sciences Publication Activity Database

    Jungwirth, Pavel; Tobias, D. J.

    2001-01-01

    Roč. 105, č. 43 (2001), s. 10468-10472 ISSN 1089-5647 R&D Projects: GA MŠk LN00A032 Institutional research plan: CEZ:AV0Z4040901 Keywords : air-solution interface * salt solutions * molecular dynamics Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 3.379, year: 2001

  13. Organic Chemistry Students' Fragmented Ideas about the Structure and Function of Nucleophiles and Electrophiles: A Concept Map Analysis

    Science.gov (United States)

    Anzovino, Mary E.; Bretz, Stacey Lowery

    2016-01-01

    Organic chemistry students struggle with multiple aspects of reaction mechanisms and the curved arrow notation used by organic chemists. Many faculty believe that an understanding of nucleophiles and electrophiles, among other concepts, is required before students can develop fluency with the electronpushing formalism (EPF). An expert concept map…

  14. Current organic chemistry

    National Research Council Canada - National Science Library

    1997-01-01

    Provides in depth reviews on current progress in the fields of asymmetric synthesis, organometallic chemistry, bioorganic chemistry, heterocyclic chemistry, natural product chemistry, and analytical...

  15. Actin grips: circular actin-rich cytoskeletal structures that mediate the wrapping of polymeric microfibers by endothelial cells.

    Science.gov (United States)

    Jones, Desiree; Park, DoYoung; Anghelina, Mirela; Pécot, Thierry; Machiraju, Raghu; Xue, Ruipeng; Lannutti, John J; Thomas, Jessica; Cole, Sara L; Moldovan, Leni; Moldovan, Nicanor I

    2015-06-01

    Interaction of endothelial-lineage cells with three-dimensional substrates was much less studied than that with flat culture surfaces. We investigated the in vitro attachment of both mature endothelial cells (ECs) and of less differentiated EC colony-forming cells to poly-ε-capro-lactone (PCL) fibers with diameters in 5-20 μm range ('scaffold microfibers', SMFs). We found that notwithstanding the poor intrinsic adhesiveness to PCL, both cell types completely wrapped the SMFs after long-term cultivation, thus attaining a cylindrical morphology. In this system, both EC types grew vigorously for more than a week and became increasingly more differentiated, as shown by multiplexed gene expression. Three-dimensional reconstructions from multiphoton confocal microscopy images using custom software showed that the filamentous (F) actin bundles took a conspicuous ring-like organization around the SMFs. Unlike the classical F-actin-containing stress fibers, these rings were not associated with either focal adhesions or intermediate filaments. We also demonstrated that plasma membrane boundaries adjacent to these circular cytoskeletal structures were tightly yet dynamically apposed to the SMFs, for which reason we suggest to call them 'actin grips'. In conclusion, we describe a particular form of F-actin assembly with relevance for cytoskeletal organization in response to biomaterials, for endothelial-specific cell behavior in vitro and in vivo, and for tissue engineering. Copyright © 2015 Elsevier Ltd. All rights reserved.

  16. Future in actinoids coordination chemistry

    International Nuclear Information System (INIS)

    Kitazawa, Takafumi

    2006-01-01

    Actinoids coordination chemistry is concerned with spent nuclear fuel reprocessing, specifically with solid-state chemistry of nuclear fuels, separation process with radioactive substances, and geological disposal of high-level radioactive substances. In the 21st century, accumulation of minor actinides, Np, Am, Cm, and others will be realized according with the present program of nuclear energy development. The present article briefly introduces general properties of actinide elements, followed by their coordination chemistry compared with rare earths coordination chemistry. Special facility needed to treat actinoids as well as their chemistry is briefly explained, together with the specific experimental apparatus such as X-ray Absorption Fine Structure (XAFS) and time-resolved laser-induced fluorescence spectrometry (TRLFS) with synchrotron radiation facilities. The effect of coordination with actinoids in the environment chemistry is important in underground disposal of high-level radioactive wastes. For theoretical analysis of the results with actinoids chemistry, relativistic calculation is needed. (S. Ohno)

  17. Structural Diversity in Alkali Metal and Alkali Metal Magnesiate Chemistry of the Bulky 2,6-Diisopropyl-N-(trimethylsilyl)anilino Ligand.

    Science.gov (United States)

    Fuentes, M Ángeles; Zabala, Andoni; Kennedy, Alan R; Mulvey, Robert E

    2016-10-10

    Bulky amido ligands are precious in s-block chemistry, since they can implant complementary strong basic and weak nucleophilic properties within compounds. Recent work has shown the pivotal importance of the base structure with enhancement of basicity and extraordinary regioselectivities possible for cyclic alkali metal magnesiates containing mixed n-butyl/amido ligand sets. This work advances alkali metal and alkali metal magnesiate chemistry of the bulky arylsilyl amido ligand [N(SiMe 3 )(Dipp)] - (Dipp=2,6-iPr 2 -C 6 H 3 ). Infinite chain structures of the parent sodium and potassium amides are disclosed, adding to the few known crystallographically characterised unsolvated s-block metal amides. Solvation by N,N,N',N'',N''-pentamethyldiethylenetriamine (PMDETA) or N,N,N',N'-tetramethylethylenediamine (TMEDA) gives molecular variants of the lithium and sodium amides; whereas for potassium, PMDETA gives a molecular structure, TMEDA affords a novel, hemi-solvated infinite chain. Crystal structures of the first magnesiate examples of this amide in [MMg{N(SiMe 3 )(Dipp)} 2 (μ-nBu)] ∞ (M=Na or K) are also revealed, though these breakdown to their homometallic components in donor solvents as revealed through NMR and DOSY studies. © 2016 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

  18. Nitrogen-rich salts of 5,5‧-bistetrazole-1,1‧-diolate: Syntheses, structures and properties

    Science.gov (United States)

    Yang, Ting; Zhang, Jian-Guo; Zhang, Zhi-Bin; Gozin, Michael

    2018-03-01

    A series of new nitrogen-rich energetic salts containing 1H,1‧H-[5,5‧-bitetrazole]-1,1‧-diol (BTO) anion and ethane-1,2-diaminium (1), 1-amino-1H-1,2,3-triazol-3-ium (2), 4-amino-4H-1,2,4-triazol-1-ium (3) and 4,5-diamino-4H-1,2,4-triazol-1-ium (4) cations were synthesized by direct salt formation or by metathesis strategy. The structures of energetic salts 1-4 were comprehensively characterized by elemental analysis, mass spectrometry, IR and NMR spectroscopies and by X-ray crystallography. DSC and TGA methods were used to study thermal properties of these salts. Additionally, the non-isothermal kinetic parameters and thermodynamic parameters were calculated by utilizing the Kissinger's and Ozawa-Doyle's methods. The enthalpies of formation for all target compounds in this study were calculated, and their sensitivity to mechanical impact and friction was tested according to BAM guidelines. We found these new energetic salts exhibit good thermal stability and have typical decomposition temperatures above 230 °C, except for the salt 2. All our salts have highly-positive enthalpies of formation (311.1-473.6 kJ mol-1) and are insensitive to impact and friction stimuli (>40 J, 120 N). With a high nitrogen-rich content, high enthalpy of formation, good thermostability and very low sensitivity to impact, some of these new salts may have a potential for application in the field of environmentally friendly insensitive energetic materials.

  19. Structural and chemical degradation mechanisms of pure YSZ and its components ZrO2 and Y2O3 in carbon-rich fuel gases.

    Science.gov (United States)

    Köck, Eva-Maria; Kogler, Michaela; Götsch, Thomas; Klötzer, Bernhard; Penner, Simon

    2016-05-25

    Structural and chemical degradation mechanisms of metal-free yttria stabilized zirconia (YSZ-8, 8 mol% Y2O3 in ZrO2) in comparison to its pure oxidic components ZrO2 and Y2O3 have been studied in carbon-rich fuel gases with respect to coking/graphitization and (oxy)carbide formation. By combining operando electrochemical impedance spectroscopy (EIS), operando Fourier-transform infrared (FT-IR) spectroscopy and X-ray photoelectron spectroscopy (XPS), the removal and suppression of CH4- and CO-induced carbon deposits and of those generated in more realistic fuel gas mixtures (syngas, mixtures of CH4 or CO with CO2 and H2O) was examined under SOFC-relevant conditions up to 1273 K and ambient pressures. Surface-near carbidization is a major problem already on the "isolated" (i.e. Nickel-free) cermet components, leading to irreversible changes of the conduction properties. Graphitic carbon deposition takes place already on the "isolated" oxides under sufficiently fuel-rich conditions, most pronounced in the pure gases CH4 and CO, but also significantly in fuel gas mixtures containing H2O and CO2. For YSZ, a comparative quantification of the total amount of deposited carbon in all gases and mixtures is provided and thus yields favorable and detrimental experimental approaches to suppress the carbon formation. In addition, the effectivity and reversibility of removal of the coke/graphite layers was comparably studied in the pure oxidants O2, CO2 and H2O and their effective contribution upon addition to the pure fuel gases CO and CH4 verified.

  20. Organic Nitrate Chemistry and Its Implications for Nitrogen Budgets in an Isoprene- and Monoterpene-Rich Atmosphere: Constraints From Aircraft (SEAC4RS) and Ground-Based (SOAS) Observations in the Southeast US

    Science.gov (United States)

    Fisher, Jenny; Jacob, D. J.; Travis, K. R.; Kim, P. S.; Marais, E. A.; Miller, C. Chan; Yu, K.; Zhu, L.; Yantosca, R. M.; Sulprizio, M. P.; hide

    2016-01-01

    Formation of organic nitrates (RONO2) during oxidation of biogenic volatile organic compounds (BVOCs: isoprene, monoterpenes) is a significant loss pathway for atmospheric nitrogen oxide radicals (NOx), but the chemistry of RONO2 formation and degradation remains uncertain. Here we implement a new BVOC oxidation mechanism (including updated isoprene chemistry, new monoterpene chemistry, and particle uptake of RONO2) in the GEOS-Chem global chemical transport model with approximately 25 times 25 km(exp 2) resolution over North America. We evaluate the model using aircraft (SEAC4RS) and ground-based (SOAS) observations of NOx, BVOCs, and RONO2 from the Southeast US in summer 2013. The updated simulation successfully reproduces the concentrations of individual gas- and particle-phase RONO2 species measured during the campaigns. Gas-phase isoprene nitrates account for 2550 of observed RONO2 in surface air, and we find that another 10 is contributed by gas-phase monoterpene nitrates. Observations in the free troposphere show an important contribution from long-lived nitrates derived from anthropogenic VOCs. During both campaigns, at least 10 of observed boundary layer RONO2 were in the particle phase. We find that aerosol uptake followed by hydrolysis to HNO3 accounts for 60 of simulated gas-phase RONO2 loss in the boundary layer. Other losses are 20 by photolysis to recycle NOx and 15 by dry deposition. RONO2 production accounts for 20 of the net regional NOx sink in the Southeast US in summer, limited by the spatial segregation between BVOC and NOx emissions. This segregation implies that RONO2 production will remain a minor sink for NOx in the Southeast US in the future even as NOx emissions continue to decline. XXXX We have used airborne and ground-based observations from two summer 2013 campaigns in the Southeast US (SEAC4RS, SOAS) to better understand the chemistry and impacts of alkyl and multi-functional organic nitrates (RONO2). We used the observations, along

  1. Effect of gamma irradiation on the structure of corn stalks and their subsequent bioconversion into protein-rich mycelial biomass of pleurotus sajor-caju

    Energy Technology Data Exchange (ETDEWEB)

    Awafo, V [Quebec Univ., Montreal, PQ (Canada)

    1994-12-31

    Lignocellulosic biomass like corn stalk is an abundant and renewable resource from which food, feed and chemicals may be derived. Enzymatic hydrolysis of native lignocellulosic material is prohibitively slow due to their compositional heterogeneity and structural complexity. In this work, ground corn stalks (20 mesh) were subjected to gamma irradiation (10-170 Mrads) as pretreatments to make them more susceptible for bioconversion into protein-rich mycelial biomass of Pleurotus sajor-caju NRRL 18757. The irradiation was carried out in air in a {sup 60}Co Underwater Calibrator (UC-15, Nordion International) at a dose rate of 2.5 Mrads/h as measured by Fricke dosimetry. No apparent structural differences were observed under the light microscope. However, the protein synthesis and the proportion of mycelial biomass increased with the increase in both the dose of irradiation and time of fermentation during the bioconversion of 1% corn stalk into mycelial biomass of Pleurotus sajor-caju. Gamma irradiation at the dose of 50 Mrads or lower did not produce any appreciable increase in the amount of protein synthesised. At 170 Mrads, the final product contained 28% protein representing a 2-fold increase from non-irradiated corn stalk and an efficiency of 36% conversion of total utilizable polysaccharides of corn stalks into mycelial biomass. The lag phase during mycelial biomass production was much more prolonged at very high doses indicating possible production of some toxic substances during irradiation. (author). 2 tabs., 6 figs.

  2. Quantum chemistry

    CERN Document Server

    Lowe, John P

    1993-01-01

    Praised for its appealing writing style and clear pedagogy, Lowe's Quantum Chemistry is now available in its Second Edition as a text for senior undergraduate- and graduate-level chemistry students. The book assumes little mathematical or physical sophistication and emphasizes an understanding of the techniques and results of quantum chemistry, thus enabling students to comprehend much of the current chemical literature in which quantum chemical methods or concepts are used as tools. The book begins with a six-chapter introduction of standard one-dimensional systems, the hydrogen atom,

  3. NUCLEAR CHEMISTRY ANNUAL REPORT 1970

    Energy Technology Data Exchange (ETDEWEB)

    Authors, Various

    1971-05-01

    Papers are presented for the following topics: (1) Nuclear Structure and Nuclear Properties - (a) Nuclear Spectroscopy and Radioactivity; (b) Nuclear Reactions and Scattering; (c) Nuclear Theory; and (d) Fission. (2) Chemical and Atomic Physics - (a) Atomic and Molecular Spectroscopy; and (b) Hyperfine Interactions. (3) Physical, Inorganic, and Analytical Chemistry - (a) X-Ray Crystallography; (b) Physical and Inorganic Chemistry; (c) Radiation Chemistry; and (d) Chemical Engineering. (4) Instrumentation and Systems Development.

  4. Multi-scale multi-physics computational chemistry simulation based on ultra-accelerated quantum chemical molecular dynamics method for structural materials in boiling water reactor

    International Nuclear Information System (INIS)

    Miyamoto, Akira; Sato, Etsuko; Sato, Ryo; Inaba, Kenji; Hatakeyama, Nozomu

    2014-01-01

    In collaboration with experimental experts we have reported in the present conference (Hatakeyama, N. et al., “Experiment-integrated multi-scale, multi-physics computational chemistry simulation applied to corrosion behaviour of BWR structural materials”) the results of multi-scale multi-physics computational chemistry simulations applied to the corrosion behaviour of BWR structural materials. In macro-scale, a macroscopic simulator of anode polarization curve was developed to solve the spatially one-dimensional electrochemical equations on the material surface in continuum level in order to understand the corrosion behaviour of typical BWR structural material, SUS304. The experimental anode polarization behaviours of each pure metal were reproduced by fitting all the rates of electrochemical reactions and then the anode polarization curve of SUS304 was calculated by using the same parameters and found to reproduce the experimental behaviour successfully. In meso-scale, a kinetic Monte Carlo (KMC) simulator was applied to an actual-time simulation of the morphological corrosion behaviour under the influence of an applied voltage. In micro-scale, an ultra-accelerated quantum chemical molecular dynamics (UA-QCMD) code was applied to various metallic oxide surfaces of Fe 2 O 3 , Fe 3 O 4 , Cr 2 O 3 modelled as same as water molecules and dissolved metallic ions on the surfaces, then the dissolution and segregation behaviours were successfully simulated dynamically by using UA-QCMD. In this paper we describe details of the multi-scale, multi-physics computational chemistry method especially the UA-QCMD method. This method is approximately 10,000,000 times faster than conventional first-principles molecular dynamics methods based on density-functional theory (DFT), and the accuracy was also validated for various metals and metal oxides compared with DFT results. To assure multi-scale multi-physics computational chemistry simulation based on the UA-QCMD method for

  5. Understanding of catalysis on early transition metal oxide-based catalysts through exploration of surface structure and chemistry during catalysis using in-situ approaches

    Energy Technology Data Exchange (ETDEWEB)

    Tao, Franklin [Univ. of Kansas, Lawrence, KS (United States). Dept. of Chemical and Petroleum Engineering. Dept. of Chemistry

    2015-09-14

    Two main categories of heterogeneous catalysts are metal and metal oxide which catalyze 80% chemical reactions at solid-gas and solid-liquid interfaces. Metal oxide catalysts are much more complicated than metal catalysts. The reason is that the cations of the metal atoms could exhibit a few different oxidation states on surface of the same catalyst particle such as Co3O4 or change of their oxidation states under different reactive environments. For a metal catalyst, there is only one oxidation state typically. In addition, surface of a metal oxide can be terminated with multiple surface functionalities including O atoms with different binding configurations and OH group. For metal, only metal atoms are exposed typically. Obviously, the complication of surface chemistry and structure of a metal oxide makes studies of surface of an oxide catalyst very challenging. Due to the complication of surface of a meal oxide, the electronic and geometric structures of surface of a metal oxide and the exposed species have received enormous attention since oxide catalysts catalyze at least 1/3 chemical reactions in chemical and energy industries. Understanding of catalytic reactions on early transition metal oxide-based catalysts is fundamentally intriguing and of great practical interest in energy- and environment-related catalysis. Exploration of surface chemistry of oxide-based catalysts at molecular level during catalysis has remained challenging though it is critical in deeply understanding catalysis on oxide-based catalysts and developing oxide-based catalysts with high activity and selectivity. Thus, the overall objective of this project is to explore surface chemistry and structure of early transition metal oxide-based catalysts through in-situ characterization of surface of catalysts, measurements of catalytic performances, and then build an intrinsic correlation of surface chemistry and structure with their catalytic performances in a few

  6. Analytical chemistry

    Energy Technology Data Exchange (ETDEWEB)

    Choi, Jae Seong

    1993-02-15

    This book is comprised of nineteen chapters, which describes introduction of analytical chemistry, experimental error and statistics, chemistry equilibrium and solubility, gravimetric analysis with mechanism of precipitation, range and calculation of the result, volume analysis on general principle, sedimentation method on types and titration curve, acid base balance, acid base titration curve, complex and firing reaction, introduction of chemical electro analysis, acid-base titration curve, electrode and potentiometry, electrolysis and conductometry, voltammetry and polarographic spectrophotometry, atomic spectrometry, solvent extraction, chromatograph and experiments.

  7. Analytical chemistry

    International Nuclear Information System (INIS)

    Choi, Jae Seong

    1993-02-01

    This book is comprised of nineteen chapters, which describes introduction of analytical chemistry, experimental error and statistics, chemistry equilibrium and solubility, gravimetric analysis with mechanism of precipitation, range and calculation of the result, volume analysis on general principle, sedimentation method on types and titration curve, acid base balance, acid base titration curve, complex and firing reaction, introduction of chemical electro analysis, acid-base titration curve, electrode and potentiometry, electrolysis and conductometry, voltammetry and polarographic spectrophotometry, atomic spectrometry, solvent extraction, chromatograph and experiments.

  8. Analytical chemistry

    Energy Technology Data Exchange (ETDEWEB)

    Chae, Myeong Hu; Lee, Hu Jun; Kim, Ha Seok

    1989-02-15

    This book give explanations on analytical chemistry with ten chapters, which deal with development of analytical chemistry, the theory of error with definition and classification, sample and treatment gravimetry on general process of gravimetry in aqueous solution and non-aqueous solution, precipitation titration about precipitation reaction and types, complexometry with summary and complex compound, oxidation-reduction equilibrium on electrode potential and potentiometric titration, solvent extraction and chromatograph and experiment with basic operation for chemical experiment.

  9. Analytical chemistry

    International Nuclear Information System (INIS)

    Chae, Myeong Hu; Lee, Hu Jun; Kim, Ha Seok

    1989-02-01

    This book give explanations on analytical chemistry with ten chapters, which deal with development of analytical chemistry, the theory of error with definition and classification, sample and treatment gravimetry on general process of gravimetry in aqueous solution and non-aqueous solution, precipitation titration about precipitation reaction and types, complexometry with summary and complex compound, oxidation-reduction equilibrium on electrode potential and potentiometric titration, solvent extraction and chromatograph and experiment with basic operation for chemical experiment.

  10. Green Chemistry

    Energy Technology Data Exchange (ETDEWEB)

    Collison, Melanie

    2011-05-15

    Green chemistry is the science of chemistry used in a way that will not use or create hazardous substances. Dr. Rui Resendes is working in this field at GreenCentre Canada, an offshoot of PARTEQ Innovations in Kingston, Ontario. GreenCentre's preliminary findings suggest their licensed product {sup S}witchable Solutions{sup ,} featuring 3 classes of solvents and a surfactant, may be useful in bitumen oil sands extraction.

  11. The influence of vegetation structure on spider species richness, diversity and community organization in the Apšuciems calcareous fen, Latvia

    Directory of Open Access Journals (Sweden)

    Štokmane, M.

    2016-07-01

    Full Text Available Calcareous fens are considered to be among the most threatened ecosystems of Europe. They are also one of the most diverse habitats as they support an incredibly rich and diverse range of plant and animal species. However, in spite of their diversity, calcareous fens are still poorly investigated, especially when referring to fen invertebrates, such as spiders. Because spiders are good bioindicators, knowledge of their ecology in rare and threatened habitats is of interest. The aim of this study was to document the composition and diversity of spider species, families and foraging guilds in the ground– and grass–layers of the Apšuciems calcareous fen, and to evaluate the influence of vegetation structure on spider community organization. In summer 2012, we collected ground–dwelling spiders using pitfall traps and grass–dwelling spiders using sweep–netting. A total of 2,937 spider individuals belonging to 19 families and 80 species was collected in the Apšuciems fen. Our results indicate that spider species and families tend to be stratified across the vertical structure of the habitat; the spider composition in the ground stratum differed from that in the grass stratum. On the contrary, however, the spider foraging guild structure between the ground–layer and the grass–layer was similar. Each of the two studied strata presented similar guilds in similar proportions. Our results also showed that spider composition differed considerably between fen parts and that much of this variability could be explained by the architectural properties of the habitat. More diverse vegetation generally supported a higher number of spider species.

  12. Sufficient Utilization of Zirconium Ions to Improve the Structure and Surface properties of Nickel-Rich Cathode Materials for Lithium-Ion Batteries.

    Science.gov (United States)

    He, Tao; Lu, Yun; Su, Yuefeng; Bao, Liying; Tan, Jing; Chen, Lai; Zhang, Qiyu; Li, Weikang; Chen, Shi; Wu, Feng

    2018-02-19

    We doped Zr 4+ ions in the outer layer of Ni 0.8 Co 0.1 Mn 0.1 (OH) 2 by coprecipitation. The distribution of Zr 4+ in the final cathode materials showed a gradient distribution because of ion migration during the thermal treatment. The doped layer was confirmed by using various analysis methods (energy-dispersive X-ray spectroscopy, XRD, X-ray photoelectron spectroscopy, and TEM), which implies that Zr 4+ can not only occupy both the transition metal slabs and Li slabs but also form a Li 2 ZrO 3 layer on the surface as a highly ion-conductive layer. The doped Zr 4+ in the transition metal slabs can stabilize the crystal structure because of the strong Zr-O bond energy, and the doped Zr 4+ in the Li slabs can act as pillar ions to improve the structural stability and reduce cation mixing. The gradient doping can take advantage of the "pillar effect" and restrain the "blocking effect" of the pillar ions, which reduces irreversible capacity loss and improves the cycling and rate performance of the Ni-rich cathode materials. The capacity retention of the modified sample reached 83.2 % after 200 cycles at 1C (200 mA g -1 ) at 2.8-4.5 V, and the discharge capacity was up to 164.7 mAh g -1 at 10C. This effective strategy can improve the structure stability of the cathode material while reducing the amount of non-electrochemical active dopant because of the gradient distribution of the dopant. In addition, the highly ion-conductive layer of Li 2 ZrO 3 on the surface can improve the rate performance of the cathode. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. Are carnivore digestive separation mechanisms revealed on structure-rich diets?: Faecal inconsistency in dogs (Canis familiaris fed day old chicks.

    Directory of Open Access Journals (Sweden)

    Annelies De Cuyper

    Full Text Available Pronounced variations in faecal consistency have been described anecdotally for some carnivore species fed a structure-rich diet. Typically two faecal consistencies are distinguished, namely hard and firm versus liquid and viscous faeces. It is possible that a separation mechanism is operating in the carnivore digestive tract, as in many herbivore species. Six beagle dogs were fed two experimental diets in a cross-over design of 7 days. Test diets consisted of chunked day old chicks differing only in particle size (fine = 7.8 mm vs coarse = 13 mm in order to vary dietary structure. Digestive retention time was measured using titanium oxide (TiO2 as marker. The total faecal output was scored for consistency and faecal fermentation profiles were evaluated through faecal short-chain fatty acid (SCFA and ammonia (NH3 analyses. A total of 181 faecal samples were collected. Dietary particle size did not affect faecal consistency, fermentative end products nor mean retention time (MRT. However, a faecal consistency dichotomy was observed with firm faeces (score 2-2.5 and soft faeces (score 4-4.5 being the most frequently occurring consistencies in an almost alternating pattern in every single dog. Firm and soft faeces differed distinctively in fermentative profiles. Although the structure difference between diets did not affect the faecal dichotomy, feeding whole prey provoked the occurrence of the latter which raises suspicion of a digestive separation mechanism in the canine digestive tract. Further faecal characterisation is however required in order to unravel the underlying mechanism.

  14. The influence of vegetation structure on spider species richness, diversity and community organization in the Apšuciems calcareous fen, Latvia

    Energy Technology Data Exchange (ETDEWEB)

    Štokmane, M.; Spuņģis, V.

    2016-07-01

    Calcareous fens are considered to be among the most threatened ecosystems of Europe. They are also one of the most diverse habitats as they support an incredibly rich and diverse range of plant and animal species. However, in spite of their diversity, calcareous fens are still poorly investigated, especially when referring to fen invertebrates, such as spiders. Because spiders are good bioindicators, knowledge of their ecology in rare and threatened habitats is of interest. The aim of this study was to document the composition and diversity of spider species, families and foraging guilds in the ground– and grass–layers of the Apšuciems calcareous fen, and to evaluate the influence of vegetation structure on spider community organization. In summer 2012, we collected ground–dwelling spiders using pitfall traps and grass–dwelling spiders using sweep–netting. A total of 2,937 spider individuals belonging to 19 families and 80 species was collected in the Apšuciems fen. Our results indicate that spider species and families tend to be stratified across the vertical structure of the habitat; the spider composition in the ground stratum differed from that in the grass stratum. On the contrary, however, the spider foraging guild structure between the ground–layer and the grass–layer was similar. Each of the two studied strata presented similar guilds in similar proportions. Our results also showed that spider composition differed considerably between fen parts and that much of this variability could be explained by the architectural properties of the habitat. More diverse vegetation generally supported a higher number of spider species. (Author)

  15. Synthesis and crystal structure of Mg2B24C, a new boron-rich boride related to 'tetragonal boron I'

    International Nuclear Information System (INIS)

    Adasch, Volker; Hess, Kai-Uwe; Ludwig, Thilo; Vojteer, Natascha; Hillebrecht, Harald

    2006-01-01

    Single crystals of Mg 2 B 24 C, a new boron-rich boridecarbide of magnesium, were synthesized as black needles and columns by reaction of the elements in Ta ampoules and BN crucibles at 1300 deg. C. The crystal structure was determined by X-ray diffraction (P-4n2, a=8.9391(13)A, c=5.0745(10)A, Z=2, 713 reflections, 64 variables, R 1 (F)=0.0235, wR 2 (I)=0.0591). It is closely related to 'tetragonal boron I' and can be described as a tetragonal rod packing of corner-linked B 12 icosahedra with C and Mg atoms in the voids. Each B 12 icosahedron has 2 B-C bonds and 10 exohedral bonds to other icosahedra, 2 within the rod and 4x2 to neighbouring rods. The isolated C atoms are 4-fold coordinated forming distorted tetrahedra. Mg is placed on two crystallographically independent positions within the three-dimensional B 12 C network. Mg 2 B 24 C is the first example for a compound related to 'tetragonal boron I' with a stoichiometric composition

  16. Chemistry Teachers' Views of Creativity

    Science.gov (United States)

    Akkanat, Çigdem; Gökdere, Murat

    2015-01-01

    The purpose of this study was to determine chemistry teachers' views of creativity. In this study, phenomenology method, one of the qualitative research patterns, was used. The participants of this study were 13 chemistry teachers working in Amasya. A semi-structured interview form was used for data collection. By using NVivo 9 qualitative…

  17. The physical basis of chemistry

    CERN Document Server

    Warren, Warren S

    2000-01-01

    If the text you're using for general chemistry seems to lack sufficient mathematics and physics in its presentation of classical mechanics, molecular structure, and statistics, this complementary science series title may be just what you're looking for. Written for the advanced lower-division undergraduate chemistry course, The Physical Basis of Chemistry, Second Edition, offers students an opportunity to understand and enrich the understanding of physical chemistry with some quantum mechanics, the Boltzmann distribution, and spectroscopy. Posed and answered are questions concerning eve

  18. In-situ Evaluation of Soil Organic Molecules: Functional Group Chemistry Aggregate Structures, Metal and Surface Complexation Using Soft X-Ray

    International Nuclear Information System (INIS)

    Myneni, Satish C.

    2008-01-01

    Organic molecules are common in all Earth surface environments, and their composition and chemistry play an important role in a variety of biogeochemical reactions, such as mineral weathering, nutrient cycling and the solubility and transport of contaminants. However, most of what we know about the chemistry of these molecules comes from spectroscopy and microscopy studies of organic molecules extracted from different natural systems using either inorganic or organic solvents. Although all these methods gave us clues about the composition of these molecules, their composition and structure change with the extraction and the type of ex-situ analysis, their true behavior is less well understood. The goal of this project is to develop synchrotron instrumentation for studying natural organics, and to apply these recently developed synchrotron X-ray spectroscopy and microscopy techniques for understanding the: (1) functional group composition of naturally occurring organic molecules; (2) macromolecular structures of organic molecules; and (3) the nature of interactions of organic molecules with mineral surfaces in different environmental conditions.

  19. D19S Mutation of the Cationic, Cysteine-Rich Protein PAF: Novel Insights into Its Structural Dynamics, Thermal Unfolding and Antifungal Function.

    Directory of Open Access Journals (Sweden)

    Christoph Sonderegger

    Full Text Available The cysteine-rich, cationic, antifungal protein PAF is abundantly secreted into the culture supernatant of the filamentous Ascomycete Penicillium chrysogenum. The five β-strands of PAF form a compact β-barrel that is stabilized by three disulphide bonds. The folding of PAF allows the formation of four surface-exposed loops and distinct charged motifs on the protein surface that might regulate the interaction of PAF with the sensitive target fungus. The growth inhibitory activity of this highly stable protein against opportunistic fungal pathogens provides great potential in antifungal drug research. To understand its mode of action, we started to investigate the surface-exposed loops of PAF and replaced one aspartic acid at position 19 in loop 2 that is potentially involved in PAF active or binding site, with a serine (Asp19 to Ser19. We analysed the overall effects, such as unfolding, electrostatic changes, sporadic conformers and antifungal activity when substituting this specific amino acid to the fairly indifferent amino acid serine. Structural analyses revealed that the overall 3D solution structure is virtually identical with that of PAF. However, PAFD19S showed slightly increased dynamics and significant differences in the surface charge distribution. Thermal unfolding identified PAFD19S to be rather a two-state folder in contrast to the three-state folder PAF. Functional comparison of PAFD19S and PAF revealed that the exchange at residue 19 caused a dramatic loss of antifungal activity: the binding and internalization of PAFD19S by target cells was reduced and the protein failed to trigger an intracellular Ca2+ response, all of which are closely linked to the antifungal toxicity of PAF. We conclude that the negatively charged residue Asp19 in loop 2 is essential for full function of the cationic protein PAF.

  20. The Chemistry of Griseofulvin

    DEFF Research Database (Denmark)

    Petersen, Asger Bjørn; Rønnest, Mads Holger; Larsen, Thomas Ostenfeld

    2014-01-01

    Specific synthetic routes are presented in schemes to illustrate the chemistry, and the analogs are presented in a table format to give an accessible overview of the structures. Several patents have been published regarding the properties of griseofulvin and its derivatives including synthesis...

  1. Chemistry-nuclear chemistry division. Progress report, October 1979-September 1980

    International Nuclear Information System (INIS)

    Ryan, R.R.

    1981-05-01

    This report presents the research and development programs pursued by the Chemistry-Nuclear Chemistry Division of the Los Alamos National Laboratory. Topics covered include advanced analytical methods, atmospheric chemistry and transport, biochemistry, biomedical research, element migration and fixation, inorganic chemistry, isotope separation and analysis, atomic and molecular collisions, molecular spectroscopy, muonic x rays, nuclear cosmochemistry, nuclear structure and reactions, radiochemical separations, theoretical chemistry, and unclassified weapons research

  2. Chemistry-nuclear chemistry division. Progress report, October 1979-September 1980

    Energy Technology Data Exchange (ETDEWEB)

    Ryan, R.R. (comp.)

    1981-05-01

    This report presents the research and development programs pursued by the Chemistry-Nuclear Chemistry Division of the Los Alamos National Laboratory. Topics covered include advanced analytical methods, atmospheric chemistry and transport, biochemistry, biomedical research, element migration and fixation, inorganic chemistry, isotope separation and analysis, atomic and molecular collisions, molecular spectroscopy, muonic x rays, nuclear cosmochemistry, nuclear structure and reactions, radiochemical separations, theoretical chemistry, and unclassified weapons research.

  3. Chemistry of surface nanostructures in lead precursor-rich PbZr{sub 0.52}Ti{sub 0.48}O{sub 3} sol–gel films

    Energy Technology Data Exchange (ETDEWEB)

    Gueye, I.; Le Rhun, G.; Gergaud, P.; Renault, O. [Univ. Grenoble Alpes, F-38000 Grenoble (France); CEA, LETI, MINATEC Campus, F-38054 Grenoble (France); Defay, E. [Luxembourg Institute of Science and Technology, Materials Research and Technology Department, 41 Rue du Brill, L-4422 Belvaux (Luxembourg); Barrett, N., E-mail: nick.barrett@cea.fr [SPEC, CEA, CNRS, Université Paris Saclay, F-91191 Gif-sur-Yvette (France)

    2016-02-15

    Highlights: • We have studied the effect of lead excess on the surface of PZT sol–gel films. • For low lead excess (10%) nanostructured surface phase is observed. • X-ray photoelectron spectroscopy shows that the surface phase is Zr oxide. - Abstract: We present a study of the chemistry of the nanostructured phase at the surface of lead zirconium titanate PbZr{sub 0.52}Ti{sub 0.48}O{sub 3} (PZT) films synthesized by sol–gel method. In sol–gel synthesis, excess lead precursor is used to maintain the target stoichiometry. Surface nanostructures appear at 10% excess whereas 30% excess inhibits their formation. Using the surface-sensitive, quantitative X-ray photoelectron spectroscopy and glancing angle X-ray diffraction we have shown that the chemical composition of the nanostructures is ZrO{sub 1.82−1.89} rather than pyrochlore often described in the literature. The presence of a possibly discontinuous layer of wide band gap ZrO{sub 1.82−1.89} could be of importance in determining the electrical properties of PZT-based metal-insulator-metal heterostructures.

  4. Spins in chemistry

    CERN Document Server

    McWeeny, Roy

    2004-01-01

    Originally delivered as a series of lectures, this volume systematically traces the evolution of the ""spin"" concept from its role in quantum mechanics to its assimilation into the field of chemistry. Author Roy McWeeny presents an in-depth illustration of the deductive methods of quantum theory and their application to spins in chemistry, following the path from the earliest concepts to the sophisticated physical methods employed in the investigation of molecular structure and properties. Starting with the origin and development of the spin concept, the text advances to an examination of sp

  5. Radiation chemistry

    International Nuclear Information System (INIS)

    Swallow, A.J.

    1983-01-01

    The subject is covered in chapters, entitled: introduction (defines scope of article as dealing with the chemistry of reactive species, (e.g. excess electrons, excited states, free radicals and inorganic ions in unusual valency states) as studied using radiation with radiation chemistry in its traditional sense and with biological and industrial applications); gases; water and simple inorganic systems; aqueous metallo-organic compounds and metalloproteins; small organic molecules in aqueous solution; microheterogeneous systems; non-aqueous liquids and solutions; solids; biological macromolecules; synthetic polymers. (U.K.)

  6. Indoor Chemistry

    DEFF Research Database (Denmark)

    Weschler, Charles J.; Carslaw, Nicola

    2018-01-01

    This review aims to encapsulate the importance, ubiquity, and complexity of indoor chemistry. We discuss the many sources of indoor air pollutants and summarize their chemical reactions in the air and on surfaces. We also summarize some of the known impacts of human occupants, who act as sources...... and sinks of indoor chemicals, and whose activities (e.g., cooking, cleaning, smoking) can lead to extremely high pollutant concentrations. As we begin to use increasingly sensitive and selective instrumentation indoors, we are learning more about chemistry in this relatively understudied environment....

  7. Chemistry of superheavy elements

    International Nuclear Information System (INIS)

    Schaedel, M.

    2012-01-01

    The chemistry of superheavy elements - or transactinides from their position in the Periodic Table - is summarized. After giving an overview over historical developments, nuclear aspects about synthesis of neutron-rich isotopes of these elements, produced in hot-fusion reactions, and their nuclear decay properties are briefly mentioned. Specific requirements to cope with the one-atom-at-a-time situation in automated chemical separations and recent developments in aqueous-phase and gas-phase chemistry are presented. Exciting, current developments, first applications, and future prospects of chemical separations behind physical recoil separators ('pre-separator') are discussed in detail. The status of our current knowledge about the chemistry of rutherfordium (Rf, element 104), dubnium (Db, element 105), seaborgium (Sg, element 106), bohrium (Bh, element 107), hassium (Hs, element 108), copernicium (Cn, element 112), and element 114 is discussed from an experimental point of view. Recent results are emphasized and compared with empirical extrapolations and with fully-relativistic theoretical calculations, especially also under the aspect of the architecture of the Periodic Table. (orig.)

  8. Reaction chemistry of cerium

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    1997-01-01

    It is truly ironic that a synthetic organic chemist likely has far greater knowledge of the reaction chemistry of cerium(IV) than an inorganic colleague. Cerium(IV) reagents have long since been employed as oxidants in effecting a wide variety of organic transformations. Conversely, prior to the late 1980s, the number of well characterized cerium(IV) complexes did not extend past a handful of known species. Though in many other areas, interest in the molecular chemistry of the 4f-elements has undergone an explosive growth over the last twenty years, the chemistry of cerium(IV) has for the most part been overlooked. This report describes reactions of cerium complexes and structure.

  9. Introductory quantum chemistry

    International Nuclear Information System (INIS)

    Chandra, A.K.

    1974-01-01

    This book on quantum chemistry is primarily intended for university students at the senior undergraduate level. It serves as an aid to the basic understanding of the important concepts of quantum mechanics introduced in the field of chemistry. Various chapters of the book are devoted to the following : (i) Waves and quanta, (ii) Operator concept in quantum chemistry, (iii) Wave mechanics of some simple systems, (iv) Perturbation theory, (v) Many-electron atoms and angular momenta (vi) Molecular orbital theory and its application to the electronic structure of diatomic molecules, (vii) Chemical bonding in polyatomic molecules and (viii) Chemical applications of Hellmann-Feynman theorem. At the end of each chapter, a set of problems is given and the answers to these problems are given at the end of the book. (A.K.)

  10. Handbook of heterocyclic chemistry

    National Research Council Canada - National Science Library

    Katritzky, Alan R

    2010-01-01

    ... Heterocyclic Chemistry I (1984) Comprehensive Heterocyclic Chemistry II (1996) Comprehensive Heterocyclic Chemistry III (2008) Comprehensive Organic Functional Group Transformations I (1995) Compreh...

  11. Structural determinants at the interface of the ARC2 and leucine-rich repeat domains control the activation of the plant immune receptors Rx1 and Gpa2.

    Science.gov (United States)

    Slootweg, Erik J; Spiridon, Laurentiu N; Roosien, Jan; Butterbach, Patrick; Pomp, Rikus; Westerhof, Lotte; Wilbers, Ruud; Bakker, Erin; Bakker, Jaap; Petrescu, Andrei-José; Smant, Geert; Goverse, Aska

    2013-07-01

    Many plant and animal immune receptors have a modular nucleotide-binding-leucine-rich repeat (NB-LRR) architecture in which a nucleotide-binding switch domain, NB-ARC, is tethered to a LRR sensor domain. The cooperation between the switch and sensor domains, which regulates the activation of these proteins, is poorly understood. Here, we report structural determinants governing the interaction between the NB-ARC and LRR in the highly homologous plant immune receptors Gpa2 and Rx1, which recognize the potato cyst nematode Globodera pallida and Potato virus X, respectively. Systematic shuffling of polymorphic sites between Gpa2 and Rx1 showed that a minimal region in the ARC2 and N-terminal repeats of the LRR domain coordinate the activation state of the protein. We identified two closely spaced amino acid residues in this region of the ARC2 (positions 401 and 403) that distinguish between autoactivation and effector-triggered activation. Furthermore, a highly acidic loop region in the ARC2 domain and basic patches in the N-terminal end of the LRR domain were demonstrated to be required for the physical interaction between the ARC2 and LRR. The NB-ARC and LRR domains dissociate upon effector-dependent activation, and the complementary-charged regions are predicted to mediate a fast reassociation, enabling multiple rounds of activation. Finally, we present a mechanistic model showing how the ARC2, NB, and N-terminal half of the LRR form a clamp, which regulates the dissociation and reassociation of the switch and sensor domains in NB-LRR proteins.

  12. Study of neutron-rich nuclei structure around the N=28 shell closure using the in-beam gamma spectroscopy technique

    International Nuclear Information System (INIS)

    Bastin, B.

    2007-10-01

    For a few years now, a loss of magicity in neutron-rich nuclei near the neutron drip-line at N=28 has been suggested and observed. Deformation in these nuclei has been observed. The deformation was explained in S isotopes as being due to a moderate reduction of the N=28 shell closure together with a proton induced collectivity originating from the near degeneracy of the proton d3/2 and s1/2 orbitals. As a consequence, the observed deformation seems to result from a subtle interplay between neutron and proton excitations. Since the proton configuration in the Si isotopes is expected to be more stable due to the Z=14 sub-shell gap, 42 Si was considered as a key nucleus in order to distinguish the different effects responsible for the structural changes observed at N=28. Even if it is at the limits of our technical possibilities, an in-beam gamma-spectroscopy experiment using two-step fragmentation and one or several nucleons knockout reaction mechanisms was performed at GANIL. The measurement of the energy of the first excited state in 42 Si, combined with the observation of 38,40 Si and the spectroscopy of 41,43 P, has given evidence for the loss of magicity at N=28 far from stability. Modifications of the effective interaction used in modern shell model calculations have been completed following this investigation, increasing its predictive character. This study confirms the role of the tensor force and the density dependence of the spin-orbit interaction in the collapse of the N=28 shell closure. (author)

  13. Reinventing Chemistry

    OpenAIRE

    Whitesides, George McClelland

    2015-01-01

    Chemistry is in a period of change, from an era focused on molecules and reactions, to one in which manipulations of systems of molecules and reactions will be essential parts of controlling larger systems. This Essay traces paths from the past to possible futures.

  14. Chemistry Notes

    Science.gov (United States)

    School Science Review, 1972

    1972-01-01

    Short articles on the kinetics of the hydrogen peroxide-iodide ion reaction, simulation of fluidization catalysis, the use of Newman projection diagrams to represent steric relationships in organic chemistry, the use of synthetic substrates for proteolytic enzyme reactions, and two simple clock reactions"--hydrolysis of halogenoalkanes and…

  15. Spallation RI beam facility and heavy element nuclear chemistry

    Energy Technology Data Exchange (ETDEWEB)

    Nagame, Yuichiro [Japan Atomic Energy Research Inst., Tokai, Ibaraki (Japan). Tokai Research Establishment

    1997-11-01

    An outline of the spallation RI (Radioactive Ion) beam facility is presented. Neutron-rich nuclides are produced in the reaction of high intensity (10-1000 {mu}A) protons with energy of 1.5 GeV and an uranium carbide target. Produced nuclides are ionized in an isotope separator on-line (ISOL) and accelerated by the JAERI tandem and the booster linac. Current progress and a future project on the development of the RI beam facility are given. Studies of transactinide elements, including the synthesis of superheavy elements, nuclear structure far from stability, and RI-probed material science are planned with RI beams. An outlook of the transactinide nuclear chemistry studies using neutron-rich RI beams is described. (author)

  16. The crystal chemistry and structural analysis of uranium oxide hydrates. Final report, May 15, 1995--December 31, 1997

    International Nuclear Information System (INIS)

    Miller, M.L.; Ewing, R.C.

    1998-01-01

    The purpose of this research program was to develop a thorough understanding of the crystal-chemical and crystal-structural systematics of uranyl oxide hydrates which are the initial corrosion products of the UO 2 in spent nuclear fuel and the principal phases in which actinides occur in the near surface environment. The scope of this program has been expanded to include all inorganic phases in which U 6+ plays a significant structural role; currently 183 phases with known crystal structures

  17. Structure And Chemistry Of Ion Masses ≤ 40 Amu In The Inner Coma Of Comet HalleyStructure And Chemistry Of Ion Masses ≤ 40 Amu In The Inner Coma Of Comet Halley

    Science.gov (United States)

    Haider, S. A.; Bhardwaj, A.

    In this paper, we have developed a chemical model to study the chemistry of 46 ions (CH5+, SH+, S+, H2S+, NH3OH+, CH3+, HCO+, H2CO+, C2H3+, C3H3+, H3CO+, H2CN+, H3S+, NH3+, CH3OH2+, CH3OH+, NH4+, H3O+, N+, NH+, NH2+, N2+, C2H+, C+, CH2+, CH+, C2N+, C3H+, C2H4+, C2H5+, CO+, O+, H+, C2+, HCN+, OH+, O2+, CHOH2+, HNO+, N2H+, H2O+, CH4+, C2H2+, (H2O)2+, H5O2+ and C3H+) corresponding to masses ≤ 40 amu in the inner coma of comet Halley. The ionization sources included in the model are solar EUV photon, photoelectron and auroral electron of solar wind origin. The production rates, loss rates and mass densities of these ions are calculated using Analytical Yield Spectrum approach and coupled continuity equation controlled by steady state photochemical model, which involves over 600 chemical reactions between ions, neutrals, photons and electrons in the coma. The calculated mass densities are compared with Giotto Ion Mass Spectrometer (IMS) and Neutral Mass Spectrometer (NMS) data at radial distances 1500 km, 3500 km and 6000 km. The nine major peaks at 12, 15, 19, 26, 28, 31, 33, 35, and 39 amu observed in IMS/NMS spectra are reproduced well by model calculation. ^

  18. Structural chemistry of the cation-ordered perovskites Sr2CaMo1-xTexO6 (0=

    International Nuclear Information System (INIS)

    Prior, Timothy J.; Couper, Victoria J.; Battle, Peter D.

    2005-01-01

    The crystal structures of Sr 2 CaMoO 6 and Sr 2 CaTeO 6 have been determined at room temperature by neutron powder diffraction. Both compounds crystallize in the perovskite structure with a rock-salt ordered array of Ca 2+ and M 6+ cations (M=Mo, Te) on the six-coordinate sites (space group P2 1 /n (no. 14); for M=Mo, a=5.76228(7), b=5.84790(7), c=8.18707(9)A, β=90.194(1) o , for M=Te, a=5.79919(9), b=5.83756(8), c=8.2175(1)A, β=90.194(1) o ). Compositions in the solid solution Sr 2 CaMo 1-x Te x O 6 have been synthesized and shown by X-ray diffraction to adopt the same ordered structure. The results are used in a discussion of the cation oxidation states in Ca 2 FeMoO 6 and to establish the similarity between the structural chemistry of hexavalent Mo and Te

  19. Click Chemistry-Facilitated Structural Diversification of Nitrothiazoles, Nitrofurans, and Nitropyrroles Enhances Antimicrobial Activity against Giardia lamblia

    Science.gov (United States)

    Kim, Wan Jung; Korthals, Keith A.; Li, Suhua; Le, Christine; Kalisiak, Jarosław; Sharpless, K. Barry; Fokin, Valery V.; Miyamoto, Yukiko

    2017-01-01

    ABSTRACT Giardia lamblia is an important and ubiquitous cause of diarrheal disease. The primary agents in the treatment of giardiasis are nitroheterocyclic drugs, particularly the imidazoles metronidazole and tinidazole and the thiazole nitazoxanide. Although these drugs are generally effective, treatment failures occur in up to 20% of cases, and resistance has been demonstrated in vivo and in vitro. Prior work had suggested that side chain modifications of the imidazole core can lead to new effective 5-nitroimidazole drugs that can combat nitro drug resistance, but the full potential of nitroheterocycles other than imidazole to yield effective new antigiardial agents has not been explored. Here, we generated derivatives of two clinically utilized nitroheterocycles, nitrothiazole and nitrofuran, as well as a third heterocycle, nitropyrrole, which is related to nitroimidazole but has not been systematically investigated as an antimicrobial drug scaffold. Click chemistry was employed to synthesize 442 novel nitroheterocyclic compounds with extensive side chain modifications. Screening of this library against representative G. lamblia strains showed a wide spectrum of in vitro activities, with many of the compounds exhibiting superior activity relative to reference drugs and several showing >100-fold increase in potency and the ability to overcome existing forms of metronidazole resistance. The majority of new compounds displayed no cytotoxicity against human cells, and several compounds were orally active against murine giardiasis in vivo. These findings provide additional impetus for the systematic development of nitroheterocyclic compounds with nonimidazole cores as alternative and improved agents for the treatment of giardiasis and potentially other infectious agents. PMID:28396548

  20. Bridging quantum chemistry and nuclear structure theory: Coupled-cluster calculations for closed- and open-shell nuclei

    International Nuclear Information System (INIS)

    Piecuch, Piotr; Wloch, Marta; Gour, Jeffrey R.; Dean, David J.; Papenbrock, Thomas; Hjorth-Jensen, Morten

    2005-01-01

    We review basic elements of the single-reference coupled-cluster theory and discuss large scale ab initio calculations of ground and excited states of 15O, 16O, and 17O using coupled-cluster methods and algorithms developed in quantum chemistry. By using realistic two-body interactions and the renormalized form of the Hamiltonian obtained with a no-core G-matrix approach, we obtain the converged results for 16O and promising preliminary results for 15O and 17O at the level of two-body interactions. The calculated properties other than energies include matter density, charge radius, and charge form factor. The relatively low costs of coupled-cluster calculations, which are characterized by the low-order polynomial scaling with the system size, enable us to probe large model spaces with up to 7 or 8 major oscillator shells, for which non-truncated shell-model calculations for nuclei with A = 15 17 active particles are presently not possible. We argue that the use of coupled-cluster methods and computer algorithms developed by quantum chemists to calculate properties of nuclei is an important step toward the development of accurate and affordable many-body theories that cross the boundaries of various physical sciences

  1. Protactinium and the intersection of actinide and transition metal chemistry

    Energy Technology Data Exchange (ETDEWEB)

    Wilson, Richard E.; De Sio, Stephanie; Vallet, Valérie

    2018-02-12

    The role of the 5f and 6d orbitals in the chemistry of the actinide elements has been of considerable interest since their discovery and synthesis. Relativistic effects cause the energetics of the 5f and 6d orbitals to change as the actinide series is traversed left to right imparting a rich and complex chemistry. The 5f and 6d atomic states cross in energy at protactinium (Pa), making it a potential intersection between transition metal and actinide chemistries. Herein, we report the synthesis of a Pa-peroxo cluster, A(6)(Pa4O(O-2)(6)F-12) [A = Rb, Cs, (CH3)(4)N], formed in pursuit of an actinide polyoxometalate. Quantum chemical calculations at the density functional theory level demonstrate equal 5f and 6d orbital participation in the chemistry of Pa and increasing 5f orbital participation for the heavier actinides. Periodic changes in orbital character to the bonding in the early actinides highlights the influence of the 5f orbitals in their reactivity and chemical structure.

  2. Effect of Synthesis Parameters on the Structure and Magnetic Properties of Magnetic Manganese Ferrite/Silver Composite Nanoparticles Synthesized by Wet Chemistry Method

    DEFF Research Database (Denmark)

    Huy, L.T.; Tam, L.T.; Phan, V.N.

    2016-01-01

    In the present work, magnetic manganese ferrite/silver (MnFe2O4-Ag) composite nanoparticles were synthesized by wet chemistry method. This synthesis process consists of two steps: first, the seed of manganese ferrite nanoparticles (MnFe2O4 NPs) was prepared by a coprecipitationmethod; second......, growth of silver nanoparticles (AgNPs) on the MnFe2O4 seed by modified photochemical reaction. We have conducted systematically the effects of synthesis parameters such as pH value, synthesis time, precursor salts concentration, mass ratio and stabilizing agents on the structure and magnetic properties......-prepared MnFe2O4-Ag magnetic nanocomposites display excellent properties of high crystallinity, long-term aggregation stability in aqueous medium, large saturation magnetization in the range of 15-20 emu/g, and small sizes of Ag-NPs similar to 20 nm. These exhibited properties made the MnFe2O4-Ag...

  3. New insights into the structure, chemistry, and properties of Cu.sub.4./sub.SnS.sub.4./sub.

    Czech Academy of Sciences Publication Activity Database

    Choudhury, A.; Mohapatra, S.; Asl, H.Y.; Lee, S.H.; Hor, Y.S.; Medvedeva, J.E.; McClane, D.L.; Hilmas, G.E.; McGuire, M.A.; May, A.H.; Wang, H.; Dash, S.; Welton, A.; Boolchand, P.; Devlin, K.P.; Aitken, J.; Herbst-Irmer, R.; Petříček, Václav

    2017-01-01

    Roč. 253, Sep (2017), s. 192-201 ISSN 0022-4596 Institutional support: RVO:68378271 Keywords : Cu 4 SnS 4 * phase transition * crystal structure * electronic properties * thermoelectrics * band structure * 119-Sn Mössbauer Subject RIV: BM - Solid Matter Physics ; Magnetism OBOR OECD: Condensed matter physics (including formerly solid state physics, supercond.) Impact factor: 2.299, year: 2016

  4. The CAPRICE RICH detector

    Energy Technology Data Exchange (ETDEWEB)

    Basini, G. [INFN, Laboratori Nazionali di Frascati, Rome (Italy); Codino, A.; Grimani, C. [Perugia Univ. (Italy)]|[INFN, Perugia (Italy); De Pascale, M.P. [Rome Univ. `Tor Vergata` (Italy). Dip. di Fisica]|[INFN, Sezione Univ. `Tor Vergata` Rome (Italy); Cafagna, F. [Bari Univ. (Italy)]|[INFN, Bari (Italy); Golden, R.L. [New Mexico State Univ., Las Cruces, NM (United States). Particle Astrophysics Lab.; Brancaccio, F.; Bocciolini, M. [Florence Univ. (Italy)]|[INFN, Florence (Italy); Barbiellini, G.; Boezio, M. [Trieste Univ. (Italy)]|[INFN, Trieste (Italy)

    1995-09-01

    A compact RICH detector has been developed and used for particle identification in a balloon borne spectrometer to measure the flux of antimatter in the cosmic radiation. This is the first RICH detector ever used in space experiments that is capable of detecting unit charged particles, such as antiprotons. The RICH and all other detectors performed well during the 27 hours long flight.

  5. Chemistry and physics

    International Nuclear Information System (INIS)

    Broerse, J.J.; Barendsen, G.W.; Kal, H.B.; Kogel, A.J. van der

    1983-01-01

    This book contains the extended abstracts of the contributions of the poster workshop sessions on chemistry and physics of the 7th international congress of radiation research. They cover the following main topics: primary processes in radiation physics and chemistry, general chemistry in radiation chemistry, DNA and model systems in radiation chemistry, molecules of biological interest in radiation chemistry, techniques in radiation chemistry, hot atom chemistry. refs.; figs.; tabs

  6. Fine chemistry

    International Nuclear Information System (INIS)

    Laszlo, P.

    1988-01-01

    The 1988 progress report of the Fine Chemistry laboratory (Polytechnic School, France) is presented. The research programs are centered on the renewal of the organic chemistry most important reactions and on the invention of new, highly efficient and highly selective reactions, by applying low cost reagents and solvents. An important research domain concerns the study and fabrication of new catalysts. They are obtained by means of the reactive sputtering of the metals and metal oxydes thin films. The Monte Carlo simulations of the long-range electrostatic interaction in a clay and the obtention of acrylamides from anhydrous or acrylic ester are summarized. Moreover, the results obtained in the field of catalysis are also given. The published papers and the congress communications are included [fr

  7. Radioanalytical chemistry

    International Nuclear Information System (INIS)

    1982-01-01

    The bibliography of Hungarian literature in the field of radioanalytical chemistry covers the four-year period 1976-1979. The list of papers contains 290 references in the alphabetical order of the first authors. The majority of the titles belongs to neutron activation analysis, labelling, separation and determination of radioactive isotopes. Other important fields like radioimmunoassay, environmental protection etc. are covered as well. (Sz.J.)

  8. Analytical chemistry

    International Nuclear Information System (INIS)

    Anon.

    1985-01-01

    The division for Analytical Chemistry continued to try and develope an accurate method for the separation of trace amounts from mixtures which, contain various other elements. Ion exchange chromatography is of special importance in this regard. New separation techniques were tried on certain trace amounts in South African standard rock materials and special ceramics. Methods were also tested for the separation of carrier-free radioisotopes from irradiated cyclotron discs

  9. Industrial chemistry engineering

    International Nuclear Information System (INIS)

    1993-01-01

    This book on industrial chemistry engineering is divided in two parts. The first part deals with industrial chemistry, inorganic industrial chemistry, organic industrial chemistry, analytical chemistry and practical questions. The last parts explain the chemical industry, a unit parts and thermodynamics in chemical industry and reference. It reveals the test subjects for the industrial chemistry engineering with a written examination and practical skill.

  10. Computational chemistry

    Science.gov (United States)

    Arnold, J. O.

    1987-01-01

    With the advent of supercomputers, modern computational chemistry algorithms and codes, a powerful tool was created to help fill NASA's continuing need for information on the properties of matter in hostile or unusual environments. Computational resources provided under the National Aerodynamics Simulator (NAS) program were a cornerstone for recent advancements in this field. Properties of gases, materials, and their interactions can be determined from solutions of the governing equations. In the case of gases, for example, radiative transition probabilites per particle, bond-dissociation energies, and rates of simple chemical reactions can be determined computationally as reliably as from experiment. The data are proving to be quite valuable in providing inputs to real-gas flow simulation codes used to compute aerothermodynamic loads on NASA's aeroassist orbital transfer vehicles and a host of problems related to the National Aerospace Plane Program. Although more approximate, similar solutions can be obtained for ensembles of atoms simulating small particles of materials with and without the presence of gases. Computational chemistry has application in studying catalysis, properties of polymers, all of interest to various NASA missions, including those previously mentioned. In addition to discussing these applications of computational chemistry within NASA, the governing equations and the need for supercomputers for their solution is outlined.

  11. Green chemistry

    International Nuclear Information System (INIS)

    Warner, John C.; Cannon, Amy S.; Dye, Kevin M.

    2004-01-01

    A grand challenge facing government, industry, and academia in the relationship of our technological society to the environment is reinventing the use of materials. To address this challenge, collaboration from an interdisciplinary group of stakeholders will be necessary. Traditionally, the approach to risk management of materials and chemicals has been through inerventions intended to reduce exposure to materials that are hazardous to health and the environment. In 1990, the Pollution Prevention Act encouraged a new tact-elimination of hazards at the source. An emerging approach to this grand challenge seeks to embed the diverse set of environmental perspectives and interests in the everyday practice of the people most responsible for using and creating new materials--chemists. The approach, which has come to be known as Green Chemistry, intends to eliminate intrinsic hazard itself, rather than focusing on reducing risk by minimizing exposure. This chapter addresses the representation of downstream environmental stakeholder interests in the upstream everyday practice that is reinventing chemistry and its material inputs, products, and waste as described in the '12 Principles of Green Chemistry'

  12. Click Chemistry-Facilitated Structural Diversification of Nitrothiazoles, Nitrofurans, and Nitropyrroles Enhances Antimicrobial Activity against Giardia lamblia.

    Science.gov (United States)

    Kim, Wan Jung; Korthals, Keith A; Li, Suhua; Le, Christine; Kalisiak, Jarosław; Sharpless, K Barry; Fokin, Valery V; Miyamoto, Yukiko; Eckmann, Lars

    2017-06-01

    Giardia lamblia is an important and ubiquitous cause of diarrheal disease. The primary agents in the treatment of giardiasis are nitroheterocyclic drugs, particularly the imidazoles metronidazole and tinidazole and the thiazole nitazoxanide. Although these drugs are generally effective, treatment failures occur in up to 20% of cases, and resistance has been demonstrated in vivo and in vitro Prior work had suggested that side chain modifications of the imidazole core can lead to new effective 5-nitroimidazole drugs that can combat nitro drug resistance, but the full potential of nitroheterocycles other than imidazole to yield effective new antigiardial agents has not been explored. Here, we generated derivatives of two clinically utilized nitroheterocycles, nitrothiazole and nitrofuran, as well as a third heterocycle, nitropyrrole, which is related to nitroimidazole but has not been systematically investigated as an antimicrobial drug scaffold. Click chemistry was employed to synthesize 442 novel nitroheterocyclic compounds with extensive side chain modifications. Screening of this library against representative G. lamblia strains showed a wide spectrum of in vitro activities, with many of the compounds exhibiting superior activity relative to reference drugs and several showing >100-fold increase in potency and the ability to overcome existing forms of metronidazole resistance. The majority of new compounds displayed no cytotoxicity against human cells, and several compounds were orally active against murine giardiasis in vivo These findings provide additional impetus for the systematic development of nitroheterocyclic compounds with nonimidazole cores as alternative and improved agents for the treatment of giardiasis and potentially other infectious agents. Copyright © 2017 American Society for Microbiology.

  13. Structure Identification Using the US EPA's CompTox Chemistry Dashboard (CompTox CoP)

    Science.gov (United States)

    Community of practice webinar presentation on the Identification of unknowns in non-targeted analyses (NTA) requires the integration of complementary data types to generate a confident consensus structure.

  14. Structure identification by Mass Spectrometry Non-Targeted Analysis using the US EPA’s CompTox Chemistry Dashboard

    Science.gov (United States)

    Identification of unknowns in mass spectrometry based non-targeted analyses (NTA) requires the integration of complementary pieces of data to arrive at a confident, consensus structure. Researchers use chemical reference databases, spectral matching, fragment prediction tools, r...

  15. Methods of quantum chemistry and nanotechnology as applied to the study of the energy states of amorphous tetrahedral structures

    Directory of Open Access Journals (Sweden)

    B. A. Golodenko

    2013-01-01

    Full Text Available The technique and results of an experimental research of power conditions of amorphous alloy hydrogenated carbide silicon is described. Application of power spectra of a silicon valence zone for definition phase structure of its amorphous hydrogenated carbide is shown. Quantitative dependence of a share carbide phases of silicon in structure of its alloy from the maintenance of methane in an initial gas mix is established.

  16. Determination of equilibrium structures of bromothymol blue revealed by using quantum chemistry with an aid of multivariate analysis of electronic absorption spectra.

    Science.gov (United States)

    Shimada, Toru; Hasegawa, Takeshi

    2017-10-05

    The pH dependent chemical structures of bromothymol blue (BTB), which have long been under controversy, are determined by employing a combined technique of multivariate analysis of electronic absorption spectra and quantum chemistry. Principle component analysis (PCA) of the pH dependent spectra apparently reveals that only two chemical species are adequate to fully account for the color changes, with which the spectral decomposition is readily performed by using augmented alternative least-squares (ALS) regression analysis. The quantity variation by the ALS analysis also reveals the practical acid dissociation constant, pK a '. The determination of pK a ' is performed for various ionic strengths, which reveals the thermodynamic acid constant (pK a =7.5) and the number of charge on each chemical species; the yellow form is negatively charged species of -1 and the blue form that of -2. On this chemical information, the quantum chemical calculation is carried out to find that BTB molecules take the pure quinoid form in an acid solution and the quinoid-phenolate form in an alkaline solution. The time-dependent density functional theory (TD-DFT) calculations for the theoretically determined chemical structures account for the peak shift of the electronic spectra. In this manner, the structures of all the chemical species appeared in equilibrium have finally been confirmed. Copyright © 2017 Elsevier B.V. All rights reserved.

  17. Determination of equilibrium structures of bromothymol blue revealed by using quantum chemistry with an aid of multivariate analysis of electronic absorption spectra

    Science.gov (United States)

    Shimada, Toru; Hasegawa, Takeshi

    2017-10-01

    The pH dependent chemical structures of bromothymol blue (BTB), which have long been under controversy, are determined by employing a combined technique of multivariate analysis of electronic absorption spectra and quantum chemistry. Principle component analysis (PCA) of the pH dependent spectra apparently reveals that only two chemical species are adequate to fully account for the color changes, with which the spectral decomposition is readily performed by using augmented alternative least-squares (ALS) regression analysis. The quantity variation by the ALS analysis also reveals the practical acid dissociation constant, pKa‧. The determination of pKa‧ is performed for various ionic strengths, which reveals the thermodynamic acid constant (pKa = 7.5) and the number of charge on each chemical species; the yellow form is negatively charged species of - 1 and the blue form that of - 2. On this chemical information, the quantum chemical calculation is carried out to find that BTB molecules take the pure quinoid form in an acid solution and the quinoid-phenolate form in an alkaline solution. The time-dependent density functional theory (TD-DFT) calculations for the theoretically determined chemical structures account for the peak shift of the electronic spectra. In this manner, the structures of all the chemical species appeared in equilibrium have finally been confirmed.

  18. Structure and evaluation of antibacterial and antitubercular properties of new basic and heterocyclic 3-formylrifamycin SV derivatives obtained via 'click chemistry' approach.

    Science.gov (United States)

    Pyta, Krystian; Klich, Katarzyna; Domagalska, Joanna; Przybylski, Piotr

    2014-09-12

    Thirty four novel derivatives of 3-formylrifamycin SV were synthesized via reductive alkylation and copper(I)-catalysed azide-alkyne cycloaddition. According to the obtained results, 'click chemistry' can be successfully applied for modification of structurally complex antibiotics such as rifamycins, with the formation of desired 1,2,3-triazole products. However, when azide-alkyne cycloaddition on 3-formylrifamycin SV derivatives demanded higher amount of catalyst, lower temperature and longer reaction time because of the high volatility of substrates, an unexpected intramolecular condensation with the formation of 3,4-dihydrobenzo[g]quinazoline heterocyclic system took place. Structures of new derivatives in solution were determined using one- and two-dimensional NMR methods and FT-IR spectroscopy. Computational DFT and PM6 methods were employed to correlate their conformation and acid-base properties to biological activity and establish SAR of the novel compounds. Microbiological, physico-chemical (logP, solubility) and structural studies of newly synthesised rifamycins indicated that for the presence of relatively high antibacterial (MIC ~0.01 nmol/mL) and antitubercular (MIC ~0.006 nmol/mL) activities, a rigid and basic substituent at C(3) arm, containing a protonated nitrogen atom "open" toward intermolecular interactions, is required. Copyright © 2014 Elsevier Masson SAS. All rights reserved.

  19. Redox properties of clay-rich sediments as assessed by mediated electrochemical analysis : Separating pyrite, siderite and structural Fe in clay minerals

    NARCIS (Netherlands)

    Hoving, Alwina L.; Sander, Michael; Bruggeman, Christophe; Behrends, Thilo

    2017-01-01

    Redox reactions with Fe-containing minerals in clay-rich sediments largely affect the speciation, mobility, and (bio-) availability of redox-sensitive contaminants. Here, we use mediated electrochemical oxidation (MEO) and reduction (MER), to quantify the electron accepting and donating capacities

  20. Primary structure and localization of a conserved immunogenic Plasmodium falciparum glutamate rich protein (GLURP) expressed in both the preerythrocytic and erythrocytic stages of the vertebrate life cycle

    DEFF Research Database (Denmark)

    Borre, M B; Dziegiel, M; Høgh, B

    1991-01-01

    A gene coding for a 220-kDa glutamate rich protein (GLURP), an exoantigen of Plasmodium falciparum, was isolated and its nucleotide sequence was determined. The deduced amino acid sequence contains 2 repeat regions. The sequence of one of these was shown to be conserved among geographically...

  1. Chemistry Division annual progress report for period ending July 31, 1981

    International Nuclear Information System (INIS)

    1982-01-01

    Research is reported on: chemistry of coal liquefaction, aqueous chemistry at high temperatures, geosciences, high-temperature chemistry and thermodynamics of structural materials, chemistry of TRU elements and compounds, separations chemistry, electrochemistry, nuclear waste chemistry, chemical physics, theoretical chemistry, inorganic chemistry of hydrogen cycles, molten salt systems, and enhanced oil recovery. Separate abstracts were prepared for the sections dealing with coal liquefaction, TRU elements and compounds, separations, nuclear wastes, and enhanced oil recovery

  2. Chemistry Division annual progress report for period ending July 31, 1981

    Energy Technology Data Exchange (ETDEWEB)

    1982-01-01

    Research is reported on: chemistry of coal liquefaction, aqueous chemistry at high temperatures, geosciences, high-temperature chemistry and thermodynamics of structural materials, chemistry of TRU elements and compounds, separations chemistry, electrochemistry, nuclear waste chemistry, chemical physics, theoretical chemistry, inorganic chemistry of hydrogen cycles, molten salt systems, and enhanced oil recovery. Separate abstracts were prepared for the sections dealing with coal liquefaction, TRU elements and compounds, separations, nuclear wastes, and enhanced oil recovery. (DLC)

  3. Chemistry and structure of coal-derived asphaltenes, Phase III. Quarterly progress report, April--June 1978

    Energy Technology Data Exchange (ETDEWEB)

    Yen, T. F.

    1978-01-01

    Solubility parameters may be calculated for coal liquid derived products by use of a semi-empirical relationship between solubility parameter and refractive index. Thermal treatment of Synthoil coal liquid oil + resin solvent fraction at 235 to 300/sup 0/C resulted in the transformation of oil and resin into asphaltene. Further support of structural characterizations was obtained by use of a combined x-ray and NMR structural characterization procedure which relies on the important x-ray structural parameter L/sub a/ (average layer diameter of the aromatic sheet). L/sub a/ values of approx. = 8 to 10 A for asphaltenes, approx. = 13.4 to 14 A for carbenes, and approx. = 14 to 16.5 A for carboids were obtained by the x-ray procedure. These data were used to calculate C/sub Au/ (aromatic carbons per structural unit) and N (number of structural units per molecule) values. For asphaltenes the results agree with those previously deduced from NMR and other techniques. The C/sub Au/ values are generally close to 14 which is the number of aromatic carbons present in a 3-ring kata-system such as anthracene or phenanthrene. The number of structural units per molecule is close to two for all the asphaltenes. Additional data were used to improve the correlation equation between weight percent OH, determined by the silylation method, and the absorbance of the monomeric OH infrared stretching band at 3600 cm/sup -1/ for asphaltenes. A similar correlation between weight percent NH, from elemental analysis of asphaltene samples containing essentially all nitrogen as pyrrolic N-H, and the infrared absorbance of the N-H stretching band at 3470 cm/sup -1/ was developed for asphaltenes.

  4. Rapid automated nuclear chemistry

    International Nuclear Information System (INIS)

    Meyer, R.A.

    1979-01-01

    Rapid Automated Nuclear Chemistry (RANC) can be thought of as the Z-separation of Neutron-rich Isotopes by Automated Methods. The range of RANC studies of fission and its products is large. In a sense, the studies can be categorized into various energy ranges from the highest where the fission process and particle emission are considered, to low energies where nuclear dynamics are being explored. This paper presents a table which gives examples of current research using RANC on fission and fission products. The remainder of this text is divided into three parts. The first contains a discussion of the chemical methods available for the fission product elements, the second describes the major techniques, and in the last section, examples of recent results are discussed as illustrations of the use of RANC

  5. Coulombic Interaction in Finnish Middle School Chemistry: A Systemic Perspective on Students' Conceptual Structure of Chemical Bonding

    Science.gov (United States)

    Joki, Jarkko; Lavonen, Jari; Juuti, Kalle; Aksela, Maija

    2015-01-01

    The aim of this study was to design a novel and holistic way to teach chemical bonding at the middle school level according to research on the teaching and learning of bonding. A further aim was to investigate high achieving middle school students' conceptual structures concerning chemical bonding by using a systemic perspective. Students in one…

  6. Synthetic Strategies towards Fullerene-Rich Dendrimer Assemblies

    Directory of Open Access Journals (Sweden)

    Jean-François Nierengarten

    2012-02-01

    Full Text Available The sphere-shaped fullerene has attracted considerable interest not least due to the peculiar electronic properties of this carbon allotrope and the fascinating materials emanating from fullerene-derived structures. The rapid development and tremendous advances in organic chemistry allow nowadays the modification of C60 to a great extent by pure chemical means. It is therefore not surprising that the fullerene moiety has also been part of dendrimers. At the initial stage, fullerenes have been examined at the center of the dendritic structure mainly aimed at possible shielding effects as exerted by the dendritic environment and light-harvesting effects due to multiple chromophores located at the periphery of the dendrimer. In recent years, also many research efforts have been devoted towards fullerene-rich nanohybrids containing multiple C60 units in the branches and/or as surface functional groups. In this review, synthetic efforts towards the construction of dendritic fullerene-rich nanostructures have been compiled and will be summarized herein.

  7. Theoretical chemistry periodicities in chemistry and biology

    CERN Document Server

    Eyring, Henry

    1978-01-01

    Theoretical Chemistry: Periodicities in Chemistry and Biology, Volume 4 covers the aspects of theoretical chemistry. The book discusses the stably rotating patterns of reaction and diffusion; the chemistry of inorganic systems exhibiting nonmonotonic behavior; and population cycles. The text also describes the mathematical modeling of excitable media in neurobiology and chemistry; oscillating enzyme reactions; and oscillatory properties and excitability of the heart cell membrane. Selected topics from the theory of physico-chemical instabilities are also encompassed. Chemists, mechanical engin

  8. Solution chemistry

    Energy Technology Data Exchange (ETDEWEB)

    None

    1973-07-01

    Research progress is reported on studies in heavy element chemistry. Topics considered are: synergistic complexes of plutonyl ion; water uptake in synergistic systems; formation constants of some uranyl BETA -diketone complexes; thermodynamic acid dissociation constants of BETA -diketones; thermodynamic formation constants of uranyl BETA -diketonates; thiocyanate complexes of some trivalent lanthanides and actinides; stability constants of actinide complexes using dinonyl naphthalenesulfonic acid extraction; TBP extraction of actinides; stability constants of complexes of Pu(III) with 5- sulfosalicycllc acid; and solvent extraction behavior of Pu( VII). (DHM)

  9. The radiation chemistry of macromolecules

    CERN Document Server

    1973-01-01

    The Radiation Chemistry of Macromolecules, Volume II is a collection of papers that discusses radiation chemistry of specific systems. Part 1 deals with radiation chemistry of substituted vinyl polymers, particularly polypropylene (PP) as its structure is intermediate between polyethylene and polyisobutylene. This part also discusses polypropylene oxide (PPOx) for it can be prepared in the atactic, isotactic, and optically active forms. One paper focuses on the fundamental chemical processes and the changes in physical properties that give rise to many different applications of polystyrene. An

  10. Effect of Pore Structure and Chemistry on the Performance of Activated Oil Sands Petroleum Coke Electrodes for use in Electrochemical Double-Layer Capacitors

    Science.gov (United States)

    Zuliani, Jocelyn Ellen

    Electrical energy storage is a limiting barrier to widespread usage and commercialization of sustainable and renewable energy sources, such as wind and solar energy, as well as integration of electric vehicles. Electrochemical double-layer capacitors (EDLCs) are a promising energy storage technology that offers the benefits of high power density, long cycle life, rapid charging rates, and moderate energy density. The energy storage mechanism of EDLCs is physical ion adsorption on the surface of porous carbon electrodes. This thesis is an investigation of three different sections relating to EDLCs: 1) techniques to properly characterize novel porous carbon electrode materials, 2) investigation of activated oil sands petroleum coke (APC) as the electrode material for EDLCs, and 3) a systematic study of the effects of porous carbon structure and chemistry on EDLC performance. In the first section, it was shown that variations in operating conditions and testing techniques can lead to discrepancies in measured and reported capacitance. Therefore, it was concluded that a standardized approach is necessary in order to properly compare different porous carbon electrodes. In the second section, APC was investigated as a novel electrode material for EDLCs. PetCoke is a carbon dense material that can be activated with potassium hydroxide to generate high surface area porous carbon materials. These materials show promising electrochemical performance in EDLCs, with capacitance values up to 400 Fg-1 in 4M potassium hydroxide aqueous electrolytes, depending on the operating conditions. Additionally, the power density of these materials is comparable to that of other carbon nanomaterials, which are more costly and challenging to produce. Finally, the third section investigates the relationship between measured capacitance, and carbon macrostructure, meso-structure, microstructure, and oxygen content. In each of these studies, the desired parameter was varied, while all others

  11. The biology and chemistry of the zoanthamine alkaloids.

    Science.gov (United States)

    Behenna, Douglas C; Stockdill, Jennifer L; Stoltz, Brian M

    2008-01-01

    Marine natural products have long played an important role in natural products chemistry and drug discovery. Mirroring the rich variety and complicated interactions of the marine environment, the substances isolated from sea creatures tend to be incredibly diverse in both molecular structure and biological activity. The natural products isolated from the polyps of marine zoanthids are no exception. The zoanthamine alkaloids, the first of which were isolated over 20 years ago, are of particular interest to the synthetic community because they feature a novel structural framework and exhibit a broad range of biological activities. In this Review, we summarize the major contributions to understanding the zoanthamine natural products with regard to their isolation and structure determination, as well as studies on their biological activity and total synthesis.

  12. Magnetism and structural chemistry of the n=2 Ruddlesden-Popper phase La3LiMnO7

    International Nuclear Information System (INIS)

    Battle, Peter D.; Burley, Jonathan C.; Gallon, Daniel J.; Grey, Clare P.; Sloan, Jeremy

    2004-01-01

    Polycrystalline samples of the n=2 Ruddlesden-Popper phase La 3 LiMnO 7 have been prepared and characterized. X-ray and neutron diffraction suggest that the structure is tetragonal with a disordered distribution of Li and Mn cations over the octahedral sites, but 6 Li MAS NMR shows that the Li and Mn are 1:1 ordered locally. Electron microscopy shows that the stacking of the cation-ordered, perovskite-like bilayers along the crystallographic z-axis is disordered on the distance scale sampled by X-ray and neutron diffraction. Magnetometry data and neutron diffraction data collected at 2 K together suggest that the Mn cations within each structural domain order antiferromagnetically at 14 K, but that the disorder along z prevents the establishment of long-range magnetic order

  13. The application of structure-based assessment to support safety and chemistry diligence to manage genotoxic impurities in active pharmaceutical ingredients during drug development.

    Science.gov (United States)

    Dobo, Krista L; Greene, Nigel; Cyr, Michelle O; Caron, Stéphane; Ku, Warren W

    2006-04-01

    Starting materials and intermediates used to synthesize pharmaceuticals are reactive in nature and may be present as impurities in the active pharmaceutical ingredient (API) used for preclinical safety studies and clinical trials. Furthermore, starting materials and intermediates may be known or suspected mutagens and/or carcinogens. Therefore, during drug development due diligence need be applied from two perspectives (1) to understand potential mutagenic and carcinogenic risks associated with compounds used for synthesis and (2) to understand the capability of synthetic processes to control genotoxic impurities in the API. Recently, a task force comprised of experts from pharmaceutical industry proposed guidance, with recommendations for classification, testing, qualification and assessing risk of genotoxic impurities. In our experience the proposed structure-based classification, has differentiated 75% of starting materials and intermediates as mutagenic and non-mutagenic with high concordance (92%) when compared with Ames results. Structure-based assessment has been used to identify genotoxic hazards, and prompted evaluation of fate of genotoxic impurities in API. These two assessments (safety and chemistry) culminate in identification of genotoxic impurities known or suspected to exceed acceptable levels in API, thereby triggering actions needed to assure appropriate control and measurement methods are in place. Hypothetical case studies are presented demonstrating this multi-disciplinary approach.

  14. RITRACKS: A Software for Simulation of Stochastic Radiation Track Structure, Micro and Nanodosimetry, Radiation Chemistry and DNA Damage for Heavy Ions

    Science.gov (United States)

    Plante, I; Wu, H

    2014-01-01

    The code RITRACKS (Relativistic Ion Tracks) has been developed over the last few years at the NASA Johnson Space Center to simulate the effects of ionizing radiations at the microscopic scale, to understand the effects of space radiation at the biological level. The fundamental part of this code is the stochastic simulation of radiation track structure of heavy ions, an important component of space radiations. The code can calculate many relevant quantities such as the radial dose, voxel dose, and may also be used to calculate the dose in spherical and cylindrical targets of various sizes. Recently, we have incorporated DNA structure and damage simulations at the molecular scale in RITRACKS. The direct effect of radiations is simulated by introducing a slight modification of the existing particle transport algorithms, using the Binary-Encounter-Bethe model of ionization cross sections for each molecular orbitals of DNA. The simulation of radiation chemistry is done by a step-by-step diffusion-reaction program based on the Green's functions of the diffusion equation]. This approach is also used to simulate the indirect effect of ionizing radiation on DNA. The software can be installed independently on PC and tablets using the Windows operating system and does not require any coding from the user. It includes a Graphic User Interface (GUI) and a 3D OpenGL visualization interface. The calculations are executed simultaneously (in parallel) on multiple CPUs. The main features of the software will be presented.

  15. Use of green chemistry methods in the extraction of dietary fibers from cactus rackets (Opuntia ficus indica): Structural and microstructural studies.

    Science.gov (United States)

    Cheikh Rouhou, Marwa; Abdelmoumen, Souhir; Thomas, Sabu; Attia, Hamadi; Ghorbel, Dorra

    2018-05-23

    This work aims to compare the development of three green chemistry methods in the extraction of cactus (Opuntia ficus indica) dietary fibers. The influence of extraction conditions (solvent nature: water, lemon juice and ethanol; extraction process: maceration and steam explosion; extraction time: 30 min, 1 h, 3 h, 5 h) on the chemical and structural composition was studied. Fourier Transform Infrared (FTIR) spectroscopy proved that all treatments do not affect the cellulose structure and could induce the reduction of hemicelluloses and lignin content. The steam treatment with lemon juice was the best treatment in term of quality of the fibers extracted. Through X-ray Diffraction (XRD) analysis, it was demonstrated that this treatment contributed to the destruction of the amorphous phase with preservation of the crystalline phase. Scanning electron microscopy (SEM) showed that the microstructure of the sample surface was uniform and contains arranged fibers. Atomic Force Microscopy (AFM) revealed fibers with 80 nm of diameter. Copyright © 2018. Published by Elsevier B.V.

  16. Characterization of local chemistry and disorder in synthetic and natural α-Al2O3 materials by X-ray absorption near edge structure spectroscopy

    International Nuclear Information System (INIS)

    Mottana, A.; Murata, T.

    1997-11-01

    X-ray absorption fine spectra at the Al K-edge were measured experimentally on and calculated theoretically via the multiple-scattering formalism for a chemically pure and physically perfect synthetic α-Al 2 O 3 (α-alumina), a natural 'ruby/sapphire' (corundum) and a series of artificial 'corundum' produced for technical purposes and used as geochemical standards. The Al K-edge spectra differ despite of the identical coordination (short-range arrangement) assumed by O around Al, and vary slightly in relation to the slightly different chemistries of the materials (substitutional defects) as well as on account of the location taken by foreign atoms in the structural lattices (positional defects). A quantitative treatment of the observed changes is made in terms of short-range modification of the coordination polyhedron and of medium- to long-range modifications in the overall structure; both of them induced by substitutions. In some technical 'corundums', the impurities of admixed 'β-alumina', where Al is both in four- and six-fold coordination, produce another small but detectable effect on Al K-edges. Therefore, XAFS spectroscopy proves its potentials for both measuring a light element such as Al, and detecting minor coordination changes and substitutions (ca. 1∼3 wt.% as oxide) of the absorber by dilute other atoms, at least under favorable conditions as those occurring in this system are

  17. Self-assembled materials and supramolecular chemistry within microfluidic environments: from common thermodynamic states to non-equilibrium structures.

    Science.gov (United States)

    Sevim, S; Sorrenti, A; Franco, C; Furukawa, S; Pané, S; deMello, A J; Puigmartí-Luis, J

    2018-05-01

    Self-assembly is a crucial component in the bottom-up fabrication of hierarchical supramolecular structures and advanced functional materials. Control has traditionally relied on the use of encoded building blocks bearing suitable moieties for recognition and interaction, with targeting of the thermodynamic equilibrium state. On the other hand, nature leverages the control of reaction-diffusion processes to create hierarchically organized materials with surprisingly complex biological functions. Indeed, under non-equilibrium conditions (kinetic control), the spatio-temporal command of chemical gradients and reactant mixing during self-assembly (the creation of non-uniform chemical environments for example) can strongly affect the outcome of the self-assembly process. This directly enables a precise control over material properties and functions. In this tutorial review, we show how the unique physical conditions offered by microfluidic technologies can be advantageously used to control the self-assembly of materials and of supramolecular aggregates in solution, making possible the isolation of intermediate states and unprecedented non-equilibrium structures, as well as the emergence of novel functions. Selected examples from the literature will be used to confirm that microfluidic devices are an invaluable toolbox technology for unveiling, understanding and steering self-assembly pathways to desired structures, properties and functions, as well as advanced processing tools for device fabrication and integration.

  18. Mechanical Stress in InP Structures Etched in an Inductively Coupled Plasma Reactor with Ar/Cl2/CH4 Plasma Chemistry

    Science.gov (United States)

    Landesman, Jean-Pierre; Cassidy, Daniel T.; Fouchier, Marc; Pargon, Erwine; Levallois, Christophe; Mokhtari, Merwan; Jimenez, Juan; Torres, Alfredo

    2018-02-01

    We investigated the crystal lattice deformation that can occur during the etching of structures in bulk InP using SiNx hard masks with Ar/Cl2/CH4 chemistries in an inductively coupled plasma reactor. Two techniques were used: degree of polarization (DOP) of the photo-luminescence, which gives information on the state of mechanical stress present in the structures, and spectrally resolved cathodo-luminescence (CL) mapping. This second technique also provides elements on the mechanical stress in the samples through analysis of the spectral shift of the CL intrinsic emission lines. Preliminary DOP mapping experiments have been conducted on the SiNx hard mask patterns without etching the underlying InP. This preliminary study demonstrated the potential of DOP to map mechanical stress quantitatively in the structures. In a second step, InP patterns with various widths between 1 μm and 20 μm, and various depths between 1 μm and 6 μm, were analyzed by the 2 techniques. DOP measurements were made both on the (100) top surface of the samples and on the (110) cleaved cross section. CL measurements were made only from the (100) surface. We observed that inside the etched features, close to the vertical etched walls, there is always some compressive deformation, while it is tensile just outside the etched features. The magnitude of these effects depends on the lateral and depth dimensions of the etched structures, and on the separation between them (the tensile deformation increases between them due to some kind of proximity effect when separation decreases).

  19. Structure and tensile properties of Fe-Cr model alloy strengthened by nano-scale NbC particles derived from controlled crystallization of Nb-rich clusters

    Energy Technology Data Exchange (ETDEWEB)

    Dai, Lei [College of Materials and Chemical Engineering, Three Gorges University, Yichang 443002 (China); Guo, Qianying [State Key Lab of Hydraulic Engineering Simulation and Safety, School of Material Science and Engineering, Tianjin University, Tianjin 300354 (China); Liu, Yongchang, E-mail: licmtju@163.com [State Key Lab of Hydraulic Engineering Simulation and Safety, School of Material Science and Engineering, Tianjin University, Tianjin 300354 (China); Yu, Liming; Li, Huijun [State Key Lab of Hydraulic Engineering Simulation and Safety, School of Material Science and Engineering, Tianjin University, Tianjin 300354 (China)

    2016-09-30

    This article describes the microstructural evolution and tensile properties of Fe-Cr model alloy strengthened by nano-scale NbC particles. According to the results obtained from X-ray diffraction and transmission electron microscope with Energy Dispersive Spectrometer, the bcc ultrafine grains and the disordered phase of Nb-rich nano-clusters were observed in the milled powders. The hot pressing (HP) resulted in a nearly equiaxed ferritic grains and dispersed nano-scale NbC (~8 nm) particles. The microstructure studies reveal that the formation of NbC nanoparticles is composed of nucleation and growth of the Nb-rich nano-clusters involving diffusion of their component. At room temperature the material exhibits an ultimate tensile strength of 700 MPa, yield strength of 650 MPa, and total elongation of 11.7 pct. The fracture surface studies reveal that a typical ductile fracture mode has occurred during tensile test.

  20. Chemical sensitive interfacial free volume studies of nanophase Al-rich alloys

    International Nuclear Information System (INIS)

    Lechner, W.; Puff, W.; Wuerschum, R.; Wilde, G.

    2006-01-01

    Full text: Al-based nanocrystalline alloys have attracted substantial interest due to their outstanding mechanical properties. These alloys can be obtained by crystallization of melt-spun amorphous precursors or by grain refinement upon repeated cold-rolling of elemental layers. For both synthesis routes, the nanocrystallization process is sensitively affected by interfacial chemistry and free volumes. In order to contribute to an atomistic understanding of the interfacial structure and processes during nanocrystallization, the present work deals with studies of interfacial free volumes by means of positron-annihilation-spectroscopy. In addition to positron lifetime spectroscopy which yields information on the size of free volumes, coincident Doppler broadening of the positron-electron annihilation photons is applied as novel technique for studying the chemistry of interfaces in nanophase materials on an atomistic scale. Al-rich alloys of the above mentioned synthesis routes were studied in this work. (author)