WorldWideScience

Sample records for complex elucidates select

  1. Transcription initiation complex structures elucidate DNA opening.

    Science.gov (United States)

    Plaschka, C; Hantsche, M; Dienemann, C; Burzinski, C; Plitzko, J; Cramer, P

    2016-05-19

    Transcription of eukaryotic protein-coding genes begins with assembly of the RNA polymerase (Pol) II initiation complex and promoter DNA opening. Here we report cryo-electron microscopy (cryo-EM) structures of yeast initiation complexes containing closed and open DNA at resolutions of 8.8 Å and 3.6 Å, respectively. DNA is positioned and retained over the Pol II cleft by a network of interactions between the TATA-box-binding protein TBP and transcription factors TFIIA, TFIIB, TFIIE, and TFIIF. DNA opening occurs around the tip of the Pol II clamp and the TFIIE 'extended winged helix' domain, and can occur in the absence of TFIIH. Loading of the DNA template strand into the active centre may be facilitated by movements of obstructing protein elements triggered by allosteric binding of the TFIIE 'E-ribbon' domain. The results suggest a unified model for transcription initiation with a key event, the trapping of open promoter DNA by extended protein-protein and protein-DNA contacts.

  2. Lanthanide-cyclodextrin complexes as probes for elucidating optical purity by NMR spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Wenzel, T.J.; Bogyo, M.S.; Lebeau, E.L. (Bates College, Lewiston, ME (United States))

    1994-06-01

    A multidentate ligand is bonded to cyclodextrins by the reaction of diethylenetriaminepentaacetic dianhydride with 6-mono- and 2-mono(ethylenediamine) derivatives of cyclodextrin. Adding Dy(III) to the cyclodextrin derivatives enhances the enantiomeric resolution in the [sup 1]H NMR spectra of carbionoxamine maleate, doxylamine succinate, pheniramine maleate, propranolol hydrochloride, and tryptophan. The enhancement is more pronounced with the secondary derivative. The Dy(III)-induced shifts can be used to elucidate the geometry of cyclodextrin-substrate inclusion complexes. Lanthanide-induced shifts are reported for complexes of aspartame, tryptophan, propranolol, and 1-anilino-8-naphthalenesulfonate with cyclodextrins, and the relative magnitudes of the shifts agree with previously reported structures of the complexes. 37 refs., 9 figs., 5 tabs.

  3. Study of application technology of ultra-high speed computer to the elucidation of complex phenomena

    International Nuclear Information System (INIS)

    Sekiguchi, Tomotsugu

    1996-01-01

    The basic design of numerical information library in the decentralized computer network was explained at the first step of constructing the application technology of ultra-high speed computer to the elucidation of complex phenomena. Establishment of the system makes possible to construct the efficient application environment of ultra-high speed computer system to be scalable with the different computing systems. We named the system Ninf (Network Information Library for High Performance Computing). The summary of application technology of library was described as follows: the application technology of library under the distributed environment, numeric constants, retrieval of value, library of special functions, computing library, Ninf library interface, Ninf remote library and registration. By the system, user is able to use the program concentrating the analyzing technology of numerical value with high precision, reliability and speed. (S.Y.)

  4. DFT and EXAFS, mutually enhancing tools for structure elucidation of Tc complexes

    International Nuclear Information System (INIS)

    Breynaert, E.; Bruggeman, C.; Maes, A.

    2005-01-01

    Full text of publication follows: The redox-sensitive fission product technetium-99 (Tc) is of great interest in nuclear waste disposal studies because of its potential for contaminating the geosphere due to its very long half-life (2.13 x 10 5 year) and high mobility under oxidising conditions, where technetium forms pertechnetate (TcO 4 - ). Under suitable reducing conditions, e.g. in the presence of an iron(II) containing solid phase which can act as an electron donor, the solubility can be limited by the reduction of pertechnetate followed by the formation of a surface precipitate [1]. However, by association with mobile humic substances (HS) or other associating/complexing species, the solubility of reduced Tc species may be drastically enhanced [2]. The elucidation of the identity and geometrical structure of the species causing this enhanced solubility often remains a difficult issue. Extended X-Ray Absorption Fluorescence Spectroscopy/ X-Ray Absorption Near Edge Spectroscopy (EXAFS/XANES) analysis can be very helpful to determine the molecular surroundings of reduced Tc organic complexes of Tc(IV) colloid-HS-associations. The interpretation of the EXAFS spectra is however not a straightforward process due to the possibly strong influence of multiple scattering paths on the spectra. Contrary to single scattering analysis which can be easily performed on the experimental EXAFS spectra, multiple scattering analysis can only be done, based on good approximations of the possible geometrical structures of the species under consideration. It has been shown that the Density Functional Theory (DFT) can be used to perform geometry optimizations of technetium species and therefore can be utilized to predict the structure of technetium complexes [3]. The success and computational effort needed for such structure predictions are however highly dependant on the quality of the initial structure from which the geometry optimization is started. Single scattering analysis of

  5. Elucidation of Mechanisms and Selectivities of Metal-Catalyzed Reactions using Quantum Chemical Methodology.

    Science.gov (United States)

    Santoro, Stefano; Kalek, Marcin; Huang, Genping; Himo, Fahmi

    2016-05-17

    solving complex problems and proposing new detailed reaction mechanisms that rationalize the experimental findings. For each of the considered reactions, a consistent mechanism is presented, the experimentally observed selectivities are reproduced, and their sources are identified. Reproducing selectivities requires high accuracy in computing relative transition state energies. As demonstrated by the results summarized in this Account, this accuracy is possible with the use of the presented methodology, benefiting of course from a large extent of cancellation of systematic errors. It is argued that as the employed models become larger, the number of rotamers and isomers that have to be considered for every stationary point increases and a careful assessment of their energies is therefore necessary in order to ensure that the lowest energy conformation is located. This issue constitutes a bottleneck of the investigation in some cases and is particularly important when analyzing selectivities, since small energy differences need to be reproduced.

  6. Product ion isotopologue pattern: A tool to improve the reliability of elemental composition elucidations of unknown compounds in complex matrices.

    Science.gov (United States)

    Kaufmann, A; Walker, S; Mol, G

    2016-04-15

    Elucidation of the elemental compositions of unknown compounds (e.g., in metabolomics) generally relies on the availability of accurate masses and isotopic ratios. This study focuses on the information provided by the abundance ratio within a product ion pair (monoisotopic versus the first isotopic peak) when isolating and fragmenting the first isotopic ion (first isotopic mass spectrum) of the precursor. This process relies on the capability of the quadrupole within the Q Orbitrap instrument to isolate a very narrow mass window. Selecting only the first isotopic peak (first isotopic mass spectrum) leads to the observation of a unique product ion pair. The lighter ion within such an isotopologue pair is monoisotopic, while the heavier ion contains a single carbon isotope. The observed abundance ratio is governed by the percentage of carbon atoms lost during the fragmentation and can be described by a hypergeometric distribution. The observed carbon isotopologue abundance ratio (product ion isotopologue pattern) gives reliable information regarding the percentage of carbon atoms lost in the fragmentation process. It therefore facilitates the elucidation of the involved precursor and product ions. Unlike conventional isotopic abundances, the product ion isotopologue pattern is hardly affected by isobaric interferences. Furthermore, the appearance of these pairs greatly aids in cleaning up a 'matrix-contaminated' product ion spectrum. The product ion isotopologue pattern is a valuable tool for structural elucidation. It increases confidence in results and permits structural elucidations for heavier ions. This tool is also very useful in elucidating the elemental composition of product ions. Such information is highly valued in the field of multi-residue analysis, where the accurate mass of product ions is required for the confirmation process. Copyright © 2016 John Wiley & Sons, Ltd. Copyright © 2016 John Wiley & Sons, Ltd.

  7. How to elucidate and control the redox sequence in vinylbenzoate and vinylpyridine bridged diruthenium complexes

    Czech Academy of Sciences Publication Activity Database

    Pevny, F.; Winter, R. F.; Sarkar, B.; Záliš, Stanislav

    2010-01-01

    Roč. 39, č. 34 (2010), s. 8000-8011 ISSN 1477-9226 R&D Projects: GA AV ČR KAN100400702; GA MŠk 1P05OC068; GA MŠk OC09043 Institutional research plan: CEZ:AV0Z40400503 Keywords : vinylbenzoate-bridged diruthenium complexes * electrochemistry * vinylpyridine-bridged diruthenium complexes Subject RIV: CG - Electrochemistry Impact factor: 3.647, year: 2010

  8. Elucidating the Protonation Site of Vanadium Peroxide Complexes And the Implications for Biomimetic Catalysis

    Energy Technology Data Exchange (ETDEWEB)

    Schneider, C.J.; Penner-Hahn, J.E.; Pecoraro, V.L.

    2009-05-27

    Coordination complexes of vanadium(5+) played a key role in understanding the structure and mechanism of vanadium-dependent haloperoxidases, particularly the effects of protonation on peroxide coordination to dioxovanadium(5+) species, and in the activation of the peroxo-oxovanadium(5+) complex for substrate oxidation. There has been no spectroscopic evidence that could test the presence of a hydroxo intermediate in a catalytically active oxovanadium(5+) complex. Herein we report the use of the pre-edge transition in X-ray absorption spectroscopy as a spectroscopic signature for V{double_bond}O bonding. Displacement of oxo donors with hydrogen peroxide or chloride donors dramatically decreases the pre-edge intensity, confirming that the source of the intense pre-edge feature is closely related to the {pi}-bonding associated with the V{double_bond}O. Protonation of a catalytically active tripodal amine oxovanadium(5+) complex has no affect on the pre-edge intensity and, therefore, rules out the possibility of a hydroxo intermediate in the catalytic cycle.

  9. Syntheses, structural elucidation, thermal properties, theoretical quantum chemical studies (DFT and biological studies of barbituric–hydrazone complexes

    Directory of Open Access Journals (Sweden)

    Amina A. Soayed

    2015-03-01

    Full Text Available Condensation of barbituric acid with hydrazine hydrate yielded barbiturichydrazone (L which was characterized using IR, 1H NMR and mass spectra. The Co(II, Ni(II and Cu(II complexes derived from this ligand have been synthesized and structurally characterized by elemental analyses, spectroscopic methods (IR, UV–Vis and ESR and thermal analyses (TGA, DTG and DTA and the structures were further elucidated using quantum chemical density functional theory. Complexes of L were found to have the ML.nH2O stoichiometry with either tetrahedral or octahedral geometry. The ESR data showed the Cu(II complex to be in a tetragonal geometry. Theoretical investigation of the electronic structure of metal complexes at the TD-DFT/B3LYP level of theory has been carried out and discussed. The fundamental vibrational wavenumbers were calculated and a good agreement between observed and scaled calculated wavenumbers was achieved. Thermal studies were performed to deduce the stabilities of the ligand and complexes. Thermodynamic parameters, such as the order of reactions (n, activation energy ΔE∗, enthalpy of reaction ΔH∗ and entropy ΔS∗ were calculated from DTA curves using Horowitz–Metzger method. The ligand L and its complexes have been screened for their antifungal and antibacterial activities and were found to possess better biological activities compared to those of unsubstituted barbituric acid complexes.

  10. Selection for components of complex characteristics - indirect selection

    International Nuclear Information System (INIS)

    Haensel, H.

    1984-01-01

    A hierarchy of complexity exists in plant characteristics. The efficiency of indirect selection for a complex characteristic by a sub-trait depends on the heritability of the complex characteristic (hsub(c)), the heritability of the sub-trait (hsub(s)), and the genotypic correlation between sub-trait and complex characteristic (rsub(s.c)). In 1961 hsub(s)Xrsub(s.c)>hsub(c) was postulated, when indirect selection becomes more efficient than direct selection. Numerical examples for this relationship are given and a table for indirect selection for yield in wheat is elaborated. Efficiency ranking of sub-traits in indirect selection may change with climate, conditions of cultivation, the level of other sub-traits, the level of the complex characteristic already reached by breeding, and the breeding material. An example shows that regression analysis for different sub-traits on the same complex characteristic, and an estimation of the differences of the within - and the between - variety slopes, may help to select the more efficient sub-trait. In another example, where simultaneous selection was made for two polygenic characteristics, one directly and the other indirectly by two sub-traits, less than half the F 5 -lines had to be continued, when using the more efficient sub-trait. (author)

  11. Well-defined azazirconacyclopropane complexes supported on silica structurally determined by 2D NMR comparative elucidation

    KAUST Repository

    El Eter, Mohamad; Hamzaoui, Bilel; Abou-Hamad, Edy; Pelletier, Jeremie; Basset, Jean-Marie

    2013-01-01

    Grafting of Zr(NMe2)4 on mesoporous silica SBA-15 afforded selectively well-defined surface species SiOZr(NMe2) (η2NMeCH2). 2D solid-state NMR (1H- 13C HETCOR, Multiple Quantum) experiments have shown a unique structural rearrangement occurring on the immobilised zirconium bis methylamido ligand. © The Royal Society of Chemistry 2013.

  12. Elucidating Duramycin’s Bacterial Selectivity and Mode of Action on the Bacterial Cell Envelope

    Directory of Open Access Journals (Sweden)

    Sahar Hasim

    2018-02-01

    Full Text Available The use of naturally occurring antimicrobial peptides provides a promising route to selectively target pathogenic agents and to shape microbiome structure. Lantibiotics, such as duramycin, are one class of bacterially produced peptidic natural products that can selectively inhibit the growth of other bacteria. However, despite longstanding characterization efforts, the microbial selectivity and mode of action of duramycin are still obscure. We describe here a suite of biological, chemical, and physical characterizations that shed new light on the selective and mechanistic aspects of duramycin activity. Bacterial screening assays have been performed using duramycin and Populus-derived bacterial isolates to determine species selectivity. Lipidomic profiles of selected resistant and sensitive strains show that the sensitivity of Gram-positive bacteria depends on the presence of phosphatidylethanolamine (PE in the cell membrane. Further the surface and interface morphology were studied by high resolution atomic force microscopy and showed a progression of cellular changes in the cell envelope after treatment with duramycin for the susceptible bacterial strains. Together, these molecular and cellular level analyses provide insight into duramycin’s mode of action and a better understanding of its selectivity.

  13. Reduction theories elucidate the origins of complex biological rhythms generated by interacting delay-induced oscillations.

    Directory of Open Access Journals (Sweden)

    Ikuhiro Yamaguchi

    Full Text Available Time delay is known to induce sustained oscillations in many biological systems such as electroencephalogram (EEG activities and gene regulations. Furthermore, interactions among delay-induced oscillations can generate complex collective rhythms, which play important functional roles. However, due to their intrinsic infinite dimensionality, theoretical analysis of interacting delay-induced oscillations has been limited. Here, we show that the two primary methods for finite-dimensional limit cycles, namely, the center manifold reduction in the vicinity of the Hopf bifurcation and the phase reduction for weak interactions, can successfully be applied to interacting infinite-dimensional delay-induced oscillations. We systematically derive the complex Ginzburg-Landau equation and the phase equation without delay for general interaction networks. Based on the reduced low-dimensional equations, we demonstrate that diffusive (linearly attractive coupling between a pair of delay-induced oscillations can exhibit nontrivial amplitude death and multimodal phase locking. Our analysis provides unique insights into experimentally observed EEG activities such as sudden transitions among different phase-locked states and occurrence of epileptic seizures.

  14. Structural and Functional Elucidation of Yeast Lanosterol 14α-Demethylase in Complex with Agrochemical Antifungals

    Science.gov (United States)

    Sagatova, Alia A.; Keniya, Mikhail V.; Negroni, Jacopo; Wilson, Rajni K.; Woods, Matthew A.; Monk, Brian C.

    2016-01-01

    Azole antifungals, known as demethylase inhibitors (DMIs), target sterol 14α-demethylase (CYP51) in the ergosterol biosynthetic pathway of fungal pathogens of both plants and humans. DMIs remain the treatment of choice in crop protection against a wide range of fungal phytopathogens that have the potential to reduce crop yields and threaten food security. We used a yeast membrane protein expression system to overexpress recombinant hexahistidine-tagged S. cerevisiae lanosterol 14α-demethylase and the Y140F or Y140H mutants of this enzyme as surrogates in order characterize interactions with DMIs. The whole-cell antifungal activity (MIC50 values) of both the R- and S-enantiomers of tebuconazole, prothioconazole (PTZ), prothioconazole-desthio, and oxo-prothioconazole (oxo-PTZ) as well as for fluquinconazole, prochloraz and a racemic mixture of difenoconazole were determined. In vitro binding studies with the affinity purified enzyme were used to show tight type II binding to the yeast enzyme for all compounds tested except PTZ and oxo-PTZ. High resolution X-ray crystal structures of ScErg11p6×His in complex with seven DMIs, including four enantiomers, reveal triazole-mediated coordination of all compounds and the specific orientation of compounds within the relatively hydrophobic binding site. Comparison with CYP51 structures from fungal pathogens including Candida albicans, Candida glabrata and Aspergillus fumigatus provides strong evidence for a highly conserved CYP51 structure including the drug binding site. The structures obtained using S. cerevisiae lanosterol 14α-demethylase in complex with these agrochemicals provide the basis for understanding the impact of mutations on azole susceptibility and a platform for the structure-directed design of the next-generation of DMIs. PMID:27907120

  15. Constructing Markov State Models to elucidate the functional conformational changes of complex biomolecules

    KAUST Repository

    Wang, Wei

    2017-10-06

    The function of complex biomolecular machines relies heavily on their conformational changes. Investigating these functional conformational changes is therefore essential for understanding the corresponding biological processes and promoting bioengineering applications and rational drug design. Constructing Markov State Models (MSMs) based on large-scale molecular dynamics simulations has emerged as a powerful approach to model functional conformational changes of the biomolecular system with sufficient resolution in both time and space. However, the rapid development of theory and algorithms for constructing MSMs has made it difficult for nonexperts to understand and apply the MSM framework, necessitating a comprehensive guidance toward its theory and practical usage. In this study, we introduce the MSM theory of conformational dynamics based on the projection operator scheme. We further propose a general protocol of constructing MSM to investigate functional conformational changes, which integrates the state-of-the-art techniques for building and optimizing initial pathways, performing adaptive sampling and constructing MSMs. We anticipate this protocol to be widely applied and useful in guiding nonexperts to study the functional conformational changes of large biomolecular systems via the MSM framework. We also discuss the current limitations of MSMs and some alternative methods to alleviate them.

  16. NMR of α-synuclein–polyamine complexes elucidates the mechanism and kinetics of induced aggregation

    Science.gov (United States)

    Fernández, Claudio O; Hoyer, Wolfgang; Zweckstetter, Markus; Jares-Erijman, Elizabeth A; Subramaniam, Vinod; Griesinger, Christian; Jovin, Thomas M

    2004-01-01

    The aggregation of α-synuclein is characteristic of Parkinson's disease (PD) and other neurodegenerative synucleinopathies. The 140-aa protein is natively unstructured; thus, ligands binding to the monomeric form are of therapeutic interest. Biogenic polyamines promote the aggregation of α-synuclein and may constitute endogenous agents modulating the pathogenesis of PD. We characterized the complexes of natural and synthetic polyamines with α-synuclein by NMR and assigned the binding site to C-terminal residues 109–140. Dissociation constants were derived from chemical shift perturbations. Greater polyamine charge (+2 → +5) correlated with increased affinity and enhancement of fibrillation, for which we propose a simple kinetic mechanism involving a dimeric nucleation center. According to the analysis, polyamines increase the extent of nucleation by ∼104 and the rate of monomer addition ∼40-fold. Significant secondary structure is not induced in monomeric α-synuclein by polyamines at 15°C. Instead, NMR reveals changes in a region (aa 22–93) far removed from the polyamine binding site and presumed to adopt the β-sheet conformation characteristic of fibrillar α-synuclein. We conclude that the C-terminal domain acts as a regulator of α-synuclein aggregation. PMID:15103328

  17. Atomic substitution in selected high-temperature superconductors: Elucidating the nature of Raman spectra excitations

    Science.gov (United States)

    Hewitt, Kevin Cecil

    2000-10-01

    In this thesis, the effects of atomic substitution on the vibrational and electronic excitations found in the Raman spectra of selected high-temperature superconductors (HTS) are studied. In particular, atomic and isotopic substitution methods have been used to determine the character of features observed in the Raman spectra of Bi2Sr2Ca n-1CunO2 n+4+delta (n = 1 - Bi2201, n = 2 - Bi2212) and YBa2Cu3O7-delta (Y123). In Bi2201, Pb substitution for Bi (and Sr) has led to the reduction and eventual removal of the structural modulation, characteristic of all members of the Bi-family of HTS. The high quality single crystals and our sensitive triple spectrometer enabled identification of a pair of low frequency modes. The modes are determined to arise from shear and compressional rigid-layer vibrations. The normal state of underdoped cuprates is characterized by a pseudogap of unknown origin. In crystals of underdoped Bi2212 a spectral peak found at 590 cm-1, previously attributed to the pairing of quasiparticles (above Tc) and hence to the formation of a normal state pseudogap, has been found to soften by 3.8% with oxygen isotope exchange. In addition, the feature is absent in fully oxygenated and yttrium underdoped crystals. In this study, the first of its kind on underdoped and isotope substituted Bi2212, the feature has been assigned to stretching vibrations of oxygen in the a-b plane. Bi2212 crystals with varying hole concentrations (0.07 Raman scattering experiments that sample the diagonal (B 2g) and principal axes (B1 g) of the BZ have led us to conclude that the superconducting gap possesses dx2-y2 symmetry, in the underdoped and overdoped regimes. It is found that the magnitude of the superconducting gap (Delta(k)) is sensitive to changes in p. Studies of the pair-breaking peak found in the B1g spectra allow us to conclude that the magnitude of the maximum gap (Deltamax) decreases monotonically with increasing hole doping, for p > 0.13. The pair

  18. Free energy landscape of siRNA-polycation complexation: Elucidating the effect of molecular geometry, polymer flexibility, and charge neutralization.

    Directory of Open Access Journals (Sweden)

    Gianvito Grasso

    Full Text Available The success of medical threatments with DNA and silencing interference RNA is strongly related to the design of efficient delivery technologies. Cationic polymers represent an attractive strategy to serve as nucleic-acid carriers with the envisioned advantages of efficient complexation, low cost, ease of production, well-defined size, and low polydispersity index. However, the balance between efficacy and toxicity (safety of these polymers is a challenge and in need of improvement. With the aim of designing more effective polycationic-based gene carriers, many parameters such as carrier morphology, size, molecular weight, surface chemistry, and flexibility/rigidity ratio need to be taken into consideration. In the present work, the binding mechanism of three cationic polymers (polyarginine, polylysine and polyethyleneimine to a model siRNA target is computationally investigated at the atomistic level. In order to better understand the polycationic carrier-siRNA interactions, replica exchange molecular dynamic simulations were carried out to provide an exhaustive exploration of all the possible binding sites, taking fully into account the siRNA flexibility together with the presence of explicit solvent and ions. Moreover, well-tempered metadynamics simulations were employed to elucidate how molecular geometry, polycation flexibility, and charge neutralization affect the siRNA-polycations free energy landscape in term of low-energy binding modes and unbinding free energy barriers. Significant differences among polymer binding modes have been detected, revealing the advantageous binding properties of polyarginine and polylysine compared to polyethyleneimine.

  19. Regional-dependent intestinal permeability and BCS classification: elucidation of pH-related complexity in rats using pseudoephedrine.

    Science.gov (United States)

    Fairstein, Moran; Swissa, Rotem; Dahan, Arik

    2013-04-01

    Based on its lower Log P value relative to metoprolol, a marker for the low/high-permeability (P(eff)) class boundary, pseudoephedrine was provisionally classified as BCS low-permeability compound. On the other hand, following oral administration, pseudoephedrine fraction dose absorbed (F(abs)) and systemic bioavailability approaches 100%. This represents a challenge to the generally recognized P(eff)-F(abs) correlation. The purpose of this study was to elucidate the underlying mechanisms behind the confusion in pseudoephedrine's BCS classification. Pseudoephedrine's BCS solubility class was determined, and its physicochemical properties and intestinal permeability were thoroughly investigated, both in vitro and in vivo in rats, considering the complexity of the whole of the small intestine. Pseudoephedrine was found to be unequivocally a high-solubility compound. All of the permeability studies revealed similar phenomenon; at any given intestinal segment/pH, the permeability of metoprolol was higher than that of pseudoephedrine, however, as the intestinal region becomes progressively distal, and the pH gradually increases, pseudoephedrine's permeability rises above that of metoprolol in the former segment. This unique permeability pattern likely explains pseudoephedrine's complete absorption. In conclusion, pseudoephedrine is a BCS Class I compound; no discrepancy between P(eff) and F(abs) is involved in its absorption. Rather, it reflects the complexity behind P(eff) when considering the whole of the intestine. We propose to allow high-permeability classification to drugs with P(eff) that matches/exceeds the low/high class benchmark anywhere throughout the intestinal tract and not restricted necessarily to the jejunum.

  20. [BMIM][PF6] Incorporation Doubles CO2 Selectivity of ZIF-8: Elucidation of Interactions and Their Consequences on Performance.

    Science.gov (United States)

    Kinik, F Pelin; Altintas, Cigdem; Balci, Volkan; Koyuturk, Burak; Uzun, Alper; Keskin, Seda

    2016-11-16

    Experiments were combined with atomically detailed simulations and density functional theory (DFT) calculations to understand the effect of incorporation of an ionic liquid (IL), 1-n-butyl-3-methylimidazolium hexafluorophosphate ([BMIM][PF 6 ]), into a metal organic framework (MOF with a zeolitic imidazolate framework), ZIF-8, on the CO 2 separation performance. The interactions between [BMIM][PF 6 ] and ZIF-8 were examined in deep detail, and their consequences on CO 2 /CH 4 , CO 2 /N 2 , and CH 4 /N 2 separation have been elucidated by using experimental measurements complemented by DFT calculations and atomically detailed simulations. Results suggest that IL-MOF interactions strongly affect the gas affinity of materials at low pressure, whereas available pore volume plays a key role for gas adsorption at high pressures. Direct interactions between IL and MOF lead to at least a doubling of CO 2 /CH 4 and CO 2 /N 2 selectivities of ZIF-8. These results provide opportunities for rational design and development of IL-incorporated MOFs with exceptional selectivity for target gas separation applications.

  1. Identification of the chemical constituents of Chinese medicine Yi-Xin-Shu capsule by molecular feature orientated precursor ion selection and tandem mass spectrometry structure elucidation.

    Science.gov (United States)

    Wang, Hong-ping; Chen, Chang; Liu, Yan; Yang, Hong-Jun; Wu, Hong-Wei; Xiao, Hong-Bin

    2015-11-01

    The incomplete identification of the chemical components of traditional Chinese medicinal formula has been one of the bottlenecks in the modernization of traditional Chinese medicine. Tandem mass spectrometry has been widely used for the identification of chemical substances. Current automatic tandem mass spectrometry acquisition, where precursor ions were selected according to their signal intensity, encounters a drawback in chemical substances identification when samples contain many overlapping signals. Compounds in minor or trace amounts could not be identified because most tandem mass spectrometry information was lost. Herein, a molecular feature orientated precursor ion selection and tandem mass spectrometry structure elucidation method for complex Chinese medicine chemical constituent analysis was developed. The precursor ions were selected according to their two-dimensional characteristics of retention times and mass-to-charge ratio ranges from herbal compounds, so that all precursor ions from herbal compounds were included and more minor chemical constituents in Chinese medicine were identified. Compared to the conventional automatic tandem mass spectrometry setups, the approach is novel and can overcome the drawback for chemical substances identification. As an example, 276 compounds from the Chinese Medicine of Yi-Xin-Shu capsule were identified. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Using IR spectroscopy and multivariate curve resolution to elucidate mechanism of heat-induced decomposition of an organic complex

    DEFF Research Database (Denmark)

    Karpushkin, Evgeny; Gvozdik, Nataliya; Kucheryavskiy, Sergey V.

    the opportunity to carry out simultaneous thermogravimetry/differential scanning calorimetry analysis and IR/Raman/mass spectrometry investigation of the evolving gaseous products. However, elucidation of the mechanism of the reactions occurring upon heat- ing is not completely straightforward, due to a number...

  3. Regional-Dependent Intestinal Permeability and BCS Classification: Elucidation of pH-Related Complexity in Rats Using Pseudoephedrine

    OpenAIRE

    Fairstein, Moran; Swissa, Rotem; Dahan, Arik

    2013-01-01

    Based on its lower Log P value relative to metoprolol, a marker for the low/high-permeability (Peff) class boundary, pseudoephedrine was provisionally classified as BCS low-permeability compound. On the other hand, following oral administration, pseudoephedrine fraction dose absorbed (Fabs) and systemic bioavailability approaches 100%. This represents a challenge to the generally recognized Peff–Fabs correlation. The purpose of this study was to elucidate the underlying mechanisms behind the ...

  4. Automatic Algorithm Selection for Complex Simulation Problems

    CERN Document Server

    Ewald, Roland

    2012-01-01

    To select the most suitable simulation algorithm for a given task is often difficult. This is due to intricate interactions between model features, implementation details, and runtime environment, which may strongly affect the overall performance. An automated selection of simulation algorithms supports users in setting up simulation experiments without demanding expert knowledge on simulation. Roland Ewald analyzes and discusses existing approaches to solve the algorithm selection problem in the context of simulation. He introduces a framework for automatic simulation algorithm selection and

  5. Elucidating Bioreductive Transformations within Physically Complex Media: Impact on the Fate and Transport of Uranium and Chromium

    International Nuclear Information System (INIS)

    P.M. Jardine; T.L. Bank; M. E. Baldwin; S.E. Fendorf; M.A. Ginder-Vogel; Kukkadapu, M.E.

    2006-01-01

    The greatest challenge to elucidating geochemical and biological chromium reduction in natural sediments is to create a sterile environment without destroying the chemical and physical properties of the system. In this study we determined the potential for geochemical and biological chromium reduction in a naturally reducing soil using carbon amendments and sterilization. To minimize alterations to the sediment samples, soils were sterilized via exposure to ?-irradiation which causes fewer changes in the physical and chemical properties of the soil compared to other methods of sterilization. The objective of our research was to determine if the absence of viable microorganisms significantly affected the extent of chromium reduction in a reducing soil. Our hypothesis was that if geochemical reduction pathways dominated the system then soil sterilization should have little to no effect on the amount and rate of chromium that was reduced. However, if the reduction of chromium in these soils was a synergistic process then significantly different amounts of chromium should be reduced in the sterilized versus non-sterilized samples

  6. Structural elucidation of dendritic host-guest complexes by X-ray crystallography and molecular dynamics simulations

    NARCIS (Netherlands)

    Chang, T.; Pieterse, K.; Broeren, M.A.C.; Kooijman, H.; Spek, A.L.; Hilbers, P.A.J.; Meijer, E.W.

    2007-01-01

    The multiple monovalent binding of adamantyl-urea poly(propyleneimine) dendrimers with carboxylic acid-urea guests was investigated using molecular dynamics simulations and X-ray crystallography to better understand the structure and behavior of the dynamic multivalent complex in solution. The

  7. On the use of X-ray absorption spectroscopy to elucidate the structure of lutetium adenosine mono- and triphosphate complexes.

    Science.gov (United States)

    Mostapha, S; Berthon, C; Fontaine-Vive, F; Gaysinski, M; Guérin, L; Guillaumont, D; Massi, L; Monfardini, I; Solari, P L; Thomas, O P; Charbonnel, M C; Den Auwer, C

    2014-02-01

    Although the physiological impact of the actinide elements as nuclear toxicants has been widely investigated for half a century, a description of their interactions with biological molecules remains limited. It is however of primary importance to better assess the determinants of actinide speciation in cells and more generally in living organisms to unravel the molecular processes underlying actinide transport and deposition in tissues. The biological pathways of this family of elements in case of accidental contamination or chronic natural exposure (in the case of uranium rich soils for instance) are therefore a crucial issue of public health and of societal impact. Because of the high chemical affinity of those actinide elements for phosphate groups and the ubiquity of such chemical functions in biochemistry, phosphate derivatives are considered as probable targets of these cations. Among them, nucleotides and in particular adenosine mono- (AMP) and triphosphate (ATP) nucleotides occur in more chemical reactions than any other compounds on the earth's surface, except water, and are therefore critical target molecules. In the present study, we are interested in trans-plutonium actinide elements, in particular americium and curium that are more rarely considered in environmental and bioaccumulation studies than early actinides like uranium, neptunium and plutonium. A first step in this strategy is to work with chemical analogues like lanthanides that are not radioactive and therefore allow extended physical chemical characterization to be conducted that are difficult to perform with radioactive materials. We describe herein the interaction of lutetium(III) with adenosine AMP and ATP. With AMP and ATP, insoluble amorphous compounds have been obtained with molar ratios of 1:2 and 1:1, respectively. With an excess of ATP, with 1:2 molar ratio, a soluble complex has been obtained. A combination of spectroscopic techniques (IR, NMR, ESI-MS, EXAFS) together with quantum

  8. SELECTED BIBLIOGRAPHY ON SUCCESSION IN COMPLEX ORGANIZATIONS.

    Science.gov (United States)

    THIEMANN, FRANCIS C.

    THIS DOCUMENT LISTS 56 JOURNAL ARTICLES, 18 BOOKS, 10 DOCTORAL DISSERTATIONS, AND TWO UNPUBLISHED PAPERS ON SUCCESSION IN COMPLEX ORGANIZATIONS PUBLISHED BETWEEN 1948 AND 1966. SOCIOLOGY CONTRIBUTED 40 OF THE BIBLIOGRAPHICAL ENTRIES, HISTORY AND POLITICAL SCIENCE 19, EDUCATION 16, PSYCHOLOGY SEVEN, AND BUSINESS FOUR. (HM)

  9. Final Report - Elucidating Bioreductive Transformations within Physically Complex Media: Impact on the Fate and Transport of Uranium and Chromium

    International Nuclear Information System (INIS)

    Benner, Shawn G.; Fendorf, Scott

    2009-01-01

    In situ stabilization (inclusive of natural attenuation) of toxic metals and radionuclides is an attractive approach for remediating many contaminated DOE sites. By immobilizing toxic metals and radionuclides in place, the removal of contaminated water to the surface for treatment as well as the associated disposal costs are avoided. To enhance in situ remediaton, microbiological reductive stabilization of contaminant metals has been, and continues to be, actively explored. It is likely that surface and subsurface microbial activity can alter the redox state of toxic metals and radionuclides, either directly or indirectly, so they are rendered immobile. Furthermore, anaerobic bacterial metabolic products will help to buffer pulses of oxidation, typically from fluxes of nitrate or molecular oxygen, and thus may stabilize reduced contaminants from oxidative mobilization. Uranium and chromium are two elements of particular concern within the DOE complex that, owing to their abundance and toxicity, appear well suited for biologically mediated reductive stabilization. Subsurface microbial activity can alter the redox state of toxic metals and radionuclides, rending them immobile. Imparting an important criterion on the probability that contaminants will undergo reductive stabilization, however, is the chemical and physical heterogeneity of the media. Our research first examined microbially induced transformation of iron (hydr)oxide minerals and their impact on contaminant attenuation. We revealed that in intricate cascade of geochemical reactions is induced by microbially produced Fe(II), and that during transformation contaminants such as U(VI) can be incorporated into the structure, and a set of Fe(II) bearing solids capable of reducing Cr(VI) and stabilizing resulting Cr(III). We also note, however, that common subsurface constituents such as phosphate can modify iron oxide transformation pathways and thus impact contaminant sequestration - 'affecting both Cr and U

  10. Elucidating Bioreductive Transformations within Physically Complex Media: Impact on the Fate and Transport of Uranium and Chromium

    International Nuclear Information System (INIS)

    Fendorf, Scott; Francis, Chris; Jardine, Phil; Benner, Shawn

    2009-01-01

    In situ stabilization (inclusive of natural attenuation) of toxic metals and radionuclides is an attractive approach for remediating many contaminated DOE sites. By immobilizing toxic metals and radionuclides in place, the removal of contaminated water to the surface for treatment as well as the associated disposal costs are avoided. To enhance in situ remediaton, microbiological reductive stabilization of contaminant metals has been, and continues to be, actively explored. It is likely that surface and subsurface microbial activity can alter the redox state of toxic metals and radionuclides, either directly or indirectly, so they are rendered immobile. Furthermore, anaerobic bacterial metabolic products will help to buffer pulses of oxidation, typically from fluxes of nitrate or molecular oxygen, and thus may stabilize reduced contaminants from oxidative mobilization. Uranium and chromium are two elements of particular concern within the DOE complex that, owing to their abundance and toxicity, appear well suited for biologically mediated reductive stabilization. Subsurface microbial activity can alter the redox state of toxic metals and radionuclides, rending them immobile. Imparting an important criterion on the probability that contaminants will undergo reductive stabilization, however, is the chemical and physical heterogeneity of the media. Our research first examined microbially induced transformation of iron (hydr)oxide minerals and their impact on contaminant attenuation. We revealed that in intricate cascade of geochemical reactions is induced by microbially produced Fe(II), and that during transformation contaminants such as U(VI) can be incorporated into the structure, and a set of Fe(II) bearing solids capable of reducing Cr(VI) and stabilizing resulting Cr(III). We also note, however, that common subsurface constituents such as phosphate can modify iron oxide transformation pathways and thus impact contaminant sequestration - affecting both Cr and U

  11. Competitive seeds-selection in complex networks

    Science.gov (United States)

    Zhao, Jiuhua; Liu, Qipeng; Wang, Lin; Wang, Xiaofan

    2017-02-01

    This paper investigates a competitive diffusion model where two competitors simultaneously select a set of nodes (seeds) in the network to influence. We focus on the problem of how to select these seeds such that, when the diffusion process terminates, a competitor can obtain more supports than its opponent. Instead of studying this problem in the game-theoretic framework as in the existing work, in this paper we design several heuristic seed-selection strategies inspired by commonly used centrality measures-Betweenness Centrality (BC), Closeness Centrality (CC), Degree Centrality (DC), Eigenvector Centrality (EC), and K-shell Centrality (KS). We mainly compare three centrality-based strategies, which have better performances in competing with the random selection strategy, through simulations on both real and artificial networks. Even though network structure varies across different networks, we find certain common trend appearing in all of these networks. Roughly speaking, BC-based strategy and DC-based strategy are better than CC-based strategy. Moreover, if a competitor adopts CC-based strategy, then BC-based strategy is a better strategy than DC-based strategy for his opponent, and the superiority of BC-based strategy decreases as the heterogeneity of the network decreases.

  12. Elucidating the role of the phenylacetic acid metabolic complex in the pathogenic activity of Rhizoctonia solani anastomosis group 3.

    Science.gov (United States)

    Bartz, Faith E; Glassbrook, Norman J; Danehower, David A; Cubeta, Marc A

    2012-01-01

    The soil fungus Rhizoctonia solani produces phytotoxic phenylacetic acid (PAA) and hydroxy (OH-) and methoxy (MeO-) derivatives of PAA. However, limited information is available on the specific role that these compounds play in the development of Rhizoctonia disease symptoms and concentration(s) required to induce a host response. Reports that PAA inhibits the growth of R. solani conflict with the established ability of the fungus to produce and metabolize PAA. Experiments were conducted to clarify the role of the PAA metabolic complex in Rhizoctonia disease. In this study the concentration of PAA and derivatives required to induce tomato root necrosis and stem canker, in the absence of the fungus, and the concentration that inhibits mycelial growth of R. solani were determined. The effect of exogenous PAA and derivatives of PAA on tomato seedling growth also was investigated. Growth of tomato seedlings in medium containing 0.1-7.5 mM PAA and derivatives induced necrosis of up to 85% of root system. Canker development resulted from injection of tomato seedling stems with 7.5 mM PAA, 3-OH-PAA, or 3-MeO-PAA. PAA in the growth medium reduced R. solani biomass, with 50% reduction observed at 7.5 mM. PAA, and derivatives were quantified from the culture medium of 14 isolates of R. solani belonging to three distinct anastomosis groups by GC-MS. The quantities ranged from below the limit of detection to 678 nM, below the concentrations experimentally determined to be phytotoxic. Correlation analyses revealed that isolates of R. solani that produced high PAA and derivatives in vitro also caused high mortality on tomato seedlings. The results of this investigation add to the body of evidence that the PAA metabolic complex is involved in Rhizoctonia disease development but do not indicate that production of these compounds is the primary or the only determinant of pathogenicity.

  13. Sleep researchers need to bring Darwin on board: elucidating functions of sleep via adaptedness and natural selection

    OpenAIRE

    Kavanau, Julian L.

    2004-01-01

    The development of neural multifunctionality – given brain regions carrying out more than one function – conferred great efficiency on brain function at early stages of evolution. This applied to animals that led relatively simple lives with few needs for long-term memories, such as many lower invertebrates – many molluscs, echinoderms, worms, etc. As more complex lifestyles and detailed focal vision evolved, needs for self-initiated and reflexive activities increased in frequency, and recogn...

  14. Direct numerical simulation of supercritical gas flow in complex nanoporous media: Elucidating the relationship between permeability and pore space geometry

    Science.gov (United States)

    Landry, C. J.; Prodanovic, M.; Eichhubl, P.

    2015-12-01

    Mudrocks and shales are currently a significant source of natural gas and understanding the basic transport properties of these formations is critical to predicting long-term production, however, the nanoporous nature of mudrocks presents a unique challenge. Mudrock pores are predominantly in the range of 1-100 nm, and within this size range the flow of gas at reservoir conditions will fall within the slip-flow and early transition-flow regime (0.001 clays). Here we present a local effective viscosity lattice Boltzmann model (LEV-LBM) constructed for flow simulation in the slip- and early-transition flow regimes, adapted here for complex geometries. At the macroscopic scale the LEV-LBM is parameterized with local effective viscosities at each node to capture the variance of the mean free path of gas molecules in a bounded system. The LEV-LBM is first validated in simple tube geometries, where excellent agreement with linearized Boltzmann solutions is found for Knudsen numbers up to 1.0. The LEV-LBM is then employed to quantify the length effect on the apparent permeability of tubes, which suggests pore network modeling of flow in the slip and early-transition regime will result in overestimation unless the length effect is considered. Furthermore, the LEV-LBM is used to evaluate the predictive value of commonly measured pore geometry characteristics such as porosity, pore size distribution, and specific solid surface area for the calculation of permeability. We show that bundle of tubes models grossly overestimate apparent permeability, as well as underestimate the increase in apparent permeability with decreasing pressure as a result of excluding topology and pore shape from calculations.

  15. Selective disruption of the AKAP signaling complexes.

    Science.gov (United States)

    Kennedy, Eileen J; Scott, John D

    2015-01-01

    Synthesis of the second messenger cAMP activates a variety of signaling pathways critical for all facets of intracellular regulation. Protein kinase A (PKA) is the major cAMP-responsive effector. Where and when this enzyme is activated has profound implications on the cellular role of PKA. A-Kinase Anchoring Proteins (AKAPs) play a critical role in this process by orchestrating spatial and temporal aspects of PKA action. A popular means of evaluating the impact of these anchored signaling events is to biochemically interfere with the PKA-AKAP interface. Hence, peptide disruptors of PKA anchoring are valuable tools in the investigation of local PKA action. This article outlines the development of PKA isoform-selective disruptor peptides, documents the optimization of cell-soluble peptide derivatives, and introduces alternative cell-based approaches that interrogate other aspects of the PKA-AKAP interface.

  16. Complexity in an Unexpected Place: Quantities in Selected Acquisition Reports

    Science.gov (United States)

    2017-12-01

    by the Army Acquisition Executive contains the following language . As a recently delegated Acquisition Category IC program, the AH-64E Apache...Complexity in an Unexpected Place: Quantities in Selected Acquisition Reports Gregory A. Davis, Project Leader Margaret L. Giles David M. Tate I...F E N S E A N A L Y S E S IDA Paper P-8490 Complexity in an Unexpected Place: Quantities in Selected Acquisition Reports Gregory A. Davis

  17. Structural elucidation of the DFG-Asp in and DFG-Asp out states of TAM kinases and insight into the selectivity of their inhibitors.

    Science.gov (United States)

    Messoussi, Abdellah; Peyronnet, Lucile; Feneyrolles, Clémence; Chevé, Gwénaël; Bougrin, Khalid; Yasri, Aziz

    2014-10-10

    Structural elucidation of the active (DFG-Asp in) and inactive (DFG-Asp out) states of the TAM family of receptor tyrosine kinases is required for future development of TAM inhibitors as drugs. Herein we report a computational study on each of the three TAM members Tyro-3, Axl and Mer. DFG-Asp in and DFG-Asp out homology models of each one were built based on the X-ray structure of c-Met kinase, an enzyme with a closely related sequence. Structural validation and in silico screening enabled identification of critical amino acids for ligand binding within the active site of each DFG-Asp in and DFG-Asp out model. The position and nature of amino acids that differ among Tyro-3, Axl and Mer, and the potential role of these residues in the design of selective TAM ligands, are discussed.

  18. Structural Elucidation of the DFG-Asp in and DFG-Asp out States of TAM Kinases and Insight into the Selectivity of Their Inhibitors

    Directory of Open Access Journals (Sweden)

    Abdellah Messoussi

    2014-10-01

    Full Text Available Structural elucidation of the active (DFG-Asp in and inactive (DFG-Asp out states of the TAM family of receptor tyrosine kinases is required for future development of TAM inhibitors as drugs. Herein we report a computational study on each of the three TAM members Tyro-3, Axl and Mer. DFG-Asp in and DFG-Asp out homology models of each one were built based on the X-ray structure of c-Met kinase, an enzyme with a closely related sequence. Structural validation and in silico screening enabled identification of critical amino acids for ligand binding within the active site of each DFG-Asp in and DFG-Asp out model. The position and nature of amino acids that differ among Tyro-3, Axl and Mer, and the potential role of these residues in the design of selective TAM ligands, are discussed.

  19. NetProt: Complex-based Feature Selection.

    Science.gov (United States)

    Goh, Wilson Wen Bin; Wong, Limsoon

    2017-08-04

    Protein complex-based feature selection (PCBFS) provides unparalleled reproducibility with high phenotypic relevance on proteomics data. Currently, there are five PCBFS paradigms, but not all representative methods have been implemented or made readily available. To allow general users to take advantage of these methods, we developed the R-package NetProt, which provides implementations of representative feature-selection methods. NetProt also provides methods for generating simulated differential data and generating pseudocomplexes for complex-based performance benchmarking. The NetProt open source R package is available for download from https://github.com/gohwils/NetProt/releases/ , and online documentation is available at http://rpubs.com/gohwils/204259 .

  20. Metformin selectively targets redox control of complex I energy transduction

    Directory of Open Access Journals (Sweden)

    Amy R. Cameron

    2018-04-01

    Full Text Available Many guanide-containing drugs are antihyperglycaemic but most exhibit toxicity, to the extent that only the biguanide metformin has enjoyed sustained clinical use. Here, we have isolated unique mitochondrial redox control properties of metformin that are likely to account for this difference. In primary hepatocytes and H4IIE hepatoma cells we found that antihyperglycaemic diguanides DG5-DG10 and the biguanide phenformin were up to 1000-fold more potent than metformin on cell signalling responses, gluconeogenic promoter expression and hepatocyte glucose production. Each drug inhibited cellular oxygen consumption similarly but there were marked differences in other respects. All diguanides and phenformin but not metformin inhibited NADH oxidation in submitochondrial particles, indicative of complex I inhibition, which also corresponded closely with dehydrogenase activity in living cells measured by WST-1. Consistent with these findings, in isolated mitochondria, DG8 but not metformin caused the NADH/NAD+ couple to become more reduced over time and mitochondrial deterioration ensued, suggesting direct inhibition of complex I and mitochondrial toxicity of DG8. In contrast, metformin exerted a selective oxidation of the mitochondrial NADH/NAD+ couple, without triggering mitochondrial deterioration. Together, our results suggest that metformin suppresses energy transduction by selectively inducing a state in complex I where redox and proton transfer domains are no longer efficiently coupled. Keywords: Diabetes, Metformin, Mitochondria, NADH, NAD+

  1. Bidirectional selection between two classes in complex social networks.

    Science.gov (United States)

    Zhou, Bin; He, Zhe; Jiang, Luo-Luo; Wang, Nian-Xin; Wang, Bing-Hong

    2014-12-19

    The bidirectional selection between two classes widely emerges in various social lives, such as commercial trading and mate choosing. Until now, the discussions on bidirectional selection in structured human society are quite limited. We demonstrated theoretically that the rate of successfully matching is affected greatly by individuals' neighborhoods in social networks, regardless of the type of networks. Furthermore, it is found that the high average degree of networks contributes to increasing rates of successful matches. The matching performance in different types of networks has been quantitatively investigated, revealing that the small-world networks reinforces the matching rate more than scale-free networks at given average degree. In addition, our analysis is consistent with the modeling result, which provides the theoretical understanding of underlying mechanisms of matching in complex networks.

  2. Elucidation of the electronic spectrum changes of KA-Al{sup 3+} complex by potentiometric titration, FTIR, {sup 13}C NMR and quantum mechanics

    Energy Technology Data Exchange (ETDEWEB)

    Piantavini, Mário S.; Gonçalves, Alan G.; Trindade, Ângela C.L.B.; Noseda, Miguel D.; Mercê, Ana L.R.; Pontarolo, Roberto, E-mail: pontarolo@ufpr.br [Universidade Federal do Paraná (UFPR), Curitiba (Brazil); Machado, Antonio E.H. [Universidade Federal de Uberlândia (UFU), MG (Brazil)

    2017-08-15

    Kojic acid (KA) is an organic acid widely used in pharmaceutical industry, mainly as a skin lightening agent. Based on the ability of KA to form complexes with ions, we found the most possible kind of complex formed with cation aluminum. KA-Al{sup 3+} complex structures were studied using potentiometric and spectrophotometric (UV) titrations, FTIR and {sup 13}C NMR. The electronic spectroscopy showed that the KA-Al{sup 3+} complexes absorb at higher wavelengths (λ{sub max}= 305 nm) than do the non-complexed KA (λ{sub max}= 269 nm), confirming complexation. The IR spectra of KA complexed and not complexed allowed to correlate the changes in the absorption of enol and carbonyl groups in absence and presence of Al{sup 3+} in aqueous solutions. The complexation suggested by the potentiometric titration and FTIR spectroscopy are in accordance with the data obtained from NMR results. Calculations based on quantum mechanics were utilized to understand the differences found in the non complexed and complexed KAH electronic spectra. (author)

  3. Elucidation of the electronic spectrum changes of KA-Al3+ complex by potentiometric titration, FTIR, 13C NMR and quantum mechanics

    International Nuclear Information System (INIS)

    Piantavini, Mário S.; Gonçalves, Alan G.; Trindade, Ângela C.L.B.; Noseda, Miguel D.; Mercê, Ana L.R.; Pontarolo, Roberto; Machado, Antonio E.H.

    2017-01-01

    Kojic acid (KA) is an organic acid widely used in pharmaceutical industry, mainly as a skin lightening agent. Based on the ability of KA to form complexes with ions, we found the most possible kind of complex formed with cation aluminum. KA-Al 3+ complex structures were studied using potentiometric and spectrophotometric (UV) titrations, FTIR and 13 C NMR. The electronic spectroscopy showed that the KA-Al 3+ complexes absorb at higher wavelengths (λ max = 305 nm) than do the non-complexed KA (λ max = 269 nm), confirming complexation. The IR spectra of KA complexed and not complexed allowed to correlate the changes in the absorption of enol and carbonyl groups in absence and presence of Al 3+ in aqueous solutions. The complexation suggested by the potentiometric titration and FTIR spectroscopy are in accordance with the data obtained from NMR results. Calculations based on quantum mechanics were utilized to understand the differences found in the non complexed and complexed KAH electronic spectra. (author)

  4. Extended shortest path selection for package routing of complex networks

    Science.gov (United States)

    Ye, Fan; Zhang, Lei; Wang, Bing-Hong; Liu, Lu; Zhang, Xing-Yi

    The routing strategy plays a very important role in complex networks such as Internet system and Peer-to-Peer networks. However, most of the previous work concentrates only on the path selection, e.g. Flooding and Random Walk, or finding the shortest path (SP) and rarely considering the local load information such as SP and Distance Vector Routing. Flow-based Routing mainly considers load balance and still cannot achieve best optimization. Thus, in this paper, we propose a novel dynamic routing strategy on complex network by incorporating the local load information into SP algorithm to enhance the traffic flow routing optimization. It was found that the flow in a network is greatly affected by the waiting time of the network, so we should not consider only choosing optimized path for package transformation but also consider node congestion. As a result, the packages should be transmitted with a global optimized path with smaller congestion and relatively short distance. Analysis work and simulation experiments show that the proposed algorithm can largely enhance the network flow with the maximum throughput within an acceptable calculating time. The detailed analysis of the algorithm will also be provided for explaining the efficiency.

  5. Elucidation of the sequence selective binding mode of the DNA minor groove binder adozelesin, by high-field 1H NMR and restrained molecular dynamics

    International Nuclear Information System (INIS)

    Cameron, L.

    1999-01-01

    Adozelesin (formerly U73-975, The Upjohn Co.) is a covalent, minor-groove binding analogue of the antitumour antibiotic (+)CC-1065. Adozelesin consists of a cyclopropapyrroloindole alkylating sub-unit identical to (+)CC-1065, plus indole and benzofuran sub-units which replace the more complex pyrroloindole B and C sub-units, respectively, of (+)CC-1065. Adozelesin is a clinically important drug candidate, since it does not contain the ethylene bridge moieties on the B and C sub-units which are thought to be responsible for the unusual delayed hepatotoxicity exhibited by (+)CC-1065. Sequencing techniques identified two consensus sequences for adozelesin binding as p(dA) and 5'(T/A)(T/A)T-A*(C/G)G. This suggests that adozelesin spans a total of five base-pairs and shows a preference for A=T base-pair rich sequences, thus avoiding steric crowding around the exocyclic NH 2 of guanine and a wide minor groove. In this project, the covalent modification of two DNA sequences, i.e. 5'd(CGTAAGCGCTTA*CG) 2 and 5'-d(CGAAAAA*CGG)· 5'-d(CCGTTTTTCG), by adozelesin was examined by high-field NMR and restrained molecular mechanics and dynamics. Previous studies of minor groove binding drugs, using techniques as diverse as NMR, X-ray crystallography and molecular modelling, indicate that the incorporation of a guanine into the consensus sequence sterically hinders binding and, more importantly, produces a wider minor groove which is a 'slack' fit for the ligand. The aim of this investigation was to provide an insight into the sequence selective binding of adozelesin to 5'-AAAAA*CG and 5'-GCTTA*CG. The 1 H NMR data revealed that, in both cases, β-helical structure and Watson-Crick base-pairing was maintained on adduct formation. The 5'-GCTTA*CG adduct displayed significant distortion of the guanine base on the non-covalently modified strand. This distortion resulted from an amalgamation of two factors. Firstly, the presence of a strong hydrogen-bond between the amide linker of the

  6. Synthesis and structure elucidation of a copper(II) Schiff-base complex: in vitro DNA binding, pBR322 plasmid cleavage and HSA binding studies.

    Science.gov (United States)

    Tabassum, Sartaj; Ahmad, Musheer; Afzal, Mohd; Zaki, Mehvash; Bharadwaj, Parimal K

    2014-11-01

    New copper(II) complex with Schiff base ligand 4-[(2-Hydroxy-3-methoxy-benzylidene)-amino]-benzoic acid (H₂L) was synthesized and characterized by spectroscopic and analytical and single crystal X-ray diffraction studies which revealed that the complex 1 exist in a distorted octahedral environment. In vitro CT-DNA binding studies were performed by employing different biophysical technique which indicated that the 1 strongly binds to DNA in comparison to ligand via electrostatic binding mode. Complex 1 cleaves pBR322 DNA via hydrolytic pathway and recognizes minor groove of DNA double helix. The HSA binding results showed that ligand and complex 1 has ability to quench the fluorescence emission intensity of Trp 214 residue available in the subdomain IIA of HSA. Copyright © 2014 Elsevier B.V. All rights reserved.

  7. [Dermoepidermic junction: a selective, complex and vital barrier].

    Science.gov (United States)

    Frede, Silvia C; Dionisio de Cabalier, María E; Zaya, Alejandro; Hliba, Ernesto

    2004-01-01

    Dermoepidermic junction (DEJ) is a highly complex region, containing a great variety of cellular elements, which despite of having different embriogenesis, interact with each other, generating different substances that keep the function and homeostasis of the greatest organ of the human body. DEJ is regarded as a highly specialized basal lamina, which acts as a highly selective pathway for the migration of cells and macromolecules, inducing cellular differentiation and micro enviromental metabolism modifications. DEJ may be divided into three zones regarding the basal lamina 1--the nearest to epidermic zone, having tonofilaments and hemidesmosomes, which keep anchored basal cells. This region is limited by the lamina densa 2--the intermediate zone, represented exclusively by lamina densa and finally the lamina 3,--the third region--extends from lamina densa to the upper dermis and extracelullar matrix. Despite there is much to learn about DEJ, the knowledge about each molecule and function of every compartment will enable us to know more about the pathogenesis of several dermatologic diseases, with a great prevalence in the clinical practice.

  8. Elucidating a Key Anti-HIV-1 and Cancer-Associated Axis: The Structure of CCL5 (Rantes) in Complex with CCR5

    Science.gov (United States)

    Tamamis, Phanourios; Floudas, Christodoulos A.

    2014-06-01

    CCL5 (RANTES) is an inflammatory chemokine which binds to chemokine receptor CCR5 and induces signaling. The CCL5:CCR5 associated chemotactic signaling is of critical biological importance and is a potential HIV-1 therapeutic axis. Several studies provided growing evidence for the expression of CCL5 and CCR5 in non-hematological malignancies. Therefore, the delineation of the CCL5:CCR5 complex structure can pave the way for novel CCR5-targeted drugs. We employed a computational protocol which is primarily based on free energy calculations and molecular dynamics simulations, and report, what is to our knowledge, the first computationally derived CCL5:CCR5 complex structure which is in excellent agreement with experimental findings and clarifies the functional role of CCL5 and CCR5 residues which are associated with binding and signaling. A wealth of polar and non-polar interactions contributes to the tight CCL5:CCR5 binding. The structure of an HIV-1 gp120 V3 loop in complex with CCR5 has recently been derived through a similar computational protocol. A comparison between the CCL5 : CCR5 and the HIV-1 gp120 V3 loop : CCR5 complex structures depicts that both the chemokine and the virus primarily interact with the same CCR5 residues. The present work provides insights into the blocking mechanism of HIV-1 by CCL5.

  9. Mulliken-Hush elucidation of the encounter (precursor) complex in intermolecular electron transfer via self-exchange of tetracyanoethylene anion-radical

    International Nuclear Information System (INIS)

    Rosokha, S.V.; Newton, M.D.; Head-Gordon, M.; Kochi, J.K.

    2006-01-01

    The paramagnetic [1:1] encounter complex (TCNE) 2 -dot is established as the important precursor in the kinetics and mechanism of electron-transfer for the self-exchange between tetracyanoethylene acceptor (TCNE) and its radical-anion as the donor. Spectroscopic observation of the dimeric complex (TCNE) 2 -dot by its intervalence absorption band at the solvent-dependent wavelength of λ IV ∼1500nm facilitates the application of Mulliken-Hush theory which reveals the significant electronic interaction extant between the pair of cofacial TCNE moieties with the sizable coupling of H DA =1000cm -1 . The transient existence of such an encounter complex provides the critical link in the electron-transfer kinetics by lowering the classical Marcus reorganization barrier by the amount of H DA in this strongly adiabatic system. Ab initio quantum-mechanical methods as applied to independent theoretical computations of both the reorganization energy (λ) and the electronic coupling element (H DA ) confirm the essential correctness of the Mulliken-Hush formalism for fast electron transfer via strongly coupled donor/acceptor encounter complexes

  10. Lanthanide complexes of macrocyclic polyoxovanadates by VO4 units: synthesis, characterization, and structure elucidation by X-ray crystallography and EXAFS spectroscopy.

    Science.gov (United States)

    Nishio, Masaki; Inami, Shinnosuke; Katayama, Misaki; Ozutsumi, Kazuhiko; Hayashi, Yoshihito

    2012-01-16

    Reactions of a tetravanadate anion, [V(4)O(12)](4-), with a series of lanthanide(III) salts yield three types of lanthanide complexes of macrocyclic polyoxovanadates: (Et(4)N)(6)[Ln(III)V(9)O(27)] [Ln = Nd (1), Sm (2), Eu (3), Gd (4), Tb (5), Dy (6)], (Et(4)N)(5)[(H(2)O)Ho(III)(V(4)O(12))(2)] (7), and (Et(4)N)(7)[Ln(III)V(10)O(30)] [Ln = Er (8), Tm (9), Yb (10), Lu (11)]. Lanthanide complexes 1-11 are isolated and characterized by IR, elemental analysis, single-crystal X-ray diffraction, and extended X-ray absorption fine structure spectroscopy (EXAFS). Lanthanide complexes 1-6 are composed of a square-antiprism eight-coordinated Ln(III) center with a macrocyclic polyoxovanadate that is constructed from nine VO(4) tetrahedra through vertex sharing. The structure of 7 is composed of a seven-coordinated Ho(III) center, which exhibits a capped trigonal-prism coordination environment by the sandwiching of two cyclic tetravanadates with a capping H(2)O ligand. Lanthanide complexes 8-11 have a six-coordinated Ln(III) center with a 10-membered vanadate ligand. The structural trend to adopt a larger coordination number for a larger lanthanide ion among the three types of structures is accompanied by a change in the vanadate ring sizes. These lanthanide complexes are examined by EXAFS spectroscopies on lanthanide L(III) absorption edges, and the EXAFS oscillations of each of the samples in the solid state and in acetonitrile are identical. The Ln-O and Ln···V bond lengths obtained from fits of the EXAFS data are consistent with the data from the single-crystal X-ray studies, reflecting retention of the structures in acetonitrile.

  11. Preferential Selectivity of Inhibitors with Human Tau Protein Kinase Gsk3 Elucidates Their Potential Roles for Off-Target Alzheimer’s Therapy

    Directory of Open Access Journals (Sweden)

    Jagadeesh Kumar Dasappa

    2013-01-01

    Full Text Available Alzheimer’s disease (AD is a neurodegenerative disorder characterized by the accumulation of amyloid beta peptides (A and neurofibrillary tangles (NFTs. The abnormal phosphorylation of tau leads to the formation of NFTs produced by the action of tau kinases, resulting in the loss of neurons and synapse, leading to dementia. Hence, tau kinases have become potential drug target candidates for small molecule inhibitors. With an aim to explore the identification of a common inhibitor, this investigation was undertaken towards analyzing all 10 tau kinases which are implicated in phosphorylation of AD. A set of 7 inhibitors with varied scaffolds were collected from the Protein Data Bank (PDB. The analysis, involving multiple sequence alignment, 3D structural alignment, catalytic active site overlap, and docking studies, has enabled elucidation of the pharmacophoric patterns for the class of 7 inhibitors. Our results divulge that tau protein kinases share a specific set of conserved structural elements for the binding of inhibitors and ATP, respectively. The scaffold of 3-aminopyrrolidine (inhibitor 6 exhibits high preferential affinity with GSK3. Surprisingly, the PDB does not contain the structural details of GSK3 with this specific inhibitor. Thus, our investigations provide vital clues towards design of novel off-target drugs for Alzheimer’s.

  12. Elucidating the 3D structures of Al(iii)-Aβ complexes: a template free strategy based on the pre-organization hypothesis.

    Science.gov (United States)

    Mujika, Jon I; Rodríguez-Guerra Pedregal, Jaime; Lopez, Xabier; Ugalde, Jesus M; Rodríguez-Santiago, Luis; Sodupe, Mariona; Maréchal, Jean-Didier

    2017-07-01

    Senile plaques are extracellular deposits found in patients with Alzheimer's Disease (AD) and are mainly formed by insoluble fibrils of β-amyloid (Aβ) peptides. The mechanistic details about how AD develops are not fully understood yet, but metals such as Cu, Zn, or Fe are proposed to have a non-innocent role. Many studies have also linked the non biological metal aluminum with AD, a species whose concentration in the environment and food has been constantly increasing since the industrial revolution. Gaining a molecular picture of how Al(iii) interacts with an Aβ peptide is of fundamental interest to improve understanding of the many variables in the evolution of AD. So far, no consensus has been reached on how this metal interacts with Aβ, partially due to the experimental complexity of detecting and quantifying the resulting Al(iii)-Aβ complexes. Computational chemistry arises as a powerful alternative to investigate how Al(iii) can interact with Aβ peptides, as suitable strategies could shed light on the metal-peptide description at the molecular level. However, the absence of any reliable template that could be used for the modeling of the metallopeptide structure makes computational insight extremely difficult. Here, we present a novel strategy to generate accurate 3D models of the Al(iii)-Aβ complexes, which still circumvents first principles simulations of metal binding to peptides of Aβ. The key to this approach lies in the identification of experimental structures of the isolated peptide that are favourably pre-organized for the binding of a given metal in configurations of the first coordination sphere that were previously identified as the most stable with amino acid models. This approach solves the problem of the absence of clear structural templates for novel metallopeptide constructs. The posterior refinement of the structures via QM/MM and MD calculations allows us to provide, for the first time, physically sound models for Al

  13. Chirality-selected phase behaviour in ionic polypeptide complexes

    Science.gov (United States)

    Perry, Sarah L.; Leon, Lorraine; Hoffmann, Kyle Q.; Kade, Matthew J.; Priftis, Dimitrios; Black, Katie A.; Wong, Derek; Klein, Ryan A.; Pierce, Charles F.; Margossian, Khatcher O.; Whitmer, Jonathan K.; Qin, Jian; de Pablo, Juan J.; Tirrell, Matthew

    2015-01-01

    Polyelectrolyte complexes present new opportunities for self-assembled soft matter. Factors determining whether the phase of the complex is solid or liquid remain unclear. Ionic polypeptides enable examination of the effects of stereochemistry on complex formation. Here we demonstrate that chirality determines the state of polyelectrolyte complexes, formed from mixing dilute solutions of oppositely charged polypeptides, via a combination of electrostatic and hydrogen-bonding interactions. Fluid complexes occur when at least one of the polypeptides in the mixture is racemic, which disrupts backbone hydrogen-bonding networks. Pairs of purely chiral polypeptides, of any sense, form compact, fibrillar solids with a β-sheet structure. Analogous behaviour occurs in micelles formed from polypeptide block copolymers with polyethylene oxide, where assembly into aggregates with either solid or fluid cores, and eventually into ordered phases at high concentrations, is possible. Chirality is an exploitable tool for manipulating material properties in polyelectrolyte complexation. PMID:25586861

  14. Anti- and Pro-Lipase Activity of Selected Medicinal, Herbal and Aquatic Plants, and Structure Elucidation of an Anti-Lipase Compound

    Directory of Open Access Journals (Sweden)

    Muhammad Abubakar Ado

    2013-11-01

    Full Text Available Plants that help in slowing down the digestion of triacylglycerols (TAGs in the pancreas and small intestine of humans play an important role in the reduction of obesity. On the other hand, there may be plants or plant parts that stimulate intestinal lipolytic activity, thus contributing to greater TAG assimilation. The aim of this study was to evaluate the aqueous methanolic extracts of ninety eight (98 medicinal, herbal and aquatic plant materials from Malaysia for their effect on porcine pancreatic lipase (PPL activity and to identify the structure of an anti-lipase compound from one of the sources. The degree of inhibition was also quantified as relative to orlistat activity against PPL (orlistat equivalents. Results revealed that while 19.4% of the extracts were found to have anti-lipase activity ≥80%, 12% were actually found to promote PPL activity. Twenty two percent (22.4% exhibited moderate inhibition (41%–80% and 2% were neutral toward PPL activity. The ripe fruit of Averrhoa carambola and the leaves of Archidendron jiringa (Jack I.C Nielsen L. (jering, Cynometra cauliflora (nam-nam and Aleurites moluccana (L. Willd (candle nut/buah keras had the highest (100% anti-lipase activity and are equivalent to 0.11 µg orlistat/mL. Plants that stimulated lipase activity included Pimpinella anisum L. (aniseed/jintan manis, activating the enzyme by 186.5%. Kaempferol 3-O-rhamnoside was isolated from the ethyl acetate fraction of C. cauliflora leaves and found to be an active lipase inhibitor. The structure was elucidated using 1H-NMR, 13C-NMR and 2D-NMR analyses.

  15. Anti- and pro-lipase activity of selected medicinal, herbal and aquatic plants, and structure elucidation of an anti-lipase compound.

    Science.gov (United States)

    Ado, Muhammad Abubakar; Abas, Faridah; Mohammed, Abdulkarim Sabo; Ghazali, Hasanah M

    2013-11-26

    Plants that help in slowing down the digestion of triacylglycerols (TAGs) in the pancreas and small intestine of humans play an important role in the reduction of obesity. On the other hand, there may be plants or plant parts that stimulate intestinal lipolytic activity, thus contributing to greater TAG assimilation. The aim of this study was to evaluate the aqueous methanolic extracts of ninety eight (98) medicinal, herbal and aquatic plant materials from Malaysia for their effect on porcine pancreatic lipase (PPL) activity and to identify the structure of an anti-lipase compound from one of the sources. The degree of inhibition was also quantified as relative to orlistat activity against PPL (orlistat equivalents). Results revealed that while 19.4% of the extracts were found to have anti-lipase activity ≥80%, 12% were actually found to promote PPL activity. Twenty two percent (22.4%) exhibited moderate inhibition (41%-80%) and 2% were neutral toward PPL activity. The ripe fruit of Averrhoa carambola and the leaves of Archidendron jiringa (Jack) I.C Nielsen L. (jering), Cynometra cauliflora (nam-nam) and Aleurites moluccana (L.) Willd (candle nut/buah keras) had the highest (100%) anti-lipase activity and are equivalent to 0.11 µg orlistat/mL. Plants that stimulated lipase activity included Pimpinella anisum L. (aniseed/jintan manis), activating the enzyme by 186.5%. Kaempferol 3-O-rhamnoside was isolated from the ethyl acetate fraction of C. cauliflora leaves and found to be an active lipase inhibitor. The structure was elucidated using 1H-NMR, 13C-NMR and 2D-NMR analyses.

  16. Structural modelling and molecular dynamics of a multi-stress responsive WRKY TF-DNA complex towards elucidating its role in stress signalling mechanisms in chickpea.

    Science.gov (United States)

    Konda, Aravind Kumar; Farmer, Rohit; Soren, Khela Ram; P S, Shanmugavadivel; Setti, Aravind

    2017-07-28

    Chickpea is a premier food legume crop with high nutritional quality and attains prime importance in the current era of 795 million people being undernourished worldwide. Chickpea production encounters setbacks due to various stresses and understanding the role of key transcription factors (TFs) involved in multiple stresses becomes inevitable. We have recently identified a multi-stress responsive WRKY TF in chickpea. The present study was conducted to predict the structure of WRKY TF to identify the DNA-interacting residues and decipher DNA-protein interactions. Comparative modelling approach produced 3D model of the WRKY TF with good stereochemistry, local/global quality and further revealed W19, R20, K21, and Y22 motifs within a vicinity of 5 Å to the DNA amongst R18, G23, Q24, K25, Y36, Y37, R38 and K47 and these positions were equivalent to the 2LEX WRKY domain of Arabidopsis. Molecular simulations analysis of reference protein -PDB ID 2LEX, along with Car-WRKY TF modelled structure with the DNA coordinates derived from PDB ID 2LEX and docked using HADDOCK were executed. Root Mean Square (RMS) Deviation and RMS Fluctuation values yielded consistently stable trajectories over 50 ns simulation. Strengthening the obtained results, neither radius of gyration, distance and total energy showed any signs of DNA-WRKY complex falling apart nor any significant dissociation event over 50 ns run. Therefore, the study provides first insights into the structural properties of multi-stress responsive WRKY TF-DNA complex in chickpea, enabling genome wide identification of TF binding sites and thereby deciphers their gene regulatory networks.

  17. Selecting profitable customers for complex services on the internet

    NARCIS (Netherlands)

    Vroomen, B; Donkers, B; Verhoef, PC; Franses, PH

    In contrast to books and compact discs, the number of complex services offered on the Internet is still small. The decision-making process for complex services is different because it has an additional intermediate step of "indication of interest." The Web site is (a) visited and searched for

  18. From HAMLET to XAMLET: The molecular complex selectively ...

    African Journals Online (AJOL)

    HAMLET (human α-lactalbumin made lethal to tumor cells) is a complex consisting of decalcinated α-lactalbumin and oleic acid. It has been shown to induce massive cell death in various cancers without serious damage to normal tissues in both in vitro and in vivo experiments. The complexity of the mechanism in the ...

  19. Synthesis, Structure Elucidation, and Redox Properties of (superscript 99)Tc Complexes of Lacunary Wells-Dawson Polyoxometalates: Insights into Molecular (superscript 99)Tc-Metal Oxide Interactions

    International Nuclear Information System (INIS)

    McGregor, Donna; Burton-Pye, Benjamin P.; Howell, Robertha C.; Mbomekalle, Israel M.; Lukens, Wayne W. Jr.; Bian, Fang; Mausolf, Edward; Poineau, Frederic; Czerwinski, Kenneth R.; Francesconi, Lynn C.

    2011-01-01

    The isotope 99 Tc (β max , 293.7; half-life, 2.1 x 10 5 years) is an abundant product of uranium-235 fission in nuclear reactors and is present throughout the radioactive waste stored in underground tanks at the Hanford and Savannah River sites. Understanding and controlling the extensive redox chemistry of 99 Tc is important in identifying tunable strategies to separate 99 Tc from spent fuel and from waste tanks and, once separated, to identify and develop an appropriately stable waste form for 99 Tc. Polyoxometalates (POMs), nanometer-sized models for metal oxide solid-state materials, are used in this study to provide a molecular level understanding of the speciation and redox chemistry of incorporated 99 Tc. In this study, 99 Tc complexes of the (α 2 -P 2 W 17 O 61 ) 10- and (α 1 -P 2 W 17 O 61 ) 10- isomers were prepared. Ethylene glycol was used as a 'transfer ligand' to minimize the formation of TcO 2 · xH 2 O. The solution structures, formulations, and purity of TcVO(α 1 /α 2 -P 2 W 17 O 61 ) 7- were determined by multinuclear NMR. X-ray absorption spectroscopy of the complexes is in agreement with the formulation and structures determined from 31 P and 183 W NMR. Preliminary electrochemistry results are consistent with the EXAFS results, showing a facile reduction of the TcVO(α 1 -P 2 W 17 O 61 ) 7- species compared to the TcVO(α 2 -P 2 W 17 O 61 ) 7- analog. The α 1 defect is unique in that a basic oxygen atom is positioned toward the α 1 site, and the Tc V O center appears to form a dative metal-metal bond with a framework W site. These attributes may lead to the assistance of protonation events that facilitate reduction. Electrochemistry comparison shows that the ReV analogs are about 200 mV more difficult to reduce in accordance with periodic trends.

  20. Synthesis, structure elucidation and redox properties of 99Tc complexes of lacunary Wells Dawson polyoxometalates: insights into molecular 99Tc - metal oxide interactions

    International Nuclear Information System (INIS)

    McGregor, Donna; Burton-Pye, Benjamin P.; Howell, Robertha C.; Mbomekalle, Israel M.; Lukens, Wayne W. Jr; Bian, Fang; Mausolf, Edward; Poineau, Frederic; Czerwinski, Kenneth R; Francesconi, Lynn C.

    2011-01-01

    The isotope 99 Tc (β max : 250 keV, half-life: 2 x 10 5 year) is an abundant product of uranium-235 fission in nuclear reactors and is present throughout the radioactive waste stored in underground tanks at Hanford and Savannah River. Understanding and controlling the extensive redox chemistry of 99 Tc is important to identify tunable strategies to separate 99 Tc from spent fuel and from waste tanks and once separated, to identify and develop an appropriately stable waste-form for 99 Tc. Polyoxometalates (POMs), nanometer sized models for metal oxide solid-state materials, are used in this study to provide a molecular level understanding of the speciation and redox chemistry of incorporated 99 Tc. In this study, 99 Tc complexes of the (α 2 -P 2 W 17 O 61 ) 10- and (α 1 -P 2 W 17 O 61 ) 10- isomers were prepared. Ethylene glycol was used as a 'transfer ligand' to minimize the formation of TcO 2 · xH 2 O. The solution structures, formulations, and purity of Tc V O(α 1 /α 2 -P 2 W 17 O 61 ) 7- were determined by multinuclear NMR. X-ray Absorption Spectroscopy of the complexes are in agreement with the formulation and structures determined from 31 P and 183 W NMR. Preliminary electrochemistry results are consistent with the EXAFS results, showing a facile reduction of the Tc V O(α 1 -P 2 W 17 O 61 ) 7- species compared to the Tc V O(α 2 -P 2 W 17 O 61 ) 7- analog. The α 1 -defect is unique in that a basic oxygen atom is positioned toward the α 1 -site and the Tc V O center appears to form a dative metal-metal bond with a framework W site. These attributes may lead to the assistance of protonation events that facilitate reduction. Electrochemistry comparison shows that the Re V analogs are about 200 mV more difficult to reduce in accordance with periodic trends.

  1. Organometallic model complexes elucidate the active gallium species in alkane dehydrogenation catalysts based on ligand effects in Ga K-edge XANES

    Energy Technology Data Exchange (ETDEWEB)

    Getsoian, Andrew “Bean”; Das, Ujjal; Camacho-Bunquin, Jeffrey; Zhang, Guanghui; Gallagher, James R.; Hu, Bo; Cheah, Singfoong; Schaidle, Joshua A.; Ruddy, Daniel A.; Hensley, Jesse E.; Krause, Theodore R.; Curtiss, Larry A.; Miller, Jeffrey T.; Hock, Adam S.

    2016-01-01

    Gallium-modified zeolites are known catalysts for the dehydrogenation of alkanes, reactivity that finds industrial application in the aromatization of light alkanes by Ga-ZSM5. While the role of gallium cations in alkane activation is well known, the oxidation state and coordination environment of gallium under reaction conditions has been the subject of debate. Edge shifts in Ga K-edge XANES spectra acquired under reaction conditions have long been interpreted as evidence for reduction of Ga(III) to Ga(I). However, a change in oxidation state is not the only factor that can give rise to a change in the XANES spectrum. In order to better understand the XANES spectra of working catalysts, we have synthesized a series of molecular model compounds and grafted surface organometallic Ga species and compared their XANES spectra to those of gallium-based catalysts acquired under reducing conditions. We demonstrate that changes in the identity and number of gallium nearest neighbors can give rise to changes in XANES spectra similar to those attributed in literature to changes in oxidation state. Specifically, spectral features previously attributed to Ga(I) may be equally well interpreted as evidence for low-coordinate Ga(III) alkyl or hydride species. These findings apply both to gallium-impregnated zeolite catalysts and to silica-supported single site gallium catalysts, the latter of which is found to be active and selective for dehydrogenation of propane and hydrogenation of propylene.

  2. Food supplements complexes for pregnant' s: composition analysis and selection features at community pharmacies

    OpenAIRE

    Tamelytė, Raimonda

    2016-01-01

    Compared food supplements complexes composition for pregnant women and adults. made a questionnaire survey. the composition of the food supplements complexes for pregnant women includes all major necessary vitamins and minerals for pregnancy. the assessment of active substances in the composition of the food supplements complexes for pregnant women are more suitable for use during pregnancy than, food supplements complexes for adults. in pharmacy, selecting food supplements complexes for preg...

  3. Band-selective excited ultrahigh resolution PSYCHE-TOCSY: fast screening of organic molecules and complex mixtures.

    Science.gov (United States)

    Kakita, Veera Mohana Rao; Vemulapalli, Sahithya Phani Babu; Bharatam, Jagadeesh

    2016-04-01

    Precise assignments of (1) H atomic sites and establishment of their through-bond COSY or TOCSY connectivity are crucial for molecular structural characterization by using (1) H NMR spectroscopy. However, this exercise is often hampered by signal overlap, primarily because of (1) H-(1) H scalar coupling multiplets, even at typical high magnetic fields. The recent developments in homodecoupling strategies for effectively suppressing the coupling multiplets into nice singlets (pure-shift), particularly, Morris's advanced broadband pure-shift yielded by chirp excitation (PSYCHE) decoupling and ultrahigh resolution PSYCHE-TOCSY schemes, have shown new possibilities for unambiguous structural elucidation of complex organic molecules. The superior broadband PSYCHE-TOCSY exhibits enhanced performance over the earlier TOCSY methods, which however warrants prolonged experimental times due to the requirement of large number of dwell increments along the indirect dimension. Herein, we present fast and band-selective analog of the broadband PSYCHE-TOCSY, which is useful for analyzing complex organic molecules that exhibit characteristic yet crowded spectral regions. The simple pulse scheme relies on band-selective excitation (BSE) followed by PSYCHE homodecoupling in the indirect dimension. The BSE-PSYCHE-TOCSY has been exemplified for Estradiol and a complex carbohydrate mixture comprised of six constituents of closely comparable molecular weights. The experimental times are greatly reduced viz., ~20 fold for Estradiol and ~10 fold for carbohydrate mixture, with respect to the broadband PSYCHE-TOCSY. Furthermore, unlike the earlier homonuclear band-selective decoupling, the BSE-PSYCHE-decoupling provides fully decoupled pure-shift spectra for all the individual chemical sites within the excited band. The BSE-PSYCHE-TOCSY is expected to have significant potential for quick screening of complex organic molecules and mixtures at ultrahigh resolution. Copyright © 2015 John Wiley

  4. Integrative Systems Biology: Elucidating Complex Traits

    DEFF Research Database (Denmark)

    Pers, Tune Hannes

    . In section ., I outline results from our bioinformaticsbased analysis of the FTO locus. Genetic variation within the FTO locus provides the hitherto strongest association between common SNPs and obesity, but the mechanisms leading to this association are still unknown. In Paper III, we demonstrate...

  5. Selective Synthesis of Manganese/Silicon Complexes in Supercritical Water

    Directory of Open Access Journals (Sweden)

    Jiancheng Wang

    2014-01-01

    Full Text Available A series of manganese salts (Mn(NO32, MnCl2, MnSO4, and Mn(Ac2 and silicon materials (silica sand, silica sol, and tetraethyl orthosilicate were used to synthesize Mn/Si complexes in supercritical water using a tube reactor. X-ray diffraction (XRD, X-ray photoelectron spectrometer (XPS, transmission electron microscopy (TEM, and scanning electron microscopy (SEM were employed to characterize the structure and morphology of the solid products. It was found that MnO2, Mn2O3, and Mn2SiO4 could be obtained in supercritical water at 673 K in 5 minutes. The roles of both anions of manganese salts and silicon species in the formation of manganese silicon complexes were discussed. The inorganic manganese salt with the oxyacid radical could be easily decomposed to produce MnO2/SiO2 and Mn2O3/SiO2. It is interesting to found that Mn(Ac2 can react with various types of silicon to produce Mn2SiO4. The hydroxyl groups of the SiO2 surface from different silicon sources enhance the reactivity of SiO2.

  6. Trans-1,4 selective polymerization of 1,3-butadiene with symmetry pincer chromium complexes activated by MMAO

    KAUST Repository

    Gong, Dirong; Jia, Xiaoyu; Wang, Baolin; Zhang, Xuequan; Huang, Kuo-Wei

    2014-01-01

    Tridentate chromium complexes (Cr1-Cr7) incorporated with symmetrical pincer ligand bis(arylimino)pyridine and bis(pyrzaolyl)pyridine have been synthesized and characterized by elemental analyis, FT-IR as well as ESI-MS. X-ray diffraction reveals solids-state structures of Cr2, Cr4 and Cr6 all adopt pseudo-octahedral coordination environment with respect to metal center. All complexes have been tested in stereoregulated polymerization of butadiene under various polymerization conditions. The trans-1,4 and cis-1,4 enchainment of resultant polymer are found to be dependent on the structure of ligand and amount of activator used. Under the optimized condition, free ortho-substitutes Cr catalysts Cr1, Cr3, Cr4 and Cr6 are capable of initiating high trans-1,4 selectivity (trans-1,4: 89.2%-92.0%) with good polymer yields (71.5%-78.0%), while counterparts with ortho-positioned alkyl groups Cr2, Cr5 and Cr7 display mixed selectivities with moderate polymer yields. The sterical effect of ligand and amount of MMAO on the catalytic performance, in particular, the stereoselectivity and polymer yield, has been also elucidated by conjugated diene polymerization mechanism. © 2014 Elsevier B.V. All rights reserved.

  7. Trans-1,4 selective polymerization of 1,3-butadiene with symmetry pincer chromium complexes activated by MMAO

    KAUST Repository

    Gong, Dirong

    2014-09-01

    Tridentate chromium complexes (Cr1-Cr7) incorporated with symmetrical pincer ligand bis(arylimino)pyridine and bis(pyrzaolyl)pyridine have been synthesized and characterized by elemental analyis, FT-IR as well as ESI-MS. X-ray diffraction reveals solids-state structures of Cr2, Cr4 and Cr6 all adopt pseudo-octahedral coordination environment with respect to metal center. All complexes have been tested in stereoregulated polymerization of butadiene under various polymerization conditions. The trans-1,4 and cis-1,4 enchainment of resultant polymer are found to be dependent on the structure of ligand and amount of activator used. Under the optimized condition, free ortho-substitutes Cr catalysts Cr1, Cr3, Cr4 and Cr6 are capable of initiating high trans-1,4 selectivity (trans-1,4: 89.2%-92.0%) with good polymer yields (71.5%-78.0%), while counterparts with ortho-positioned alkyl groups Cr2, Cr5 and Cr7 display mixed selectivities with moderate polymer yields. The sterical effect of ligand and amount of MMAO on the catalytic performance, in particular, the stereoselectivity and polymer yield, has been also elucidated by conjugated diene polymerization mechanism. © 2014 Elsevier B.V. All rights reserved.

  8. Electromagnetic waves in complex systems selected theoretical and applied problems

    CERN Document Server

    Velychko, Lyudmyla

    2016-01-01

    This book gives guidance to solve problems in electromagnetics, providing both examples of solving serious research problems as well as the original results to encourage further investigations. The book contains seven chapters on various aspects of resonant wave scattering, each solving one original problem. All of them are unified by the authors’ desire to show advantages of rigorous approaches at all stages, from the formulation of a problem and the selection of a method to the interpretation of results. The book reveals a range of problems associated with wave propagation and scattering in natural and artificial environments or with the design of antennas elements. The authors invoke both theoretical (analytical and numerical) and experimental techniques for handling the problems. Attention is given to mathematical simulations, computational efficiency, and physical interpretation of the experimental results. The book is written for students, graduate students and young researchers. .

  9. Examining the evidence for major histocompatibility complex-dependent mate selection in humans and nonhuman primates

    Czech Academy of Sciences Publication Activity Database

    Winternitz, Jamie Caroline; Abbate, J. L.

    2015-01-01

    Roč. 6, 13 May (2015), s. 73-88 ISSN 1179-7274 Institutional support: RVO:68081766 Keywords : major histocompatibility complex * sexual selection * olfaction * facial attraction * parasite resistance * inbreeding avoidance Subject RIV: EB - Genetics ; Molecular Biology

  10. Influence of Introduced Substituents on the Anion-selectivity of [14]Tetraazaannulene Complexes.

    Science.gov (United States)

    Moriuchi-Kawakami, Takayo; Obita, Minako; Tsujinaka, Toshiki; Shibutani, Yasuhiko

    2015-01-01

    Nickel(II) complexes of [14]tetraazaannulene derivatives incorporating aromatic rings into their azaannulene framework were synthesized, and the anion-selectivity of the [14]tetraazaannulene nickel complexes 1 - 4 was evaluated by potentiometric measurements with solvent polymeric membrane electrodes. All of the [14]Tetraazaannulene nickel complexes, except 3, were found to exhibit high selectivity for the I(-) ion over the SCN(-) ion, although considerable interference of the ClO4(-) ion was observed in all 1 - 4 complexes. Concerning the anion-selectivities of 1 and 4, the incorporation of naphthalene rings into the azaannulene framework decreased not only the interference of the ClO4(-) ion but also the I(-) ion-selectivity over the SCN(-) ion. Comparison studies between the dibenzotetraaza[14]annulene nickel complexes 1 - 3 indicated that differences in the attached substituents of the [14]tetraazaannulene nickel complexes greatly influenced the ion-selectivity as ionophores. According to our computational results, the ionophoric properties of [14]tetraazaannulene nickel complexes 1 - 4 were influenced by their electrostatic properties rather than their topological properties.

  11. ASYMMETRIC PRICE TRANSMISSION MODELING: THE IMPORTANCE OF MODEL COMPLEXITY AND THE PERFORMANCE OF THE SELECTION CRITERIA

    Directory of Open Access Journals (Sweden)

    Henry de-Graft Acquah

    2013-01-01

    Full Text Available Information Criteria provides an attractive basis for selecting the best model from a set of competing asymmetric price transmission models or theories. However, little is understood about the sensitivity of the model selection methods to model complexity. This study therefore fits competing asymmetric price transmission models that differ in complexity to simulated data and evaluates the ability of the model selection methods to recover the true model. The results of Monte Carlo experimentation suggest that in general BIC, CAIC and DIC were superior to AIC when the true data generating process was the standard error correction model, whereas AIC was more successful when the true model was the complex error correction model. It is also shown that the model selection methods performed better in large samples for a complex asymmetric data generating process than with a standard asymmetric data generating process. Except for complex models, AIC's performance did not make substantial gains in recovery rates as sample size increased. The research findings demonstrate the influence of model complexity in asymmetric price transmission model comparison and selection.

  12. Complexity control algorithm based on adaptive mode selection for interframe coding in high efficiency video coding

    Science.gov (United States)

    Chen, Gang; Yang, Bing; Zhang, Xiaoyun; Gao, Zhiyong

    2017-07-01

    The latest high efficiency video coding (HEVC) standard significantly increases the encoding complexity for improving its coding efficiency. Due to the limited computational capability of handheld devices, complexity constrained video coding has drawn great attention in recent years. A complexity control algorithm based on adaptive mode selection is proposed for interframe coding in HEVC. Considering the direct proportionality between encoding time and computational complexity, the computational complexity is measured in terms of encoding time. First, complexity is mapped to a target in terms of prediction modes. Then, an adaptive mode selection algorithm is proposed for the mode decision process. Specifically, the optimal mode combination scheme that is chosen through offline statistics is developed at low complexity. If the complexity budget has not been used up, an adaptive mode sorting method is employed to further improve coding efficiency. The experimental results show that the proposed algorithm achieves a very large complexity control range (as low as 10%) for the HEVC encoder while maintaining good rate-distortion performance. For the lowdelayP condition, compared with the direct resource allocation method and the state-of-the-art method, an average gain of 0.63 and 0.17 dB in BDPSNR is observed for 18 sequences when the target complexity is around 40%.

  13. Selected Topics on Managing Complexity and Information Systems Engineering: Editorial Introduction to Issue 8 of CSIMQ

    Directory of Open Access Journals (Sweden)

    Peter Forbrig

    2016-10-01

    Full Text Available Business process models greatly contribute to analyze and understand the activities of enterprises. However, it is still a challenge to cope with the complexity of systems specifications and their requirements. This issue of the journal of Complex Systems Informatics and Modeling (CSIMQ presents papers that discuss topics on managing complexity and information systems engineering. The papers are extended versions of selected papers from the workshop on Continuous Requirements Engineering held at the requirements engineering conference REFSQ 2016 in Gothenburg, the workshop on Managed Complexity held at the business informatics conference BIR 2016 in Prague, and the CAiSE 2016 Forum held in Ljubljana.

  14. Low-Complexity Transmit Antenna Selection and Beamforming for Large-Scale MIMO Communications

    Directory of Open Access Journals (Sweden)

    Kun Qian

    2014-01-01

    Full Text Available Transmit antenna selection plays an important role in large-scale multiple-input multiple-output (MIMO communications, but optimal large-scale MIMO antenna selection is a technical challenge. Exhaustive search is often employed in antenna selection, but it cannot be efficiently implemented in large-scale MIMO communication systems due to its prohibitive high computation complexity. This paper proposes a low-complexity interactive multiple-parameter optimization method for joint transmit antenna selection and beamforming in large-scale MIMO communication systems. The objective is to jointly maximize the channel outrage capacity and signal-to-noise (SNR performance and minimize the mean square error in transmit antenna selection and minimum variance distortionless response (MVDR beamforming without exhaustive search. The effectiveness of all the proposed methods is verified by extensive simulation results. It is shown that the required antenna selection processing time of the proposed method does not increase along with the increase of selected antennas, but the computation complexity of conventional exhaustive search method will significantly increase when large-scale antennas are employed in the system. This is particularly useful in antenna selection for large-scale MIMO communication systems.

  15. A Primer for Model Selection: The Decisive Role of Model Complexity

    Science.gov (United States)

    Höge, Marvin; Wöhling, Thomas; Nowak, Wolfgang

    2018-03-01

    Selecting a "best" model among several competing candidate models poses an often encountered problem in water resources modeling (and other disciplines which employ models). For a modeler, the best model fulfills a certain purpose best (e.g., flood prediction), which is typically assessed by comparing model simulations to data (e.g., stream flow). Model selection methods find the "best" trade-off between good fit with data and model complexity. In this context, the interpretations of model complexity implied by different model selection methods are crucial, because they represent different underlying goals of modeling. Over the last decades, numerous model selection criteria have been proposed, but modelers who primarily want to apply a model selection criterion often face a lack of guidance for choosing the right criterion that matches their goal. We propose a classification scheme for model selection criteria that helps to find the right criterion for a specific goal, i.e., which employs the correct complexity interpretation. We identify four model selection classes which seek to achieve high predictive density, low predictive error, high model probability, or shortest compression of data. These goals can be achieved by following either nonconsistent or consistent model selection and by either incorporating a Bayesian parameter prior or not. We allocate commonly used criteria to these four classes, analyze how they represent model complexity and what this means for the model selection task. Finally, we provide guidance on choosing the right type of criteria for specific model selection tasks. (A quick guide through all key points is given at the end of the introduction.)

  16. Synaptic Basis for Differential Orientation Selectivity between Complex and Simple Cells in Mouse Visual Cortex.

    Science.gov (United States)

    Li, Ya-tang; Liu, Bao-hua; Chou, Xiao-lin; Zhang, Li I; Tao, Huizhong W

    2015-08-05

    In the primary visual cortex (V1), orientation-selective neurons can be categorized into simple and complex cells primarily based on their receptive field (RF) structures. In mouse V1, although previous studies have examined the excitatory/inhibitory interplay underlying orientation selectivity (OS) of simple cells, the synaptic bases for that of complex cells have remained obscure. Here, by combining in vivo loose-patch and whole-cell recordings, we found that complex cells, identified by their overlapping on/off subfields, had significantly weaker OS than simple cells at both spiking and subthreshold membrane potential response levels. Voltage-clamp recordings further revealed that although excitatory inputs to complex and simple cells exhibited a similar degree of OS, inhibition in complex cells was more narrowly tuned than excitation, whereas in simple cells inhibition was more broadly tuned than excitation. The differential inhibitory tuning can primarily account for the difference in OS between complex and simple cells. Interestingly, the differential synaptic tuning correlated well with the spatial organization of synaptic input: the inhibitory visual RF in complex cells was more elongated in shape than its excitatory counterpart and also was more elongated than that in simple cells. Together, our results demonstrate that OS of complex and simple cells is differentially shaped by cortical inhibition based on its orientation tuning profile relative to excitation, which is contributed at least partially by the spatial organization of RFs of presynaptic inhibitory neurons. Simple and complex cells, two classes of principal neurons in the primary visual cortex (V1), are generally thought to be equally selective for orientation. In mouse V1, we report that complex cells, identified by their overlapping on/off subfields, has significantly weaker orientation selectivity (OS) than simple cells. This can be primarily attributed to the differential tuning selectivity

  17. Newly Synthesized Doxorubicin Complexes with Selected Metals—Synthesis, Structure and Anti-Breast Cancer Activity

    Directory of Open Access Journals (Sweden)

    Agata Jabłońska-Trypuć

    2017-07-01

    Full Text Available Doxorubicin (DOX is very effective chemotherapeutic agent, however it has several major drawbacks. Therefore the motivation for developing novel drug complexes as anticancer agents with different mechanism of action has arisen. The aim of the present study was to evaluate the influence of newly synthesized DOX complexes with selected metals (Mg, Mn, Co, Ni, Fe, Cu, Zn on apoptosis, cell cycle, viability, proliferation and cytotoxicity in the breast cancer cell line MCF-7. Complexation of DOX with metals has likewise been the subject of our research. The current work showed that the tested bivalent metals at a given pH condition formed metal:DOX complexes in a ratio of 2:1, while iron complexes with DOX in a ratio of 3:1. The studies also showed that selected metal-DOX complexes (Mg-DOX, Mn-DOX, Ni-DOX at 0.5 µM concentration significantly decreased cell viability and proliferation, however they increased caspase 7 activity. Results also indicated that studied metal-DOX complexes showed high cytotoxicity in MCF-7 cells. Therefore they were chosen for cell cycle check-points and apoptosis/necrosis analysis studied by flow cytometry. Obtained results suggest that doxorubicin complexed by specified metals can be considered as a potential anti-breast cancer agent, which is characterized by a higher efficacy than a parent drug.

  18. A low complexity algorithm for multiple relay selection in two-way relaying Cognitive Radio networks

    KAUST Repository

    Alsharoa, Ahmad M.

    2013-06-01

    In this paper, a multiple relay selection scheme for two-way relaying cognitive radio network is investigated. We consider a cooperative Cognitive Radio (CR) system with spectrum sharing scenario using Amplify-and-Forward (AF) protocol, where licensed users and unlicensed users operate on the same frequency band. The main objective is to maximize the sum rate of the unlicensed users allowed to share the spectrum with the licensed users by respecting a tolerated interference threshold. A practical low complexity heuristic approach is proposed to solve our formulated optimization problem. Selected numerical results show that the proposed algorithm reaches a performance close to the performance of the optimal multiple relay selection scheme either with discrete or continuous power distributions while providing a considerable saving in terms of computational complexity. In addition, these results show that our proposed scheme significantly outperforms the single relay selection scheme. © 2013 IEEE.

  19. Directional selection can drive the evolution of modularity in complex traits.

    Science.gov (United States)

    Melo, Diogo; Marroig, Gabriel

    2015-01-13

    Modularity is a central concept in modern biology, providing a powerful framework for the study of living organisms on many organizational levels. Two central and related questions can be posed in regard to modularity: How does modularity appear in the first place, and what forces are responsible for keeping and/or changing modular patterns? We approached these questions using a quantitative genetics simulation framework, building on previous results obtained with bivariate systems and extending them to multivariate systems. We developed an individual-based model capable of simulating many traits controlled by many loci with variable pleiotropic relations between them, expressed in populations subject to mutation, recombination, drift, and selection. We used this model to study the problem of the emergence of modularity, and hereby show that drift and stabilizing selection are inefficient at creating modular variational structures. We also demonstrate that directional selection can have marked effects on the modular structure between traits, actively promoting a restructuring of genetic variation in the selected population and potentially facilitating the response to selection. Furthermore, we give examples of complex covariation created by simple regimes of combined directional and stabilizing selection and show that stabilizing selection is important in the maintenance of established covariation patterns. Our results are in full agreement with previous results for two-trait systems and further extend them to include scenarios of greater complexity. Finally, we discuss the evolutionary consequences of modular patterns being molded by directional selection.

  20. Complex patterns of multivariate selection on the ejaculate of a broadcast spawning marine invertebrate.

    Science.gov (United States)

    Fitzpatrick, John L; Simmons, Leigh W; Evans, Jonathan P

    2012-08-01

    Assessing how selection operates on several, potentially interacting, components of the ejaculate is a challenging endeavor. Ejaculates can be subject to natural and/or sexual selection, which can impose both linear (directional) and nonlinear (stabilizing, disruptive, and correlational) selection on different ejaculate components. Most previous studies have examined linear selection of ejaculate components and, consequently, we know very little about patterns of nonlinear selection on the ejaculate. Even less is known about how selection acts on the ejaculate as a functionally integrated unit, despite evidence of covariance among ejaculate components. Here, we assess how selection acts on multiple ejaculate components simultaneously in the broadcast spawning sessile invertebrate Mytilus galloprovincialis using the statistical tools of multivariate selection analyses. Our analyses of relative fertilization rates revealed complex patterns of selection on sperm velocity, motility, and morphology. Interestingly, the most successful ejaculates were made up of slower swimming sperm with relatively low percentages of motile cells, and sperm with smaller head volumes that swam in highly pronounced curved swimming trajectories. These results are consistent with an emerging body of literature on fertilization kinetics in broadcast spawners, and shed light on the fundamental nature of selection acting on the ejaculate as a functionally integrated unit. © 2012 The Author(s). Evolution© 2012 The Society for the Study of Evolution.

  1. Selective determination of cyanide complexes of copper, zinc and cadmium in electrolytes by spectrophotometric titration

    International Nuclear Information System (INIS)

    Kuznetsov, V.V.; Korchagina, O.A.; Samorukova, O.L.

    1986-01-01

    Selective, sensitive and rapid method for determining Cd, Zn, Cu and their mixtures in cyanide electrolytes of galvanic bathes has been developed. Analysis is performed by means of indicator spectrophotometric titration with barium and strontium salts of cadmium cyanide complexes in organic-aqueous solvents

  2. A Short Introduction to Model Selection, Kolmogorov Complexity and Minimum Description Length (MDL)

    NARCIS (Netherlands)

    Nannen, Volker

    2010-01-01

    The concept of overtting in model selection is explained and demon- strated. After providing some background information on information theory and Kolmogorov complexity, we provide a short explanation of Minimum Description Length and error minimization. We conclude with a discussion of the typical

  3. Neutral Theory: From Complex Population History to Natural Selection and Sociocultural Phenomena in Human Populations.

    Science.gov (United States)

    Austerlitz, Frédéric; Heyer, Evelyne

    2018-06-01

    Here, we present a synthetic view on how Kimura's Neutral theory has helped us gaining insight on the different evolutionary forces that shape human evolution. We put this perspective in the frame of recent emerging challenges: the use of whole genome data for reconstructing population histories, natural selection on complex polygenic traits, and integrating cultural processes in human evolution.

  4. Coupled variable selection for regression modeling of complex treatment patterns in a clinical cancer registry.

    Science.gov (United States)

    Schmidtmann, I; Elsäßer, A; Weinmann, A; Binder, H

    2014-12-30

    For determining a manageable set of covariates potentially influential with respect to a time-to-event endpoint, Cox proportional hazards models can be combined with variable selection techniques, such as stepwise forward selection or backward elimination based on p-values, or regularized regression techniques such as component-wise boosting. Cox regression models have also been adapted for dealing with more complex event patterns, for example, for competing risks settings with separate, cause-specific hazard models for each event type, or for determining the prognostic effect pattern of a variable over different landmark times, with one conditional survival model for each landmark. Motivated by a clinical cancer registry application, where complex event patterns have to be dealt with and variable selection is needed at the same time, we propose a general approach for linking variable selection between several Cox models. Specifically, we combine score statistics for each covariate across models by Fisher's method as a basis for variable selection. This principle is implemented for a stepwise forward selection approach as well as for a regularized regression technique. In an application to data from hepatocellular carcinoma patients, the coupled stepwise approach is seen to facilitate joint interpretation of the different cause-specific Cox models. In conditional survival models at landmark times, which address updates of prediction as time progresses and both treatment and other potential explanatory variables may change, the coupled regularized regression approach identifies potentially important, stably selected covariates together with their effect time pattern, despite having only a small number of events. These results highlight the promise of the proposed approach for coupling variable selection between Cox models, which is particularly relevant for modeling for clinical cancer registries with their complex event patterns. Copyright © 2014 John Wiley & Sons

  5. Computational Experiment Study on Selection Mechanism of Project Delivery Method Based on Complex Factors

    Directory of Open Access Journals (Sweden)

    Xiang Ding

    2014-01-01

    Full Text Available Project delivery planning is a key stage used by the project owner (or project investor for organizing design, construction, and other operations in a construction project. The main task in this stage is to select an appropriate project delivery method. In order to analyze different factors affecting the PDM selection, this paper establishes a multiagent model mainly to show how project complexity, governance strength, and market environment affect the project owner’s decision on PDM. Experiment results show that project owner usually choose Design-Build method when the project is very complex within a certain range. Besides, this paper points out that Design-Build method will be the prior choice when the potential contractors develop quickly. This paper provides the owners with methods and suggestions in terms of showing how the factors affect PDM selection, and it may improve the project performance.

  6. Border control: selectivity of chloroplast protein import and regulation at the TOC-complex.

    Science.gov (United States)

    Demarsy, Emilie; Lakshmanan, Ashok M; Kessler, Felix

    2014-01-01

    Plants have evolved complex and sophisticated molecular mechanisms to regulate their development and adapt to their surrounding environment. Particularly the development of their specific organelles, chloroplasts and other plastid-types, is finely tuned in accordance with the metabolic needs of the cell. The normal development and functioning of plastids require import of particular subsets of nuclear encoded proteins. Most preproteins contain a cleavable sequence at their N terminal (transit peptide) serving as a signal for targeting to the organelle and recognition by the translocation machinery TOC-TIC (translocon of outer membrane complex-translocon of inner membrane complex) spanning the dual membrane envelope. The plastid proteome needs constant remodeling in response to developmental and environmental factors. Therefore selective regulation of preprotein import plays a crucial role in plant development. In this review we describe the diversity of transit peptides and TOC receptor complexes, and summarize the current knowledge and potential directions for future research concerning regulation of the different Toc isoforms.

  7. Low complexity transmit antenna selection with power balancing in OFDM systems

    KAUST Repository

    Park, Kihong

    2010-10-01

    In this paper, we consider multi-carrier systems with multiple transmit antennas under the power balancing constraint, which is defined as the constraint that the power on each antenna should be limited under a certain level due to the linearity of the power amplifier of the RF chain. Applying transmit antenna selection and fixed-power variable-rate transmission per subcarrier as a function of channel variations, we propose an implementation-friendly antenna selection method which offers a reduced complexity in comparison with the optimal antenna selection scheme. More specifically, in order to solve the subcarrier imbalance across the antennas, we operate a two-step reallocation procedure to minimize the loss of spectral efficiency. We also provide an analytic lower bound on the spectral efficiency for the proposed scheme. From selected numerical results, we show that our suboptimal scheme offers almost the same spectral efficiency as the optimal one. © 2010 IEEE.

  8. Radium removal from Canadian uranium mining effluents by a radium-selective ion exchange complexer

    International Nuclear Information System (INIS)

    1984-07-01

    A laboratory test program was initiated by the Department of Energy, Mines and Resources as part of the National Uranium Tailings Program to investigate the applicability of a radium-selective ion exchange complexer for removing radium from Canadian uranium mining effluents. The ion exchange complexer was shown to be efficient in removing radium from contaminated water of uranium mining operations, with the ultimate loading capacity of the resin on one type of water treated being determined as approximately 1,600 Bq/cm 3 of new resin. The results showed that the resin was effective in removing radium but not any other contaminants

  9. A Comparison of Multidimensional Item Selection Methods in Simple and Complex Test Designs

    Directory of Open Access Journals (Sweden)

    Eren Halil ÖZBERK

    2017-03-01

    Full Text Available In contrast with the previous studies, this study employed various test designs (simple and complex which allow the evaluation of the overall ability score estimations across multiple real test conditions. In this study, four factors were manipulated, namely the test design, number of items per dimension, correlation between dimensions and item selection methods. Using the generated item and ability parameters, dichotomous item responses were generated in by using M3PL compensatory multidimensional IRT model with specified correlations. MCAT composite ability score accuracy was evaluated using absolute bias (ABSBIAS, correlation and the root mean square error (RMSE between true and estimated ability scores. The results suggest that the multidimensional test structure, number of item per dimension and correlation between dimensions had significant effect on item selection methods for the overall score estimations. For simple structure test design it was found that V1 item selection has the lowest absolute bias estimations for both long and short tests while estimating overall scores. As the model gets complex KL item selection method performed better than other two item selection method.

  10. Complex Behavior in a Selective Aging Neuron Model Based on Small World Networks

    International Nuclear Information System (INIS)

    Zhang Guiqing; Chen Tianlun

    2008-01-01

    Complex behavior in a selective aging simple neuron model based on small world networks is investigated. The basic elements of the model are endowed with the main features of a neuron function. The structure of the selective aging neuron model is discussed. We also give some properties of the new network and find that the neuron model displays a power-law behavior. If the brain network is small world-like network, the mean avalanche size is almost the same unless the aging parameter is big enough.

  11. Ornament Complexity Is Correlated with Sexual Selection: (A Comment on Raia et al., "Cope's Rule and the Universal Scaling Law of Ornament Complexity").

    Science.gov (United States)

    Holman, Luke; Bro-Jørgensen, Jakob

    2016-08-01

    Raia et al. propose that the evolution of the shape and complexity of animal ornaments (e.g., deer antlers) can be explained by interspecific variation in body size and is not influenced by sexual selection. They claim to show that ornament complexity is related to body size by an 0.25-power law and argue that this finding precludes a role for sexual selection in the evolution of ornament complexity. However, their study does not test alternative hypotheses and mismeasures antler shape allometry by omitting much of the published data. We show that an index of sexual selection (sexual size dimorphism) is positively correlated with size-corrected antler complexity and that the allometric slope of complexity is substantially greater than 0.25, contra Raia et al. We conclude that sexual selection and physical constraints both affect the evolution of antler shape.

  12. Ratio of total-to-selective extinction in the Taurus dark cloud complex

    International Nuclear Information System (INIS)

    Vrba, F.J.; Rydgren, A.E.; Space Telescope Science Institute, Baltimore, MD)

    1985-01-01

    UBVRI and JHK photometry, as well as spectral classifications are presented for seven reddened early-type field stars that are observed through the Taurus dark cloud complex. The ratio of total-to-selective extinction is derived for each star by the color-difference method. For six stars with absolute magnitudes in violet of more than 1.7 and less than 3.2 mag, a normal ratio R of total-to-selective extinction of about 3.1 is found. The mildly anomalous R value of about 3.5 for the well-studied star HD 29647 was also confirmed. The results provide further evidence that the interstellar extinction law in the Taurus dark cloud complex is basically normal for lines of sight with absolute magnitudes in violet of less than 3 mag. 24 references

  13. Complex Dynamics of Droplet Traffic in a Bifurcating Microfluidic Channel: Periodicity, Multistability, and Selection Rules

    Science.gov (United States)

    Sessoms, D. A.; Amon, A.; Courbin, L.; Panizza, P.

    2010-10-01

    The binary path selection of droplets reaching a T junction is regulated by time-delayed feedback and nonlinear couplings. Such mechanisms result in complex dynamics of droplet partitioning: numerous discrete bifurcations between periodic regimes are observed. We introduce a model based on an approximation that makes this problem tractable. This allows us to derive analytical formulae that predict the occurrence of the bifurcations between consecutive regimes, establish selection rules for the period of a regime, and describe the evolutions of the period and complexity of droplet pattern in a cycle with the key parameters of the system. We discuss the validity and limitations of our model which describes semiquantitatively both numerical simulations and microfluidic experiments.

  14. Selective transport of metal ions through cation exchange membrane in the presence of a complexing agent

    Energy Technology Data Exchange (ETDEWEB)

    Tingchia Huang; Jaukai Wang (National Cheng Kung Univ., Tainan (Taiwan, Province of China))

    1993-01-01

    Selective transport of metal ions through a cation exchange membrane was studied in stirred batch dialyzer for the systems Ni[sup 2+]-Cu[sup 2+] and Cu[sup 2+]-Fe[sup 3+]. Oxalic acid, malonic acid, citric acid, glycine, and ethylenediaminetetraacetic acid were employed as the complexing agents added in the feed solution in order to increase the permselectivity of metal ions. The experimental results show that the selective transport behavior of metal ions depends on the valence and the concentration of metal ions, the stoichiometric ratio of complexing agent to metal ions, and the pH value of the feed solution, but is independent of the concentration of counterion in the stripping phase. A theoretical approach was formulated on the basis of the Nernst-Planck equation and interface quasi-equilibrium. Theoretical solutions obtained from numerical calculation were in agreement with the experimental data.

  15. Selection of rational technical solutions in designing a robotized assembly complex

    International Nuclear Information System (INIS)

    Petrov, B.M.; Rasulbekov, R.I.

    1984-01-01

    One of the methods permitting a more objective approach to decision making in design is the method of ordered search which, in combination with the methods of expert estimate was used in designing the robotized assembly-finishing complex for automobile tires. The assembly-finishing complex consists of a number of functionally independent parts, i.e., modules provided with manipulators and mutually connected by a transport system with intermediate storage. The modified method of ordered search, examined in the present work, was therefore used for each module separately, and not for the complex as a whole. We will examine the main principles of our approach to the selection of design solutions for the example of a module for laying on the bottom-cushion cords

  16. Selection and Characterization of Palmitic Acid Responsive Patients with an OXPHOS Complex I Defect

    Directory of Open Access Journals (Sweden)

    Tom E. J. Theunissen

    2017-10-01

    a clinical and biochemical level that a high fat diet can be beneficial for complex I patients and that our cell line assay will be an easy tool for the selection of patients, who might potentially benefit from this therapeutic diet.

  17. Effective selection criteria for assessing the resistance of stink bugs complex in soybean

    Directory of Open Access Journals (Sweden)

    Fabiani da Rocha

    2014-10-01

    Full Text Available Soybean plants with resistance to the stink bug complex are currently selected by extremely labor-intensive methods, which limit the evaluation of a large number of genotypes. Thus, this paper proposed the use of an alternative trait underlying the selection of resistant genotypes under field conditions with natural infestation: the weight of healthy seeds (WHS. To this end, 24 genotypes were evaluated under two management systems: with systematic chemical control of insects (management I, and without control (management II. Different indices were calculated using grain weight (YP of management I and WHS of management II (YS . The high correlation between YS and the indices mean productivity, stress tolerance and geometric mean productivity, plus the agreement in determining the groups of genotypes with resistance and high yield indicate that WHS is a useful character in simultaneous selection for these traits.

  18. Selection, trans-species polymorphism, and locus identification of major histocompatibility complex class IIβ alleles of New World ranid frogs

    Science.gov (United States)

    Kiemnec-Tyburczy, Karen M.; Richmond, Jonathan Q.; Savage, Anna E.; Zamudio, Kelly R.

    2010-01-01

    Genes encoded by the major histocompatibility complex (MHC) play key roles in the vertebrate immune system. However, our understanding of the evolutionary processes and underlying genetic mechanisms shaping these genes is limited in many taxa, including amphibians, a group currently impacted by emerging infectious diseases. To further elucidate the evolution of the MHC in frogs (anurans) and develop tools for population genetics, we surveyed allelic diversity of the MHC class II ??1 domain in both genomic and complementary DNA of seven New World species in the genus Rana (Lithobates). To assign locus affiliation to our alleles, we used a "gene walking" technique to obtain intron 2 sequences that flanked MHC class II?? exon 2. Two distinct intron sequences were recovered, suggesting the presence of at least two class II?? loci in Rana. We designed a primer pair that successfully amplified an orthologous locus from all seven Rana species. In total, we recovered 13 alleles and documented trans-species polymorphism for four of the alleles. We also found quantitative evidence of selection acting on amino acid residues that are putatively involved in peptide binding and structural stability of the ??1 domain of anurans. Our results indicated that primer mismatch can result in polymerase chain reaction (PCR) bias, which influences the number of alleles that are recovered. Using a single locus may minimize PCR bias caused by primer mismatch, and the gene walking technique was an effective approach for generating single-copy orthologous markers necessary for future studies of MHC allelic variation in natural amphibian populations. ?? 2010 Springer-Verlag.

  19. Tetradentate-arm Schiff base derived from the condensation reaction of 3,3′-dihydroxybenzidine, glyoxal/diacetyl and 2-aminophenol: Designing, structural elucidation and properties of their binuclear metal(II complexes

    Directory of Open Access Journals (Sweden)

    E. Akila

    2017-05-01

    Full Text Available The novel binuclear Schiff base complexes were prepared by the reaction of 3,3′-dihydroxybenzidine, glyoxal/diacetyl and 2-aminophenol in 1:2:2 M ratio. The binucleating Schiff base ligand and its complexes of Cu(II, Ni(II and VO(II ions were characterized by elemental analysis, molar conductance, 1H NMR, infrared, electronic spectra, cyclic voltammetry, thermal, magnetic and EPR studies. The low molar conductance values of the complexes support the non-electrolytic in nature. In IR spectra, the comparison of shift in frequency of the complexes with the ligand reveals the coordination of donor atom to the metal atom. The binuclear nature of the complexes is assessed from their magnetic susceptibility values. The electronic and EPR spectra of the metal complexes provide information about the geometry of the complexes and are in good agreement with the proposed square planar geometry for Cu(II, Ni(II and square pyramidal for VO(II complexes. Molecular modeling has been used to suggest the structure of the complexes. The DNA cleavage ability of the complexes was monitored by gel electrophoresis using supercoiled pUC18 DNA. The metal complexes were screened for their antibacterial activities against pathogenic bacteria like Staphylococcus aureus, Escherichia coli, Klebsiella pneumoniae and Bacillus subtilis. The activity data show that the metal complexes are more potent activity than the parent Schiff base ligand against microorganisms.

  20. GEOMETRIC COMPLEXITY ANALYSIS IN AN INTEGRATIVE TECHNOLOGY EVALUATION MODEL (ITEM FOR SELECTIVE LASER MELTING (SLM#

    Directory of Open Access Journals (Sweden)

    S. Merkt

    2012-01-01

    Full Text Available

    ENGLISH ABSTRACT: Selective laser melting (SLM is becoming an economically viable choice for manufacturing complex serial parts. This paper focuses on a geometric complexity analysis as part of the integrative technology evaluation model (ITEM presented here. In contrast to conventional evaluation methodologies, the ITEM considers interactions between product and process innovations generated by SLM. The evaluation of manufacturing processes that compete with SLM is the main goal of ITEM. The paper includes a complexity analysis of a test part from Festo AG. The paper closes with a discussion of how the expanded design freedom of SLM can be used to improve company operations, and how the complexity analysis presented here can be seen as a starting point for feature-based complexity analysis..

    AFRIKAANSE OPSOMMING: Selektiewe lasersmelting word geleidelik ’n gangbare ekonomiese keuse vir die vervaar-diging van opeenvolgende komplekse onderdele. Die navorsing is toegespits op die ontleding van meetkundige kompleksiteit as ’n gedeelte van ’n integrerende tegnologiese evalueringsmodel. Gemeet teen konvensionele evalueringsmodelle behandel die genoemde metode interaksies tussen produkte- en prosesinnovasies wat gegenereer word. Die navorsing behandel ’n kompleksiteitsontleding van ’n toetsonderdeel van die firma FESTO AG. Die resultaat toon hoe kompleksiteits-analise gebruik kan word as die vertrekpunt vir eienskapsgebaseerde analise.

  1. Selective recognition of monohydrogen phosphate by fluorescence enhancement of a new cerium complex

    International Nuclear Information System (INIS)

    Ganjali, Mohammad Reza; Hosseini, Morteza; Memari, Zahra; Faridbod, Farnoush; Norouzi, Parviz; Goldooz, Hassan; Badiei, Alireza

    2011-01-01

    Highlights: ► Finding a new fluorescent enhancing chemosensor for phosphate ions. ► Synthesis of a new complex (bis(8-hydroxy quinoline-5-solphonate) cerium(III) chloride (Ce(QS) 2 Cl)) as a practical fluorescent probe. ► Analysis of phosphate content in three kinds of fertilizers, mixed fertilizer (N–P–K), triple super phosphate (TSP), and single super phosphate (SSP) (from Zarrin Kood Co., Tehran, Iran). - Abstract: Bis(8-hydroxy quinoline-5-solphonate) cerium(III) chloride (Ce(QS) 2 Cl) (L) was synthesized and then used as a novel fluorescent sensor for anion recognition. Preliminarily study showed that fluorescence of L enhanced selectively in the presence of HPO 4 2− ion. This enhancement is attributed to a 1:1 complex formation between L and HPO 4 2− anion. The association constant of 1:1 complex of L-HPO 4 2− was calculated as 3.0 × 10 6 . Thus, L was utilized as a basis for a selective detection of HPO 4 2− anion in solution. The linear response range of the proposed fluorescent chemo-sensor covers a concentration range of HPO 4 2− from 3.3 × 10 −7 to 5.0 × 10 −6 mol L −1 with a detection limit of 2.5 × 10 −8 mol L −1 . L showed selective and sensitive fluorescence enhancement response toward HPO 4 2− ion in comparison with I 3 − , NO 3 − , CN − , CO 3 2− , Br − , Cl − , F − , H 2 PO 4 − and SO 4 2− ions. It was probably attributed to the higher stability of the inorganic complex between HPO 4 2− ion and L. The method was successfully applied for analysis of phosphate ions in some fertilizers samples.

  2. Knocking on wood: base metal complexes as catalysts for selective oxidation of lignin models and extracts.

    Science.gov (United States)

    Hanson, Susan K; Baker, R Tom

    2015-07-21

    This work began as part of a biomass conversion catalysis project with UC Santa Barbara funded by the first NSF Chemical Bonding Center, CATSB. Recognizing that catalytic aerobic oxidation of diol C-C bonds could potentially be used to break down lignocellulose, we began to synthesize oxovanadium complexes and explore their fundamental reactivity. Of course there were theories regarding the oxidation mechanism, but our mechanistic studies soon revealed a number of surprises of the type that keep all chemists coming back to the bench! We realized that these reactions were also exciting in that they actually used the oxygen-on-every-carbon property of biomass-derived molecules to control the selectivity of the oxidation. When we found that these oxovanadium complexes tended to convert sugars predominantly to formic acid and carbon dioxide, we replaced one of the OH groups with an ether and entered the dark world of lignin chemistry. In this Account, we summarize results from our collaboration and from our individual labs. In particular, we show that oxidation selectivity (C-C vs C-O bond cleavage) of lignin models using air and vanadium complexes depends on the ancillary ligands, the reaction solvent, and the substrate structure (i.e., phenolic vs non-phenolic). Selected vanadium complexes in the presence of added base serve as effective alcohol oxidation catalysts via a novel base-assisted dehydrogenation pathway. In contrast, copper catalysts effect direct C-C bond cleavage of these lignin models, presumably through a radical pathway. The most active vanadium catalyst exhibits unique activity for the depolymerization of organosolv lignin. After Weckhuysen's excellent 2010 review on lignin valorization, the number of catalysis studies and approaches on both lignin models and extracts has expanded rapidly. Today we are seeing new start-ups and lignin production facilities sprouting up across the globe as we all work to prove wrong the old pulp and paper chemist

  3. Luminescent platinum(II) complexes with functionalized N-heterocyclic carbene or diphosphine selectively probe mismatched and abasic DNA

    OpenAIRE

    Che, CM; Chen, T; To, WP; Zou, T; FUNG, SK; Lok, CN; YANG, C; Cao, B

    2016-01-01

    The selective targeting of mismatched DNA overexpressed in cancer cells is an appealing strategy in designing cancer diagnosis and therapy protocols. Few luminescent probes that specifically detect intracellular mismatched DNA have been reported. Here we used Pt(II) complexes with luminescence sensitive to subtle changes in the local environment and report several Pt(II) complexes that selectively bind to and identify DNA mismatches. We evaluated the complexes' DNA-binding characteristics by ...

  4. Blind trials of computer-assisted structure elucidation software

    Directory of Open Access Journals (Sweden)

    Moser Arvin

    2012-02-01

    Full Text Available Abstract Background One of the largest challenges in chemistry today remains that of efficiently mining through vast amounts of data in order to elucidate the chemical structure for an unknown compound. The elucidated candidate compound must be fully consistent with the data and any other competing candidates efficiently eliminated without doubt by using additional data if necessary. It has become increasingly necessary to incorporate an in silico structure generation and verification tool to facilitate this elucidation process. An effective structure elucidation software technology aims to mimic the skills of a human in interpreting the complex nature of spectral data while producing a solution within a reasonable amount of time. This type of software is known as computer-assisted structure elucidation or CASE software. A systematic trial of the ACD/Structure Elucidator CASE software was conducted over an extended period of time by analysing a set of single and double-blind trials submitted by a global audience of scientists. The purpose of the blind trials was to reduce subjective bias. Double-blind trials comprised of data where the candidate compound was unknown to both the submitting scientist and the analyst. The level of expertise of the submitting scientist ranged from novice to expert structure elucidation specialists with experience in pharmaceutical, industrial, government and academic environments. Results Beginning in 2003, and for the following nine years, the algorithms and software technology contained within ACD/Structure Elucidator have been tested against 112 data sets; many of these were unique challenges. Of these challenges 9% were double-blind trials. The results of eighteen of the single-blind trials were investigated in detail and included problems of a diverse nature with many of the specific challenges associated with algorithmic structure elucidation such as deficiency in protons, structure symmetry, a large number of

  5. Predation determines different selective pressure on pea aphid host races in a complex agricultural mosaic.

    Directory of Open Access Journals (Sweden)

    Adalbert Balog

    Full Text Available Field assessments were conducted to examine the interplay between host plant and predation in complex agricultural mosaic on pea aphid clover and alfalfa races. In one experiment, we examined the relative fitness on clover race (CR and alfalfa race (AR pea aphids on broad bean, red clover and alfalfa alone. But because clover is typically grown in a more complex agricultural mosaic with alfalfa and broad bean, a second experiment was conducted to assess the fitness consequences under predation in a more complex agricultural field setting that also included potential apparent competition with AR pea aphids. In a third experiment we tested for the effect of differential host race density on the fitness of the other host race mediated by a predator effect. CR pea aphids always had fitness losses when on broad bean (had lower fitness on broad bean relative to red clover and fitness benefits when on red clover (higher fitness on red clover relative to broad bean, whether or not in apparent competition with alfalfa race aphids on bean and alfalfa. AR suffered fitness loss on both alfalfa and bean in apparent competition with CR on clover. Therefore we can conclude that the predation rate between host races was highly asymmetrical. The complexity of the agricultural mosaic thus can influence prey selection by predators on different host plants. These may have evolutionary consequences through context dependent fitness benefits on particular host plants.

  6. A novel reduced-complexity group detection structure in MIMO frequency selective fading channels

    KAUST Repository

    Qaraqe, Khalid A.; Ahimian, Nariman R.; Alouini, Mohamed-Slim

    2010-01-01

    In this paper a novel reduced complexity detection method named modified symbol flipping method is introduced and its advantages on reducing the burden of the calculations at the receiver compared to the optimum maximum likelihood detection method on multiple input- multiple output frequency selective fading channels are explained. The initial concept of the symbol flipping method is derived from a preliminary detection scheme named bit flipping which was introduced in [1]. The detection structure employed in this paper is ing, detection, and cancellation. On the detection stage, the proposed method is employed and the results are compared to the group maximum likelihood detection scheme proposed in [2]. Simulation results show that a 6 dB performance gain can be achieved at the expense of a slight increase in complexity in comparison with the conventional symbol flipping scheme. © 2010 Crown.

  7. A novel reduced-complexity group detection structure in MIMO frequency selective fading channels

    KAUST Repository

    Qaraqe, Khalid A.

    2010-09-01

    In this paper a novel reduced complexity detection method named modified symbol flipping method is introduced and its advantages on reducing the burden of the calculations at the receiver compared to the optimum maximum likelihood detection method on multiple input- multiple output frequency selective fading channels are explained. The initial concept of the symbol flipping method is derived from a preliminary detection scheme named bit flipping which was introduced in [1]. The detection structure employed in this paper is ing, detection, and cancellation. On the detection stage, the proposed method is employed and the results are compared to the group maximum likelihood detection scheme proposed in [2]. Simulation results show that a 6 dB performance gain can be achieved at the expense of a slight increase in complexity in comparison with the conventional symbol flipping scheme. © 2010 Crown.

  8. Methods Dealing with Complexity in Selecting Joint Venture Contractors for Large-Scale Infrastructure Projects

    Directory of Open Access Journals (Sweden)

    Ru Liang

    2018-01-01

    Full Text Available The magnitude of business dynamics has increased rapidly due to increased complexity, uncertainty, and risk of large-scale infrastructure projects. This fact made it increasingly tough to “go alone” into a contractor. As a consequence, joint venture contractors with diverse strengths and weaknesses cooperatively bid for bidding. Understanding project complexity and making decision on the optimal joint venture contractor is challenging. This paper is to study how to select joint venture contractors for undertaking large-scale infrastructure projects based on a multiattribute mathematical model. Two different methods are developed to solve the problem. One is based on ideal points and the other one is based on balanced ideal advantages. Both of the two methods consider individual difference in expert judgment and contractor attributes. A case study of Hong Kong-Zhuhai-Macao-Bridge (HZMB project in China is used to demonstrate how to apply these two methods and their advantages.

  9. Low-Complexity Iterative Receiver for Space-Time Coded Signals over Frequency Selective Channels

    Directory of Open Access Journals (Sweden)

    Mohamed Siala

    2002-05-01

    Full Text Available We propose a low-complexity turbo-detector scheme for frequency selective multiple-input multiple-output channels. The detection part of the receiver is based on a List-type MAP equalizer which is a state-reduction algorithm of the MAP algorithm using per-survivor technique. This alternative achieves a good tradeoff between performance and complexity provided a small amount of the channel is neglected. In order to induce the good performance of this equalizer, we propose to use a whitened matched filter (WMF which leads to a white-noise “minimum phase” channel model. Simulation results show that the use of the WMF yields significant improvement, particularly over severe channels. Thanks to the iterative turbo processing (detection and decoding are iterated several times, the performance loss due to the use of the suboptimum List-type equalizer is recovered.

  10. Selective Release of anti–TB Drugs Complex from Smart Copolymeric Bioactive nano–carriers

    Directory of Open Access Journals (Sweden)

    Alejandro Arredondo–Peñaranda

    2014-07-01

    Full Text Available Smart nano–copolymeric matrices have been employed to load and release anti tuberculosis (anti – TB drugs combinated complexes of Ethambutol (EMB, Isoniazid (INH, Rifampicin (RMP and Pyrazinamide (PZA. Copolymeric nanocarriers were synthesized using a microemulsion polymerization method previously reported. These nanocarriers can show selective swelling–collapse response under changes in local environments such a temperature, pH, solvent composition and electrical stimuli. The employ of these kinds of systems permits a controlled and selective delivery and release on specific human tissues. High Performance Liquid Chromatography technique was used to allow the detection of combinated mixtures of different active principles of anti–TB drugs using an acetonitrile mobile phase at 0.5 mL/min of flow rate whit a Spherisorb ODS2, C18 column. The results obtained suggest that the employ of smart nanohydrogels is a novel method in several tuberculosis therapies.

  11. Complex and changing patterns of natural selection explain the evolution of the human hip.

    Science.gov (United States)

    Grabowski, Mark; Roseman, Charles C

    2015-08-01

    Causal explanations for the dramatic changes that occurred during the evolution of the human hip focus largely on selection for bipedal function and locomotor efficiency. These hypotheses rest on two critical assumptions. The first-that these anatomical changes served functional roles in bipedalism-has been supported in numerous analyses showing how postcranial changes likely affected locomotion. The second-that morphological changes that did play functional roles in bipedalism were the result of selection for that behavior-has not been previously explored and represents a major gap in our understanding of hominin hip evolution. Here we use evolutionary quantitative genetic models to test the hypothesis that strong directional selection on many individual aspects of morphology was responsible for the large differences observed across a sample of fossil hominin hips spanning the Plio-Pleistocene. Our approach uses covariance among traits and the differences between relatively complete fossils to estimate the net selection pressures that drove the major transitions in hominin hip evolution. Our findings show a complex and changing pattern of natural selection drove hominin hip evolution, and that many, but not all, traits hypothesized to play functional roles in bipedalism evolved as a direct result of natural selection. While the rate of evolutionary change for all transitions explored here does not exceed the amount expected if evolution was occurring solely through neutral processes, it was far above rates of evolution for morphological traits in other mammalian groups. Given that stasis is the norm in the mammalian fossil record, our results suggest that large shifts in the adaptive landscape drove hominin evolution. Copyright © 2015 Elsevier Ltd. All rights reserved.

  12. Selective chromogenic and fluorogenic peptide substrates for the assay of cysteine peptidases in complex mixtures.

    Science.gov (United States)

    Semashko, Tatiana A; Vorotnikova, Elena A; Sharikova, Valeriya F; Vinokurov, Konstantin S; Smirnova, Yulia A; Dunaevsky, Yakov E; Belozersky, Mikhail A; Oppert, Brenda; Elpidina, Elena N; Filippova, Irina Y

    2014-03-15

    This study describes the design, synthesis, and use of selective peptide substrates for cysteine peptidases of the C1 papain family, important in many biological processes. The structure of the newly synthesized substrates is Glp-Xaa-Ala-Y (where Glp=pyroglutamyl; Xaa=Phe or Val; and Y=pNA [p-nitroanilide], AMC [4-amino-7-methylcoumaride], or AFC [4-amino-7-trifluoromethyl-coumaride]). Substrates were synthesized enzymatically to guarantee selectivity of the reaction and optical purity of the target compounds, simplifying the scheme of synthesis and isolation of products. The hydrolysis of the synthesized substrates was evaluated by C1 cysteine peptidases from different organisms and with different functions, including plant enzymes papain, bromelain, ficin, and mammalian lysosomal cathepsins B and L. The new substrates were selective for C1 cysteine peptidases and were not hydrolyzed by serine, aspartic, or metallo peptidases. We demonstrated an application of the selectivity of the synthesized substrates during the chromatographic separation of a multicomponent set of digestive peptidases from a beetle, Tenebrio molitor. Used in combination with the cysteine peptidase inhibitor E-64, these substrates were able to differentiate cysteine peptidases from peptidases of other classes in midgut extracts from T. molitor larvae and larvae of the genus Tribolium; thus, they are useful in the analysis of complex mixtures containing peptidases from different classes. Published by Elsevier Inc.

  13. Red Queen Processes Drive Positive Selection on Major Histocompatibility Complex (MHC Genes.

    Directory of Open Access Journals (Sweden)

    Maciej Jan Ejsmond

    2015-11-01

    Full Text Available Major Histocompatibility Complex (MHC genes code for proteins involved in the incitation of the adaptive immune response in vertebrates, which is achieved through binding oligopeptides (antigens of pathogenic origin. Across vertebrate species, substitutions of amino acids at sites responsible for the specificity of antigen binding (ABS are positively selected. This is attributed to pathogen-driven balancing selection, which is also thought to maintain the high polymorphism of MHC genes, and to cause the sharing of allelic lineages between species. However, the nature of this selection remains controversial. We used individual-based computer simulations to investigate the roles of two phenomena capable of maintaining MHC polymorphism: heterozygote advantage and host-pathogen arms race (Red Queen process. Our simulations revealed that levels of MHC polymorphism were high and driven mostly by the Red Queen process at a high pathogen mutation rate, but were low and driven mostly by heterozygote advantage when the pathogen mutation rate was low. We found that novel mutations at ABSs are strongly favored by the Red Queen process, but not by heterozygote advantage, regardless of the pathogen mutation rate. However, while the strong advantage of novel alleles increased the allele turnover rate, under a high pathogen mutation rate, allelic lineages persisted for a comparable length of time under Red Queen and under heterozygote advantage. Thus, when pathogens evolve quickly, the Red Queen is capable of explaining both positive selection and long coalescence times, but the tension between the novel allele advantage and persistence of alleles deserves further investigation.

  14. Selective Sensing of Tyrosine Phosphorylation in Peptides Using Terbium(III Complexes

    Directory of Open Access Journals (Sweden)

    Jun Sumaoka

    2016-01-01

    Full Text Available Phosphorylation of tyrosine residues in proteins, as well as their dephosphorylation, is closely related to various diseases. However, this phosphorylation is usually accompanied by more abundant phosphorylation of serine and threonine residues in the proteins and covers only 0.05% of the total phosphorylation. Accordingly, highly selective detection of phosphorylated tyrosine in proteins is an urgent subject. In this review, recent developments in this field are described. Monomeric and binuclear TbIII complexes, which emit notable luminescence only in the presence of phosphotyrosine (pTyr, have been developed. There, the benzene ring of pTyr functions as an antenna and transfers its photoexcitation energy to the TbIII ion as the emission center. Even in the coexistence of phosphoserine (pSer and phosphothreonine (pThr, pTyr can be efficintly detected with high selectivity. Simply by adding these TbIII complexes to the solutions, phosphorylation of tyrosine in peptides by protein tyrosine kinases and dephosphorylation by protein tyrosine phosphatases can be successfully visualized in a real-time fashion. Furthermore, the activities of various inhibitors on these enzymes are quantitatively evaluated, indicating a strong potential of the method for efficient screening of eminent inhibitors from a number of candidates.

  15. Ammonium boranes for the selective complexation of cyanide or fluoride ions in water.

    Science.gov (United States)

    Hudnall, Todd W; Gabbaï, François P

    2007-10-03

    With the recognition of aqueous fluoride and cyanide ions as an objective, we have investigated the anion binding properties of two isomeric ammonium boranes, namely [p-(Mes2B)C6H4(NMe3)]+ ([1]+) and [o-(Mes2B)C6H4(NMe3)]+ ([2]+). These cationic boranes, which could be obtained by reaction of the known 4- and 2-dimesitylboryl-N,N-dimethylaniline with MeOTf, have been investigated both experimentally and computationally. They both react with fluoride and cyanide ions in organic solvents to afford the corresponding fluoroborate/ or cyanoborate/ammonium zwitterions 1F, 1CN, 2F, and 2CN. In aqueous solution, however, these cationic boranes behave as remarkably selective receptors. Indeed, [1]+ only complexes cyanide ions while [2]+ only complexes fluoride ions. In H2O/DMSO 60:40 vol (HEPES 6 mM, pH 7), the cyanide binding constant of [1]+ and the fluoride binding constant of [2]+ are respectively equal to 3.9 (+/-0.1) x 108 and 910 (+/-50) M-1. Structural and computational studies indicate that both steric and electronic effects contribute to the unusual selectivity displayed by these cationic boranes. Owing to favorable Coulombic effects, the para-derivative [1]+ has a very high affinity for cyanide; yet these effects are not sufficiently intense to allow complexation of the more efficiently hydrated and less basic fluoride anion. In the case of the ortho-derivative [2]+, the proximity of the ammonium moiety leads to an increase in the Lewis acidity of the boron center thus making fluoride binding possible. However, steric effects prevent cyanide coordination to the boron center of [2]+. Finally, cation [1]+ and [2]+ bind their dedicated anions reversibly and show a negligible response in the presence of other common anions including Cl-, Br-, I-, NO3-, OAc-, H2PO4-, and HSO4-.

  16. Selective Decontamination Effect of Metal Ions in Soil Using Supercritical CO2 and TBP Complex

    International Nuclear Information System (INIS)

    Park, Jihye; Park, Kwangheon; Jung, Wonyoung

    2014-01-01

    Decontamination of soil pollution is difficult because the type of contamination largely depends on the characteristics of the pollutant and the area. Also, existing soil decontamination methods generate large quantities of secondary waste and additional process costs. For this reason, new decontamination methods are always under active investigation. A method involving the use of supercritical carbon dioxide with excellent permeability in place of chemical solvents is currently being studied. Unlike other heavy metals in fission products, uranium is used as fuel, and must be handled carefully. Therefore, in this paper, we studied a supercritical carbon dioxide method for decontaminating heavy metal ions in soil using tri-n-butyl phosphate(TBP), which is well known as a ligand for the extraction of metal ions of actinium. We investigated the decontamination effect of heavy metal ions in the soil using TBP-HNO 3 Complex and supercritical carbon dioxide. The study results showed that when heavy metals in soil are extracted using supercritical carbon dioxide, the extraction efficiency is different according to the type of pollutant metal ions in the soil. When TBP-HNO 3 Complex is used with an extractant, uranium extraction is very effective, but lithium, strontium, and cesium extraction is not effective. Therefore, in the case of a mixture of uranium and other metals such as lithium, strontium, cesium, and so on in soil contaminated by fission product leaks from nuclear power plants, we can selectively decontaminate uranium with supercritical carbon dioxide and TBP-HNO 3 Complex

  17. Development of an efficient E. coli expression and purification system for a catalytically active, human Cullin3-RINGBox1 protein complex and elucidation of its quaternary structure with Keap1

    International Nuclear Information System (INIS)

    Small, Evan; Eggler, Aimee; Mesecar, Andrew D.

    2010-01-01

    Research highlights: → A novel expression strategy was used to purify Cul3-Rbx1 from E. coli. → The Cul3-Rbx1 complex is fully active and catalyzes ubiquitination of Nrf2 in vitro. → Cul3, Rbx1, and Keap1 form a complex with unique stoichiometry of 1:1:2. -- Abstract: The Cullin3-based E3 ubiquitin ligase complex is thought to play an important role in the cellular response to oxidative stress and xenobiotic assault. While limited biochemical studies of the ligase's role in these complex signaling pathways are beginning to emerge, structural studies are lagging far behind due to the inability to acquire sufficient quantities of full-length, highly pure and active Cullin3. Here we describe the design and construction of an optimized expression and purification system for the full-length, human Cullin3-RINGBox 1 (Rbx1) protein complex from Escherichia coli. The dual-expression system is comprised of codon-optimized Cullin3 and Rbx1 genes co-expressed from a single pET-Duet-1 plasmid. Rapid purification of the Cullin3-Rbx1 complex is achieved in two steps via an affinity column followed by size-exclusion chromatography. Approximately 15 mg of highly pure and active Cullin3-Rbx1 protein from 1 L of E. coli culture can be achieved. Analysis of the quaternary structure of the Cullin3-Rbx1 and Cullin3-Rbx1-Keap1 complexes by size-exclusion chromatography and analytical ultracentrifugation indicates a 1:1 stoichiometry for the Cullin3-Rbx1 complex (MW = 111 kDa), and a 1:1:2 stoichiometry for the Cullin3-Rbx1-Keap1 complex (MW = 280 kDa). This latter complex has a novel quaternary structural organization for cullin E3 ligases, and it is fully active based on an in vitro Cullin3-Rbx1-Keap1-Nrf2 ubiquitination activity assay that was developed and optimized in this study.

  18. Development of an efficient E. coli expression and purification system for a catalytically active, human Cullin3-RINGBox1 protein complex and elucidation of its quaternary structure with Keap1

    Energy Technology Data Exchange (ETDEWEB)

    Small, Evan [Department of Biochemistry, University of Illinois at Chicago, Chicago, IL 60607 (United States); Eggler, Aimee [Department of Biological Sciences, Purdue University, 240 S. Martin Jischke Drive, West Lafayette, IN 47907-1971 (United States); Mesecar, Andrew D., E-mail: amesecar@purdue.edu [Department of Biological Sciences, Purdue University, 240 S. Martin Jischke Drive, West Lafayette, IN 47907-1971 (United States)

    2010-10-01

    Research highlights: {yields} A novel expression strategy was used to purify Cul3-Rbx1 from E. coli. {yields} The Cul3-Rbx1 complex is fully active and catalyzes ubiquitination of Nrf2 in vitro. {yields} Cul3, Rbx1, and Keap1 form a complex with unique stoichiometry of 1:1:2. -- Abstract: The Cullin3-based E3 ubiquitin ligase complex is thought to play an important role in the cellular response to oxidative stress and xenobiotic assault. While limited biochemical studies of the ligase's role in these complex signaling pathways are beginning to emerge, structural studies are lagging far behind due to the inability to acquire sufficient quantities of full-length, highly pure and active Cullin3. Here we describe the design and construction of an optimized expression and purification system for the full-length, human Cullin3-RINGBox 1 (Rbx1) protein complex from Escherichia coli. The dual-expression system is comprised of codon-optimized Cullin3 and Rbx1 genes co-expressed from a single pET-Duet-1 plasmid. Rapid purification of the Cullin3-Rbx1 complex is achieved in two steps via an affinity column followed by size-exclusion chromatography. Approximately 15 mg of highly pure and active Cullin3-Rbx1 protein from 1 L of E. coli culture can be achieved. Analysis of the quaternary structure of the Cullin3-Rbx1 and Cullin3-Rbx1-Keap1 complexes by size-exclusion chromatography and analytical ultracentrifugation indicates a 1:1 stoichiometry for the Cullin3-Rbx1 complex (MW = 111 kDa), and a 1:1:2 stoichiometry for the Cullin3-Rbx1-Keap1 complex (MW = 280 kDa). This latter complex has a novel quaternary structural organization for cullin E3 ligases, and it is fully active based on an in vitro Cullin3-Rbx1-Keap1-Nrf2 ubiquitination activity assay that was developed and optimized in this study.

  19. Complex signatures of selection for the melanogenic loci TYR, TYRP1 and DCT in humans

    Directory of Open Access Journals (Sweden)

    Boyano María

    2008-02-01

    Full Text Available Abstract Background The observed correlation between ultraviolet light incidence and skin color, together with the geographical apportionment of skin reflectance among human populations, suggests an adaptive value for the pigmentation of the human skin. We have used Affymetrix U133a v2.0 gene expression microarrays to investigate the expression profiles of a total of 9 melanocyte cell lines (5 from lightly pigmented donors and 4 from darkly pigmented donors plus their respective unirradiated controls. In order to reveal signatures of selection in loci with a bearing on skin pigmentation in humans, we have resequenced between 4 to 5 kb of the proximal regulatory regions of three of the most differently expressed genes, in the expectation that variation at regulatory regions might account for intraespecific morphological diversity, as suggested elsewhere. Results Contrary to our expectations, expression profiles did not cluster the cells into unirradiated versus irradiated melanocytes, or into lightly pigmented versus darkly pigmented melanocytes. Instead, expression profiles correlated with the presence of Bovine Pituitary Extract (known to contain α-MSH in the media. This allowed us to differentiate between melanocytes that are synthesizing melanin and those that are not. TYR, TYRP1 and DCT were among the five most differently expressed genes between these two groups. Population genetic analyses of sequence haplotypes of the proximal regulatory flanking-regions included Tajima's D, HEW and DHEW neutrality tests analysis. These were complemented with EHH tests (among others in which the significance was obtained by a novel approach using extensive simulations under the coalescent model with recombination. We observe strong evidence for positive selection for TYRP1 alleles in Africans and for DCT and TYRP1 in Asians. However, the overall picture reflects a complex pattern of selection, which might include overdominance for DCT in Europeans

  20. Selection within organisms in the nineteenth century: Wilhelm Roux's complex legacy.

    Science.gov (United States)

    Heams, Thomas

    2012-09-01

    Selectionism, or the extension of darwinian chance/selection dynamics beyond the individual level, has a long history in biological thought. It has generated important theories in immunology or neurology, and turns out to be a convincing framework to account for the intrinsic stochastic nature of core events in cellular biology. When looking back at the intellectual origins of selectionism, the essay by the German embryologist Wilhelm Roux, Der Kampf der Theile im Organismus (The Struggle of the Parts in the Organism - 1881) might be one, if not the earliest reference after the darwinian revolution. It describes the individual as a multilevel structure, where each level results from a 'darwinian' struggle of its parts (molecules, cells, tissues, organs). But Roux's theory, far from being a simple extension of natural selection, has complex and even conflictual relationships with darwinism. This essay is worth rediscovering as a subtle historical testimony of the evolutionary and developmental life sciences debates of its time. Moreover, some of its theses may also enrich some current debates among evolutionary biologists over levels of selection, and among cellular and molecular biologists over the status of determinism in biology today. Copyright © 2012 Elsevier Ltd. All rights reserved.

  1. Elucidating reaction mechanisms on quantum computers

    Science.gov (United States)

    Reiher, Markus; Wiebe, Nathan; Svore, Krysta M.; Wecker, Dave; Troyer, Matthias

    2017-07-01

    With rapid recent advances in quantum technology, we are close to the threshold of quantum devices whose computational powers can exceed those of classical supercomputers. Here, we show that a quantum computer can be used to elucidate reaction mechanisms in complex chemical systems, using the open problem of biological nitrogen fixation in nitrogenase as an example. We discuss how quantum computers can augment classical computer simulations used to probe these reaction mechanisms, to significantly increase their accuracy and enable hitherto intractable simulations. Our resource estimates show that, even when taking into account the substantial overhead of quantum error correction, and the need to compile into discrete gate sets, the necessary computations can be performed in reasonable time on small quantum computers. Our results demonstrate that quantum computers will be able to tackle important problems in chemistry without requiring exorbitant resources.

  2. Elucidating reaction mechanisms on quantum computers

    Science.gov (United States)

    Reiher, Markus; Wiebe, Nathan; Svore, Krysta M.; Wecker, Dave; Troyer, Matthias

    2017-01-01

    With rapid recent advances in quantum technology, we are close to the threshold of quantum devices whose computational powers can exceed those of classical supercomputers. Here, we show that a quantum computer can be used to elucidate reaction mechanisms in complex chemical systems, using the open problem of biological nitrogen fixation in nitrogenase as an example. We discuss how quantum computers can augment classical computer simulations used to probe these reaction mechanisms, to significantly increase their accuracy and enable hitherto intractable simulations. Our resource estimates show that, even when taking into account the substantial overhead of quantum error correction, and the need to compile into discrete gate sets, the necessary computations can be performed in reasonable time on small quantum computers. Our results demonstrate that quantum computers will be able to tackle important problems in chemistry without requiring exorbitant resources. PMID:28674011

  3. Elucidating reaction mechanisms on quantum computers.

    Science.gov (United States)

    Reiher, Markus; Wiebe, Nathan; Svore, Krysta M; Wecker, Dave; Troyer, Matthias

    2017-07-18

    With rapid recent advances in quantum technology, we are close to the threshold of quantum devices whose computational powers can exceed those of classical supercomputers. Here, we show that a quantum computer can be used to elucidate reaction mechanisms in complex chemical systems, using the open problem of biological nitrogen fixation in nitrogenase as an example. We discuss how quantum computers can augment classical computer simulations used to probe these reaction mechanisms, to significantly increase their accuracy and enable hitherto intractable simulations. Our resource estimates show that, even when taking into account the substantial overhead of quantum error correction, and the need to compile into discrete gate sets, the necessary computations can be performed in reasonable time on small quantum computers. Our results demonstrate that quantum computers will be able to tackle important problems in chemistry without requiring exorbitant resources.

  4. Numerical simulation of complex part manufactured by selective laser melting process

    Science.gov (United States)

    Van Belle, Laurent

    2017-10-01

    Selective Laser Melting (SLM) process belonging to the family of the Additive Manufacturing (AM) technologies, enable to build parts layer by layer, from metallic powder and a CAD model. Physical phenomena that occur in the process have the same issues as conventional welding. Thermal gradients generate significant residual stresses and distortions in the parts. Moreover, the large and complex parts to manufacturing, accentuate the undesirable effects. Therefore, it is essential for manufacturers to offer a better understanding of the process and to ensure production reliability of parts with high added value. This paper focuses on the simulation of manufacturing turbine by SLM process in order to calculate residual stresses and distortions. Numerical results will be presented.

  5. Efficient and selective N-alkylation of amines with alcohols catalysed by manganese pincer complexes

    Science.gov (United States)

    Elangovan, Saravanakumar; Neumann, Jacob; Sortais, Jean-Baptiste; Junge, Kathrin; Darcel, Christophe; Beller, Matthias

    2016-01-01

    Borrowing hydrogen (or hydrogen autotransfer) reactions represent straightforward and sustainable C–N bond-forming processes. In general, precious metal-based catalysts are employed for this effective transformation. In recent years, the use of earth abundant and cheap non-noble metal catalysts for this process attracted considerable attention in the scientific community. Here we show that the selective N-alkylation of amines with alcohols can be catalysed by defined PNP manganese pincer complexes. A variety of substituted anilines are monoalkylated with different (hetero)aromatic and aliphatic alcohols even in the presence of other sensitive reducible functional groups. As a special highlight, we report the chemoselective monomethylation of primary amines using methanol under mild conditions. PMID:27708259

  6. Site-selective electroless nickel plating on patterned thin films of macromolecular metal complexes.

    Science.gov (United States)

    Kimura, Mutsumi; Yamagiwa, Hiroki; Asakawa, Daisuke; Noguchi, Makoto; Kurashina, Tadashi; Fukawa, Tadashi; Shirai, Hirofusa

    2010-12-01

    We demonstrate a simple route to depositing nickel layer patterns using photocross-linked polymer thin films containing palladium catalysts, which can be used as adhesive interlayers for fabrication of nickel patterns on glass and plastic substrates. Electroless nickel patterns can be obtained in three steps: (i) the pattern formation of partially quaterized poly(vinyl pyridine) by UV irradiation, (ii) the formation of macromolecular metal complex with palladium, and (iii) the nickel metallization using electroless plating bath. Metallization is site-selective and allows for a high resolution. And the resulting nickel layered structure shows good adhesion with glass and plastic substrates. The direct patterning of metallic layers onto insulating substrates indicates a great potential for fabricating micro/nano devices.

  7. Selective Cerebro-Myocardial Perfusion in Complex Neonatal Aortic Arch Pathology: Midterm Results.

    Science.gov (United States)

    Hoxha, Stiljan; Abbasciano, Riccardo Giuseppe; Sandrini, Camilla; Rossetti, Lucia; Menon, Tiziano; Barozzi, Luca; Linardi, Daniele; Rungatscher, Alessio; Faggian, Giuseppe; Luciani, Giovanni Battista

    2018-04-01

    Aortic arch repair in newborns and infants has traditionally been accomplished using a period of deep hypothermic circulatory arrest. To reduce neurologic and cardiac dysfunction related to circulatory arrest and myocardial ischemia during complex aortic arch surgery, an alternative and novel strategy for cerebro-myocardial protection was recently developed, where regional low-flow perfusion is combined with controlled and independent coronary perfusion. The aim of the present retrospective study was to assess short-term and mid-term results of selective and independent cerebro-myocardial perfusion in neonatal aortic arch surgery. From April 2008 to August 2015, 28 consecutive neonates underwent aortic arch surgery under cerebro-myocardial perfusion. There were 17 male and 11 female, with median age of 15 days (3-30 days) and median body weight of 3 kg (1.6-4.2 kg), 9 (32%) of whom with low body weight (cerebro-myocardial perfusion was 30 ± 11 min (15-69 min). Renal dysfunction, requiring a period of peritoneal dialysis was observed in 10 (36%) patients, while liver dysfunction was noted only in 3 (11%). There were three (11%) early and two late deaths during a median follow-up of 2.9 years (range 6 months-7.7 years), with an actuarial survival of 82% at 7 years. At latest follow-up, no patient showed signs of cardiac or neurologic dysfunction. The present experience shows that a strategy of selective and independent cerebro-myocardial perfusion is safe, versatile, and feasible in high-risk neonates with complex congenital arch pathology. Encouraging outcomes were noted in terms of cardiac and neurological function, with limited end-organ morbidity. © 2018 International Center for Artificial Organs and Transplantation and Wiley Periodicals, Inc.

  8. Active Interaction Mapping as a tool to elucidate hierarchical functions of biological processes.

    Science.gov (United States)

    Farré, Jean-Claude; Kramer, Michael; Ideker, Trey; Subramani, Suresh

    2017-07-03

    Increasingly, various 'omics data are contributing significantly to our understanding of novel biological processes, but it has not been possible to iteratively elucidate hierarchical functions in complex phenomena. We describe a general systems biology approach called Active Interaction Mapping (AI-MAP), which elucidates the hierarchy of functions for any biological process. Existing and new 'omics data sets can be iteratively added to create and improve hierarchical models which enhance our understanding of particular biological processes. The best datatypes to further improve an AI-MAP model are predicted computationally. We applied this approach to our understanding of general and selective autophagy, which are conserved in most eukaryotes, setting the stage for the broader application to other cellular processes of interest. In the particular application to autophagy-related processes, we uncovered and validated new autophagy and autophagy-related processes, expanded known autophagy processes with new components, integrated known non-autophagic processes with autophagy and predict other unexplored connections.

  9. Selective cerebro-myocardial perfusion in complex congenital aortic arch pathology: a novel technique.

    Science.gov (United States)

    De Rita, Fabrizio; Lucchese, Gianluca; Barozzi, Luca; Menon, Tiziano; Faggian, Giuseppe; Mazzucco, Alessandro; Luciani, Giovanni Battista

    2011-11-01

    Simultaneous cerebro-myocardial perfusion has been described in neonatal and infant arch surgery, suggesting a reduction in cardiac morbidity. Here reported is a novel technique for selective cerebral perfusion combined with controlled and independent myocardial perfusion during surgery for complex or recurrent aortic arch lesions. From April 2008 to April 2011, 10 patients with arch pathology underwent surgery (two hypoplastic left heart syndrome [HLHS], four recurrent arch obstruction, two aortic arch hypoplasia + ventricular septal defect [VSD], one single ventricle + transposition of the great arteries + arch hypoplasia, one interrupted aortic arch type B + VSD). Median age was 63 days (6 days-36 years) and median weight 4.0 kg (1.6-52). Via midline sternotomy, an arterial cannula (6 or 8 Fr for infants) was directly inserted into the innominate artery or through a polytetrafluoroethylene (PTFE) graft (for neonates cerebro-myocardial perfusion was 39 ± 18 min (17-69). Weaning from cardiopulmonary bypass was achieved without inotropic support in three and with low dose in seven patients. One patient required veno-arterial extracorporeal membrane oxygenation. Four patients, body weight cerebro-myocardial perfusion is feasible in patients with complex or recurrent aortic arch disease, starting from premature newborn less than 2.0 kg of body weight to adults. The technique is as safe as previously reported methods of cerebro-myocardial perfusion and possibly more versatile. © 2011, Copyright the Authors. Artificial Organs © 2011, International Center for Artificial Organs and Transplantation and Wiley Periodicals, Inc.

  10. Deconvolution of Complex 1D NMR Spectra Using Objective Model Selection.

    Directory of Open Access Journals (Sweden)

    Travis S Hughes

    Full Text Available Fluorine (19F NMR has emerged as a useful tool for characterization of slow dynamics in 19F-labeled proteins. One-dimensional (1D 19F NMR spectra of proteins can be broad, irregular and complex, due to exchange of probe nuclei between distinct electrostatic environments; and therefore cannot be deconvoluted and analyzed in an objective way using currently available software. We have developed a Python-based deconvolution program, decon1d, which uses Bayesian information criteria (BIC to objectively determine which model (number of peaks would most likely produce the experimentally obtained data. The method also allows for fitting of intermediate exchange spectra, which is not supported by current software in the absence of a specific kinetic model. In current methods, determination of the deconvolution model best supported by the data is done manually through comparison of residual error values, which can be time consuming and requires model selection by the user. In contrast, the BIC method used by decond1d provides a quantitative method for model comparison that penalizes for model complexity helping to prevent over-fitting of the data and allows identification of the most parsimonious model. The decon1d program is freely available as a downloadable Python script at the project website (https://github.com/hughests/decon1d/.

  11. Fast and Accurate Identification of Cross-Linked Peptides for the Structural Analysis of Large Protein Complexes and Elucidation of Interaction Networks. / Tahir, Salman; Bukowski-Wills, Jimi-Carlo; Rasmussen, Morten; Rappsilber, Juri

    DEFF Research Database (Denmark)

    Rasmussen, Morten

    to investigate protein structure and protein-protein interactions. When applied to single proteins or small purified protein complexes, this methodology works well. However certain challenges arise when applied to more complex samples. One of the main problems is the combinatorial increase in the search space...... simplify a spectrum because we remove all peaks that are accounted for by the fragmentation of peptide one. This approach is highly sensitive and scales well as revealed by searching our data of synthetic cross-links against a large sequence database. Currently, against a protein database of >1300 proteins...... a spectrum is searched in 0.35 seconds - a vast improvement when compared to the exhaustive search method of combining every potential cross-link for each spectrum(60 hours). In fact the search time is comparable, if not better, than existing linear search engines. Furthermore, we auto-validate the results...

  12. Screening tests for hazard classification of complex waste materials – Selection of methods

    International Nuclear Information System (INIS)

    Weltens, R.; Vanermen, G.; Tirez, K.; Robbens, J.; Deprez, K.; Michiels, L.

    2012-01-01

    In this study we describe the development of an alternative methodology for hazard characterization of waste materials. Such an alternative methodology for hazard assessment of complex waste materials is urgently needed, because the lack of a validated instrument leads to arbitrary hazard classification of such complex waste materials. False classification can lead to human and environmental health risks and also has important financial consequences for the waste owner. The Hazardous Waste Directive (HWD) describes the methodology for hazard classification of waste materials. For mirror entries the HWD classification is based upon the hazardous properties (H1–15) of the waste which can be assessed from the hazardous properties of individual identified waste compounds or – if not all compounds are identified – from test results of hazard assessment tests performed on the waste material itself. For the latter the HWD recommends toxicity tests that were initially designed for risk assessment of chemicals in consumer products (pharmaceuticals, cosmetics, biocides, food, etc.). These tests (often using mammals) are not designed nor suitable for the hazard characterization of waste materials. With the present study we want to contribute to the development of an alternative and transparent test strategy for hazard assessment of complex wastes that is in line with the HWD principles for waste classification. It is necessary to cope with this important shortcoming in hazardous waste classification and to demonstrate that alternative methods are available that can be used for hazard assessment of waste materials. Next, by describing the pros and cons of the available methods, and by identifying the needs for additional or further development of test methods, we hope to stimulate research efforts and development in this direction. In this paper we describe promising techniques and argument on the test selection for the pilot study that we have performed on different

  13. New selective ligands for caesium. Application to Cs+/Na+ separation by nano-filtration-complexation in aqueous phase

    International Nuclear Information System (INIS)

    Pellet-Rostaing, S.; Chitry, F.; Lemaire, M.; Guy, A.; Foos, J.

    2000-01-01

    Separating traces of caesium from aqueous medium containing high sodium concentration is a harsh problem because caesium and sodium have a similar behaviour in aqueous medium. The aim of our study was to select a highly caesium-selective ligand in a nano-filtration-complexation process in order to achieve Cs + /Na + separation. This process involve a nano-filtration step combined with a preliminary complexation step. Caesium complexes are retained by the nano-filtration membrane whereas free sodium cations pass through it. We tried to find a relation between the ligands structure and their activity towards caesium-complexation. Among the synthesized receptors, Tetra-hydroxylated bis-crown-6 calix[4]arene was found to be the more caesium-selective ligand (S=β(Cs + )/β(Na+)=6600). Combined with a nano-filtration process, this ligand helped reaching 90% caesium retention in a highly concentrated aqueous medium ([NaNO 3 ] = 3 mol/L). (authors)

  14. The complex formation of selected actinides (U, Np, Cm) with microbial ligands

    International Nuclear Information System (INIS)

    Glorius, Maja

    2009-01-01

    One of the urgent tasks in the field of nuclear technology is the final storage of radioactive substances. As a part of the safety requirements the protection of humans and the environment from the danger of radioactive substances in case of the release from the final storage is essential. For performing long-term safety calculations the detailed understanding of the physico-chemical effects and influences which cause the mobilisation and transport of actinides are necessary. The presented work was a discrete part of a project, which was focused on the clarification of the influence of microorganisms on the migration of actinides in case of the release of actinides from a final storage. The influence of microbial produced substances on the mobilisation of selected actinides was studied thereby. The microbial produced substances studied in this project were synthesized by bacteria from the Pseudomonas genus under special conditions. Fluorescent Pseudomonads secrete bacterial pyoverdin-type siderophores with a high potential to complex and transport metals, especially iron(III). The aim of the project was to determine how and under which conditions the bioligands are able to complex also radioactive substances and therefore to transport them. For this work the alpha-emitting actinides uranium, curium and neptunium were chosen because their long-life cycle and their radiotoxicity are a matter of particular interest. This work dealed with the interaction of the actinides U(VI), Np(V) and Cm(III) with model ligands simulating the functionality of the pyoverdins. So, such bioligands can essentially influence the behaviour of actinides in the environment. The results of this work contribute to a better understanding and assessment of the influence of the microbial ligands to the mobilisation and migration of the radionuclides. The outcomes could be used to quantify the actinide-mobilising effect of the bioligands, which are released, for example, in the vicinity of a

  15. Uranium exploration target selection for proterozoic iron oxide/breccia complex type deposits in India

    International Nuclear Information System (INIS)

    Dwivedy, K.K.; Sinha, K.K.

    1997-01-01

    Multimetal iron oxide/breccia complex (IOBC) type deposits exemplified by Olympic Dam in Australia, fall under low grade, large tonnage deposits. A multidisciplinary integrated exploration programme consisting of airborne surveys, ground geological surveys, geophysical and geochemical investigations and exploratory drilling, supported adequately by the state of the art analytical facilities, data processing using various software and digital image processing has shown moderate success in the identification of target areas for this type of deposits in the Proterozoic terrains of India. Intracratonic, anorogenic, continental rift to continental margin environment have been identified in a very wide spectrum of rock associations. The genesis and evolution of such associations during the Middle Proterozoic period have been reviewed and applied for target selection in the (i) Son-Narmada rift valley zone; (ii) areas covered by Dongargarh Supergroup of rocks in Madhya Pradesh; (iii) areas exposing ferruginous breccia in the western part of the Singhbhum Shear Zone (SSZ) around Lotapahar; (iv) Siang Group of rocks in Arunachal Pradesh; (v) Crystalline rocks of Garo Hills around Anek; and (vi) Chhotanagpur Gneissic complex in the Bahia-Ulatutoli tract of Ranchi Plateau. Of theses six areas, the Son-Narmada rift area appears to be the most promising area for IOBC type deposits. Considering occurrences of the uranium anomalies near Meraraich, Kundabhati, Naktu and Kudar and positive favourability criteria observed in a wide variety of rocks spatially related to the rifts and shears, certain sectors in Son-Narmada rift zone have been identified as promising for intense subsurface exploration. 20 refs, 4 figs, 1 tab

  16. Genomic Selection in the Era of Next Generation Sequencing for Complex Traits in Plant Breeding.

    Science.gov (United States)

    Bhat, Javaid A; Ali, Sajad; Salgotra, Romesh K; Mir, Zahoor A; Dutta, Sutapa; Jadon, Vasudha; Tyagi, Anshika; Mushtaq, Muntazir; Jain, Neelu; Singh, Pradeep K; Singh, Gyanendra P; Prabhu, K V

    2016-01-01

    Genomic selection (GS) is a promising approach exploiting molecular genetic markers to design novel breeding programs and to develop new markers-based models for genetic evaluation. In plant breeding, it provides opportunities to increase genetic gain of complex traits per unit time and cost. The cost-benefit balance was an important consideration for GS to work in crop plants. Availability of genome-wide high-throughput, cost-effective and flexible markers, having low ascertainment bias, suitable for large population size as well for both model and non-model crop species with or without the reference genome sequence was the most important factor for its successful and effective implementation in crop species. These factors were the major limitations to earlier marker systems viz., SSR and array-based, and was unimaginable before the availability of next-generation sequencing (NGS) technologies which have provided novel SNP genotyping platforms especially the genotyping by sequencing. These marker technologies have changed the entire scenario of marker applications and made the use of GS a routine work for crop improvement in both model and non-model crop species. The NGS-based genotyping have increased genomic-estimated breeding value prediction accuracies over other established marker platform in cereals and other crop species, and made the dream of GS true in crop breeding. But to harness the true benefits from GS, these marker technologies will be combined with high-throughput phenotyping for achieving the valuable genetic gain from complex traits. Moreover, the continuous decline in sequencing cost will make the WGS feasible and cost effective for GS in near future. Till that time matures the targeted sequencing seems to be more cost-effective option for large scale marker discovery and GS, particularly in case of large and un-decoded genomes.

  17. Selective whole genome amplification for resequencing target microbial species from complex natural samples.

    Science.gov (United States)

    Leichty, Aaron R; Brisson, Dustin

    2014-10-01

    Population genomic analyses have demonstrated power to address major questions in evolutionary and molecular microbiology. Collecting populations of genomes is hindered in many microbial species by the absence of a cost effective and practical method to collect ample quantities of sufficiently pure genomic DNA for next-generation sequencing. Here we present a simple method to amplify genomes of a target microbial species present in a complex, natural sample. The selective whole genome amplification (SWGA) technique amplifies target genomes using nucleotide sequence motifs that are common in the target microbe genome, but rare in the background genomes, to prime the highly processive phi29 polymerase. SWGA thus selectively amplifies the target genome from samples in which it originally represented a minor fraction of the total DNA. The post-SWGA samples are enriched in target genomic DNA, which are ideal for population resequencing. We demonstrate the efficacy of SWGA using both laboratory-prepared mixtures of cultured microbes as well as a natural host-microbe association. Targeted amplification of Borrelia burgdorferi mixed with Escherichia coli at genome ratios of 1:2000 resulted in >10(5)-fold amplification of the target genomes with genomic extracts from Wolbachia pipientis-infected Drosophila melanogaster resulted in up to 70% of high-throughput resequencing reads mapping to the W. pipientis genome. By contrast, 2-9% of sequencing reads were derived from W. pipientis without prior amplification. The SWGA technique results in high sequencing coverage at a fraction of the sequencing effort, thus allowing population genomic studies at affordable costs. Copyright © 2014 by the Genetics Society of America.

  18. Selective separation of yttrium by CA-100 in the presence of a complexing agent

    International Nuclear Information System (INIS)

    Sun Xiaobo; Wang Yige; Li Deqian

    2006-01-01

    The selective separation of Y from yttrium solution containing small heavy rare earth (HRE) impurities (Ho, Er, Tm, Yb, Lu) by liquid-liquid extraction using CA-100 in the presence of a water-soluble complexing agent of ethylenediaminetetraacetic acid (EDTA) was experimentally studied at 298 K. Experiments were carried out in two feeds, Feed-I: [RE] f = 4.94 x 10 -3 M, Y = 98.5%, HRE (Ho, Er, Tm, Yb, Lu) = 1.5%; Feed-II: [RE] f = 4.94 x 10 -3 M, Y = 99.9%, HRE (Ho, Er, Tm, Yb, Lu) = 0.1%, as a function of equilibrium pH (pH eq ), the concentration ratio of [EDTA]:[HRE impurities]. It was shown that the extraction of HRE in the presence of EDTA was suppressed when compared to that of Y because of the masking effect, while the selective extraction of Y was enhanced and the separation factors increased to maximum at appropriate condition for Feed-I: Y/Ho = 1.53, Y/Er 3.09, Y/Tm = 5.61, Y/Yb = 12.04, Y/Lu = 27.51 at pH 4.37 and [EDTA]:[HRE impurities] = 4:1, for Feed-II: Y/Ho = 1.32, Y/Er = 1.91, Y/Tm = 2.00, Y/Yb 3.05, Y/Lu = 3.33 at pH 4.42 and [EDTA]:[HRE impurities] = 8:1. The separation and purification of Y by this method was discussed

  19. Ionic flotation of complexing oxyanions. Thermodynamics of uranyl complexation in a sulfuric medium. Definition of selectivity conditions of the process

    International Nuclear Information System (INIS)

    Bouzat, G.

    1987-01-01

    Oxyanion ionic flotation process with dodecylamine hydrochloride as collector is studied by investigation of flotation and filtration recovery curves, suspension turbidity, conductimetric measurements, and solubility of ionic species. The process is controlled by chemical reactions of precipitation and by adsorption of surfactant confering hydrophobic or hydrophilic surface properties to the solid phase respectively when one or two monolayers of surfactant are successively adsorbed. Equilibrium constants (in terms of activity) of the uranium (VI) complexation with sulphate oxyanions are calculated through Raman spectroscopic study of uranyl sulphate aqueous solutions. The complexation results in a shift of the symmetrical stretching vibration band of U0 2 to low wavenumbers and an increase of their cross section. The solubility curves of ionic species in the precipitation of uranyl -sulphate complexes by dodecylamine hydrochloride are modelled. The knowledge of solubility products, activity coefficients of the species and critical micellar concentration of the surfactant allow the modelling of flotation recovery curves. Temperature and collector structure modifications are studied in terms of optimization parameters and uranium extraction of mine drainage water is processed. Residual concentration of surfactant is considerably lowered by adsorption on montmorillonite

  20. Quantitative disease resistance: to better understand parasite-mediated selection on major histocompatibility complex.

    Science.gov (United States)

    Westerdahl, Helena; Asghar, Muhammad; Hasselquist, Dennis; Bensch, Staffan

    2012-02-07

    We outline a descriptive framework of how candidate alleles of the immune system associate with infectious diseases in natural populations of animals. Three kinds of alleles can be separated when both prevalence of infection and infection intensity are measured--qualitative disease resistance, quantitative disease resistance and susceptibility alleles. Our descriptive framework demonstrates why alleles for quantitative resistance and susceptibility cannot be separated based on prevalence data alone, but are distinguishable on infection intensity. We then present a case study to evaluate a previous finding of a positive association between prevalence of a severe avian malaria infection (GRW2, Plasmodium ashfordi) and a major histocompatibility complex (MHC) class I allele (B4b) in great reed warblers Acrocephalus arundinaceus. Using the same dataset, we find that individuals with allele B4b have lower GRW2 infection intensities than individuals without this allele. Therefore, allele B4b provides quantitative resistance rather than increasing susceptibility to infection. This implies that birds carrying B4b can mount an immune response that suppresses the acute-phase GRW2 infection, while birds without this allele cannot and may die. We argue that it is important to determine whether MHC alleles related to infections are advantageous (quantitative and qualitative resistance) or disadvantageous (susceptibility) to obtain a more complete picture of pathogen-mediated balancing selection.

  1. Optimal complex exponentials BEM and channel estimation in doubly selective channel

    International Nuclear Information System (INIS)

    Song, Lijun; Lei, Xia; Yu, Feng; Jin, Maozhu

    2016-01-01

    Over doubly selective channel, the optimal complex exponentials BEM (CE-BEM) is required to characterize the transmission in transform domain in order to reducing the huge number of the estimated parameters during directly estimating the impulse response in time domain. This paper proposed an improved CE-BEM to alleviating the high frequency sampling error caused by conventional CE-BEM. On the one hand, exploiting the improved CE-BEM, we achieve the sampling point is in the Doppler spread spectrum and the maximum sampling frequency is equal to the maximum Doppler shift. On the other hand we optimize the function and dimension of basis in CE-BEM respectively ,and obtain the closed solution of the EM based channel estimation differential operator by exploiting the above optimal BEM. Finally, the numerical results and theoretic analysis show that the dimension of basis is mainly depend on the maximum Doppler shift and signal-to-noise ratio (SNR), and if fixing the number of the pilot symbol, the dimension of basis is higher, the modeling error is smaller, while the accuracy of the parameter estimation is reduced, which implies that we need to achieve a tradeoff between the modeling error and the accuracy of the parameter estimation and the basis function influences the accuracy of describing the Doppler spread spectrum after identifying the dimension of the basis.

  2. Highly selective detection of glutathione using a NIP/Cu2+ complex fluorescent probe

    International Nuclear Information System (INIS)

    Liang Wenrui; Zhao Zhi; Zhang Yang; Wang Qiusheng; Zhao Xin; Ouyang Jie

    2012-01-01

    A novel fluorescent compound, 4-(trimethyl ammonium chloride)acetamide-2-(1H-naphtho[2,3-d]imidazol-2-yl)phenol (TMACA-NIP), was synthesized and used as a fluorescent probe for detecting glutathione reduced (GSH). The new NIP-based probe exhibited high fluorescence in water, which was quenched during the presence of copper (II) due to the complexation between TMACA-NIP and Cu 2+ . But after adding GSH into the TMACA-NIP and Cu 2+ system, the fluorescence of TMACA-NIP was recovered because the binding force between GSH and Cu 2+ is stronger than that between TMACA-NIP and Cu 2+ , which destroys the equilibrium between NIP and copper (II) ions and releases the fluorescence probe of TMACA-NIP. This three-component competing system of NIP/Cu 2+ /GSH can be used to detect GSH simply and rapidly. - Highlights: ► A novel fluorescence probe was developed to detect GSH that operates in aqueous solution. ► TMACA-NIP was synthesized and employed as “read-out” units of NIP/Cu 2+ /GSH. ► NIP-based probe shows high selectivity over other sulfhydryl compounds.

  3. From single-site tantalum complexes to nanoparticles of TaxNy and TaOxNy supported on silica: elucidation of synthesis chemistry by dynamic nuclear polarization surface enhanced NMR spectroscopy and X-ray absorption spectroscopy

    KAUST Repository

    Mohandas, Janet Chakkamadathil

    2017-06-08

    Air-stable catalysts consisting of tantalum nitride nanoparticles represented as a mixture of TaxNy and TaOxNy with diameters in the range of 0.5 to 3 nm supported on highly dehydroxylated silica were synthesized from TaMe5 (Me = methyl) and dimeric Ta-2(OMe)(10) with guidance by the principles of surface organometallic chemistry (SOMC). Characterization of the supported precursors and the supported nanoparticles formed from them was carried out by IR, NMR, UV-Vis, extended X-ray absorption fine structure, and X-ray photoelectron spectroscopies complemented with XRD and high-resolution TEM, with dynamic nuclear polarization surface enhanced NMR spectroscopy being especially helpful by providing enhanced intensities of the signals of H-1, C-13, Si-29, and N-15 at their natural abundances. The characterization data provide details of the synthesis chemistry, including evidence of (a) O-2 insertion into Ta-CH3 species on the support and (b) a binuclear to mononuclear transformation of species formed from Ta-2(OMe)(10) on the support. A catalytic test reaction, cyclooctene epoxidation, was used to probe the supported nanoparticles, with 30% H2O2 serving as the oxidant. The catalysts gave selectivities up to 98% for the epoxide at conversions as high as 99% with a 3.4 wt% loading of Ta present as TaxNy/TaOxNy.

  4. U(VI) complexation with selected flavonoids investigated by absorption and emission spectroscopy at light acidic conditions

    Energy Technology Data Exchange (ETDEWEB)

    Guenther, Alix; Geipel, Gerhard [Helmholtz-Zentrum Dresden-Rossendorf e.V., Dresden (Germany). Biogeochemistry

    2017-06-01

    Flavonoids are secondary plant compounds and have important properties. Beside their antioxidant activity and effects as enzyme inhibitors, they can bind metals ions. The possible release of flavonoids from the root into the soil can affect the migration of radionuclides in the biological and geological environment. In this work, the complexation behavior of selected flavonols and a flavonol glycoside towards U(VI) were spectroscopically investigated and the corresponding complex stability constants were determined.

  5. U(VI) complexation with selected flavonoids investigated by absorption and emission spectroscopy at light acidic conditions

    International Nuclear Information System (INIS)

    Guenther, Alix; Geipel, Gerhard

    2017-01-01

    Flavonoids are secondary plant compounds and have important properties. Beside their antioxidant activity and effects as enzyme inhibitors, they can bind metals ions. The possible release of flavonoids from the root into the soil can affect the migration of radionuclides in the biological and geological environment. In this work, the complexation behavior of selected flavonols and a flavonol glycoside towards U(VI) were spectroscopically investigated and the corresponding complex stability constants were determined.

  6. Mobility of organic complexes of some non-TRU fission and activation products: a selective review

    Energy Technology Data Exchange (ETDEWEB)

    Wiggins, D.J.; Franz, J.A.

    1978-05-01

    Zr, Nb, Ni, and possibly Tc are mobile in the presence of aqueous organic complexing agents to a certain extent. Low pH appears to be required for efficient complex formations with organic ligands in aqueous media. Zr complexes with a number of synthetic chelating agents such as EDTA, and DTPA to form stable, water-soluble complexes in acidic and neutral aqueous systems. Zr also complexes with HIMDA or HXG to form a stable, water soluble complex in any aqueous system and with ..cap alpha..-hydroxy carboxylic acids in alkaline aqueous systems. Uncomplexed Zr would be readily absorbed by or precipitated on soil. It is predicted that the organic complexes of Zr would be absorbed less by soil than uncomplexed zirconium. Nb generally forms the most stable complexes with nitrogen containing chelating ligands such as EDTA, and less stable complexes with ..cap alpha..-hydroxy carboxylic acids and monodentate ligands. Uncomplexed Nb would be efficiently absorbed by or precipitated on soil from aqueous systems. Despite the high stability constants of complexed Nb, one would predict that organic complexes of niobium would be absorbed by soil because of hydrolysis of complexed Nb to insoluble hydrous niobium oxide. Ni complexes strongly with a number of oxygen and nitrogen containing organic ligands. Uncomplexed Ni is absorbed by soil in acidic and neutral aqueous systems and precipitated on soil in alkaline aqueous systems. Two complexes of Ni are known to be absorbed to a much lesser extent by soil (Ni-DTPA, Ni-EDTA). Fulvic acid and synthetic chelating agents are known to greatly enhance the movement of Ni in soil and to reduce Ni absorption by soil. Tc complexes with organic ligands in a reducing environment but the behavior of these complexes in a nonreducing environment is unknown. 8 tables, 3 figs. 62 refs.

  7. Mobility of organic complexes of some non-TRU fission and activation products: a selective review

    International Nuclear Information System (INIS)

    Wiggins, D.J.; Franz, J.A.

    1978-05-01

    Zr, Nb, Ni, and possibly Tc are mobile in the presence of aqueous organic complexing agents to a certain extent. Low pH appears to be required for efficient complex formations with organic ligands in aqueous media. Zr complexes with a number of synthetic chelating agents such as EDTA, and DTPA to form stable, water-soluble complexes in acidic and neutral aqueous systems. Zr also complexes with HIMDA or HXG to form a stable, water soluble complex in any aqueous system and with α-hydroxy carboxylic acids in alkaline aqueous systems. Uncomplexed Zr would be readily absorbed by or precipitated on soil. It is predicted that the organic complexes of Zr would be absorbed less by soil than uncomplexed zirconium. Nb generally forms the most stable complexes with nitrogen containing chelating ligands such as EDTA, and less stable complexes with α-hydroxy carboxylic acids and monodentate ligands. Uncomplexed Nb would be efficiently absorbed by or precipitated on soil from aqueous systems. Despite the high stability constants of complexed Nb, one would predict that organic complexes of niobium would be absorbed by soil because of hydrolysis of complexed Nb to insoluble hydrous niobium oxide. Ni complexes strongly with a number of oxygen and nitrogen containing organic ligands. Uncomplexed Ni is absorbed by soil in acidic and neutral aqueous systems and precipitated on soil in alkaline aqueous systems. Two complexes of Ni are known to be absorbed to a much lesser extent by soil (Ni-DTPA, Ni-EDTA). Fulvic acid and synthetic chelating agents are known to greatly enhance the movement of Ni in soil and to reduce Ni absorption by soil. Tc complexes with organic ligands in a reducing environment but the behavior of these complexes in a nonreducing environment is unknown. 8 tables, 3 figs. 62 refs

  8. Metalophthalocyanine complexes as ion-carriers in membrane-selective electrodes for detection of thiosalicylic acid

    International Nuclear Information System (INIS)

    Shahrokhian, Saeed; Souri, Ali

    2004-01-01

    The potentiometric response properties of several PVC-based membrane electrodes using phthalocyanine complexes of aluminum (AlPc), nickel (NiPc) and copper (CuPc) as anion carriers, toward thiosalicylic acid (TSA) were investigated. The influences of lipophilic ionic additives (cationic and anionic) and the pH of the buffered solutions were used for the interpretation of the mechanism of the potentiometric response of sensors. The sensitivity, linear range, detection limit, and potentiometric selectivity of the membrane sensors show a considerable dependence on the nature of central metal of the ionophore. The membrane electrodes based on AlPc demonstrate sub-Nernstian responses toward TSA over the range of 0.01 to 1x10 -5 M. In the case of NiPc and CuPc as ionophores and in the presence of trioctylmethyl ammonium (TOMA + ) as a cationic additive, a Nernstian response could be established in a range of 4 orders of magnitudes of TSA concentration (0.01 to 1x10 -6 M). The results of potentiometric investigations revealed that from thermodynamic point of view, the axial coordination of thiosalicylate with the central metal of NiPc and CuPc is more efficient with respect to AlPc. This preference in response to TSA was discussed on the basis of the softness nature of NiPc and CuPc and more affinity for coordination with the thiolate group of thiosalicylate as a soft anion. These potentiometric sensors manifest prominent advantages of high selectivity for TSA over the various inorganic and organic anions, fast response times and micromolar detection limits and can be used over a wide pH range of 4.0-8.0. The prepared electrodes based on NiPc and CuPc were successfully applied in the potentiometric titration of sub-milimolar quantities of Hg 2+ in aqueous solutions and very good recovery results were obtained in these measurements. The results of complexometric studies between Hg 2+ and TSA using electrodes based on NiPc and CuPc as indicator electrodes were compared with

  9. Selective Fiber Degeneration in the Peripheral Nerve of a Patient With Severe Complex Regional Pain Syndrome

    Directory of Open Access Journals (Sweden)

    Adrien Yvon

    2018-04-01

    Full Text Available Aims: Complex regional pain syndrome (CRPS is characterized by chronic debilitating pain disproportional to the inciting event and accompanied by motor, sensory, and autonomic disturbances. The pathophysiology of CRPS remains elusive. An exceptional case of severe CRPS leading to forearm amputation provided the opportunity to examine nerve histopathological features of the peripheral nerves.Methods: A 35-year-old female developed CRPS secondary to low voltage electrical injury. The CRPS was refractory to medical therapy and led to functional loss of the forelimb, repeated cutaneous wound infections leading to hospitalization. Specifically, the patient had exhausted a targeted conservative pain management programme prior to forearm amputation. Radial, median, and ulnar nerve specimens were obtained from the amputated limb and analyzed by light and transmission electron microscopy (TEM.Results: All samples showed features of selective myelinated nerve fiber degeneration (47–58% of fibers on electron microscopy. Degenerating myelinated fibers were significantly larger than healthy fibers (p < 0.05, and corresponded to the larger Aα fibers (motor/proprioception whilst smaller Aδ (pain/temperature fibers were spared. Groups of small unmyelinated C fibers (Remak bundles also showed evidence of degeneration in all samples.Conclusions: We are the first to show large fiber degeneration in CRPS using TEM. Degeneration of Aα fibers may lead to an imbalance in nerve signaling, inappropriately triggering the smaller healthy Aδ fibers, which transmit pain and temperature. These findings suggest peripheral nerve degeneration may play a key role in CRPS. Improved knowledge of pathogenesis will help develop more targeted treatments.

  10. Limits to behavioral evolution: the quantitative genetics of a complex trait under directional selection.

    Science.gov (United States)

    Careau, Vincent; Wolak, Matthew E; Carter, Patrick A; Garland, Theodore

    2013-11-01

    Replicated selection experiments provide a powerful way to study how "multiple adaptive solutions" may lead to differences in the quantitative-genetic architecture of selected traits and whether this may translate into differences in the timing at which evolutionary limits are reached. We analyze data from 31 generations (n=17,988) of selection on voluntary wheel running in house mice. The rate of initial response, timing of selection limit, and height of the plateau varied significantly between sexes and among the four selected lines. Analyses of litter size and realized selection differentials seem to rule out counterposing natural selection as a cause of the selection limits. Animal-model analyses showed that although the additive genetic variance was significantly lower in selected than control lines, both before and after the limits, the decrease was not sufficient to explain the limits. Moreover, directional selection promoted a negative covariance between additive and maternal genetic variance over the first 10 generations. These results stress the importance of replication in selection studies of higher-level traits and highlight the fact that long-term predictions of response to selection are not necessarily expected to be linear because of the variable effects of selection on additive genetic variance and maternal effects. © 2013 The Author(s). Evolution © 2013 The Society for the Study of Evolution.

  11. Self-organization and natural selection in the evolution of complex despotic societies

    NARCIS (Netherlands)

    Hemelrijk, C.K.

    2002-01-01

    Differences between related species are usually explained as separate adaptations produced by individual selection. I discuss in this paper how related species, which differ in many respects, may evolve by a combination of individual selection, self-organization, and group-selection, requiring an

  12. Catalytic ozonation not relying on hydroxyl radical oxidation: A selective and competitive reaction process related to metal-carboxylate complexes

    KAUST Repository

    Zhang, Tao

    2014-01-01

    Catalytic ozonation following non-hydroxyl radical pathway is an important technique not only to degrade refractory carboxylic-containing organic compounds/matter but also to avoid catalyst deactivation caused by metal-carboxylate complexation. It is unknown whether this process is effective for all carboxylates or selective to special molecule structures. In this work, the selectivity was confirmed using O3/(CuO/CeO2) and six distinct ozone-resistant probe carboxylates (i.e., acetate, citrate, malonate, oxalate, pyruvate and succinate). Among these probe compounds, pyruvate, oxalate, and citrate were readily degraded following the rate order of oxalate>citrate>pyruvate, while the degradation of acetate, malonate, and succinate was not promoted. The selectivity was independent on carboxylate group number of the probe compounds and solution pH. Competitive degradation was observed for carboxylate mixtures following the preference order of citrate, oxalate, and finally pyruvate. The competitive degradation was ascribed to competitive adsorption on the catalyst surface. It was revealed that the catalytically degradable compounds formed bidentate chelating or bridging complexes with surface copper sites of the catalyst, i.e., the active sites. The catalytically undegradable carboxylates formed monodentate complexes with surface copper sites or just electrostatically adsorbed on the catalyst surface. The selectivity, relying on the structure of surface metal-carboxylate complex, should be considered in the design of catalytic ozonation process. © 2013 Elsevier B.V.

  13. The search for Pleiades in trait constellations: functional integration and phenotypic selection in the complex flowers of Morrenia brachystephana (Apocynaceae).

    Science.gov (United States)

    Baranzelli, M C; Sérsic, A N; Cocucci, A A

    2014-04-01

    Pollinator-mediated natural selection on single traits, such as corolla tube or spur length, has been well documented. However, flower phenotypes are usually complex, and selection is expected to act on several traits that functionally interact rather than on a single isolated trait. Despite the fact that selection on complex phenotypes is expectedly widespread, multivariate selection modelling on such phenotypes still remains under-explored in plants. Species of the subfamily Asclepiadoideae (Apocynaceae) provide an opportunity to study such complex flower contrivances integrated by fine-scaled organs from disparate developmental origin. We studied the correlation structure among linear floral traits (i) by testing a priori morphological, functional or developmental hypotheses among traits and (ii) by exploring the organization of flower covariation, considering alternative expectations of modular organization or whole flower integration through conditional dependence analysis (CDA) and integration matrices. The phenotypic selection approach was applied to determine whether floral traits involved in the functioning of the pollination mechanism were affected by natural selection. Floral integration was low, suggesting that flowers are organized in more than just one correlation pleiad; our hypothetical functional correlation matrix was significantly correlated with the empirical matrix, and the CDA revealed three putative modules. Analyses of phenotypic selection showed significant linear and correlational gradients, lending support to expectations of functional interactions between floral traits. Significant correlational selection gradients found involved traits of different floral whorls, providing evidence for the existence of functional integration across developmental domains. © 2014 The Authors. Journal of Evolutionary Biology © 2014 European Society For Evolutionary Biology.

  14. Synthesis and characterization of templated ion exchange resins for the selective complexation of actinide ions. 1998 annual progress report

    International Nuclear Information System (INIS)

    Murray, G.M.; Uy, O.M.

    1998-01-01

    'The purpose of this research is to develop polymeric extractants for the selective complexation of uranyl ions (and subsequently other actinyl and actinide ions) from aqueous solutions (lakes, streams, waste tanks and body fluids). Selectivity for a specific actinide ion is obtained by providing polymers with cavities lined with complexing ligands so arranged as to match the charge, coordination number, coordination geometry, and size of the actinide metal ion. These cavity-containing polymers will be produced using a specific actinide ion (or surrogate) as a template around which monomeric complexing ligands will be polymerized. The polymers will provide useful sequestering agents for removing actinide ions from wastes and will form the basis for a variety of analytical techniques for actinide determinations.'

  15. Structure elucidation of the O-specific polysaccharide by NMR spectroscopy and selective cleavage and genetic characterization of the O-antigen of Escherichia albertii O5.

    Science.gov (United States)

    Naumenko, Olesya I; Zheng, Han; Wang, Jianping; Senchenkova, Sof'ya N; Wang, Hong; Shashkov, Alexander S; Chizhov, Alexander O; Li, Qun; Knirel, Yuriy A; Xiong, Yanwen

    2018-03-02

    The O-specific polysaccharide (O-antigen) was obtained by mild acid degradation of the lipopolysaccharide of Escherichia albertii O5 (strain T150248) and studied by sugar analysis, selective cleavages of glycosidic linkages, and 1D and 2D 1 H and 13 C NMR spectroscopy. Partial solvolysis with anh (anhydrous) CF 3 CO 2 H and hydrolysis with 0.05 M CF 3 CO 2 H cleaved predominantly the glycosidic linkage of β-GalpNAc or β-Galf, respectively, whereas the linkages of α-GlcpNAc and β-Galp were stable. Mixtures of the corresponding tri- and tetra-saccharides thus obtained were studied by NMR spectroscopy and high-resolution ESI MS. The following new structure was established for the tetrasaccharide repeat (O-unit) of the O-polysaccharide: →4)-α-d-GlcpNAc-(1 → 4)-β-d-Galp6Ac-(1 → 6)-β-d-Galf-(1 → 3)-β-d-GalpNAc-(1→where the degree of O-acetylation of d-Galp is ∼70%. The O-polysaccharide studied has a β-d-Galp-(1 → 6)-β-d-Galf-(1 → 3)-β-d-GalpNAc trisaccharide fragment in common with the O-polysaccharides of E. albertii O7, Escherichia coli O124 and O164, and Shigella dysenteriae type 3 studied earlier. The orf5-7 in the O-antigen gene cluster of E. albertii O5 are 47%, 78%, and 75% identical on the amino acid level to genes for predicted enzymes of E. albertii O7, including Galp-transferase wfeS, UDP-d-Galp mutase glf, and Galf-transferase wfeT, respectively, which are putatively involved with the synthesis of the shared trisaccharide fragment of the O-polysaccharides. The occurrence upstream of the O-antigen gene cluster of a 4-epimerase gene gnu for conversion of undecaprenyl diphosphate-linked d-GlcNAc (UndPP-d-GlcNAc) into UndPP-d-GalNAc indicates that d-GalNAc is the first monosaccharide of the O-unit, and hence the O-units are interlinked in the O-polysaccharide of E. albertii O5 by the β-d-GalpNAc-(1 → 4)-α-d-GlcpNAc linkage. Copyright © 2017. Published by Elsevier Ltd.

  16. Structural elucidation of nanocrystalline biomaterials

    Energy Technology Data Exchange (ETDEWEB)

    Maltsev, S.

    2008-10-23

    Bone diseases, such as osteoporosis and osteoarthritis, are the second most prevalent health problem worldwide. In Germany approximately 5 millions people are affected by arthritis. Investigating biomineralization processes and bone molecular structure is of key importance for developing new drugs for preventing and healing bone diseases. Nuclear magnetic resonance (NMR) was the primary technique used due to its advantages in characterising poorly ordered and disordered materials. Compared to all the diffraction techniques that widely applied in structural investigations, the usefulness of NMR is independent of long range molecular order. This makes NMR an outstanding technique for studies of complex/amorphous materials. Conventional NMR experiments (single pulse, spin-echo, cross polarization (CP), etc.) as well as their modifications and high-end techniques (2D HETCOR, REDOR, etc.) were used in this work. Combining the contributions from different techniques enhances the information content of the investigations and can increase the precision of the overall conclusions. Also XRD, TEM and FTIR were applied to different extent in order to get a general idea of nanocrystalline hydroxyapatite crystallite structure. Results: - A new approach named 'Solid-state NMR spectroscopy using the lost I spin magnetization in polarization transfer experiments' has been developed for measuring the transferred I spin magnetization from abundant nuclei, which is normally lost when detecting the S spin magnetization. - A detailed investigation of nanocrystalline hydroxyapatite core was made to prove that proton environment of the phosphates units and phosphorus environment of hydroxyl units are the same as in highly crystalline hydroxyapatite sample. - Using XRD it was found that the surface of the hydroxyapatite nanocrystals is not completely disordered, as it was suggested before, but resembles the hydroxyapatite structure with HPO{sub 4}{sup 2-} (and some CO{sub 3}{sup

  17. Structural elucidation of nanocrystalline biomaterials

    Energy Technology Data Exchange (ETDEWEB)

    Maltsev, S

    2008-10-23

    Bone diseases, such as osteoporosis and osteoarthritis, are the second most prevalent health problem worldwide. In Germany approximately 5 millions people are affected by arthritis. Investigating biomineralization processes and bone molecular structure is of key importance for developing new drugs for preventing and healing bone diseases. Nuclear magnetic resonance (NMR) was the primary technique used due to its advantages in characterising poorly ordered and disordered materials. Compared to all the diffraction techniques that widely applied in structural investigations, the usefulness of NMR is independent of long range molecular order. This makes NMR an outstanding technique for studies of complex/amorphous materials. Conventional NMR experiments (single pulse, spin-echo, cross polarization (CP), etc.) as well as their modifications and high-end techniques (2D HETCOR, REDOR, etc.) were used in this work. Combining the contributions from different techniques enhances the information content of the investigations and can increase the precision of the overall conclusions. Also XRD, TEM and FTIR were applied to different extent in order to get a general idea of nanocrystalline hydroxyapatite crystallite structure. Results: - A new approach named 'Solid-state NMR spectroscopy using the lost I spin magnetization in polarization transfer experiments' has been developed for measuring the transferred I spin magnetization from abundant nuclei, which is normally lost when detecting the S spin magnetization. - A detailed investigation of nanocrystalline hydroxyapatite core was made to prove that proton environment of the phosphates units and phosphorus environment of hydroxyl units are the same as in highly crystalline hydroxyapatite sample. - Using XRD it was found that the surface of the hydroxyapatite nanocrystals is not completely disordered, as it was suggested before, but resembles the hydroxyapatite structure with HPO{sub 4}{sup 2-} (and some CO{sub 3}{sup 2

  18. Preparation of significant complexes of selected transition elements with appropriate ligands

    International Nuclear Information System (INIS)

    Abbas, Hala Hassan

    2000-06-01

    New complexes of copper (II), nickel (II) and cobalt (II) have been prepared using triphenylphosphine and benzofurazan-1-oxide as ligands. Benzofurazan-1-oxide was prepared from the reaction between o-nitrophenyl azide and toluene as a catalyst. These complexes have been identified by means of infrared spectra and also melting points determination. The coordination bonding was found to be through phosphorus-metal and nitrogen metal. The melting points and colour confirmed are used as initial confirmation or identification procedure. Stability constants were studied to the new complexes prepared which is in good agreement with reported value for similar complexes. (Author)

  19. Preparation of significant complexes of selected transition elements with appropriate ligands

    International Nuclear Information System (INIS)

    Abbas, Hala Hassan

    2000-06-01

    New complexes of copper (II), nickel (II) and cobalt (II) have been prepared using triphenylphosphine and benzofurazan-1-oxide as ligands. Benzofurazan-1-oxide was prepared from the reaction between o-nitrophenyl azide and toluene as a catalyst. These complexes have been identified by means of infra-red spectra and also melting points determination. The coordination bonding was found to be through phosphorus-metal and nitrogen-metal. The melting points and colour confirmed are used as initial confirmation or identification procedure. Stability constants were studied to the new complexes prepared which is in good agreement with reported value for similar complexes. (Author)

  20. The Naïve Overfitting Index Selection (NOIS): A new method to optimize model complexity for hyperspectral data

    Science.gov (United States)

    Rocha, Alby D.; Groen, Thomas A.; Skidmore, Andrew K.; Darvishzadeh, Roshanak; Willemen, Louise

    2017-11-01

    The growing number of narrow spectral bands in hyperspectral remote sensing improves the capacity to describe and predict biological processes in ecosystems. But it also poses a challenge to fit empirical models based on such high dimensional data, which often contain correlated and noisy predictors. As sample sizes, to train and validate empirical models, seem not to be increasing at the same rate, overfitting has become a serious concern. Overly complex models lead to overfitting by capturing more than the underlying relationship, and also through fitting random noise in the data. Many regression techniques claim to overcome these problems by using different strategies to constrain complexity, such as limiting the number of terms in the model, by creating latent variables or by shrinking parameter coefficients. This paper is proposing a new method, named Naïve Overfitting Index Selection (NOIS), which makes use of artificially generated spectra, to quantify the relative model overfitting and to select an optimal model complexity supported by the data. The robustness of this new method is assessed by comparing it to a traditional model selection based on cross-validation. The optimal model complexity is determined for seven different regression techniques, such as partial least squares regression, support vector machine, artificial neural network and tree-based regressions using five hyperspectral datasets. The NOIS method selects less complex models, which present accuracies similar to the cross-validation method. The NOIS method reduces the chance of overfitting, thereby avoiding models that present accurate predictions that are only valid for the data used, and too complex to make inferences about the underlying process.

  1. Peptide biomarkers used for the selective breeding of a complex polygenic trait in honey bees.

    Science.gov (United States)

    Guarna, M Marta; Hoover, Shelley E; Huxter, Elizabeth; Higo, Heather; Moon, Kyung-Mee; Domanski, Dominik; Bixby, Miriam E F; Melathopoulos, Andony P; Ibrahim, Abdullah; Peirson, Michael; Desai, Suresh; Micholson, Derek; White, Rick; Borchers, Christoph H; Currie, Robert W; Pernal, Stephen F; Foster, Leonard J

    2017-08-21

    We present a novel way to select for highly polygenic traits. For millennia, humans have used observable phenotypes to selectively breed stronger or more productive livestock and crops. Selection on genotype, using single-nucleotide polymorphisms (SNPs) and genome profiling, is also now applied broadly in livestock breeding programs; however, selection on protein/peptide or mRNA expression markers has not yet been proven useful. Here we demonstrate the utility of protein markers to select for disease-resistant hygienic behavior in the European honey bee (Apis mellifera L.). Robust, mechanistically-linked protein expression markers, by integrating cis- and trans- effects from many genomic loci, may overcome limitations of genomic markers to allow for selection. After three generations of selection, the resulting marker-selected stock outperformed an unselected benchmark stock in terms of hygienic behavior, and had improved survival when challenged with a bacterial disease or a parasitic mite, similar to bees selected using a phenotype-based assessment for this trait. This is the first demonstration of the efficacy of protein markers for industrial selective breeding in any agricultural species, plant or animal.

  2. Evaluating the complexation behavior and regeneration of boron selective glucaminium-based ionic liquids when used as extraction solvents

    International Nuclear Information System (INIS)

    Joshi, Manishkumar D.; Steyer, Daniel J.; Anderson, Jared L.

    2012-01-01

    Highlights: ► Glucaminium-based ILs exhibit high selectivity for boron species using DLLME. ► The concentration of glucaminium-based IL affects type of boron complex formed. ► Use of 0.1 M HCl allows for regeneration of the IL solvent following extraction. ► Selectivity of the glucaminium-based ILs for boron species in seawater is similar to Milli-Q water. - Abstract: Glucaminium-based ionic liquids are a new class of solvents capable of extracting boron-species from water with high efficiency. The complexation behavior of these ILs with borate was thoroughly studied using 11 B NMR. Two different complexes, namely, monochelate complex and bischelate complex, were observed. 11 B NMR was used extensively to determine the formation constants for monochelate and bischelate complexes. The IL concentration was observed to have a significant effect on the IL–borate complexes. Using an in situ dispersive liquid–liquid microextraction (in situ DLLME) method, the extraction efficiency for boron species was increased dramatically when lithium bis[(trifluoromethyl)sulfonyl]imide (LiNTf 2 ) was used as the metathesis salt in an aqueous solution containing 0.1 M sodium chloride. IL regeneration after extraction was achieved using 0.1 M hydrochloric acid. The extraction efficiency of boron species was consistent when the IL was employed after three regeneration cycles. The selectivity of the IL for boron species in synthetic seawater samples was similar to performing the same extraction from Milli-Q water samples.

  3. SUCROSE SYNTHASE: ELUCIDATION OF COMPLEX POST-TRANSLATIONAL REGULATORY MECHANISMS

    Energy Technology Data Exchange (ETDEWEB)

    Steven C. Huber

    2009-05-12

    Studies have focused on the enzyme sucrose synthase, which plays an important role in the metabolism of sucrose in seeds and tubers. There are three isoforms of SUS in maize, referred to as SUS1, SUS-SH1, and SUS2. SUS is generally considered to be tetrameric protein but recent evidence suggests that SUS can also occur as a dimeric protein. The formation of tetrameric SUS is regulated by sucrose concentration in vitro and this could also be an important factor in the cellular localization of the protein. We found that high sucrose concentrations, which promote tetramer formation, also inhibit the binding of SUS1 to actin filaments in vitro. Previously, high sucrose concentrations were shown to promote SUS association with the plasma membrane. The specific regions of the SUS molecule involved in oligomerization are not known, but we identified a region of the SUS1 moelcule by bioinformatic analysis that was predicted to form a coiled coil. We demonstrated that this sequence could, in fact, self-associate as predicted for a coiled coil, but truncation analysis with the full-length recombinant protein suggested that it was not responsible for formation of dimers or tetramers. However, the coiled coil may function in binding of other proteins to SUS1. Overall, sugar availability may differentially influence the binding of SUS to cellular structures, and these effects may be mediated by changes in the oligomeric nature of the enzyme.

  4. Structural Observability and Sensor Node Selection for Complex Networks Governed by Nonlinear Balance Equations

    NARCIS (Netherlands)

    Kawano, Yu; Cao, Ming

    2017-01-01

    We define and then study the structural observability for a class of complex networks whose dynamics are governed by the nonlinear balance equations. Although related notions of observability of such complex networks have been studied before and in particular, necessary conditions have been reported

  5. Host–guest complexes of mixed glycol-bipyridine cryptands: prediction of ion selectivity by quantum chemical calculations, part V

    Directory of Open Access Journals (Sweden)

    Svetlana Begel

    2013-06-01

    Full Text Available The selectivity of the cryptands [2.2.bpy] and [2.bpy.bpy] for the endohedral complexation of alkali, alkaline-earth and earth metal ions was predicted on the basis of the DFT (B3LYP/LANL2DZp calculated structures and complex-formation energies. The cavity size in both cryptands lay between that for [2.2.2] and [bpy.bpy.bpy], such that the complexation of K+, Sr2+ and Tl3+ is most favorable. While the [2.2.bpy] is moderately larger, preferring Rb+ complexation and demonstrating equal priority for Sr2+ and Ba2+, the slightly smaller [2.bpy.bpy] yields more stable cryptates with Na+ and Ca2+. Although the CH2-units containing molecular bars fixed at the bridgehead nitrogen atoms determine the flexibility of the cryptands, the twist angles associated with the bipyridine and glycol building blocks also contribute considerably.

  6. Calixarene receptors in the selective separation of alachlor. Characterization of the separated complexes

    International Nuclear Information System (INIS)

    Garcia G, M.C.

    2004-01-01

    Pesticides have been necessary in the agriculture since the plagues control have been remedied thanks to them but it has also provoked pollution. Nowadays, there are several methods which help to decrease or remedy such a pollution provoked. Unfortunately, any of them work out the environmental problem totally. Therefore, alternatives have to be found. The organic and tri dimensional characteristics of these macrocycles afford them a high versatility in such a way that these hosts can interact with organic guests selectively. Alachlor is a chlorinated organic herbicide useful in the plagues control of annual grasses and many broad-leave weeds which grow in maize, peanuts and soyabean. The ability of calixarenes to host organic guests with chemical characteristics similar to pesticides let them to be good candidates to compete with others methods which are used presently to separate organic pesticides. In this direction one of the advantages of proposing the use of calixarenes is, its facility of being modified in the lower and/or upper rims, to adapt them to aqueous, organic, gaseous and aqueous-organic media. Once the characteristics of reagents informed in the literature were confirmed and complemented with others found in this work, we studied, in solution, the interaction of the calixarenes with alachlor using 1 x 10 -5 to 1 x 10 -3 M solutions in acetonitrile for calixarenes fitted with phosphinoyl pendant arms in the lower rim, B n bL n , n= 4, 6) and in chloroform for parents calixarenes (H n bL n n = 4, 6, 8). Meticulous studies monitored by UV-Vis and luminescence were carried out, and the best stoichiometry to be used in further studies resulted to be 1(host): 1(alachlor). Therefore, we chose the 1 x 10 -4 M concentration to find how long the host-guest should be interacting in order to guarantee the formation in solution of the calixarene-alachlor species. It was found 168 h for the alachlor-B n bL n interaction while 165 h were necessary with H n bL n

  7. Low complexity transmit antenna selection with power balancing in OFDM systems

    KAUST Repository

    Park, Kihong; Ko, Youngchai; Alouini, Mohamed-Slim

    2010-01-01

    of the power amplifier of the RF chain. Applying transmit antenna selection and fixed-power variable-rate transmission per subcarrier as a function of channel variations, we propose an implementation-friendly antenna selection method which offers a reduced

  8. Inferring selection in the Anopheles gambiae species complex: an example from immune-related serine protease inhibitors

    Directory of Open Access Journals (Sweden)

    Little Tom J

    2009-06-01

    Full Text Available Abstract Background Mosquitoes of the Anopheles gambiae species complex are the primary vectors of human malaria in sub-Saharan Africa. Many host genes have been shown to affect Plasmodium development in the mosquito, and so are expected to engage in an evolutionary arms race with the pathogen. However, there is little conclusive evidence that any of these mosquito genes evolve rapidly, or show other signatures of adaptive evolution. Methods Three serine protease inhibitors have previously been identified as candidate immune system genes mediating mosquito-Plasmodium interaction, and serine protease inhibitors have been identified as hot-spots of adaptive evolution in other taxa. Population-genetic tests for selection, including a recent multi-gene extension of the McDonald-Kreitman test, were applied to 16 serine protease inhibitors and 16 other genes sampled from the An. gambiae species complex in both East and West Africa. Results Serine protease inhibitors were found to show a marginally significant trend towards higher levels of amino acid diversity than other genes, and display extensive genetic structuring associated with the 2La chromosomal inversion. However, although serpins are candidate targets for strong parasite-mediated selection, no evidence was found for rapid adaptive evolution in these genes. Conclusion It is well known that phylogenetic and population history in the An. gambiae complex can present special problems for the application of standard population-genetic tests for selection, and this may explain the failure of this study to detect selection acting on serine protease inhibitors. The pitfalls of uncritically applying these tests in this species complex are highlighted, and the future prospects for detecting selection acting on the An. gambiae genome are discussed.

  9. Structure elucidation of secondary natural products

    International Nuclear Information System (INIS)

    Seger, C.

    2001-06-01

    The presented thesis deals with the structure elucidation of secondary natural products. Most of the compounds under investigation were terpenes, especially triterpenes, alkaloids and stilbenoids. Besides characterizing a multitude of already known and also new compounds, it was possible to detect and correct wrongly assigned literature data. The methodological aspect of this thesis lies - beside in the utilization of modern 2D NMR spectroscopy - in the evaluation of computer assisted structure elucidation (CASE) techniques in the course of spectroscopy supported structure elucidation processes. (author)

  10. Chromate Adsorption on Selected Soil Minerals: Surface Complexation Modeling Coupled with Spectroscopic Investigation.

    Czech Academy of Sciences Publication Activity Database

    Veselská, V.; Fajgar, Radek; Číhalová, S.; Bolanz, R.M.; Göttlicher, J.; Steininger, R.; Siddique, J.A.; Komárek, M.

    2016-01-01

    Roč. 318, NOV 15 (2016), s. 433-442 ISSN 0304-3894 Institutional support: RVO:67985858 Keywords : surface complexation modeling * chromate * soil minerals Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 6.065, year: 2016

  11. Selectivity in inter polymer complexation involving phenolic copolymer, poly electrolytes, non-ionic polymers and transition metal ions

    International Nuclear Information System (INIS)

    Vasheghani Farahani, B.; Hosseinpour Rajabi, F.

    2006-01-01

    Selectivity in inter polymer complex formation involving a typical four-component phenolic copolymer (ρ-chloro phenol-ρ-aminophenol-ρ-toluidine-ρ-cresol- HCHO copolymer), poly electrolytes such as polyethylene imine and polyacrylic acid, a non-ionic homopolymer polyvinyl pyrrolidone, and some transition metal ions (e.g., Cu (II), Ni (11)) have been studied in dimethylformamide-methanol solvents mixture. The coordinating groups of phenolic copolymer form complexes through hydrogen bonding and ion-dipole interactions. The different stages of interactions have been studied by several experimental techniques, e.g., viscometry, potentiometry and conductometry. Some schemes have been suggested to explain the mode of interaction between these components

  12. Selective and non-extractive spectrophotometric determination of cefdinir in formulations based on donor-acceptor complex formation

    Directory of Open Access Journals (Sweden)

    Babita K. Singh

    2010-01-01

    Full Text Available Cefdinir has broad spectrum of activity and high prescription rates, hence its counterfeiting seems imminent. We have proposed a simple, fast, selective and non-extractive spectrophotometric method for the content assay of cefdinir in formulations. The method is based on complexation of cefdinir and Fe under reducing condition in a buffered medium (pH 11 to form a magenta colored donor-acceptor complex (λ max = 550 nm; apparent molar absorptivity = 3720 L mol-1 cm-1. No other cephalosporins, penicillins and common excipients interfere under the test conditions. The Beer's law is followed in the concentration range 8-160 µg mL-1.

  13. Selectivity in stripping of alkali-metal cations from crown ether carboxylate complexes

    International Nuclear Information System (INIS)

    Bartsch, R.A.; Walkowiak, W.; Robison, T.W.

    1992-01-01

    To probe the effect of structural variations within the ionophore upon the efficiency and selectivity of solvent extraction, a variety of crown ether carboxylic acids and phosphonic acid monoesters have been synthesized. In other studies the influence of the organic diluent upon extraction efficiency and selectivity has been probed for such proton-ionizable crown ethers. In the present investigation, attention is focused upon selectivity in the stripping step. Although the efficiency of metal ion stripping is often examined in solvent extraction studies, the selectivity of competitive metal ion release under different conditions is much less frequently considered. In this study, competitive stripping of metal ions from chloroform solutions of five-alkali-metal crown ether carboxylates by varying concentrations of aqueous hydrochloric acid is examined. Alkali metals used were Li, Na, K, Rb, and Cs

  14. Evidence for positive selection in putative virulence factors within the Paracoccidioides brasiliensis species complex.

    Directory of Open Access Journals (Sweden)

    Daniel R Matute

    Full Text Available Paracoccidioides brasiliensis is a dimorphic fungus that is the causative agent of paracoccidioidomycosis, the most important prevalent systemic mycosis in Latin America. Recently, the existence of three genetically isolated groups in P. brasiliensis was demonstrated, enabling comparative studies of molecular evolution among P. brasiliensis lineages. Thirty-two gene sequences coding for putative virulence factors were analyzed to determine whether they were under positive selection. Our maximum likelihood-based approach yielded evidence for selection in 12 genes that are involved in different cellular processes. An in-depth analysis of four of these genes showed them to be either antigenic or involved in pathogenesis. Here, we present evidence indicating that several replacement mutations in gp43 are under positive balancing selection. The other three genes (fks, cdc42 and p27 show very little variation among the P. brasiliensis lineages and appear to be under positive directional selection. Our results are consistent with the more general observations that selective constraints are variable across the genome, and that even in the genes under positive selection, only a few sites are altered. We present our results within an evolutionary framework that may be applicable for studying adaptation and pathogenesis in P. brasiliensis and other pathogenic fungi.

  15. Effects of cochlear compression and frequency selectivity on pitch discrimination of complex tones with unresolved harmonics

    DEFF Research Database (Denmark)

    Bianchi, Federica; Fereczkowski, Michal; Zaar, Johannes

    2015-01-01

    Physiological studies have shown that noise-induced sensorineural hearing loss (SNHL) enhances the amplitude of envelope coding in auditory-nerve fibers. As pitch coding of unresolved complex tones is assumed to rely on temporal envelope coding mechanisms, this study investigated...... for the RP condition. Overall, these findings suggest that both reduced cochlear compression and auditory filter broadening alter the envelope representation of unresolved complex tones, leading to changes in pitch-discrimination performance....... pitchdiscrimination performance in listeners with SNHL. Pitch-discrimination thresholds were obtained in 14 normal-hearing (NH) and 10 hearingimpaired (HI) listeners for sine-phase (SP) and random-phase (RP) unresolved complex tones. The HI listeners performed, on average, similarly as the NH listeners in the SP...

  16. Selective two-step titration of thorium by sulfate displacement of the diethylenetriaminepentaacetic acid complex

    International Nuclear Information System (INIS)

    Kiefer, P.

    1980-07-01

    Thorium and other metals are complexed with excess diethylenetriaminepentaacetic acid (DTPA) at pH 1.4, the excess DTPA is titrated with Bi(III) to a xylenol orange end point, sulfate is added to complex Th(IV), and the displaced DTPA again is titrated with Bi(III). Of 61 metal ions and nonmetal anions tested, only Ga(III), Sc(III), tungstate, citrate, oxalate, and thiosulfate interfere seriously. Lesser interferences are In(III), Zr(IV), V(IV), and permanganate. The standard deviation is 2 μg for 56 to 840 μg Th

  17. Complex Formation of Selected Radionuclides with Ligands Commonly Found in Ground Water: Low Molecular Organic Acids

    DEFF Research Database (Denmark)

    Jensen, Bror Skytte; Jensen, H.

    1985-01-01

    A general approach to the analysis of potentiometric data on complex formation between cations and polybasic amphoteric acids is described. The method is used for the characterisation of complex formation between Cs+, Sr2+, Co2+, La 3+, and Eu3+ with a α-hydroxy acids, tartaric acid and citric ac......, and with the α-amino acids, aspartic acid and L-cysteine. The cations have been chosen as typical components of reactor waste, and the acids because they are often found as products of microbial activity in pits or wherever organic material decays...

  18. Structure of the ligand-binding domain (LBD) of human androgen receptor in complex with a selective modulator LGD2226

    International Nuclear Information System (INIS)

    Wang, Feng; Liu, Xiao-qin; Li, He; Liang, Kai-ni; Miner, Jeffrey N.; Hong, Mei; Kallel, E. Adam; Oeveren, Arjan van; Zhi, Lin; Jiang, Tao

    2006-01-01

    Crystal structure of the ligand-binding domain of androgen receptor in complex with LGD2226. The androgen receptor (AR) is a ligand-inducible steroid hormone receptor that mediates androgen action, determining male sexual phenotypes and promoting spermatogenesis. As the androgens play a dominant role in male sexual development and function, steroidal androgen agonists have been used clinically for some years. However, there is a risk of potential side effects and most steroidal androgens cannot be dosed orally, which limits the use of these substances. 1,2-Dihydro-6-N,N-bis(2,2,2-trifluoroethyl) amino-4-trifluoromethyl-2-quinolinone (LGD2226) is a synthetic nonsteroidal ligand and a novel selective AR modulator. The crystal structure of the complex of LGD2226 with the androgen receptor ligand-binding domain (AR LBD) at 2.1 Å was solved and compared with the structure of the AR LBD–R1881 complex. It is hoped that this will aid in further explaining the selectivity of LGD2226 observed in in vitro and in vivo assays and in developing more selective and effective therapeutic agents

  19. Synthesis, Characterization, and Variable-Temperature NMR Studies of Silver(I) Complexes for Selective Nitrene Transfer.

    Science.gov (United States)

    Huang, Minxue; Corbin, Joshua R; Dolan, Nicholas S; Fry, Charles G; Vinokur, Anastasiya I; Guzei, Ilia A; Schomaker, Jennifer M

    2017-06-05

    An array of silver complexes supported by nitrogen-donor ligands catalyze the transformation of C═C and C-H bonds to valuable C-N bonds via nitrene transfer. The ability to achieve high chemoselectivity and site selectivity in an amination event requires an understanding of both the solid- and solution-state behavior of these catalysts. X-ray structural characterizations were helpful in determining ligand features that promote the formation of monomeric versus dimeric complexes. Variable-temperature 1 H and DOSY NMR experiments were especially useful for understanding how the ligand identity influences the nuclearity, coordination number, and fluxional behavior of silver(I) complexes in solution. These insights are valuable for developing improved ligand designs.

  20. A monofunctional platinum complex coordinated to a rhodium metalloinsertor selectively binds mismatched DNA in the minor groove.

    Science.gov (United States)

    Weidmann, Alyson G; Barton, Jacqueline K

    2015-10-05

    We report the synthesis and characterization of a bimetallic complex derived from a new family of potent and selective metalloinsertors containing an unusual Rh-O axial coordination. This complex incorporates a monofunctional platinum center containing only one labile site for coordination to DNA, rather than two, and coordinates DNA nonclassically through adduct formation in the minor groove. This conjugate displays bifunctional, interdependent binding of mismatched DNA via metalloinsertion at a mismatch as well as covalent platinum binding. DNA sequencing experiments revealed that the preferred site of platinum coordination is not the traditional N7-guanine site in the major groove, but rather N3-adenine in the minor groove. The complex also displays enhanced cytotoxicity in mismatch repair-deficient and mismatch repair-proficient human colorectal carcinoma cell lines compared to the chemotherapeutic cisplatin, and it triggers cell death via an apoptotic pathway, rather than the necrotic pathway induced by rhodium metalloinsertors.

  1. A complex selection signature at the human AVPR1B gene

    Directory of Open Access Journals (Sweden)

    Cagliani Rachele

    2009-06-01

    Full Text Available Abstract Background The vasopressin receptor type 1b (AVPR1B is mainly expressed by pituitary corticotropes and it mediates the stimulatory effects of AVP on ACTH release; common AVPR1B haplotypes have been involved in mood and anxiety disorders in humans, while rodents lacking a functional receptor gene display behavioral defects and altered stress responses. Results Here we have analyzed the two exons of the gene and the data we present suggest that AVPR1B has been subjected to natural selection in humans. In particular, analysis of exon 2 strongly suggests the action of balancing selection in African populations and Europeans: the region displays high nucleotide diversity, an excess of intermediate-frequency alleles, a higher level of within-species diversity compared to interspecific divergence and a genealogy with common haplotypes separated by deep branches. This relatively unambiguous situation coexists with unusual features across exon 1, raising the possibility that a nonsynonymous variant (Gly191Arg in this region has been subjected to directional selection. Conclusion Although the underlying selective pressure(s remains to be identified, we consider this to be among the first documented examples of a gene involved in mood disorders and subjected to natural selection in humans; this observation might add support to the long-debated idea that depression/low mood might have played an adaptive role during human evolution.

  2. A complex selection signature at the human AVPR1B gene.

    Science.gov (United States)

    Cagliani, Rachele; Fumagalli, Matteo; Pozzoli, Uberto; Riva, Stefania; Cereda, Matteo; Comi, Giacomo P; Pattini, Linda; Bresolin, Nereo; Sironi, Manuela

    2009-06-01

    The vasopressin receptor type 1b (AVPR1B) is mainly expressed by pituitary corticotropes and it mediates the stimulatory effects of AVP on ACTH release; common AVPR1B haplotypes have been involved in mood and anxiety disorders in humans, while rodents lacking a functional receptor gene display behavioral defects and altered stress responses. Here we have analyzed the two exons of the gene and the data we present suggest that AVPR1B has been subjected to natural selection in humans. In particular, analysis of exon 2 strongly suggests the action of balancing selection in African populations and Europeans: the region displays high nucleotide diversity, an excess of intermediate-frequency alleles, a higher level of within-species diversity compared to interspecific divergence and a genealogy with common haplotypes separated by deep branches. This relatively unambiguous situation coexists with unusual features across exon 1, raising the possibility that a nonsynonymous variant (Gly191Arg) in this region has been subjected to directional selection. Although the underlying selective pressure(s) remains to be identified, we consider this to be among the first documented examples of a gene involved in mood disorders and subjected to natural selection in humans; this observation might add support to the long-debated idea that depression/low mood might have played an adaptive role during human evolution.

  3. Selective Oxidation of Glycerol with 3% H2O2 Catalyzed by LDH-Hosted Cr(III Complex

    Directory of Open Access Journals (Sweden)

    Gongde Wu

    2015-11-01

    Full Text Available A series of layered double hydroxides (LDHs –hosted sulphonato-salen Cr(III complexes were prepared and characterized by various physico-chemical measurements, such as Fourier transform infrared spectroscopy (FTIR, ultraviolet-visible spectroscopy (UV-Vis, powder X-ray diffraction (XRD, transmission electron microscope (TEM, scanning electron microscope (SEM and elemental analysis. Additionally, their catalytic performances were investigated in the selective oxidation of glycerol (GLY using 3% H2O2 as an oxidant. It was found that all the LDH-hosted Cr(III complexes exhibited significantly enhanced catalytic performance compared to the homogeneous Cr(III complex. Additionally, it was worth mentioning that the metal composition of LDH plates played an important role in the catalytic performances of LDH-hosted Cr(III complex catalysts. Under the optimal reaction conditions, the highest GLY conversion reached 85.5% with 59.3% of the selectivity to 1,3-dihydroxyacetone (DHA. In addition, the catalytic activity remained after being recycled five times.

  4. Release of polyanions from polyelectrolyte complexes by selective degradation of the polycation

    Czech Academy of Sciences Publication Activity Database

    Etrych, Tomáš; Boustta, M.; Leclercq, L.; Vert, M.

    2006-01-01

    Roč. 21, č. 2 (2006), s. 89-105 ISSN 0883-9115 Institutional research plan: CEZ:AV0Z40500505 Keywords : polyelectrolyte complex * enzymatic degradation * hydrolytic degradation Subject RIV: CD - Macromolecular Chemistry Impact factor: 0.925, year: 2006

  5. N-acyl thioureas - selective ligands for complexing of heavy metals and noble metals

    International Nuclear Information System (INIS)

    Schuster, M.

    1992-01-01

    Acyl thioureas are complexing agents for heavy metals that are easily produced and very stable. Their favourable toxicological data make them particularly suitable for industrial applications, e.g. detoxification of metallic process solutions or solvent extraction of metals. (orig.) [de

  6. Selective transformations of complex molecules are enabled by aptameric protective groups

    NARCIS (Netherlands)

    Bastian, Andreas A.; Marcozzi, Alessio; Herrmann, Andreas

    2012-01-01

    Emerging trends in drug discovery are prompting a renewed interest in natural products as a source of chemical diversity and lead structures. However, owing to the structural complexity of many natural compounds, the synthesis of derivatives is not easily realized. Here, we demonstrate a

  7. Bibenzimidazole containing mixed ligand cobalt(III) complex as a selective receptor for iodide

    Digital Repository Service at National Institute of Oceanography (India)

    Indumathy, R.; Parameswarana, P.S.; Aiswarya, C.V.; Nair, B.U.

    Two new mixed ligand cobalt(III) complexes containing bibenzimidazole (bbenzimH2) ligand with composition [Co(phen)2bbenzimH2](ClO4)3 (1) and [Co(bpy)2bbenzimH2](ClO4...

  8. Hormones and the Evolution of Complex Traits: Insights from Artificial Selection on Behavior.

    Science.gov (United States)

    Garland, Theodore; Zhao, Meng; Saltzman, Wendy

    2016-08-01

    Although behavior may often be a fairly direct target of natural or sexual selection, it cannot evolve without changes in subordinate traits that cause or permit its expression. In principle, changes in endocrine function could be a common mechanism underlying behavioral evolution because they are well positioned to mediate integrated responses to behavioral selection. More specifically, hormones can influence both motivational (e.g., brain) and performance (e.g., muscles) components of behavior simultaneously and in a coordinated fashion. If the endocrine system is often "used" as a general mechanism to effect responses to selection, then correlated responses in other aspects of behavior, life history, and organismal performance (e.g., locomotor abilities) should commonly occur because any cell with appropriate receptors could be affected. Ways in which behavior coadapts with other aspects of the phenotype can be studied directly through artificial selection and experimental evolution. Several studies have targeted rodent behavior for selective breeding and reported changes in other aspects of behavior, life history, and lower-level effectors of these organismal traits, including endocrine function. One example involves selection for high levels of voluntary wheel running, one aspect of physical activity, in four replicate High Runner (HR) lines of mice. Circulating levels of several hormones (including insulin, testosterone, thyroxine, triiodothyronine) have been characterized, three of which-corticosterone, leptin, and adiponectin-differ between HR and control lines, depending on sex, age, and generation. Potential changes in circulating levels of other behaviorally and metabolically relevant hormones, as well as in other components of the endocrine system (e.g., receptors), have yet to be examined. Overall, results to date identify promising avenues for further studies on the endocrine basis of activity levels. © The Author 2016. Published by Oxford University

  9. Dynamic differentiation of GABAA-sensitive influences on orientation selectivity of complex cells in the cat striate cortex.

    Science.gov (United States)

    Pfleger, B; Bonds, A B

    1995-01-01

    The influence of GABAA receptors on orientation selectivity of cat complex cells was tested by iontophoresis of the GABAA receptor blockers bicuculline and N-methyl-bicuculline while stimulating with drifting sinusoidal gratings. Reduction of orientation tuning was markedly less than reported in previous studies that used drifting bars as visual stimuli. Only 3/31 cells lost orientation selectivity, with an average increase in bandwidth of 33%, as opposed to half the cells losing selectivity and a bandwidth increase for the remainder of 47% as reported previously. Infusion of GABAA blockers revealed a prominent stimulus onset transient response, lasting about 120 ms, that showed a broadening of orientation selectivity comparable to that found using drifting bars under similar circumstances. We believe that drifting gratings emphasize a steady-state response component that retains, in the presence of GABAA blockers, significant orientation selectivity. Because the onset transient is initially unselective for orientation, we suggest that the steady-state, orientation-selective response component develops from an alternate inhibitory mechanism, possibly mediated by GABAB receptors.

  10. Design, synthesis, and evaluation of polyhydroxamate chelators for selective complexation of actinides

    International Nuclear Information System (INIS)

    Gopalan, A.; Jacobs, H.; Koshti, N.; Stark, P.; Huber, V.; Dasaradhi, L.; Caswell, W.; Smith, P.; Jarvinen, G.

    1995-01-01

    Specific chelating polymers targeted for actinides have much relevance to problems involving remediation of nuclear waste. Goal is to develop polymer supported, ion specific extraction systems for removing actinides and other hazardous metal ions from wastewaters. This is part of an effort to develop chelators for removing actinide ions such as Pu from soils and waste streams. Selected ligands are being attached to polymeric backbones to create novel chelating polymers. These polymers and other water soluble and insoluble polymers have been synthesized and are being evaluated for ability to selectively remove target metal ions from process waste streams

  11. Chromate adsorption on selected soil minerals: Surface complexation modeling coupled with spectroscopic investigation

    Energy Technology Data Exchange (ETDEWEB)

    Veselská, Veronika, E-mail: veselskav@fzp.czu.cz [Department of Environmental Geosciences, Faculty of Environmental Sciences, Czech University of Life Sciences Prague, Kamýcka 129, CZ-16521, Prague (Czech Republic); Fajgar, Radek [Department of Analytical and Material Chemistry, Institute of Chemical Process Fundamentals of the CAS, v.v.i., Rozvojová 135/1, CZ-16502, Prague (Czech Republic); Číhalová, Sylva [Department of Environmental Geosciences, Faculty of Environmental Sciences, Czech University of Life Sciences Prague, Kamýcka 129, CZ-16521, Prague (Czech Republic); Bolanz, Ralph M. [Institute of Geosciences, Friedrich-Schiller-University Jena, Carl-Zeiss-Promenade 10, DE-07745, Jena (Germany); Göttlicher, Jörg; Steininger, Ralph [ANKA Synchrotron Radiation Facility, Karlsruhe Institute of Technology, Hermann-von-Helmholtz-Platz 1, DE-76344, Eggenstein-Leopoldshafen (Germany); Siddique, Jamal A.; Komárek, Michael [Department of Environmental Geosciences, Faculty of Environmental Sciences, Czech University of Life Sciences Prague, Kamýcka 129, CZ-16521, Prague (Czech Republic)

    2016-11-15

    Highlights: • Study of Cr(VI) adsorption on soil minerals over a large range of conditions. • Combined surface complexation modeling and spectroscopic techniques. • Diffuse-layer and triple-layer models used to obtain fits to experimental data. • Speciation of Cr(VI) and Cr(III) was assessed. - Abstract: This study investigates the mechanisms of Cr(VI) adsorption on natural clay (illite and kaolinite) and synthetic (birnessite and ferrihydrite) minerals, including its speciation changes, and combining quantitative thermodynamically based mechanistic surface complexation models (SCMs) with spectroscopic measurements. Series of adsorption experiments have been performed at different pH values (3–10), ionic strengths (0.001–0.1 M KNO{sub 3}), sorbate concentrations (10{sup −4}, 10{sup −5}, and 10{sup −6} M Cr(VI)), and sorbate/sorbent ratios (50–500). Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, and X-ray absorption spectroscopy were used to determine the surface complexes, including surface reactions. Adsorption of Cr(VI) is strongly ionic strength dependent. For ferrihydrite at pH <7, a simple diffuse-layer model provides a reasonable prediction of adsorption. For birnessite, bidentate inner-sphere complexes of chromate and dichromate resulted in a better diffuse-layer model fit. For kaolinite, outer-sphere complexation prevails mainly at lower Cr(VI) loadings. Dissolution of solid phases needs to be considered for better SCMs fits. The coupled SCM and spectroscopic approach is thus useful for investigating individual minerals responsible for Cr(VI) retention in soils, and improving the handling and remediation processes.

  12. Selective Gene Delivery for Integrating Exogenous DNA into Plastid and Mitochondrial Genomes Using Peptide-DNA Complexes.

    Science.gov (United States)

    Yoshizumi, Takeshi; Oikawa, Kazusato; Chuah, Jo-Ann; Kodama, Yutaka; Numata, Keiji

    2018-05-14

    Selective gene delivery into organellar genomes (mitochondrial and plastid genomes) has been limited because of a lack of appropriate platform technology, even though these organelles are essential for metabolite and energy production. Techniques for selective organellar modification are needed to functionally improve organelles and produce transplastomic/transmitochondrial plants. However, no method for mitochondrial genome modification has yet been established for multicellular organisms including plants. Likewise, modification of plastid genomes has been limited to a few plant species and algae. In the present study, we developed ionic complexes of fusion peptides containing organellar targeting signal and plasmid DNA for selective delivery of exogenous DNA into the plastid and mitochondrial genomes of intact plants. This is the first report of exogenous DNA being integrated into the mitochondrial genomes of not only plants, but also multicellular organisms in general. This fusion peptide-mediated gene delivery system is a breakthrough platform for both plant organellar biotechnology and gene therapy for mitochondrial diseases in animals.

  13. Examining the evidence for major histocompatibility complex-dependent mate selection in humans and nonhuman primates

    Czech Academy of Sciences Publication Activity Database

    Winternitz, Jamie Caroline; Abbate, J. L.

    2015-01-01

    Roč. 6, 13 May (2015), s. 73-88 ISSN 1179-7274 R&D Projects: GA MŠk(CZ) EE2.3.30.0048 Institutional support: RVO:67985939 Keywords : secual selection * olfaction * facial attraction * inbreeding avoidance * parasite resistance Subject RIV: EB - Genetics ; Molecular Biology OBOR OECD: Genetics and heredity (medical genetics to be 3)

  14. Southern complex: geology, geochemistry, mineralogy, and mineral chemistry of selected uranium- and thorium-rich granites

    International Nuclear Information System (INIS)

    Hoffman, M.A.

    1987-01-01

    Four major rock groups are defined in the Southern Complex: the Bell Creek Granite (BCG), the Clotted Granitoids (CGR), the Albite Granite (AGR), and the Migmatite Complex. Metatexites of the Migmatite Complex are the oldest rocks and include paleosome of a metasedimentary and metavolcanic protolith represented by Banded Iron Formation, Banded Amphibolite, and Banded Gneisses, and interlayered or crosscutting leucogranites. The CGR span the range from metatexite to diatexite and represent in-situ partial melting of metapelitic layers in the protolith during intrusion of the BCG. The BCG cuts the migmatites, is locally cut by the CGR, and was derived by partial melting of a dominantly metasedimentary protolith at some depth below the presently exposed migmatites during a regional tectonothermal event. The Albite Granite is a 2km diameter, muscovite-fluorite-columbite-bearing intrusive stock that cuts all other major units. The thorium history of the BCG is a function of the history of monazite. The thorium history of the CGR is also dominated by monazite but the thorium content of this unit cannot be entirely accounted for by original restite monazite. The uranium history of the BCG and CGR was dominated by magmatic differentiation and post magmatic, metamorphic and supergene redistributions and is largely independent of the thorium history. The thorium and uranium history of the AGR was dominated by magmatic/deuteric processes unlike the BCG and CGR

  15. Dinuclear ru-aqua complexes for selective epoxidation catalysis based on supramolecular substrate orientation effects

    KAUST Repository

    Di Giovanni, Carlo; Poater, Albert; Benet-Buchholz, Jordi; Cavallo, Luigi; Solà , Miquel; Llobet, Antoni A.

    2014-01-01

    Ru-aqua complex {[RuII(trpy)(H2O)] 2(μ-pyr-dc)}+ is a powerful epoxidation catalyst for a wide range of linear and cyclic alkenes. High turnover numbers (TNs), up to 17000, and turnover frequencies (TOF), up to 24120 h-1 (6.7 s -1), have been obtained using PhIO as oxidant. This species presents an outstanding stereospecificity for both cis and trans olefins towards the formation of their corresponding cis and trans epoxides. In addition, it shows different reactivity to cis and trans olefins due to a substrate orientation supramolecular effect transmitted by its ligand scaffold. This effect together with the impressive reaction rates are rationalized using electrochemical techniques and DFT calculations. A new Ru-aqua complex that behaves as a powerful epoxidation catalyst for a wide range of linear and cyclic alkenes is reported. High turnover numbers and frequencies are obtained by using PhIO as oxidant. The complex shows an outstanding stereospecificity for both cis and trans olefins towards the formation of their corresponding cis and trans epoxides (see figure). © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Dinuclear ru-aqua complexes for selective epoxidation catalysis based on supramolecular substrate orientation effects

    KAUST Repository

    Di Giovanni, Carlo

    2014-03-03

    Ru-aqua complex {[RuII(trpy)(H2O)] 2(μ-pyr-dc)}+ is a powerful epoxidation catalyst for a wide range of linear and cyclic alkenes. High turnover numbers (TNs), up to 17000, and turnover frequencies (TOF), up to 24120 h-1 (6.7 s -1), have been obtained using PhIO as oxidant. This species presents an outstanding stereospecificity for both cis and trans olefins towards the formation of their corresponding cis and trans epoxides. In addition, it shows different reactivity to cis and trans olefins due to a substrate orientation supramolecular effect transmitted by its ligand scaffold. This effect together with the impressive reaction rates are rationalized using electrochemical techniques and DFT calculations. A new Ru-aqua complex that behaves as a powerful epoxidation catalyst for a wide range of linear and cyclic alkenes is reported. High turnover numbers and frequencies are obtained by using PhIO as oxidant. The complex shows an outstanding stereospecificity for both cis and trans olefins towards the formation of their corresponding cis and trans epoxides (see figure). © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Selective Segmentation for Global Optimization of Depth Estimation in Complex Scenes

    Directory of Open Access Journals (Sweden)

    Sheng Liu

    2013-01-01

    Full Text Available This paper proposes a segmentation-based global optimization method for depth estimation. Firstly, for obtaining accurate matching cost, the original local stereo matching approach based on self-adapting matching window is integrated with two matching cost optimization strategies aiming at handling both borders and occlusion regions. Secondly, we employ a comprehensive smooth term to satisfy diverse smoothness request in real scene. Thirdly, a selective segmentation term is used for enforcing the plane trend constraints selectively on the corresponding segments to further improve the accuracy of depth results from object level. Experiments on the Middlebury image pairs show that the proposed global optimization approach is considerably competitive with other state-of-the-art matching approaches.

  18. Selective chromogenic and fluorogenic peptide substrates for the assay of cysteine peptidases in complex mixtures

    Czech Academy of Sciences Publication Activity Database

    Semashko, T. A.; Vorotnikova, E. A.; Sharikova, V. F.; Vinokurov, Konstantin; Smirnova, Y. A.; Dunaevsky, Y. E.; Belozersky, M. A.; Oppert, B.; Elpidina, E. N.; Filippova, I. Y.

    2014-01-01

    Roč. 449, č. 1 (2014), s. 179-187 ISSN 0003-2697 Grant - others:Russian Foundation for Basic Research(RU) 12-04-01562-a; Russian Foundation for Basic Research(RU) 12-03-01057-a; ISTC (RU) 3455 Institutional support: RVO:60077344 Keywords : cysteine peptidases * substrates of peptidases * selective peptide substrates Subject RIV: CE - Biochemistry Impact factor: 2.219, year: 2014 http://www.sciencedirect.com/science/article/pii/S0003269713006180#

  19. Procedure for Selection of Suitable Resources in Interactions in Complex Dynamic Systems Using Artificial Immunity

    Directory of Open Access Journals (Sweden)

    Naors Y. anadalsaleem

    2017-03-01

    Full Text Available The dynamic optimization procedure for -dimensional vector function of a system, the state of which is interpreted as adaptable immune cell, is considered Using the results of the theory of artificial immune systems. The procedures for estimate of monitoring results are discussed. The procedure for assessing the entropy is recommended as a general recursive estimation algorithm. The results are focused on solving the optimization problems of cognitive selection of suitable physical resources, what expands the scope of Electromagnetic compatibility.

  20. Structure of the Regulator of G Protein Signaling 8 (RGS8)-Gαq Complex: MOLECULAR BASIS FOR Gα SELECTIVITY.

    Science.gov (United States)

    Taylor, Veronica G; Bommarito, Paige A; Tesmer, John J G

    2016-03-04

    Regulator of G protein signaling (RGS) proteins interact with activated Gα subunits via their RGS domains and accelerate the hydrolysis of GTP. Although the R4 subfamily of RGS proteins generally accepts both Gαi/o and Gαq/11 subunits as substrates, the R7 and R12 subfamilies select against Gαq/11. In contrast, only one RGS protein, RGS2, is known to be selective for Gαq/11. The molecular basis for this selectivity is not clear. Previously, the crystal structure of RGS2 in complex with Gαq revealed a non-canonical interaction that could be due to interfacial differences imposed by RGS2, the Gα subunit, or both. To resolve this ambiguity, the 2.6 Å crystal structure of RGS8, an R4 subfamily member, was determined in complex with Gαq. RGS8 adopts the same pose on Gαq as it does when bound to Gαi3, indicating that the non-canonical interaction of RGS2 with Gαq is due to unique features of RGS2. Based on the RGS8-Gαq structure, residues in RGS8 that contact a unique α-helical domain loop of Gαq were converted to those typically found in R12 subfamily members, and the reverse substitutions were introduced into RGS10, an R12 subfamily member. Although these substitutions perturbed their ability to stimulate GTP hydrolysis, they did not reverse selectivity. Instead, selectivity for Gαq seems more likely determined by whether strong contacts can be maintained between α6 of the RGS domain and Switch III of Gαq, regions of high sequence and conformational diversity in both protein families. © 2016 by The American Society for Biochemistry and Molecular Biology, Inc.

  1. Design of hypoxia-targeting radiopharmaceuticals: selective uptake of copper-64 complexes in hypoxic cells in vitro

    International Nuclear Information System (INIS)

    Dearling, J.L.J.; Lewis, J.S.; Mullen, G.E.D.; Rae, M.T.; Zweit, J.; Blower, P.J.

    1998-01-01

    The well-known perfusion tracer CuPTSM, labelled with 62 Cu or 64 Cu, is believed to be trapped in cells non-selectively by a bioreductive mechanism. It is proposed that by modifying the ligand to increase its electron donor strength (for example by adding alkyl functionality or replacing sulphur ligands with oxygen ligands), the copper complexes will become less easily reduced and tracers with selectivity for hypoxic tissues could thus be developed. The aim of this work was to prepare 64 Cu-labelled complexes of two series of ligands, based on the bis(thiosemicarbazone) (13 ligands) and bis(salicylaldimine) (3 ligands) skeletons, and to evaluate the hypoxia dependence of their uptake in cells. The complexes were incubated with Chinese hamster ovary cells under normoxic and hypoxic conditions, and the cells isolated by centrifugation to determine radioactivity uptake at various time points up to 90 min. Several members of both series demonstrated significant (P 60 Cu, 61 Cu, 62 Cu, 64 Cu) and targeted radiotherapy ( 64 Cu, 67 Cu). (orig.)

  2. Metabolomic elucidation of pork from different crossbreds

    DEFF Research Database (Denmark)

    Bertram, Hanne Christine S.; Straadt, Ida Krestine; Clausen, Morten Rahr

    , and correlations between individual metabolites and sensory attributes were elucidated. A high content of carnosine in the meat was associated with a low value of many sensory attributes related to meat flavor/taste. Surprsingly, IMP and inosine were in general not correlated with sensory attributes related...... to meat flavor/taste. Water-holding capacity and oxygen radical absorbance capacity (ORAC) of the meat were determined to elucidate the correlations between individual metabolites and these two parameters that are of importance for the technological meat quality. In conclusion, the present study reveals...

  3. Preparation of new technetium-99m NNS/X complexes and selection for brain imaging agent

    Institute of Scientific and Technical Information of China (English)

    HE; Qiange; CHEN; Xiangji; MIAO; Yubin; LIU; Boli

    2004-01-01

    Based on excellent experiment results of 99mTcO-MPBDA-Cl, two new ligands MPTDA and MPDAA are synthesized. Then series of 99mTcO3+ complexes are prepared through adding different halide anions, followed by tests of physical chemistry qualities and biodistribution experiments. And results of these experiments show that complexes formed with MPTDA and MPDAA have better lipophilicity than those formed with MPBDA, still maintain the good brain retention ability of this type of compounds, but radioactivity uptake in blood is higher than that of 99mTcO-MPBDA and ratios of brain/blood are reduced. Obvious affections are fetched out on brain uptake and retention if fluoride, bromide or iodide anions are added. Results of experiments can be explained in reason with theoretic computation. It is confirmed that 99mTcO-MPBDA-Cl has potential to develop a new type of brain imaging agent considering integrated factors such as brain uptake, retention and toxicity.

  4. Substitution urethroplasty of complex and long-segment urethral strictures: a rationale for procedure selection.

    Science.gov (United States)

    Xu, Yue-Min; Qiao, Yong; Sa, Ying-Long; Wu, Den-Long; Zhang, Xin-Ru; Zhang, Jion; Gu, Bao-Jun; Jin, San-Bao

    2007-04-01

    We evaluated the applications and outcomes of substitution urethroplasty, using a variety of techniques, in 65 patients with complex, long-segment urethral strictures. From January 1995 to December 2005, 65 patients with complex urethral strictures >8cm in length underwent substitution urethroplasty. Of the 65 patients, 43 underwent one-stage urethral reconstruction using mucosal grafts (28 colonic mucosal graft, 12 buccal mucosal graft, and 3 bladder mucosal graft), 17 patients underwent one-stage urethroplasty using pedicle flaps, and 5 patients underwent staged Johanson's urethroplasty. The mean follow-up time was 4.8 yr (range; 0.8-10 yr), with an overall success rate of 76.92% (50 of 65 cases). Complications developed in 15 patients (23.08%) and included recurrent stricture in 7 (10.77%), urethrocutaneous fistula in 3 (4.62%), coloabdominal fistula in 1 (1.54%), penile chordee in 2 (3.08%), and urethral pseudodiverticulum in 2 (3.08%). Recurrent strictures and urethral pseudodiverticulum were treated successfully with a subsequent procedure, including repeat urethroplasty in six cases and urethrotomy or dilation in three. Coloabdominal fistula was corrected only by dressing change; five patients await further reconstruction. Penile skin, colonic mucosal, and buccal mucosal grafts are excellent materials for substitution urethroplasty. Colonic mucosal graft urethroplasty is a feasible procedure for complicated urethral strictures involving the entire or multiple portions of the urethra and the technique may also be considered for urethral reconstruction in patients in whom other conventional procedures failed.

  5. Dissecting children's observational learning of complex actions through selective video displays.

    Science.gov (United States)

    Flynn, Emma; Whiten, Andrew

    2013-10-01

    Children can learn how to use complex objects by watching others, yet the relative importance of different elements they may observe, such as the interactions of the individual parts of the apparatus, a model's movements, and desirable outcomes, remains unclear. In total, 140 3-year-olds and 140 5-year-olds participated in a study where they observed a video showing tools being used to extract a reward item from a complex puzzle box. Conditions varied according to the elements that could be seen in the video: (a) the whole display, including the model's hands, the tools, and the box; (b) the tools and the box but not the model's hands; (c) the model's hands and the tools but not the box; (d) only the end state with the box opened; and (e) no demonstration. Children's later attempts at the task were coded to establish whether they imitated the hierarchically organized sequence of the model's actions, the action details, and/or the outcome. Children's successful retrieval of the reward from the box and the replication of hierarchical sequence information were reduced in all but the whole display condition. Only once children had attempted the task and witnessed a second demonstration did the display focused on the tools and box prove to be better for hierarchical sequence information than the display focused on the tools and hands only. Copyright © 2013 Elsevier Inc. All rights reserved.

  6. Potentiometric and NMR complexation studies of phenylboronic acid PBA and its aminophosphonate analog with selected catecholamines

    Science.gov (United States)

    Ptak, Tomasz; Młynarz, Piotr; Dobosz, Agnieszka; Rydzewska, Agata; Prokopowicz, Monika

    2013-05-01

    Boronic acids are a class of intensively explored compounds, which according to their specific properties have been intensively explored in last decades. Among them phenylboronic acids and their derivatives are most frequently examined as receptors for diverse carbohydrates. In turn, there is a large gap in basic research concerning complexation of catecholamines by these compounds. Therefore, we decided to undertake studies on interaction of chosen catecholamines, namely: noradrenaline (norephinephrine), dopamine, L-DOPA, DOPA-P (phosphonic analog of L-DOPA) and catechol, with simple phenyl boronic acid PBA by means of potentiometry and NMR spectroscopy. For comparison, the binding properties of recently synthesized phenylboronic receptor 1 bearing aminophosphonate function in meta-position were investigated and showed promising ability to bind catecholamines. The protonation and stability constants of PBA and receptor 1 complexes were examined by potentiometry. The obtained results demonstrated that PBA binds the catecholamines with the following affinity order: noradrenaline ⩾ dopamine ≈ L-DOPA > catechol > DOPA-P, while its modified analog 1 reveals slightly different preferences: dopamine > noradrenaline > catechol > L-DOPA > DOPA-P.

  7. Selective removal of phosphate for analysis of organic acids in complex samples.

    Science.gov (United States)

    Deshmukh, Sandeep; Frolov, Andrej; Marcillo, Andrea; Birkemeyer, Claudia

    2015-04-03

    Accurate quantitation of compounds in samples of biological origin is often hampered by matrix interferences one of which occurs in GC-MS analysis from the presence of highly abundant phosphate. Consequently, high concentrations of phosphate need to be removed before sample analysis. Within this context, we screened 17 anion exchange solid-phase extraction (SPE) materials for selective phosphate removal using different protocols to meet the challenge of simultaneous recovery of six common organic acids in aqueous samples prior to derivatization for GC-MS analysis. Up to 75% recovery was achieved for the most organic acids, only the low pKa tartaric and citric acids were badly recovered. Compared to the traditional approach of phosphate removal by precipitation, SPE had a broader compatibility with common detection methods and performed more selectively among the organic acids under investigation. Based on the results of this study, it is recommended that phosphate removal strategies during the analysis of biologically relevant small molecular weight organic acids consider the respective pKa of the anticipated analytes and the detection method of choice. Copyright © 2015 Elsevier B.V. All rights reserved.

  8. Uranium sorption to natural substrates-insights provided by isotope exchange, selective extraction and surface complexation modelling approaches

    International Nuclear Information System (INIS)

    Waite, T.D.; Payne T.E.; Davis, J.A.

    1993-01-01

    An extensive experimental program has been conducted over the last three years into the interaction of U(VI) with both single oxides and clays and complex natural substrates from the weathered zone in the vicinity of a uranium ore body in northern Australia. While iron oxides have frequently been considered to account for much of the uptake on such natural substrates, the results of laboratory open-quotes pH edgeclose quotes studies and of isotope exchange and selective extraction studies suggest that other phases must also play a significant role in controlling the partitioning of U(VI) between solid and solution phases. Supporting studies on kaolinite, the dominant clay in this system, provide insight into the most appropriate method of modelling the interaction of U(VI) with these natural substrates. The problems still remaining in adequately describing sorption of radionuclides and trace elements to complex natural substrates are discussed

  9. Selection of low-level radioactive waste disposal sites using screening models versus more complex methodologies

    International Nuclear Information System (INIS)

    Uslu, I.; Fields, D.E.

    1993-01-01

    The task of choosing a waste-disposal site from a set of candidate sites requires an approach capable of objectively handling many environmental variables for each site. Several computer methodologies have been developed to assist in the process of choosing a site for the disposal of low-level radioactive waste; however, most of these models are costly to apply, in terms of computer resources and the time and effort required by professional modelers, geologists, and waste-disposal experts. The authors describe how the relatively simple DRASTIC methodology (a standardized system for evaluating groundwater pollution potential using hydrogeologic settings) may be used for open-quotes pre-screeningclose quotes of sites to determine which subset of candidate sites is worthy of more detailed screening. Results of site comparisons made with DRASTIC are compared with results obtained using PRESTO-II methodology, which is representative of the more complex release-transport-human exposure methodologies. 6 refs., 1 fig., 1 tab

  10. Radiolytic and photochemical reduction of carbon dioxide in solution catalyzed by transition metal complexes with some selected macrocycles

    International Nuclear Information System (INIS)

    Grodkowski, J.

    2004-01-01

    The main goal of the work presented in this report is an explanation of the mechanism of carbon dioxide (CO 2 ) reduction catalyzed by transition metal complexes with some selected macrocycles. The catalytic function of two electron exchange centers in the reduction of CO 2 , an inner metal and a macrocycle ring, was defined. Catalytic effects of rhodium, iron and cobalt porphyrins, cobalt and iron phthalocyanines and corroles as well as cobalt corrins have been investigated. CO 2 reduction by iron ions without presence of macrocycles and also in presence of copper compounds in aqueous solutions have been studied as well

  11. Does Pictorial Elucidation Foster Recollection of Idioms?

    Science.gov (United States)

    Boers, Frank; Piquer Piriz, Ana Maria; Stengers, Helene; Eyckmans, June

    2009-01-01

    Experimental evidence suggests that pictorial elucidation helps learners comprehend and remember the meaning of second language (L2) idioms. In this article we address the question whether it also helps retention of the form of idioms, i.e. their precise lexical composition. In a small-scale experiment, the meaning of English idioms was clarified…

  12. Synthesis and NMR Elucidation of Novel Pentacycloundecane ...

    African Journals Online (AJOL)

    Herein we report the synthesis and NMR elucidation of five novel pentacycloundecane (PCU)-derived short peptides as potential HIV protease inhibitors. 1H and 13C spectral analysis show major overlapping of methine resonance of the PCU 'cage' thereby making it extremely difficult to assign the NMR signals. Attachment ...

  13. Synthesis and NMR elucidation of novel pentacycloundecane ...

    African Journals Online (AJOL)

    NICO

    SYNTHESIS AND NMR ELUCIDATION OF NOVEL. PENTACYCLOUNDECANE DERIVED PEPTIDES. Rajshekhar Karpoormath, a. Oluseye K. Onajole, a. Thavendran Govender, b. Glenn E. M. Maguire, a and Hendrik G. Kruger a* a. School of Chemistry, University of KwaZulu-Natal, Durban 4001, South Africa b. School of ...

  14. Structure of the Human Dopamine D3 Receptor in Complex with a D2/D3 Selective Antagonist

    Energy Technology Data Exchange (ETDEWEB)

    Chien, Ellen Y.T.; Liu, Wei; Zhao, Qiang; Katritch, Vsevolod; Han, Gye Won; Hanson, Michael A.; Shi, Lei; Newman, Amy Hauck; Javitch, Jonathan A.; Cherezov, Vadim; Stevens, Raymond C. (Cornell); (Scripps); (NIDA); (Columbia); (UCSD); (Receptos)

    2010-11-30

    Dopamine modulates movement, cognition, and emotion through activation of dopamine G protein-coupled receptors in the brain. The crystal structure of the human dopamine D3 receptor (D3R) in complex with the small molecule D2R/D3R-specific antagonist eticlopride reveals important features of the ligand binding pocket and extracellular loops. On the intracellular side of the receptor, a locked conformation of the ionic lock and two distinctly different conformations of intracellular loop 2 are observed. Docking of R-22, a D3R-selective antagonist, reveals an extracellular extension of the eticlopride binding site that comprises a second binding pocket for the aryl amide of R-22, which differs between the highly homologous D2R and D3R. This difference provides direction to the design of D3R-selective agents for treating drug abuse and other neuropsychiatric indications.

  15. Positive Darwinian selection in the piston that powers proton pumps in complex I of the mitochondria of Pacific salmon.

    Directory of Open Access Journals (Sweden)

    Michael R Garvin

    Full Text Available The mechanism of oxidative phosphorylation is well understood, but evolution of the proteins involved is not. We combined phylogenetic, genomic, and structural biology analyses to examine the evolution of twelve mitochondrial encoded proteins of closely related, yet phenotypically diverse, Pacific salmon. Two separate analyses identified the same seven positively selected sites in ND5. A strong signal was also detected at three sites of ND2. An energetic coupling analysis revealed several structures in the ND5 protein that may have co-evolved with the selected sites. These data implicate Complex I, specifically the piston arm of ND5 where it connects the proton pumps, as important in the evolution of Pacific salmon. Lastly, the lineage to Chinook experienced rapid evolution at the piston arm.

  16. Positive Darwinian selection in the piston that powers proton pumps in complex I of the mitochondria of Pacific salmon.

    Science.gov (United States)

    Garvin, Michael R; Bielawski, Joseph P; Gharrett, Anthony J

    2011-01-01

    The mechanism of oxidative phosphorylation is well understood, but evolution of the proteins involved is not. We combined phylogenetic, genomic, and structural biology analyses to examine the evolution of twelve mitochondrial encoded proteins of closely related, yet phenotypically diverse, Pacific salmon. Two separate analyses identified the same seven positively selected sites in ND5. A strong signal was also detected at three sites of ND2. An energetic coupling analysis revealed several structures in the ND5 protein that may have co-evolved with the selected sites. These data implicate Complex I, specifically the piston arm of ND5 where it connects the proton pumps, as important in the evolution of Pacific salmon. Lastly, the lineage to Chinook experienced rapid evolution at the piston arm.

  17. Positive Darwinian Selection in the Piston That Powers Proton Pumps in Complex I of the Mitochondria of Pacific Salmon

    Science.gov (United States)

    Garvin, Michael R.; Bielawski, Joseph P.; Gharrett, Anthony J.

    2011-01-01

    The mechanism of oxidative phosphorylation is well understood, but evolution of the proteins involved is not. We combined phylogenetic, genomic, and structural biology analyses to examine the evolution of twelve mitochondrial encoded proteins of closely related, yet phenotypically diverse, Pacific salmon. Two separate analyses identified the same seven positively selected sites in ND5. A strong signal was also detected at three sites of ND2. An energetic coupling analysis revealed several structures in the ND5 protein that may have co-evolved with the selected sites. These data implicate Complex I, specifically the piston arm of ND5 where it connects the proton pumps, as important in the evolution of Pacific salmon. Lastly, the lineage to Chinook experienced rapid evolution at the piston arm. PMID:21969854

  18. Structure of the Human FANCL RING-Ube2T Complex Reveals Determinants of Cognate E3-E2 Selection

    Science.gov (United States)

    Hodson, Charlotte; Purkiss, Andrew; Miles, Jennifer Anne; Walden, Helen

    2014-01-01

    Summary The combination of an E2 ubiquitin-conjugating enzyme with an E3 ubiquitin-ligase is essential for ubiquitin modification of a substrate. Moreover, the pairing dictates both the substrate choice and the modification type. The molecular details of generic E3-E2 interactions are well established. Nevertheless, the determinants of selective, specific E3-E2 recognition are not understood. There are ∼40 E2s and ∼600 E3s giving rise to a possible ∼24,000 E3-E2 pairs. Using the Fanconi Anemia pathway exclusive E3-E2 pair, FANCL-Ube2T, we report the atomic structure of the FANCL RING-Ube2T complex, revealing a specific and extensive network of additional electrostatic and hydrophobic interactions. Furthermore, we show that these specific interactions are required for selection of Ube2T over other E2s by FANCL. PMID:24389026

  19. Neurons in the thalamic reticular nucleus are selective for diverse and complex visual features

    Science.gov (United States)

    Vaingankar, Vishal; Soto-Sanchez, Cristina; Wang, Xin; Sommer, Friedrich T.; Hirsch, Judith A.

    2012-01-01

    All visual signals the cortex receives are influenced by the perigeniculate sector (PGN) of the thalamic reticular nucleus, which receives input from relay cells in the lateral geniculate and provides feedback inhibition in return. Relay cells have been studied in quantitative depth; they behave in a roughly linear fashion and have receptive fields with a stereotyped center-surround structure. We know far less about reticular neurons. Qualitative studies indicate they simply pool ascending input to generate non-selective gain control. Yet the perigeniculate is complicated; local cells are densely interconnected and fire lengthy bursts. Thus, we employed quantitative methods to explore the perigeniculate using relay cells as controls. By adapting methods of spike-triggered averaging and covariance analysis for bursts, we identified both first and second order features that build reticular receptive fields. The shapes of these spatiotemporal subunits varied widely; no stereotyped pattern emerged. Companion experiments showed that the shape of the first but not second order features could be explained by the overlap of On and Off inputs to a given cell. Moreover, we assessed the predictive power of the receptive field and how much information each component subunit conveyed. Linear-non-linear (LN) models including multiple subunits performed better than those made with just one; further each subunit encoded different visual information. Model performance for reticular cells was always lesser than for relay cells, however, indicating that reticular cells process inputs non-linearly. All told, our results suggest that the perigeniculate encodes diverse visual features to selectively modulate activity transmitted downstream. PMID:23269915

  20. Stability constant determinations for technetium (IV) complexation with selected amino carboxylate ligands in high nitrate solutions

    Energy Technology Data Exchange (ETDEWEB)

    Omoto, Trevor; Wall, Nathalie A. [Washington State Univ., Pullman, WA (United States). Dept. of Chemistry

    2017-10-01

    The stability constants for Tc(IV) complexation with the ligands IDA, NTA, HEDTA, and DTPA were determined in varied nitrate concentrations using liquid-liquid extraction methods. The determined log β{sub 101} stability constants at 0.5 M NaNO{sub 3} were found to be 9.2±0.3, 10.3±0.3, and 15.3±0.3 for IDA, NTA, and HEDTA, respectively. The log β{sub 111} stability constant for DTPA was determined to be 22.0±0.6. These determined stability constants show a slight decrease in magnitude as a function of increasing NaNO{sub 3} concentration. These stability constants were used to model the total dissolution of Tc(IV) in acidic aqueous solutions in the presence of each ligand. The results of these predictive models indicate that amino carboxylic ligands have a high potential for increasing the aqueous dissolution of Tc(IV); at pH 2.3, 0.01 M ligand yield dissolved Tc(IV) concentrations of 1.42.10{sup -5} M, 1.33.10{sup -5} M, 6.07.10{sup -6} M, 9.65.10{sup -7} M, for DTPA, HEDTA, NTA, and IDA, respectively.

  1. BET Bromodomain Inhibition Releases the Mediator Complex from Select cis-Regulatory Elements.

    Science.gov (United States)

    Bhagwat, Anand S; Roe, Jae-Seok; Mok, Beverly Y L; Hohmann, Anja F; Shi, Junwei; Vakoc, Christopher R

    2016-04-19

    The bromodomain and extraterminal (BET) protein BRD4 can physically interact with the Mediator complex, but the relevance of this association to the therapeutic effects of BET inhibitors in cancer is unclear. Here, we show that BET inhibition causes a rapid release of Mediator from a subset of cis-regulatory elements in the genome of acute myeloid leukemia (AML) cells. These sites of Mediator eviction were highly correlated with transcriptional suppression of neighboring genes, which are enriched for targets of the transcription factor MYB and for functions related to leukemogenesis. A shRNA screen of Mediator in AML cells identified the MED12, MED13, MED23, and MED24 subunits as performing a similar regulatory function to BRD4 in this context, including a shared role in sustaining a block in myeloid maturation. These findings suggest that the interaction between BRD4 and Mediator has functional importance for gene-specific transcriptional activation and for AML maintenance. Copyright © 2016 The Authors. Published by Elsevier Inc. All rights reserved.

  2. Bioinspired tannic acid-copper complexes as selective coating for nanofiltration membranes

    KAUST Repository

    Chakrabarty, Tina

    2017-04-27

    Bio-polyphenols that are present in tea, date fruits, chockolate and many other plants have been recognized as scaffold material for the manufacture of composite filtration membranes. These phenolic biomolecules possess abundant gallol (1,2,3-trihydroxyphenyl) and catechol (1,2-dihydroxyphenyl) functional groups, which allow the spontaneous formation of a thin polymerized layer at the right pH conditions. Here, we report a facile and cost-effective method to coat porous membranes via the complexation of tannic acid (TA) and cupric acetate (mono hydrate) through co-deposition. The modified membranes were investigated by XPS, ATR/FTIR, water contact angle, SEM and water permeance for a structural and morphological analysis. The obtained results reveal that the modified membranes with TA and cupric acetate (CuII) developed a thin skin layer, which showed excellent hydrophilicity with good water permeance. These membranes were tested with different molecular weight polyethylene glycols (PEG) in aqueous solution; the MWCO was around 600 Daltons.

  3. Neurons in the thalamic reticular nucleus are selective for diverse and complex visual features

    Directory of Open Access Journals (Sweden)

    Vishal eVaingankar

    2012-12-01

    Full Text Available All visual signals the cortex receives are influenced by the perigeniculate sector of the thalamic reticular nucleus, which receives input from relay cells in the lateral geniculate and provides feedback inhibition in return. Relay cells have been studied in quantitative depth; they behave in a roughly linear fashion and have receptive fields with a stereotyped centre-surround structure. We know far less about reticular neurons. Qualitative studies indicate they simply pool ascending input to generate nonselective gain control. Yet the perigeniculate is complicated; local cells are densely interconnected and fire lengthy bursts. Thus, we employed quantitative methods to explore the perigeniculate, using relay cells as controls. By adapting methods of spike-triggered averaging and covariance analysis for bursts, we identified both first and second order features that build reticular receptive fields. The shapes of these spatiotemporal subunits varied widely; no stereotyped pattern emerged. Companion experiments showed that the shape of the first but not second order features could be explained by the overlap of On and Off inputs to a given cell. Moreover, we assessed the predictive power of the receptive field and how much information each component subunit conveyed. Linear-nonlinear models including multiple subunits performed better than those made with just one; further each subunit encoded different visual information. Model performance for reticular cells was always lesser than for relay cells, however, indicating that reticular cells process inputs nonlinearly. All told, our results suggest that the perigeniculate encodes diverse visual features to selectively modulate activity transmitted downstream

  4. Selective laser melting-enabled electrospinning: Introducing complexity within electrospun membranes.

    Science.gov (United States)

    Paterson, Thomas E; Beal, Selina N; Santocildes-Romero, Martin E; Sidambe, Alfred T; Hatton, Paul V; Asencio, Ilida Ortega

    2017-06-01

    Additive manufacturing technologies enable the creation of very precise and well-defined structures that can mimic hierarchical features of natural tissues. In this article, we describe the development of a manufacturing technology platform to produce innovative biodegradable membranes that are enhanced with controlled microenvironments produced via a combination of selective laser melting techniques and conventional electrospinning. This work underpins the manufacture of a new generation of biomaterial devices that have significant potential for use as both basic research tools and components of therapeutic implants. The membranes were successfully manufactured and a total of three microenvironment designs (niches) were chosen for thorough characterisation. Scanning electron microscopy analysis demonstrated differences in fibre diameters within different areas of the niche structures as well as differences in fibre density. We also showed the potential of using the microfabricated membranes for supporting mesenchymal stromal cell culture and proliferation. We demonstrated that mesenchymal stromal cells grow and populate the membranes penetrating within the niche-like structures. These findings demonstrate the creation of a very versatile tool that can be used in a variety of tissue regeneration applications including bone healing.

  5. Introduction of π-complexation into porous aromatic framework for highly selective adsorption of ethylene over ethane

    KAUST Repository

    Li, Baiyan

    2014-06-18

    In this work, we demonstrate for the first time the introduction of π-complexation into a porous aromatic framework (PAF), affording significant increase in ethylene uptake capacity, as illustrated in the context of Ag(I) ion functionalized PAF-1, PAF-1-SO3Ag. IAST calculations using single-component-isotherm data and an equimolar ethylene/ethane ratio at 296 K reveal that PAF-1-SO3Ag shows exceptionally high ethylene/ethane adsorption selectivity (Sads: 27 to 125), far surpassing benchmark zeolite and any other MOF reported in literature. The formation of π-complexation between ethylene molecules and Ag(I) ions in PAF-1-SO 3Ag has been evidenced by the high isosteric heats of adsorption of C2H4 and also proved by in situ IR spectroscopy studies. Transient breakthrough experiments, supported by simulations, indicate the feasibility of PAF-1-SO3Ag for producing 99.95%+ pure C 2H4 in a Pressure Swing Adsorption operation. Our work herein thus suggests a new perspective to functionalizing PAFs and other types of advanced porous materials for highly selective adsorption of ethylene over ethane. © 2014 American Chemical Society.

  6. Functional polyterthiophene-appended uranyl-salophen complex: electropolymerization and ion-selective response for monohydrogen phosphate.

    Science.gov (United States)

    Kim, Junghwan; Kang, Dong Min; Shin, Sung Chul; Choi, Myong Yong; Kim, Jineun; Lee, Shim Sung; Kim, Jae Sang

    2008-04-28

    We have synthesized a bis(terthiophene)-appended uranyl-salophen complex, comprising N,N'-bis[4-(5,2':5',2''-terthiophen-3'-yl)salicylidene]-1,2-ethanediamine-uranyl complexes (TUS), and used it as a monomer for the electrochemical polymerizations (poly-TUS) on glassy carbon surfaces to prepare functionalized conducting polymer (CP) films. The poly-TUS films prepared from propylene carbonate/0.1 M tetrabutyl ammonium perchlorate (TBAP) on a glassy carbon electrode have both the functionality of ion-to-electron transducers (solid contact) and Lewis-acidic binding sites for a monohydrogen phosphate (MHP) ion-selective electrode (ISE). The CP/poly-TUS sensor showed a linear range between 1.0 x 10(-1) and 1.0 x 10(-4.5) M with a near-Nernstian behavior (-30.4 mV decade(-1)) at a pH of 8.2. The detection limit of the electrode was 10(-5.0) M and the response time was improved (polyvinyl chloride (PVC) liquid membrane with or without tridodecylmethylammonium chloride (TDMACl) as an additive was also constructed and its performance as an MHP-ISE were studied. The superior selectivity and sensitivity of the CP/poly-TUS sensor enabled the direct measurement of MHP in a wide variety of applications.

  7. The Results of Complex Selective Logging in Beech-Hornbeam Tree Stands of the Greater Caucasus in Azerbaijan

    Directory of Open Access Journals (Sweden)

    A. B. Yakhyaev

    2014-06-01

    Full Text Available The results of complex selective logging conducted in beech-hornbeam tree stands on the northeastern slope of the Greater Caucasus are analyzed in the paper. Experiments were carried out in two forestry districts, involving beech stands, comprising 2–3 units, with 30° slopes, in beech forests with woodruff, fescue and forb forest types. It has been revealed that for recovering the main tree species, as well as for increasing productivity and sustainability of the beech-hornbeam tree stands, which was spread out in the northern exposures, 2–3 repetitions of complex selective logging are recommended. It is recommended that in order to increase the amount of beech in the tree stand composition to 6–8 units in young stands and to 4–6 units at the slopes of south exposures, to complete 3–4 thinning operations, with the increasing beech share to 4–5 units in the upper story and in the undergrowth.

  8. Introduction of π-complexation into porous aromatic framework for highly selective adsorption of ethylene over ethane

    KAUST Repository

    Li, Baiyan; Zhang, Yiming; Krishna, Rajamani; Yao, Kexin; Han, Yu; Wu, Zili; Ma, Dingxuan; Shi, Zhan; Pham, Tony T.; Space, Brian; Liu, Jian; Thallapally, Praveen K.; Liu, Jun; Chrzanowski, Matthew; Ma, Shengqian

    2014-01-01

    In this work, we demonstrate for the first time the introduction of π-complexation into a porous aromatic framework (PAF), affording significant increase in ethylene uptake capacity, as illustrated in the context of Ag(I) ion functionalized PAF-1, PAF-1-SO3Ag. IAST calculations using single-component-isotherm data and an equimolar ethylene/ethane ratio at 296 K reveal that PAF-1-SO3Ag shows exceptionally high ethylene/ethane adsorption selectivity (Sads: 27 to 125), far surpassing benchmark zeolite and any other MOF reported in literature. The formation of π-complexation between ethylene molecules and Ag(I) ions in PAF-1-SO 3Ag has been evidenced by the high isosteric heats of adsorption of C2H4 and also proved by in situ IR spectroscopy studies. Transient breakthrough experiments, supported by simulations, indicate the feasibility of PAF-1-SO3Ag for producing 99.95%+ pure C 2H4 in a Pressure Swing Adsorption operation. Our work herein thus suggests a new perspective to functionalizing PAFs and other types of advanced porous materials for highly selective adsorption of ethylene over ethane. © 2014 American Chemical Society.

  9. Evidence of Selection against Complex Mitotic-Origin Aneuploidy during Preimplantation Development

    Science.gov (United States)

    McCoy, Rajiv C.; Demko, Zachary P.; Ryan, Allison; Banjevic, Milena; Hill, Matthew; Sigurjonsson, Styrmir; Rabinowitz, Matthew; Petrov, Dmitri A.

    2015-01-01

    Whole-chromosome imbalances affect over half of early human embryos and are the leading cause of pregnancy loss. While these errors frequently arise in oocyte meiosis, many such whole-chromosome abnormalities affecting cleavage-stage embryos are the result of chromosome missegregation occurring during the initial mitotic cell divisions. The first wave of zygotic genome activation at the 4–8 cell stage results in the arrest of a large proportion of embryos, the vast majority of which contain whole-chromosome abnormalities. Thus, the full spectrum of meiotic and mitotic errors can only be detected by sampling after the initial cell divisions, but prior to this selective filter. Here, we apply 24-chromosome preimplantation genetic screening (PGS) to 28,052 single-cell day-3 blastomere biopsies and 18,387 multi-cell day-5 trophectoderm biopsies from 6,366 in vitro fertilization (IVF) cycles. We precisely characterize the rates and patterns of whole-chromosome abnormalities at each developmental stage and distinguish errors of meiotic and mitotic origin without embryo disaggregation, based on informative chromosomal signatures. We show that mitotic errors frequently involve multiple chromosome losses that are not biased toward maternal or paternal homologs. This outcome is characteristic of spindle abnormalities and chaotic cell division detected in previous studies. In contrast to meiotic errors, our data also show that mitotic errors are not significantly associated with maternal age. PGS patients referred due to previous IVF failure had elevated rates of mitotic error, while patients referred due to recurrent pregnancy loss had elevated rates of meiotic error, controlling for maternal age. These results support the conclusion that mitotic error is the predominant mechanism contributing to pregnancy losses occurring prior to blastocyst formation. This high-resolution view of the full spectrum of whole-chromosome abnormalities affecting early embryos provides insight

  10. Evidence of Selection against Complex Mitotic-Origin Aneuploidy during Preimplantation Development.

    Directory of Open Access Journals (Sweden)

    Rajiv C McCoy

    2015-10-01

    Full Text Available Whole-chromosome imbalances affect over half of early human embryos and are the leading cause of pregnancy loss. While these errors frequently arise in oocyte meiosis, many such whole-chromosome abnormalities affecting cleavage-stage embryos are the result of chromosome missegregation occurring during the initial mitotic cell divisions. The first wave of zygotic genome activation at the 4-8 cell stage results in the arrest of a large proportion of embryos, the vast majority of which contain whole-chromosome abnormalities. Thus, the full spectrum of meiotic and mitotic errors can only be detected by sampling after the initial cell divisions, but prior to this selective filter. Here, we apply 24-chromosome preimplantation genetic screening (PGS to 28,052 single-cell day-3 blastomere biopsies and 18,387 multi-cell day-5 trophectoderm biopsies from 6,366 in vitro fertilization (IVF cycles. We precisely characterize the rates and patterns of whole-chromosome abnormalities at each developmental stage and distinguish errors of meiotic and mitotic origin without embryo disaggregation, based on informative chromosomal signatures. We show that mitotic errors frequently involve multiple chromosome losses that are not biased toward maternal or paternal homologs. This outcome is characteristic of spindle abnormalities and chaotic cell division detected in previous studies. In contrast to meiotic errors, our data also show that mitotic errors are not significantly associated with maternal age. PGS patients referred due to previous IVF failure had elevated rates of mitotic error, while patients referred due to recurrent pregnancy loss had elevated rates of meiotic error, controlling for maternal age. These results support the conclusion that mitotic error is the predominant mechanism contributing to pregnancy losses occurring prior to blastocyst formation. This high-resolution view of the full spectrum of whole-chromosome abnormalities affecting early embryos

  11. Selective Decontamination Effect of Metal Ions in Soil Using Supercritical CO{sub 2} and TBP Complex

    Energy Technology Data Exchange (ETDEWEB)

    Park, Jihye; Park, Kwangheon; Jung, Wonyoung [Kyunghee Univ., Yongin (Korea, Republic of)

    2014-10-15

    Decontamination of soil pollution is difficult because the type of contamination largely depends on the characteristics of the pollutant and the area. Also, existing soil decontamination methods generate large quantities of secondary waste and additional process costs. For this reason, new decontamination methods are always under active investigation. A method involving the use of supercritical carbon dioxide with excellent permeability in place of chemical solvents is currently being studied. Unlike other heavy metals in fission products, uranium is used as fuel, and must be handled carefully. Therefore, in this paper, we studied a supercritical carbon dioxide method for decontaminating heavy metal ions in soil using tri-n-butyl phosphate(TBP), which is well known as a ligand for the extraction of metal ions of actinium. We investigated the decontamination effect of heavy metal ions in the soil using TBP-HNO{sub 3} Complex and supercritical carbon dioxide. The study results showed that when heavy metals in soil are extracted using supercritical carbon dioxide, the extraction efficiency is different according to the type of pollutant metal ions in the soil. When TBP-HNO{sub 3} Complex is used with an extractant, uranium extraction is very effective, but lithium, strontium, and cesium extraction is not effective. Therefore, in the case of a mixture of uranium and other metals such as lithium, strontium, cesium, and so on in soil contaminated by fission product leaks from nuclear power plants, we can selectively decontaminate uranium with supercritical carbon dioxide and TBP-HNO{sub 3} Complex.

  12. Indirect complexometric determination of mercury(II in synthetic alloys and complexes using ethanethiol as a selective masking agent

    Directory of Open Access Journals (Sweden)

    J. KARTHIKEYAN

    2006-03-01

    Full Text Available Acomplexometric method for the determination of mercury(II in presence of other metal ions, based on the selective masking action of ethanethiol towards mercury(II is described. Mercury(II present in a given sample solution is first complexed with an excess of EDTAand the unreacted EDTAis titrated against zinc sulphate solution at pH 5–6 (hexamine buffer using xylenol orange as the indicator. An excess of a 0.3 % solution of ethanethiol is then added to displace EDTA from the Hg(II–EDTA complex. The released EDTAis titrated with a standard zinc sulphate solution. Reproducible and accurate results are obtained for 4–85 mg of mercury(II with a relative error of less than ± 0.46 % and coefficient of variation of not more than 0.47 %. The effects of the presence of various ions were studied. The method can be used for the analysis of mercury in its synthetic alloy mixtures and also in complexes.

  13. Complexation of f elements by tripodal ligands containing aromatic nitrogens. Application to the selective extraction of actinides(III)

    International Nuclear Information System (INIS)

    Wietzke, Raphael

    1999-01-01

    This work initiates a research project, whose aim is the actinides(lll)/lanthanides(III) separation by liquid-liquid extraction. We were interested in the study of the coordination chemistry of lanthanides(III) and uranium(III) (uranium(III) as model for the actinides(III)), with the aim to show differences between the two families and to better understand the coordination properties involved in the extraction process. We studied the lanthanide(III) and uranium(III) complexation with tripodal ligands containing aromatic nitrogens. Several tripodal ligands were synthesized varying the type and the number of the donor atoms. The lanthanide(III) complexes have been characterized in the solid state and in solution (by several techniques: "1H NMR, ESMS, luminescence, UV spectrophotometry, conductometry). Differences in the coordination were found depending on the nature of the donor atoms. The new ligands, tris(2-pyrazinylmethyl)amine (tpza) et tris(N,N-diethyl-2-carbamoyl-6- pyridylmethyl)amine (tpaa), have shown a selectivity for the actinides(III) with promising results in liquid-liquid extraction. The comparison between the lanthanum(III) and uranium(III) complexes with the ligand tpza showed differences in the bonding nature, which could be attributed to a covalent contribution to the metal-ligand bond. (author) [fr

  14. Complex comprised of dextran magnetite and conjugated cisplatin exhibiting selective hyperthermic and controlled-release potential

    Directory of Open Access Journals (Sweden)

    Akinaga Sonoda

    2010-07-01

    Full Text Available Akinaga Sonoda1, Norihisa Nitta1, Ayumi Nitta-Seko1, Shinich Ohta1, Shigeyuki Takamatsu2, Yoshio Ikehata3, Isamu Nagano3, Jun-ichiro Jo4, Yasuhiko Tabata4, Masashi Takahashi1, Osamu Matsui3, Kiyoshi Murata11Department of Radiology, Shiga University of Medical Science, Setatsukinowa-cho, Otsu, Shiga, 520-2192, Japan; 2Department of Radiology, Graduate School of Medical Science, Kanazawa University, Takara-machi 13-1, Kanazawa Ishikawa, 920-8641, Japan; 3Department of Natural Science and Technology, Graduate School of Engineering, Kanazawa University, Kakuma-machi, Kanazawa, Ishikawa 920-1192, Japan; 4Department of Biomaterials, Institute for Frontier Medical Sciences, Kyoto University, Shogoin kawara-machi 53, Sakyo-ku 606-8507, Kyoto, JapanAbstract: We developed a dextran-magnetite conjugated cisplatin (DM-Cis complex for use in thermal ablation and as a chemotherapeutic drug. To produce DM-Cis we reacted Cis with 1 mL DM (56 mg/mL iron. The temperature rise of DM-Cis was measured in vitro and in vivo under a portable induction-heating (IH device. Platinum desorption from DM-Cis over 24 hours was measured in bovine serum. In in vivo accumulation and magnet and exothermic experiments we used four rat groups. In group 1 we delivered DM-Cis intraperitoneally (ip and placed magnets subcutaneously (sc. In group 2 we injected saline (ip and placed magnets (sc. In group 3 we injected DM-Cis (ip and placed a sc incision (sham. The control (group 4 received an ip injection of saline. Rectus abdominis muscle tissue was stained with hematoxylin-eosin and iron-stained tissue areas (µm2 were calculated. The maximum platinum concentration in DM-Cis was approximately 105.6 µg/mL. Over 24 hours, 33.48% of platinum from DM-Cis was released. There was a significant difference (P < 0.05 in the iron-stained area between group 1 and the other groups. The temperature in muscle tissue registered a maximum of 56°C after about 4 min. DM-Cis may represent a

  15. The nearly neutral and selection theories of molecular evolution under the fisher geometrical framework: substitution rate, population size, and complexity.

    Science.gov (United States)

    Razeto-Barry, Pablo; Díaz, Javier; Vásquez, Rodrigo A

    2012-06-01

    The general theories of molecular evolution depend on relatively arbitrary assumptions about the relative distribution and rate of advantageous, deleterious, neutral, and nearly neutral mutations. The Fisher geometrical model (FGM) has been used to make distributions of mutations biologically interpretable. We explored an FGM-based molecular model to represent molecular evolutionary processes typically studied by nearly neutral and selection models, but in which distributions and relative rates of mutations with different selection coefficients are a consequence of biologically interpretable parameters, such as the average size of the phenotypic effect of mutations and the number of traits (complexity) of organisms. A variant of the FGM-based model that we called the static regime (SR) represents evolution as a nearly neutral process in which substitution rates are determined by a dynamic substitution process in which the population's phenotype remains around a suboptimum equilibrium fitness produced by a balance between slightly deleterious and slightly advantageous compensatory substitutions. As in previous nearly neutral models, the SR predicts a negative relationship between molecular evolutionary rate and population size; however, SR does not have the unrealistic properties of previous nearly neutral models such as the narrow window of selection strengths in which they work. In addition, the SR suggests that compensatory mutations cannot explain the high rate of fixations driven by positive selection currently found in DNA sequences, contrary to what has been previously suggested. We also developed a generalization of SR in which the optimum phenotype can change stochastically due to environmental or physiological shifts, which we called the variable regime (VR). VR models evolution as an interplay between adaptive processes and nearly neutral steady-state processes. When strong environmental fluctuations are incorporated, the process becomes a selection model

  16. Habitat selection of two gobies (Microgobius gulosus, Gobiosoma robustum): influence of structural complexity, competitive interactions and presence of a predator

    Science.gov (United States)

    Schofield, P.J.

    2003-01-01

    Herein I compare the relative importance of preference for structurally complex habitat against avoidance of competitors and predators in two benthic fishes common in the Gulf of Mexico. The code goby Gobiosoma robustum Ginsburg and clown goby Microgobius gulosus (Girard) are common, ecologically similar fishes found throughout the Gulf of Mexico and in the southeastern Atlantic Ocean. In Florida Bay, these fishes exhibit habitat partitioning: G. robustum is most abundant in seagrass-dominated areas while M. gulosus is most abundant in sparsely vegetated habitats. In a small-scale field survey, I documented the microhabitat use of these species where their distributions overlap. In a series of laboratory experiments, I presented each species with structured (artificial seagrass) versus nonstructured (bare sand) habitats and measured their frequency of choosing either habitat type. I then examined the use of structured versus nonstructured habitats when the two species were placed together in a mixed group. Finally, I placed a predator (Opsanus beta) in the experimental aquaria to determine how its presence influenced habitat selection. In the field, G. robustum was more abundant in seagrass and M. gulosus was more abundant in bare mud. In the laboratory, both species selected grass over sand in allopatry. However, in sympatry, M. gulosus occupied sand more often when paired with G. robustum than when alone. G. robustum appears to directly influence the habitat choice of M. gulosus: It seems that M. gulosus is pushed out of the structured habitat that is the preferred habitat of G. robustum. Thus, competition appears to modify the habitat selection of these species when they occur in sympatry. Additionally, the presence of the toadfish was a sufficient stimulus to provoke both M. gulosus and G. robustum to increase their selection for sand (compared to single-species treatments). Distribution patterns of M. gulosus and G. robustum

  17. Using Genomics for Natural Product Structure Elucidation.

    Science.gov (United States)

    Tietz, Jonathan I; Mitchell, Douglas A

    2016-01-01

    Natural products (NPs) are the most historically bountiful source of chemical matter for drug development-especially for anti-infectives. With insights gleaned from genome mining, interest in natural product discovery has been reinvigorated. An essential stage in NP discovery is structural elucidation, which sheds light not only on the chemical composition of a molecule but also its novelty, properties, and derivatization potential. The history of structure elucidation is replete with techniquebased revolutions: combustion analysis, crystallography, UV, IR, MS, and NMR have each provided game-changing advances; the latest such advance is genomics. All natural products have a genetic basis, and the ability to obtain and interpret genomic information for structure elucidation is increasingly available at low cost to non-specialists. In this review, we describe the value of genomics as a structural elucidation technique, especially from the perspective of the natural product chemist approaching an unknown metabolite. Herein we first introduce the databases and programs of interest to the natural products chemist, with an emphasis on those currently most suited for general usability. We describe strategies for linking observed natural product-linked phenotypes to their corresponding gene clusters. We then discuss techniques for extracting structural information from genes, illustrated with numerous case examples. We also provide an analysis of the biases and limitations of the field with recommendations for future development. Our overview is not only aimed at biologically-oriented researchers already at ease with bioinformatic techniques, but also, in particular, at natural product, organic, and/or medicinal chemists not previously familiar with genomic techniques.

  18. Correction: A binary catalyst system of a cationic Ru-CNC pincer complex with an alkali metal salt for selective hydroboration of carbon dioxide.

    Science.gov (United States)

    Ng, Chee Koon; Wu, Jie; Hor, T S Andy; Luo, He-Kuan

    2016-12-22

    Correction for 'A binary catalyst system of a cationic Ru-CNC pincer complex with an alkali metal salt for selective hydroboration of carbon dioxide' by Chee Koon Ng et al., Chem. Commun., 2016, 52, 11842-11845.

  19. A power set-based statistical selection procedure to locate susceptible rare variants associated with complex traits with sequencing data.

    Science.gov (United States)

    Sun, Hokeun; Wang, Shuang

    2014-08-15

    Existing association methods for rare variants from sequencing data have focused on aggregating variants in a gene or a genetic region because of the fact that analysing individual rare variants is underpowered. However, these existing rare variant detection methods are not able to identify which rare variants in a gene or a genetic region of all variants are associated with the complex diseases or traits. Once phenotypic associations of a gene or a genetic region are identified, the natural next step in the association study with sequencing data is to locate the susceptible rare variants within the gene or the genetic region. In this article, we propose a power set-based statistical selection procedure that is able to identify the locations of the potentially susceptible rare variants within a disease-related gene or a genetic region. The selection performance of the proposed selection procedure was evaluated through simulation studies, where we demonstrated the feasibility and superior power over several comparable existing methods. In particular, the proposed method is able to handle the mixed effects when both risk and protective variants are present in a gene or a genetic region. The proposed selection procedure was also applied to the sequence data on the ANGPTL gene family from the Dallas Heart Study to identify potentially susceptible rare variants within the trait-related genes. An R package 'rvsel' can be downloaded from http://www.columbia.edu/∼sw2206/ and http://statsun.pusan.ac.kr. © The Author 2014. Published by Oxford University Press. All rights reserved. For Permissions, please e-mail: journals.permissions@oup.com.

  20. Complexing and analysis of cation selectivity of neutral phosphoryl-containing tripodaud of tris((0-diphenyl-phosphinoylmethyl)phenoxyethyl)amine to lithium sodium and potassium, in acetonitrile. Lithium selectivity and polymeclear compleses

    International Nuclear Information System (INIS)

    Baulin, V.E.; Solov'ev, V.P.; Strakhova, N.N.; Kazachenko, V.P.

    1996-01-01

    A new phosphoryl-containing tripodand-tris-[(0-diphenyl-phosphinoylmethyl)phenoxyethyl] amine-was synthesized. Constants of stability, enthalpy and entropy of reactions of tripodond complexing with lithium, sodium, potassium thiocyanates in acetonitrile at 298 k were determined. Investigation of complexing by the methods of calorimetry, 7 Li and 23 Na NMR, mass-spectrometry enabled to conclude that ligand formed polynuclear complexes with lithium thiocyanate of 2/1 and 3/1 composition along with 1/1 complex. High selectivity of podand to lithium cation in acetonitrile was conditioned by formation of polynuclear complexes. Refs. 29, figs. 3

  1. Description, microhabitat selection and infection patterns of sealworm larvae (Pseudoterranova decipiens species complex, nematoda: ascaridoidea) in fishes from Patagonia, Argentina

    Science.gov (United States)

    2013-01-01

    Background Third-stage larvae of the Pseudoterranova decipiens species complex (also known as sealworms) have been reported in at least 40 marine fish species belonging to 21 families and 10 orders along the South American coast. Sealworms are a cause for concern because they can infect humans who consume raw or undercooked fish. However, despite their economic and zoonotic importance, morphological and molecular characterization of species of Pseudoterranova in South America is still scarce. Methods A total of 542 individual fish from 20 species from the Patagonian coast of Argentina were examined for sealworms. The body cavity, the muscles, internal organs, and the mesenteries were examined to detect nematodes. Sealworm larvae were removed from their capsules and fixed in 70% ethanol. For molecular identification, partial fragments of the mitochondrial cytochrome c oxidase subunit 1 gene (cox1) were amplified for 10 isolates from 4 fish species. Morphological and morphometric data of sealworms were also obtained. Results A total of 635 larvae were collected from 12 fish species. The most infected fish was Prionotus nudigula, followed by Percophis brasiliensis, Acanthistius patachonicus, Paralichthys isosceles, and Pseudopercis semifasciata. Sequences obtained for the cox1 of sealworms from A. patachonicus, P. isosceles, P. brasiliensis and P. nudigula formed a reciprocally monophyletic lineage with published sequences of adult specimens of Pseudoterranova cattani from the South American sea lion Otaria flavescens, and distinct from the remaining 5 species of Pseudoterranova. A morphological description, including drawings and scanning electron microscopy photomicrographs of these larvae is provided. Sealworms collected from Argentinean fishes did not differ in their diagnostic traits from the previously described larvae of P. cattani. However a discriminant analysis suggests that specimens from P. nudigula were significantly larger than those from other fishes

  2. Description, microhabitat selection and infection patterns of sealworm larvae (Pseudoterranova decipiens species complex, nematoda: ascaridoidea) in fishes from Patagonia, Argentina.

    Science.gov (United States)

    Hernández-Orts, Jesús S; Aznar, Francisco J; Blasco-Costa, Isabel; García, Néstor A; Víllora-Montero, María; Crespo, Enrique A; Raga, Juan A; Montero, Francisco E

    2013-08-29

    Third-stage larvae of the Pseudoterranova decipiens species complex (also known as sealworms) have been reported in at least 40 marine fish species belonging to 21 families and 10 orders along the South American coast. Sealworms are a cause for concern because they can infect humans who consume raw or undercooked fish. However, despite their economic and zoonotic importance, morphological and molecular characterization of species of Pseudoterranova in South America is still scarce. A total of 542 individual fish from 20 species from the Patagonian coast of Argentina were examined for sealworms. The body cavity, the muscles, internal organs, and the mesenteries were examined to detect nematodes. Sealworm larvae were removed from their capsules and fixed in 70% ethanol. For molecular identification, partial fragments of the mitochondrial cytochrome c oxidase subunit 1 gene (cox1) were amplified for 10 isolates from 4 fish species. Morphological and morphometric data of sealworms were also obtained. A total of 635 larvae were collected from 12 fish species. The most infected fish was Prionotus nudigula, followed by Percophis brasiliensis, Acanthistius patachonicus, Paralichthys isosceles, and Pseudopercis semifasciata. Sequences obtained for the cox1 of sealworms from A. patachonicus, P. isosceles, P. brasiliensis and P. nudigula formed a reciprocally monophyletic lineage with published sequences of adult specimens of Pseudoterranova cattani from the South American sea lion Otaria flavescens, and distinct from the remaining 5 species of Pseudoterranova. A morphological description, including drawings and scanning electron microscopy photomicrographs of these larvae is provided. Sealworms collected from Argentinean fishes did not differ in their diagnostic traits from the previously described larvae of P. cattani. However a discriminant analysis suggests that specimens from P. nudigula were significantly larger than those from other fishes. Most of the sealworms were

  3. In vivo immunologic selection of class I major histocompatibility complex gene deletion variants from the B16-BL6 melanoma.

    Science.gov (United States)

    Talmadge, J E; Talmadge, C B; Zbar, B; McEwen, R; Meeker, A K; Tribble, H

    1987-06-01

    The mechanism by which tumor allografts escape host immunologic attack was investigated. B16-BL6 cells (the bladder 6 subline of the B16 melanoma) (H-2b) were transfected with a gene (Dd) encoding an allogeneic class I major histocompatibility complex antigen. Clones that expressed Dd antigen were injected into the footpads of nonimmune syngeneic mice, syngeneic immune mice, and nude mice. Under conditions of immunologic selection a clone that contained multiple copies of the transfected gene formed variants that lacked the transfected gene. Primary tumors and pulmonary metastases of immunized mice and pulmonary metastases of nonimmunized mice had lost the Dd gene and, in most cases, all of the associated plasmid. In contrast, in immunodeficient nude mice, primary tumors and pulmonary metastases retained the Dd gene and the associated plasmid. Deletion of genes encoding cell surface antigens may be one of the mechanisms by which allogeneic tumors escape immunologic attack.

  4. Functional polyterthiophene-appended uranyl-salophen complex: Electropolymerization and ion-selective response for monohydrogen phosphate

    International Nuclear Information System (INIS)

    Kim, Junghwan; Kang, Dong Min; Shin, Sung Chul; Choi, Myong Yong; Kim, Jineun; Lee, Shim Sung; Kim, Jae Sang

    2008-01-01

    We have synthesized a bis(terthiophene)-appended uranyl-salophen complex, comprising N,N'-bis[4-(5,2':5',2''-terthiophen-3'-yl)salicylidene] -1,2-ethanediamine-uranyl complexes (TUS), and used it as a monomer for the electrochemical polymerizations (poly-TUS) on glassy carbon surfaces to prepare functionalized conducting polymer (CP) films. The poly-TUS films prepared from propylene carbonate/0.1 M tetrabutyl ammonium perchlorate (TBAP) on a glassy carbon electrode have both the functionality of ion-to-electron transducers (solid contact) and Lewis-acidic binding sites for a monohydrogen phosphate (MHP) ion-selective electrode (ISE). The CP/poly-TUS sensor showed a linear range between 1.0 x 10 -1 and 1.0 x 10 -4.5 M with a near-Nernstian behavior (-30.4 mV decade -1 ) at a pH of 8.2. The detection limit of the electrode was 10 -5.0 M and the response time was improved (<10 s) compared to that of conventional ISEs (<20 s). For comparison, a conventional ISE (with an internal aqueous solution) based on a TUS monomer/o-nitrophenyl octylether (o-NPOE)/polyvinyl chloride (PVC) liquid membrane with or without tridodecylmethylammonium chloride (TDMACl) as an additive was also constructed and its performance as an MHP-ISE were studied. The superior selectivity and sensitivity of the CP/poly-TUS sensor enabled the direct measurement of MHP in a wide variety of applications

  5. A computer program to calculate nuclide yields in complex decay chain for selection of optimum irradiation and cooling condition

    International Nuclear Information System (INIS)

    Takeda, Tsuneo

    1977-11-01

    This report is prepared as a user's input manual for a computer code CODAC-No.5 and provides a general description of the code and instructions for its use. The code represents a modified version of the CODAC-No.4 code. The code developed is capable of calculating radioactive nuclide yields in an any given complex decay and activation chain independent of irradiation history. In this code, eighteen kinds of valuable tables and graphs can be prepared for output. They are available for selection of optimum irradiation and cooling conditions and for other intentions in accordance with irradiation and cooling. For a example, the ratio of a nuclide yield to total nuclide yield depending on irradiation and cooling times is obtained. In these outputs, several kinds of complex and intricate equations and others are included. This code has almost the same input forms as that of CODAC-No.4 code excepting input of irradiation history data. Input method and formats used for this code are very simple for any kinds of nuclear data. List of FORTRAN statements, examples of input data and output results and list of input parameters and its definitions are given in this report. (auth.)

  6. Crystallization and Preliminary Diffraction Analysis of the CAL PDZ Domain in Complex with a Selective Peptide Inhibitor

    Energy Technology Data Exchange (ETDEWEB)

    J Amacher; P Cushing; J Weiner; D Madden

    2011-12-31

    Cystic fibrosis (CF) is associated with loss-of-function mutations in the CF transmembrane conductance regulator (CFTR), which regulates epithelial fluid and ion homeostasis. The CFTR cytoplasmic C-terminus interacts with a number of PDZ (PSD-95/Dlg/ZO-1) proteins that modulate its intracellular trafficking and chloride-channel activity. Among these, the CFTR-associated ligand (CAL) has a negative effect on apical-membrane expression levels of the most common disease-associated mutant {Delta}F508-CFTR, making CAL a candidate target for the treatment of CF. A selective peptide inhibitor of the CAL PDZ domain (iCAL36) has recently been developed and shown to stabilize apical expression of {Delta}F508-CFTR, enhancing net chloride-channel activity, both alone and in combination with the folding corrector corr-4a. As a basis for structural studies of the CAL-iCAL36 interaction, a purification protocol has been developed that increases the oligomeric homogeneity of the protein. Here, the cocrystallization of the complex in space group P2{sub 1}2{sub 1}2{sub 1}, with unit-cell parameters a = 35.9, b = 47.7, c = 97.3 {angstrom}, is reported. The crystals diffracted to 1.4 {angstrom} resolution. Based on the calculated Matthews coefficient (1.96 {angstrom}{sup 3} Da{sup -1}), it appears that the asymmetric unit contains two complexes.

  7. Spectroscopic databases - A tool for structure elucidation

    Energy Technology Data Exchange (ETDEWEB)

    Luksch, P [Fachinformationszentrum Karlsruhe, Gesellschaft fuer Wissenschaftlich-Technische Information mbH, Eggenstein-Leopoldshafen (Germany)

    1990-05-01

    Spectroscopic databases have developed to useful tools in the process of structure elucidation. Besides the conventional library searches, new intelligent programs have been added, that are able to predict structural features from measured spectra or to simulate for a given structure. The example of the C13NMR/IR database developed at BASF and available on STN is used to illustrate the present capabilities of online database. New developments in the field of spectrum simulation and methods for the prediction of complete structures from spectroscopic information are reviewed. (author). 10 refs, 5 figs.

  8. Synthesis of mixed-ligand cobalt complexes and their applications in high cis-1,4-selective butadiene polymerization

    KAUST Repository

    Liu, Wen

    2015-08-03

    Incomplete oxidation of (N-di-tert-butylphosphino)-6-(2-methyl-2’H-benzoimidazole)-2-aminepyridine dichlorocobalt (PN3CoCl2) in DMF results in a unique co-crystal I formed with three parts including DMF, unit A and unit B complex with Co1 and Co2, respectively, (PN3 ligand in unit A: (N-di-tert-butylphosphino)-6-(2’-methyl-2’H-benzoimidazole)-2-aminepyridine, and O=PN3 ligand in unit B: (N-di-tert-butylphosphinoxide)-6-(2’-methyl-2’H-benzoimidazole)-2-aminepyridine) with 1:1:1 molar ratio. Co1 and Co2 complexes both display a five-coordinated distorted-square-pyramidal geometry around the metal center. The Co1 center is coordinated with PN3 ligand via two N atoms from pyridine, benzoimidazole moiety as well as one P atom, and the Co2 center is coordinated with the oxidized ligandO=PN3 via two N atoms from pyridine, benzoimidazole moiety as well as one O atom from DMF molecule, while the oxidized phosphine moiety (O=P) being excluded from the coordination sphere. Activated with AlEt2Cl, the co-crystallized complexes I are able to actively convert butadiene to polybutadiene, affording cis-1,4 polybutadiene with cis-1,4 unit up to 95.5-97.8% and number average molecular weight of cal. 105g/mol. The high cis-1,4 selectivity and monomodal GPC curve of resultant polymer imply that the identical active species generated from two distinctive cobalt centers.

  9. Synthesis of mixed-ligand cobalt complexes and their applications in high cis-1,4-selective butadiene polymerization

    KAUST Repository

    Liu, Wen; Pan, Weijing; Wang, Peng; Li, Wei; Mu, Jingshan; Weng, Gengsheng; Jia, Xiaoyu; Gong, Dirong; Huang, Kuo-Wei

    2015-01-01

    Incomplete oxidation of (N-di-tert-butylphosphino)-6-(2-methyl-2’H-benzoimidazole)-2-aminepyridine dichlorocobalt (PN3CoCl2) in DMF results in a unique co-crystal I formed with three parts including DMF, unit A and unit B complex with Co1 and Co2, respectively, (PN3 ligand in unit A: (N-di-tert-butylphosphino)-6-(2’-methyl-2’H-benzoimidazole)-2-aminepyridine, and O=PN3 ligand in unit B: (N-di-tert-butylphosphinoxide)-6-(2’-methyl-2’H-benzoimidazole)-2-aminepyridine) with 1:1:1 molar ratio. Co1 and Co2 complexes both display a five-coordinated distorted-square-pyramidal geometry around the metal center. The Co1 center is coordinated with PN3 ligand via two N atoms from pyridine, benzoimidazole moiety as well as one P atom, and the Co2 center is coordinated with the oxidized ligandO=PN3 via two N atoms from pyridine, benzoimidazole moiety as well as one O atom from DMF molecule, while the oxidized phosphine moiety (O=P) being excluded from the coordination sphere. Activated with AlEt2Cl, the co-crystallized complexes I are able to actively convert butadiene to polybutadiene, affording cis-1,4 polybutadiene with cis-1,4 unit up to 95.5-97.8% and number average molecular weight of cal. 105g/mol. The high cis-1,4 selectivity and monomodal GPC curve of resultant polymer imply that the identical active species generated from two distinctive cobalt centers.

  10. Synthesis of Inorganic Nanocomposites by Selective Introduction of Metal Complexes into a Self-Assembled Block Copolymer Template

    Directory of Open Access Journals (Sweden)

    Hiroaki Wakayama

    2015-01-01

    Full Text Available Inorganic nanocomposites have characteristic structures that feature expanded interfaces, quantum effects, and resistance to crack propagation. These structures are promising for the improvement of many materials including thermoelectric materials, photocatalysts, and structural materials. Precise control of the inorganic nanocomposites’ morphology, size, and chemical composition is very important for these applications. Here, we present a novel fabrication method to control the structures of inorganic nanocomposites by means of a self-assembled block copolymer template. Different metal complexes were selectively introduced into specific polymer blocks of the block copolymer, and subsequent removal of the block copolymer template by oxygen plasma treatment produced hexagonally packed porous structures. In contrast, calcination removal of the block copolymer template yielded nanocomposites consisting of metallic spheres in a matrix of a metal oxide. These results demonstrate that different nanostructures can be created by selective use of processes to remove the block copolymer templates. The simple process of first mixing block copolymers and magnetic nanomaterial precursors and then subsequently removing the block copolymer template enables structural control of magnetic nanomaterials, which will facilitate their applicability in patterned media, including next-generation perpendicular magnetic recording media.

  11. Crystal Structure of the FGFR4/LY2874455 Complex Reveals Insights into the Pan-FGFR Selectivity of LY2874455.

    Science.gov (United States)

    Wu, Daichao; Guo, Ming; Philips, Michael A; Qu, Lingzhi; Jiang, Longying; Li, Jun; Chen, Xiaojuan; Chen, Zhuchu; Chen, Lin; Chen, Yongheng

    2016-01-01

    Aberrant FGFR4 signaling has been documented abundantly in various human cancers. The majority of FGFR inhibitors display significantly reduced potency toward FGFR4 compared to FGFR1-3. However, LY2874455 has similar inhibition potency for FGFR1-4 with IC50 less than 6.4 nM. To date, there is no published crystal structure of LY2874455 in complex with any kinase. To better understand the pan-FGFR selectivity of LY2874455, we have determined the crystal structure of the FGFR4 kinase domain bound to LY2874455 at a resolution of 2.35 Å. LY2874455, a type I inhibitor for FGFR4, binds to the ATP-binding pocket of FGFR4 in a DFG-in active conformation with three hydrogen bonds and a number of van der Waals contacts. After alignment of the kinase domain sequence of 4 FGFRs, and superposition of the ATP binding pocket of 4 FGFRs, our structural analyses reveal that the interactions of LY2874455 to FGFR4 are largely conserved in 4 FGFRs, explaining at least partly, the broad inhibitory activity of LY2874455 toward 4 FGFRs. Consequently, our studies reveal new insights into the pan-FGFR selectivity of LY2874455 and provide a structural basis for developing novel FGFR inhibitors that target FGFR1-4 broadly.

  12. Structural Complexity and Ecosystem Functions in a Natural Mixed Forest under a Single-Tree Selection Silviculture

    Directory of Open Access Journals (Sweden)

    Toshiya Yoshida

    2017-11-01

    Full Text Available The objective of forest management has become broader, and it is essential to harmonize timber production with conservation of the forest ecosystem. Selection cutting is recognized as a major alternative of clear-cutting, because it can maintain the complexity and heterogeneity of a natural forest; however, its long-term evaluations are limited. This study compared various attributes of stand structures, which are indicators of biodiversity and ecosystem carbon stock between managed and unmanaged blocks (12.6 ha area in total in a natural mixed forest in Hokkaido, the northernmost island of Japan. We found that 30 years’ implementation of single-tree selection did not affect the volume, size structure, species diversity nor spatial distribution of overstory trees in the managed stands. Also, the total carbon stock in the managed stands was almost equal to that of the unmanaged stands. In contrast, several structural attributes and indicator elements that are significant for biodiversity (such as large-diameter live trees, dead trees, cavities, epiphytic bryophytes, and some avian guilds showed marked decrease in the managed stands. We conclude that it is required to leave these structures and elements to some extent for deriving the merit of the management as an alternative silvicultural regime in the region.

  13. A nanosized cadmium(II)-imprinted polymer for use in selective trace determination of cadmium in complex matrices

    International Nuclear Information System (INIS)

    Behbahani, Mohammad; Bagheri, Akbar; Barati, Mozhgan; Pourali, Ali Reza; Tapeh, Nasim Akbari Ghareh; Bojdi, Majid Kalate

    2013-01-01

    We describe a nanosized Cd(II)-imprinted polymer that was prepared from 4-vinyl pyridine (the functional monomer), ethyleneglycol dimethacrylate (the cross-linker), 2,2′-azobisisobutyronitrile (the radical initiator), neocuproine (the ligand), and Cd(II) (the template ion) by precipitation polymerization in acetonitrile as the solvent. The imprinted polymer was characterized by X-ray diffraction, thermogravimetric analysis, differential thermal analysis, and scanning electron microscopy. The maximum adsorption capacity of the nanosized sorbent was calculated to be 64 mg g −1 . Cadmium(II) was then quantified by FAAS. The relative standard deviation and limit of detection are 4.2 % and 0.2 μg L −1 , respectively. The imprinted polymer displays improve selectivity for Cd(II) ions over a range of competing metal ions with the same charge and similar ionic radius. This nanosized sorbent is an efficient solid phase for selective extraction and preconcentration of Cd(II) in complex matrices. The method was successfully applied to the trace determination of Cd(II) in food and water samples. (author)

  14. Fabrication of copper-selective PVC membrane electrode based on newly synthesized copper complex of Schiff base as carrier

    Directory of Open Access Journals (Sweden)

    Sulekh Chandra

    2016-09-01

    Full Text Available The newly synthesized copper(II complex of Schiff base p-hydroxyacetophenone semicarbazone was explored as neutral ionophore for the fabrication of poly(vinylchloride (PVC based membrane electrode selective to Cu(II ions. The electrode shows a Nernstian slope of 29.8 ± 0.3 mV/decade with improved linear range of 1.8 × 10−7 to 1.0 × 10−1 M, comparatively lower detection limit 5.7 × 10−8 M between pH range of 2.0–8.0, giving a relatively fast response within 5s and can be used for at least 16 weeks without any divergence in potential. The selectivity coefficient was calculated using the fixed interference method (FIM. The electrode can also be used in partially non-aqueous media having up to 25% (v/v methanol, ethanol or acetone content with no significant change in the value of slope or working concentration range. It was successfully applied for the direct determination of copper content in water and tea samples with satisfactory results. The electrode has been used in the potentiometric titration of Cu2+ with EDTA.

  15. Highly selective single-use fluoride ion optical sensor based on aluminum(III)-salen complex in thin polymeric film

    International Nuclear Information System (INIS)

    Badr, Ibrahim H.A.; Meyerhoff, Mark E.

    2005-01-01

    A highly selective optical sensor for fluoride ion based on the use of an aluminum(III)-salen complex as an ionophore within a thin polymeric film is described. The sensor is prepared by embedding the aluminum(III)-salen ionophore and a suitable lipophilic pH-sensitive indicator (ETH-7075) in a plasticized poly(vinyl chloride) (PVC) film. Optical response to fluoride occurs due to fluoride extraction into the polymer via formation of a strong complex with the aluminum(III)-salen species. Co-extraction of protons occurs simultaneously, with protonation of the indicator dye yielding the optical response at 529 nm. Films prepared using dioctylsebacate (DOS) are shown to exhibit better response (e.g., linear range, detection limit, and optical signal stability) compared to those prepared using ortho-nitrophenyloctyl ether (o-NPOE). Films formulated with aluminum(III)-salen and ETH-7075 indicator in 2 DOS:1 PVC, exhibit a significantly enhanced selectivity for fluoride over a wide range of lipophilic anions including salicylate, perchlorate, nitrate, and thiocyanate. The optimized films exhibit a sub-micromolar detection limit, using glycine-phosphate buffer, pH 3.00, as the test sample. The response times of the fluoride optical sensing films are in the range of 1-10 min depending on the fluoride ion concentration in the sample. The sensor exhibits very poor reversibility owing to a high co-extraction constant (log K = 8.5 ± 0.4), indicating that it can best be employed as a single-use transduction device. The utility of the aluminum(III)-salen based fluoride sensitive films as single-use sensors is demonstrated by casting polymeric films on the bottom of standard polypropylene microtiter plate wells (96 wells/plate). The modified microtiter plate optode format sensors exhibit response characteristics comparable to the classical optode films cast on quartz slides. The modified microtiter is utilized for the analysis of fluoride in diluted anti-cavity fluoride rinse

  16. Study of the selectivity of poly-nitrogenous extracting molecules in the complexation of actinides (III) and lanthanides (III) in solution in anhydrous pyridine

    International Nuclear Information System (INIS)

    Riviere, Ch.

    2000-01-01

    The aim of this work is to better understand the factors which contribute to the separation of lanthanides(III) and actinides(III). Polydentate nitrogenous molecules present an interesting selectivity. A thermodynamic study of the complexation in pyridine of lanthanide and uranium by the bipyridine ligand (bipy) has been carried out. The formation constants and the thermodynamic values of the different complexes have been determined. It has been shown that the bipy complexes formation is controlled by the enthalpy and unfavored by the entropy. The conductometry has revealed too a significant difference in the uranium and lanthanides complexation by the bipyridine ligand. The use of the phenanthroline ligand induces a better complexation of the metallic ions but the selectivity is not improved. On the other hand, the decrease of the basicity and the increase of the ligand denticity (for instance in the case of the use of ter-pyridine) favour the selectivity without improving the complexation. The selectivity difference for the complexation of actinides(III) and lanthanides(III) by the different studied ligands (independent systems) has been confirmed by experiments of inter-metals competition. (O.M.)

  17. Towards a selective adsorbent for arsenate and selenite in the presence of phosphate: Assessment of adsorption efficiency, mechanism, and binary separation factors of the chitosan-copper complex.

    Science.gov (United States)

    Yamani, Jamila S; Lounsbury, Amanda W; Zimmerman, Julie B

    2016-01-01

    The potential for a chitosan-copper polymer complex to select for the target contaminants in the presence of their respective competitive ions was evaluated by synthesizing chitosan-copper beads (CCB) for the treatment of (arsenate:phosphate), (selenite:phosphate), and (selenate:sulfate). Based on work by Rhazi et al., copper (II) binds to the amine moiety on the chitosan backbone as a monodentate complex (Type I) and as a bidentate complex crosslinking two polymer chains (Type II), depending on pH and copper loading. In general, the Type I complex exists alone; however, beyond threshold conditions of pH 5.5 during synthesis and a copper loading of 0.25 mol Cu(II)/mol chitosan monomer, the Type I and Type II complexes coexist. Subsequent chelation of this chitosan-copper ligand to oxyanions results in enhanced and selective adsorption of the target contaminants in complex matrices with high background ion concentrations. With differing affinities for arsenate, selenite, and phosphate, the Type I complex favors phosphate chelation while the Type II complex favors arsenate chelation due to electrostatic considerations and selenite chelation due to steric effects. No trend was exhibited for the selenate:sulfate system possibly due to the high Ksp of the corresponding copper salts. Binary separation factors, α12, were calculated for the arsenate-phosphate and selenite-phosphate systems, supporting the mechanistic hypothesis. While, further research is needed to develop a synthesis method for the independent formation of the Type II complexes to select for target contaminants in complex matrices, this work can provide initial steps in the development of a selective adsorbent. Copyright © 2015 Elsevier Ltd. All rights reserved.

  18. 3,9-Dithia-6-azaundecane-appended Iridium (III) Complex for the Selective Detection of Hg2+ in Aqueous Acetonitrile

    International Nuclear Information System (INIS)

    Ann, Jee Hye; Li, Yinan; Hyun, Myung Ho

    2012-01-01

    Detection of mercuric ion (Hg 2+ ) originated from natural or industrial sources is very important because it is extremely toxic even at low levels and causes serious environmental and health problems. Consequently, many efforts have been devoted to the development of sensitive chemosensors for the detection of Hg 2+ . For example, various fluorescent chemosensors based on rhodamine, nitrobenzoxadiazole, fluorescein, boradiazaindacene (BODIPY), dansyl, pyrene, or other fluorophores have been developed for the selective detection of Hg 2+ . While various fluorescent chemosensors for the selective detection of Hg 2+ have been developed, phosphorescent chemosensors for the selective detection of Hg 2+ are relatively rare. Among various phosphors, iridium (III) complexes with sulfur containing cyclometalated ligands have been used as phosphorescent chemosensors for the selective detection of Hg 2+ . Azacrown ether-appended iridium (III) complex developed in our laboratory has also been utilized as a phosphorescent chemosensor for the selective detection of Hg 2+ . As an another iridium (III) complex-based phosphorescent chemosensors for the selective detection of Hg 2+ , in this study, we wish to prepare iridium (III) complex containing two 3,9-dithia-6-azaundecane units as chelating ligands for metal ions. Some fluorophores containing 3,9-dithia-6-azaundecane unit have been successfully applied for the selective detection of Hg 2+ . In this instance, iridium (III) complex containing two 3,9-dithia-6-azaundecane units is expected to be useful as a phosphorescent chemosensor for the selective detection of Hg 2+ . Iridium (III) complex containing two 3,9-dithia-6-azaundecane units was prepared starting from 2-phenylpyridine according to the procedure shown in Scheme 1. 2-Phenylpyridine was transformed into chloride bridged dimeric iridium complex, [(ppy) 2 IrCl] 2 , via the reported procedure. By treating [(ppy) 2 IrCl] 2 with 4,4'-bis(bromomethyl)-2,2'-bipyridine, which

  19. 3,9-Dithia-6-azaundecane-appended Iridium (III) Complex for the Selective Detection of Hg{sup 2+} in Aqueous Acetonitrile

    Energy Technology Data Exchange (ETDEWEB)

    Ann, Jee Hye; Li, Yinan; Hyun, Myung Ho [Pusan National Univ., Busan (Korea, Republic of)

    2012-10-15

    Detection of mercuric ion (Hg{sup 2+}) originated from natural or industrial sources is very important because it is extremely toxic even at low levels and causes serious environmental and health problems. Consequently, many efforts have been devoted to the development of sensitive chemosensors for the detection of Hg{sup 2+}. For example, various fluorescent chemosensors based on rhodamine, nitrobenzoxadiazole, fluorescein, boradiazaindacene (BODIPY), dansyl, pyrene, or other fluorophores have been developed for the selective detection of Hg{sup 2+}. While various fluorescent chemosensors for the selective detection of Hg{sup 2+} have been developed, phosphorescent chemosensors for the selective detection of Hg{sup 2+} are relatively rare. Among various phosphors, iridium (III) complexes with sulfur containing cyclometalated ligands have been used as phosphorescent chemosensors for the selective detection of Hg{sup 2+}. Azacrown ether-appended iridium (III) complex developed in our laboratory has also been utilized as a phosphorescent chemosensor for the selective detection of Hg{sup 2+}. As an another iridium (III) complex-based phosphorescent chemosensors for the selective detection of Hg{sup 2+}, in this study, we wish to prepare iridium (III) complex containing two 3,9-dithia-6-azaundecane units as chelating ligands for metal ions. Some fluorophores containing 3,9-dithia-6-azaundecane unit have been successfully applied for the selective detection of Hg{sup 2+}. In this instance, iridium (III) complex containing two 3,9-dithia-6-azaundecane units is expected to be useful as a phosphorescent chemosensor for the selective detection of Hg{sup 2+}. Iridium (III) complex containing two 3,9-dithia-6-azaundecane units was prepared starting from 2-phenylpyridine according to the procedure shown in Scheme 1. 2-Phenylpyridine was transformed into chloride bridged dimeric iridium complex, [(ppy){sub 2}IrCl]{sub 2}, via the reported procedure. By treating [(ppy){sub 2}Ir

  20. Characterisation of a complex thin walled structure fabricated by selective laser melting using a ferritic oxide dispersion strengthened steel

    Energy Technology Data Exchange (ETDEWEB)

    Boegelein, Thomas, E-mail: t.boegelein@liv.ac.uk; Louvis, Eleftherios; Dawson, Karl; Tatlock, Gordon J.; Jones, Andy R.

    2016-02-15

    Oxide dispersion strengthened (ODS) alloys exhibit superior mechanical and physical properties due to the presence of nanoscopic Y(Al, Ti) oxide precipitates, but their manufacturing process is complex. The present study is aimed at further investigation of the application of an alternative, Additive Manufacturing (AM) technique, Selective Laser Melting (SLM), to the production of consolidated ODS alloy components. Mechanically alloyed PM2000 (ODS-FeCrAl) powders have been consolidated and a fine dispersion of Y-containing precipitates were observed in an as built thin-walled component, but these particles were typically poly-crystalline and contained a variety of elements including O, Al, Ti, Cr and Fe. Application of post-build heat treatments resulted in the modification of particle structures and compositions; in the annealed condition most precipitates were transformed to single crystal yttrium aluminium oxides. During the annealing treatment, precipitate distributions homogenised and localised variations in number density were diminished. The resulting volume fractions of those precipitates were 25–40% lower than have been reported in conventionally processed PM2000, which was attributed to Y-rich slag-like surface features and inclusions formed during SLM. - Highlights: • A wall structure was grown from ODS steel powder using selective laser melting. • A fine dispersion of nano-precipitates was apparent in as-build material. • Precipitates were multi-phased containing several elements, e.g. O, Ti, Al, Fe, Cr, Y. • Post-build annealing changed those into typically single-crystalline Y–Al–O. • The anneal also reduced and stabilised the volume fraction of precipitates to ~ 0.006.

  1. Structure elucidation of a novel oligosaccharide (Medalose) from camel milk

    Science.gov (United States)

    Gangwar, Lata; Singh, Rinku; Deepak, Desh

    2018-02-01

    Free oligosaccharides are the third most abundant solid component in milk after lactose and lipids. The study of milk oligosaccharides indicate that nutrients are not only benefits the infant's gut but also perform a number of other functions which include stimulation of growth, receptor analogues to inhibit binding of pathogens and substances that promote postnatal brain development. Surveys reveal that camel milk oligosaccharides possess varied biological activities that help in the treatment of diabetes, asthma, anaemia, piles and also a food supplement to milking mothers. In this research, camel milk was selected for its oligosaccharide contents, which was then processed by Kobata and Ginsburg method followed by the HPLC and CC techniques. Structure elucidation of isolated compound was done by the chemical degradation, chemical transformation and comparison of chemical shift of NMR data of natural and acetylated oligosaccharide structure reporter group theory, the 1H, 13C NMR, 2D-NMR (COSY, TOCSY and HSQC) techniques, and mass spectrometry. The structure was elucidated as under: MEDALOSE

  2. An engineered genetic selection for ternary protein complexes inspired by a natural three-component hitchhiker mechanism.

    Science.gov (United States)

    Lee, Hyeon-Cheol; Portnoff, Alyse D; Rocco, Mark A; DeLisa, Matthew P

    2014-12-22

    The bacterial twin-arginine translocation (Tat) pathway is well known to translocate correctly folded monomeric and dimeric proteins across the tightly sealed cytoplasmic membrane. We identified a naturally occurring heterotrimer, the Escherichia coli aldehyde oxidoreductase PaoABC, that is co-translocated by the Tat translocase according to a ternary "hitchhiker" mechanism. Specifically, the PaoB and PaoC subunits, each devoid of export signals, are escorted to the periplasm in a piggyback fashion by the Tat signal peptide-containing subunit PaoA. Moreover, export of PaoA was blocked when either PaoB or PaoC was absent, revealing a surprising interdependence for export that is not seen for classical secretory proteins. Inspired by this observation, we created a bacterial three-hybrid selection system that links the formation of ternary protein complexes with antibiotic resistance. As proof-of-concept, a bispecific antibody was employed as an adaptor that physically crosslinked one antigen fused to a Tat export signal with a second antigen fused to TEM-1 β-lactamase (Bla). The resulting non-covalent heterotrimer was exported in a Tat-dependent manner, delivering Bla to the periplasm where it hydrolyzed β-lactam antibiotics. Collectively, these results highlight the remarkable flexibility of the Tat system and its potential for studying and engineering ternary protein interactions in living bacteria.

  3. A theory for bioinorganic chemical reactivity of oxometal complexes and analogous oxidants: the exchange and orbital-selection rules.

    Science.gov (United States)

    Usharani, Dandamudi; Janardanan, Deepa; Li, Chunsen; Shaik, Sason

    2013-02-19

    Over the past decades metalloenzymes and their synthetic models have emerged as an area of increasing research interest. The metalloenzymes and their synthetic models oxidize organic molecules using oxometal complexes (OMCs), especially oxoiron(IV)-based ones. Theoretical studies have helped researchers to characterize the active species and to resolve mechanistic issues. This activity has generated massive amounts of data on the relationship between the reactivity of OMCs and the transition metal's identity, oxidation state, ligand sphere, and spin state. Theoretical studies have also produced information on transition state (TS) structures, reaction intermediates, barriers, and rate-equilibrium relationships. For example, the experimental-theoretical interplay has revealed that nonheme enzymes carry out H-abstraction from strong C-H bonds using high-spin (S = 2) oxoiron(IV) species with four unpaired electrons on the iron center. However, other reagents with higher spin states and more unpaired electrons on the metal are not as reactive. Still other reagents carry out these transformations using lower spin states with fewer unpaired electrons on the metal. The TS structures for these reactions exhibit structural selectivity depending on the reactive spin states. The barriers and thermodynamic driving forces of the reactions also depend on the spin state. H-Abstraction is preferred over the thermodynamically more favorable concerted insertion into C-H bonds. Currently, there is no unified theoretical framework that explains the totality of these fascinating trends. This Account aims to unify this rich chemistry and understand the role of unpaired electrons on chemical reactivity. We show that during an oxidative step the d-orbital block of the transition metal is enriched by one electron through proton-coupled electron transfer (PCET). That single electron elicits variable exchange interactions on the metal, which in turn depend critically on the number of

  4. Synthetic Elucidation of Design Principles for Molecular Qubits

    Science.gov (United States)

    Graham, Michael James

    Quantum information processing (QIP) is an emerging computational paradigm with the potential to enable a vast increase in computational power, fundamentally transforming fields from structural biology to finance. QIP employs qubits, or quantum bits, as its fundamental units of information, which can exist in not just the classical states of 0 or 1, but in a superposition of the two. In order to successfully perform QIP, this superposition state must be sufficiently long-lived. One promising paradigm for the implementation of QIP involves employing unpaired electrons in coordination complexes as qubits. This architecture is highly tunable and scalable, however coordination complexes frequently suffer from short superposition lifetimes, or T2. In order to capitalize on the promise of molecular qubits, it is necessary to develop a set of design principles that allow the rational synthesis of complexes with sufficiently long values of T2. In this dissertation, I report efforts to use the synthesis of series of complexes to elucidate design principles for molecular qubits. Chapter 1 details previous work by our group and others in the field. Chapter 2 details the first efforts of our group to determine the impact of varying spin and spin-orbit coupling on T2. Chapter 3 examines the effect of removing nuclear spins on coherence time, and reports a series of vanadyl bis(dithiolene) complexes which exhibit extremely long coherence lifetimes, in excess of the 100 mus threshold for qubit viability. Chapters 4 and 5 form two complimentary halves of a study to determine the exact relationship between electronic spin-nuclear spin distance and the effect of the nuclear spins on T2. Finally, chapter 6 suggests next directions for the field as a whole, including the potential for work in this field to impact the development of other technologies as diverse as quantum sensors and magnetic resonance imaging contrast agents.

  5. Elucidation of the mechanism for anomalous blueshift

    International Nuclear Information System (INIS)

    Kotaki, Hideyuki; Kando, Masaki; Koga, J.K.; Nakajima, Kazuhisa

    2004-01-01

    The anomalous blue shift of high intensity laser which was discovered by the present authors occurs in the process of gas ionization accompanied with the self-focusing. This shift does not depend either on the laser power or on the gas density and all photons are shifted by a certain frequency, while the one which has been known in common depends on both the intensity and density and only some part of the laser photons is shifted. In order to elucidate this phenomenon, the occurrence conditions of the anomalous blue shift were investigated and the results are compared with theory. The shifts were measured by focusing the laser beam in the gas-filled chamber with an off-axis-parabolic mirror and with a convex lens. When the reflective lens was used the amount of the shift depended significantly on the ionization rate of the plasma, while it depended on the pulse width when the transmission lens was used indicating that the shift is determined by the valence due to the ionization at the focusing point. (S. Funahashi)

  6. Biochemical research elucidating metabolic pathways in Pneumocystis*

    Directory of Open Access Journals (Sweden)

    Kaneshiro E.S.

    2010-12-01

    Full Text Available Advances in sequencing the Pneumocystis carinii genome have helped identify potential metabolic pathways operative in the organism. Also, data from characterizing the biochemical and physiological nature of these organisms now allow elucidation of metabolic pathways as well as pose new challenges and questions that require additional experiments. These experiments are being performed despite the difficulty in doing experiments directly on this pathogen that has yet to be subcultured indefinitely and produce mass numbers of cells in vitro. This article reviews biochemical approaches that have provided insights into several Pneumocystis metabolic pathways. It focuses on 1 S-adenosyl-L-methionine (AdoMet; SAM, which is a ubiquitous participant in numerous cellular reactions; 2 sterols: focusing on oxidosqualene cyclase that forms lanosterol in P. carinii; SAM:sterol C-24 methyltransferase that adds methyl groups at the C-24 position of the sterol side chain; and sterol 14α-demethylase that removes a methyl group at the C-14 position of the sterol nucleus; and 3 synthesis of ubiquinone homologs, which play a pivotal role in mitochondrial inner membrane and other cellular membrane electron transport.

  7. Selective extraction of lithium with a macrocyclic trinuclear complex of (1,3,5-trimethylbenzene)ruthenium(II) bridged by 2,3-dioxopyridine.

    Science.gov (United States)

    Katsuta, Shoichi; Imoto, Takahiro; Kudo, Yoshihiro; Takeda, Yasuyuki

    2008-10-01

    A macrocyclic trinuclear complex of (1,3,5-trimethylbenzene)ruthenium(II) bridged by 2,3-dioxopyridine was synthesized, and the extraction properties for lithium and sodium picrates were investigated in a dichloromethane/water system at 25 degrees C. The complex was found to have extremely high extractability and selectivity for lithium picrate; the logarithmic values of the extraction constants are 5.86 and 2.63 for Li(+) and Na(+), respectively. By using this complex as an extractant, nearly quantitative extraction and separation of Li(+) from Na(+) could be achieved by a single extraction.

  8. Zeolite-encapsulated Co(II), Mn(II), Cu(II) and Cr(III) salen complexes as catalysts for efficient selective oxidation of benzyl alcohol

    Science.gov (United States)

    Li, F. H.; Bi, H.; Huang, D. X.; Zhang, M.; Song, Y. B.

    2018-01-01

    Co(II), Mn(II), Cu(II) and Cr(III) salen type complexes were synthesized in situ in Y zeolite by the reaction of ion-exchanged metal ions with the flexible ligand molecules that had diffused into the cavities. Data of characterization indicates the formation of metal salen complexes in the pores without affecting the zeolite framework structure, the absence of any extraneous species and the geometry of encapsulated complexes. The catalytic activity results show that Cosalcyen Y exhibited higher catalytic activity in the water phase selective oxidation of benzyl alcohol, which could be attributed to their geometry and the steric environment of the metal actives sites.

  9. PT-1 selectively activates AMPK-γ1 complexes in mouse skeletal muscle, but activates all three γ subunit complexes in cultured human cells by inhibiting the respiratory chain

    DEFF Research Database (Denmark)

    Jensen, Thomas Elbenhardt; Ross, Fiona A; Kleinert, Maximilian

    2015-01-01

    strategy to combat diseases such as cancer and type 2 diabetes. We report that the AMPK activator PT-1 selectively increased the activity of γ1- but not γ3-containing complexes in incubated mouse muscle. PT-1 increased the AMPK-dependent phosphorylation of the autophagy-regulating kinase ULK1 on Ser555...

  10. Determining ancestry proportions in complex admixture scenarios in South Africa using a novel proxy ancestry selection method.

    Directory of Open Access Journals (Sweden)

    Emile R Chimusa

    Full Text Available Admixed populations can make an important contribution to the discovery of disease susceptibility genes if the parental populations exhibit substantial variation in susceptibility. Admixture mapping has been used successfully, but is not designed to cope with populations that have more than two or three ancestral populations. The inference of admixture proportions and local ancestry and the imputation of missing genotypes in admixed populations are crucial in both understanding variation in disease and identifying novel disease loci. These inferences make use of reference populations, and accuracy depends on the choice of ancestral populations. Using an insufficient or inaccurate ancestral panel can result in erroneously inferred ancestry and affect the detection power of GWAS and meta-analysis when using imputation. Current algorithms are inadequate for multi-way admixed populations. To address these challenges we developed PROXYANC, an approach to select the best proxy ancestral populations. From the simulation of a multi-way admixed population we demonstrate the capability and accuracy of PROXYANC and illustrate the importance of the choice of ancestry in both estimating admixture proportions and imputing missing genotypes. We applied this approach to a complex, uniquely admixed South African population. Using genome-wide SNP data from over 764 individuals, we accurately estimate the genetic contributions from the best ancestral populations: isiXhosa [Formula: see text], ‡Khomani SAN [Formula: see text], European [Formula: see text], Indian [Formula: see text], and Chinese [Formula: see text]. We also demonstrate that the ancestral allele frequency differences correlate with increased linkage disequilibrium in the South African population, which originates from admixture events rather than population bottlenecks.The collective term for people of mixed ancestry in southern Africa is "Coloured," and this is officially recognized in South

  11. Hypoxia and the Edema Syndrome: Elucidation of a Mechanism of Teratogenesis

    Science.gov (United States)

    The elucidation of mechanisms and pathogenesis of birth defects is exceedingly complex. Consequently, there are few examples where the etiology of birth defects caused by a specific agent has been well described. One such example is the "Edema Syndrome" first described by Casimer...

  12. Activation of the C-H bond: catalytic hydroxylation of hydrocarbons by new cobaltic alkylperoxydic complexes; selective and catalytic cycloalkane dehydrogenation in presence of uranium for hydrogen transfer

    International Nuclear Information System (INIS)

    Brazi, E.

    1987-01-01

    The aim of the thesis is to improve efficiency and selectivity of chemical reactions for alkane transformations. In the first part decomposition of hydroperoxides and hydrocarbon hydroxylation by cobalt complexes is studied. In the second part cycloalkanes are dehydrogenated into aromatics with a Pt catalyst, trapping hydrogen by uranium. Uranium hydride UH 3 can yield very pure hydrogen at reasonable temperature [fr

  13. Dimerization of Terminal Aryl Alkynes Catalyzed by Iron(II) Amine-Pyrazolyl Tripodal Complexes with E/Z Selectivity Controlled by tert-Butoxide

    KAUST Repository

    Xue, Fei

    2018-05-09

    The catalytic activity of iron(II) complexes with functionalized amine-pyrazolyl tripodal ligands toward dimerization of terminal alkynes in the presence a base (KOtBu or NaOtBu) has been studied. An unusual E/Z selectivity of the reaction determined by tert-butoxide was observed.

  14. Maintaining a focus on opportunities at work : The interplay between age, job complexity, and the use of selection, optimization, and compensation strategies

    NARCIS (Netherlands)

    Zacher, Hannes; Frese, Michael

    The concept of focus on opportunities describes how many new goals, options, and possibilities employees believe to have in their personal future at work. This study investigated the specific and shared effects of age, job complexity, and the use of successful aging strategies called selection,

  15. A rationally designed amino-borane complex in a metal organic framework: A novel reusable hydrogen storage and size-selective reduction material

    KAUST Repository

    Wang, Xinbo

    2015-01-01

    A novel amino-borane complex inside a stable metal organic framework was synthesized for the first time. It releases hydrogen at a temperature of 78 °C with no volatile contaminants and can be well reused. Its application as a size-selective reduction material in organic synthesis was also demonstrated. © The Royal Society of Chemistry 2015.

  16. Dimerization of Terminal Aryl Alkynes Catalyzed by Iron(II) Amine-Pyrazolyl Tripodal Complexes with E/Z Selectivity Controlled by tert-Butoxide

    KAUST Repository

    Xue, Fei; Song, Xiaolu; Lin, Ting Ting; Munkerup, Kristin; Albawardi, Saad Fahad; Huang, Kuo-Wei; Hor, T. S. Andy; Zhao, Jin

    2018-01-01

    The catalytic activity of iron(II) complexes with functionalized amine-pyrazolyl tripodal ligands toward dimerization of terminal alkynes in the presence a base (KOtBu or NaOtBu) has been studied. An unusual E/Z selectivity of the reaction determined by tert-butoxide was observed.

  17. Elucidating the neurotoxic effects of MDMA and its analogs.

    Science.gov (United States)

    Karuppagounder, Senthilkumar S; Bhattacharya, Dwipayan; Ahuja, Manuj; Suppiramaniam, Vishnu; Deruiter, Jack; Clark, Randall; Dhanasekaran, Muralikrishnan

    2014-04-17

    There is a rapid increase in the use of methylenedioxymethamphetamine (MDMA) and its structural congeners/analogs globally. MDMA and MDMA-analogs have been synthesized illegally in furtive dwellings and are abused due to its addictive potential. Furthermore, MDMA and MDMA-analogs have shown to have induced several adverse effects. Hence, understanding the mechanisms mediating this neurotoxic insult of MDMA-analogs is of immense importance for the public health in the world. We synthesized and investigated the neurotoxic effects of MDMA and its analogs [4-methylenedioxyamphetamine (MDA), 2, 6-methylenedioxyamphetamine (MDMA), and N-ethyl-3, 4-methylenedioxyamphetamine (MDEA)]. The stimulatory or the dopaminergic agonist effects of MDMA and MDMA-analogs were elucidated using the established 6-hydroxydopamine lesioned animal model. Additionally, we also investigated the neurotoxic mechanisms of MDMA and MDMA-analogs on mitochondrial complex-I activity and reactive oxygen species generation. MDMA and MDMA-analogs exhibited stimulatory activity as compared to amphetamines and also induced several behavioral changes in the rodents. MDMA and MDMA-analogs enhanced the reactive oxygen generation and inhibited mitochondrial complex-I activity which can lead to neurodegeneration. Hence the mechanism of neurotoxicity, MDMA and MDMA-analogs can enhance the release of monoamines, alter the monoaminergic neurotransmission, and augment oxidative stress and mitochondrial abnormalities leading to neurotoxicity. Thus, our study will help in developing effective pharmacological and therapeutic approaches for the treatment of MDMA and MDMA-analog abuse. Copyright © 2014 Elsevier Inc. All rights reserved.

  18. Towards a comprehensive X-ray approach for studying the photosynthetic manganese complex-XANES, K{alpha}/K{beta}/K{beta}-satellite emission lines, RIXS, and comparative computational approaches for selected model complexes

    Energy Technology Data Exchange (ETDEWEB)

    Zaharieva, I; Chernev, P; Risch, M; Gerencser, L; Haumann, M; Dau, H [Free University Berlin, FB Physik, Arnimallee 14, D-14195 Berlin (Germany); Berggren, G; Shevchenko, D; Anderlund, M [Dept. of Photochemistry and Molecular Science, Uppsala University, Box 523, S-751 20 Uppsala (Sweden); Weng, T C, E-mail: holger.dau@fu-berlin.d, E-mail: michael.haumann@fu-berlin.d [European Synchrotron Radiation Facility, BP 220, F-38043 Grenoble Cedex (France)

    2009-11-15

    Advanced X-ray spectroscopy experiments can contribute to elucidation of the mechanism of water oxidation in biological (tetra-manganese complex of Photosystem II) and artificial systems. Although the electronic structure of the catalytic metal site is of high interest, it is experimentally not easily accessible. Therefore, we and other researchers are working towards a comprehensive approach involving a combination of methods, namely (1) quantitative analysis of X-ray absorption near-edge structure (XANES) spectra collected at the K-edge and, in the long run, at the L-edge of manganese; (2) high-resolution X-ray emission spectroscopy (XES) of K{alpha} and K{beta} lines, (3) two-dimensional resonant inelastic X-ray scattering (RIXS) spectra. Collection of these spectroscopic data sets requires state-of-the-art synchrotron radiation facilities as well as experimental strategies to minimize the radiation-induced modifications of the samples. Data analysis requires the use and development of appropriate theoretical tools. Here, we present exemplary data collected for three multi-nuclear synthetic Mn complexes with the Mn ions in the oxidation states II, III, and IV, and for Mn{sup VII} of the permanganate ion. Emission spectra are calculated for the Mn{sup VII} ion using both multiple-scattering (MS) approach and time-dependent density functional theory (TDDFT).

  19. Determinants for Tight and Selective Binding of a Medicinal Dicarbene Gold(I) Complex to a Telomeric DNA G-Quadruplex: a Joint ESI MS and XRD Investigation.

    Science.gov (United States)

    Bazzicalupi, Carla; Ferraroni, Marta; Papi, Francesco; Massai, Lara; Bertrand, Benoît; Messori, Luigi; Gratteri, Paola; Casini, Angela

    2016-03-18

    The dicarbene gold(I) complex [Au(9-methylcaffein-8-ylidene)2 ]BF4 is an exceptional organometallic compound of profound interest as a prospective anticancer agent. This gold(I) complex was previously reported to be highly cytotoxic toward various cancer cell lines in vitro and behaves as a selective G-quadruplex stabilizer. Interactions of the gold complex with various telomeric DNA models have been analyzed by a combined ESI MS and X-ray diffraction (XRD) approach. ESI MS measurements confirmed formation of stable adducts between the intact gold(I) complex and Tel 23 DNA sequence. The crystal structure of the adduct formed between [Au(9-methylcaffein-8-ylidene)2 ](+) and Tel 23 DNA G-quadruplex was solved. Tel 23 maintains a characteristic propeller conformation while binding three gold(I) dicarbene moieties at two distinct sites. Stacking interactions appear to drive noncovalent binding of the gold(I) complex. The structural basis for tight gold(I) complex/G-quadruplex recognition and its selectivity are described. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. Evolution of the additive genetic variance–covariance matrix under continuous directional selection on a complex behavioural phenotype

    Science.gov (United States)

    Careau, Vincent; Wolak, Matthew E.; Carter, Patrick A.; Garland, Theodore

    2015-01-01

    Given the pace at which human-induced environmental changes occur, a pressing challenge is to determine the speed with which selection can drive evolutionary change. A key determinant of adaptive response to multivariate phenotypic selection is the additive genetic variance–covariance matrix (G). Yet knowledge of G in a population experiencing new or altered selection is not sufficient to predict selection response because G itself evolves in ways that are poorly understood. We experimentally evaluated changes in G when closely related behavioural traits experience continuous directional selection. We applied the genetic covariance tensor approach to a large dataset (n = 17 328 individuals) from a replicated, 31-generation artificial selection experiment that bred mice for voluntary wheel running on days 5 and 6 of a 6-day test. Selection on this subset of G induced proportional changes across the matrix for all 6 days of running behaviour within the first four generations. The changes in G induced by selection resulted in a fourfold slower-than-predicted rate of response to selection. Thus, selection exacerbated constraints within G and limited future adaptive response, a phenomenon that could have profound consequences for populations facing rapid environmental change. PMID:26582016

  1. Evolution of the additive genetic variance-covariance matrix under continuous directional selection on a complex behavioural phenotype.

    Science.gov (United States)

    Careau, Vincent; Wolak, Matthew E; Carter, Patrick A; Garland, Theodore

    2015-11-22

    Given the pace at which human-induced environmental changes occur, a pressing challenge is to determine the speed with which selection can drive evolutionary change. A key determinant of adaptive response to multivariate phenotypic selection is the additive genetic variance-covariance matrix ( G: ). Yet knowledge of G: in a population experiencing new or altered selection is not sufficient to predict selection response because G: itself evolves in ways that are poorly understood. We experimentally evaluated changes in G: when closely related behavioural traits experience continuous directional selection. We applied the genetic covariance tensor approach to a large dataset (n = 17 328 individuals) from a replicated, 31-generation artificial selection experiment that bred mice for voluntary wheel running on days 5 and 6 of a 6-day test. Selection on this subset of G: induced proportional changes across the matrix for all 6 days of running behaviour within the first four generations. The changes in G: induced by selection resulted in a fourfold slower-than-predicted rate of response to selection. Thus, selection exacerbated constraints within G: and limited future adaptive response, a phenomenon that could have profound consequences for populations facing rapid environmental change. © 2015 The Author(s).

  2. Recent advances in hopanoids analysis: Quantification protocols overview, main research targets and selected problems of complex data exploration.

    Science.gov (United States)

    Zarzycki, Paweł K; Portka, Joanna K

    2015-09-01

    Pentacyclic triterpenoids, particularly hopanoids, are organism-specific compounds and are generally considered as useful biomarkers that allow fingerprinting and classification of biological, environmental and geological samples. Simultaneous quantification of various hopanoids together with battery of related non-polar and low-molecular mass compounds may provide principal information for geochemical and environmental research focusing on both modern and ancient investigations. Target compounds can be derived from microbial biomass, water columns, sediments, coals, crude fossils or rocks. This create number of analytical problems due to different composition of the analytical matrix and interfering compounds and therefore, proper optimization of quantification protocols for such biomarkers is still the challenge. In this work we summarizing typical analytical protocols that were recently applied for quantification of hopanoids like compounds from different samples. Main steps including components of interest extraction, pre-purification, fractionation, derivatization and quantification involving gas (1D and 2D) as well as liquid separation techniques (liquid-liquid extraction, solid-phase extraction, planar and low resolution column chromatography, high-performance liquid chromatography) are described and discussed from practical point of view, mainly based on the experimental papers that were published within last two years, where significant increase in hopanoids research was noticed. The second aim of this review is to describe the latest research trends concerning determination of hopanoids and related low-molecular mass lipids analyzed in various samples including sediments, rocks, coals, crude oils and plant fossils as well as stromatolites and microbial biomass cultivated under different conditions. It has been found that majority of the most recent papers are based on uni- or bivariate approach for complex data analysis. Data interpretation involves

  3. [Application of hair analysis of selected psychoactive substances for medico-legal purposes. Part II. Cases of complex fatal poisonings: interactions of heroine - cocaine - amphetamines].

    Science.gov (United States)

    Rojek, Sebastian; Kłys, Małgorzata; Rzepecka-Woźniak, Ewa; Konopka, Tomasz

    2010-01-01

    The study represents an attempt at employing segmental hair analysis in complex poisonings with xenobiotic mixtures of heroine - cocaine - amphetamines in the context of the cause of death as a consequence of complex interaction mechanisms which occurred prior to death. Two cases of complex poisonings: heroine - cocaine and heroine - cocaine - amphetamines were analyzed and documented with macro- and microscopic examinations and complex toxicological examinations, including the analysis of classic biological material, i.e. samples of selective blood, and alternative material, i.e. hair samples. Determinations of opioids, cocaine and its metabolite and amphetamines in the hair biological matrix were performed using high performance liquid chromatography--atmospheric pressure chemical ionization--tandem mass spectrometry (HPLC-APCI-MS-MS). Segmental hair analysis of the investigated cases indicated a prolonged intake of similar psychoactive substances and a developed adaptation of the addicted to interaction mechanisms, which, however, led gradually to multiorgan anatomopathological changes, and in consequence to death.

  4. Selective ligand activity at Nur/retinoid X receptor complexes revealed by dimer-specific bioluminescence resonance energy transfer-based sensors

    Science.gov (United States)

    Giner, Xavier C; Cotnoir-White, David; Mader, Sylvie; Lévesque, Daniel

    2017-01-01

    Retinoid X receptors (RXR) play a role as master regulators due to their capacity to form heterodimers with other nuclear receptors. Accordingly, retinoid signaling is involved in multiple biological processes, including development, cell differentiation, metabolism and cell death. However, the role and functions of RXR in different heterodimer complexes remain unsolved, mainly because most RXR drugs (called rexinoids) are not selective to specific heterodimer complexes. This also strongly limits the use of rexinoids for specific therapeutic approaches. In order to better characterize rexinoids at specific nuclear receptor complexes, we have developed and optimized luciferase protein complementation-based Bioluminescence Resonance Energy Transfer (BRET) assays, which can directly measure recruitment of a co-activator motif fused to yellow fluorescent protein (YFP) by specific nuclear receptor dimers. To validate the assays, we compared rexinoid modulation of co-activator recruitment by RXR homodimer, and heterodimers Nur77/RXR and Nurr1/RXR. Results reveal that some rexinoids display selective co-activator recruitment activities with homo- or hetero-dimer complexes. In particular, SR11237 (BMS649) has increased potency for recruitment of co-activator motif and transcriptional activity with the Nur77/RXR heterodimer compared to other complexes. This technology should prove useful to identify new compounds with specificity for individual dimeric species formed by nuclear receptors. PMID:26148973

  5. Catalytic ozonation not relying on hydroxyl radical oxidation: A selective and competitive reaction process related to metal-carboxylate complexes

    KAUST Repository

    Zhang, Tao; Croue, Jean-Philippe

    2014-01-01

    Catalytic ozonation following non-hydroxyl radical pathway is an important technique not only to degrade refractory carboxylic-containing organic compounds/matter but also to avoid catalyst deactivation caused by metal-carboxylate complexation

  6. Complexation of trivalent cationic lanthanides by N.O donor ligands: physico-chemical studies of the association and selectivity in solution

    International Nuclear Information System (INIS)

    Bravard, F.

    2004-01-01

    The aim of this work is to study the complexation of f-elements in solution by ligands incorporating N-heterocyclic donors. These ligands display interesting properties for the selective separation of An(III)/Ln(III) have been studied to obtain a better understanding of the coordination properties with f-elements and to develop more selective extractants. The hepta-dentate ligand tpaam shows an affinity for Ln(III) similar to the tetradentate ligand tpa in water even when the three additional amide groups are bonded to the metal. Even though the complexation with tpa is exothermic, that with tpaam is endothermic with a more positive entropy. The dehydration of the cation disfavours the formation of Ln(III) complexes with ligands containing weak donors. The analysis of the solution paramagnetic relaxation times of the tpaam complexes is in agreement with data in the solid-state. There is little difference between the formation constants of the Ln 3+ complexes with different ligands (tpaam, tpzen, tpa and tpza) as determined by UV-vis spectrophotometry in anhydrous acetonitrile. The limitations encountered during this study are intrinsic to the ligands studied. The preliminary study of two tetrapodal ligands containing acid and pyridine groups (L py )or pyrazine (L pz ) show the formation of 1:1 complexes in water. Analysis of the formation constants of the corresponding Gd(III) complexes shows that replacement of a pyridine group by pyrazine result in a loss of stability of 1.6 logarithmic units. (author) [fr

  7. A label-free luminescent switch-on assay for ATP using a G-quadruplex-selective iridium(III) complex.

    Science.gov (United States)

    Leung, Ka-Ho; Lu, Lihua; Wang, Modi; Mak, Tsun-Yin; Chan, Daniel Shiu-Hin; Tang, Fung-Kit; Leung, Chung-Hang; Kwan, Hiu-Yee; Yu, Zhiling; Ma, Dik-Lung

    2013-01-01

    We report herein the G-quadruplex-selective property of a luminescent cyclometallated iridium(III) complex for the detection of adenosine-5'-triphosphate (ATP) in aqueous solution. The ATP-binding aptamer was employed as the ATP recognition unit, while the iridium(III) complex was used to monitor the formation of the G-quadruplex structure induced by ATP. The sensitivity and fold enhancement of the assay were higher than those of the previously reported assay using the organic dye crystal violet as a fluorescent probe. This label-free luminescent switch-on assay exhibits high sensitivity and selectivity towards ATP with a limit of detection of 2.5 µM.

  8. Selective Hydrogen Generation from Formic Acid with Well-Defined Complexes of Ruthenium and Phosphorus-Nitrogen PN3-Pincer Ligand

    KAUST Repository

    Pan, Yupeng

    2016-04-22

    An unsymmetrically protonated PN3-pincer complex in which ruthenium is coordinated by one nitrogen and two phosphorus atoms was employed for the selective generation of hydrogen from formic acid. Mechanistic studies suggest that the imine arm participates in the formic acid activation/deprotonation step. A long life time of 150 h with a turnover number over 1 million was achieved. Grabbing hold: A PN3-pincer complex was employed for the selective hydrogen generation from formic acid. Mechanistic studies suggest the imine arm participates in the formic acid activation/deprotonation step. A long life time of 150 h with a turnover number over 1 million was achieved. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Base-Free Selective Oxidation of Glycerol over LDH Hosted Transition Metal Complexes Using 3% H2O2 as Oxidant

    Directory of Open Access Journals (Sweden)

    Xiaoli Wang

    2016-07-01

    Full Text Available A series of transition metal sulphonato-Schiff base complexes were intercalated into Mg–Al layered-double hydroxides (LDHs. The obtained catalysts were characterized by FTIR, XRD, N2 sorption, SEM and elemental analysis, and then were used in the selective oxidation of glycerol (GLY using 3% H2O2 as an oxidant. It was found that their catalytic performances were closely related to the loading of active complexes, the Schiff base ligands and the metal centers of the catalysts, as well as the reaction conditions. The optimal conversion of GLY was 85.0%, while the selectivity of 1,3-dihydroxyacetone (DHA was 56.5%. Moreover, the catalysts could be reused at least 10 times.

  10. A label-free luminescent switch-on assay for ATP using a G-quadruplex-selective iridium(III complex.

    Directory of Open Access Journals (Sweden)

    Ka-Ho Leung

    Full Text Available We report herein the G-quadruplex-selective property of a luminescent cyclometallated iridium(III complex for the detection of adenosine-5'-triphosphate (ATP in aqueous solution. The ATP-binding aptamer was employed as the ATP recognition unit, while the iridium(III complex was used to monitor the formation of the G-quadruplex structure induced by ATP. The sensitivity and fold enhancement of the assay were higher than those of the previously reported assay using the organic dye crystal violet as a fluorescent probe. This label-free luminescent switch-on assay exhibits high sensitivity and selectivity towards ATP with a limit of detection of 2.5 µM.

  11. The SET1 Complex Selects Actively Transcribed Target Genes via Multivalent Interaction with CpG Island Chromatin.

    Science.gov (United States)

    Brown, David A; Di Cerbo, Vincenzo; Feldmann, Angelika; Ahn, Jaewoo; Ito, Shinsuke; Blackledge, Neil P; Nakayama, Manabu; McClellan, Michael; Dimitrova, Emilia; Turberfield, Anne H; Long, Hannah K; King, Hamish W; Kriaucionis, Skirmantas; Schermelleh, Lothar; Kutateladze, Tatiana G; Koseki, Haruhiko; Klose, Robert J

    2017-09-05

    Chromatin modifications and the promoter-associated epigenome are important for the regulation of gene expression. However, the mechanisms by which chromatin-modifying complexes are targeted to the appropriate gene promoters in vertebrates and how they influence gene expression have remained poorly defined. Here, using a combination of live-cell imaging and functional genomics, we discover that the vertebrate SET1 complex is targeted to actively transcribed gene promoters through CFP1, which engages in a form of multivalent chromatin reading that involves recognition of non-methylated DNA and histone H3 lysine 4 trimethylation (H3K4me3). CFP1 defines SET1 complex occupancy on chromatin, and its multivalent interactions are required for the SET1 complex to place H3K4me3. In the absence of CFP1, gene expression is perturbed, suggesting that normal targeting and function of the SET1 complex are central to creating an appropriately functioning vertebrate promoter-associated epigenome. Copyright © 2017 The Authors. Published by Elsevier Inc. All rights reserved.

  12. The SET1 Complex Selects Actively Transcribed Target Genes via Multivalent Interaction with CpG Island Chromatin

    Directory of Open Access Journals (Sweden)

    David A. Brown

    2017-09-01

    Full Text Available Chromatin modifications and the promoter-associated epigenome are important for the regulation of gene expression. However, the mechanisms by which chromatin-modifying complexes are targeted to the appropriate gene promoters in vertebrates and how they influence gene expression have remained poorly defined. Here, using a combination of live-cell imaging and functional genomics, we discover that the vertebrate SET1 complex is targeted to actively transcribed gene promoters through CFP1, which engages in a form of multivalent chromatin reading that involves recognition of non-methylated DNA and histone H3 lysine 4 trimethylation (H3K4me3. CFP1 defines SET1 complex occupancy on chromatin, and its multivalent interactions are required for the SET1 complex to place H3K4me3. In the absence of CFP1, gene expression is perturbed, suggesting that normal targeting and function of the SET1 complex are central to creating an appropriately functioning vertebrate promoter-associated epigenome.

  13. η6-Cycloparaphenylene transition metal complexes: synthesis, structure, photophysical properties, and application to the selective monofunctionalization of cycloparaphenylenes.

    Science.gov (United States)

    Kubota, Natsumi; Segawa, Yasutomo; Itami, Kenichiro

    2015-01-28

    The synthesis, structure, photophysical properties, and reactivity of cycloparaphenylenes (CPPs) coordinated to group 6 transition metal fragments are described. The η(6)-coordination of [9]CPP or [12]CPP with M(CO)6 (M = Cr, Mo, W) afforded the corresponding [n]CPP-M(CO)3 complexes (n = 9, 12; M = Cr, Mo, W). In the (1)H NMR spectra of these complexes, characteristic upfield-shifted singlet signals corresponding to the four hydrogen atoms attached to the coordinated C6H4 ring of the CPPs were observed at 5.4-5.9 ppm. The complex [9]CPP-Cr(CO)3 could be successfully isolated in spite of its instability. X-ray crystallographic analysis and computational studies of [9]CPP-Cr(CO)3 revealed that chromium-CPP coordination occurs at the convex surface of [9]CPP both in the solid state and in solution. TD-DFT calculations suggested that the emerging high-wavenumber absorption peak upon coordination of [9]CPP to Cr(CO)3 should be assigned to a weak HOMO-LUMO transition. Moreover, by using the complex [9]CPP-Cr(CO)3, a rapid and highly monoselective CPP functionalization has been achieved. The established one-pot method, consisting of complexation, deprotonation, nucleophilic substitution, and decomplexation steps, yielded silyl-, boryl-, and methoxycarbonyl-substituted CPPs in up to 93% yield relative to reacted starting material.

  14. Selecting a change and evaluating its impact on the performance of a complex adaptive health care delivery system

    Directory of Open Access Journals (Sweden)

    Malaz A Boustani

    2010-05-01

    Full Text Available Malaz A Boustani1,2,3,4, Stephanie Munger1,2, Rajesh Gulati3,4, Mickey Vogel4, Robin A Beck3,4, Christopher M Callahan1,2,3,41Indiana University Center for Aging Research, 2Regenstrief Institute Inc., 3Indiana University School of Medicine, Department of Medicine, Division of General Internal Medicine and Geriatrics, 4Indiana University Medical Group-Primary Care; Indianapolis, IN USAAbstract: Complexity science suggests that our current health care delivery system acts as a complex adaptive system (CAS. Such systems represent a dynamic and flexible network of individuals who can coevolve with their ever changing environment. The CAS performance fluctuates and its members’ interactions continuously change over time in response to the stress generated by its surrounding environment. This paper will review the challenges of intervening and introducing a planned change into a complex adaptive health care delivery system. We explore the role of the “reflective adaptive process” in developing delivery interventions and suggest different evaluation methodologies to study the impact of such interventions on the performance of the entire system. We finally describe the implementation of a new program, the Aging Brain Care Medical Home as a case study of our proposed evaluation process.Keywords: complexity, aging brain, implementation, complex adaptive system, sustained change, care delivery

  15. Deconstructing selectivity in the gold-promoted cyclization of alkynyl benzothioamides to six-membered mesoionic carbene or acyclic carbene complexes

    KAUST Repository

    Vummaleti, Sai V. C.; Falivene, Laura; Poater, Albert; Cavallo, Luigi

    2014-01-01

    We demonstrate that the experimentally observed switch in selectivity from 5-exo-dig to 6-endo-dig cyclization of an alkynyl substrate, promoted by Au I and AuIII complexes, is connected to a switch from thermodynamic to kinetic reaction control. The AuIII center pushes alkyne coordination toward a single Au-C(alkyne) σ-bond, conferring carbocationic character (and reactivity) to the distal alkyne C atom. © 2014 American Chemical Society.

  16. Deconstructing selectivity in the gold-promoted cyclization of alkynyl benzothioamides to six-membered mesoionic carbene or acyclic carbene complexes

    KAUST Repository

    Vummaleti, Sai V. C.

    2014-05-02

    We demonstrate that the experimentally observed switch in selectivity from 5-exo-dig to 6-endo-dig cyclization of an alkynyl substrate, promoted by Au I and AuIII complexes, is connected to a switch from thermodynamic to kinetic reaction control. The AuIII center pushes alkyne coordination toward a single Au-C(alkyne) σ-bond, conferring carbocationic character (and reactivity) to the distal alkyne C atom. © 2014 American Chemical Society.

  17. A binary catalyst system of a cationic Ru-CNC pincer complex with an alkali metal salt for selective hydroboration of carbon dioxide.

    Science.gov (United States)

    Ng, Chee Koon; Wu, Jie; Hor, T S Andy; Luo, He-Kuan

    2016-09-27

    Binary catalyst systems comprising a cationic Ru-CNC pincer complex and an alkali metal salt were developed for selective hydroboration of CO 2 utilizing pinacolborane at r.t. and 1 atm CO 2 , with the combination of [Ru(CNC Bn )(CO) 2 (H)][PF 6 ] and KOCO 2 t Bu producing formoxyborane in 76% yield. A bicyclic catalytic mechanism was proposed and discussed.

  18. Elucidating high-dimensional cancer hallmark annotation via enriched ontology.

    Science.gov (United States)

    Yan, Shankai; Wong, Ka-Chun

    2017-09-01

    Cancer hallmark annotation is a promising technique that could discover novel knowledge about cancer from the biomedical literature. The automated annotation of cancer hallmarks could reveal relevant cancer transformation processes in the literature or extract the articles that correspond to the cancer hallmark of interest. It acts as a complementary approach that can retrieve knowledge from massive text information, advancing numerous focused studies in cancer research. Nonetheless, the high-dimensional nature of cancer hallmark annotation imposes a unique challenge. To address the curse of dimensionality, we compared multiple cancer hallmark annotation methods on 1580 PubMed abstracts. Based on the insights, a novel approach, UDT-RF, which makes use of ontological features is proposed. It expands the feature space via the Medical Subject Headings (MeSH) ontology graph and utilizes novel feature selections for elucidating the high-dimensional cancer hallmark annotation space. To demonstrate its effectiveness, state-of-the-art methods are compared and evaluated by a multitude of performance metrics, revealing the full performance spectrum on the full set of cancer hallmarks. Several case studies are conducted, demonstrating how the proposed approach could reveal novel insights into cancers. https://github.com/cskyan/chmannot. Copyright © 2017 Elsevier Inc. All rights reserved.

  19. Ligand-Centered Electron-Transfer Redox Processes for Manganese, Iron, and Cobalt Complexes in Relation to Selected Catalytic Systems

    Science.gov (United States)

    1989-05-01

    of Fe(acac)3 exhibits oxidation features common to acac- and its complexes. Table VIH (b) summarizes the EI/ 2 values for the oxidations of a number of...Data supplied by Dr. Pablo Cofr6 of the Universidad Cat6lica de Chile . 141. Chin, D.-H.; Chiericato, G., Jr.; Nanni, E. J., Jr.; Sawyer, D. T. 1. Am

  20. Mixed complex combinations with a new schiff base used as membranes ion-selective for copper and nickel ions, analytical applications)

    International Nuclear Information System (INIS)

    Mitu, L.; Tigae, C.

    2009-01-01

    Four electrodes with liquid membrane, Cu/sup 2+/ -selective and Ni/sup 2+/ -selective, not previously described in the literature, were prepared and characterized. Electrodes 1 and 2 are based on mixed complexes of Cu(II) and Ni(II) with isonicotinoylhydrazone-2-aldehyde pyrrole (INH2AP= HL/sup 1/) as ligand and electrodes 3 and 4 are based on the mixed complexes with isonicotinoyl- hydrazone-2-hydroxy-l-naphthaldehyde (INH2HNA = H/sub 2/L/sup 2/ ) Cu/sup 2+/. selective and Ni/sup 2+/ -selective electrodes have been used to determine the copper and nickel ions in aqueous solutions, by both direct potentiometric and potentiometric titration with EDTA. They have also been used for determining the Cu/sup 2+/ and Ni/sup 2+/ ions in industrial waters by direct potentiometry. The analytical results obtained have been checked by the standard addition method and by comparison with determinations through atomic absorption spectrometry. (author)

  1. MS-377, a selective sigma receptor ligand, indirectly blocks the action of PCP in the N-methyl-D-aspartate receptor ion-channel complex in primary cultured rat neuronal cells.

    Science.gov (United States)

    Karasawa, Jun-ichi; Yamamoto, Hideko; Yamamoto, Toshifumi; Sagi, Naoki; Horikomi, Kazutoshi; Sora, Ichiro

    2002-02-22

    MS-377 ((R)-(+)-1-(4-chlorophenyl)-3-[4-(2-methoxyethyl)piperazin-1-yl]methyl-2-pyrrolidinone L-tartrate) is a antipsychotic agent that binds to sigma-1 receptor. MS-377 showed anti-dopaminergic and anti-serotonergic activities and antagonistic action against phencyclidine (PCP)-induced behaviors in an animal model. These anti-psychotic activities of MS-377 are attributable to association with sigma-1 receptor. However, the mechanism by which the sigma-1 receptor ligands exact those numerous effects remains to be elucidated. In the present study, we evaluated the effect of MS-377 on N-methyl-D-aspartate (NMDA) receptor ion-channel complex in primary cultured rat neuronal cells. First, we examined the effect of MS-377 on NMDA-induced Ca2+ influx with fura-2/ AM loaded cells. MS-377 showed no effects on the basal Ca2+ concentration and NMDA-induced Ca2+ influx by itself PCP and SKF-10047 reduced the NMDA-induced increase in intracellular Ca2+ concentration. Pre-incubation of 1 microM MS-377 was found to significantly block the reduction by PCP or SKF-10047 of the NMDA-induced Ca2+ influx. Second, the effect of MS-377 on [3H]MK-801 intact cell binding was examined. PCP, haloperidol and (+)-pentazocine inhibited [3H]MK-801 binding, although MS-377 showed no effect by itself Pre-treatment of MS-377 markedly reversed the inhibition of [3H]MK-801 binding by PCP in a dose-dependent manner. These effects of MS-377 may depend on its affinity for the sigma-1 receptor, because MS-377 is a selective sigma-1 receptor ligand without any affinity for NMDA receptor ion-channel complex. These observations suggest that the MS-377 indirectly modulated the NMDA receptor ion-channel complex, and the anti-psychotic activities of MS-377, in part, are attributable to such on action via sigma-1 receptor.

  2. Time and space resolved deep metagenomics to investigate selection pressures on low abundant species in complex environments

    DEFF Research Database (Denmark)

    Albertsen, Mads; Saunders, Aaron Marc; Nielsen, Kåre Lehmann

    and between EBPR plants we sequenced a total of 10 samples from 3 different plants over a 3 year period at a depth of 25 Gb each. In addition, one time point was selected for deep sequencing, generating 200 Gb of sequence divided between replicates. Quantitative FISH analysis using >30 oligonucleotide probes...

  3. Unexpected, spontaneous and selective formation of colloidal Pt 3Sn nanoparticles using organometallic Pt and Sn complexes

    KAUST Repository

    Boualleg, Malika; Baudouin, David; Basset, Jean-Marie; Bayard, Franç ois; Candy, Jean Pierre; Jumas, Jean Claude; Veyre, Laurent; Thieuleux, Chloé

    2010-01-01

    The facile and selective synthesis of small crystalline Pt3Sn alloy nanoparticles was performed at room temperature under H2, using a colloidal approach without the use of extra-stabilizing ligands. The Pt 3Sn alloy was found to be obtained

  4. Unexpected, spontaneous and selective formation of colloidal Pt 3Sn nanoparticles using organometallic Pt and Sn complexes

    KAUST Repository

    Boualleg, Malika

    2010-01-01

    The facile and selective synthesis of small crystalline Pt3Sn alloy nanoparticles was performed at room temperature under H2, using a colloidal approach without the use of extra-stabilizing ligands. The Pt 3Sn alloy was found to be obtained spontaneously as the unique phase regardless of the number of tin equivalents introduced. © 2010 The Royal Society of Chemistry.

  5. Current use was established and Cochrane guidance on selection of social theories for systematic reviews of complex interventions was developed.

    Science.gov (United States)

    Noyes, Jane; Hendry, Maggie; Booth, Andrew; Chandler, Jackie; Lewin, Simon; Glenton, Claire; Garside, Ruth

    2016-07-01

    To identify examples of how social theories are used in systematic reviews of complex interventions to inform production of Cochrane guidance. Secondary analysis of published/unpublished examples of theories of social phenomena for use in reviews of complex interventions identified through scoping searches, engagement with key authors and methodologists supplemented by snowballing and reference searching. Theories were classified (low-level, mid-range, grand). Over 100 theories were identified with evidence of proliferation over the last 5 years. New low-level theories (tools, taxonomies, etc) have been developed for classifying and reporting complex interventions. Numerous mid-range theories are used; one example demonstrated how control theory had changed the review's findings. Review-specific logic models are increasingly used, but these can be challenging to develop. New low-level and mid-range psychological theories of behavior change are evolving. No reviews using grand theory (e.g., feminist theory) were identified. We produced a searchable Wiki, Mendeley Inventory, and Cochrane guidance. Use of low-level theory is common and evolving; incorporation of mid-range theory is still the exception rather than the norm. Methodological work is needed to evaluate the contribution of theory. Choice of theory reflects personal preference; application of theory is a skilled endeavor. Crown Copyright © 2016. Published by Elsevier Inc. All rights reserved.

  6. Strategies for efficiently selecting PHA producing mixed microbial cultures using complex feedstocks: Feast and famine regime and uncoupled carbon and nitrogen availabilities.

    Science.gov (United States)

    Oliveira, Catarina S S; Silva, Carlos E; Carvalho, Gilda; Reis, Maria A

    2017-07-25

    Production of polyhydroxyalkanoates (PHAs) by open mixed microbial cultures (MMCs) has been attracting increasing interest as an alternative technology to PHA production by pure cultures, due to the potential for lower costs associated with the use of open systems (eliminating the requirement for sterile conditions) and the utilisation of cheap feedstock (industrial and agricultural wastes). Such technology relies on the efficient selection of an MMC enriched in PHA-accumulating organisms. Fermented cheese whey, a protein-rich complex feedstock, has been used previously to produce PHA using the feast and famine regime for selection of PHA accumulating cultures. While this selection strategy was found efficient when operated at relatively low organic loading rate (OLR, 2g-CODL -1 d -1 ), great instability and low selection efficiency of PHA accumulating organisms were observed when higher OLR (ca. 6g-CODL -1 d -1 ) was applied. High organic loading is desirable as a means to enhance PHA productivity. In the present study, a new selection strategy was tested with the aim of improving selection for high OLR. It was based on uncoupling carbon and nitrogen supply and was implemented and compared with the conventional feast and famine strategy. For this, two selection reactors were fed with fermented cheese whey applying an OLR of ca. 8.5g-CODL -1 (with 3.8g-CODL -1 resulting from organic acids and ethanol), and operated in parallel under similar conditions, except for the timing of nitrogen supplementation. Whereas in the conventional strategy nitrogen and carbon substrates were added simultaneously at the beginning of the cycle, in the uncoupled substrates strategy, nitrogen addition was delayed to the end of the feast phase (i.e. after exogenous carbon was exhausted). The two different strategies selected different PHA-storing microbial communities, dominated by Corynebacterium and a Xantomonadaceae, respectively with the conventional and the new approaches. The new

  7. Rare earth metal bis(amide) complexes bearing amidinate ancillary ligands: synthesis, characterization, and performance as catalyst precursors for cis-1,4 selective polymerization of isoprene.

    Science.gov (United States)

    Luo, Yunjie; Fan, Shimin; Yang, Jianping; Fang, Jianghua; Xu, Ping

    2011-03-28

    A family of rare earth metal bis(amide) complexes bearing monoanionic amidinate [RC(N-2,6-Me(2)C(6)H(3))(2)](-) (R = cyclohexyl (Cy), phenyl (Ph)) as ancillary ligands were synthesized and characterized. One-pot salt metathesis reaction of anhydrous LnCl(3) with one equivalent of amidinate lithium [RC(N-2,6-Me(2)C(6)H(3))(2)]Li, following the introduction of two equivalents of NaN(SiMe(3))(2) in THF at room temperature afforded the neutral and unsolvated mono(amidinate) rare earth metal bis(amide) complexes [RC(N-2,6-Me(2)C(6)H(3))(2)]Y[N(SiMe(3))(2)](2) (R = Cy (1); R = Ph (2)), and the "ate" mono(amidinate) rare earth metal bis(amide) complex [CyC(N-2,6-Me(2)C(6)H(3))(2)]Lu[N(SiMe(3))(2)](2)(μ-Cl)Li(THF)(3) (3) in 61-72% isolated yields. These complexes were characterized by elemental analysis, NMR spectroscopy, FT-IR spectroscopy, and X-ray single crystal diffraction. Single crystal structural determination revealed that the central metal in complexes 1 and 2 adopts a distorted tetrahedral geometry, and in complex 3 forms a distorted trigonal bipyramidal geometry. In the presence of AlMe(3), and in combination with one equimolar amount of [Ph(3)C][B(C(6)F(5))(4)], complexes 1 and 2 showed high activity towards isoprene polymerization to give high molecular weight polyisoprene (M(n) > 10(4)) with good cis-1,4 selectivity (>90%).

  8. Density-related changes in selection pattern for major histocompatibility complex genes in fluctuating populations of voles

    Czech Academy of Sciences Publication Activity Database

    Bryja, Josef; Charbonnel, N.; Berthier, K.; Galan, M.; Cosson, J.-F.

    2007-01-01

    Roč. 16, č. 23 (2007), s. 5084-5097 ISSN 0962-1083 R&D Projects: GA AV ČR IAA600930608 EU Projects: European Commission(XE) 10284 - EDEN Institutional research plan: CEZ:AV0Z60930519 Source of funding: R - rámcový projekt EK Keywords : Arvicola terrestris * balancing selection * local adaptation * MHC * population cycles Subject RIV: EB - Genetics ; Molecular Biology Impact factor: 5.169, year: 2007

  9. Genetic structure and contrasting selection pattern at two major histocompatibility complex genes in wild house mouse populations

    Czech Academy of Sciences Publication Activity Database

    Čížková, Dagmar; Goüy de Bellocq, J.; Baird, S. J. E.; Piálek, Jaroslav; Bryja, Josef

    2011-01-01

    Roč. 106, č. 5 (2011), s. 727-740 ISSN 0018-067X R&D Projects: GA AV ČR IAA600930608; GA ČR GA206/08/0640 Institutional research plan: CEZ:AV0Z60930519 Keywords : MHC * house mouse * selection * population structure * trans-species polymorphism Subject RIV: EB - Genetics ; Molecular Biology Impact factor: 4.597, year: 2011

  10. Selecting Measures to Evaluate Complex Sociotechnical Systems: An Empirical Comparison of a Task-based and Constraint-based Method

    Science.gov (United States)

    2013-07-01

    personnel selection, work methods, labour standards and an individual’s motivation to perform work. His work became less relevant as tasks became more...people were employed to do and was able to show that non-physical factors such as job satisfaction and the psychological states of workers contributed...all threats, flight conditions, consequences of their actions (for example, damaging the aircraft during a “hard” landing) and expressed satisfaction

  11. Polymeric membrane sensors based on Cd(II) Schiff base complexes for selective iodide determination in environmental and medicinal samples.

    Science.gov (United States)

    Singh, Ashok Kumar; Mehtab, Sameena

    2008-01-15

    The two cadmium chelates of schiff bases, N,N'-bis(salicylidene)-1,4-diaminobutane, (Cd-S(1)) and N,N'-bis(salicylidene)-3,4-diaminotoluene (Cd-S(2)), have been synthesized and explored as ionophores for preparing PVC-based membrane sensors selective to iodide(I) ion. Potentiometric investigations indicate high affinity of these receptors for iodide ion. Polyvinyl chloride (PVC)-based membranes of Cd-S(1) and Cd-S(2) using as hexadecyltrimethylammonium bromide (HTAB) cation discriminator and o-nitrophenyloctyl ether (o-NPOE), dibutylphthalate (DBP), acetophenone (AP) and tributylphosphate (TBP) as plasticizing solvent mediators were prepared and investigated as iodide-selective sensors. The best performance was shown by the membrane of composition (w/w) of (Cd-S(1)) (7%):PVC (31%):DBP (60%):HTAB (2%). The sensor works well over a wide concentration range 5.3x10(-7) to 1.0x10(-2)M with Nernstian compliance (59.2mVdecade(-1) of activity) within pH range 2.5-9.0 with a response time of 11s and showed good selectivity for iodide ion over a number of anions. The sensor exhibits adequate life (3 months) with good reproducibility (S.D.+/-0.24mV) and could be used successfully for the determination of iodide content in environmental water samples and mouth wash samples.

  12. Low Major Histocompatibility Complex Class II Variation in the Endangered Indo-Pacific Humpback Dolphin (Sousa chinensis): Inferences About the Role of Balancing Selection.

    Science.gov (United States)

    Zhang, Xiyang; Lin, Wenzhi; Zhou, Ruilian; Gui, Duan; Yu, Xinjian; Wu, Yuping

    2016-03-01

    It has been widely reported that the major histocompatibility complex (MHC) is under balancing selection due to its immune function across terrestrial and aquatic mammals. The comprehensive studies at MHC and other neutral loci could give us a synthetic evaluation about the major force determining genetic diversity of species. Previously, a low level of genetic diversity has been reported among the Indo-Pacific humpback dolphin (Sousa chinensis) in the Pearl River Estuary (PRE) using both mitochondrial marker and microsatellite loci. Here, the expression and sequence polymorphism of 2 MHC class II genes (DQB and DRB) in 32 S. chinensis from PRE collected between 2003 and 2011 were investigated. High ratios of non-synonymous to synonymous substitution rates, codon-based selection analysis, and trans-species polymorphism (TSP) support the hypothesis that balancing selection acted on S. chinensis MHC sequences. However, only 2 haplotypes were detected at either DQB or DRB loci. Moreover, the lack of deviation from the Hardy-Weinberg expectation at DRB locus combined with the relatively low heterozygosity at both DQB locus and microsatellite loci suggested that balancing selection might not be sufficient, which further suggested that genetic drift associated with historical bottlenecks was not mitigated by balancing selection in terms of the loss of MHC and neutral variation in S. chinensis. The combined results highlighted the importance of maintaining the genetic diversity of the endangered S. chinensis. © The American Genetic Association 2016. All rights reserved. For permissions, please e-mail: journals.permissions@oup.com.

  13. Rolling cycle amplification based single-color quantum dots–ruthenium complex assembling dyads for homogeneous and highly selective detection of DNA

    Energy Technology Data Exchange (ETDEWEB)

    Su, Chen; Liu, Yufei; Ye, Tai; Xiang, Xia; Ji, Xinghu; He, Zhike, E-mail: zhkhe@whu.edu.cn

    2015-01-01

    Graphical abstract: A universal, label-free, homogeneous, highly sensitive, and selective fluorescent biosensor for DNA detection is developed by using rolling-circle amplification (RCA) based single-color quantum dots–ruthenium complex (QDs–Ru) assembling dyads. - Highlights: • The single-color QDs–Ru assembling dyads were applied in homogeneous DNA assay. • This biosensor exhibited high selectivity against base mismatched sequences. • This biosensor could be severed as universal platform for the detection of ssDNA. • This sensor could be used to detect the target in human serum samples. • This DNA sensor had a good selectivity under the interference of other dsDNA. - Abstract: In this work, a new, label-free, homogeneous, highly sensitive, and selective fluorescent biosensor for DNA detection is developed by using rolling-circle amplification (RCA) based single-color quantum dots–ruthenium complex (QDs–Ru) assembling dyads. This strategy includes three steps: (1) the target DNA initiates RCA reaction and generates linear RCA products; (2) the complementary DNA hybridizes with the RCA products to form long double-strand DNA (dsDNA); (3) [Ru(phen){sub 2}(dppx)]{sup 2+} (dppx = 7,8-dimethyldipyrido [3,2-a:2′,3′-c] phenanthroline) intercalates into the long dsDNA with strong fluorescence emission. Due to its strong binding propensity with the long dsDNA, [Ru(phen){sub 2}(dppx)]{sup 2+} is removed from the surface of the QDs, resulting in restoring the fluorescence of the QDs, which has been quenched by [Ru(phen){sub 2}(dppx)]{sup 2+} through a photoinduced electron transfer process and is overlaid with the fluorescence of dsDNA bonded Ru(II) polypyridyl complex (Ru-dsDNA). Thus, high fluorescence intensity is observed, and is related to the concentration of target. This sensor exhibits not only high sensitivity for hepatitis B virus (HBV) ssDNA with a low detection limit (0.5 pM), but also excellent selectivity in the complex matrix. Moreover

  14. Platinum-group elements fractionation by selective complexing, the Os, Ir, Ru, Rh-arsenide-sulfide systems above 1020 °C

    Science.gov (United States)

    Helmy, Hassan M.; Bragagni, Alessandro

    2017-11-01

    The platinum-group element (PGE) contents in magmatic ores and rocks are normally in the low μg/g (even in the ng/g) level, yet they form discrete platinum-group mineral (PGM) phases. IPGE (Os, Ir, Ru) + Rh form alloys, sulfides, and sulfarsenides while Pt and Pd form arsenides, tellurides, bismuthoids and antimonides. We experimentally investigate the behavior of Os, Ru, Ir and Rh in As-bearing sulfide system between 1300 and 1020 °C and show that the prominent mineralogical difference between IPGE (+Rh) and Pt and Pd reflects different chemical preference in the sulfide melt. At temperatures above 1200 °C, Os shows a tendency to form alloys. Ruthenium forms a sulfide (laurite RuS2) while Ir and Rh form sulfarsenides (irarsite IrAsS and hollingworthite RhAsS, respectively). The chemical preference of PGE is selective: IPGE + Rh form metal-metal, metal-S and metal-AsS complexes while Pt and Pd form semimetal complexes. Selective complexing followed by mechanical separation of IPGE (and Rh)-ligand from Pt- and Pd-ligand associations lead to PGE fractionation.

  15. The selective cleanup of complex matrices and simultaneous separation of benzo[a]pyrene by solid-phase extraction with MgO microspheres as sorbents.

    Science.gov (United States)

    Jin, Jing; Li, Yun; Zhang, Zhiping; Su, Fan; Qi, Peipei; Lu, Xianbo; Chen, Jiping

    2011-12-23

    A new method for the selective cleanup of complex matrices and simultaneous separation of benzo[a]pyrene (BaP) was developed in this study. This method was based on solid-phase extraction (SPE) using magnesium oxide microspheres as sorbents, and it eliminated interferences from various impurities, such as lipids, sulphur, pigments, halobenzenes, polychlorodibenzo-p-dioxins and polychlorodibenzofurans. Several parameters, including the volume of rinsing and eluting solvents, the type of loading solvents and SPE sorbents, were optimized systematically. The capability for impurity removal was verified by gel permeation chromatography, gas chromatography, and liquid chromatography. Compared to commercial sorbents (silica gel, florisil and alumina), MgO microspheres exhibited excellent performance in the selective isolation of BaP and removal of impurities. The proposed method was applied to detect BaP in complex samples (sediments, soils, fish, and porcine liver). The limit of quantification (LOQ) was 1.04 ngL(-1), and the resulting regression coefficient (r(2)) was greater than 0.999 over a broad concentration range (9.5-7600 ngL(-1)). In contrast to traditional methods, the proposed method can give rise to higher recovery (85.1-100.8%) and better selectivity with simpler operation and less consumption of organic solvents (20-40 mL). Copyright © 2011 Elsevier B.V. All rights reserved.

  16. Elucidation of Operon Structures across Closely Related Bacterial Genomes

    Science.gov (United States)

    Li, Guojun

    2014-01-01

    About half of the protein-coding genes in prokaryotic genomes are organized into operons to facilitate co-regulation during transcription. With the evolution of genomes, operon structures are undergoing changes which could coordinate diverse gene expression patterns in response to various stimuli during the life cycle of a bacterial cell. Here we developed a graph-based model to elucidate the diversity of operon structures across a set of closely related bacterial genomes. In the constructed graph, each node represents one orthologous gene group (OGG) and a pair of nodes will be connected if any two genes, from the corresponding two OGGs respectively, are located in the same operon as immediate neighbors in any of the considered genomes. Through identifying the connected components in the above graph, we found that genes in a connected component are likely to be functionally related and these identified components tend to form treelike topology, such as paths and stars, corresponding to different biological mechanisms in transcriptional regulation as follows. Specifically, (i) a path-structure component integrates genes encoding a protein complex, such as ribosome; and (ii) a star-structure component not only groups related genes together, but also reflects the key functional roles of the central node of this component, such as the ABC transporter with a transporter permease and substrate-binding proteins surrounding it. Most interestingly, the genes from organisms with highly diverse living environments, i.e., biomass degraders and animal pathogens of clostridia in our study, can be clearly classified into different topological groups on some connected components. PMID:24959722

  17. Spectroscopic mapping and selective electronic tuning of molecular orbitals in phosphorescent organometallic complexes – a new strategy for OLED materials

    Directory of Open Access Journals (Sweden)

    Pascal R. Ewen

    2014-11-01

    Full Text Available The improvement of molecular electronic devices such as organic light-emitting diodes requires fundamental knowledge about the structural and electronic properties of the employed molecules as well as their interactions with neighboring molecules or interfaces. We show that highly resolved scanning tunneling microscopy (STM and spectroscopy (STS are powerful tools to correlate the electronic properties of phosphorescent complexes (i.e., triplet emitters with their molecular structure as well as the local environment around a single molecule. We used spectroscopic mapping to visualize several occupied and unoccupied molecular frontier orbitals of Pt(II complexes adsorbed on Au(111. The analysis showed that the molecules exhibit a peculiar localized strong hybridization that leads to partial depopulation of a dz² orbital, while the ligand orbitals are almost unchanged. We further found that substitution of functional groups at well-defined positions can alter specific molecular orbitals without influencing the others. The results open a path toward the tailored design of electronic and optical properties of triplet emitters by smart ligand substitution, which may improve the performance of future OLED devices.

  18. Selective transport and incorporation of highly charged metal and metal complex ions in self-assembled polyelectrolyte multilayer membranes

    International Nuclear Information System (INIS)

    Toutianoush, Ali; Tieke, Bernd

    2002-01-01

    The transport of aqueous salts containing mono-, di- and trivalent metal and tetravalent metal complex ions across ultrathin polyvinylammonium/polyvinylsulphate (PVA/PVS) membranes is described. The membranes were prepared by electrostatic layer-by-layer (LBL) assembly of the two polyelectrolytes. Using spectroscopic measurements and permeability studies, it is demonstrated that the transport of copper(II) chloride, lanthanum(III) chloride, barium chloride and potassium hexacyanoferrate(II) is accompanied by the permanent incorporation of the metal and metal complex ions in the membrane. Upon the uptake of copper, lanthanum and hexacyanoferrate ions, the membranes become cross-linked so that the permeation rates of other salts not taken up by the membrane, e.g. sodium chloride, potassium chloride and magnesium chloride, are decreased. The uptake of barium ions leads to a decrease of the cross-linking density of the membrane so that the permeation rate of NaCl is increased. Possible mechanisms for the ion uptake are discussed

  19. Data compression can discriminate broilers by selection line, detect haplotypes, and estimate genetic potential for complex phenotypes.

    Science.gov (United States)

    Hudson, N J; Hawken, R J; Okimoto, R; Sapp, R L; Reverter, A

    2017-09-01

    Accurately establishing the relationships among individuals lays the foundation for genetic analyses such as genome-wide association studies and identification of selection signatures. Of particular interest to the poultry industry are estimates of genetic merit based on molecular data. These estimates can be commercially exploited in marker-assisted breeding programs to accelerate genetic improvement. Here, we test the utility of a new method we have recently developed to estimate animal relatedness and applied it to genetic parameter estimation in commercial broilers. Our approach is based on the concept of data compression from information theory. Using the real-world compressor gzip to estimate normalized compression distance (NCD) we have built compression-based relationship matrices (CRM) for 988 chickens from 4 commercial broiler lines-2 male and 2 female lines. For all pairs of individuals, we found a strong negative relationship between the commonly used genomic relationship matrix (GRM) and NCD. This reflects the fact that "similarity" is the inverse of "distance." The CRM explained more genetic variation than the corresponding GRM in 2 of 3 phenotypes, with corresponding improvements in accuracy of genomic-enabled predictions of breeding value. A sliding-window version of the analysis highlighted haplotype regions of the genome apparently under selection in a line-specific manner. In the male lines, we retrieved high population-specific scores for IGF-1 and a cognate receptor, INSR. For the female lines, we detected an extreme score for a region containing a reproductive hormone receptor (GNRHR). We conclude that our compression-based method is a valid approach to established relationships and identify regions under selective pressure in commercial lines of broiler chickens. © 2017 Poultry Science Association Inc.

  20. Selection for long and short sleep duration in Drosophila melanogaster reveals the complex genetic network underlying natural variation in sleep.

    Science.gov (United States)

    Harbison, Susan T; Serrano Negron, Yazmin L; Hansen, Nancy F; Lobell, Amanda S

    2017-12-01

    Why do some individuals need more sleep than others? Forward mutagenesis screens in flies using engineered mutations have established a clear genetic component to sleep duration, revealing mutants that convey very long or short sleep. Whether such extreme long or short sleep could exist in natural populations was unknown. We applied artificial selection for high and low night sleep duration to an outbred population of Drosophila melanogaster for 13 generations. At the end of the selection procedure, night sleep duration diverged by 9.97 hours in the long and short sleeper populations, and 24-hour sleep was reduced to 3.3 hours in the short sleepers. Neither long nor short sleeper lifespan differed appreciably from controls, suggesting little physiological consequences to being an extreme long or short sleeper. Whole genome sequence data from seven generations of selection revealed several hundred thousand changes in allele frequencies at polymorphic loci across the genome. Combining the data from long and short sleeper populations across generations in a logistic regression implicated 126 polymorphisms in 80 candidate genes, and we confirmed three of these genes and a larger genomic region with mutant and chromosomal deficiency tests, respectively. Many of these genes could be connected in a single network based on previously known physical and genetic interactions. Candidate genes have known roles in several classic, highly conserved developmental and signaling pathways-EGFR, Wnt, Hippo, and MAPK. The involvement of highly pleiotropic pathway genes suggests that sleep duration in natural populations can be influenced by a wide variety of biological processes, which may be why the purpose of sleep has been so elusive.

  1. Selection for long and short sleep duration in Drosophila melanogaster reveals the complex genetic network underlying natural variation in sleep.

    Directory of Open Access Journals (Sweden)

    Susan T Harbison

    2017-12-01

    Full Text Available Why do some individuals need more sleep than others? Forward mutagenesis screens in flies using engineered mutations have established a clear genetic component to sleep duration, revealing mutants that convey very long or short sleep. Whether such extreme long or short sleep could exist in natural populations was unknown. We applied artificial selection for high and low night sleep duration to an outbred population of Drosophila melanogaster for 13 generations. At the end of the selection procedure, night sleep duration diverged by 9.97 hours in the long and short sleeper populations, and 24-hour sleep was reduced to 3.3 hours in the short sleepers. Neither long nor short sleeper lifespan differed appreciably from controls, suggesting little physiological consequences to being an extreme long or short sleeper. Whole genome sequence data from seven generations of selection revealed several hundred thousand changes in allele frequencies at polymorphic loci across the genome. Combining the data from long and short sleeper populations across generations in a logistic regression implicated 126 polymorphisms in 80 candidate genes, and we confirmed three of these genes and a larger genomic region with mutant and chromosomal deficiency tests, respectively. Many of these genes could be connected in a single network based on previously known physical and genetic interactions. Candidate genes have known roles in several classic, highly conserved developmental and signaling pathways-EGFR, Wnt, Hippo, and MAPK. The involvement of highly pleiotropic pathway genes suggests that sleep duration in natural populations can be influenced by a wide variety of biological processes, which may be why the purpose of sleep has been so elusive.

  2. DFT investigation on the selective complexation of Fe3+ and Al3+ with hydroxypyridinones used for treatment of the aluminium and iron overload diseases.

    Science.gov (United States)

    Kaviani, Sadegh; Izadyar, Mohammad; Housaindokht, Mohammad Reza

    2018-03-01

    The chelating agents for Al 3+ and Fe 3+ metal cations with therapeutic applications have been considered in the recent years. In designing of the hydroxypyridinones (HPOs) as the therapeutic chelating agents for iron and aluminium overload pathologies, quantum mechanical (QM) calculations are necessary for predicting the binding energies and thermodynamic parameters of the metal-HPO complexes. Three derivatives of the HPOs called 3-hydroxy-1,2-dimethylpyridin-4(1H)-one (DFP), 3-hydroxy-4(1H)-pyridinone (HOPO) and 5-hydroxy-2-(hydroxymethyl)pyridin-4(1H)-one (P1) were investigated for complexation with Fe 3+ and Al 3+ metal ions. Because of the maximum interaction between Fe 3+ and HPOs, all HPOs form stable complexes with Fe 3+ metal ion. Moreover, it was found that [Fe-P1] 2+ is a more stable complex than [Fe-DFP] 2+ and [Fe-3,4-HOPO] 2+ in the gas phase and water, confirming that P1 is the strongest selective iron chelator. The more stability of [Fe-P1] 2+ was attributed to an intramolecular hydrogen bond formation between the hydrogen atom of NH group and the oxygen atom of CH 2 OH chain. All complexes of the HPOs with Fe 3+ and Al 3+ were formed through the oxygen atoms of the CO and OH groups of the HPO. Natural bond orbital analysis showed that the interaction of the lone pair electrons of the oxygen atom of the chelator and antibonding orbitals of the Al 3+ and Fe 3+ are important in the complex formation. Topological parameters at the bond critical points confirmed the effective interaction between the Al 3+ and Fe 3+ metal ions and HPO as well as the nature of the metal-oxygen bonds. Copyright © 2018 Elsevier Inc. All rights reserved.

  3. Nanosized As2O3/Fe2O3 complexes combined with magnetic fluid hyperthermia selectively target liver cancer cells.

    Science.gov (United States)

    Wang, Zi-Yu; Song, Jian; Zhang, Dong-Sheng

    2009-06-28

    To study the methods of preparing the magnetic nano-microspheres of Fe(2)O(3) and As(2)O(3)/Fe(2)O(3) complexes and their therapeutic effects with magnetic fluid hyperthermia (MFH). Nanospheres were prepared by chemical co-precipitation and their shape and diameter were observed. Hemolysis, micronucleus, cell viability, and LD(50) along with other in vivo tests were performed to evaluate the Fe(2)O(3) microsphere biocompatibility. The inhibition ratio of tumors after Fe(2)O(3) and As(2)O(3)/Fe(2)O(3) injections combined with induced hyperthermia in xenograft human hepatocarcinoma was calculated. Fe(2)O(3) and As(2)O(3)/Fe(2)O(3) particles were round with an average diameter of 20 nm and 100 nm as observed under transmission electron microscope. Upon exposure to an alternating magnetic field (AMF), the temperature of the suspension of magnetic particles increased to 41-51 degrees C, depending on different particle concentrations, and remained stable thereafter. Nanosized Fe(2)O(3) microspheres are a new kind of biomaterial without cytotoxic effects. The LD(50) of both Fe(2)O(3) and As(2)O(3)/Fe(2)O(3) in mice was higher than 5 g/kg. One to four weeks after Fe(2)O(3) and As(2)O(3)/Fe(2)O(3) complex injections into healthy pig livers, no significant differences were found in serum AST, ALT, BUN and Cr levels among the pigs of all groups (P > 0.05), and no obvious pathological alterations were observed. After exposure to alternating magnetic fields, the inhibition ratio of the tumors was significantly different from controls in the Fe(2)O(3) and As(2)O(3)/Fe(2)O(3) groups (68.74% and 82.79%, respectively; P < 0.01). Tumors of mice in treatment groups showed obvious necrosis, while normal tissues adjoining the tumor and internal organs did not. Fe(2)O(3) and As(2)O(3)/Fe(2)O(3) complexes exerted radiofrequency-induced hyperthermia and drug toxicity on tumors without any liver or kidney damage. Therefore, nanospheres are ideal carriers for tumor-targeted therapy.

  4. Extractive spectrophotometric determination of five selected drugs by ion-pair complex formation with bromothymol blue in pure form and pharmaceutical preparations

    Directory of Open Access Journals (Sweden)

    Sneha G. Nair

    2015-12-01

    Full Text Available Simple, precise, selective, and expeditious spectrophotometric methods have been developed for the determination of itopride (ITO, midodrine (MID, diclofenac (DIC, mesalamine (MES, and sumatriptan (SUM in their pure form as well as in pharmaceutical preparations. The method was based on ion-pair complex formation between the drugs and anionic dye, bromothymol blue in an acidic medium (pH 2.0–4.0. The yellow colored complexes formed were quantitatively extracted into chloroform and measured at 411, 410, 413, 412, and 414 nm wavelength for ITO, MID, DIC, MES, and SUM, respectively. Beer’s law was obeyed in the concentration range of 3.0–30 µg/mL for ITO, 1.0–20 µg/mL for MID, 1.5–40 µg/mL for DIC, 1.2–12 µg/mL for MES, and 0.5–15 µg/mL for SUM. The stoichiometry of the complexes formed between the drugs and the dye was 1:1 as determined by Job’s method of continuous variation. The association constant (KIP of the ion-pair complexes formed was evaluated using Benesi–Hildebrand equation. Limit of detection, limit of quantification, and Sandell’s sensitivity of the methods were also estimated. The proposed methods were successfully employed for the determination of these drugs in their pharmaceutical dosage forms.

  5. Ligand design for site-selective metal coordination: synthesis of transition-metal complexes with η{sup 6}-coordination of the central ring of anthracene

    Energy Technology Data Exchange (ETDEWEB)

    Karslyan, Eduard E.; Borissova, Alexandra O.; Perekalin, Dmitry S. [Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, Moscow (Russian Federation)

    2017-05-08

    A polycyclic aromatic ligand for site-selective metal coordination was designed by using DFT calculations. The computational prediction was confirmed by experiments: 2,3,6,7-tetramethoxy-9,10-dimethylanthracene initially reacts with [(C{sub 5}H{sub 5})Ru(MeCN){sub 3}]BF{sub 4} to give the kinetic product with a [(C{sub 5}H{sub 5})Ru]{sup +} fragment coordinated at the terminal ring, which is then transformed into the thermodynamic product with coordination through the central ring. These isomeric complexes have markedly different UV/Vis spectra, which was explained by analysis of the frontier orbitals. At the same time, the calculations suggest that electrostatic interactions are mainly responsible for the site selectivity of the coordination. (copyright 2017 Wiley-VCH Verlag GmbH and Co. KGaA, Weinheim)

  6. The Sleep Elaboration-Awake Pruning (SEAP) theory of memory: long term memories grow in complexity during sleep and undergo selection while awake. Clinical, psychopharmacological and creative implications.

    Science.gov (United States)

    Charlton, Bruce G; Andras, Peter

    2009-07-01

    Long term memory (LTM) systems need to be adaptive such that they enhance an organism's reproductive fitness and self-reproducing in order to maintain their complexity of communications over time in the face of entropic loss of information. Traditional 'representation-consolidation' accounts conceptualize memory adaptiveness as due to memories being 'representations' of the environment, and the longevity of memories as due to 'consolidation' processes. The assumption is that memory representations are formed while an animal is awake and interacting with the environment, and these memories are consolidated mainly while the animal is asleep. So the traditional view of memory is 'instructionist' and assumes that information is transferred from the environment into the brain. By contrast, we see memories as arising endogenously within the brain's LTM system mainly during sleep, to create complex but probably maladaptive memories which are then simplified ('pruned') and selected during the awake period. When awake the LTM system is brought into a more intense interaction with past and present experience. Ours is therefore a 'selectionist' account of memory, and could be termed the Sleep Elaboration-Awake Pruning (or SEAP) theory. The SEAP theory explains the longevity of memories in the face of entropy by the tendency for memories to grow in complexity during sleep; and explains the adaptiveness of memory by selection for consistency with perceptions and previous memories during the awake state. Sleep is therefore that behavioural state during which most of the internal processing of the system of LTM occurs; and the reason sleep remains poorly understood is that its primary activity is the expansion of long term memories. By re-conceptualizing the relationship between memory, sleep and the environment; SEAP provides a radically new framework for memory research, with implications for the measurement of memory and the design of empirical investigations in clinical

  7. Thermodynamic models to elucidate the enantioseparation of drugs with two stereogenic centers by micellar electrokinetic chromatography.

    Science.gov (United States)

    Guo, Xuming; Liu, Qiuxia; Hu, Shaoqiang; Guo, Wenbo; Yang, Zhuo; Zhang, Yonghua

    2017-08-25

    An equilibrium model depicting the simultaneous protonation of chiral drugs and partitioning of protonated ions and neutral molecules into chiral micelles in micellar electrokinetic chromatography (MEKC) has been introduced. It was used for the prediction and elucidation of complex changes in migration order patterns with experimental conditions in the enantioseparation of drugs with two stereogenic centers. Palonosetron hydrochloride (PALO), a weakly basic drug with two stereogenic centers, was selected as a model drug. Its four stereoisomers were separated by MEKC using sodium cholate (SC) as chiral selector and surfactant. Based on the equilibrium model, equations were derived for a calculation of the effective mobility and migration time of each stereoisomer at a certain pH. The migration times of four stereoisomers at different pHs were calculated and then the migration order patterns were constructed with derived equations. The results were in accord with the experiment. And the contribution of each mechanism to the separation and its influence on the migration order pattern was analyzed separately by introducing virtual isomers, i.e., hypothetical stereoisomers with only one parameter changed relative to a real PALO stereoisomer. A thermodynamic model for a judgment of the correlation of interactions between two stereogenic centers of stereoisomers and chiral selector was also proposed. According to this model, the interactions of two stereogenic centers of PALO stereoisomers in both neutral molecules and protonated ions with chiral selector are not independent, so the chiral recognition in each pair of enantiomers as well as the recognition for diastereomers is not simply the algebraic sum of the contributions of two stereogenic centers due to their correlation. Copyright © 2017 Elsevier B.V. All rights reserved.

  8. Elucidating Small-Scale Animal-Fluid Interactions in the Deep Sea

    Science.gov (United States)

    Katija, K.; Sherman, A.; Graves, D.; Kecy, C. D.; Klimov, D.; Robison, B. H.

    2016-02-01

    The midwater region of the ocean (below the euphotic zone and above the benthos) is one of the largest ecosystems on our planet, yet remains one of the least explored. Little-known marine organisms that inhabit midwater have developed life strategies that contribute to their evolutionary success, and understanding interactions with their physical, fluid environment will shed light on these strategies. Although significant advances in underwater vehicle technologies have improved access to midwater, small-scale, in situ fluid mechanics measurement methods that seek to quantify the interactions that midwater organisms have with their physical environment are lacking. Here we present DeepPIV, an instrumentation package affixed to remotely operated vehicles that quantifies fluid motions from the surface of the ocean down to 4000 m depths. Utilizing ambient suspended particulate, fluid-structure interactions can be evaluated on a range of marine organisms in midwater and on the benthos. As a proof of concept for DeepPIV, we targeted giant larvaceans (Bathochordaeus stygias) in Monterey Bay that create mucus houses to filter food. Once mucus houses become clogged, they are abandoned by the larvacean, and are left to sink to the ocean bottom; in Monterey Bay, sinking mucus houses contribute to nearly a third of the particulate on the ocean bottom. Little is known about the structure of these mucus houses and the function they play in selectively filtering particles. Using DeepPIV, we reveal the complex structures and flows generated within larvacean mucus houses, which are used to ultimately elucidate how these structures function.

  9. Synthesis and characterisation of nitrogen poly-heterocyclic molecules using as selective complexing agents of metallic cations

    International Nuclear Information System (INIS)

    Alphonse, F.A.

    2003-12-01

    Separation of actinides (III) from lanthanides (III) is a crucial problem in the reprocessing of used nuclear fuels. Experimental results shown that soft donor extractants such as nitrogen polydentate heterocycles containing a NCCNCCN coordination site are potentials ligands for selective extraction of actinides (III). In those cases, two types of liquid-liquid extractions are employed: synergistic combination with lipophilic acid extractants and direct extraction. On the basis of the Hard and Soft Acids and Bases theory and basicity evaluation, new extractants were defined. We have first studied the synthesis of potential 1,3,5-triazine ligands designed for extraction in synergy with α-bromodecanoic acid. Secondly, we have examined the synthesis of bis-triazinyl-pyridine ligands for direct extraction studies. Extraction tests were carried out and perspectives of synthesis were deducted from those extraction results. (author)

  10. Selective decrease of components of the creatine kinase system and ATP synthase complex in chronic Chagas disease cardiomyopathy.

    Directory of Open Access Journals (Sweden)

    Priscila Camillo Teixeira

    2011-06-01

    Full Text Available BACKGROUND: Chronic Chagas disease cardiomyopathy (CCC is an inflammatory dilated cardiomyopathy with a worse prognosis than other cardiomyopathies. CCC occurs in 30 % of individuals infected with Trypanosoma cruzi, endemic in Latin America. Heart failure is associated with impaired energy metabolism, which may be correlated to contractile dysfunction. We thus analyzed the myocardial gene and protein expression, as well as activity, of key mitochondrial enzymes related to ATP production, in myocardial samples of end-stage CCC, idiopathic dilated (IDC and ischemic (IC cardiomyopathies. METHODOLOGY/PRINCIPAL FINDINGS: Myocardium homogenates from CCC (N=5, IC (N=5 and IDC (N=5 patients, as well as from heart donors (N=5 were analyzed for protein and mRNA expression of mitochondrial creatine kinase (CKMit and muscular creatine kinase (CKM and ATP synthase subunits aplha and beta by immunoblotting and by real-time RT-PCR. Total myocardial CK activity was also assessed. Protein levels of CKM and CK activity were reduced in all three cardiomyopathy groups. However, total CK activity, as well as ATP synthase alpha chain protein levels, were significantly lower in CCC samples than IC and IDC samples. CCC myocardium displayed selective reduction of protein levels and activity of enzymes crucial for maintaining cytoplasmic ATP levels. CONCLUSIONS/SIGNIFICANCE: The selective impairment of the CK system may be associated to the loss of inotropic reserve observed in CCC. Reduction of ATP synthase alpha levels is consistent with a decrease in myocardial ATP generation through oxidative phosphorylation. Together, these results suggest that the energetic deficit is more intense in the myocardium of CCC patients than in the other tested dilated cardiomyopathies.

  11. Water-soluble tetrapodal N, O ligands incorporating soft N-heterocycles for the selective complexation of Am(III) over Ln(III)

    Energy Technology Data Exchange (ETDEWEB)

    Heitzmann, M.; Gateau, Ch.; Delangle, P. [CEA Grenoble, Inac, Service de Chimie Inorganique et Biologique, UMR E 3 CEA UJF, FRE CNRS 3200, F-38054 Grenoble (France); Chareyre, L.; Miguirditchian, M.; Charbonnel, M.Ch. [CEA Marcoule, DEN, DRCP, SCPS, F-30207, Bagnols-sur-Ceze (France)

    2010-07-01

    A series of four water-soluble N, O-tetrapodal ligands derived from ethylenediamine, bearing hard acetate groups and soft N-heterocycles, either pyridine or pyrazine, was developed to study the impact of the softness of N-donors on the complexation properties with trivalent f ions. Two novel ligands of enhanced soft character, bearing three pyridines (L{sup 3py}) or three pyrazines (L{sup 3pz}), were synthesized and the related lanthanide complexes were studied in solution. The ligand containing three pyridyl-methyl moieties L{sup 3py} gives complexes with a coordination similar to EDTA, i.e. a hexa-dentate coordination mode as indicated by NMR and luminescence decays (q = 3) and stability constants in the range log {beta}{sub 110} = 6.99-9.3 (La-Lu). On the other hand, the softest molecule L{sup 3pz} forms much less stable complexes with log {beta}{sub 110} = 4.0-4.4 (La-Eu). The selective back-extraction of Am(III) from organic solutions containing 4f and 5f elements was tested with the four water-soluble complexing agents. The ligand L{sup 3pz} demonstrates poor stripping ability and selectivity. In contrast, the three ligands L{sup py}, L{sup pz} and L{sup 3py} give interesting back-extraction results with Eu/Am separation factors ranging from 36 to 46, which are significantly higher than with HEDTA. This exemplifies the role of the N-hetero-cycle softness in enhancing the separation between Am(III) and Eu(III). Interestingly, the pyrazine-based ligand, L{sup pz}, demonstrates the best stripping properties, with a distribution factor that approaches that of HEDTA in the same conditions (D{sub Am{approx}}0.3). This molecule is a good compromise between softness and hardness and forms complexes still stable at pH 3 due to its low basicity. (authors)

  12. Influence of FGR complexity modelling on the practical results in gas pressure calculation of selected fuel elements from Dukovany NPP

    International Nuclear Information System (INIS)

    Lahodova, M.

    2001-01-01

    A modernization fuel system and advanced fuel for operation up to the high burnup are used in present time in Dukovany NPP. Reloading of the cores are evaluated using computer codes for thermomechanical behavior of the most loaded fuel rods. The paper presents results of parametric calculations performed by the NRI Rez integral code PIN, version 2000 (PIN2k) to assess influence of fission gas release modelling complexity on achieved results. The representative Dukovany NPP fuel rod irradiation history data are used and two cases of fuel parameter variables (soft and hard) are chosen for the comparison. Involved FGR models where the GASREL diffusion model developed in the NRI Rez plc and standard Weisman model that is recommended in the previous version of the PIN integral code. FGR calculation by PIN2k with GASREL model represents more realistic results than standard Weisman's model. Results for linear power, fuel centre temperature, FGR and gas pressure versus burnup are given for two fuel rods

  13. Methods for generating complex networks with selected structural properties for simulations: A review and tutorial for neuroscientists

    Directory of Open Access Journals (Sweden)

    Brenton J Prettejohn

    2011-03-01

    Full Text Available Many simulations of networks in computational neuroscience assume completely homogenous random networks of the Erd"{o}s-R'{e}nyi type, or regular networks, despite it being recognized for some time that anatomical brain networks are more complex in their connectivity and can, for example, exhibit the `scale-free' and `small-world' properties. We review the most well known algorithms for constructing networks with given non-homogeneous statistical properties and provide simple pseudo-code for reproducing such networks in software simulations. We also review some useful mathematical results and approximations associated with the statistics that describe these network models, including degree distribution, average path length and clustering coefficient. We demonstrate how such results can be used as partial verification and validation of implementations. Finally, we discuss a sometimes overlooked modeling choice that can be crucially important for the properties of simulated networks: that of network directedness. The most well known network algorithms produce undirected networks, and we emphasize this point by highlighting how simple adaptations can instead produce directed networks.

  14. Efficient and selective singlet oxygen sensitized NIR luminescence of a neodymium(III) complex and its application in biological imaging

    Energy Technology Data Exchange (ETDEWEB)

    Lo, Wai-Sum [Department of Applied Biology and Chemical Technology, The Hong Kong Polytechnic University, Hong Kong Special Administrative Region (Hong Kong); Li, Hongguang [Department of Chemistry, Hong Kong Baptist University, Kowloon Tong, Hong Kong Special Administrative Region (Hong Kong); Law, Ga-Lai, E-mail: ga-lai.law@polyu.edu.hk [Department of Applied Biology and Chemical Technology, The Hong Kong Polytechnic University, Hong Kong Special Administrative Region (Hong Kong); Wong, Wing-Tak, E-mail: bcwtwong@polyu.edu.hk [Department of Applied Biology and Chemical Technology, The Hong Kong Polytechnic University, Hong Kong Special Administrative Region (Hong Kong); Wong, Ka-Leung, E-mail: klwong@hkbu.edu.hk [Department of Chemistry, Hong Kong Baptist University, Kowloon Tong, Hong Kong Special Administrative Region (Hong Kong)

    2016-01-15

    A responsive neodymium NIR emission ({sup 4}F{sub 3/2}→{sup 4}I{sub 11/2,} {sub 9/2}) was recorded upon binding with singlet oxygen (K{sub B}=1.79×10{sup 6} M{sup −1}) via the anthracene moiety. The motif ytterbium analog served as a negative control with no significant NIR enhancement/quenching with the addition of the same amount of singlet oxygen. Our complex was also found to react with {sup 1}O{sub 2} generated by a known photosensitizer TMPyP inside HeLa cells without inducing cell death and display no significant cytotoxicity. - Highlights: • A turn-on NIR-emissive {sup 1}O{sub 2} probe has been synthesized for potential biological applications. • It has a binding constant of 1.9×10{sup 6} M{sup −1} and the emission intensity has a 5-fold increase upon binding. • The probe was also found to quench singlet oxygen in vitro generated by known photosensitizer TMPyP.

  15. A combined coalescence gene-dropping tool for evaluating genomic selection in complex scenarios (ms2gs).

    Science.gov (United States)

    Pérez-Enciso, M; Legarra, A

    2016-04-01

    We present ms2gs, a combined coalescence - gene dropping (i.e. backward-forward) simulator for complex traits. It therefore aims at combining the advantages of both approaches. It is primarily conceived for very short term, recent scenarios such as those that are of interest in animal and plant breeding. It is very flexible in terms of defining QTL architecture and SNP ascertainment bias, and it allows for easy modelling of alternative markers such as RADs. It can use real sequence or chip data or generate molecular polymorphisms via the coalescence. It can generate QTL conditional on extant molecular information, such as low-density genotyping. It models (simplistically) sequence, imputation or genotyping errors. It requires as input both genotypic data in plink or ms formats, and a pedigree that is used to perform the gene dropping. By default, it compares accuracy for BLUP, SNP ascertained data, sequence, and causal SNPs. It employs VanRaden's linear (GBLUP) and nonlinear method for incorporating molecular information. To illustrate the program, we present a small application in a half-sib population and a multiparental (MAGIC) cross. The program, manual and examples are available at https://github.com/mperezenciso/ms2gs. © 2016 Blackwell Verlag GmbH.

  16. EXPERIENCE OF USING A NON-SELECTIVE BETA-BLOCKER IN COMPLEX THERAPY OF REPOLARIZATION DISORDERS IN YOUNG ATHLETES

    Directory of Open Access Journals (Sweden)

    A. Yu. Tikhomirov

    2017-01-01

    Full Text Available Purpose. To study the effectiveness of various schemes of correction of repolarization disorder syndrome, including with the use of beta-blockers, in young athletes of the initial training group.Materials and methods. At the first stage, 410 children involved in sports sections were examined. The average age of the examined was 12.22 ± 3.11 years. At the second stage, the athletes (boys of the initial training group were selected from the surveyed contingent, engaged in martial arts. The groups were formed: A – people with violation of myocardial repolarization processes (72 patients, the average age 10,50 ± 0,35 years, the control group – people without changes in an electrocardiogram (33 people, the average age 10.36 ± 0, 62 years old. All underwent an electrocardiographic study at rest and after physical activity on the Innomed HS80GL apparatus with analysis of the main indicators. The vegetative status and the state of adaptation were estimated by Kerdo index and adaptive potential by Baevsky. After the examination, the subgroup A1 (40 people was prescribed metabolic and antioxidant drugs. Additionally, in the subgroup A2 (32 people, a non-selective beta-blocker was included in the treatment regimen. The course of treatment is 10 days. The analysis of indicators was carried out in 10 days and in a month after the initiation treatment. Statistical processing was carried out in the program Statistica.Results. An earlier disappearance of cardialgia was determined in the subgroup A2 (p < 0.05, whereas in the subgroup A1, 5% of patients had complaints not only at the end of the course, but also a month later after the initiation treatment. The more rapid positive dynamics of the electrocardiographic pattern with a more stable result was observed with the prescription of a beta-blocker.Conclusion. It was proved the advisability of prescribing of beta-blockers in the treatment of beginning athletes with violation of myocardial repolarization

  17. Highlighting the complexities of a groundwater pilot study during an avian influenza outbreak: Methods, lessons learned, and select contaminant results

    Science.gov (United States)

    Hubbard, Laura E.; Kolpin, Dana W.; Fields, Chad L.; Hladik, Michelle L.; Iwanowicz, Luke

    2017-01-01

    The highly pathogenic avian influenza (H5N2) outbreak in the Midwestern United States (US) in 2015 was historic due to the number of birds and poultry operations impacted and the corresponding economic loss to the poultry industry and was the largest animal health emergency in US history. The U.S. Geological Survey (USGS), with the assistance of several state and federal agencies, aided the response to the outbreak by developing a study to determine the extent of virus transport in the environment. The study goals were to: develop the appropriate sampling methods and protocols for measuring avian influenza virus (AIV) in groundwater, provide the first baseline data on AIV and outbreak- and poultry-related contaminant occurrence and movement into groundwater, and document climatological factors that may have affected both survival and transport of AIV to groundwater during the months of the 2015 outbreak. While site selection was expedient, there were often delays in sample response times due to both relationship building between agencies, groups, and producers and logistical time constraints. This study's design and sampling process highlights the unpredictable nature of disease outbreaks and the corresponding difficulty in environmental sampling of such events. The lessons learned, including field protocols and approaches, can be used to improve future research on AIV in the environment.

  18. Tackling the challenge of selective analytical clean-up of complex natural extracts: the curious case of chlorophyll removal.

    Science.gov (United States)

    Bijttebier, Sebastiaan; D'Hondt, Els; Noten, Bart; Hermans, Nina; Apers, Sandra; Voorspoels, Stefan

    2014-11-15

    Alkaline saponification is often used to remove interfering chlorophylls and lipids during carotenoids analysis. However, saponification also hydrolyses esterified carotenoids and is known to induce artifacts. To avoid carotenoid artifact formation during saponification, Larsen and Christensen (2005) developed a gentler and simpler analytical clean-up procedure involving the use of a strong basic resin (Ambersep 900 OH). They hypothesised a saponification mechanism based on their Liquid Chromatography-Photodiode Array (LC-PDA) data. In the present study, we show with LC-PDA-accurate mass-Mass Spectrometry that the main chlorophyll removal mechanism is not based on saponification, apolar adsorption or anion exchange, but most probably an adsorption mechanism caused by H-bonds and dipole-dipole interactions. We showed experimentally that esterified carotenoids and glycerolipids were not removed, indicating a much more selective mechanism than initially hypothesised. This opens new research opportunities towards a much wider scope of applications (e.g. the refinement of oils rich in phytochemical content). Copyright © 2014 Elsevier Ltd. All rights reserved.

  19. Characterizing complex polysera produced by antigen-specific immunization through the use of affinity-selected mimotopes.

    Directory of Open Access Journals (Sweden)

    Galina Denisova

    Full Text Available BACKGROUND: Antigen-based (as opposed to whole organism vaccines are actively being pursued for numerous indications. Even though different formulations may produce similar levels of total antigen-specific antibody, the composition of the antibody response can be quite distinct resulting in different levels of therapeutic activity. METHODOLOGY/PRINCIPAL FINDINGS: Using plasmid-based immunization against the proto-oncogene HER-2 as a model, we have demonstrated that affinity-selected epitope mimetics (mimotopes can provide a defined signature of a polyclonal antibody response. Further, using novel computer algorithms that we have developed, these mimotopes can be used to predict epitope targets. CONCLUSIONS/SIGNIFICANCE: By combining our novel strategy with existing methods of epitope prediction based on physical properties of an individual protein, we believe that this method offers a robust method for characterizing the breadth of epitope-specificity within a specific polyserum. This strategy is useful as a tool for monitoring immunity following vaccination and can also be used to define relevant epitopes for the creation of novel vaccines.

  20. Highlighting the complexities of a groundwater pilot study during an avian influenza outbreak: Methods, lessons learned, and select contaminant results.

    Science.gov (United States)

    Hubbard, Laura E; Kolpin, Dana W; Fields, Chad L; Hladik, Michelle L; Iwanowicz, Luke R

    2017-10-01

    The highly pathogenic avian influenza (H5N2) outbreak in the Midwestern United States (US) in 2015 was historic due to the number of birds and poultry operations impacted and the corresponding economic loss to the poultry industry and was the largest animal health emergency in US history. The U.S. Geological Survey (USGS), with the assistance of several state and federal agencies, aided the response to the outbreak by developing a study to determine the extent of virus transport in the environment. The study goals were to: develop the appropriate sampling methods and protocols for measuring avian influenza virus (AIV) in groundwater, provide the first baseline data on AIV and outbreak- and poultry-related contaminant occurrence and movement into groundwater, and document climatological factors that may have affected both survival and transport of AIV to groundwater during the months of the 2015 outbreak. While site selection was expedient, there were often delays in sample response times due to both relationship building between agencies, groups, and producers and logistical time constraints. This study's design and sampling process highlights the unpredictable nature of disease outbreaks and the corresponding difficulty in environmental sampling of such events. The lessons learned, including field protocols and approaches, can be used to improve future research on AIV in the environment. Published by Elsevier Inc.

  1. Simplifying the complex 1H NMR spectra of fluorine-substituted benzamides by spin system filtering and spin-state selection: multiple-quantum-single-quantum correlation.

    Science.gov (United States)

    Baishya, Bikash; Reddy, G N Manjunatha; Prabhu, Uday Ramesh; Row, T N Guru; Suryaprakash, N

    2008-10-23

    The proton NMR spectra of fluorine-substituted benzamides are very complex (Figure 1) due to severe overlap of (1)H resonances from the two aromatic rings, in addition to several short and long-range scalar couplings experienced by each proton. With no detectable scalar couplings between the inter-ring spins, the (1)H NMR spectra can be construed as an overlap of spectra from two independent phenyl rings. In the present study we demonstrate that it is possible to separate the individual spectrum for each aromatic ring by spin system filtering employing the multiple-quantum-single-quantum correlation methodology. Furthermore, the two spin states of fluorine are utilized to simplify the spectrum corresponding to each phenyl ring by the spin-state selection. The demonstrated technique reduces spectral complexity by a factor of 4, in addition to permitting the determination of long-range couplings of less than 0.2 Hz and the relative signs of heteronuclear couplings. The technique also aids the judicious choice of the spin-selective double-quantum-single-quantum J-resolved experiment to determine the long-range homonuclear couplings of smaller magnitudes.

  2. Indigo Carmine-Cu complex probe exhibiting dual colorimetric/fluorimetric sensing for selective determination of mono hydrogen phosphate ion and its logic behavior

    Science.gov (United States)

    Tavallali, Hossein; Deilamy-Rad, Gohar; Moaddeli, Ali; Asghari, Khadijeh

    2017-08-01

    A new selective probe based on copper complex of Indigo Carmine (IC-Cu2) for colorimetric, naked-eye, and fluorimetric recognition of mono hydrogen phosphate (MHP) ion in H2O/DMSO (4:1 v/v, 1.0 mmol L- 1 HEPES buffer solution pH 7.5) was developed. Detection limit of HPO42 - determination, achieved by fluorimetric and 3lorimetric method, are 0.071 and 1.46 μmol L- 1, respectively. Potential, therefore is clearly available in IC-Cu2 complex to detect HPO42 - in micromolar range via dual visible color change and fluorescence response. Present method shows high selectivity toward HPO42 - over other phosphate species and other anions and was successfully utilized for analysis of P2O5 content of a fertilizer sample. The results obtained by proposed chemosensor presented good agreement with those obtained the colorimetric reference method. INHIBIT and IMPLICATION logic gates operating at molecular level have been achieved using Cu2 + and HPO42 - as chemical inputs and UV-Vis absorbance signal as output.

  3. Indigo Carmine-Cu complex probe exhibiting dual colorimetric/fluorimetric sensing for selective determination of mono hydrogen phosphate ion and its logic behavior.

    Science.gov (United States)

    Tavallali, Hossein; Deilamy-Rad, Gohar; Moaddeli, Ali; Asghari, Khadijeh

    2017-08-05

    A new selective probe based on copper complex of Indigo Carmine (IC-Cu 2 ) for colorimetric, naked-eye, and fluorimetric recognition of mono hydrogen phosphate (MHP) ion in H 2 O/DMSO (4:1v/v, 1.0mmolL -1 HEPES buffer solution pH7.5) was developed. Detection limit of HPO 4 2- determination, achieved by fluorimetric and 3 lorimetric method, are 0.071 and 1.46μmolL -1 , respectively. Potential, therefore is clearly available in IC-Cu 2 complex to detect HPO 4 2- in micromolar range via dual visible color change and fluorescence response. Present method shows high selectivity toward HPO 4 2- over other phosphate species and other anions and was successfully utilized for analysis of P 2 O 5 content of a fertilizer sample. The results obtained by proposed chemosensor presented good agreement with those obtained the colorimetric reference method. INHIBIT and IMPLICATION logic gates operating at molecular level have been achieved using Cu 2+ and HPO 4 2- as chemical inputs and UV-Vis absorbance signal as output. Copyright © 2017. Published by Elsevier B.V.

  4. Selective C–C Coupling Reaction of Dimethylphenol to Tetramethyldiphenoquinone Using Molecular Oxygen Catalyzed by Cu Complexes Immobilized in Nanospaces of Structurally-Ordered Materials

    Directory of Open Access Journals (Sweden)

    Zen Maeno

    2015-02-01

    Full Text Available Two high-performance Cu catalysts were successfully developed by immobilization of Cu ions in the nanospaces of poly(propylene imine (PPI dendrimer and magadiite for the selective C–C coupling of 2,6-dimethylphenol (DMP to 3,3',5,5'-tetramethyldiphenoquinone (DPQ with O2 as a green oxidant. The PPI dendrimer encapsulated Cu ions in the internal nanovoids to form adjacent Cu species, which exhibited significantly high catalytic activity for the regioselective coupling reaction of DMP compared to previously reported enzyme and metal complex catalysts. The magadiite-immobilized Cu complex acted as a selective heterogeneous catalyst for the oxidative C–C coupling of DMP to DPQ. This heterogeneous catalyst was recoverable from the reaction mixture by simple filtration, reusable without loss of efficiency, and applicable to a continuous flow reactor system. Detailed characterization using ultraviolet-visible (UV-vis, Fourier transform infrared (FTIR, electronic spin resonance (ESR, and X-ray absorption fine structure (XAFS spectroscopies and the reaction mechanism investigation revealed that the high catalytic performances of these Cu catalysts were ascribed to the adjacent Cu species generated within the nanospaces of the PPI dendrimer and magadiite.

  5. Systematic Constraint Selection Strategy for Rate-Controlled Constrained-Equilibrium Modeling of Complex Nonequilibrium Chemical Kinetics

    Science.gov (United States)

    Beretta, Gian Paolo; Rivadossi, Luca; Janbozorgi, Mohammad

    2018-04-01

    Rate-Controlled Constrained-Equilibrium (RCCE) modeling of complex chemical kinetics provides acceptable accuracies with much fewer differential equations than for the fully Detailed Kinetic Model (DKM). Since its introduction by James C. Keck, a drawback of the RCCE scheme has been the absence of an automatable, systematic procedure to identify the constraints that most effectively warrant a desired level of approximation for a given range of initial, boundary, and thermodynamic conditions. An optimal constraint identification has been recently proposed. Given a DKM with S species, E elements, and R reactions, the procedure starts by running a probe DKM simulation to compute an S-vector that we call overall degree of disequilibrium (ODoD) because its scalar product with the S-vector formed by the stoichiometric coefficients of any reaction yields its degree of disequilibrium (DoD). The ODoD vector evolves in the same (S-E)-dimensional stoichiometric subspace spanned by the R stoichiometric S-vectors. Next we construct the rank-(S-E) matrix of ODoD traces obtained from the probe DKM numerical simulation and compute its singular value decomposition (SVD). By retaining only the first C largest singular values of the SVD and setting to zero all the others we obtain the best rank-C approximation of the matrix of ODoD traces whereby its columns span a C-dimensional subspace of the stoichiometric subspace. This in turn yields the best approximation of the evolution of the ODoD vector in terms of only C parameters that we call the constraint potentials. The resulting order-C RCCE approximate model reduces the number of independent differential equations related to species, mass, and energy balances from S+2 to C+E+2, with substantial computational savings when C ≪ S-E.

  6. Customized a Ti6Al4V Bone Plate for Complex Pelvic Fracture by Selective Laser Melting

    Directory of Open Access Journals (Sweden)

    Di Wang

    2017-01-01

    Full Text Available In pelvic fracture operations, bone plate shaping is challenging and the operation time is long. To address this issue, a customized bone plate was designed and produced using selective laser melting (SLM technology. The key steps of this study included designing the customized bone plate, metal 3D printing, vacuum heat treatment, surface post-processing, operation rehearsal, and clinical application and evaluation. The joint surface of the bone plate was placed upwards with respect to the build platform to keep it away from the support and to improve the quality of the joint surface. Heat conduction was enhanced by adding a cone-type support beneath the bone plate to prevent low-quality fabrication due to poor heat conductivity of the Ti-6Al-4V powder. The residual stress was eliminated by exposing the SLM-fabricated titanium-alloy bone plate to a vacuum heat treatment. Results indicated that the bone plate has a hardness of HV1 360–HV1 390, an ultimate tensile strength of 1000–1100 MPa, yield strength of 900–950 MPa, and an elongation of 8%–10%. Pre-operative experiments and operation rehearsal were performed using the customized bone plate and the ABC-made pelvic model. Finally, the customized bone plate was clinically applied. The intraoperative C-arm and postoperative X-ray imaging results indicated that the customized bone plate matched well to the damaged pelvis. The customized bone plate fixed the broken bone and guides pelvis restoration while reducing operation time to about two hours. The customized bone plate eliminated the need for preoperative titanium plate pre-bending, thereby greatly reducing surgical wounds and operation time.

  7. Customized a Ti6Al4V Bone Plate for Complex Pelvic Fracture by Selective Laser Melting.

    Science.gov (United States)

    Wang, Di; Wang, Yimeng; Wu, Shibiao; Lin, Hui; Yang, Yongqiang; Fan, Shicai; Gu, Cheng; Wang, Jianhua; Song, Changhui

    2017-01-04

    In pelvic fracture operations, bone plate shaping is challenging and the operation time is long. To address this issue, a customized bone plate was designed and produced using selective laser melting (SLM) technology. The key steps of this study included designing the customized bone plate, metal 3D printing, vacuum heat treatment, surface post-processing, operation rehearsal, and clinical application and evaluation. The joint surface of the bone plate was placed upwards with respect to the build platform to keep it away from the support and to improve the quality of the joint surface. Heat conduction was enhanced by adding a cone-type support beneath the bone plate to prevent low-quality fabrication due to poor heat conductivity of the Ti-6Al-4V powder. The residual stress was eliminated by exposing the SLM-fabricated titanium-alloy bone plate to a vacuum heat treatment. Results indicated that the bone plate has a hardness of HV1 360-HV1 390, an ultimate tensile strength of 1000-1100 MPa, yield strength of 900-950 MPa, and an elongation of 8%-10%. Pre-operative experiments and operation rehearsal were performed using the customized bone plate and the ABC-made pelvic model. Finally, the customized bone plate was clinically applied. The intraoperative C-arm and postoperative X-ray imaging results indicated that the customized bone plate matched well to the damaged pelvis. The customized bone plate fixed the broken bone and guides pelvis restoration while reducing operation time to about two hours. The customized bone plate eliminated the need for preoperative titanium plate pre-bending, thereby greatly reducing surgical wounds and operation time.

  8. Integrated analysis of RNA-binding protein complexes using in vitro selection and high-throughput sequencing and sequence specificity landscapes (SEQRS).

    Science.gov (United States)

    Lou, Tzu-Fang; Weidmann, Chase A; Killingsworth, Jordan; Tanaka Hall, Traci M; Goldstrohm, Aaron C; Campbell, Zachary T

    2017-04-15

    RNA-binding proteins (RBPs) collaborate to control virtually every aspect of RNA function. Tremendous progress has been made in the area of global assessment of RBP specificity using next-generation sequencing approaches both in vivo and in vitro. Understanding how protein-protein interactions enable precise combinatorial regulation of RNA remains a significant problem. Addressing this challenge requires tools that can quantitatively determine the specificities of both individual proteins and multimeric complexes in an unbiased and comprehensive way. One approach utilizes in vitro selection, high-throughput sequencing, and sequence-specificity landscapes (SEQRS). We outline a SEQRS experiment focused on obtaining the specificity of a multi-protein complex between Drosophila RBPs Pumilio (Pum) and Nanos (Nos). We discuss the necessary controls in this type of experiment and examine how the resulting data can be complemented with structural and cell-based reporter assays. Additionally, SEQRS data can be integrated with functional genomics data to uncover biological function. Finally, we propose extensions of the technique that will enhance our understanding of multi-protein regulatory complexes assembled onto RNA. Copyright © 2016 Elsevier Inc. All rights reserved.

  9. Evaluation of a rapid radiometric differentiation test for the Mycobacterium tuberculosis complex by selective inhibition with p-nitro-alpha-acetylamino-beta-hydroxypropiophenone

    International Nuclear Information System (INIS)

    Laszlo, A.; Siddiqi, S.H.

    1984-01-01

    This study is an evaluation of a rapid technique for the differentiation of the Mycobacterium tuberculosis complex from other mycobacteria, using p-nitro-alpha-acetylamino-beta- hydroxypropiophenone (NAP) as a selective inhibitory agent. A total of 416 coded cultures, 234 cultures belonging to the M. tuberculosis complex and 182 cultures belonging to 35 other mycobacterial species, were tested in two laboratories for p-nitro-alpha-acetylamino-beta- hydroxypropiophenone inhibition to concentrations of 5 and 10 micrograms of NAP per ml in Middlebrook 7H12 liquid medium. Two testing modes were compared: the indirect, in which a large bacterial inoculum was used from an isolated culture on a solid medium, and the direct, which used a small inoculum from 7H12 medium. A decrease or no increase in daily 14 CO 2 output as measured by a BACTEC system was considered evidence of inhibition. The data presented show that a concentration of 5 micrograms of NAP per ml can effectively separate the M. tuberculosis complex from other mycobacterial species in 4 to 6 days. The direct test data show that, unlike other conventional biochemical tests, it does not require a heavy inoculum of mycobacteria and can therefore be performed soon after growth is detected by the radiometric method

  10. Regio- and stereo-selective polymerization of 1,3-butadiene catalyzed by phosphorus–nitrogen PN3-pincer cobalt(ii) complexes

    KAUST Repository

    Gong, Dirong

    2016-11-11

    A new family of cobalt complexes (CoCl2-H, CoCl2-Me, CoCl2-iPr, CoBr2-H, CoBr2-Me, CoBr2-iPr, CoI2-H, CoI2-Me, and CoI2-iPr) supported by a PN3 ligand (6-(N,N′-di-t-butylphosphino)-2-pyrazol-yl-aminopyridine) have been prepared and fully characterized by FT-IR, elemental analysis, and X-ray analysis. The X-ray analysis reveals a trigonal bipyramidal conformation in the solid state for all representative complexes, CoCl2-H, CoBr2-H, CoBr2-iPr and CoI2-Me. The cobalt center is chelated by the PN3 ligand through the pyridinyl nitrogen, the pyrazol nitrogen and the phosphorus donor, with a long Co-P bond distance indicating a labile character. On activation with AlEt2Cl, Al2Et3Cl3, MAO, [Ph3C]+[B(C6F5)4]-/AliBu3 or AliBu3, cis-1,4 selective butadiene polymerization was achieved with up to 98.6% selectivity. The polymerization results show that the cis-1,4 selectivity is influenced by the steric hindrance, increasing with the bulkiness of the substituent groups (CoX2-iPr > CoX2-Me > CoX2-H) at the 3,5-positions of the pyrazole moiety, together with a slight decrease in activity. The activity changes in the order CoCl2L ≈ CoBr2L > CoI2L (for the same ligand L) when MAO is used as the activator, while the high level of cis-1,4 selectivity is maintained. It is possible to switch the selectivity from cis-1,4 to syndiotactic-1,2 by adding PPh3 © The Royal Society of Chemistry.

  11. A Discovery Strategy for Selective Inhibitors of c-Src in Complex with the Focal Adhesion Kinase SH3/SH2-binding Region.

    Science.gov (United States)

    Moroco, Jamie A; Baumgartner, Matthew P; Rust, Heather L; Choi, Hwan Geun; Hur, Wooyoung; Gray, Nathanael S; Camacho, Carlos J; Smithgall, Thomas E

    2015-08-01

    The c-Src tyrosine kinase co-operates with the focal adhesion kinase to regulate cell adhesion and motility. Focal adhesion kinase engages the regulatory SH3 and SH2 domains of c-Src, resulting in localized kinase activation that contributes to tumor cell metastasis. Using assay conditions where c-Src kinase activity required binding to a tyrosine phosphopeptide based on the focal adhesion kinase SH3-SH2 docking sequence, we screened a kinase-biased library for selective inhibitors of the Src/focal adhesion kinase peptide complex versus c-Src alone. This approach identified an aminopyrimidinyl carbamate compound, WH-4-124-2, with nanomolar inhibitory potency and fivefold selectivity for c-Src when bound to the phospho-focal adhesion kinase peptide. Molecular docking studies indicate that WH-4-124-2 may preferentially inhibit the 'DFG-out' conformation of the kinase active site. These findings suggest that interaction of c-Src with focal adhesion kinase induces a unique kinase domain conformation amenable to selective inhibition. © 2014 John Wiley & Sons A/S.

  12. Elucidating Microbial Adaptation Dynamics via Autonomous Exposure and Sampling

    Science.gov (United States)

    Grace, Joseph M.; Verseux, Cyprien; Gentry, Diana; Moffet, Amy; Thayabaran, Ramanen; Wong, Nathan; Rothschild, Lynn

    2013-01-01

    The adaptation of micro-organisms to their environments is a complex process of interaction between the pressures of the environment and of competition. Reducing this multifactorial process to environmental exposure in the laboratory is a common tool for elucidating individual mechanisms of evolution, such as mutation rates. Although such studies inform fundamental questions about the way adaptation and even speciation occur, they are often limited by labor-intensive manual techniques. Current methods for controlled study of microbial adaptation limit the length of time, the depth of collected data, and the breadth of applied environmental conditions. Small idiosyncrasies in manual techniques can have large effects on outcomes; for example, there are significant variations in induced radiation resistances following similar repeated exposure protocols. We describe here a project under development to allow rapid cycling of multiple types of microbial environmental exposure. The system allows continuous autonomous monitoring and data collection of both single species and sampled communities, independently and concurrently providing multiple types of controlled environmental pressure (temperature, radiation, chemical presence or absence, and so on) to a microbial community in dynamic response to the ecosystem's current status. When combined with DNA sequencing and extraction, such a controlled environment can cast light on microbial functional development, population dynamics, inter- and intra-species competition, and microbe-environment interaction. The project's goal is to allow rapid, repeatable iteration of studies of both natural and artificial microbial adaptation. As an example, the same system can be used both to increase the pH of a wet soil aliquot over time while periodically sampling it for genetic activity analysis, or to repeatedly expose a culture of bacteria to the presence of a toxic metal, automatically adjusting the level of toxicity based on the

  13. From single-site tantalum complexes to nanoparticles of Ta x N y and TaO x N y supported on silica: elucidation of synthesis chemistry by dynamic nuclear polarization surface enhanced NMR spectroscopy and X-ray absorption spectroscopy.

    Science.gov (United States)

    Mohandas, Janet C; Abou-Hamad, Edy; Callens, Emmanuel; Samantaray, Manoja K; Gajan, David; Gurinov, Andrei; Ma, Tao; Ould-Chikh, Samy; Hoffman, Adam S; Gates, Bruce C; Basset, Jean-Marie

    2017-08-01

    Air-stable catalysts consisting of tantalum nitride nanoparticles represented as a mixture of Ta x N y and TaO x N y with diameters in the range of 0.5 to 3 nm supported on highly dehydroxylated silica were synthesized from TaMe 5 (Me = methyl) and dimeric Ta 2 (OMe) 10 with guidance by the principles of surface organometallic chemistry (SOMC). Characterization of the supported precursors and the supported nanoparticles formed from them was carried out by IR, NMR, UV-Vis, extended X-ray absorption fine structure, and X-ray photoelectron spectroscopies complemented with XRD and high-resolution TEM, with dynamic nuclear polarization surface enhanced NMR spectroscopy being especially helpful by providing enhanced intensities of the signals of 1 H, 13 C, 29 Si, and 15 N at their natural abundances. The characterization data provide details of the synthesis chemistry, including evidence of (a) O 2 insertion into Ta-CH 3 species on the support and (b) a binuclear to mononuclear transformation of species formed from Ta 2 (OMe) 10 on the support. A catalytic test reaction, cyclooctene epoxidation, was used to probe the supported nanoparticles, with 30% H 2 O 2 serving as the oxidant. The catalysts gave selectivities up to 98% for the epoxide at conversions as high as 99% with a 3.4 wt% loading of Ta present as Ta x N y /TaO x N y .

  14. Covalent co-immobilization of heparin/laminin complex that with different concentration ratio on titanium surface for selectively direction of platelets and vascular cells behavior

    International Nuclear Information System (INIS)

    Wang, Jian; Chen, Yuan; Liu, Tao; Wang, Xue; Liu, Yang; Wang, Yuan; Chen, Junying; Huang, Nan

    2014-01-01

    Highlights: • Extracellular matrix inspired surface modification with fibronectin, heparin and VEGF to construct a favorable microenvironment for selectively anticoagulant and promote endothelialization. • Take the advantage of specific intermolecular interaction, the bioactivity of above biomolecules was more efficiently maintained in compared with the common used covalent immobilization method. • Poly-l-lysine was used as a novel interlayer for surface amination, and in comparison, PLL coating was more feasible and the degradation product had no harm to human body. - Abstract: Surface biofunctional modification of coronary artery stent to improve the hemocompatibility and selectively accelerate endothelium regeneration but prevent restenosis have been become a new hotspot. For this, a novel method was developed in this work by co-immobilization of Ln and heparin complex on poly-L-lysine modified Ti surface. Take the advantage of the specific interaction between Ln and heparin, Ln and heparin complexes with different concentration ratios were set up for creating different exposure density of these two types of biomolecules. According to biocompatibility evaluation results, the Hep/Ln complexes modified surface displayed less platelet adhesion and activation. Especially, on L(150)H and L(200)H surface, the AT III binding quantity, APTT value and anti-coagulation property of modified surface were significantly promoted. Furthermore, the adherent density and proliferation activity of ECs and EPCs were positively correlated with Ln concentration. Notably, the proliferation of both ECs and EPCs on L(100)H, L(150)H and L(200)H surface were greatly promoted. Another hand, the proliferation activity of SMCs was significantly inhibited on Hep/Ln modified surfaces, which was considered mainly due to the inhibitory effect of heparin to SMCs. According to the existing results, this study demonstrated that in a certain range of heparin and laminin concentration ratio

  15. A Method for Selective Depletion of Zn(II) Ions from Complex Biological Media and Evaluation of Cellular Consequences of Zn(II) Deficiency

    Science.gov (United States)

    Richardson, Christopher E. R.; Cunden, Lisa S.; Butty, Vincent L.; Nolan, Elizabeth M.; Lippard, Stephen J.; Shoulders, Matthew D.

    2018-01-01

    We describe the preparation, evaluation, and application of an S100A12 protein-conjugated solid support, hereafter the “A12-resin,” that can remove 99% of Zn(II) from complex biological solutions without significantly perturbing the concentrations of other metal ions. The A12-resin can be applied to selectively deplete Zn(II) from diverse tissue culture media and from other biological fluids, including human serum. To further demonstrate the utility of this approach, we investigated metabolic, transcriptomic, and metallomic responses of HEK293 cells cultured in medium depleted of Zn(II) using S100A12. The resulting data provide insight into how cells respond to acute Zn(II) deficiency. We expect that the A12-resin will facilitate interrogation of disrupted Zn(II) homeostasis in biological settings, uncovering novel roles for Zn(II) in biology. PMID:29334734

  16. DFT Mechanistic Study of the Selective Terminal C-H Activation of n-Pentane with a Tungsten Allyl Nitrosyl Complex

    KAUST Repository

    Lee, Richmond

    2017-01-17

    Mechanistic insights into the selective C-H terminal activation of n-pentane with tungsten allyl nitrosyl complex reported by Legzdins were gained by employing density functional theory with B3LYP hybrid functional. Using Bader’s atom in molecules (AIM) analysis on the elementary steps of the hydrogen transfer process, TS1 and TS2, it was observed that the calculated H-transfer models were closely similar to Hall’s metal-assisted σ-bond metathesis through bond critical point (BCP) comparisons. One distinguishable feature was the fact that the formal oxidation state of the W changed in the concerted H-transfer process. To better differentiate, we term these processes as ‘Formal Reductive Hydrogen Transfer’ (FRHT) for TS1 and ‘Formal Oxidative Hydrogen Transfer’ (FOHT) for TS2.

  17. DFT Mechanistic Study of the Selective Terminal C-H Activation of n-Pentane with a Tungsten Allyl Nitrosyl Complex

    KAUST Repository

    Lee, Richmond; Tan, Davin; Liu, Chaoli; Li, Huaifeng; Guo, Hao; Shyue, Jing-Jong; Huang, Kuo-Wei

    2017-01-01

    Mechanistic insights into the selective C-H terminal activation of n-pentane with tungsten allyl nitrosyl complex reported by Legzdins were gained by employing density functional theory with B3LYP hybrid functional. Using Bader’s atom in molecules (AIM) analysis on the elementary steps of the hydrogen transfer process, TS1 and TS2, it was observed that the calculated H-transfer models were closely similar to Hall’s metal-assisted σ-bond metathesis through bond critical point (BCP) comparisons. One distinguishable feature was the fact that the formal oxidation state of the W changed in the concerted H-transfer process. To better differentiate, we term these processes as ‘Formal Reductive Hydrogen Transfer’ (FRHT) for TS1 and ‘Formal Oxidative Hydrogen Transfer’ (FOHT) for TS2.

  18. Isolation and Elucidation of 15-Acetylguanacone from Soursop ...

    African Journals Online (AJOL)

    ADOWIE PERE

    002/C. The structure of compound 200/A2 was elucidated using 1H-NMR spectroscopy, infrared spectroscopy .... Molecular Docking Experiments, Protein preparation ... ligand conformations in the binding sites through the .... Molecular dynamics simulation of diacetyl-guancone. Bioorgnic and Medicinal Chemistry 15: 4369-.

  19. Elucidation and in planta reconstitution of the parthenolide biosynthetic pathway

    DEFF Research Database (Denmark)

    Liu, Qing; Manzano, David; Tanić, Nikola

    2014-01-01

    Parthenolide, the main bioactive compound of the medicinal plant feverfew (Tanacetum parthenium), is a promising anti-cancer drug. However, the biosynthetic pathway of parthenolide has not been elucidated yet. Here we report on the isolation and characterization of all the genes from feverfew tha...

  20. Reducing NO(x) emissions from a nitric acid plant of domestic petrochemical complex: enhanced conversion in conventional radial-flow reactor of selective catalytic reduction process.

    Science.gov (United States)

    Abbasfard, Hamed; Hashemi, Seyed Hamid; Rahimpour, Mohammad Reza; Jokar, Seyyed Mohammad; Ghader, Sattar

    2013-01-01

    The nitric acid plant of a domestic petrochemical complex is designed to annually produce 56,400 metric tons (based on 100% nitric acid). In the present work, radial-flow spherical bed reactor (RFSBR) for selective catalytic reduction of nitric oxides (NO(x)) from the stack of this plant was modelled and compared with the conventional radial-flow reactor (CRFR). Moreover, the proficiency of a radial-flow (water or nitrogen) membrane reactor was also compared with the CRFR which was found to be inefficient at identical process conditions. In the RFSBR, the space between the two concentric spheres is filled by a catalyst. A mathematical model, including conservation of mass has been developed to investigate the performance of the configurations. The model was checked against the CRFR in a nitric acid plant located at the domestic petrochemical complex. A good agreement was observed between the modelling results and the plant data. The effects of some important parameters such as pressure and temperature on NO(x) conversion were analysed. Results show 14% decrease in NO(x) emission annually in RFSBR compared with the CRFR, which is beneficial for the prevention of NO(x) emission, global warming and acid rain.

  1. A bis(3-hydroxy-4-pyridinone)-EDTA derivative as a strong chelator for M3+ hard metal ions: complexation ability and selectivity.

    Science.gov (United States)

    Gama, Sofia; Dron, Paul; Chaves, Silvia; Farkas, Etelka; Santos, M Amélia

    2009-08-21

    The study of chelating compounds is very important to solve problems related to human metal overload. 3-Hydroxy-3-pyridinones (HP), namely deferiprone, have been clinically used for chelating therapy of Fe and Al over the last decade. A multi-disciplinary search for alternative molecules led us to develop poly-(3-hydroxy-4-pyridinones) to increase metal chelation efficacy. We present herein a complexation study of a new bis-(3-hydroxy-4-pyridinone)-EDTA derivative with a set of M(3+) hard metal ions (M = Fe, Al, Ga), as well as Zn(2+), a biologically relevant metal ion. Thus a systematic aqueous solution equilibrium study was performed using potentiometric and spectroscopic techniques (UV-Vis, NMR methods). These set of results enables the establishment of specific models as well as the determination of thermodynamic stability constants and coordination modes of the metal complexes. The results indicate that this ligand has a higher affinity for chelating to these hard metal ions than deferiprone, and that the coordination occurs mostly through the HP moieties. Furthermore, it was also found that this ligand has a higher selectivity for chelating to M(3+) hard metal ions (M = Fe, Al, Ga) than Zn(2+).

  2. Robust binding between carbon nitride nanosheets and a binuclear ruthenium(II) complex enabling durable, selective CO{sub 2} reduction under visible light in aqueous solution

    Energy Technology Data Exchange (ETDEWEB)

    Kuriki, Ryo; Ishitani, Osamu; Maeda, Kazuhiko [Department of Chemistry, School of Science, Tokyo Institute of Technology (Japan); Yamamoto, Muneaki; Yoshida, Tomoko [Advanced Research Institute for Natural Science and Technology, Osaka City University (Japan); Higuchi, Kimitaka; Yamamoto, Yuta; Akatsuka, Masato; Yagi, Shinya [Institute of Materials and Systems for Sustainability, Nagoya University (Japan); Lu, Daling [Suzukakedai Materials Analysis Division, Technical Department, Tokyo Institute of Technology, Yokohama (Japan)

    2017-04-18

    Carbon nitride nanosheets (NS-C{sub 3}N{sub 4}) were found to undergo robust binding with a binuclear ruthenium(II) complex (RuRu') even in basic aqueous solution. A hybrid material consisting of NS-C{sub 3}N{sub 4} (further modified with nanoparticulate Ag) and RuRu' promoted the photocatalytic reduction of CO{sub 2} to formate in aqueous media, in conjunction with high selectivity (approximately 98 %) and a good turnover number (>2000 with respect to the loaded Ru complex). These represent the highest values yet reported for a powder-based photocatalytic system during CO{sub 2} reduction under visible light in an aqueous environment. We also assessed the desorption of RuRu' from the Ag/C{sub 3}N{sub 4} surface, a factor that can contribute to a loss of activity. It was determined that desorption is not induced by salt additives, pH changes, or photoirradiation, which partly explains the high photocatalytic performance of this material. (copyright 2017 Wiley-VCH Verlag GmbH and Co. KGaA, Weinheim)

  3. Modeling of retention of some fission products and actinides by ion-exchange chromatography with a complexing agent. Application to the determination of selectivity coefficients

    International Nuclear Information System (INIS)

    Gurdale-Tack, K.; Aubert, M.; Chartier, F.

    2000-01-01

    For an accurate determination of the isotopic and elemental composition of americium (Am), curium (Cm), neodymium (Nd) and cesium (Cs) in spent nuclear fuels, performed by Thermal Ionization Mass Spectrometry (TIMS) and Inductively Coupled Plasma Mass Spectrometry (ICP-MS), it is necessary to separate these elements before analysis. This separation is mandatory because of isobaric interferences between americium and curium, neodymium and samarium (Sm) and between cesium and barium (Ba). This is the reason why Ba and Sm are analyzed with the other four elements. Separation is carried out by cation-exchange chromatography on a silica-based stationary phase in the presence of a complexing eluent. The complexing agent is 2-hydroxy-2-methyl butanoic acid (HMB), a monoprotic acid (HL) with a pK a of 3.6. Cations (M n+ ) interact with it to form ML y (n-y)+ complexes. Optimization of chromatographic separation conditions requires monitoring of the pH and eluent composition. The influence of each parameter on metal ion retention and on selectivity was investigated. The first studies on standard solutions with Sm(III), Nd(III), Cs(I) and Ba(II) showed that four conditions allow efficient separation. However, only one allows good separation with a real solution of spent nuclear fuels. This condition is a chelating agent concentration of 0.1 mol.l -1 and a pH of 4.2. With the other conditions, co-elution is observed for Cs(I) and Am(III). The overall results were used to study the retention mechanisms. The aim of this modeling is a closer knowledge of the form in which (M n+ and/or ML y (n-y)+ ...) each cationic element is extracted into the stationary phase. In fact, while cations can exist in the eluent in various forms depending on the analytical conditions, their forms may be different in the stationary phase. (authors)

  4. Microwave-Assisted Synthesis of Arene Ru(II Complexes Induce Tumor Cell Apoptosis Through Selectively Binding and Stabilizing bcl-2 G-Quadruplex DNA

    Directory of Open Access Journals (Sweden)

    Yanhua Chen

    2016-05-01

    Full Text Available A series of arene Ru(II complexes coordinated with phenanthroimidazole derivatives, [(η6-C6H6Ru(lCl]Cl(1b L = p-ClPIP = 2-(4-Chlorophenylimidazole[4,5f] 1,10-phenanthroline; 2b L = m-ClPIP = 2-(3-Chlorophenylimidazole[4,5f] 1,10-phenanthroline; 3b L = p-NPIP = 2-(4-Nitrophenylimidazole[4,5f] 1,10-phenanthroline; 4b L = m-NPIP = 2-(3-Nitrophenyl imidazole [4,5f] 1,10-phenanthroline were synthesized in yields of 89.9%–92.7% under conditions of microwave irradiation heating for 30 min to liberate four arene Ru(II complexes (1b, 2b, 3b, 4b. The anti-tumor activity of 1b against various tumor cells was evaluated by MTT assay. The results indicated that this complex blocked the growth of human lung adenocarcinoma A549 cells with an IC50 of 16.59 μM. Flow cytometric analysis showed that apoptosis of A549 cells was observed following treatment with 1b. Furthermore, the in vitro DNA-binding behaviors that were confirmed by spectroscopy indicated that 1b could selectively bind and stabilize bcl-2 G-quadruplex DNA to induce apoptosis of A549 cells. Therefore, the synthesized 1b has impressive bcl-2 G-quadruplex DNA-binding and stabilizing activities with potential applications in cancer chemotherapy.

  5. Heterobimetallic transition metal/rare earth metal bifunctional catalysis: a Cu/Sm/Schiff base complex for syn-selective catalytic asymmetric nitro-Mannich reaction.

    Science.gov (United States)

    Handa, Shinya; Gnanadesikan, Vijay; Matsunaga, Shigeki; Shibasaki, Masakatsu

    2010-04-07

    The full details of a catalytic asymmetric syn-selective nitro-Mannich reaction promoted by heterobimetallic Cu/Sm/dinucleating Schiff base complexes are described, demonstrating the effectiveness of the heterobimetallic transition metal/rare earth metal bifunctional catalysis. The first-generation system prepared from Cu(OAc)(2)/Sm(O-iPr)(3)/Schiff base 1a = 1:1:1 with an achiral phenol additive was partially successful for achieving the syn-selective catalytic asymmetric nitro-Mannich reaction. The substrate scope and limitations of the first-generation system remained problematic. After mechanistic studies on the catalyst prepared from Sm(O-iPr)(3), we reoptimized the catalyst preparation method, and a catalyst derived from Sm(5)O(O-iPr)(13) showed broader substrate generality as well as higher reactivity and stereoselectivity compared to Sm(O-iPr)(3). The optimal system with Sm(5)O(O-iPr)(13) was applicable to various aromatic, heteroaromatic, and isomerizable aliphatic N-Boc imines, giving products in 66-99% ee and syn/anti = >20:1-13:1. Catalytic asymmetric synthesis of nemonapride is also demonstrated using the catalyst derived from Sm(5)O(O-iPr)(13).

  6. Crystal structure of human cyclin-dependent kinase-2 complex with MK2 inhibitor TEI-I01800: insight into the selectivity

    Energy Technology Data Exchange (ETDEWEB)

    Fujino, Aiko; Fukushima, Kei; Kubota, Takaharu; Kosugi, Tomomi; Takimoto-Kamimura, Midori, E-mail: m.kamimura@teijin.co.jp [Teijin Pharma Limited, 4-3-2 Asahigaoka, Hino-shi, Tokyo 191-8512 (Japan)

    2013-11-01

    The Gly-rich loop of cyclin-dependent kinase 2 (CDK2) bound to TEI-I01800 as an MK2 specific inhibitor forms a β-sheet which is a common structure in CDK2–ligand complexes. Here, the reason why TEI-I01800 does not become a strong inhibitor against CDK2 based on the conformation of TEI-I01800 is presented. Mitogen-activated protein kinase-activated protein kinase 2 (MK2 or MAPKAP-K2) is a Ser/Thr kinase from the p38 mitogen-activated protein kinase signalling pathway and plays an important role in inflammatory diseases. The crystal structure of the MK2–TEI-I01800 complex has been reported; its Gly-rich loop was found to form an α-helix, not a β-sheet as has been observed for other Ser/Thr kinases. TEI-I01800 is 177-fold selective against MK2 compared with CDK2; in order to understand the inhibitory mechanism of TEI-I01800, the cyclin-dependent kinase 2 (CDK2) complex structure with TEI-I01800 was determined at 2.0 Å resolution. Interestingly, the Gly-rich loop of CDK2 formed a β-sheet that was different from that of MK2. In MK2, TEI-I01800 changed the secondary structure of the Gly-rich loop from a β-sheet to an α-helix by collision between Leu70 and a p-ethoxyphenyl group at the 7-position and bound to MK2. However, for CDK2, TEI-I01800 bound to CDK2 without this structural change and lost the interaction with the substituent at the 7-position. In summary, the results of this study suggest that the reason for the selectivity of TEI-I01800 is the favourable conformation of TEI-I01800 itself, making it suitable for binding to the α-form MK2.

  7. Drug Elucidation: Invertebrate Genetics Sheds New Light on the Molecular Targets of CNS Drugs

    Directory of Open Access Journals (Sweden)

    Donard S. Dwyer

    2014-07-01

    Full Text Available Many important drugs approved to treat common human diseases were discovered by serendipity, without a firm understanding of their modes of action. As a result, the side effects and interactions of these medications are often unpredictable, and there is limited guidance for improving the design of next-generation drugs. Here, we review the innovative use of simple model organisms, especially Caenorhabditis elegans, to gain fresh insights into the complex biological effects of approved CNS medications. Whereas drug discovery involves the identification of new drug targets and lead compounds/biologics, and drug development spans preclinical testing to FDA approval, drug elucidation refers to the process of understanding the mechanisms of action of marketed drugs by studying their novel effects in model organisms. Drug elucidation studies have revealed new pathways affected by antipsychotic drugs, e.g., the insulin signaling pathway, a trace amine receptor and a nicotinic acetylcholine receptor. Similarly, novel targets of antidepressant drugs and lithium have been identified in C. elegans, including lipid-binding/transport proteins and the SGK-1 signaling pathway, respectively. Elucidation of the mode of action of anesthetic agents has shown that anesthesia can involve mitochondrial targets, leak currents and gap junctions. The general approach reviewed in this article has advanced our knowledge about important drugs for CNS disorders and can guide future drug discovery efforts.

  8. Novel comprehensive multidimensional liquid chromatography approach for elucidation of the microbosphere of shikimate-producing Escherichia coli SP1.1/pKD15.071 strain.

    Science.gov (United States)

    Cacciola, Francesco; Mangraviti, Domenica; Rigano, Francesca; Donato, Paola; Dugo, Paola; Mondello, Luigi; Cortes, Hernan J

    2018-06-01

    Shikimic acid is a intermediate of aromatic amino acid biosynthesis and the preferred starting material for production of the most commonly prescribed anti-influenza drug, Tamiflu. Its six-membered carbocyclic ring is adorned with several chiral centers and various functionalities, making shikimic acid a valuable chiral synthon. When microbially-produced, in addition to shikimic acid, numerous other metabolites are exported out of the cytoplasm and accumulate in the culture medium. This extracellular matrix of metabolites is referred to as the microbosphere. Due to the high sample complexity, in this study, the microbosphere of shikimate-producing Escherichia coli SP1.1/pKD15.071 was analyzed by liquid chromatography and comprehensive two-dimensional liquid chromatography coupled to photodiode array and mass spectrometry detection. GC analysis of the trimethylsilyl derivatives was also carried out in order to support the elucidation of the selected metabolites in the microbosphere. The elucidation of the metabolic fraction of this bacterial strain might be of valid aid for improving, through genetic changes, the concentration and yield of shikimic acid synthesized from glucose. Graphical abstract.

  9. Selective, autoantibody-immune complex mediated proportional and functional changes of specific NK-cell subsets in early seropositive but not seronegative rheumatoid arthritis

    NARCIS (Netherlands)

    Chalan, P.; Brouwer, Liesbeth; Bijzet, J.; Kroesen, B.-J.; Boots, Annemieke

    2015-01-01

    Background: Despite substantial data demonstrating NK-cell impairment in rheumatoid arthritis (RA), the exact role of NK-cells in RA immunopathogenesis remains unclear. Objectives: We studied the involvement of CD56dim and CD56bright NK-cells in the early stages of RA development to elucidate their

  10. Toward a Method for Exposing and Elucidating Ethical Issues with Human Cognitive Enhancement Technologies.

    Science.gov (United States)

    Hofmann, Bjørn

    2017-04-01

    To develop a method for exposing and elucidating ethical issues with human cognitive enhancement (HCE). The intended use of the method is to support and facilitate open and transparent deliberation and decision making with respect to this emerging technology with great potential formative implications for individuals and society. Literature search to identify relevant approaches. Conventional content analysis of the identified papers and methods in order to assess their suitability for assessing HCE according to four selection criteria. Method development. Amendment after pilot testing on smart-glasses. Based on three existing approaches in health technology assessment a method for exposing and elucidating ethical issues in the assessment of HCE technologies was developed. Based on a pilot test for smart-glasses, the method was amended. The method consists of six steps and a guiding list of 43 questions. A method for exposing and elucidating ethical issues in the assessment of HCE was developed. The method provides the ground work for context specific ethical assessment and analysis. Widespread use, amendments, and further developments of the method are encouraged.

  11. Elucidating rhizosphere processes by mass spectrometry – A review

    Energy Technology Data Exchange (ETDEWEB)

    Rugova, Ariana [Division of Analytical Chemistry, Department of Chemistry, University of Natural Resources and Life Sciences-BOKU, Vienna (Austria); Puschenreiter, Markus [Department of Forest and Soil Sciences, Rhizosphere Ecology and Biogeochemistry Group, University of Natural Resources and Life Sciences-BOKU, Vienna (Austria); Koellensperger, Gunda [Institute of Analytical Chemistry, Faculty of Chemistry, University of Vienna, Vienna (Austria); Hann, Stephan, E-mail: stephan.hann@boku.ac.at [Division of Analytical Chemistry, Department of Chemistry, University of Natural Resources and Life Sciences-BOKU, Vienna (Austria)

    2017-03-01

    The presented review discusses state-of-the-art mass spectrometric methods, which have been developed and applied for investigation of chemical processes in the soil-root interface, the so-called rhizosphere. Rhizosphere soil's physical and chemical characteristics are to a great extent influenced by a complex mixture of compounds released from plant roots, i.e. root exudates, which have a high impact on nutrient and trace element dynamics in the soil-root interface as well as on microbial activities or soil physico-chemical characteristics. Chemical characterization as well as accurate quantification of the compounds present in the rhizosphere is a major prerequisite for a better understanding of rhizosphere processes and requires the development and application of advanced sampling procedures in combination with highly selective and sensitive analytical techniques. During the last years, targeted and non-targeted mass spectrometry-based methods have emerged and their combination with specific separation methods for various elements and compounds of a wide polarity range have been successfully applied in several studies. With this review we critically discuss the work that has been conducted within the last decade in the context of rhizosphere research and elemental or molecular mass spectrometry emphasizing different separation techniques as GC, LC and CE. Moreover, selected applications such as metal detoxification or nutrient acquisition will be discussed regarding the mass spectrometric techniques applied in studies of root exudates in plant-bacteria interactions. Additionally, a more recent isotope probing technique as novel mass spectrometry based application is highlighted. - Highlights: • State-of-the-art mass spectrometry methods developed and applied in rhizosphere research are reviewed. • Elemental and molecular mass spectrometry emphasizing different separation techniques (GC, LC or CE) are discussed. • Case studies on metal detoxification

  12. Elucidating rhizosphere processes by mass spectrometry - A review.

    Science.gov (United States)

    Rugova, Ariana; Puschenreiter, Markus; Koellensperger, Gunda; Hann, Stephan

    2017-03-01

    The presented review discusses state-of-the-art mass spectrometric methods, which have been developed and applied for investigation of chemical processes in the soil-root interface, the so-called rhizosphere. Rhizosphere soil's physical and chemical characteristics are to a great extent influenced by a complex mixture of compounds released from plant roots, i.e. root exudates, which have a high impact on nutrient and trace element dynamics in the soil-root interface as well as on microbial activities or soil physico-chemical characteristics. Chemical characterization as well as accurate quantification of the compounds present in the rhizosphere is a major prerequisite for a better understanding of rhizosphere processes and requires the development and application of advanced sampling procedures in combination with highly selective and sensitive analytical techniques. During the last years, targeted and non-targeted mass spectrometry-based methods have emerged and their combination with specific separation methods for various elements and compounds of a wide polarity range have been successfully applied in several studies. With this review we critically discuss the work that has been conducted within the last decade in the context of rhizosphere research and elemental or molecular mass spectrometry emphasizing different separation techniques as GC, LC and CE. Moreover, selected applications such as metal detoxification or nutrient acquisition will be discussed regarding the mass spectrometric techniques applied in studies of root exudates in plant-bacteria interactions. Additionally, a more recent isotope probing technique as novel mass spectrometry based application is highlighted. Copyright © 2017 Elsevier B.V. All rights reserved.

  13. Elucidating rhizosphere processes by mass spectrometry – A review

    International Nuclear Information System (INIS)

    Rugova, Ariana; Puschenreiter, Markus; Koellensperger, Gunda; Hann, Stephan

    2017-01-01

    The presented review discusses state-of-the-art mass spectrometric methods, which have been developed and applied for investigation of chemical processes in the soil-root interface, the so-called rhizosphere. Rhizosphere soil's physical and chemical characteristics are to a great extent influenced by a complex mixture of compounds released from plant roots, i.e. root exudates, which have a high impact on nutrient and trace element dynamics in the soil-root interface as well as on microbial activities or soil physico-chemical characteristics. Chemical characterization as well as accurate quantification of the compounds present in the rhizosphere is a major prerequisite for a better understanding of rhizosphere processes and requires the development and application of advanced sampling procedures in combination with highly selective and sensitive analytical techniques. During the last years, targeted and non-targeted mass spectrometry-based methods have emerged and their combination with specific separation methods for various elements and compounds of a wide polarity range have been successfully applied in several studies. With this review we critically discuss the work that has been conducted within the last decade in the context of rhizosphere research and elemental or molecular mass spectrometry emphasizing different separation techniques as GC, LC and CE. Moreover, selected applications such as metal detoxification or nutrient acquisition will be discussed regarding the mass spectrometric techniques applied in studies of root exudates in plant-bacteria interactions. Additionally, a more recent isotope probing technique as novel mass spectrometry based application is highlighted. - Highlights: • State-of-the-art mass spectrometry methods developed and applied in rhizosphere research are reviewed. • Elemental and molecular mass spectrometry emphasizing different separation techniques (GC, LC or CE) are discussed. • Case studies on metal detoxification and

  14. Elucidating Functional Aspects of P-type ATPases

    DEFF Research Database (Denmark)

    Autzen, Henriette Elisabeth

    2015-01-01

    and helped enlighten how thapsigargin, a potent inhibitor of SERCA1a, depends on a water mediated hydrogen bond network when bound to SERCA1a. Furthermore, molecular dynamics (MD) simulations of the same P-type ATPase were used to assess a long-standing question whether cholesterol affects SERCA1a through...... similar to that of the wild type (WT) protein. The discrepancy between the newly determined crystal structure of LpCopA and the functional manifestations of the missense mutation in human CopA, could indicate that LpCopA is insufficient in structurally elucidating the effect of disease-causing mutations...... in the human CopA proteins. MD simulations, which combine coarse-grained (CG) and atomistic procedures, were set up in order to elucidate mechanistic implications exerted by the lipid bilayer on LpCopA. The MD simulations of LpCopA corroborated previous and new in vivo activity data and showed...

  15. Ravynic acid, an antibiotic polyeneyne tetramic acid from Penicillium sp. elucidated through synthesis.

    Science.gov (United States)

    Myrtle, J D; Beekman, A M; Barrow, R A

    2016-09-21

    A new antibiotic natural product, ravynic acid, has been isolated from a Penicillium sp. of fungus, collected from Ravensbourne National Park. The 3-acylpolyenyne tetramic acid structure was definitively elucidated via synthesis. Highlights of the synthetic method include the heat induced formation of the 3-acylphosphorane tetramic acid and a selective Wittig cross-coupling to efficiently prepare the natural compounds carbon skeleton. The natural compound was shown to inhibit the growth of Staphylococcus aureus down to concentrations of 2.5 µg mL(-1).

  16. Elucidation of Molecular Pathogenic Mechanisms of Norrie Disease

    OpenAIRE

    Luhmann, Ulrich F.O.

    2010-01-01

    Summary Norrie disease (ND) is a rare X-linked recessive congenital blindness, sometimes associated with deafness and mental retardation. In this thesis the molecular pathogenic mechanisms of this syndrome should be elucidated using the Ndph knockout mouse model. Gene expression studies but also histology and protein biochemistry were used to characterize the affected organs, eye and brain. Gene expression analyses of eyes at p21 using cDNA subtrac...

  17. Elucidate Innovation Performance of Technology-driven Mergers and Acquisitions

    Energy Technology Data Exchange (ETDEWEB)

    Huang, L.; Wang, K.; Yu, H.; Shang, L.; Mitkova, L.

    2016-07-01

    The importance and value of Mergers and Acquisitions (M&As) have increased with the expectancy to obtain key technology capabilities and rapid impact on innovation. This article develops an original analytical framework to elucidate the impact of the technology and product relatedness (similarity/complementarity) of the Technology-driven M&A’ partners on post-innovation performance. We present results drawing on a multiple case studies of Chinese High-Tech firms from three industries. (Author)

  18. Next generation transcriptomics and genomics elucidate biological complexity of microglia in health and disease

    NARCIS (Netherlands)

    Wes, Paul D; Holtman, Inge R; Boddeke, Erik W G M; Möller, Thomas; Eggen, Bart J L

    2015-01-01

    Genome-wide expression profiling technology has resulted in detailed transcriptome data for a wide range of tissues, conditions and diseases. In neuroscience, expression datasets were mostly generated using whole brain tissue samples, resulting in data from a mixture of cell types, including glial

  19. NMR of alpha-synuclein-polyamine complexes elucidates the mechanism and kinetics of induced aggregation

    NARCIS (Netherlands)

    Fernández, Claudio O.; Hoyer, Wolfgang; Zweckstetter, Markus; Jares-Erijman, Elizabeth A.; Subramaniam, Vinod; Griesinger, Christian; Jovin, Thomas M.

    2004-01-01

    The aggregation of α-synuclein is characteristic of Parkinson's disease (PD) and other neurodegenerative synucleinopathies. The 140-aa protein is natively unstructured; thus, ligands binding to the monomeric form are of therapeutic interest. Biogenic polyamines promote the aggregation of α-synuclein

  20. Constructing Markov State Models to elucidate the functional conformational changes of complex biomolecules

    KAUST Repository

    Wang, Wei; Cao, Siqin; Zhu, Lizhe; Huang, Xuhui

    2017-01-01

    bioengineering applications and rational drug design. Constructing Markov State Models (MSMs) based on large-scale molecular dynamics simulations has emerged as a powerful approach to model functional conformational changes of the biomolecular system

  1. Exploring the selectivity of auto-inducer complex with LuxR using molecular docking, mutational studies and molecular dynamics simulations

    Science.gov (United States)

    Rajamanikandan, Sundaraj; Srinivasan, Pappu

    2017-03-01

    Bacteria communicate with one another using extracellular signaling molecules called auto-inducers (AHLs), a process termed as quorum sensing. The quorum sensing process allows bacteria to regulate various physiological activities. In this regard, quorum sensing master regulator LuxR from Vibrio harveyi represents an attractive therapeutic target for the development of novel anti-quorum sensing agents. Eventhough the binding of AHL complex with LuxR is evidenced in earlier reports, but their mode of binding is not clearly determined. Therefore, in the present work, molecular docking, in silico mutational studies, molecular dynamics simulations and free energy calculations were performed to understand the selectivity of AHL into the binding site of LuxR. The results revealed that Asn133 and Gln137 residues play a crucial role in recognizing AHL more effectively into the binding site of LuxR with good binding free energy. In addition to that, the carbonyl group presents in the lactone ring and amide group of AHL plays a vital role in the formation of hydrogen bond interactions with the protein. Further, structure based virtual screening was performed using ChemBridge database to screen potent lead molecules against LuxR. 4-benzyl-2-pyrrolidinone and N-[2(1-cyclohexen-1-yl) enthyl]-N'(2-ethoxyphenyl) were selected based on dock score, binding affinity and mode of interactions with the receptor. Furthermore, binding free energy, density functional theory and ADME prediction were performed to rank the lead molecules. Thus, the identified lead molecules can be used for the development of anti-quorum sensing drugs.

  2. Elucidating Mechanisms of Molecular Recognition Between Human Argonaute and miRNA Using Computational Approaches

    KAUST Repository

    Jiang, Hanlun

    2016-12-06

    MicroRNA (miRNA) and Argonaute (AGO) protein together form the RNA-induced silencing complex (RISC) that plays an essential role in the regulation of gene expression. Elucidating the underlying mechanism of AGO-miRNA recognition is thus of great importance not only for the in-depth understanding of miRNA function but also for inspiring new drugs targeting miRNAs. In this chapter we introduce a combined computational approach of molecular dynamics (MD) simulations, Markov state models (MSMs), and protein-RNA docking to investigate AGO-miRNA recognition. Constructed from MD simulations, MSMs can elucidate the conformational dynamics of AGO at biologically relevant timescales. Protein-RNA docking can then efficiently identify the AGO conformations that are geometrically accessible to miRNA. Using our recent work on human AGO2 as an example, we explain the rationale and the workflow of our method in details. This combined approach holds great promise to complement experiments in unraveling the mechanisms of molecular recognition between large, flexible, and complex biomolecules.

  3. Elucidating Mechanisms of Molecular Recognition Between Human Argonaute and miRNA Using Computational Approaches.

    Science.gov (United States)

    Jiang, Hanlun; Zhu, Lizhe; Héliou, Amélie; Gao, Xin; Bernauer, Julie; Huang, Xuhui

    2017-01-01

    MicroRNA (miRNA) and Argonaute (AGO) protein together form the RNA-induced silencing complex (RISC) that plays an essential role in the regulation of gene expression. Elucidating the underlying mechanism of AGO-miRNA recognition is thus of great importance not only for the in-depth understanding of miRNA function but also for inspiring new drugs targeting miRNAs. In this chapter we introduce a combined computational approach of molecular dynamics (MD) simulations, Markov state models (MSMs), and protein-RNA docking to investigate AGO-miRNA recognition. Constructed from MD simulations, MSMs can elucidate the conformational dynamics of AGO at biologically relevant timescales. Protein-RNA docking can then efficiently identify the AGO conformations that are geometrically accessible to miRNA. Using our recent work on human AGO2 as an example, we explain the rationale and the workflow of our method in details. This combined approach holds great promise to complement experiments in unraveling the mechanisms of molecular recognition between large, flexible, and complex biomolecules.

  4. Dynamical structure analysis of crystalline-state reaction and elucidation of chemical reactivity in crystalline environment

    International Nuclear Information System (INIS)

    Ohashi, Yuji

    2010-01-01

    It was found that a chiral alkyl group bonded to the cobalt atom in a cobalt complex crystal was racemized with retention of the single crystal form on exposure to visible light. Such reactions, which are called crystalline-state reactions, have been found in a variety of cobalt complex crystals. The concept of reaction cavity was introduced to explain the reaction rate quantitatively and the chirality of the photo-product. The new diffractometers and detectors were made for rapid data collection. The reaction mechanism was also elucidated using neutron diffraction analysis. The unstable reaction intermediates were analyzed using cryo-trapping method. The excited-state structures were obtained at the equilibrium state between ground and excited states. (author)

  5. Spanish normative studies in young adults (NEURONORMA young adults project): norms for the Rey-Osterrieth Complex Figure (copy and memory) and Free and Cued Selective Reminding Test.

    Science.gov (United States)

    Palomo, R; Casals-Coll, M; Sánchez-Benavides, G; Quintana, M; Manero, R M; Rognoni, T; Calvo, L; Aranciva, F; Tamayo, F; Peña-Casanova, J

    2013-05-01

    The Rey-Osterrieth Complex Figure (ROCF) and the Free and Cued Selective Reminding Test (FCSRT) are widely used in clinical practice. The ROCF assesses visual perception, constructional praxis, and visuo-spatial memory. The FCSRT assesses verbal learning and memory. In this study, as part of the Spanish normative studies project in young adults (NEURONORMA young adults), we present age- and education-adjusted normative data for both tests obtained by using linear regression techniques. The sample consisted of 179 healthy participants ranging in age from 18 to 49 years. We provide tables for converting raw scores to scaled scores in addition to tables with scores adjusted by socio-demographic factors. The results showed that education affects scores for some of the memory tests and the figure-copying task. Age was only found to have an effect on the performance of visuo-spatial memory tests, and the effect of sex was negligible. The normative data obtained will be extremely useful in the clinical neuropsychological evaluation of young Spanish adults. Copyright © 2011 Sociedad Española de Neurología. Published by Elsevier Espana. All rights reserved.

  6. The use of laser-induced fluorescence or ultraviolet detectors for sensitive and selective analysis of tobramycin or erythropoietin in complex samples

    Science.gov (United States)

    Ahmed, Hytham M.; Ebeid, Wael B.

    2015-05-01

    Complex samples analysis is a challenge in pharmaceutical and biopharmaceutical analysis. In this work, tobramycin (TOB) analysis in human urine samples and recombinant human erythropoietin (rhEPO) analysis in the presence of similar protein were selected as representative examples of such samples analysis. Assays of TOB in urine samples are difficult because of poor detectability. Therefore laser induced fluorescence detector (LIF) was combined with a separation technique, micellar electrokinetic chromatography (MEKC), to determine TOB through derivatization with fluorescein isothiocyanate (FITC). Borate was used as background electrolyte (BGE) with negative-charged mixed micelles as additive. The method was successively applied to urine samples. The LOD and LOQ for Tobramycin in urine were 90 and 200 ng/ml respectively and recovery was >98% (n = 5). All urine samples were analyzed by direct injection without sample pre-treatment. Another use of hyphenated analytical technique, capillary zone electrophoresis (CZE) connected to ultraviolet (UV) detector was also used for sensitive analysis of rhEPO at low levels (2000 IU) in the presence of large amount of human serum albumin (HSA). Analysis of rhEPO was achieved by the use of the electrokinetic injection (EI) with discontinuous buffers. Phosphate buffer was used as BGE with metal ions as additive. The proposed method can be used for the estimation of large number of quality control rhEPO samples in a short period.

  7. Adaptive algorithm of selecting optimal variant of errors detection system for digital means of automation facility of oil and gas complex

    Science.gov (United States)

    Poluyan, A. Y.; Fugarov, D. D.; Purchina, O. A.; Nesterchuk, V. V.; Smirnova, O. V.; Petrenkova, S. B.

    2018-05-01

    To date, the problems associated with the detection of errors in digital equipment (DE) systems for the automation of explosive objects of the oil and gas complex are extremely actual. Especially this problem is actual for facilities where a violation of the accuracy of the DE will inevitably lead to man-made disasters and essential material damage, at such facilities, the diagnostics of the accuracy of the DE operation is one of the main elements of the industrial safety management system. In the work, the solution of the problem of selecting the optimal variant of the errors detection system of errors detection by a validation criterion. Known methods for solving these problems have an exponential valuation of labor intensity. Thus, with a view to reduce time for solving the problem, a validation criterion is compiled as an adaptive bionic algorithm. Bionic algorithms (BA) have proven effective in solving optimization problems. The advantages of bionic search include adaptability, learning ability, parallelism, the ability to build hybrid systems based on combining. [1].

  8. Impact of clonal competition for peptide-MHC complexes on the CD8[superscript +] T-cell repertoire selection in a persistent viral infection

    Energy Technology Data Exchange (ETDEWEB)

    Wynn, Katherine K.; Fulton, Zara; Cooper, Leanne; Silins, Sharon L.; Gras, Stephanie; Archbold, Julia K.; Tynan, Fleur E.; Miles, John J.; McCluskey, James; Burrows, Scott R.; Rossjohn, Jamie; Khanna, Rajiv (Monash); (Queensland Inst. of Med. Rsrch.); (Melbourne)

    2008-04-29

    CD8{sup +} T-cell responses to persistent viral infections are characterized by the accumulation of an oligoclonal T-cell repertoire and a reduction in the naive T-cell pool. However, the precise mechanism for this phenomenon remains elusive. Here we show that human cytomegalovirus (HCMV)-specific CD8{sup +} T cells recognizing distinct epitopes from the pp65 protein and restricted through an identical HLA class I allele (HLA B*3508) exhibited either a highly conserved public T-cell repertoire or a private, diverse T-cell response, which was uniquely altered in each donor following in vitro antigen exposure. Selection of a public T-cell receptor (TCR) was coincident with an atypical major histocompatibility complex (MHC)-peptide structure, in that the epitope adopted a helical conformation that bulged from the peptide-binding groove, while a diverse TCR profile was observed in response to the epitope that formed a flatter, more 'featureless' landscape. Clonotypes with biased TCR usage demonstrated more efficient recognition of virus-infected cells, a greater CD8 dependency, and were more terminally differentiated in their phenotype when compared with the T cells expressing diverse TCR. These findings provide new insights into our understanding on how the biology of antigen presentation in addition to the structural features of the pMHC-I might shape the T-cell repertoire and its phenotype.

  9. An azine based sensor for selective detection of Cu2 + ions and its copper complex for sensing of phosphate ions in physiological conditions and in living cells

    Science.gov (United States)

    Tiwari, Karishma; Kumar, Sumit; Kumar, Vipan; Kaur, Jeevanjot; Arora, Saroj; Mahajan, Rakesh Kumar

    2018-02-01

    A simple and cost effective unsymmetrical azine based Schiff base, 5-diethylamino-2-[(2-hydroxy-benzylidene)hydrazonomethyl]-phenol (1) was synthesized which selectively detect Cu2 + ions in the presence of other competitive ions through ;naked eye; in physiological conditions (EtOH-buffer (1:1, v/v, HEPES 10 mM, pH = 7.4)). The presence of Cu2 + induce color change from light yellow green to yellow with the appearance of a new band at 450 nm in UV-Vis spectra of Schiff base 1. The fluorescence of Schiff base 1 (10 μM) was quenched completely in the presence of 2.7 equiv. of Cu2 + ions. Sub-micromolar limit of detection (LOD = 3.4 × 10- 7 M), efficient Stern-Volmer quenching constant (KSV = 1.8 × 105 L mol- 1) and strong binding constant (log Kb = 5.92) has been determined with the help of fluorescence titration profile. Further, 1 - Cu2 + complex was employed for the detection of phosphate ions (PO43 -, HPO42 - and H2PO4-) at micromolar concentrations in EtOH-buffer of pH 7.4 based on fluorescence recovery due to the binding of Cu2 + with phosphate ions. Solubility at low concentration in aqueous medium, longer excitation (406 nm) and emission wavelength (537 nm), and biocompatibility of Schiff base 1 formulates its use in live cell imaging.

  10. Study of the selectivity of poly-nitrogenous extracting molecules in the complexation of actinides (III) and lanthanides (III) in solution in anhydrous pyridine; Etude de la selectivite de molecules extractantes polyazotees dans la complexation des actinides (III) et des lanthanides (III) en solution dans la pyridine anhydre

    Energy Technology Data Exchange (ETDEWEB)

    Riviere, Ch

    2000-10-05

    The aim of this work is to better understand the factors which contribute to the separation of lanthanides(III) and actinides(III). Polydentate nitrogenous molecules present an interesting selectivity. A thermodynamic study of the complexation in pyridine of lanthanide and uranium by the bipyridine ligand (bipy) has been carried out. The formation constants and the thermodynamic values of the different complexes have been determined. It has been shown that the bipy complexes formation is controlled by the enthalpy and unfavored by the entropy. The conductometry has revealed too a significant difference in the uranium and lanthanides complexation by the bipyridine ligand. The use of the phenanthroline ligand induces a better complexation of the metallic ions but the selectivity is not improved. On the other hand, the decrease of the basicity and the increase of the ligand denticity (for instance in the case of the use of ter-pyridine) favour the selectivity without improving the complexation. The selectivity difference for the complexation of actinides(III) and lanthanides(III) by the different studied ligands (independent systems) has been confirmed by experiments of inter-metals competition. (O.M.)

  11. Study to elucidate formation pathways of selected roast-smelling odorants upon extrusion cooking.

    Science.gov (United States)

    Davidek, Tomas; Festring, Daniel; Dufossé, Thierry; Novotny, Ondrej; Blank, Imre

    2013-10-30

    The formation pathways of the N-containing roast-smelling compounds 2-acetyl-1-pyrroline, 2-acetyl-1(or 3),4,5,6-tetrahydropyridine, and their structural analogues 2-propionyl-1-pyrroline and 2-propionyl-1(or 3),4,5,6-tetrahydropyridine were studied upon extrusion cooking using the CAMOLA approach. The samples were produced under moderate extrusion conditions (135 °C, 20% moisture, 400 rpm) employing a rice-based model recipe enriched with flavor precursors ([U-(13)C6]-D-glucose, D-glucose, glycine, L-proline, and L-ornithine). The obtained data indicate that the formation of these compounds upon extrusion follows pathways similar to those reported for nonsheared model systems containing D-glucose and L-proline. 2-Acetyl-1-pyrroline is formed (i) by acylation of 1-pyrroline via C2 sugar fragments (major pathway) and (ii) via ring-opening of 1-pyrroline incorporating C3 sugar fragments (minor pathway), whereas 2-propionyl-1-pyrroline incorporates exclusively C3 sugar fragments. 2-Acetyl-1(or 3),4,5,6-tetrahydropyridine and the corresponding propionyl analogue incorporate C3 and C4 sugar fragments, respectively. In addition, it has been shown that the formation of 2-acetyl-1-pyrroline in low-moisture systems depends on the pH value of the reaction mixture.

  12. Structure elucidation of some insect pheromones : a contribution to the development of selective pest control agents

    NARCIS (Netherlands)

    Persoons, C.J.

    1977-01-01

    The use of pheromones is one of the methods currently being investigated intensively as an alternative method of insect control. The various ways in which pheromones might be used in insect control programmes are briefly discussed in Chapter 1.

    Chapter 2 gives a detailed description of the

  13. Elucidating the role of select cytoplasmic proteins in altering diffusion of integrin receptors.

    Science.gov (United States)

    Sander, Suzanne; Arora, Neha; Smith, Emily A

    2012-06-01

    Cytoplasmic proteins that affect integrin diffusion in the cell membrane are identified using a combination of fluorescence recovery after photobleaching (FRAP) and RNA interference. Integrin receptors are essential for many cellular events, and alterations in lateral diffusion are one mechanism for modulating their function. In cells expressing native cytoplasmic protein concentrations and spread on a slide containing integrin extracellular ligand, 45 ± 2% of the integrin is mobile with a time-dependent 5.2 ± 0.9 × 10(-9) cm(2)/s diffusion coefficient at 1 s. The time exponent is 0.90 ± 0.07, indicating integrin diffusion moderately slows at longer times. The role of a specific cytoplasmic protein in altering integrin diffusion is revealed through changes in the FRAP curve after reducing the cytoplasmic protein's expression. Decreased expression of cytoplasmic proteins rhea, focal adhesion kinase (FAK), or steamer duck decreases the integrin mobile fraction. For rhea and FAK, there is a concomitant shift to Brownian (i.e., time-independent) diffusion at reduced concentrations of these proteins. In contrast, when the expression of actin 42A, dreadlocks, paxillin, integrin-linked kinase (ILK), or vinculin is reduced, integrin diffusion generally becomes more constrained with an increase in the integrin mobile fraction. This same change in integrin diffusion is measured in the absence of integrin extracellular ligand. The results indicate breaking the extracellular ligand-integrin-cytoskeletal linkage alters integrin diffusion properties, and, in most cases, there is no correlation between integrin and lipid diffusion properties.

  14. Elucidation of the electrochromic mechanism of nanostructured iron oxides films

    Energy Technology Data Exchange (ETDEWEB)

    Garcia-Lobato, M.A.; Martinez, Arturo I.; Castro-Roman, M. [Center for Research and Advanced Studies of the National Polytechnic Institute, Cinvestav Campus Saltillo, Carr. Saltillo-Monterrey Km. 13, Ramos Arizpe, Coah. 25900 (Mexico); Perry, Dale L. [Mail Stop 70A1150, Lawrence Berkeley National Laboratory, University of California, Berkeley, CA 94720 (United States); Zarate, R.A. [Departamento de Fisica, Facultad de Ciencias, Universidad Catolica del Norte, Casilla 1280, Antofagasta (Chile); Escobar-Alarcon, L. (Departamento de Fisica, Instituto Nacional de Investigaciones Nucleares, A.P. 18-1027, 11801 Mexico)

    2011-02-15

    Nanostructured hematite thin films were electrochemically cycled in an aqueous solution of LiOH. Through optical, structural, morphological, and magnetic measurements, the coloration mechanism of electrochromic iron oxide thin films was elucidated. The conditions for double or single electrochromic behavior are given in this work. During the electrochemical cycling, it was found that topotactic transformations of hexagonal crystal structures are favored; i.e. {alpha}-Fe{sub 2}O{sub 3} to Fe(OH){sub 2} and subsequently to {delta}-FeOOH. These topotactic redox reactions are responsible for color changes of iron oxide films. (author)

  15. Elucidation of reaction mechanism for m -cresol hydrodeoxygenation over Fe based catalysts: A kinetic study

    Energy Technology Data Exchange (ETDEWEB)

    Hong, Yongchun; Wang, Yong

    2017-09-01

    Fe based catalysts are promising for hydrodeoxygenation (HDO) of lignin derived phenolics due to their high selectivity for aromatics. In this work, the reaction mechanism of m-cresol HDO on Fe catalysts and the kinetic consequence with Pd addition were elucidated by examining the effect of H2, H2O and m-cresol pressures on toluene formation rate on Fe and PdFe catalysts. A direct CO bond cleavage mechanism is proposed for HDO catalysis on both Fe and PdFe catalysts, while Pd provides a facilitated reaction pathway at the PdFe interface and therefore promotes the catalysis on Fe without changing the high selectivity towards aromatics.

  16. Computer-assisted methods for molecular structure elucidation: realizing a spectroscopist's dream

    Directory of Open Access Journals (Sweden)

    Elyashberg Mikhail

    2009-03-01

    Full Text Available Abstract Background This article coincides with the 40 year anniversary of the first published works devoted to the creation of algorithms for computer-aided structure elucidation (CASE. The general principles on which CASE methods are based will be reviewed and the present state of the art in this field will be described using, as an example, the expert system Structure Elucidator. Results The developers of CASE systems have been forced to overcome many obstacles hindering the development of a software application capable of drastically reducing the time and effort required to determine the structures of newly isolated organic compounds. Large complex molecules of up to 100 or more skeletal atoms with topological peculiarity can be quickly identified using the expert system Structure Elucidator based on spectral data. Logical analysis of 2D NMR data frequently allows for the detection of the presence of COSY and HMBC correlations of "nonstandard" length. Fuzzy structure generation provides a possibility to obtain the correct solution even in those cases when an unknown number of nonstandard correlations of unknown length are present in the spectra. The relative stereochemistry of big rigid molecules containing many stereocenters can be determined using the StrucEluc system and NOESY/ROESY 2D NMR data for this purpose. Conclusion The StrucEluc system continues to be developed in order to expand the general applicability, provide improved workflows, usability of the system and increased reliability of the results. It is expected that expert systems similar to that described in this paper will receive increasing acceptance in the next decade and will ultimately be integrated directly to analytical instruments for the purpose of organic analysis. Work in this direction is in progress. In spite of the fact that many difficulties have already been overcome to deliver on the spectroscopist's dream of "fully automated structure elucidation" there is

  17. Development of the direct modification method of the ruthenium complex on conductive diamond surfaces and the selective detection of bio-related materials

    Energy Technology Data Exchange (ETDEWEB)

    Yamanaka, Y.; Miyamoto, M.; Tanaka, Y.; Nagumo, A.; Katsuki, Y.; Fukuda, Y.; Yoshimatsu, M.; Takeshige, A. [Department of Biology and Chemistry, School of Science, Yamaguchi University, 1677-1 Yoshida, Yamaguchi-shi, Yamaguchi 753-8512 (Japan); Kondo, T. [Department of Industrial Chemistry, Faculty of Engineering, Tokyo University of Science, 1-3 Kagurazaka, Shinjuku-ku, Tokyo 162-8601 (Japan); Fujishima, A. [Kanagawa Advanced Science and Technology (KAST), 3-2-1 Sakato, Takastu-ku, Kawasaki-shi, Kanagawa 213-0012 (Japan); Honda, K. [Department of Biology and Chemistry, School of Science, Yamaguchi University, 1677-1 Yoshida, Yamaguchi-shi, Yamaguchi 753-8512 (Japan)], E-mail: khonda@yamaguchi-u.ac.jp

    2008-06-30

    The tris-2,2'-(bipyridine) ruthenium(II) complex derivative, which shows the electrogenerated chemiluminescence (ECL) reaction, was directly immobilized on the boron-doped diamond (BDD) surface with three types of modification to form C-N, C-O and C-C bond between them. The objective of this study is to find the most appropriate modification method for the highest amount of immobilization on diamond and the highest stability for electrochemical reaction in the high potential ranges. By making use of this photofunctional BDD, the establishment of an analytical system for the selective and high-sensitive detection of oxalic acid in human urine using the ECL reaction was attempted. Comparing the stability for the ECL reaction among three modified BDD (MBDD) electrodes using the long-term potential cycling, in the initial of cycling, the ECL peak intensity for modified BDD linked with C-C bond (MBDD(C-C)), with C-N bond (MBDD(C-N)) and with C-O bond after the exposure to O{sub 2} plasma (MBDD(C-O{sub pl})) were in the same range. At MBDD(C-C), the ECL intensity was very stable and initial value was maintained even after 200 min of the potential cycling, but the ECL intensities for other modified BDD were rapidly decreased, indicating that the modification method through C-C bond can provide the high density and stable modification. Using MBDD(C-C), the analysis for oxalic acid in human urine was carried out by the high-performance liquid chromatography (HPLC) and flow injection analysis (FIA) systems in that the electrochemical amperometric detector (ECD) and ECL detector with modified BDD were installed. In the HPLC-ECD chromatogram, many peaks including uric acid and ascorbic acid were observed. On the other hand, only one peak was detected in the HPLC-ECL chromatogram, indicating that oxalic acid could be selectively detected in human urine using the ECL reaction at modified BDD. The linear dynamic range and the lowest detection limit (S/N = 3) for the oxalic

  18. A Comparative Study of the Effectiveness of Two Strategies of Etymological Elaboration and Pictorial Elucidation on Idiom Learning: A Case of Young EFL Iranian Learners

    Science.gov (United States)

    Haghshenas, Mahsa Sadat Mousavi; Hashemian, Mahmood

    2016-01-01

    This study examined the effect of etymological elaboration, pictorial elucidation, and integration of these 2 strategies on idiom learning by L2 learners. A total number of 80 homogeneous intermediate learners studying English at 3 language institutes in Isfahan, Iran, were selected. The intermediate participants were selected as the result of…

  19. Oxidative stress in Complex Regional Pain Syndrome (CRPS): no systemically elevated levels of malondialdehyde, F2-isoprostanes and 8OHdG in a selected sample of patients.

    Science.gov (United States)

    Fischer, Sigrid G L; Perez, Roberto S G M; Nouta, Jan; Zuurmond, Wouter W A; Scheffer, Peter G

    2013-04-10

    Exaggerated inflammation and oxidative stress are involved in the pathogenesis of Complex Regional Pain Syndrome (CRPS). However, studies assessing markers for oxidative stress in CRPS patients are limited. In this study, markers for lipid peroxidation (malondialdehyde and F2-isoprostanes) and DNA damage (8-hydroxy-2-deoxyguanosine) were measured in nine patients (mean age 50.1 ± 17.1 years) with short term CRPS-1 (median 3 months) and nine age and sex matched healthy volunteers (mean age 49.3 ± 16.8 years) to assess and compare the level of oxidative stress. No differences were found in plasma between CRPS patients and healthy volunteers for malondialdehyde (5.2 ± 0.9 µmol/L vs. 5.4 ± 0.5 µmol/L) F2-isoprostanes (83.9 ± 18.7 pg/mL vs. 80.5 ± 12.3 pg/mL) and 8-hydroxy-2-deoxyguanosine (92.6 ± 25.5 pmol/L vs. 86.9 ± 19.0 pmol/L). Likewise, in urine, no differences were observed between CRPS patients and healthy volunteers for F2-isoprostanes (117 ng/mmol, IQR 54.5-124.3 vs. 85 ng/mmol, IQR 55.5-110) and 8-hydroxy-2-deoxyguanosine (1.4 ± 0.7 nmol/mmol vs. 1.4 ± 0.5 nmol/mmol). Our data show no elevation of systemic markers of oxidative stress in CRPS patients compared to matched healthy volunteers. Future research should focus on local sampling methods of oxidative stress with adequate patient selection based on CRPS phenotype and lifestyle.

  20. Ternary complexes of folate-PEG-appended dendrimer (G4)/α-cyclodextrin conjugate, siRNA and low-molecular-weight polysaccharide sacran as a novel tumor-selective siRNA delivery system.

    Science.gov (United States)

    Ohyama, Ayumu; Higashi, Taishi; Motoyama, Keiichi; Arima, Hidetoshi

    2017-06-01

    We previously developed a tumor-selective siRNA carrier by preparing polyamidoamine dendrimer (generation 4, G4) conjugates with α-cyclodextrin and folate-polyethylene glycol (Fol-PαC (G4)). In the present study, we developed ternary complexes of Fol-PαC (G4)/siRNA with low-molecular-weight-sacrans to achieve more effective siRNA transfer activity. Among the different molecular-weight sacrans, i.e. sacran 100, 1000 and 10,000 (MW 44,889Da, 943,692Da and 1,488,281Da, respectively), sacran 100 significantly increased the cellular uptake and the RNAi effects of Fol-PαC (G4)/siRNA binary complex with negligible cytotoxicity in KB cells (folate receptor-α positive cells). In addition, the ζ-potential and particle size of Fol-PαC (G4)/siRNA complex were decreased by the ternary complexation with sacran 100. Importantly, the in vivo RNAi effect of the ternary complex after the intravenous administration to tumor-bearing BALB/c mice was significantly higher than that of the binary complex. In conclusion, Fol-PαC (G4)/siRNA/sacran 100 ternary complex has a potential as a novel tumor-selective siRNA delivery system. Copyright © 2017 Elsevier B.V. All rights reserved.

  1. Elucidating the Pathogenesis of Pre-eclampsia Using In Vitro Models of Spiral Uterine Artery Remodelling.

    Science.gov (United States)

    McNally, Ross; Alqudah, Abdelrahim; Obradovic, Danilo; McClements, Lana

    2017-10-23

    The aim of the study is to perform a critical assessment of in vitro models of pre-eclampsia using complementary human and cell line-based studies. Molecular mechanisms involved in spiral uterine artery (SUA) remodelling and trophoblast functionality will also be discussed. A number of proteins and microRNAs have been implicated as key in SUA remodelling, which could be explored as early biomarkers or therapeutic targets for prevention of pre-eclampsia. Various 2D and 3D in vitro models involving trophoblast cells, endothelial cells, immune cells and placental tissue were discussed to elucidate the pathogenesis of pre-eclampsia. Nevertheless, pre-eclampsia is a multifactorial disease, and the mechanisms involved in its pathogenesis are complex and still largely unknown. Further studies are required to provide better understanding of the key processes leading to inappropriate placental development which is the root cause of pre-eclampsia. This new knowledge could identify novel biomarkers and treatment strategies.

  2. Tannin structural elucidation and quantitative ³¹P NMR analysis. 1. Model compounds.

    Science.gov (United States)

    Melone, Federica; Saladino, Raffaele; Lange, Heiko; Crestini, Claudia

    2013-10-02

    Tannins and flavonoids are secondary metabolites of plants that display a wide array of biological activities. This peculiarity is related to the inhibition of extracellular enzymes that occurs through the complexation of peptides by tannins. Not only the nature of these interactions, but more fundamentally also the structure of these heterogeneous polyphenolic molecules are not completely clear. This first paper describes the development of a new analytical method for the structural characterization of tannins on the basis of tannin model compounds employing an in situ labeling of all labile H groups (aliphatic OH, phenolic OH, and carboxylic acids) with a phosphorus reagent. The ³¹P NMR analysis of ³¹P-labeled samples allowed the unprecedented quantitative and qualitative structural characterization of hydrolyzable tannins, proanthocyanidins, and catechin tannin model compounds, forming the foundations for the quantitative structural elucidation of a variety of actual tannin samples described in part 2 of this series.

  3. Complexation of buffer constituents with neutral complexation agents: part II. Practical impact in capillary zone electrophoresis.

    Science.gov (United States)

    Beneš, Martin; Riesová, Martina; Svobodová, Jana; Tesařová, Eva; Dubský, Pavel; Gaš, Bohuslav

    2013-09-17

    This article elucidates the practical impact of the complexation of buffer constituents with complexation agents on electrophoretic results, namely, complexation constant determination, system peak development, and proper separation of analytes. Several common buffers, which were selected based on the pH study in Part I of this paper series (Riesová, M.; Svobodová, J.; Tošner, Z.; Beneš, M.; Tesařová, E.; Gaš, B. Anal. Chem., 2013, DOI: 10.1021/ac4013804); e.g., CHES, MES, MOPS, Tricine were used to demonstrate behavior of such complex separation systems. We show that the value of a complexation constant determined in the interacting buffers environment depends not only on the analyte and complexation agent but it is also substantially affected by the type and concentration of buffer constituents. As a result, the complexation parameters determined in the interacting buffers cannot be regarded as thermodynamic ones and may provide misleading information about the strength of complexation of the compound of interest. We also demonstrate that the development of system peaks in interacting buffer systems significantly differs from the behavior known for noncomplexing systems, as the mobility of system peaks depends on the concentration and type of neutral complexation agent. Finally, we show that the use of interacting buffers can totally ruin the results of electrophoretic separation because the buffer properties change as the consequence of the buffer constituents' complexation. As a general conclusion, the interaction of buffer constituents with the complexation agent should always be considered in any method development procedures.

  4. The Capabilities of Chaos and Complexity

    Directory of Open Access Journals (Sweden)

    David L. Abel

    2009-01-01

    Full Text Available To what degree could chaos and complexity have organized a Peptide or RNA World of crude yet necessarily integrated protometabolism? How far could such protolife evolve in the absence of a heritable linear digital symbol system that could mutate, instruct, regulate, optimize and maintain metabolic homeostasis? To address these questions, chaos, complexity, self-ordered states, and organization must all be carefully defined and distinguished. In addition their cause-and-effect relationships and mechanisms of action must be delineated. Are there any formal (non physical, abstract, conceptual, algorithmic components to chaos, complexity, self-ordering and organization, or are they entirely physicodynamic (physical, mass/energy interaction alone? Chaos and complexity can produce some fascinating self-ordered phenomena. But can spontaneous chaos and complexity steer events and processes toward pragmatic benefit, select function over non function, optimize algorithms, integrate circuits, produce computational halting, organize processes into formal systems, control and regulate existing systems toward greater efficiency? The question is pursued of whether there might be some yet-to-be discovered new law of biology that will elucidate the derivation of prescriptive information and control. “System” will be rigorously defined. Can a low-informational rapid succession of Prigogine’s dissipative structures self-order into bona fide organization?

  5. Complexes Tickling the $ubject

    Directory of Open Access Journals (Sweden)

    Matthew Gildersleeve

    2016-11-01

    Full Text Available This article continues my earlier work of reading Jung with Lacan. This article will develop Zizek’s work on Lacan’s concept of objet petit a by relating it to a phenomenological interpretation of Jung. I use a number of different examples, including Zizek’s interpretation of Francis Bacon, Edvard Munch, Hans Holbein and Johann Gottlieb Fichte, to describe the objet petit a and its relationship to a phenomenological interpretation of complexes. By integrating other Lacanian concepts, such as subject, drive, fantasy, jouissance, gaze, desire, and ego as well as the imaginary, symbolic and Real, this work also highlights how Hegel and Heidegger can elucidate the relationship between objet petit a and complexes. Jung’s transcendent function and the Rosarium Philosophorum also elucidate the relationship between Jung and Lacan.

  6. Elucidation of polymer induced DNA condensation. Visualisation at the single molecular level

    International Nuclear Information System (INIS)

    Martin, Alison Laura

    2002-01-01

    formation, this question has been addressed in two ways. Firstly, in an attempt to form intermediates of the condensation process, DNA has been exposed to cationic moieties over a range of cationic charge to DNA nucleotide ratios. The morphologies of the resulting complexes have been analysed, and hypotheses have been constructed, regarding the mechanisms of DNA condensate formation. The second methodology adopted involved the visualisation of the formation of DNA condensates in real time. DNA-cation complexes have been visualised in a near in situ environment, allowing dynamic tertiary conformational change of individual DNA condensates to be observed. The investigations presented here are among the first to utilise atomic force microscopy, operating in an aqueous environment, to elucidate DNA condensate morphology and dynamic conformational change in real time, and to apply atomic force microscopy in the characterisation of potential gene delivery vectors. (author)

  7. Calixarene receptors in the selective separation of alachlor. Characterization of the separated complexes; Receptores calixarenicos en la separacion selectiva de alaclor. Caracterizacion de los complejos separados

    Energy Technology Data Exchange (ETDEWEB)

    Garcia G, M C

    2004-07-01

    Pesticides have been necessary in the agriculture since the plagues control have been remedied thanks to them but it has also provoked pollution. Nowadays, there are several methods which help to decrease or remedy such a pollution provoked. Unfortunately, any of them work out the environmental problem totally. Therefore, alternatives have to be found. The organic and tri dimensional characteristics of these macrocycles afford them a high versatility in such a way that these hosts can interact with organic guests selectively. Alachlor is a chlorinated organic herbicide useful in the plagues control of annual grasses and many broad-leave weeds which grow in maize, peanuts and soyabean. The ability of calixarenes to host organic guests with chemical characteristics similar to pesticides let them to be good candidates to compete with others methods which are used presently to separate organic pesticides. In this direction one of the advantages of proposing the use of calixarenes is, its facility of being modified in the lower and/or upper rims, to adapt them to aqueous, organic, gaseous and aqueous-organic media. Once the characteristics of reagents informed in the literature were confirmed and complemented with others found in this work, we studied, in solution, the interaction of the calixarenes with alachlor using 1 x 10{sup -5} to 1 x 10{sup -3} M solutions in acetonitrile for calixarenes fitted with phosphinoyl pendant arms in the lower rim, B{sub n}bL{sup n}, n= 4, 6) and in chloroform for parents calixarenes (H{sub n}bL{sup n} n = 4, 6, 8). Meticulous studies monitored by UV-Vis and luminescence were carried out, and the best stoichiometry to be used in further studies resulted to be 1(host): 1(alachlor). Therefore, we chose the 1 x 10{sup -4} M concentration to find how long the host-guest should be interacting in order to guarantee the formation in solution of the calixarene-alachlor species. It was found 168 h for the alachlor-B{sub n}bL{sup n} interaction

  8. Structure Elucidation of Unknown Metabolites in Metabolomics by Combined NMR and MS/MS Prediction.

    Science.gov (United States)

    Boiteau, Rene M; Hoyt, David W; Nicora, Carrie D; Kinmonth-Schultz, Hannah A; Ward, Joy K; Bingol, Kerem

    2018-01-17

    We introduce a cheminformatics approach that combines highly selective and orthogonal structure elucidation parameters; accurate mass, MS/MS (MS²), and NMR into a single analysis platform to accurately identify unknown metabolites in untargeted studies. The approach starts with an unknown LC-MS feature, and then combines the experimental MS/MS and NMR information of the unknown to effectively filter out the false positive candidate structures based on their predicted MS/MS and NMR spectra. We demonstrate the approach on a model mixture, and then we identify an uncatalogued secondary metabolite in Arabidopsis thaliana . The NMR/MS² approach is well suited to the discovery of new metabolites in plant extracts, microbes, soils, dissolved organic matter, food extracts, biofuels, and biomedical samples, facilitating the identification of metabolites that are not present in experimental NMR and MS metabolomics databases.

  9. Selective Catalytic Hydrogenation of Arenols by a Well-Defined Complex of Ruthenium and Phosphorus–Nitrogen PN3–Pincer Ligand Containing a Phenanthroline Backbone

    KAUST Repository

    Li, Huaifeng; Wang, Yuan; Lai, Zhiping; Huang, Kuo-Wei

    2017-01-01

    Selective catalytic hydrogenation of aromatic compounds is extremely challenging using transition-metal catalysts. Hydrogenation of arenols to substituted tetrahydronaphthols or cyclohexanols has been reported only with heterogeneous catalysts. Herein, we demonstrate the selective hydrogenation of arenols to the corresponding tetrahydronaphthols or cyclohexanols catalyzed by a phenanthroline-based PN3-ruthenium pincer catalyst.

  10. Selective Catalytic Hydrogenation of Arenols by a Well-Defined Complex of Ruthenium and Phosphorus–Nitrogen PN3–Pincer Ligand Containing a Phenanthroline Backbone

    KAUST Repository

    Li, Huaifeng

    2017-05-30

    Selective catalytic hydrogenation of aromatic compounds is extremely challenging using transition-metal catalysts. Hydrogenation of arenols to substituted tetrahydronaphthols or cyclohexanols has been reported only with heterogeneous catalysts. Herein, we demonstrate the selective hydrogenation of arenols to the corresponding tetrahydronaphthols or cyclohexanols catalyzed by a phenanthroline-based PN3-ruthenium pincer catalyst.

  11. Streamlined structure elucidation of an unknown compound in a pigment formulation.

    Science.gov (United States)

    Yüce, Imanuel; Morlock, Gertrud E

    2016-10-21

    A fast and reliable quality control is important for ink manufacturers to ensure a constant production grade of mixtures and chemical formulations, and unknown components attract their attention. Structure elucidating techniques seem time-consuming in combination with column-based methods, but especially the low solubility of pigment formulations is challenging the analysis. In contrast, layer chromatography is more tolerant with regard to pigment particles. One PLC plate for NMR and FTIR analyses and one HPTLC plate for recording of high resolution mass spectra, MS/MS spectra and for gathering information on polarity and spectral properties were needed to characterize a structure, exemplarily shown for an unknown component in pigment Red 57:1 to be 3-hydroxy-2-naphtoic acid. A preparative layer chromatography (PLC) workflow was developed that used an Automated Multiple Development 2 (AMD 2) system. The 0.5-mm PLC plate could still be operated in the AMD 2 system and allowed a smooth switch from the analytical to the preparative gradient separation. Through automated gradient development and the resulting focusing of bands, the sharpness of the PLC bands was improved. For NMR, the necessary high load of the target compound on the PLC plate was achieved via a selective solvent extraction that discriminated the polar sample matrix and thus increased the application volume of the extract that could maximally be applied without overloading. By doing so, the yield for NMR analysis was improved by a factor of 9. The effectivity gain through a simple, but thoroughly chosen extraction solvent is often overlooked, and for educational purpose, it was clearly illustrated and demonstrated by an extended solvent screening. Thus, PLC using an automated gradient development after a selective extraction was proven to be a new powerful combination for structural elucidation by NMR. Copyright © 2016 Elsevier B.V. All rights reserved.

  12. A highly selective and non-reaction based chemosensor for the detection of Hg2+ ions using a luminescent iridium(III complex.

    Directory of Open Access Journals (Sweden)

    Daniel Shiu-Hin Chan

    Full Text Available We report herein a novel luminescent iridium(III complex with two hydrophobic carbon chains as a non-reaction based chemosensor for the detection of Hg(2+ ions in aqueous solution (<0.002% of organic solvent attributed to the probe solution. Upon the addition of Hg(2+ ions, the emission intensity of the complex was significantly enhanced and this change could be monitored by the naked eye under UV irradiation. The iridium(III complex shows high specificity for Hg(2+ ions over eighteen other cations. The system is capable of detecting micromolar levels of Hg(2+ ions, which is within the range of many chemical systems.

  13. [Neuropsychological approach to elucidating delusion and psychotic symptoms].

    Science.gov (United States)

    Kato, Motoichiro

    2012-01-01

    Neuropsychological symptom-oriented approach is a critical method to elucidate delusion and psychotic symptoms in patients with focal brain damages and schizophrenia. In Capgras delusion (CD), the delusional misidentification of familiar people disguised as others, the patients with right amygdala damage and bilateral ventromedial prefrontal lesions have a deficient or reduced emotional valence of the person with intact configurational processes of the face. Reduplicative paramnesia (RP) is a specific phenomenon characterized by subjective certainty that a familiar place or person has been duplicated. Clinical evidences indicated that the patient with RP following right prefrontal damages showed the lack of emotional valence for the present hospital. This abnormal sense of familiarity triggered the deficits of the orientation of self to the outside world, that is, double orientation, resulting in the development of geographical reduplicative paramnesia. In line with the pathogenesis of CD and RP after brain damages, the delusion in schizophrenia may have a germ as developmental origins, which include the aberrant or salient perceptual experiences and abnormal sense of agency, and might be further aggravated by the impairment of causal reasoning process such as the jumping-to-conclusions bias.

  14. 环戊二烯基钌配合物催化的高选择性苯乙炔二聚反应%HIGHLY SELECTIVE CATALYTIC DIMERIZATION OF PHENYLACETYLENE BY CYCLOPENTADIENYL RUTHENIUM COMPLEXES

    Institute of Scientific and Technical Information of China (English)

    金军挺; 黄吉玲; 陶晓春; 钱延龙

    1999-01-01

    @@ Transition metal vinylidene complexes (M=C=CHR) have attracted a great deal of attention in recent years as a new type of organometallic intermediates that may have unusual reactivity[1]. Their reactivity has been explored and their application to organic synthesis is developed[2]. Recent reports on the ruthenium-vinylidene complexes[3]suggest that the reaction of ruthenium-vinylidene complexes with a base generates the coordinatively unsaturated ruthenium acetylide species, which are involved in a number of catalytic and stoichiometric reactions of alkynes. For example,the coordinatively unsaturated ruthenium acetylide species C5Me5Ru(PPh3)-C≡CPh,formed from the reaction of the vinylidene complex C5Me5Ru(PPh3) (Cl)=C=CHPh with a base was reactive toward a variety of small molecules and active in catalytic dimerization of terminal alkynes[4]. The dimerization of terminal alkyne is an effective method of forming enynes, but its synthetic application in organic synthesis has been limited dueto low selectivity for dimeric products[5]. In this communication, we report that three ruthenium complexes were used as catalysts for the highly selective dimerization of phenylacetylene.

  15. Formation of less-known structurally complex ζb and orthorhombic quasicrystalline approximant εn on solidification of selected Al–Pd–Cr alloys

    Czech Academy of Sciences Publication Activity Database

    Adamech, A.; Černičková, I.; Ďuriška, L.; Kolesár, V.; Drienovský, M.; Bednarčík, J.; Svoboda, Milan; Janovec, J.

    2014-01-01

    Roč. 97, NOV (2014), s. 189-198 ISSN 1044-5803 Institutional support: RVO:68081723 Keywords : complex metallic alloys * aluminium alloys * intermetallics Subject RIV: JG - Metallurgy Impact factor: 1.845, year: 2014

  16. Calixarene receptors in the selective separation of alachlor. Characterization of the separated complexes; Receptores calixarenicos en la separacion selectiva de alaclor. Caracterizacion de los complejos separados

    Energy Technology Data Exchange (ETDEWEB)

    Garcia G, M.C

    2004-07-01

    Pesticides have been necessary in the agriculture since the plagues control have been remedied thanks to them but it has also provoked pollution. Nowadays, there are several methods which help to decrease or remedy such a pollution provoked. Unfortunately, any of them work out the environmental problem totally. Therefore, alternatives have to be found. The organic and tri dimensional characteristics of these macrocycles afford them a high versatility in such a way that these hosts can interact with organic guests selectively. Alachlor is a chlorinated organic herbicide useful in the plagues control of annual grasses and many broad-leave weeds which grow in maize, peanuts and soyabean. The ability of calixarenes to host organic guests with chemical characteristics similar to pesticides let them to be good candidates to compete with others methods which are used presently to separate organic pesticides. In this direction one of the advantages of proposing the use of calixarenes is, its facility of being modified in the lower and/or upper rims, to adapt them to aqueous, organic, gaseous and aqueous-organic media. Once the characteristics of reagents informed in the literature were confirmed and complemented with others found in this work, we studied, in solution, the interaction of the calixarenes with alachlor using 1 x 10{sup -5} to 1 x 10{sup -3} M solutions in acetonitrile for calixarenes fitted with phosphinoyl pendant arms in the lower rim, B{sub n}bL{sup n}, n= 4, 6) and in chloroform for parents calixarenes (H{sub n}bL{sup n} n = 4, 6, 8). Meticulous studies monitored by UV-Vis and luminescence were carried out, and the best stoichiometry to be used in further studies resulted to be 1(host): 1(alachlor). Therefore, we chose the 1 x 10{sup -4} M concentration to find how long the host-guest should be interacting in order to guarantee the formation in solution of the calixarene-alachlor species. It was found 168 h for the alachlor-B{sub n}bL{sup n} interaction

  17. Genetic studies towards elucidation of drought tolerance of potato

    NARCIS (Netherlands)

    Tessema, Biructa Bekele

    2017-01-01

    Drought is a major threat to agricultural production, which makes drought tolerance a prime target for breeding approaches towards crop improvement. Drought is a complex polygenic trait and poses a challenge for drought tolerance breeding. Improving crops for drought tolerance at least requires

  18. elucidating the mechanism of the adsorption of mucin

    African Journals Online (AJOL)

    dcu user

    Kinetic and mechanistic studies of electron transfer reaction of butane-1,3-diol and Cr(VI) ion in ... The oxidation of diols other than. 1,2-diols by transition metal ions and their complexes has received little attention. An increased interest in these reactions was noticed after the oxidation of propane-1,3-, butane-1,3- and ...

  19. Affinity selection of Nipah and Hendra virus-related vaccine candidates from a complex random peptide library displayed on bacteriophage virus-like particles

    Energy Technology Data Exchange (ETDEWEB)

    Peabody, David S.; Chackerian, Bryce; Ashley, Carlee; Carnes, Eric; Negrete, Oscar

    2017-01-24

    The invention relates to virus-like particles of bacteriophage MS2 (MS2 VLPs) displaying peptide epitopes or peptide mimics of epitopes of Nipah Virus envelope glycoprotein that elicit an immune response against Nipah Virus upon vaccination of humans or animals. Affinity selection on Nipah Virus-neutralizing monoclonal antibodies using random sequence peptide libraries on MS2 VLPs selected peptides with sequence similarity to peptide sequences found within the envelope glycoprotein of Nipah itself, thus identifying the epitopes the antibodies recognize. The selected peptide sequences themselves are not necessarily identical in all respects to a sequence within Nipah Virus glycoprotein, and therefore may be referred to as epitope mimics VLPs displaying these epitope mimics can serve as vaccine. On the other hand, display of the corresponding wild-type sequence derived from Nipah Virus and corresponding to the epitope mapped by affinity selection, may also be used as a vaccine.

  20. The Enhancement of the Selectivity of Complex Reactions by a Catalytic Membrane Reactor -Ethylene Oxidation Over a Ag Catalyst Supported in a Ceramic Membrane-

    OpenAIRE

    馮, 臨; 小林, 正義; Lin, FENG; Masayoshi, KOBAYASHI

    1991-01-01

    This research demonstrated that, using a membrane reactor consisting of a tubular, microporous, glass-ceramic membrane, it is possible to achieve selective oxidation of ethylene to ethylene oxide with an Ag catalyst. In experiments which a reaction temperature range of 115 to 300℃ and a contact time of 1.5 to 5 seconds, resulting data illustrated the following characteristics of this membrane reactor : 1) compared with a classic tubular reactor, the selectivity of ethylene oxide is increased ...

  1. Reinvestigating 2,5-di(pyridin-2-yl)pyrazine ruthenium complexes : Selective deuteration and Raman spectroscopy as tools to probe ground and excited-state electronic structure in homo- and heterobimetallic complexes

    NARCIS (Netherlands)

    Schulz, M.; Hirschmann, J.; Draksharapu, A.; Singh Bindra, G.; Soman, S.; Paul, A.; Groarke, R.; T. Pryce, M.; Rau, S.; R. Browne, W.; Vos, J.

    2011-01-01

    The mono- (1) and dinuclear (2) ruthenium(II) bis(2,2'-bipyridine) complexes of 2,5-di(pyridin-2-yl)pyrazine (2,5-dpp), for which the UV/Vis absorption and emission as well as electrochemical properties have been described earlier, are reinvestigated here by resonance, surface enhanced and transient

  2. Sensitive and selective spectrophotometric assay of piroxicam in pure form, capsule and human blood serum samples via ion-pair complex formation

    Science.gov (United States)

    Alizadeh, Nina; Keyhanian, Fereshteh

    2014-09-01

    A simple, accurate and highly sensitive spectrophotometric method has been developed for the rapid determination of piroxicam (PX) in pure and pharmaceutical formulations. The proposed method involves formation of stable yellow colored ion-pair complexes of the amino derivative (basic nitrogen) of PX with three sulphonphthalein acid dyes namely; bromocresol green (BCG), bromothymol blue (BTB), bromophenol blue (BPB) in acidic medium. The colored species exhibited absorption maxima at 438, 429 and 432 nm with molar absorptivity values of 9.400 × 103, 1.218 × 103 and 1.02 × 104 L mol-1 cm-1 for PX-BCG, PX-BTB and PX-BPB complexes, respectively. The effect of optimum conditions via acidity, reagent concentration, time and solvent were studied. The reactions were extremely rapid at room temperature and the absorbance values remained constant for 48 h. Beer’s law was obeyed with a good correlation coefficient in the concentration ranges 1-100 μg mL-1 for BCG, BTB complexes and 1-95 μg mL-1 for BPB complex. The composition ratio of the ion-pair complexes were found to be 1:1 in all cases as established by Job’s method. No interference was observed from common additives and excipients which may be present in the pharmaceutical preparations. The proposed method was successfully applied for the determination of PX in capsule and human blood serum samples with good accuracy and precision.

  3. Detecting Site-Specific Physicochemical Selective Pressures: Applications to the Class I HLA of the Human Major Histocompatibility Complex and the SRK of the Plant Sporophytic Self-Incompatibility System

    DEFF Research Database (Denmark)

    Sainudiin, Raazesh; Wong, Wendy Shuk Wan; Yogeeswaran, Krithika

    2005-01-01

    :transversion biases. Here, we apply this method to two positively selected receptors involved in ligand-recognition: the class I alleles of the human major histocompatibility complex (MHC) of known structure and the S-locus receptor kinase (SRK) of the sporophytic self-incompatibility system (SSI) in cruciferous...... Bayes approach is used to identify sites that may be important for ligand recognition in these proteins....

  4. [(≢SiO)TaVCl2Me2]: A well-defined silica-supported tantalum(V) surface complex as catalyst precursor for the selective cocatalyst-free trimerization of ethylene

    KAUST Repository

    Chen, Yin; Callens, Emmanuel; Abou-Hamad, Edy; Merle, Nicolas; White, Andrew J P; Taoufik, Mostafa; Copé ret, Christophe; Le Roux, Erwan; Basset, Jean-Marie

    2012-01-01

    On the surface of it: In the absence of co-catalyst, a well-defined silica-supported surface organometallic complex [(≢SiO)Ta VCl2Me2] selectively catalyzes the oligomerization of ethylene. The use of surface organometallic species allows three different pathways to be determined for the reduction of TaV to TaIII species under pressure of ethylene. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. [(≢SiO)TaVCl2Me2]: A well-defined silica-supported tantalum(V) surface complex as catalyst precursor for the selective cocatalyst-free trimerization of ethylene

    KAUST Repository

    Chen, Yin

    2012-10-22

    On the surface of it: In the absence of co-catalyst, a well-defined silica-supported surface organometallic complex [(≢SiO)Ta VCl2Me2] selectively catalyzes the oligomerization of ethylene. The use of surface organometallic species allows three different pathways to be determined for the reduction of TaV to TaIII species under pressure of ethylene. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. Observations and Measurements of Wing Parameters of the Selected Beetle Species and the Design of a Mechanism Structure Implementing a Complex Wing Movement

    Directory of Open Access Journals (Sweden)

    Geisler T.

    2016-12-01

    Full Text Available Beetle wings perform a flapping movement, consisting of the rotation relative to the two axes. This paper presents the results of observations and measurements of wings operating parameters in different planes of some beetle species. High speed photos and videos were used. The concept of the mechanism performing a complex wing movement was proposed and developed.

  7. The Transcription Bubble of the RNA Polymerase-Promoter Open Complex Exhibits Conformational Heterogeneity and Millisecond-Scale Dynamics : Implications for Transcription Start-Site Selection

    NARCIS (Netherlands)

    Robb, Nicole C.; Cordes, Thorben; Hwang, Ling Chin; Gryte, Kristofer; Duchi, Diego; Craggs, Timothy D.; Santoso, Yusdi; Weiss, Shimon; Ebright, Richard H.; Kapanidis, Achillefs N.

    2013-01-01

    Bacterial transcription is initiated after RNA polymerase (RNAP) binds to promoter DNA, melts similar to 14 bp around the transcription start site and forms a single-stranded "transcription bubble" within a catalytically active RNAP-DNA open complex (RPo). There is significant flexibility in the

  8. Observations and Measurements of Wing Parameters of the Selected Beetle Species and the Design of a Mechanism Structure Implementing a Complex Wing Movement

    Science.gov (United States)

    Geisler, T.

    2016-12-01

    Beetle wings perform a flapping movement, consisting of the rotation relative to the two axes. This paper presents the results of observations and measurements of wings operating parameters in different planes of some beetle species. High speed photos and videos were used. The concept of the mechanism performing a complex wing movement was proposed and developed.

  9. Oxidative Stress in Complex Regional Pain Syndrome (CRPS): No Systemically Elevated Levels of Malondialdehyde, F2-Isoprostanes and 8OHdG in a Selected Sample of Patients

    NARCIS (Netherlands)

    Fischer, S.G.L.; Perez, R.S.G.M.; Nouta, J.; Zuurmond, W.W.A.; Scheffer, P.G.

    2013-01-01

    Exaggerated inflammation and oxidative stress are involved in the pathogenesis of Complex Regional Pain Syndrome (CRPS). However, studies assessing markers for oxidative stress in CRPS patients are limited. In this study, markers for lipid peroxidation (malondialdehyde and F2-isoprostanes) and DNA

  10. Software concepts for the build-up of complex systems - selection and realization taking as example a program system for calculation of hypothetical core meltdown accidents

    International Nuclear Information System (INIS)

    Scheuermann, W.

    1994-10-01

    Development and application of simulation systems for the analysis of complex processes require on the one hand and detailed engineering knowledge of the plant and the processes to be simulated and on the other hand a detailled knowledge about software engineering, numerics and data structures. The cooperation of specialists of both areas will become easier if it is possible to reduce the complexicity of the problems to be solved in a way that the analyses will not be disturbed and the communication between different disciplines will not become unnecessarily complicated. One solution to reduce the complexity is to consider computer science as an engineering discipline which provides mainly abstract elements and to allow engineers to build application systems based on these abstract elements. The principle of abstraction leads through the processes of modularisation and the solution of the interface problem to an almost problem independent system architecture where the elements of the system (modules, model components and models) operate only on those data assigned to them. In addition the development of abstract data types allows the formal description of the relations and interactions between system elements. This work describes how these ideas can be concretized to build complex systems which allow reliable and effective problem solutions. These ideas were applied successfully during the design, realization and application of the code system KESS, which allows the analysis of core melt down accidents in pressurized water reactors. (orig.) [de

  11. Elucidation of structural isomers from the homogeneous rhodium-catalyzed isomerization of vegetable oils.

    Science.gov (United States)

    Andjelkovic, Dejan D; Min, Byungrok; Ahn, Dong; Larock, Richard C

    2006-12-13

    The structural isomers formed by the homogeneous rhodium-catalyzed isomerization of several vegetable oils have been elucidated. A detailed study of the isomerization of the model compound methyl linoleate has been performed to correlate the distribution of conjugated isomers, the reaction kinetics, and the mechanism of the reaction. It has been shown that [RhCl(C8H8)2]2 is a highly efficient and selective isomerization catalyst for the production of highly conjugated vegetable oils with a high conjugated linoleic acid (CLA) content, which is highly desirable in the food industry. The combined fraction of the two major CLA isomers [(9Z,11E)-CLA and (10E,12Z)-CLA] in the overall CLA mixture is in the range from 76.2% to 93.4%. The high efficiency and selectivity of this isomerization method along with the straightforward purification process render this approach highly promising for the preparation of conjugated oils and CLA. Proposed improvements in catalyst recovery and reusability will only make this method more appealing to the food, paint, coating, and polymer industries in the future.

  12. Regio- and stereo-selective polymerization of 1,3-butadiene catalyzed by phosphorus–nitrogen PN3-pincer cobalt(ii) complexes

    KAUST Repository

    Gong, Dirong; Zhang, Xuequan; Huang, Kuo-Wei

    2016-01-01

    ligand through the pyridinyl nitrogen, the pyrazol nitrogen and the phosphorus donor, with a long Co-P bond distance indicating a labile character. On activation with AlEt2Cl, Al2Et3Cl3, MAO, [Ph3C]+[B(C6F5)4]-/AliBu3 or AliBu3, cis-1,4 selective

  13. Capillary electrophoresis with capacitively coupled contactless conductivity detection: A universal tool for the determination of supported liquid membrane selectivity in electromembrane extraction of complex samples

    Czech Academy of Sciences Publication Activity Database

    Kubáň, Pavel; Boček, Petr

    2012-01-01

    Roč. 1267, SI (2012), s. 96-101 ISSN 0021-9673 R&D Projects: GA ČR GAP206/10/1219 Institutional research plan: CEZ:AV0Z40310501 Keywords : supported liquid membranes * selectivity measurements * capillary electrophoresis Subject RIV: CB - Analytical Chemistry, Separation Impact factor: 4.612, year: 2012

  14. Study of selective Fischer-Tropsch catalysts synthesized by the destruction of bimetallic carbonyl complexes on activated γ-Al2O3 support

    International Nuclear Information System (INIS)

    Maksimov, Yu.V.; Matveev, V.V.; Suzdalev, I.P.; Khomenko, T.I.; Kadushin, A.A.

    1990-01-01

    The bimetallic catalysts obtained by the deposition of a Fe-Co binuclear cluster on the dehydroxylated γ-Al 2 O 3 are studied and compared to some other relative systems. These bimetallic catalysts are found to be active and selective in olefin synthesis. This is connected with the formation of Fe-Co contact which is detectable by Moessbauer spectroscopy. (orig.)

  15. Elucidating the vacuum structure of the Aoki phase

    International Nuclear Information System (INIS)

    Azcoiti, Vicente; Di Carlo, Giuseppe; Follana, Eduardo; Vaquero, Alejandro

    2013-01-01

    In this paper, we discuss the vacuum structure of QCD with two flavors of Wilson fermions, inside the Aoki phase. We provide numerical evidence, coming from HMC simulations in 4 4 , 6 4 and 8 4 lattices, supporting a vacuum structure for this model at strong coupling more complex than the one assumed in the standard wisdom, with new vacua where the expectation value of iψ ¯ γ 5 ψ can take non-zero values, and which can not be connected with the Aoki vacua by parity–flavor symmetry transformations

  16. Selection of the DC-60 cyclotron as the basic facility for the Inter-disciplinary research complex in the L.N. Gumilev Eurasian State University. Chapter 2

    International Nuclear Information System (INIS)

    2003-01-01

    In the Chapter 2 the DC-60 specialized accelerator project of the Inter-disciplinary research complex in the L.N. Gumilev Eurasian State University is described. The DC-60 cyclotron is intended for applied studies which can be accomplished on both the ion beams of the electron cyclotron resonance source with voltage up to 25 kV and the accelerated ions from carbon to xenon. The cyclotron is design on the base of compact magnet with weight about 74 tonnes, and it mean magnetic field is 1.6 T, section angle - 50 Deg. Design of the Inter-disciplinary research complex building in the L.N. Gumilev Eurasian State University is described as well. Technical performances of the building and their parameters are given

  17. Effects of selected endocrine disruptors on meiotic maturation, cumulus expansion, syntesis of hyaluronan and progesterone by porcine oocyte-cumulus complexes

    Czech Academy of Sciences Publication Activity Database

    Mlynarčíková, A.; Nagyová, Eva; Ficková, M.; Scsuková, S.

    2009-01-01

    Roč. 23, - (2009), s. 371-377 ISSN 0887-2333 R&D Projects: GA ČR GA305/05/0960 Grant - others:VEGA(SK) 2/6171/26; EU(XE) QLK4-CT-2002-02637 Institutional research plan: CEZ:AV0Z50450515 Keywords : oocyte-cumulus complex * meiotic maturation * cumulus expansion Subject RIV: EB - Genetics ; Molecular Biology Impact factor: 2.060, year: 2009

  18. Hydrogen/deuterium exchange, a unique and effective method for MS fragmentation behavior elucidation of ginkgolides and its application to systematic research in Ginkgo biloba.

    Science.gov (United States)

    Niu, Xingliang; Luo, Jun; Xu, Deran; Zou, Hongyan; Kong, Lingyi

    2017-02-05

    Ginkgolides, the main active constituents of Ginkgo biloba, possess significant selectively inhibition on platelet-activating factor and pancreatic lipase and attract wide attention in pharmacological research area. In our study, an effective hydrogen/deuterium (H/D) exchange method was developed by exchanging the α-Hs of lactone groups in ginkgolides with Ds, which was very useful for the elucidation of the fragmentation patterns of ginkgolides in Quadrupole Time-of-flight Mass Spectrometry (Q-TOF-MS), especially in accurately distinguishing the type and position of substituent in framework of ginkgolides. Then, a systematic research strategy for qualitative and quantitative analysis of ginkgolides, based on H/D exchange, tandem solid-phase extraction and LC-Q-TOF-MS, was developed, which was successfully applied in each medicinal part of G. biloba, which indicated that ginkgolide B was the most abundant ginkgolide in the seeds of G. biloba (60.6μg/g). This research was the successful application of H/D exchange in natural products, and proved that H/D exchange is a potential method for analysis research of complex TCMs active constituents. Copyright © 2016 Elsevier B.V. All rights reserved.

  19. Preparation and characterization of mesoporous VO(x)-TiO2 complex oxides for the selective oxidation of methanol to dimethoxymethane.

    Science.gov (United States)

    Liu, Jingwei; Sun, Qing; Fu, Yuchuan; Shen, Jianyi

    2009-07-15

    Mesoporous VO(x)-TiO(2) with high surface areas were prepared using the procedure of evaporation-induced self-assembly combined with ammonia posttreatment. The samples were characterized by X-ray diffraction (XRD), laser Raman spectroscopy (LRS), transmission electron microscopy (TEM), N(2) adsorption, temperature-programmed reduction (H(2)-TPR), microcalorimetry for the adsorption of NH(3), and isopropanol probe reaction. Their catalytic activities were evaluated for the reaction of selective oxidation of methanol to dimethoxymethane (DMM). It was found that the VO(x)-TiO(2) materials exhibited high surface areas with pore diameters of 4 nm. The vanadia species were highly dispersed in the VO(x)-TiO(2) within 30 wt% VO(x) content, evidenced by the results of XRD and LRS. The VO(x)-TiO(2) samples exhibited both surface acidic and redox properties. The surface acidity was further enhanced on the addition of SO(4)2-. The catalyst SO(4)2-/30VO(x)-TiO(2) exhibited good performance for the selective oxidation of methanol (57% conversion) to DMM (83% selectivity) at 423 K.

  20. Structure elucidation of chromogen resulting from jaffe's reaction

    International Nuclear Information System (INIS)

    Hussain, I.; Tariq, M.I.; Siddiqui, H.L.

    2009-01-01

    Jaffe's reaction is a reaction of creatinine with alkaline picric acid resulting in red chromogen. This color is being used widely for the estimation of creatinine in biological fluids without knowing the exact structure of the chromogen. The red species is isolated and its UV/Visible, /sup 1/H- and /sup 13/C- NMR studies are carried out. It is found that the red species is not a pure compound but a mixture of stereoisomers. Moreover, the red species in water reflects the same UV /Visible spectra as given by the reaction of creatinine with alkaline picrate in aqueous media The red species is a 2:3 molar Meisenheimer a-complex of creatinine-picric acid. (author)

  1. Elucidating Grinding Mechanism by Theoretical and Experimental Investigations

    Directory of Open Access Journals (Sweden)

    AMM Sharif Ullah

    2018-02-01

    Full Text Available Grinding is one of the essential manufacturing processes for producing brittle or hard materials-based precision parts (e.g., optical lenses. In grinding, a grinding wheel removes the desired amount of material by passing the same area on the workpiece surface multiple times. How the topography of a workpiece surface evolves with these passes is thus an important research issue, which has not yet been addressed elaborately. The present paper tackles this issue from both the theoretical and the experimental points of view. In particular, this paper presents the results of experimental and theoretical investigations on the multi-pass surface grinding operations where the workpiece surface is made of glass and the grinding wheel consists of cBN abrasive grains. Both investigations confirm that a great deal of stochasticity is involved in the grinding mechanism, and the complexity of the workpiece surface gradually increases along with the number of passes.

  2. [Elucidation of key genes in sex determination in genetics teaching].

    Science.gov (United States)

    Li, Meng; He, Zhumei

    2014-06-01

    Sex is an important and complex feature of organisms, which is controlled by the genetic and environmental factors. The genetic factors, i.e., genes, are vital in sex determination. However, not all the related genes play the same roles, and some key genes play a vital role in the sex determination and differentiation. With the development of the modern genetics, a great progress on the key genes has been made in sex determination. In this review, we summarize the mechanism of sex determination and the strategy of how to study the key genes in sex determination. It will help us to understand the mechanism of sex determination better in the teaching of genetics.

  3. Elucidating Grinding Mechanism by Theoretical and Experimental Investigations.

    Science.gov (United States)

    Ullah, Amm Sharif; Caggiano, Alessandra; Kubo, Akihiko; Chowdhury, M A K

    2018-02-09

    Grinding is one of the essential manufacturing processes for producing brittle or hard materials-based precision parts (e.g., optical lenses). In grinding, a grinding wheel removes the desired amount of material by passing the same area on the workpiece surface multiple times. How the topography of a workpiece surface evolves with these passes is thus an important research issue, which has not yet been addressed elaborately. The present paper tackles this issue from both the theoretical and the experimental points of view. In particular, this paper presents the results of experimental and theoretical investigations on the multi-pass surface grinding operations where the workpiece surface is made of glass and the grinding wheel consists of cBN abrasive grains. Both investigations confirm that a great deal of stochasticity is involved in the grinding mechanism, and the complexity of the workpiece surface gradually increases along with the number of passes.

  4. Selective mutism.

    Science.gov (United States)

    Hua, Alexandra; Major, Nili

    2016-02-01

    Selective mutism is a disorder in which an individual fails to speak in certain social situations though speaks normally in other settings. Most commonly, this disorder initially manifests when children fail to speak in school. Selective mutism results in significant social and academic impairment in those affected by it. This review will summarize the current understanding of selective mutism with regard to diagnosis, epidemiology, cause, prognosis, and treatment. Studies over the past 20 years have consistently demonstrated a strong relationship between selective mutism and anxiety, most notably social phobia. These findings have led to the recent reclassification of selective mutism as an anxiety disorder in the Diagnostic and Statistical Manual of Mental Disorders, 5th Edition. In addition to anxiety, several other factors have been implicated in the development of selective mutism, including communication delays and immigration/bilingualism, adding to the complexity of the disorder. In the past few years, several randomized studies have supported the efficacy of psychosocial interventions based on a graduated exposure to situations requiring verbal communication. Less data are available regarding the use of pharmacologic treatment, though there are some studies that suggest a potential benefit. Selective mutism is a disorder that typically emerges in early childhood and is currently conceptualized as an anxiety disorder. The development of selective mutism appears to result from the interplay of a variety of genetic, temperamental, environmental, and developmental factors. Although little has been published about selective mutism in the general pediatric literature, pediatric clinicians are in a position to play an important role in the early diagnosis and treatment of this debilitating condition.

  5. Synthesis and characterisation of nitrogen poly-heterocyclic molecules using as selective complexing agents of metallic cations; Synthese et caracterisation de molecules polyheterocycliques azotees utilisables en tant que complexants selectifs de cations metalliques

    Energy Technology Data Exchange (ETDEWEB)

    Alphonse, F.A

    2003-12-15

    Separation of actinides (III) from lanthanides (III) is a crucial problem in the reprocessing of used nuclear fuels. Experimental results shown that soft donor extractants such as nitrogen polydentate heterocycles containing a NCCNCCN coordination site are potentials ligands for selective extraction of actinides (III). In those cases, two types of liquid-liquid extractions are employed: synergistic combination with lipophilic acid extractants and direct extraction. On the basis of the Hard and Soft Acids and Bases theory and basicity evaluation, new extractants were defined. We have first studied the synthesis of potential 1,3,5-triazine ligands designed for extraction in synergy with {alpha}-bromodecanoic acid. Secondly, we have examined the synthesis of bis-triazinyl-pyridine ligands for direct extraction studies. Extraction tests were carried out and perspectives of synthesis were deducted from those extraction results. (author)

  6. Selective targeting of the mTORC1/2 protein kinase complexes leads to antileukemic effects in vitro and in vivo

    International Nuclear Information System (INIS)

    Schuster, K; Zheng, J; Arbini, A A; Zhang, C C; Scaglioni, P P

    2011-01-01

    The BCR/ABL tyrosine kinase promotes leukemogenesis through activation of several targets that include the phosphoinositide 3-kinase (PI3K). Tyrosine kinase inhibitors (TKIs), which target BCR/ABL, induce striking clinical responses. However, therapy with TKIs is associated with limitations such as drug intolerance, inability to universally eradicate the disease and emergence of BCR/ABL drug-resistant mutants. To overcome these limitations, we tested whether inhibition of the PI3K/target of rapamycin (mTOR) signaling pathway has antileukemic effect in primary hematopoietic stem cells and BA/F3 cells expressing the BCR/ABL oncoprotein. We determined that dual inhibition of PI3K/mTOR causes growth arrest and apoptosis leading to profound antileukemic effects both in vitro and in vivo. We also established that pharmacologic inhibition of the mTORC1/mTORC2 complexes is sufficient to cause these antileukemic effects. Our results support the development of inhibitors of the mTORC1/2 complexes for the therapy of leukemias that either express BCR/ABL or display deregulation of the PI3K/mTOR signaling pathway

  7. ESI-MS studies of the reactions of novel platinum(II) complexes containing O,O'-chelated acetylacetonate and sulfur ligands with selected model proteins.

    Science.gov (United States)

    Marzo, Tiziano; De Pascali, Sandra A; Gabbiani, Chiara; Fanizzi, Francesco P; Messori, Luigi; Pratesi, Alessandro

    2017-08-01

    A group of mixed-ligand Pt(II) complexes bearing acetylacetonate and sulphur ligands were recently developed in the University of Lecce as a new class of prospective anticancer agents that manifested promising pharma-cological properties in preliminary in vitro and in vivo tests. Though modelled on the basis of cisplatin, these Pt(II) complexes turned out to exhibit a profoundly distinct mode of action as they were found to act mainly on non-genomic targets rather than on DNA. Accordingly, we have explored here their reactions with two representative model proteins through an established ESI-MS procedure with the aim to describe their general interaction mechanism with protein targets. A pronounced reactivity with the tested proteins was indeed documented; the nature of the resulting metallodrug-protein interactions could be characterised in depth in the various cases. Preferential binding to protein targets compared to DNA is supported by independent ICP-OES measurements. The implications of these findings are discussed.

  8. Hybridization in the Ensatina Ring Species, Strong selection against hybrids at a hybrid zone in the ensatina ring species complex and its evolutionary implications

    Energy Technology Data Exchange (ETDEWEB)

    Alexandrino, Joao; Baird, Stuart J.E.; Lawson, Lucinda; Macey, J. Robert; Moritz, Craig; Wake, David B.

    2005-04-22

    The analysis of interactions between lineages at varying levels of genetic divergence can provide insights into the process of speciation through the accumulation of incompatible mutations. Ring species, and especially the Ensatina eschscholtzii system exemplify this approach. The plethodontid salamanders Ensatina eschscholtzii xanthoptica and Ensatina eschscholtzii platensis hybridize in the Central Sierran foothills of California. We compared the genetic structure across two transects (southern and northern Calaveras Co.), one of which was re-sampled over 20 years, and examined diagnostic molecular markers (eight allozyme loci and mitochondrial DNA) and a diagnostic quantitative trait (color pattern). Key results across all studies were: (i) cline centers for all markers were coincident and the zones were narrow, with width estimates of 730m to 2000m; (ii) cline centers at the northern Calaveras transect were coincident between 1981 and 2001, demonstrating repeatability over 5 generations; (iii) there are very few if any putative F1's, but a relatively high number of backcrossed individuals (57-86 percent) in the central portion of transects; (iv) we found substantial linkage disequilibrium in all three studies and strong heterozygote deficit both in northern Calaveras, in 2001, and southern Calaveras. Both linkage disequilibrium and heterozygote deficit show maximum values near the center of the zones (R and Fis, approx. equal to 0.5). Using estimates of cline width and dispersal, we infer strong selection against hybrids (s* approx. equal to 46-75 percent). This is sufficient to promote accumulation of differences at loci that are neutral or under divergent selection, but would still allow for introgression of adaptive alleles. The evidence for strong, but incomplete isolation across this centrally located contact is consistent with theory suggesting a gradual increase in postzygotic incompatibility between allopatric populations subject to divergent

  9. Data analysis at the CMS level-1 trigger: migrating complex selection algorithms from offline analysis and high-level trigger to the trigger electronics

    CERN Document Server

    Wulz, Claudia

    2017-01-01

    With ever increasing luminosity at the LHC, optimum online data selection is becoming more and more important. While in the case of some experiments (LHCb and ALICE) this task is being completely transferred to computer farms, the others -- ATLAS and CMS -- will not be able to do this in the medium-term future for technological, detector-related reasons. Therefore, these experiments pursue the complementary approach of migrating more and more of the offline and high-level trigger intelligence into the trigger electronics. The presentation illustrates how the level-1 trigger of the CMS experiment and in particular its concluding stage, the so-called ``Global Trigger", take up this challenge.

  10. A Characeae Cells Plasma Membrane as a Model for Selection of Bioactive Compounds and Drugs: Interaction of HAMLET-Like Complexes with Ion Channels of Chara corallina Cells Plasmalemma.

    Science.gov (United States)

    Kataev, Anatoly; Zherelova, Olga; Grishchenko, Valery

    2016-12-01

    Interaction of a HAMLET-like La-OA cytotoxic complex (human α-lactalbumin-oleic acid) and its constituents with the excitable plasmalemma of giant Chara corallina cells was investigated. The voltage-clamp technique was used to study Ca 2+ and Cl - transient currents in the plasmalemma of intact cells. The action of the complex and OA on the target cell membrane has a dose-dependent character. It was found that the La-OA complex has an inhibiting effect on Ca 2+ current across the plasmalemma, while α-lactalbumin alone does not affect the electrophysiological characteristics of the cellular membrane. However, oleic acid blocks Ca 2+ current across the plasmalemma. This is accompanied by the induction of a non-selective conductivity in the cellular membrane, a decrease in the resting potential and plasma membrane resistance of algal cells. We propose that the cytotoxicity of La-OA and other HAMLET-like complexes is determined by oleic acid acting as a blocker of potential-dependent Ca 2+ channels in the plasma membrane of target cells. The presented results show that the study model of green algae C. corallina cells plasmalemma is a convenient tool for the investigation of ion channels in many animal cells.

  11. A Parsimonious Model of the Rabbit Action Potential Elucidates the Minimal Physiological Requirements for Alternans and Spiral Wave Breakup.

    Science.gov (United States)

    Gray, Richard A; Pathmanathan, Pras

    2016-10-01

    Elucidating the underlying mechanisms of fatal cardiac arrhythmias requires a tight integration of electrophysiological experiments, models, and theory. Existing models of transmembrane action potential (AP) are complex (resulting in over parameterization) and varied (leading to dissimilar predictions). Thus, simpler models are needed to elucidate the "minimal physiological requirements" to reproduce significant observable phenomena using as few parameters as possible. Moreover, models have been derived from experimental studies from a variety of species under a range of environmental conditions (for example, all existing rabbit AP models incorporate a formulation of the rapid sodium current, INa, based on 30 year old data from chick embryo cell aggregates). Here we develop a simple "parsimonious" rabbit AP model that is mathematically identifiable (i.e., not over parameterized) by combining a novel Hodgkin-Huxley formulation of INa with a phenomenological model of repolarization similar to the voltage dependent, time-independent rectifying outward potassium current (IK). The model was calibrated using the following experimental data sets measured from the same species (rabbit) under physiological conditions: dynamic current-voltage (I-V) relationships during the AP upstroke; rapid recovery of AP excitability during the relative refractory period; and steady-state INa inactivation via voltage clamp. Simulations reproduced several important "emergent" phenomena including cellular alternans at rates > 250 bpm as observed in rabbit myocytes, reentrant spiral waves as observed on the surface of the rabbit heart, and spiral wave breakup. Model variants were studied which elucidated the minimal requirements for alternans and spiral wave break up, namely the kinetics of INa inactivation and the non-linear rectification of IK.The simplicity of the model, and the fact that its parameters have physiological meaning, make it ideal for engendering generalizable mechanistic

  12. Combining pharmacophore fingerprints and PLS-discriminant analysis for virtual screening and SAR elucidation

    DEFF Research Database (Denmark)

    Askjær, Sune; Langgård, Morten

    2008-01-01

    The criterion of success for the initial stages of a ligand-based drug-discovery project is dual. First, a set of suitable lead compounds has to be identified. Second, a level of a preliminary structure-activity relationship (SAR) of the identified ligands has to be established in order to guide ...... by the protein-binding site known from X-ray complexes. The result of this analysis assists in explaining the efficiency of 2D pharmacophore fingerprints as descriptors in virtual screening....... the lead optimization toward a final drug candidate. This paper presents a combined approach to solving these two problems of ligand-based virtual screening and elucidation of SAR based on interplay between pharmacophore fingerprints and interpretation of PLS-discriminant analysis (PLS-DA) models....... The virtual screening capability of the PLS-DA method is compared to group fusion maximum similarity searching in a test using four graph-based pharmacophore fingerprints over a range of 10 diverse targets. The PLS-DA method was generally found to do better than the Smax method. The GpiDAPH3 and PCH...

  13. Elucidation of self-induced sloshing occurrence mechanism using numerical analysis

    International Nuclear Information System (INIS)

    Saeki, Soichi; Madarame, Haruki; Okamoto, Koji; Tanaka, Nobukazu.

    1995-01-01

    In liquid metal-cooled fast breeder reactors, there is free liquid surface in a reactor vessel and others, and by reducing the size of the reactor vessel and others, it is necessary to increase the flow velocity of liquid sodium coolant. In the free liquid surface in which fast circulating flow exists, undesirable phenomena like waving and bubble catching are feared. The self-induced sloshing taken up in this study is one of these phenomena. Since the actual machine has complex three-dimensional structure, in order to forecast the occurrence of sloshing, it is necessary to elucidate the mechanism of vibration occurrence. The mechanism of occurrence of self-induced sloshing due to horizontal and vertical plane jets has been explained a number of times so far. In this study, by applying the model of the occurrence mechanism of Fukaya to horizontal plane jet, the self-induced sloshing due to horizontal plane jet was simulated by numerical analysis. Based on the results, it was attempted to examine the vibration energy supplied to sloshing in a whole flow field and the dependence of sloshing region on water depth and flow velocity. The numerical simulation, the analysis of the occurrence mechanism by using the numerical analysis code and the results are reported. (K.I.)

  14. Multi-omics approach to elucidate the gut microbiota activity: Metaproteomics and metagenomics connection.

    Science.gov (United States)

    Guirro, Maria; Costa, Andrea; Gual-Grau, Andreu; Mayneris-Perxachs, Jordi; Torrell, Helena; Herrero, Pol; Canela, Núria; Arola, Lluís

    2018-02-10

    Over the last few years, the application of high-throughput meta-omics methods has provided great progress in improving the knowledge of the gut ecosystem and linking its biodiversity to host health conditions, offering complementary support to classical microbiology. Gut microbiota plays a crucial role in relevant diseases such as obesity or cardiovascular disease (CVD), and its regulation is closely influenced by several factors, such as dietary composition. In fact, polyphenol-rich diets are the most palatable treatment to prevent hypertension associated with CVD, although the polyphenol-microbiota interactions have not been completely elucidated. For this reason, the aim of this study was to evaluate microbiota effect in obese rats supplemented by hesperidin, after being fed with cafeteria or standard diet, using a multi meta-omics approaches combining strategy of metagenomics and metaproteomics analysis. We reported that cafeteria diet induces obesity, resulting in changes in the microbiota composition, which are related to functional alterations at proteome level. In addition, hesperidin supplementation alters microbiota diversity and also proteins involved in important metabolic pathways. Overall, going deeper into strategies to integrate omics sciences is necessary to understand the complex relationships between the host, gut microbiota, and diet. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Elucidation of Peptide-Directed Palladium Surface Structure for Biologically Tunable Nanocatalysts

    Energy Technology Data Exchange (ETDEWEB)

    Bedford, Nicholas M.; Ramezani-Dakhel, Hadi; Slocik, Joseph M.; Briggs, Beverly D.; Ren, Yang; Frenkel, Anatoly I.; Petkov, Valeri; Heinz, Hendrik; Naik, Rajesh R.; Knecht, Mark R.

    2015-05-01

    Peptide-enabled synthesis of inorganic nanostructures represents an avenue to access catalytic materials with tunable and optimized properties. This is achieved via peptide complexity and programmability that is missing in traditional ligands for catalytic nanomaterials. Unfortunately, there is limited information available to correlate peptide sequence to particle structure and catalytic activity to date. As such, the application of peptide-enabled nanocatalysts remains limited to trial and error approaches. In this paper, a hybrid experimental and computational approach is introduced to systematically elucidate biomolecule-dependent structure/function relationships for peptide-capped Pd nanocatalysts. Synchrotron X-ray techniques were used to uncover substantial particle surface structural disorder, which was dependent upon the amino acid sequence of the peptide capping ligand. Nanocatalyst configurations were then determined directly from experimental data using reverse Monte Carlo methods and further refined using molecular dynamics simulation, obtaining thermodynamically stable peptide-Pd nanoparticle configurations. Sequence-dependent catalytic property differences for C-C coupling and olefin hydrogenation were then eluddated by identification of the catalytic active sites at the atomic level and quantitative prediction of relative reaction rates. This hybrid methodology provides a clear route to determine peptide-dependent structure/function relationships, enabling the generation of guidelines for catalyst design through rational tailoring of peptide sequences

  16. A silica-supported double-decker silsesquioxane provides a second skin for the selective generation of bipodal surface organometallic complexes

    KAUST Repository

    Espinas, Jeff

    2012-11-12

    A well-defined silica-based material with a homogeneous nanolayer presenting identical pairs of vicinal silanols has been prepared by reaction of the surface organometallic species [≡SiOZr(CH 2CMe 3) 3], obtained on a silica dehydroxylated at 900 °C, with the double-decker-shaped silsesquioxane (OH) 2DD(OH) 2. The surface structure has been established using extensive NMR characterization ( 1H, 13C, 29Si, HETCOR, double-quantum, triple-quantum). Treatment with Zr(CH 2CMe 3) 4 leads to the first well-defined single-site bipodal grafted bis-neopentyl zirconium complex. © 2012 American Chemical Society.

  17. A silica-supported double-decker silsesquioxane provides a second skin for the selective generation of bipodal surface organometallic complexes

    KAUST Repository

    Espinas, Jeff; Pelletier, Jeremie; Abou-Hamad, Edy; Emsley, Lyndon; Basset, Jean-Marie

    2012-01-01

    A well-defined silica-based material with a homogeneous nanolayer presenting identical pairs of vicinal silanols has been prepared by reaction of the surface organometallic species [≡SiOZr(CH 2CMe 3) 3], obtained on a silica dehydroxylated at 900 °C, with the double-decker-shaped silsesquioxane (OH) 2DD(OH) 2. The surface structure has been established using extensive NMR characterization ( 1H, 13C, 29Si, HETCOR, double-quantum, triple-quantum). Treatment with Zr(CH 2CMe 3) 4 leads to the first well-defined single-site bipodal grafted bis-neopentyl zirconium complex. © 2012 American Chemical Society.

  18. Elucidating the Interdependence of Drug Resistance from Combinations of Mutations.

    Science.gov (United States)

    Ragland, Debra A; Whitfield, Troy W; Lee, Sook-Kyung; Swanstrom, Ronald; Zeldovich, Konstantin B; Kurt-Yilmaz, Nese; Schiffer, Celia A

    2017-11-14

    HIV-1 protease is responsible for the cleavage of 12 nonhomologous sites within the Gag and Gag-Pro-Pol polyproteins in the viral genome. Under the selective pressure of protease inhibition, the virus evolves mutations within (primary) and outside of (secondary) the active site, allowing the protease to process substrates while simultaneously countering inhibition. The primary protease mutations impede inhibitor binding directly, while the secondary mutations are considered accessory mutations that compensate for a loss in fitness. However, the role of secondary mutations in conferring drug resistance remains a largely unresolved topic. We have shown previously that mutations distal to the active site are able to perturb binding of darunavir (DRV) via the protein's internal hydrogen-bonding network. In this study, we show that mutations distal to the active site, regardless of context, can play an interdependent role in drug resistance. Applying eigenvalue decomposition to collections of hydrogen bonding and van der Waals interactions from a series of molecular dynamics simulations of 15 diverse HIV-1 protease variants, we identify sites in the protease where amino acid substitutions lead to perturbations in nonbonded interactions with DRV and/or the hydrogen-bonding network of the protease itself. While primary mutations are known to drive resistance in HIV-1 protease, these findings delineate the significant contributions of accessory mutations to resistance. Identifying the variable positions in the protease that have the greatest impact on drug resistance may aid in future structure-based design of inhibitors.

  19. BAY 87-2243, a highly potent and selective inhibitor of hypoxia-induced gene activation has antitumor activities by inhibition of mitochondrial complex I

    International Nuclear Information System (INIS)

    Ellinghaus, Peter; Heisler, Iring; Unterschemmann, Kerstin; Haerter, Michael; Beck, Hartmut; Greschat, Susanne; Ehrmann, Alexander; Summer, Holger; Flamme, Ingo; Oehme, Felix; Thierauch, Karlheinz; Michels, Martin; Hess-Stumpp, Holger; Ziegelbauer, Karl

    2013-01-01

    The activation of the transcription factor hypoxia-inducible factor-1 (HIF-1) plays an essential role in tumor development, tumor progression, and resistance to chemo- and radiotherapy. In order to identify compounds targeting the HIF pathway, a small molecule library was screened using a luciferase-driven HIF-1 reporter cell line under hypoxia. The high-throughput screening led to the identification of a class of aminoalkyl-substituted compounds that inhibited hypoxia-induced HIF-1 target gene expression in human lung cancer cell lines at low nanomolar concentrations. Lead structure BAY 87-2243 was found to inhibit HIF-1α and HIF-2α protein accumulation under hypoxic conditions in non-small cell lung cancer (NSCLC) cell line H460 but had no effect on HIF-1α protein levels induced by the hypoxia mimetics desferrioxamine or cobalt chloride. BAY 87-2243 had no effect on HIF target gene expression levels in RCC4 cells lacking Von Hippel–Lindau (VHL) activity nor did the compound affect the activity of HIF prolyl hydroxylase-2. Antitumor activity of BAY 87-2243, suppression of HIF-1α protein levels, and reduction of HIF-1 target gene expression in vivo were demonstrated in a H460 xenograft model. BAY 87-2243 did not inhibit cell proliferation under standard conditions. However under glucose depletion, a condition favoring mitochondrial ATP generation as energy source, BAY 87-2243 inhibited cell proliferation in the nanomolar range. Further experiments revealed that BAY 87-2243 inhibits mitochondrial complex I activity but has no effect on complex III activity. Interference with mitochondrial function to reduce hypoxia-induced HIF-1 activity in tumors might be an interesting therapeutic approach to overcome chemo- and radiotherapy-resistance of hypoxic tumors

  20. Selective Flow-Injection Quantification of Ultra-trace Amounts of Cr(VI) via On-line Complexation and Preconcentration with APDC Followed by Determination by Electrothermal Atomic Absorption Spectrometry

    DEFF Research Database (Denmark)

    Nielsen, Steffen; Hansen, Elo Harald

    1998-01-01

    A rapid, sensitive and selective time-based flow injection (FI) preconcentration procedure is described for the determination of ultra-trace amounts of Cr(VI) via on-line reaction with ammonium pyrrolidine dithiocarbamate (APDC) and formation of the Cr(VI)-PDC complex. The preconcentration...... to direct introduction of 55 mu l samples, yielding a detection limit (3 sigma) of 4.2 ng l(-1). The sample frequency was 21.2 samples per hour. The proposed method was evaluated by analyzing drinking water, a NIST Cr(VI)-reference material and synthetic sea water. A major contribution to successful...

  1. A quinoline-based Cu2 + ion complex fluorescence probe for selective detection of inorganic phosphate anion in aqueous solution and its application to living cells

    Science.gov (United States)

    Dai, Yanpeng; Wang, Peng; Fu, Jiaxin; Yao, Kun; Xu, Kuoxi; Pang, Xiaobin

    2017-08-01

    A quinaldine functionalized probe QP has been designed and synthesized. It exhibited selective turn-off fluorescence response toward Cu2 + ion over most of the biologically important ions at physiological pH. The binding ratio of the probe QP and Cu2 + ion was determined to be 1:1 through fluorescence titration, Job's plot and ESI-MS. The binding constant (K) of Cu2 + to probe QP was found to be 2.12 × 104 M- 1. Further, the Cu2 + ensemble of probe QP was found to respond H2PO4- and HPO42 - among other important biological anions via fluorescence turn-on response at physiological pH. Fluorescence microscopy imaging using living Hela cells showed that probe QP could be used as an effective fluorescent probe for detecting Cu2 + cation and H2PO4- and HPO42 - anions in living cells.

  2. A systems approach to integrative biology: an overview of statistical methods to elucidate association and architecture.

    Science.gov (United States)

    Ciaccio, Mark F; Finkle, Justin D; Xue, Albert Y; Bagheri, Neda

    2014-07-01

    An organism's ability to maintain a desired physiological response relies extensively on how cellular and molecular signaling networks interpret and react to environmental cues. The capacity to quantitatively predict how networks respond to a changing environment by modifying signaling regulation and phenotypic responses will help inform and predict the impact of a changing global enivronment on organisms and ecosystems. Many computational strategies have been developed to resolve cue-signal-response networks. However, selecting a strategy that answers a specific biological question requires knowledge both of the type of data being collected, and of the strengths and weaknesses of different computational regimes. We broadly explore several computational approaches, and we evaluate their accuracy in predicting a given response. Specifically, we describe how statistical algorithms can be used in the context of integrative and comparative biology to elucidate the genomic, proteomic, and/or cellular networks responsible for robust physiological response. As a case study, we apply this strategy to a dataset of quantitative levels of protein abundance from the mussel, Mytilus galloprovincialis, to uncover the temperature-dependent signaling network. © The Author 2014. Published by Oxford University Press on behalf of the Society for Integrative and Comparative Biology. All rights reserved. For permissions please email: journals.permissions@oup.com.

  3. Comprehensive secondary structure elucidation of four genera of the family Pospiviroidae.

    Directory of Open Access Journals (Sweden)

    Tamara Giguère

    Full Text Available Viroids are small, circular, single stranded RNA molecules that infect plants. Since they are non-coding, their structures play a critical role in their life cycles. To date, little effort has been spend on elucidating viroid structures in solution due to both the experimental difficulties and the time-consuming nature of the methodologies implicated. Recently, the technique of high-throughput selective 2'-hydroxyl acylation analyzed by primer extension (SHAPE was adapted for the probing of the members of family Avsunviroidae, all of whom replicate in the chloroplast and demonstrate ribozyme activity. In the present work, twelve viroid species belonging to four different genera of the family Pospiviroidae, whose members are characterized by the presence of a central conserved region (CCR and who replicate in nucleus of the host, were probed. Given that the structures of five distinct viroid species from the family Pospiviroidae have been previously reported, an overview of the different structural characteristics for all genera and the beginning of a manual classification of the different viroids based on their structural features are presented here.

  4. Elucidation of terpenoid metabolism in Scoparia dulcis by RNA-seq analysis.

    Science.gov (United States)

    Yamamura, Yoshimi; Kurosaki, Fumiya; Lee, Jung-Bum

    2017-03-07

    Scoparia dulcis biosynthesize bioactive diterpenes, such as scopadulcic acid B (SDB), which are known for their unique molecular skeleton. Although the biosynthesis of bioactive diterpenes is catalyzed by a sequence of class II and class I diterpene synthases (diTPSs), the mechanisms underlying this process are yet to be fully identified. To elucidate these biosynthetic machinery, we performed a high-throughput RNA-seq analysis, and de novo assembly of clean reads revealed 46,332 unique transcripts and 40,503 two unigenes. We found diTPSs genes including a putative syn-copalyl diphosphate synthase (SdCPS2) and two kaurene synthase-like (SdKSLs) genes. Besides them, total 79 full-length of cytochrome P450 (CYP450) genes were also discovered. The expression analyses showed selected CYP450s associated with their expression pattern of SdCPS2 and SdKSL1, suggesting that CYP450 candidates involved diterpene modification. SdCPS2 represents the first predicted gene to produce syn-copalyl diphosphate in dicots. In addition, SdKSL1 potentially contributes to the SDB biosynthetic pathway. Therefore, these identified genes associated with diterpene biosynthesis lead to the development of genetic engineering focus on diterpene metabolism in S. dulcis.

  5. Human Drug Discrimination: Elucidating the Neuropharmacology of Commonly Abused Illicit Drugs.

    Science.gov (United States)

    Bolin, B Levi; Alcorn, Joseph L; Reynolds, Anna R; Lile, Joshua A; Stoops, William W; Rush, Craig R

    2016-06-07

    Drug-discrimination procedures empirically evaluate the control that internal drug states have over behavior. They provide a highly selective method to investigate the neuropharmacological underpinnings of the interoceptive effects of drugs in vivo. As a result, drug discrimination has been one of the most widely used assays in the field of behavioral pharmacology. Drug-discrimination procedures have been adapted for use with humans and are conceptually similar to preclinical drug-discrimination techniques in that a behavior is differentially reinforced contingent on the presence or absence of a specific interoceptive drug stimulus. This chapter provides a basic overview of human drug-discrimination procedures and reviews the extant literature concerning the use of these procedures to elucidate the underlying neuropharmacological mechanisms of commonly abused illicit drugs (i.e., stimulants, opioids, and cannabis) in humans. This chapter is not intended to review every available study that used drug-discrimination procedures in humans. Instead, when possible, exemplary studies that used a stimulant, opioid, or Δ 9 -tetrahydrocannabinol (the primary psychoactive constituent of cannabis) to assess the discriminative-stimulus effects of drugs in humans are reviewed for illustrative purposes. We conclude by commenting on the current state and future of human drug-discrimination research.

  6. Immunohistochemical examination of plexiform-like complex vascular lesions in the lungs of broiler chickens selected for susceptibility to idiopathic pulmonary arterial hypertension.

    Science.gov (United States)

    Hamal, Krishna R; Erf, Gisela F; Anthony, Nicholas B; Wideman, Robert F

    2012-01-01

    Idiopathic pulmonary arterial hypertension (IPAH) is a disease of unknown cause that is characterized by elevated pulmonary arterial pressure and pulmonary vascular resistance, and by extensive vascular remodelling. In human IPAH patients, remodelling of the pulmonary vasculature results in the formation of plexiform lesions in the terminal pulmonary arterioles. Various molecules are expressed in the human plexiform lesions, including alpha smooth muscle actin, von Willebrand factor, vascular endothelial growth factor, vascular endothelial growth factor receptor type 2, hypoxia inducible factor-1α, survivin, tenascin, collagen, fibronectin, and various immune/inflammatory cells such as, cytotoxic lymphocytes, B lymphocytes, MHC class II cells, and monocytes/macrophages are also present. Plexiform lesions rarely develop in the lungs of laboratory animals, but plexiform-like complex vascular lesions (CVL) do develop spontaneously in the lungs of broiler chickens from an IPAH-susceptible line. To examine angioproliferative and immune-system-related activities associated with CVL in broiler lungs, paraformaldehyde-fixed, paraffin-embedded lung sections from 8-week-old to 24-week-old broiler chickens were stained immunohistochemically using monoclonal or polyclonal antibodies specific for angioproliferative molecules and immune/inflammatory cells. The CVL in the lungs of broiler chickens exhibited positive staining for both angioproliferative molecules and immune/inflammatory cells. These observations combined with the close histological resemblance of broiler CVL to the plexiform lesions of human IPAH patients further validates chickens from our IPAH-susceptible line as an excellent animal model of spontaneous plexogenic arteriopathy.

  7. 3D printing of an aortic aneurysm to facilitate decision making and device selection for endovascular aneurysm repair in complex neck anatomy.

    Science.gov (United States)

    Tam, Matthew D B S; Laycock, Stephen D; Brown, James R I; Jakeways, Matthew

    2013-12-01

    To describe rapid prototyping or 3-dimensional (3D) printing of aneurysms with complex neck anatomy to facilitate endovascular aneurysm repair (EVAR). A 75-year-old man had a 6.6-cm infrarenal aortic aneurysm that appeared on computed tomographic angiography to have a sharp neck angulation of ~90°. However, although the computed tomography (CT) data were analyzed using centerline of flow, the true neck length and relations of the ostial origins were difficult to determine. No multidisciplinary consensus could be reached as to which stent-graft to use owing to these borderline features of the neck anatomy. Based on past experience with rapid prototyping technology, a decision was taken to print a model of the aneurysm to aid in visualization of the neck anatomy. The CT data were segmented, processed, and converted into a stereolithographic format representing the lumen as a 3D volume, from which a full-sized replica was printed within 24 hours. The model demonstrated that the neck was adequate for stent-graft repair using the Aorfix device. Rapid prototyping of aortic aneurysms is feasible and can aid decision making and device delivery. Further work is required to test the value of 3D replicas in planning procedures and their impact on procedure time, radiation dose, and procedure cost.

  8. Selective Production of 2-Methylfuran by Gas-Phase Hydrogenation of Furfural on Copper Incorporated by Complexation in Mesoporous Silica Catalysts.

    Science.gov (United States)

    Jiménez-Gómez, Carmen Pilar; Cecilia, Juan A; Moreno-Tost, Ramón; Maireles-Torres, Pedro

    2017-04-10

    Copper species have been incorporated in mesoporous silica (MS) through complexation with the amine groups of dodecylamine, which was used as a structure-directing agent in the synthesis. A series of Cu/SiO 2 catalysts (xCu-MS) with copper loadings (x) from 2.5 to 20 wt % was synthesized and evaluated in the gas-phase hydrogenation of furfural (FUR). The most suitable catalytic performance in terms of 2-methylfuran yield was obtained with an intermediate copper content (10 wt %). This 10Cu-MS catalyst exhibits a 2-methylfuran yield higher than 95 mol % after 5 h time-on-stream (TOS) at a reaction temperature of 210 °C with a H 2 /FUR molar ratio of 11.5 and a weight hourly space velocity (WHSV) of 1.5 h -1 . After 14 h TOS, this catalyst still showed a yield of 80 mol %. In all cases, carbonaceous deposits on the external surface were the cause of the catalyst deactivation, although sintering of the copper particles was observed for higher copper loadings. This intermediate copper loading (10 wt %) offered a suitable balance between resistance to sintering and tendency to form carbonaceous deposits. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Whole genome analysis of selected human and animal rotaviruses identified in Uganda from 2012 to 2014 reveals complex genome reassortment events between human, bovine, caprine and porcine strains.

    Science.gov (United States)

    Bwogi, Josephine; Jere, Khuzwayo C; Karamagi, Charles; Byarugaba, Denis K; Namuwulya, Prossy; Baliraine, Frederick N; Desselberger, Ulrich; Iturriza-Gomara, Miren

    2017-01-01

    Rotaviruses of species A (RVA) are a common cause of diarrhoea in children and the young of various other mammals and birds worldwide. To investigate possible interspecies transmission of RVAs, whole genomes of 18 human and 6 domestic animal RVA strains identified in Uganda between 2012 and 2014 were sequenced using the Illumina HiSeq platform. The backbone of the human RVA strains had either a Wa- or a DS-1-like genetic constellation. One human strain was a Wa-like mono-reassortant containing a DS-1-like VP2 gene of possible animal origin. All eleven genes of one bovine RVA strain were closely related to those of human RVAs. One caprine strain had a mixed genotype backbone, suggesting that it emerged from multiple reassortment events involving different host species. The porcine RVA strains had mixed genotype backbones with possible multiple reassortant events with strains of human and bovine origin.Overall, whole genome characterisation of rotaviruses found in domestic animals in Uganda strongly suggested the presence of human-to animal RVA transmission, with concomitant circulation of multi-reassortant strains potentially derived from complex interspecies transmission events. However, whole genome data from the human RVA strains causing moderate and severe diarrhoea in under-fives in Uganda indicated that they were primarily transmitted from person-to-person.

  10. Elucidation of the Structure Formation of Polymer-Conjugated Proteins in Solution and Block Copolymer Templates

    Science.gov (United States)

    Ferebee, Rachel L.

    The broader technical objective of this work is to contribute to the development of enzyme-functionalized nanoporous membranes that can function as autonomous and target selective dynamic separators. The scientific objective of the research performed within this thesis is to elucidate the parameters that control the mixing of proteins in organic host materials and in block copolymers templates in particular. A "biomimetic" membrane system that uses enzymes to selectively neutralize targets and trigger a change in permeability of nanopores lined with a pH-responsive polymer has been fabricated and characterized. Mechanical and functional stability, as well as scalability, have been demonstrated for this system. Additional research has focused on the role of polymeric ligands on the solubility characteristics of the model protein, Bovine Serum Albumin (BSA). For this purpose BSA was conjugated with poly(ethylene glycol) (PEG) ligands of varied degree of polymerization and grafting density. Combined static and dynamic light scattering was used (in conjunction with MALDI-TOF) to determine the second virial coefficient in PBS solutions. At a given mass fraction PEG or average number of grafts, the solubility of BSA-PEG conjugates is found to increase with the degree of polymerization of conjugated PEG. This result informs the synthesis of protein-conjugate systems that are optimized for the fabrication of block copolymer blend materials with maximum protein loading. Blends of BSA-PEG conjugates and block copolymer (BCP) matrices were fabricated to evaluate the dispersion morphology and solubility limits in a model system. Electron microscopy was used to evaluate the changes in lamellar spacing with increased filling fraction of BSA-PEG conjugates.

  11. Three-dimensional-printed cardiac prototypes aid surgical decision-making and preoperative planning in selected cases of complex congenital heart diseases: Early experience and proof of concept in a resource-limited environment.

    Science.gov (United States)

    Kappanayil, Mahesh; Koneti, Nageshwara Rao; Kannan, Rajesh R; Kottayil, Brijesh P; Kumar, Krishna

    2017-01-01

    Three-dimensional. (3D) printing is an innovative manufacturing process that allows computer-assisted conversion of 3D imaging data into physical "printouts" Healthcare applications are currently in evolution. The objective of this study was to explore the feasibility and impact of using patient-specific 3D-printed cardiac prototypes derived from high-resolution medical imaging data (cardiac magnetic resonance imaging/computed tomography [MRI/CT]) on surgical decision-making and preoperative planning in selected cases of complex congenital heart diseases (CHDs). Five patients with complex CHD with previously unresolved management decisions were chosen. These included two patients with complex double-outlet right ventricle, two patients with criss-cross atrioventricular connections, and one patient with congenitally corrected transposition of great arteries with pulmonary atresia. Cardiac MRI was done for all patients, cardiac CT for one; specific surgical challenges were identified. Volumetric data were used to generate patient-specific 3D models. All cases were reviewed along with their 3D models, and the impact on surgical decision-making and preoperative planning was assessed. Accurate life-sized 3D cardiac prototypes were successfully created for all patients. The models enabled radically improved 3D understanding of anatomy, identification of specific technical challenges, and precise surgical planning. Augmentation of existing clinical and imaging data by 3D prototypes allowed successful execution of complex surgeries for all five patients, in accordance with the preoperative planning. 3D-printed cardiac prototypes can radically assist decision-making, planning, and safe execution of complex congenital heart surgery by improving understanding of 3D anatomy and allowing anticipation of technical challenges.

  12. Statistical electromagnetics: Complex cavities

    NARCIS (Netherlands)

    Naus, H.W.L.

    2008-01-01

    A selection of the literature on the statistical description of electromagnetic fields and complex cavities is concisely reviewed. Some essential concepts, for example, the application of the central limit theorem and the maximum entropy principle, are scrutinized. Implicit assumptions, biased

  13. Photocytotoxic lanthanide complexes

    Indian Academy of Sciences (India)

    Department of Inorganic and Physical Chemistry, Indian Institute of Science, Bangalore 560 ... complexes showing photoactivated DNA cleavage activity and cytotoxicity in cancer cells. .... considerable importance for their selectivity in killing.

  14. Optimization of reaction conditions in selective oxidation of styrene over fine crystallite spinel-type CaFe2O4 complex oxide catalyst

    International Nuclear Information System (INIS)

    Pardeshi, Satish K.; Pawar, Ravindra Y.

    2010-01-01

    The CaFe 2 O 4 spinel-type catalyst was synthesized by citrate gel method and well characterized by thermogravimetric analysis, atomic absorption spectroscopy, Fourier-transform infrared spectroscopy, X-ray diffraction and transmission electron microscopy. The crystallization temperature of the spinel particle prepared by citrate gel method was 600 o C which was lower than that of ferrite prepared by other methods. CaFe 2 O 4 catalysts prepared by citrate gel method show better activity for styrene oxidation in the presence of dilute H 2 O 2 (30%) as an oxidizing agent. In this reaction the oxidative cleavage of carbon-carbon double bond of styrene takes place selectively with 38 ± 2 mol% conversion. The major product of the reaction is benzaldehyde up to 91 ± 2 mol% and minor product phenyl acetaldehyde up to 9 ± 2 mol%, respectively. The products obtained in the styrene oxidation reaction were analyzed by gas chromatography and mass spectroscopy. The influence of the catalyst, reaction time, temperature, amount of catalyst, styrene/H 2 O 2 molar ratio and solvents on the conversion and product distribution were studied.

  15. pH-sensitive polymeric cisplatin-ion complex with styrene-maleic acid copolymer exhibits tumor-selective drug delivery and antitumor activity as a result of the enhanced permeability and retention effect.

    Science.gov (United States)

    Saisyo, Atsuyuki; Nakamura, Hideaki; Fang, Jun; Tsukigawa, Kenji; Greish, Khaled; Furukawa, Hiroyuki; Maeda, Hiroshi

    2016-02-01

    Cisplatin (CDDP) is widely used to treat various cancers. However, its distribution to normal tissues causes serious adverse effects. For this study, we synthesized a complex of styrene-maleic acid copolymer (SMA) and CDDP (SMA-CDDP), which formed polymeric micelles, to achieve tumor-selective drug delivery based on the enhanced permeability and retention (EPR) effect. SMA-CDDP is obtained by regulating the pH of the reaction solution of SMA and CDDP. The mean SMA-CDDP particle size was 102.5 nm in PBS according to electrophoretic light scattering, and the CDDP content was 20.1% (w/w). The release rate of free CDDP derivatives from the SMA-CDDP complex at physiological pH was quite slow (0.75%/day), whereas it was much faster at pH 5.5 (4.4%/day). SMA-CDDP thus had weaker in vitro toxicity at pH 7.4 but higher cytotoxicity at pH 5.5. In vivo pharmacokinetic studies showed a 5-fold higher tumor concentration of SMA-CDDP than of free CDDP. SMA-CDDP had more effective antitumor potential but lower toxicity than did free CDDP in mice after i.v. administration. Administration of parental free CDDP at 4 mg/kg×3 caused a weight loss of more than 5%; SMA-CDDP at 60 mg/kg (CDDP equivalent)×3 caused no significant weight change but markedly suppressed S-180 tumor growth. These findings together suggested using micelles of the SMA-CDDP complex as a cancer chemotherapeutic agent because of beneficial properties-tumor-selective accumulation and relatively rapid drug release at the acidic pH of the tumor-which resulted in superior antitumor effects and fewer side effects compared with free CDDP. Copyright © 2015 Elsevier B.V. All rights reserved.

  16. Selective hydrolysis of phosphate monoester by a supramolecular phosphatase formed by the self-assembly of a bis(Zn(2+)-cyclen) complex, cyanuric acid, and copper in an aqueous solution (cyclen = 1,4,7,10-tetraazacyclododecane).

    Science.gov (United States)

    Zulkefeli, Mohd; Suzuki, Asami; Shiro, Motoo; Hisamatsu, Yosuke; Kimura, Eiichi; Aoki, Shin

    2011-10-17

    In Nature, organized nanoscale structures such as proteins and enzymes are formed in aqueous media via intermolecular interactions between multicomponents. Supramolecular and self-assembling strategies provide versatile methods for the construction of artificial chemical architectures for controlling reaction rates and the specificities of chemical reactions, but most are designed in hydrophobic environments. The preparation of artificial catalysts that have potential in aqueous media mimicking natural enzymes such as hydrolases remains a great challenge in the fields of supramolecular chemistry. Herein, we describe that a dimeric Zn(2+) complex having a 2,2'-bipyridyl linker, cyanuric acid, and a Cu(2+) ion automatically assembles in an aqueous solution to form a 4:4:4 complex, which is stabilized by metal-ligand coordination bonds, π-π-stacking interactions, and hydrogen bonding and contains μ-Cu(2)(OH)(2) cores analogous to the catalytic centers of phosphatase, a dinuclear metalloenzyme. The 4:4:4 complex selectively accelerates the hydrolysis of a phosphate monoester, mono(4-nitrophenyl)phosphate, at neutral pH.

  17. Phosphorescent Organic Light Emitting Diodes Implementing Platinum Complexes

    Science.gov (United States)

    Ecton, Jeremy Exton

    Organic light emitting diodes (OLEDs) are a promising approach for display and solid state lighting applications. However, further work is needed in establishing the availability of efficient and stable materials for OLEDs with high external quantum efficiency's (EQE) and high operational lifetimes. Recently, significant improvements in the internal quantum efficiency or ratio of generated photons to injected electrons have been achieved with the advent of phosphorescent complexes with the ability to harvest both singlet and triplet excitons. Since then, a variety of phosphorescent complexes containing heavy metal centers including Os, Ni, Ir, Pd, and Pt have been developed. Thus far, the majority of the work in the field has focused on iridium based complexes. Platinum based complexes, however, have received considerably less attention despite demonstrating efficiency's equal to or better than their iridium analogs. In this study, a series of OLEDs implementing newly developed platinum based complexes were demonstrated with efficiency's or operational lifetimes equal to or better than their iridium analogs for select cases. In addition to demonstrating excellent device performance in OLEDs, platinum based complexes exhibit unique photophysical properties including the ability to form excimer emission capable of generating broad white light emission from a single emitter and the ability to form narrow band emission from a rigid, tetradentate molecular structure for select cases. These unique photophysical properties were exploited and their optical and electrical properties in a device setting were elucidated. Utilizing the unique properties of a tridentate Pt complex, Pt-16, a highly efficient white device employing a single emissive layer exhibited a peak EQE of over 20% and high color quality with a CRI of 80 and color coordinates CIE(x=0.33, y=0.33). Furthermore, by employing a rigid, tetradentate platinum complex, PtN1N, with a narrow band emission into a

  18. Selective binding of carotenoids with a shorter conjugated chain to the LH2 antenna complex and those with a longer conjugated chain to the reaction center from Rubrivivax gelatinosus.

    Science.gov (United States)

    Kakitani, Yoshinori; Fujii, Ritsuko; Hayakawa, Yoshihiro; Kurahashi, Masahiro; Koyama, Yasushi; Harada, Jiro; Shimada, Keizo

    2007-06-19

    Rubrivivax gelatinosus having both the spheroidene and spirilloxanthin biosynthetic pathways produces carotenoids (Cars) with a variety of conjugated chains, which consist of different numbers of conjugated double bonds (n), including the C=C (m) and C=O (o) bonds. When grown under anaerobic conditions, the wild type produces Cars for which n = m = 9-13, whereas under semiaerobic conditions, it additionally produces Cars for which n = m + o = 10 + 1, 13 + 1, and 13 + 2. On the other hand, a mutant, in which the latter pathway is genetically blocked, produces only Cars for which n = 9 and 10 under anaerobic conditions and n = 9, 10, and 10 + 1 under semianaerobic conditions. Those Cars that were extracted from the LH2 complex (LH2) and the reaction center (RC), isolated from the wild-type and the mutant Rvi. gelatinosus, were analyzed by HPLC, and their structures were determined by mass spectrometry and 1H NMR spectroscopy. The selective binding of Cars to those pigment-protein complexes has been characterized as follows. (1) Cars with a shorter conjugated chain are selectively bound to LH2 whereas Cars with a longer conjugated chain to the RC. (2) Shorter chain Cars with a hydroxyl group are bound to LH2 almost exclusively. This rule holds either in the absence or in the presence of the keto group. The natural selection of shorter chain Cars by LH2 and longer chain Cars by the RC is discussed, on the basis of the results now available, in relation to the light-harvesting and photoprotective functions of Cars.

  19. Selective Complexation of Cyanide and Fluoride Ions with Ammonium Boranes: A Theoretical Study on Sensing Mechanism Involving Intramolecular Charge Transfer and Configurational Changes.

    Science.gov (United States)

    Bhat, Haamid R; Jha, Prakash C

    2017-05-18

    The anion binding selectivity and the recognition mechanism of two isomeric boranes, namely, 4-[bis(2,4,6-trimethylphenyl)boranyl]-N,N,N-trimethylaniline ([p-(Mes 2 B)C 6 H 4 (NMe 3 )] + , 1, where "Mes" represents mesitylene and "Me" represents methyl) and 2-[bis(2,4,6-trimethylphenyl)boranyl]-N,N,N-trimethylaniline ([o-(Mes 2 B)C 6 H 4 (NMe 3 )] + , 2) has been investigated using density functional theory (DFT) and time dependent-density functional theory (TD-DFT) methods. Natural population analysis indicates that the central boron atoms in 1 and 2 are the most active centers for nucleophilic addition of anions. The negative magnitude of free energy changes (ΔG) reveals that out of CN - , F - , Cl - , Br - , NO 3 - , and HSO 4 - only the binding of CN - and F - with 1 and 2 is thermodynamically feasible and spontaneous. In addition, the calculated binding energies reveal that the CN - is showing lesser binding affinity than F - both with 1 and 2, while other ions, viz. NO 3 - , HSO 4 - , Br - , and Cl - , either do not bind at all or show very insignificant binding energy. The first excited states (S 1 ) of 1 and 2 are shown to be the local excited states with π → σ* transition by frontier molecular orbital analysis, whereas fourth excited states (S 4 ) of 4-[bis(2,4,6-trimethylphenyl)boranyl]-N,N,N-trimethylaniline cyanide ([p-(Mes 2 B)C 6 H 4 (NMe 3 )] CN, 1CN, the cyano form of 1) and 4-[bis(2,4,6-trimethylphenyl)boranyl]-N,N,N-trimethylaniline fluoride ([p-(Mes 2 B)C 6 H 4 (NMe 3 )] F, 1F, the fluoro form of 1) and fifth excited state (S 5 ) of 2-[bis(2,4,6-trimethylphenyl)boranyl]-N,N,N-trimethylaniline fluoride ([o-(Mes 2 B)C 6 H 4 (NMe 3 )] F, 2F, the fluoro form of 2) are charge separation states that are found to be responsible for the intramolecular charge transfer (ICT) process. The synergistic effect of ICT and partial configuration changes induce fluorescence quenching in 1CN, 1F, and 2F after a significant internal conversion (IC) from S 4 and

  20. Decoding the non-coding genome: elucidating genetic risk outside the coding genome.

    Science.gov (United States)

    Barr, C L; Misener, V L

    2016-01-01

    Current evidence emerging from genome-wide association studies indicates that the genetic underpinnings of complex traits are likely attributable to genetic variation that changes gene expression, rather than (or in combination with) variation that changes protein-coding sequences. This is particularly compelling with respect to psychiatric disorders, as genetic changes in regulatory regions may result in differential transcriptional responses to developmental cues and environmental/psychosocial stressors. Until recently, however, the link between transcriptional regulation and psychiatric genetic risk has been understudied. Multiple obstacles have contributed to the paucity of research in this area, including challenges in identifying the positions of remote (distal from the promoter) regulatory elements (e.g. enhancers) and their target genes and the underrepresentation of neural cell types and brain tissues in epigenome projects - the availability of high-quality brain tissues for epigenetic and transcriptome profiling, particularly for the adolescent and developing brain, has been limited. Further challenges have arisen in the prediction and testing of the functional impact of DNA variation with respect to multiple aspects of transcriptional control, including regulatory-element interaction (e.g. between enhancers and promoters), transcription factor binding and DNA methylation. Further, the brain has uncommon DNA-methylation marks with unique genomic distributions not found in other tissues - current evidence suggests the involvement of non-CG methylation and 5-hydroxymethylation in neurodevelopmental processes but much remains unknown. We review here knowledge gaps as well as both technological and resource obstacles that will need to be overcome in order to elucidate the involvement of brain-relevant gene-regulatory variants in genetic risk for psychiatric disorders. © 2015 John Wiley & Sons Ltd and International Behavioural and Neural Genetics Society.

  1. Targeted intervention: Computational approaches to elucidate and predict relapse in alcoholism.

    Science.gov (United States)

    Heinz, Andreas; Deserno, Lorenz; Zimmermann, Ulrich S; Smolka, Michael N; Beck, Anne; Schlagenhauf, Florian

    2017-05-01

    Alcohol use disorder (AUD) and addiction in general is characterized by failures of choice resulting in repeated drug intake despite severe negative consequences. Behavioral change is hard to accomplish and relapse after detoxification is common and can be promoted by consumption of small amounts of alcohol as well as exposure to alcohol-associated cues or stress. While those environmental factors contributing to relapse have long been identified, the underlying psychological and neurobiological mechanism on which those factors act are to date incompletely understood. Based on the reinforcing effects of drugs of abuse, animal experiments showed that drug, cue and stress exposure affect Pavlovian and instrumental learning processes, which can increase salience of drug cues and promote habitual drug intake. In humans, computational approaches can help to quantify changes in key learning mechanisms during the development and maintenance of alcohol dependence, e.g. by using sequential decision making in combination with computational modeling to elucidate individual differences in model-free versus more complex, model-based learning strategies and their neurobiological correlates such as prediction error signaling in fronto-striatal circuits. Computational models can also help to explain how alcohol-associated cues trigger relapse: mechanisms such as Pavlovian-to-Instrumental Transfer can quantify to which degree Pavlovian conditioned stimuli can facilitate approach behavior including alcohol seeking and intake. By using generative models of behavioral and neural data, computational approaches can help to quantify individual differences in psychophysiological mechanisms that underlie the development and maintenance of AUD and thus promote targeted intervention. Copyright © 2016 Elsevier Inc. All rights reserved.

  2. Hypoxia targeting copper complexes

    International Nuclear Information System (INIS)

    Dearling, J.L.

    1998-11-01

    The importance and incidence of tumour hypoxia, its measurement and current treatments available, including pharmacological and radiopharmacological methods of targeting hypoxia, are discussed. A variety of in vitro and in vivo methods for imposing hypoxia have been developed and are reviewed. Copper, its chemistry, biochemistry and radiochemistry, the potential for use of copper radionuclides and its use to date in this field is considered with particular reference to the thiosemicarbazones. Their biological activity, metal chelation, in vitro and in vivo studies of their radiocopper complexes and the potential for their use as hypoxia targeting radiopharmaceuticals is described. The reduction of the copper(II) complex to copper(l), its pivotal importance in their biological behaviour, and the potential for manipulation of this to effect hypoxia selectivity are described. An in vitro method for assessing the hypoxia selectivity of radiopharmaceuticals is reported. The rapid deoxygenation and high viability of a mammalian cell culture in this system is discussed and factors which may affect the cellular uptake of a radiopharmaceutical are described. The design, synthesis and complexation with copper and radiocopper of a range of bis(thiosemicarbazones) is reported. Synthesis of these compounds is simple giving high yields of pure products. The characteristics of the radiocopper complexes ( 64 Cu) including lipophilicity and redox activity are reported (reduction potentials in the range -0.314 - -0.590 V). High cellular uptakes of the radiocopper complexes of the ligands, in hypoxic and normoxic EMT6 and CHO320 cells, were observed. Extremes of selectivity are shown ranging from the hypoxia selective 64 Cu(II)ATSM to normoxic cell selective 64 Cu(II)GTS. The selectivities observed are compared with the physico chemical characteristics of the complexes. A good correlation exists between selectivity of the complex and its Cu(II)/Cu(I) reduction potential, with hypoxia

  3. Using Genetic Buffering Relationships Identified in Fission Yeast To Elucidate the Molecular Pathology of Tuberous Sclerosis

    Science.gov (United States)

    2016-07-01

    tsc1 and tsc2 loss of function mutations in Schizosaccharomyces pombe. Northeast Regional Yeast Meeting, June 16-17, University at Buffalo, The State...AWARD NUMBER: W81XWH-14-1-0169 TITLE: Using Genetic Buffering Relationships Identified in Fission Yeast To Elucidate the Molecular Pathology of...SUBTITLE Using Genetic Buffering Relationships Identified in Fission 5a. CONTRACT NUMBER W81XWH-14-1-0169 Yeast to Elucidate the Molecular Pathology

  4. Collision-Induced Dissociation Mass Spectrometry: A Powerful Tool for Natural Product Structure Elucidation.

    Science.gov (United States)

    Johnson, Andrew R; Carlson, Erin E

    2015-11-03

    Mass spectrometry is a powerful tool in natural product structure elucidation, but our ability to directly correlate fragmentation spectra to these structures lags far behind similar efforts in peptide sequencing and proteomics. Often, manual data interpretation is required and our knowledge of the expected fragmentation patterns for many scaffolds is limited, further complicating analysis. Here, we summarize advances in natural product structure elucidation based upon the application of collision induced dissociation fragmentation mechanisms.

  5. Phenotypic diversity in autosomal-dominant cone-rod dystrophy elucidated by adaptive optics retinal imaging.

    Science.gov (United States)

    Song, Hongxin; Rossi, Ethan A; Stone, Edwin; Latchney, Lisa; Williams, David; Dubra, Alfredo; Chung, Mina

    2018-01-01

    Several genes causing autosomal-dominant cone-rod dystrophy (AD-CRD) have been identified. However, the mechanisms by which genetic mutations lead to cellular loss in human disease remain poorly understood. Here we combine genotyping with high-resolution adaptive optics retinal imaging to elucidate the retinal phenotype at a cellular level in patients with AD-CRD harbouring a defect in the GUCA1A gene. Nine affected members of a four-generation AD-CRD pedigree and three unaffected first-degree relatives underwent clinical examinations including visual acuity, fundus examination, Goldmann perimetry, spectral domain optical coherence tomography and electroretinography. Genome-wide scan followed by bidirectional sequencing was performed on all affected participants. High-resolution imaging using a custom adaptive optics scanning light ophthalmoscope (AOSLO) was performed for selected participants. Clinical evaluations showed a range of disease severity from normal fundus appearance in teenaged patients to pronounced macular atrophy in older patients. Molecular genetic testing showed a mutation in in GUCA1A segregating with disease. AOSLO imaging revealed that of the two teenage patients with mild disease, one had severe disruption of the photoreceptor mosaic while the other had a normal cone mosaic. AOSLO imaging demonstrated variability in the pattern of cone and rod cell loss between two teenage cousins with early AD-CRD, who had similar clinical features and had the identical disease-causing mutation in GUCA1A . This finding suggests that a mutation in GUCA1A does not lead to the same degree of AD-CRD in all patients. Modifying factors may mitigate or augment disease severity, leading to different retinal cellular phenotypes. © Article author(s) (or their employer(s) unless otherwise stated in the text of the article) 2018. All rights reserved. No commercial use is permitted unless otherwise expressly granted.

  6. Molecular analyses of gut contents: elucidating the feeding of co-occurring salps in the Lazarev Sea from a different perspective

    OpenAIRE

    Metfies, Katja; Nicolaus, Anja; Harbou, Lena von; Bathmann, Ulrich; Peeken, Ilka

    2014-01-01

    The diet of Antarctic salps was elucidated by investigating their gut content using “Automated Ribosomal Intergenic Spacer Analysis” and 454-pyrosequencing. Salp samples were collected during the Lazarev Krill Study in the Western Weddell Sea (summer 2005/06 and 2007/08, fall 2004, and winter 2006). Two salp species, Salpa thompsoni and Ihlea racovitzai, both occur in the Southern Ocean, can overlap geographically and seasonally. Here we provide evidence that despite the non-selective feeding...

  7. Complexity explained

    CERN Document Server

    Erdi, Peter

    2008-01-01

    This book explains why complex systems research is important in understanding the structure, function and dynamics of complex natural and social phenomena. Readers will learn the basic concepts and methods of complex system research.

  8. Selective solid phase extraction for separation and preconcentration of palladium from Gold Ore and anode slime after complexation with a N{sub 4}O{sub 2} mixed donor ligand derivative

    Energy Technology Data Exchange (ETDEWEB)

    Bulut, Volkan Numan [Macka Vocational School, Karadeniz Technical University, Macka/ Trabzon (Turkey); Tufekci, Mehmet; Duran, Celal; Kantekin, Halit [Faculty of Arts and Sciences, Department of Chemistry, Karadeniz Technical University, Trabzon (Turkey); Soylak, Mustafa [Faculty of Science, Department of Chemistry, Erciyes University, Kayseri (Turkey)

    2010-07-15

    A selective and sensitive method for the preconcentration, separation, and determination of palladium with flame atomic absorption spectrometry using 4,15-bis[(4-methylphenyl)sulfonyl]-20,21-dinitro-2,3,4,5,6,7,9,10,12,13,14,15,16,17-tetradecahydro-8,11-ethano-1,18,4,8,11,15-benzodioxa tetraaza cycloicosine (TNACIN) on XAD-2010 was developed. TNACIN-Pd(II) complex formed acidic aqueous solution (0.075-0.100 M HNO{sub 3}) was accumulated on XAD-2010 and then eluted with 1 M HCl in acetone. The effects of some analytical parameters including pH, TNACIN amount, sample volume, eluent type, and concentration, sample flow rate and matrix ions were studied for optimization of the method. Detection limit and precision were calculated for Pd(II). This method was also verified with CRM and internal standard, and satisfactory results were obtained. (Abstract Copyright [2010], Wiley Periodicals, Inc.)

  9. 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.

  10. Elucidation of functions of micro-organisms and animals in forest biosystem. Shinrin seitaikei ni okeru biseibutsu oyobi dobutsu no kino no kaimei

    Energy Technology Data Exchange (ETDEWEB)

    1991-10-25

    This paper describes a report on elucidating functions of micro-organisms and animals in a forest biosystem. Classification of forest micro-organisms and elucidation of their physiology, ecology, and roles in the biosystem: Characteristics of tree root putterfaction bacteria, which cause withering of windbreaks in the Ishigaki Island, Japan were elucidated, and identifying the culture hyphae has become possible. Chemicals effective for their control were discovered, which enable their extermination. Investigations on soil molds using artificial acid rains clarified that the exterminating agents display their effects when sprinkled repeatedly over an extended period even in low concentrations. Classification of forest animals and elucidation of their physiology, ecology, and interactions among animals: A method was developed to photograph three-dimensionally the shapes of perforations made by earthworms using a soft X-ray and analyze them using a computer, which is being used for investigation. The perforation pattern is complex, and the hole diameters are in proportion with sizes of earthworms. Taxonomic studies on the Japanese lesser grain borers are close to completion. Damping-off of certain kinds of plantr exhibited parasitism of a kind of grain borerr and mycobionts without exceptions. An artificial burrow was devised for ecological investigation on field mice. 1 tab.

  11. Potential elucidation of a novel CTL epitope in HIV-1 protease by the protease inhibitor resistance mutation L90M.

    Directory of Open Access Journals (Sweden)

    Werner Smidt

    Full Text Available The combination of host immune responses and use of antiretrovirals facilitate partial control of human immunodeficiency virus type 1 (HIV-1 infection and result in delayed progression to Acquired Immunodeficiency Syndrome (AIDS. Both treatment and host immunity impose selection pressures on the highly mutable HIV-1 genome resulting in antiretroviral resistance and immune escape. Researchers have shown that antiretroviral resistance mutations can shape cytotoxic T-lymphocyte immunity by altering the epitope repertoire of HIV infected cells. Here it was discovered that an important antiretroviral resistance mutation, L90M in HIV protease, occurs at lower frequencies in hosts that harbor the B*15, B*48 or A*32 human leukocyte antigen subtypes. A likely reason is the elucidation of novel epitopes by L90M. NetMHCPan predictions reveal increased affinity of the peptide spanning the HIV protease region, PR 89-97 and PR 90-99 to HLA-B*15/B*48 and HLA-A*32 respectively due to the L90M substitution. The higher affinity could increase the chance of the epitope being presented and recognized by Cytotoxic T-lymphocytes and perhaps provide additional immunological pressures in the presence of antiretroviral attenuating mutations. This evidence supports the notion that knowledge of HLA allotypes in HIV infected individuals could augment antiretroviral treatment by the elucidation of epitopes due to antiretroviral resistance mutations in HIV protease.

  12. Potential elucidation of a novel CTL epitope in HIV-1 protease by the protease inhibitor resistance mutation L90M.

    Science.gov (United States)

    Smidt, Werner

    2013-01-01

    The combination of host immune responses and use of antiretrovirals facilitate partial control of human immunodeficiency virus type 1 (HIV-1) infection and result in delayed progression to Acquired Immunodeficiency Syndrome (AIDS). Both treatment and host immunity impose selection pressures on the highly mutable HIV-1 genome resulting in antiretroviral resistance and immune escape. Researchers have shown that antiretroviral resistance mutations can shape cytotoxic T-lymphocyte immunity by altering the epitope repertoire of HIV infected cells. Here it was discovered that an important antiretroviral resistance mutation, L90M in HIV protease, occurs at lower frequencies in hosts that harbor the B*15, B*48 or A*32 human leukocyte antigen subtypes. A likely reason is the elucidation of novel epitopes by L90M. NetMHCPan predictions reveal increased affinity of the peptide spanning the HIV protease region, PR 89-97 and PR 90-99 to HLA-B*15/B*48 and HLA-A*32 respectively due to the L90M substitution. The higher affinity could increase the chance of the epitope being presented and recognized by Cytotoxic T-lymphocytes and perhaps provide additional immunological pressures in the presence of antiretroviral attenuating mutations. This evidence supports the notion that knowledge of HLA allotypes in HIV infected individuals could augment antiretroviral treatment by the elucidation of epitopes due to antiretroviral resistance mutations in HIV protease.

  13. Elucidation of complex nature of PEG induced drought-stress response in rice root using comparative proteomics approach

    Directory of Open Access Journals (Sweden)

    Lalit Agrawal

    2016-09-01

    Full Text Available Along with many adaptive strategies, dynamic changes in protein abundance seem to be the common strategy to cope up with abiotic stresses which can be best explored through proteomics. Understanding of drought response is the key to decipher regulatory mechanism of better adaptation. Rice (Oryza sativa L. proteome represents a phenomenal source of proteins that govern traits of agronomic importance, such as drought tolerance. In this study, a comparison of root cytoplasmic proteome was done for a drought tolerant rice (Heena cultivar in PEG induced drought conditions. A total of 510 protein spots were observed by PDQuest analysis and 125 differentially regulated spots were subjected for MALDI-TOF MS-MS analysis out of which 102 protein spots identified which further led to identification of 78 proteins with a significant score. These 78 differentially expressed proteins appeared to be involved in different biological pathways. The largest percentage of identified proteins was involved in bioenergy and metabolism (29% and mainly consists of malate dehydrogenase, succinyl-CoA, putative acetyl-CoA synthetase and pyruvate dehydrogenase etc. This was followed by proteins related to cell defense and rescue (22% such as monodehydroascorbate reductase and stress-induced protein sti1, then by protein biogenesis and storage class (21% e.g. putative thiamine biosynthesis protein, putative beta-alanine synthase and cysteine synthase. Further, cell signaling (9% proteins like actin and prolyl endopeptidase and proteins with miscellaneous function (19% like Sgt1 and some hypothetical protein were also represented a large contribution towards drought regulatory mechanism in rice. We propose that protein biogenesis, cell defense and superior homeostasis may render better drought-adaptation. These findings might expedite the functional determination of the drought-responsive proteins and their prioritisation as potential molecular targets for perfect adaptation.

  14. Aminopurvalanol A, a Potent, Selective, and Cell Permeable Inhibitor of Cyclins/Cdk Complexes, Causes the Reduction of in Vitro Fertilizing Ability of Boar Spermatozoa, by Negatively Affecting the Capacitation-Dependent Actin Polymerization

    Directory of Open Access Journals (Sweden)

    Nicola Bernabò

    2017-12-01

    Full Text Available The adoption of high-througput technologies demonstrated that in mature spermatozoa are present proteins that are thought to be not present or active in sperm cells, such as those involved in control of cell cycle. Here, by using an in silico approach based on the application of networks theory, we found that Cyclins/Cdk complexes could play a central role in signal transduction active during capacitation. Then, we tested this hypothesis in the vitro model. With this approach, spermatozoa were incubated under capacitating conditions in control conditions (CTRL or in the presence of Aminopurvalanol A a potent, selective and cell permeable inhibitor of Cyclins/Cdk complexes at different concentrations (2, 10, and 20 μM. We found that this treatment caused dose-dependent inhibition of sperm fertilizing ability. We attribute this event to the loss of acrosome integrity due to the inhibition of physiological capacitation-dependent actin polymerization, rather than to a detrimental effect on membrane lipid remodeling or on other signaling pathways such as tubulin reorganization or MAPKs activation. In our opinion, these data could revamp the knowledge on biochemistry of sperm capacitation and could suggest new perspectives in studying male infertility.

  15. Elucidating the molecular physiology of lantibiotic NAI-107 production in Microbispora ATCC-PTA-5024

    DEFF Research Database (Denmark)

    Gallo, Giuseppe; Renzone, Giovanni; Palazzotto, Emilia

    2016-01-01

    by a complex regulatory and metabolic network that may be elucidated by the integration of genomic, proteomic and bioinformatic tools. Accordingly, an extensive evaluation of the proteomic changes associated with NAI-107 production was performed on Microbispora ATCC-PTA-5024 by combining two......; ii) during three time-points (117, 140, and 162 h) at D stage characterized by different profiles of NAI-107 yield accumulation (117 and 140 h) and decrement (162 h). Regulatory, metabolic and unknown-function proteins, were identified and functionally clustered, revealing that nutritional signals......, regulatory cascades and primary metabolism shift-down trigger the accumulation of protein components involved in nitrogen and phosphate metabolism, cell wall biosynthesis/maturation, lipid metabolism, osmotic stress response, multi-drug resistance, and NAI-107 transport. The stimulating role on physiological...

  16. Catalysts for selective hydrogenation of furfural derived from the double complex salt [Pd(NH 3 ) 4 ](ReO 4 ) 2 on γ-Al 2 O 3

    Energy Technology Data Exchange (ETDEWEB)

    Thompson, Simon T.; Lamb, H. Henry

    2017-06-01

    The double complex salt [Pd(NH3)4](ReO4)2 was employed as precursor of supported bimetallic catalysts for selective hydrogenation of furfural. Direct reduction of [Pd(NH3)4](ReO4)2 on γ-Al2O3 in flowing H2 at 400 °C yields bimetallic nanoparticles 1–2 nm in size that exhibit significant interaction between the metals, as evidenced by temperature-programmed hydride decomposition (complete suppression of β-PdHx formation), extended X-ray absorption fine structure spectroscopy at the Pd K and Re LIII edges (PdRe distance = 2.72 Å), and scanning transmission electron microscopy with energy dispersive X-ray analysis. In contrast, calcination of [Pd(NH3)4](ReO4)2 on γ-Al2O3 at 350 °C in air and subsequent reduction in H2 at 400 °C results in metal segregation and formation of large (>50 nm) supported Pd particles; Re species cover the Pd particles and γ-Al2O3 support. A PdRe 1:2 catalyst prepared by sequential impregnation and calcination using HReO4 and [Pd(NH3)4](NO3)2 has a similar morphology. The catalyst derived by direct reduction of [Pd(NH3)4](ReO4)2 on γ-Al2O3 exhibits remarkably high activity for selective hydrogenation of furfural to furfuryl alcohol (FAL) at 150 °C and 1 atm. Suppression of H2 chemisorption via elimination of Pd threefold sites, as evidenced by CO diffuse-reflectance infrared Fourier transform spectroscopy, correlates with increased FAL selectivity.

  17. Classic selective sweeps revealed by massive sequencing in cattle.

    Directory of Open Access Journals (Sweden)

    Saber Qanbari

    2014-02-01

    Full Text Available Human driven selection during domestication and subsequent breed formation has likely left detectable signatures within the genome of modern cattle. The elucidation of these signatures of selection is of interest from the perspective of evolutionary biology, and for identifying domestication-related genes that ultimately may help to further genetically improve this economically important animal. To this end, we employed a panel of more than 15 million autosomal SNPs identified from re-sequencing of 43 Fleckvieh animals. We mainly applied two somewhat complementary statistics, the integrated Haplotype Homozygosity Score (iHS reflecting primarily ongoing selection, and the Composite of Likelihood Ratio (CLR having the most power to detect completed selection after fixation of the advantageous allele. We find 106 candidate selection regions, many of which are harboring genes related to phenotypes relevant in domestication, such as coat coloring pattern, neurobehavioral functioning and sensory perception including KIT, MITF, MC1R, NRG4, Erbb4, TMEM132D and TAS2R16, among others. To further investigate the relationship between genes with signatures of selection and genes identified in QTL mapping studies, we use a sample of 3062 animals to perform four genome-wide association analyses using appearance traits, body size and somatic cell count. We show that regions associated with coat coloring significantly (P<0.0001 overlap with the candidate selection regions, suggesting that the selection signals we identify are associated with traits known to be affected by selection during domestication. Results also provide further evidence regarding the complexity of the genetics underlying coat coloring in cattle. This study illustrates the potential of population genetic approaches for identifying genomic regions affecting domestication-related phenotypes and further helps to identify specific regions targeted by selection during speciation, domestication and

  18. Structural complexities in the active layers of organic electronics.

    Science.gov (United States)

    Lee, Stephanie S; Loo, Yueh-Lin

    2010-01-01

    The field of organic electronics has progressed rapidly in recent years. However, understanding the direct structure-function relationships between the morphology in electrically active layers and the performance of devices composed of these materials has proven difficult. The morphology of active layers in organic electronics is inherently complex, with heterogeneities existing across multiple length scales, from subnanometer to micron and millimeter range. A major challenge still facing the organic electronics community is understanding how the morphology across all of the length scales in active layers collectively determines the device performance of organic electronics. In this review we highlight experiments that have contributed to the elucidation of structure-function relationships in organic electronics and also point to areas in which knowledge of such relationships is still lacking. Such knowledge will lead to the ability to select active materials on the basis of their inherent properties for the fabrication of devices with prespecified characteristics.

  19. Release of Inattentional Blindness by High Working Memory Load: Elucidating the Relationship between Working Memory and Selective Attention

    Science.gov (United States)

    de Fockert, Jan W.; Bremner, Andrew J.

    2011-01-01

    An unexpected stimulus often remains unnoticed if attention is focused elsewhere. This inattentional blindness has been shown to be increased under conditions of high memory load. Here we show that increasing working memory load can also have the opposite effect of reducing inattentional blindness (i.e., improving stimulus detection) if stimulus…

  20. Insights into structural features of HDAC1 and its selectivity inhibition elucidated by Molecular dynamic simulation and Molecular Docking.

    Science.gov (United States)

    Sixto-López, Yudibeth; Bello, Martiniano; Correa-Basurto, José

    2018-03-06

    Histone deacetylases (HDACs) are a family of proteins whose main function is the removal of acetyl groups from lysine residues located on histone and non-histone substrates, which regulates gene transcription and other activities in cells. HDAC1 dysfunction has been implicated in cancer development and progression; thus, its inhibition has emerged as a new therapeutic strategy. Two additional metal binding sites (Site 1 and Site 2) in HDACs have been described that are primarily occupied by potassium ions, suggesting a possible structural role that affects HDAC activity. In this work, we explored the structural role of potassium ions in Site 1 and Site 2 and how they affect the interactions of compounds with high affinities for HDAC1 (AC1OCG0B, Chlamydocin, Dacinostat and Quisinostat) and SAHA (a pan-inhibitor) using molecular docking and molecular dynamics (MD) simulations in concert with a Molecular-Mechanics-Generalized-Born-Surface-Area (MMGBSA) approach. Four models were generated: one with a potassium ion (K + ) in both sites (HDAC1 k ), a second with K + only at site 1 (HDAC1 ks1 ), a third with K + only at site 2 (HDAC1 ks2 ) and a fourth with no K + (HDAC1 wk ). We found that the presence or absence of K + not only impacted the structural flexibility of HDAC1, but also its molecular recognition, consistent with experimental findings. These results could therefore be useful for further structure-based drug design studies addressing new HDAC1 inhibitors.