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Sample records for halide complex formation

  1. Complexes of alkylphenols with aluminium halides

    International Nuclear Information System (INIS)

    Golounin, A.V.

    1997-01-01

    Interaction of aluminium halides with alkylphenols is studied through the NMR method. The peculiarity of complex formation of pentamethylphenol with AlI 3 is revealed. By AlI 3 action on the pentamethylphenol the complexes are formed both of keto- and oxy form [ru

  2. Complexes in polyvalent metal - Alkali halide melts

    International Nuclear Information System (INIS)

    Akdeniz, Z.; Tosi, M.P.

    1991-03-01

    Experimental evidence is available in the literature on the local coordination of divalent and trivalent metal ions by halogens in some 140 liquid mixtures of their halides with alkali halides. After brief reference to classification criteria for main types of local coordination, we focus on statistical mechanical models that we are developing for Al-alkali halide mixtures. Specifically, we discuss theoretically the equilibrium between (AlF 6 ) 3- and (AlF 4 ) - complexes in mixtures of AlF 3 and NaF as a function of composition in the NaF-rich region, the effect of the alkali counterion on this equilibrium, the possible role of (AlF 5 ) 2- as an intermediate species in molten cryolite, and the origin of the different complexing behaviours of Al-alkali fluorides and chlorides. We also present a theoretical scenario for processes of structure breaking and electron localization in molten cryolite under addition of sodium metal. (author). 26 refs, 2 tabs

  3. Abiotic Formation of Methyl Halides in the Terrestrial Environment

    Science.gov (United States)

    Keppler, F.

    2011-12-01

    Methyl chloride and methyl bromide are the most abundant chlorine and bromine containing organic compounds in the atmosphere. Since both compounds have relatively long tropospheric lifetimes they can effectively transport halogen atoms from the Earth's surface, where they are released, to the stratosphere and following photolytic oxidation form reactive halogen gases that lead to the chemical destruction of ozone. Methyl chloride and methyl bromide account for more than 20% of the ozone-depleting halogens delivered to the stratosphere and are predicted to grow in importance as the chlorine contribution to the stratosphere from anthropogenic CFCs decline. Today methyl chloride and methyl bromide originate mainly from natural sources with only a minor fraction considered to be of anthropogenic origin. However, until as recently as 2000 most of the methyl chloride and methyl bromide input to the atmosphere was considered to originate from the oceans, but investigations in recent years have clearly demonstrated that terrestrial sources such as biomass burning, wood-rotting fungi, coastal salt marshes, tropical vegetation and organic matter degradation must dominate the atmospheric budgets of these trace gases. However, many uncertainties still exist regarding strengths of both sources and sinks, as well as the mechanisms of formation of these naturally occurring halogenated gases. A better understanding of the atmospheric budget of both methyl chloride and methyl bromide is therefore required for reliable prediction of future ozone depletion. Biotic and abiotic methylation processes of chloride and bromide ion are considered to be the dominant pathways of formation of these methyl halides in nature. In this presentation I will focus on abiotic formation processes in the terrestrial environment and the potential parameters that control their emissions. Recent advances in our understanding of the abiotic formation pathway of methyl halides will be discussed. This will

  4. Formation of structured nanophases in halide crystals

    Czech Academy of Sciences Publication Activity Database

    Kulveit, Jan; Demo, Pavel; Polák, Karel; Sveshnikov, Alexey; Kožíšek, Zdeněk

    2013-01-01

    Roč. 5, č. 6 (2013), s. 561-564 ISSN 2164-6627 R&D Projects: GA ČR GAP108/12/0891 Institutional support: RVO:68378271 Keywords : halide crystals * nucleation Subject RIV: BM - Solid Matter Physics ; Magnetism http://www.aspbs.com/asem.html#v5n6

  5. Metal halide-phosphorus halide-alkyl halide complexes: reaction with niobium and tantalum pentachlorides

    International Nuclear Information System (INIS)

    Puri, D.M.; Saini, M.S.

    1978-01-01

    The reactions of niobium and tantalum pentachlorides with trichlorophosphine and phenyldichlorophosphine have been studied in presence of alkylating agents such as sec-butyl chloride, iso-butyl chloride, tert-butyl chloride, tert-anylchloride, cyclohexyl chloride and triphenylmethyl chloride. Solid products have been isolated and characterised by vibrational spectroscopy as ionic complexes of alkyl- and/or aryl-phosphonium cations with hexachloroniobate and hexachlorotantalate anions. (author)

  6. Vibrational Spectra of Discrete UO22+ Halide Complexes in the Gas Phase

    International Nuclear Information System (INIS)

    Groenewold, G.S.; Van Stipdonk, Michael J.; Oomens, Jos; De Jong, Wibe A.; Gresham, Garold L.; Mcilwain, Michael

    2010-01-01

    The intrinsic binding of halide ions to the metal center in the uranyl molecule is a topic of ongoing research interest in both the actinide separations and theoretical communities. Investigations of structure in the condensed phases is frequently obfuscated by solvent interactions that can alter ligand binding and spectroscopic properties. The approach taken in this study is to move the uranyl halide complexes into the gas phase where they are free from solvent interactions, and then interrogate their vibrational spectroscopy using infrared multiple photon dissociation (IRMPD). The spectra of cationic coordination complexes having the composition (UO 2 (X)(ACO) 3 ) + (where X = F, Cl, Br and I; ACO = acetone) were acquired using electrospray for ion formation, and monitoring the ion signal from the photoelimination of ACO ligands. The studies showed that the asymmetric ν 3 UO 2 frequency was insensitive to halide identity as X was varied from Cl to I, suggesting that in these pseudo-octahedral complexes, changing the nucleophilicity of the halide did not appreciably alter its binding in the complex. The ν 3 peak in the spectrum of the F-containing complex was 9 cm -1 lower indicating stronger coordination in this complex. Similarly the ACO carbonyl stretches showed that the C=O frequency was relatively insensitive to the identity of the halide, although a modest shift to higher wavenumber was seen for the complexes with the more nucleophilic anions, consistent with the idea that they loosen solvent binding. Surprisingly, the ν 1 stretch was activated when the softer anions Cl, Br and I were present in the complexes. IR studies of the anionic complexes (UO 2 X 3 ) - (where X = Cl - , Br - and I - ) compared the ν 3 UO 2 modes versus halide, and showed that the ν 3 values decreased with increasing anion nucleophilicity. This observation was consistent with DFT calculations that indicated that (UO 2 X 2 ) - -X, and (UO 2 X 2 )·-X - dissociation energies

  7. Structure of some complex halides of uranium(III)

    International Nuclear Information System (INIS)

    Volkov, V.A.; Suglobova, I.G.; Chirkst, D.E.

    1987-01-01

    Polycrystals of some halide complexes of uranium(III) were obtained and investigated by x-ray diffraction. The M 2 UCl 5 compounds (M = K, Rb) are isostructural with K 2 PrCl 5 ; RbU 2 Cl 7 is of the same type as RbDy 2 Cl 7 or KDy 2 Cl 7 . The coordination number of the uranium is 7. The M 2 UBr 5 compounds (M = K-Cs) are isostructural with Cs 2 DyCl 5 , and the coordination number of the uranium is 6. Rb 2 NaUCl 6 is a 12L-hexagonal polytype, the structural analog of Cs 2 NaCrF 6 . The most characteristic coordination number of uranium in the UHal 3 -MHal systems is 8 for Hal = F, 7 for Hal = Cl, and 6 for Hal = Br

  8. THERMODYNAMICS OF MICELLE FORMATION BY 1-METHYL-4-ALKYLPYRIDINIUM HALIDES

    NARCIS (Netherlands)

    BIJMA, K; ENGBERTS, JBFN; HAANDRIKMAN, G; VANOS, NM; BLANDAMER, MJ; BUTT, MD; CULLIS, PM

    This paper reports enthalpies of micellization for a series of 1-methyl-4-alkylpyridinium halide surfactants at 303.2 K with different lengths and degrees of branching of the 4-alkyl chain and different sizes of counterions using two microcalorimeters (LKB 2277 and Omega Microcal). The standard

  9. Homocoupling of benzyl halides catalyzed by POCOP-nickel pincer complexes

    KAUST Repository

    Chen, Tao

    2012-08-01

    Two types of POCOP-nickel(II) pincer complexes were prepared by mixing POCOP pincer ligands and NiX 2 in toluene at reflux. The resulting nickel complexes efficiently catalyze the homocoupling reactions of benzyl halides in the presence of zinc. The coupled products were obtained in excellent to quantitative yields. © 2012 Elsevier Ltd. All rights reserved.

  10. The chemistry of positronium. Part VI: inhibition and enhancement of positronium formation in aqueous solutions of halides, sulfide and thiocyanate

    International Nuclear Information System (INIS)

    Duplatre, G.; Abbe, J.C.; Maddock, A.G.; Haessler, A.

    1977-01-01

    The formation of positronium in aqueous solutions of halides, sulfide and thiocyanate has been investigated. Inhibiting and enhancing reactions of positronium formation are found. The results are discussed in terms of the spur model

  11. The impact of alkali metal halide electron donor complexes in the photocatalytic degradation of pentachlorophenol

    Energy Technology Data Exchange (ETDEWEB)

    Khuzwayo, Z., E-mail: zack.khuzwayo@up.ac.za; Chirwa, E.M.N

    2017-01-05

    Highlights: • Facilitation of photocatalysis using simple metal-halides as VB hole scavengers. • Recombination prevention by coupled valence and conduction band approaches. • Determination of anions critical levels beyond which process retardation occurs. • Determination of the photocatalytic process rate of reaction kinetics. - Abstract: The performance of photocatalytic oxidation of chemical pollutants is subjected to the presence of anion complexes in natural waters. This study investigated the influence of alkali metal (Na{sup +} (sodium), K{sup +} (potassium)) halides (Cl{sup −} (chloride), Br{sup −} (bromide), F{sup −} (fluoride)) as inorganic ion sources in the photocatalytic degradation of pentachlorophenol (PCP) in batch systems. It was found that the exclusive presence of halides in the absence of an electron acceptor adequately facilitated the photocatalyst process below critical levels of anion populations, where beyond the critical point the process was significantly hindered. Below the determined critical point, the performance in some cases near matches that of the facilitation of the photocatalytic process by exclusive oxygen, acting as an electron scavenger. The coupling of halide ions and oxygenation presented significantly improved photo-oxidation of PCP, this was confirmed by the inclusion of formic acid as a comparative electron donor. The Langmuir-Hinshelwood kinetic expression was used to calculate the performance rate kinetics. The probable impact of the halide anions was discussed with regards to the process of electron hole pair recombination prevention.

  12. Phase recording for formation of holographic optical elements on silver-halide photographic emulsions

    Science.gov (United States)

    Ganzherli, Nina M.; Gulyaev, Sergey N.; Maurer, Irina A.; Chernykh, Dmitrii F.

    2009-05-01

    Holographic fabrication methods of regular and nonregular relief-phase structures on silver-halide photographic emulsions are considered. Methods of gelatin photodestruction under short-wave ultra-violet radiation and chemical hardening with the help of dichromated solutions were used as a technique for surface relief formation. The developed techniques permitted us to study specimens of holographic diffusers and microlens rasters with small absorption and high light efficiency.

  13. Conformational isomerism in mixed-ligand complexes of 2,2'-bipyridine and triphenylphosphine with copper(I) halides

    International Nuclear Information System (INIS)

    Barron, P.F.; Engelhardt, L.M.; Healy, P.C.; Kildea, J.D.; White, A.H.

    1988-01-01

    Mixed-ligand complexes of triphenylphosphine and 2,2'-bipyridine and copper(I) halides have been synthesized. The 31 P NMR spectra of the complexes were measured and are reported along with data for complete structural characterization of the complexes. The results indicate a novel dichotomy of conformational isomers to be present in the chloride lattice. The Cu-P bond length was found to not vary with different halides. 8 refs., 4 figs., 6 tabs

  14. F-center and self-trapped exciton formation in strongly excited alkali halide crystals

    International Nuclear Information System (INIS)

    Kravchenko, V.A.; Yakovlev, V.Yu.

    1988-01-01

    Method of luminescent and absorption spectroscopy with time resolution was used to study the effect of density of electron pulse excitation (t p =10 -8 s, P=(10 5 -10 8 ) WXcm -2 ) on efficiency of η ε two-halide autolocalized exciton (TALE) and F-centers (η F ) formation in CsI, CsBr, KBr, KI alkali halide crystals. It was established that for all studied systems the elevation of P power of electron beam (EB) from 10 5 up to 5X10 7 WXcm -2 resulted to sufficient decrease of production efficiency and yield of TALE luminescence. In the case when F-centers of colour are induced predominantly by pulsed irradiation in crystals, F-center yield is independent of P. If F-centers and TALE are produced in comparable amounts (CsBr crystals, T=80 K), η ε decrease with P growth is accompanied by η F growth

  15. Reversible photo-induced trap formation in mixed-halide hybrid perovskites for photovoltaics.

    Science.gov (United States)

    Hoke, Eric T; Slotcavage, Daniel J; Dohner, Emma R; Bowring, Andrea R; Karunadasa, Hemamala I; McGehee, Michael D

    2015-01-01

    We report on reversible, light-induced transformations in (CH 3 NH 3 )Pb(Br x I 1- x ) 3 . Photoluminescence (PL) spectra of these perovskites develop a new, red-shifted peak at 1.68 eV that grows in intensity under constant, 1-sun illumination in less than a minute. This is accompanied by an increase in sub-bandgap absorption at ∼1.7 eV, indicating the formation of luminescent trap states. Light soaking causes a splitting of X-ray diffraction (XRD) peaks, suggesting segregation into two crystalline phases. Surprisingly, these photo-induced changes are fully reversible; the XRD patterns and the PL and absorption spectra revert to their initial states after the materials are left for a few minutes in the dark. We speculate that photoexcitation may cause halide segregation into iodide-rich minority and bromide-enriched majority domains, the former acting as a recombination center trap. This instability may limit achievable voltages from some mixed-halide perovskite solar cells and could have implications for the photostability of halide perovskites used in optoelectronics.

  16. Time Domain View of Liquid-like Screening and Large Polaron Formation in Lead Halide Perovskites

    Science.gov (United States)

    Joshi, Prakriti Pradhan; Miyata, Kiyoshi; Trinh, M. Tuan; Zhu, Xiaoyang

    The structural softness and dynamic disorder of lead halide perovskites contributes to their remarkable optoelectronic properties through efficient charge screening and large polaron formation. Here we provide a direct time-domain view of the liquid-like structural dynamics and polaron formation in single crystal CH3NH3PbBr3 and CsPbBr3 using femtosecond optical Kerr effect spectroscopy in conjunction with transient reflectance spectroscopy. We investigate structural dynamics as function of pump energy, which enables us to examine the dynamics in the absence and presence of charge carriers. In the absence of charge carriers, structural dynamics are dominated by over-damped picosecond motions of the inorganic PbBr3- sub-lattice and these motions are strongly coupled to band-gap electronic transitions. Carrier injection from across-gap optical excitation triggers additional 0.26 ps dynamics in CH3NH3PbBr3 that can be attributed to the formation of large polarons. In comparison, large polaron formation is slower in CsPbBr3 with a time constant of 0.6 ps. We discuss how such dynamic screening protects charge carriers in lead halide perovskites. US Department of Energy, Office of Science - Basic Energy Sciences.

  17. High Pressure Optical Studies of the Thallous Halides and of Charge-Transfer Complexes

    Science.gov (United States)

    Jurgensen, Charles Willard

    High pressure was used to study the insulator -to-metal transition in sulfur and the thallous halides and to study the intermolecular interactions in charge -transfer complexes. The approach to the band overlap insulator -to-metal transition was studied in three thallous halides and sulfur by optical absorption measurements of the band gap as a function of pressure. The band gap of sulfur continuously decreases with pressure up to the insulator -to-metal transition which occurs between 450 and 485 kbars. The results on the thallous halides indicate that the indirect gap decreases more rapidly than the direct gap; the closing of the indirect gap is responsible for the observed insulator -to-metal transitions. High pressure electronic and vibrational spectroscopic measurements on the solid-state complexes of HMB-TCNE were used to study the intermolecular interactions of charge -transfer complexes. The vibrational frequency shifts indicate that the degree of charge transfer increases with pressure which is independently confirmed by an increase in the molar absorptivity of the electronic charge-transfer peak. Induction and dispersion forces contribute towards a red shift of the charge-transfer peak; however, charge-transfer resonance contributes toward a blue shift and this effect is dominant for the HMB-TCNE complexes. High pressure electronic spectra were used to study the effect of intermolecular interactions on the electronic states of TCNQ and its complexes. The red shifts with pressure of the electronic spectra of TCNQ and (TCNQ)(' -) in polymer media and of crystalline TCNQ can be understood in terms of Van der Waals interactions. None of the calculations which considered intradimer distance obtained the proper behavior for either the charge-transfer of the locally excited states of the complexes. The qualitative behavior of both states can be interpreted as the effect of increased mixing of the locally excited and charge transfer states.

  18. Complexity and formative experiences

    Directory of Open Access Journals (Sweden)

    Roque Strieder

    2017-12-01

    Full Text Available The contemporaneity is characterized by instability and diversity calling into question certainties and truths proposed in modernity. We recognize that the reality of things and phenomena become effective as a set of events, interactions, retroactions and chances. This different frame extends the need for revision of the epistemological foundations that sustain educational practices and give them sense. The complex thinking is an alternative option for acting as a counterpoint to classical science and its reductionist logic and knowledge compartmentalization, as well as to answer to contemporary epistemological and educational challenges. It aims to associate different areas and forms of knowledge, without, however merge them, distinguishing without separating the several disciplines and instances of the realities. This study, in theoretical references, highlights the relevance of complex approaches to support formative experiences because also able to produce complexities in reflections about educational issues. We conclude that formative possibilities from complexity potentialize the resignification of human’s conception and the understanding of its singularity in interdependence; The understanding that pedagogical and educational activities is a constant interrogation about the possibilities of knowing the knowledge and reframe learning, far beyond knowing its functions and utilitarian purposes; and, as a formative possibility, places us on the trail of responsibility, not as something eventual, but present and indicative of freedom to choose to stay or go beyond.

  19. Structural variety in solvated lanthanoid (III) halide complexes

    International Nuclear Information System (INIS)

    Deacon, G.B; Feng, T.; Scott, N.M.; Junk, P.C.; James Cook University, Townsville, QLD; Meyer, G.; Skelton, B.W.; White, A.H.

    2000-01-01

    Treatment of lanthanum metal with CH 2 Br 2 or CH 2 I 2 in tetrahydrofuran (thf) under ultrasound conditions yields the corresponding [LaX 3 (thf) 4 ] (X Br, I) complexes in good yield. Recrystallization of [LaBr 3 (thf) 4 ] from 1,2-dimethoxyethane (dme) or bis(2-methoxyethyl) ether (dig-lyme) generates [LaBr 2 (μ-Br)(dme) 2 ] 2 and [LaBr 2 (dig-lyme) 2 ][LaBr 4 (diglyme)]. Treatment of lanthanoid metals with hexachloroethane in dme yields [LnCl 3 (dme) 2 ] (Ln = La, Nd, Er or Yb) and in acetonitrile [YbCl 2 (MeCN) 5 ] 2 [YbCl 3 (MeCN)(-Cl) 2 YbCl 3 (MeCN)]. The reaction of Yb metal pieces with 1,2-dibromoethane in thf and dme gave single crystals of [YbBr 3 (thf) 3 ] and [YbBr 3 (dme) 2 ], respectively. The X-ray determined structure of [LaBr 3 (thf) 4 ] shows a seven-coordinate monomer with pentagonal-bipyramidal stereochemistry and apical bromide ligands. For [YbBr 3 (thf) 3 ], a monomeric structure with mer-octahedral stereochemistry is observed. In [LaBr 2 (μ-Br)(dme) 2 ] 2 , two eight-coordinate La centres are linked by two bridging bromides. The dme ligands have a trans relationship to each other, and cis terminal bromides are transoid to the bridging bromides with dodecahedral stereochemistry for La. By contrast, the 1: 1.5 diglyme adduct is found to be ionic [LaBr 2 (diglyme) 2 ][LaBr 4 (diglyme)], with an eight-coordinate bicapped trigonal-prismatic lanthanum cation and a seven-coordinate pentagonal-bipyramidal lanthanum anion. In the cation, the bromide ligands are cis to each other, and in the anion, two bromides are equatorial and two are axial. In [YbBr 3 (dme) 2 ], [YbCl 3 (dme) 2 ] and [ErCl 3 (dme) 2 ], a seven-coordinate pentagonal-bipyramidal arrangement exists with apical halogen ligands. Far-infrared data, and in particular the absence of absorptions attributable to I(La-Cl ter ), suggest that [LaCl 3 (dme)] is polymeric with six bridging chlorides per lanthanum. For [YbCl 2 (MeCN) 5 ] 2 [YbCl 3 (MeCN)(-Cl) 2 YbCl 3 -(MeCN)], a remarkable

  20. Formation of random and regular relief-phase structures on silver halide photographic emulsions by holographic methods

    Science.gov (United States)

    Ganzherli, N. M.; Gulyaev, S. N.; Gurin, A. S.; Kramushchenko, D. D.; Maurer, I. A.; Chernykh, D. F.

    2009-07-01

    The formation of diffusers and microlens rasters on silver halide emulsions by holographic methods is considered. Two techniques for converting amplitude holographic recording to relief-phase recording, selective curing and irradiation of the emulsion gelatin by short-wavelength UV radiation, are compared.

  1. Metal Halide Perovskite Supercrystals: Gold-Bromide Complex Triggered Assembly of CsPbBr3 Nanocubes.

    Science.gov (United States)

    Wang, Kun-Hua; Yang, Jun-Nan; Ni, Qian-Kun; Yao, Hong-Bin; Yu, Shu-Hong

    2018-01-16

    Using nanocrystals as "artificial atoms" to construct supercrystals is an interesting process to explore the stacking style of nanoscale building blocks and corresponding collective properties. Various types of semiconducting supercrystals have been constructed via the assembly of nanocrystals driven by the entropic, electrostatic, or van der Waals interactions. We report a new type of metal halide perovskite supercrystals via the gold-bromide complex triggered assembly of newly emerged attractive CsPbBr 3 nanocubes. Through introducing gold-bromide (Au-Br) complexes into CsPbBr 3 nanocubes suspension, the self-assembly process of CsPbBr 3 nanocubes to form supercrystals was investigated with the different amount of Au-Br complexes added to the suspensions, which indicates that the driven force of the formation of CsPbBr 3 supercrystals included the van der Waals interactions among carbon chains and electrostatic interactions between Au-Br complexes and surfactants. Accordingly, the optical properties change with the assembly of CsPbBr 3 nanocubes and the variation of mesoscale structures of supercrystals with heating treatment was revealed as well, demonstrating the ionic characteristics of CsPbBr 3 nanocrystals. The fabricated CsPbBr 3 supercrystal presents a novel type of semiconducting supercrystals that will open an avenue for the assembly of ionic nanocrystals.

  2. Far IR spectra of Th(IV) halide complexes of some heterocyclic bases

    International Nuclear Information System (INIS)

    Srivastava, A.K.; Agarwal, R.K.; Srivastava, M.; Kapoor, V.; Srivastava, T.N.

    1981-01-01

    The synthesis and IR spectra of Th(IV) perchlorato, nitrato and thiocyanato complexes of some heterocyclic bases have been reported. Halogens are common ligands in coordination chemistry forming coordinate bonds with metals readily. Metal halogen (M-X) stretching bands show a strong absorption in the far-IR region. Very little information is available on Th-X stretching frequencies. In the present communication, adducts of Th(IV) halide with certain nitrogen heterocyclic bases such as pyridine, α-picoline, 2-amino pyridine, 2:4-lutidine, 2:6-lutidine, quinoline, 2,2'-bipyridine and 1,10-phenanthroline were synthesised and characterised. Experimental details are given. Results are presented and discussed. (author)

  3. AB INITIO molecular orbital studies of some high temperature metal halide complexes

    International Nuclear Information System (INIS)

    Curtiss, L.A.

    1978-01-01

    The use of ab initio molecular orbital calculations to aid in the characterization, i.e., structures and energies, of metal halide complexes present in high temperature salt vapors has been investigated. Standard LCAO-SCF methods were used and calculations were carried out using the minimal STO-3G basis set. The complexes included in this study were Al 2 F 6 , Al 2 Cl 6 , AlF 3 NH 3 , AlCl 3 NH 3 , and AlF 3 N 2 . The Al 2 X 6 complexes are found to have D/sub 2h/ symmetry in agreement with most experimental results. A planar form was found to be considerably higher in energy. The AlX 3 NH 3 complexes are found to have C/sub 3v/ symmetry with a small barrier to rotation about the Al-N axis. The AlF 3 N 2 complex is found to be weakly bound together with a binding energy of -8.2 kcal/mole at the STO-3G level

  4. Reactivity of Zinc Halide Complexes Containing Camphor-Derived Guanidine Ligands with Technical rac-Lactide

    Directory of Open Access Journals (Sweden)

    Angela Metz

    2017-11-01

    Full Text Available Three new zinc complexes with monoamine–guanidine hybridligands have been prepared, characterized by X-ray crystallography and NMR spectroscopy, and tested in the solvent-free ring-opening polymerization of rac-lactide. Initially the ligands were synthesized from camphoric acid to obtain TMGca and DMEGca and then reacted with zinc(II halides to form zinc complexes. All complexes have a distorted tetrahedral coordination. They were utilized as catalysts in the solvent-free polymerization of technical rac-lactide at 150 °C. Colorless polylactide (PLA can be produced and after 2 h conversion up to 60% was reached. Furthermore, one zinc chlorido complex was tested with different qualities of lactide (technical and recrystallized and with/without the addition of benzyl alcohol as a co-initiator. The kinetics were monitored by in situ FT-IR or 1H NMR spectroscopy. All kinetic measurements show first-order behavior with respect to lactide. The influence of the chiral complexes on the stereocontrol of PLA was examined. Moreover, with MALDI-ToF measurements the end-group of the obtained polymer was determined. DFT and NBO calculations give further insight into the coordination properties. All in all, these systems are robust against impurities and water in the lactide monomer and show great catalytic activity in the ROP of lactide.

  5. Redox properties of biscyclopentadienyl uranium(V) imido-halide complexes: a relativistic DFT study.

    Science.gov (United States)

    Elkechai, Aziz; Kias, Farida; Talbi, Fazia; Boucekkine, Abdou

    2014-06-01

    Calculations of ionization energies (IE) and electron affinities (EA) of a series of biscyclopentadienyl imido-halide uranium(V) complexes Cp*2U(=N-2,6-(i)Pr2-C6H3)(X) with X =  F, Cl, Br, and I, related to the U(IV)/U(V) and U(V)/U(VI) redox systems, were carried out, for the first time, using density functional theory (DFT) in the framework of the relativistic zeroth order regular approximation (ZORA) coupled with the conductor-like screening model (COSMO) solvation approach. A very good linear correlation (R(2) =  0.993) was obtained, between calculated ionization energies at the ZORA/BP86/TZP level, and the experimental half-wave oxidation potentials E1/2. A similar linear correlation between the computed electron affinities and the electrochemical reduction U(IV)/U(III) potentials (R(2) =  0.996) is obtained. The importance of solvent effects and of spin-orbit coupling is definitively confirmed. The molecular orbital analysis underlines the crucial role played by the 5f orbitals of the central metal whereas the Nalewajski-Mrozek (N-M) bond indices explain well the bond distances variations following the redox processes. The IE variation of the complexes, i.e., IE(F) uranium charges and E1/2 in the reduction process of the U(V) species.

  6. Transfer Hydro-dehalogenation of Organic Halides Catalyzed by Ruthenium(II) Complex.

    Science.gov (United States)

    You, Tingjie; Wang, Zhenrong; Chen, Jiajia; Xia, Yuanzhi

    2017-02-03

    A simple and efficient Ru(II)-catalyzed transfer hydro-dehalogenation of organic halides using 2-propanol solvent as the hydride source was reported. This methodology is applicable for hydro-dehalogenation of a variety of aromatic halides and α-haloesters and amides without additional ligand, and quantitative yields were achieved in many cases. The potential synthetic application of this method was demonstrated by efficient gram-scale transformation with catalyst loading as low as 0.5 mol %.

  7. Special features of the formation of high-conductivity phases of halides of alkali metals at superhigh pressures

    International Nuclear Information System (INIS)

    Babushkin, A.N.; Babushkina, G.V.

    1999-01-01

    The halides of alkali metals are the simplest crystals with the ionic nature of chemical bonds and are used widely as modelling materials in high-pressure physics. As a result of previous theoretical and experimental (optical, structural, electro-physical and shock-waves) investigations it was shown that these materials may be characterised by the overlapping of the valency and conduction bands and by the formation of groups of free charge carriers at pressures of the megabaric level. However, the authors know of no data on the direct investigations of the electrophysical properties of the halides of alkali metals at such high static pressures. The end of this investigation was to examine the temperature dependences of the electrical conductivity and thermal EMF of halides of alkali metals AX (A = Na, K, Rb, Cs, X = Cl, Br, I) in a wide temperature range at pressures from 10 to 50 GPa in order to reveal the general leisure since governing the change of their electronic structures, in particular, the transition to the state with the activation-type or metallic conductivity

  8. Complexity of formation in holography

    International Nuclear Information System (INIS)

    Chapman, Shira; Marrochio, Hugo; Myers, Robert C.

    2017-01-01

    It was recently conjectured that the quantum complexity of a holographic boundary state can be computed by evaluating the gravitational action on a bulk region known as the Wheeler-DeWitt patch. We apply this complexity=action duality to evaluate the ‘complexity of formation’ (DOI: 10.1103/PhysRevLett.116.191301; 10.1103/PhysRevD.93.086006), i.e. the additional complexity arising in preparing the entangled thermofield double state with two copies of the boundary CFT compared to preparing the individual vacuum states of the two copies. We find that for boundary dimensions d>2, the difference in the complexities grows linearly with the thermal entropy at high temperatures. For the special case d=2, the complexity of formation is a fixed constant, independent of the temperature. We compare these results to those found using the complexity=volume duality.

  9. Complexity of formation in holography

    Energy Technology Data Exchange (ETDEWEB)

    Chapman, Shira [Perimeter Institute for Theoretical Physics,Waterloo, ON N2L 2Y5 (Canada); Marrochio, Hugo [Perimeter Institute for Theoretical Physics,Waterloo, ON N2L 2Y5 (Canada); Department of Physics & Astronomy and Guelph-Waterloo Physics Institute,University of Waterloo, Waterloo, ON N2L 3G1 (Canada); Myers, Robert C. [Perimeter Institute for Theoretical Physics,Waterloo, ON N2L 2Y5 (Canada)

    2017-01-16

    It was recently conjectured that the quantum complexity of a holographic boundary state can be computed by evaluating the gravitational action on a bulk region known as the Wheeler-DeWitt patch. We apply this complexity=action duality to evaluate the ‘complexity of formation’ (DOI: 10.1103/PhysRevLett.116.191301; 10.1103/PhysRevD.93.086006), i.e. the additional complexity arising in preparing the entangled thermofield double state with two copies of the boundary CFT compared to preparing the individual vacuum states of the two copies. We find that for boundary dimensions d>2, the difference in the complexities grows linearly with the thermal entropy at high temperatures. For the special case d=2, the complexity of formation is a fixed constant, independent of the temperature. We compare these results to those found using the complexity=volume duality.

  10. Copper(I), silver(I) and gold(I) halide complexes with the dithioformamidinium dihalides

    Science.gov (United States)

    Peyronel, Giorgio; Malavasi, Wanda; Pignedoli, Anna

    Some copper(I), silver(I) and gold(I) halide complexes with the dithioformamidinium dihalides (Tu 2X 2) were prepared and studied by infrared spectroscopy and conductometry: 3CuX.2Tu 2X 2(XCl,I), CuBr.Tu 2Br 2, 4CuBr.3.5Tu 2Br 2.MeOH, 2CuBr.Tu 2Br 2.0.66EtOH, 3CuI.2Tu 2I 2, 2AgCl.2.5Tu 2Cl 2, 3AgCl.2Tu 2Cl 2.0.5EtOH, 3AgCl.Tu 2Cl 2, 2AgBr.2Tu 2Br 2.0.5Tu 2(NO 3) 2.H 2O, AgBr.Tu 2Br 2, 4AgBr.Tu 2Br 2, 4AgI.0.5Tu 2I 2.EtOH, AuCl.1.5Tu 2Cl 2, 4AuCl.3.5Tu 2Cl 2.2DMF, AuBr.4Tu 2Br 2, AuBr.2Tu 2Br 2.1.5DMF, AuI.5Tu 2I 2, AuI.Tu 2I 2. A decrease of the ν(NH), δ(NH 2) and ν(CN 2) frequencies and an increase of the ν(CS) frequencies indicate an N-coordination of the dithioformamidinium cation to the metal ions; ν(MN) and ν(MX) frequencies are tentatively assigned in the far-infrared spectra.

  11. A PEG/copper(i) halide cluster as an eco-friendly catalytic system for C-N bond formation.

    Science.gov (United States)

    Li, Cheng-An; Ji, Wei; Qu, Jian; Jing, Su; Gao, Fei; Zhu, Dun-Ru

    2018-05-22

    The catalytic activities of eight copper(i) halide clusters assembled from copper(i) halide and ferrocenyltelluroethers, 1-8, were investigated in C-N formation under various conditions. A catalytic procedure using poly(ethylene glycol) (PEG-400) as a greener alternative organic solvent has been developed. The PEG-400/5 system can achieve 99% targeted yield with a mild reaction temperature and short reaction time. After the isolation of the products by extraction with diethyl ether, this PEG-400/cluster system could be easily recycled. Spectroscopic studies elucidate a stepwise mechanism: firstly, proton-coupled electron transfer (PCET) involving the transfer of an electron from Cu+ and a proton from imidazole results in the formation of a labile penta-coordinated Cu2+ and aryl radical; the following effective electron transfer from the ferrocene unit reduces Cu2+ and forms the target product; finally, the ferrocenium unit is reduced by the I- anion. The merits of this eco-friendly synthesis are the efficient utilization of reagents and easy recyclability.

  12. Halide ions complex and deprotonate dipicolinamides and isophthalamides: assessment by mass spectrometry and UV-visible spectroscopy.

    Science.gov (United States)

    Carasel, I Alexandru; Yamnitz, Carl R; Winter, Rudolph K; Gokel, George W

    2010-12-03

    The F(-), Cl(-), and Br(-) binding selectivity of bis(p-nitroanilide)s of dipicolinic and isophthalic acids was studied by using competitive electrospray mass spectrometry and UV-Visible spectroscopy. Both hosts prefer binding Cl(-) over either F(-) or Br(-). Host deprotonation was observed to some extent in all experiments in which the host was exposed to halide ions. When F(-) was present, host deprotonation was often the major process, whereas little deprotonation was observed by Cl(-) or Br(-), which preferred complexation. A solution of either host changed color when mixed with a F(-), H(2)PO(4)(-), di- or triphenylacetate solution.

  13. A spectrophotometric study of aqueous Au(III) halide-hydroxide complexes at 25-80 °C

    Science.gov (United States)

    Usher, Al; McPhail, D. C.; Brugger, Joël

    2009-06-01

    The mobility and transport of gold in low-temperature waters and brines is affected by the aqueous speciation of gold, which is sensitive in particular to pH, oxidation and halide concentrations. In this study, we use UV-Vis spectrophotometry to identify and measure the thermodynamic properties of Au(III) aqueous complexes with chloride, bromide and hydroxide. Au(III) forms stable square planar complexes with hydroxide and halide ligands. Based on systematic changes in the absorption spectra of solutions in three binary systems NaCl-NaBr, NaCl-NaOH and NaBr-NaOH at 25 °C, we derived log dissociation constants for the following mixed and end-member halide and hydroxide complexes: [AuCl 3Br] -, [AuCl 2Br 2] -, [AuBr 3Cl] - and [AuBr 4] -; [AuCl 3(OH)] -, [AuCl 2(OH) 2] -, [AuCl(OH) 3] - and [Au(OH) 4] -; and [AuBr 3(OH)] -, [AuBr 2(OH) 2] - and [AuBr(OH) 3] -. These are the first reported results for the mixed chloride-bromide complexes. Increasing temperature to 80 °C resulted in an increase in the stability of the mixed chloride-bromide complexes, relative to the end-member chloride and bromide complexes. For the [AuCl (4-n)(OH) n] - series of complexes ( n = 0-4), there is an excellent agreement between our spectrophotometric results and previous electrochemical results of Chateau et al. [Chateau et al. (1966)]. In other experiments, the iodide ion (I -) was found to be unstable in the presence of Au(III), oxidizing rapidly to I 2(g) and causing Au to precipitate. Predicted Au(III) speciation indicates that Au(III) chloride-bromide complexes can be important in transporting gold in brines with high bromide-chloride ratios (e.g., >0.05), under oxidizing (atmospheric), acidic (pH < 5) conditions. Native gold solubility under atmospheric oxygen conditions is predicted to increase with decreasing pH in acidic conditions, increasing pH in alkaline conditions, increasing chloride, especially at acid pH, and increasing bromide for bromide/chloride ratios greater than 0

  14. Chemoselective Radical Dehalogenation and C-C Bond Formation on Aryl Halide Substrates Using Organic Photoredox Catalysts.

    Science.gov (United States)

    Poelma, Saemi O; Burnett, G Leslie; Discekici, Emre H; Mattson, Kaila M; Treat, Nicolas J; Luo, Yingdong; Hudson, Zachary M; Shankel, Shelby L; Clark, Paul G; Kramer, John W; Hawker, Craig J; Read de Alaniz, Javier

    2016-08-19

    Despite the number of methods available for dehalogenation and carbon-carbon bond formation using aryl halides, strategies that provide chemoselectivity for systems bearing multiple carbon-halogen bonds are still needed. Herein, we report the ability to tune the reduction potential of metal-free phenothiazine-based photoredox catalysts and demonstrate the application of these catalysts for chemoselective carbon-halogen bond activation to achieve C-C cross-coupling reactions as well as reductive dehalogenations. This procedure works both for conjugated polyhalides as well as unconjugated substrates. We further illustrate the usefulness of this protocol by intramolecular cyclization of a pyrrole substrate, an advanced building block for a family of natural products known to exhibit biological activity.

  15. Zinc(II) halide complexes with 2-methoxyaniline ligand: Synthesis, characterization, thermal analyses, crystal structure determination and luminescent properties

    Science.gov (United States)

    Amani, Vahid

    2018-03-01

    Three new mononuclear zinc(II) complexes, [Zn(2-MeO-C6H4NH2)2X2] (X is Cl in 1, Br in 2 and I in 3), were prepared from the reactions of ZnX2 with 2-methoxyaniline (2-MeO-C6H4NH2) ligand in methanol. Suitable crystals of these complexes were obtained for X-ray diffraction measurements by slow evaporation of methanol solution at room temperature. The three complexes were thoroughly characterized by thermogravimetric analysis, elemental analysis (CHNO), spectral methods (IR, UV-Vis, 13C{1H}NMR, 1H NMR and luminescence), and single crystal X-ray diffraction. The X-ray structural analysis indicated that in the structures of these complexes, the zinc(II) cation is four-coordinated in a distorted tetrahedral configuration by two N atoms from two 2-methoxyanyline ligands and two halide anions. Also, in these complexes intermolecular interactions, for example Nsbnd H⋯X hydrogen bonds (in 1-3), Csbnd H⋯X hydrogen bonds (in 3), Csbnd H⋯π interactions (in 1 and 2) and π⋯π interactions (in 3), are effective in the stabilization of the crystal structures. In addition, the luminescence spectra of all complexes in methanolic solution show that the intensity of their emission bands is stronger than that for free 2-methoxyaniline ligand.

  16. UV-visible spectroscopy of macrocyclic alkyl, nitrosyl and halide complexes of cobalt and rhodium. Experiment and calculation.

    Science.gov (United States)

    Hull, Emily A; West, Aaron C; Pestovsky, Oleg; Kristian, Kathleen E; Ellern, Arkady; Dunne, James F; Carraher, Jack M; Bakac, Andreja; Windus, Theresa L

    2015-02-28

    Transition metal complexes (NH3)5CoX(2+) (X = CH3, Cl) and L(H2O)MX(2+), where M = Rh or Co, X = CH3, NO, or Cl, and L is a macrocyclic N4 ligand are examined by both experiment and computation to better understand their electronic spectra and associated photochemistry. Specifically, irradiation into weak visible bands of nitrosyl and alkyl complexes (NH3)5CoCH3(2+) and L(H2O)M(III)X(2+) (X = CH3 or NO) leads to photohomolysis that generates the divalent metal complex and ˙CH3 or ˙NO, respectively. On the other hand, when X = halide or NO2, visible light photolysis leads to dissociation of X(-) and/or cis/trans isomerization. Computations show that visible bands for alkyl and nitrosyl complexes involve transitions from M-X bonding orbitals and/or metal d orbitals to M-X antibonding orbitals. In contrast, complexes with X = Cl or NO2 exhibit only d-d bands in the visible, so that homolytic cleavage of the M-X bond requires UV photolysis. UV-Vis spectra are not significantly dependent on the structure of the equatorial ligands, as shown by similar spectral features for (NH3)5CoCH3(2+) and L(1)(H2O)CoCH3(2+).

  17. Preparation, infrared, raman and nmr spectra of N,N'-diethylthiourea complexes with zinc(II), cadmium(II) and mercury(II) halides

    Energy Technology Data Exchange (ETDEWEB)

    Marcotrigiano, G [Bari Univ. (Italy). Cattedra di Chimica, Facolta di Medicina-Veterinaria

    1976-05-01

    Several complexes of N,N'-diethylthiourea (Dietu) with zinc(II), cadmium(II) and mercury(II) halides were prepared and characterized by i.r. (4000-60 cm/sup -1/), raman (400-60 cm/sup -1/), in the solid state and n.m.r. and conductometric methods in solution. The complexes Zn(Dietu)/sub 2/X/sub 2/, Cd(Dietu)/sub 2/X/sub 2/ (X=Cl, Br, I) and Hg(Dietu)/sub 2/X/sub 2/ (X=Br, I) are tetrahedral species in which intramolecular -NH...X interactions have been observed. The 1:1 mercury(II) complexes, Hg(Dietu)X/sub 2/ (X=Cl, Br), appear to have a dimeric tetrahedral halide-bridged structure in the solid state. In all these complexes N,N'-diethylthiourea is sulphur-bonded to the metal.

  18. Polynuclear complexes of copper(I) halides: coordination chemistry and catalytic transformations of alkynes

    International Nuclear Information System (INIS)

    Mykhalichko, B M; Mys'kiv, M G; Temkin, Oleg N

    2000-01-01

    Characteristic features of the coordination chemistry of Cu(I) and mechanisms of catalytic conversions of alkynes in the CuCl-MCl-H 2 O-HC≡CR system (MCl is alkali metal or ammonium chloride or amine hydrochloride; R=H, CH 2 OH, CH=CH 2 , etc.) are analysed based on studies of the compositions and structures of copper(I) chloride (bromide) complexes, alkyne π-complexes and ethynyl organometallic polynuclear compounds formed in this system in solutions and in the crystalline state. The role of polynuclear complexes in various reactions of alkynes is discussed. The bibliography includes 149 references.

  19. Formability of ABX3 (X=F,Cl,Br,I) halide perovskites

    International Nuclear Information System (INIS)

    Li Chonghea; Lu Xionggang; Ding Weizhong; Feng Liming; Gao Yonghui; Guo Ziming

    2008-01-01

    In this study a total of 186 complex halide systems were collected; the formabilities of ABX 3 (X = F, Cl, Br and I) halide perovskites were investigated using the empirical structure map, which was constructed by Goldschmidt's tolerance factor and the octahedral factor. A model for halide perovskite formability was built up. In this model obtained, for all 186 complex halides systems, only one system (CsF-MnF 2 ) without perovskite structure and six systems (RbF-PbF 2 , CsF- BeF 2 , KCl-FeCl 2 , TlI-MnI 2 , RbI-SnI 2 , TlI-PbI 2 ) with perovskite structure were wrongly classified, so its predicting accuracy reaches 96%. It is also indicated that both the tolerance factor and the octahedral factor are a necessary but not sufficient condition for ABX 3 halide perovskite formability, and a lowest limit of the octahedral factor exists for halide perovskite formation. This result is consistent with our previous report for ABO 3 oxide perovskite, and may be helpful to design novel halide materials with the perovskite structure. (orig.)

  20. Halide/pseudohalide complexes of cadmium(II) with benzimidazole: Synthesis, crystal structures and fluorescence properties

    Science.gov (United States)

    Zhao, Hai-Yan; Yang, Fu-Li; Li, Na; Wang, Xiao-Jing

    2017-11-01

    Two new dinuclear Cd(II) complexes, [CdL1Cl2]2·H2O (1) and [CdL1(N3)2]2·CH3OH (2) and one dicyanamide bridged one-dimensional polynuclear network [CdL1(μ1,5-dca)dca]n (3) of the potentially tridentate NNN-donor Schiff base 2-((1H-benzimidazol-2-yl-ethylimino)-methyl)pyridine (L1) and another dinucler Cd(II) complex [CdL2Cl(dca)]2 (4) of a similar NNN-donor Schiff base ligand 2-((1H-benzimidazol-2-yl-propylimino)-methyl)pyridine (L2), have been synthesized and characterized by elemental analyses, IR and single crystal X-ray crystallography. The ligands L1 and L2 are [1 + 1] condensation products of pyridine-2-carbaldehyde with 2-aminoethyl-1H-benzimidazole and 2-aminopropyl-1H-benzimidazole, respectively. In the complexes 1 and 4 the two Cd(II) centers are held together by the bridged chloride ligands, while in 2 the two Cd(II) centers are bridged by μ1,1-azide ions. Complex 3 has a one-dimensional infinite chain structure in which Cd(II) ions are bridged by single dicyanamide groups in end-to-end fashion. All the metal centers have a distorted octahedral geometry and H-bonding or π⋯π interactions are operative to bind the complex units in the solid state. Furthermore, these complexes have been investigated by thermogravimetric analyses and fluorescence spectra.

  1. Nickel(II) complexes of N2S2 donor set ligand and halide ...

    Indian Academy of Sciences (India)

    aDepartment of Chemistry, Burdwan University, Golapbag, Burdwan 713 104, India. bDepartment of .... tion containing the organic compound (L) (338.0 mg, .... Viscosity values were cal- ... 3.08 and 3.09 which indicate all complexes are high.

  2. Methods for producing single crystal mixed halide perovskites

    Science.gov (United States)

    Zhu, Kai; Zhao, Yixin

    2017-07-11

    An aspect of the present invention is a method that includes contacting a metal halide and a first alkylammonium halide in a solvent to form a solution and maintaining the solution at a first temperature, resulting in the formation of at least one alkylammonium halide perovskite crystal, where the metal halide includes a first halogen and a metal, the first alkylammonium halide includes the first halogen, the at least one alkylammonium halide perovskite crystal includes the metal and the first halogen, and the first temperature is above about 21.degree. C.

  3. Modeling of catalytically active metal complex species and intermediates in reactions of organic halides electroreduction.

    Science.gov (United States)

    Lytvynenko, Anton S; Kolotilov, Sergey V; Kiskin, Mikhail A; Eremenko, Igor L; Novotortsev, Vladimir M

    2015-02-28

    The results of quantum chemical modeling of organic and metal-containing intermediates that occur in electrocatalytic dehalogenation reactions of organic chlorides are presented. Modeling of processes that take place in successive steps of the electrochemical reduction of representative C1 and C2 chlorides - CHCl3 and Freon R113 (1,1,2-trifluoro-1,2,2-trichloroethane) - was carried out by density functional theory (DFT) and second-order Møller-Plesset perturbation theory (MP2). It was found that taking solvation into account using an implicit solvent model (conductor-like screening model, COSMO) or considering explicit solvent molecules gave similar results. In addition to modeling of simple non-catalytic dehalogenation, processes with a number of complexes and their reduced forms, some of which were catalytically active, were investigated by DFT. Complexes M(L1)2 (M = Fe, Co, Ni, Cu, Zn, L1H = Schiff base from 2-pyridinecarbaldehyde and the hydrazide of 4-pyridinecarboxylic acid), Ni(L2) (H2L2 is the Schiff base from salicylaldehyde and 1,2-ethylenediamine, known as salen) and Co(L3)2Cl2, representing a fragment of a redox-active coordination polymer [Co(L3)Cl2]n (L3 is the dithioamide of 1,3-benzenedicarboxylic acid), were considered. Gradual changes in electronic structure in a series of compounds M(L1)2 were observed, and correlations between [M(L1)2](0) spin-up and spin-down LUMO energies and the relative energies of the corresponding high-spin and low-spin reduced forms, as well as the shape of the orbitals, were proposed. These results can be helpful for determination of the nature of redox-processes in similar systems by DFT. No specific covalent interactions between [M(L1)2](-) and the R113 molecule (M = Fe, Co, Ni, Zn) were found, which indicates that M(L1)2 electrocatalysts act rather like electron transfer mediators via outer-shell electron transfer. A relaxed surface scan of the adducts {M(L1)2·R113}(-) (M = Ni or Co) versus the distance between the

  4. Associated equilibria with participatian of single and mixed silver, lead and cadmium halide complexes in mixtures of molten alkali and alkaline earth metal nitrates

    International Nuclear Information System (INIS)

    Gouk, Kh.S.; Gupta, R.K.; Vekma, K.V.

    1983-01-01

    Associated equilibria in the systems, which contain single and mixed silver, cadmium and lead halide complexes in the KNO 3 -Ba(N0 3 ) 2 (87.6:12.4 and 89:11 mol.%) and NaNO 3 -Ba(NO 3 ) 2 (94.2-5.8 mol%) melts in the temperature range from 568.2 up to 698.2 K are investigated. Applicability of equations derivated on the base of quasi-lattice model to description of temperature coefficients of association constants is analized

  5. Defect formation and desorption of metal atoms from alkali halide crystals under low energy electron bombardment studied by optical absorption and mass spectroscopy

    International Nuclear Information System (INIS)

    Seifert, N.R.

    1993-04-01

    This work presents an extensive investigation of electronically induced desorption of ground-state alkali atoms from alkali halides and for the first time correlates directly the desorption with the stability and spatial distribution of the defects formed during bombardment. The electron impact results in the formation of stable F-centers and F-center clusters in the bulk of the crystals. In striking contrast a significant metallization of the surface is observed. Even at temperatures as low as 90 deg C the metallization is achieved within the time resolution of our detection system, which can only be explained by the rapid diffusion of hot holes. Superimposed to the fast and short diffusion of hot holes is the slow F-center diffusion. Measuring the distribution of defects with low energy ion sputtering techniques indicates that at least in the case of LiF the observed diffusion constant of F-centers agrees with values derived by using methods different from that applied here. At low temperatures the formation of F-center clusters and metal on the surface dominates. Colloid formation clearly requires higher temperatures (typically around 200 deg C). This is a strong evidence that efficient F-center diffusion is necessary for the formation of metallic particles (colloids) in the bulk of the crystals. Desorption of alkali atoms from alkali halides at temperatures around room temperature is due to weakly bound alkali atoms. For elevated temperatures the stability of the metallic clusters in the bulk of the crystals (i.e. colloids) are the rate limiting process. (author)

  6. STAR FORMATION ACROSS THE W3 COMPLEX

    Energy Technology Data Exchange (ETDEWEB)

    Román-Zúñiga, Carlos G.; Ybarra, Jason E.; Tapia, Mauricio [Instituto de Astronomía, Universidad Nacional Autónoma de México, Unidad Académica en Ensenada, Km 103 Carr. Tijuana–Ensenada, Ensenada 22860 (Mexico); Megías, Guillermo D. [Facultad de Física. Universidad de Sevilla. Dpto. Física Atómica, Molecular y Nuclear, Sevilla, E-41080 (Spain); Lada, Elizabeth A. [Astronomy Department, University of Florida, 211 Bryant Space Sciences Center, FL 32611 (United States); Alves, Joáo F. [Institute of Astronomy, University of Vienna, Türkenschanzstr. 17, A-1180 Vienna (Austria)

    2015-09-15

    We present a multi-wavelength analysis of the history of star formation in the W3 complex. Using deep, near-infrared ground-based images combined with images obtained with Spitzer and Chandra observatories, we identified and classified young embedded sources. We identified the principal clusters in the complex and determined their structure and extension. We constructed extinction-limited samples for five principal clusters and constructed K-band luminosity functions that we compare with those of artificial clusters with varying ages. This analysis provided mean ages and possible age spreads for the clusters. We found that IC 1795, the centermost cluster of the complex, still hosts a large fraction of young sources with circumstellar disks. This indicates that star formation was active in IC 1795 as recently as 2 Myr ago, simultaneous to the star-forming activity in the flanking embedded clusters, W3-Main and W3(OH). A comparison with carbon monoxide emission maps indicates strong velocity gradients in the gas clumps hosting W3-Main and W3(OH) and shows small receding clumps of gas at IC 1795, suggestive of rapid gas removal (faster than the T Tauri timescale) in the cluster-forming regions. We discuss one possible scenario for the progression of cluster formation in the W3 complex. We propose that early processes of gas collapse in the main structure of the complex could have defined the progression of cluster formation across the complex with relatively small age differences from one group to another. However, triggering effects could act as catalysts for enhanced efficiency of formation at a local level, in agreement with previous studies.

  7. Making and Breaking of Lead Halide Perovskites

    KAUST Repository

    Manser, Joseph S.

    2016-02-16

    A new front-runner has emerged in the field of next-generation photovoltaics. A unique class of materials, known as organic metal halide perovskites, bridges the gap between low-cost fabrication and exceptional device performance. These compounds can be processed at low temperature (typically in the range 80–150 °C) and readily self-assemble from the solution phase into high-quality semiconductor thin films. The low energetic barrier for crystal formation has mixed consequences. On one hand, it enables inexpensive processing and both optical and electronic tunability. The caveat, however, is that many as-formed lead halide perovskite thin films lack chemical and structural stability, undergoing rapid degradation in the presence of moisture or heat. To date, improvements in perovskite solar cell efficiency have resulted primarily from better control over thin film morphology, manipulation of the stoichiometry and chemistry of lead halide and alkylammonium halide precursors, and the choice of solvent treatment. Proper characterization and tuning of processing parameters can aid in rational optimization of perovskite devices. Likewise, gaining a comprehensive understanding of the degradation mechanism and identifying components of the perovskite structure that may be particularly susceptible to attack by moisture are vital to mitigate device degradation under operating conditions. This Account provides insight into the lifecycle of organic–inorganic lead halide perovskites, including (i) the nature of the precursor solution, (ii) formation of solid-state perovskite thin films and single crystals, and (iii) transformation of perovskites into hydrated phases upon exposure to moisture. In particular, spectroscopic and structural characterization techniques shed light on the thermally driven evolution of the perovskite structure. By tuning precursor stoichiometry and chemistry, and thus the lead halide charge-transfer complexes present in solution, crystallization

  8. Reactions of guanine with methyl chloride and methyl bromide: O6-methylation versus charge transfer complex formation

    Science.gov (United States)

    Shukla, P. K.; Mishra, P. C.; Suhai, S.

    Density functional theory (DFT) at the B3LYP/6-31+G* and B3LYP/AUG-cc-pVDZ levels was employed to study O6-methylation of guanine due to its reactions with methyl chloride and methyl bromide and to obtain explanation as to why the methyl halides cause genotoxicity and possess mutagenic and carcinogenic properties. Geometries of the various isolated species involved in the reactions, reactant complexes (RCs), and product complexes (PCs) were optimized in gas phase. Transition states connecting the reactant complexes with the product complexes were also optimized in gas phase at the same levels of theory. The reactant complexes, product complexes, and transition states were solvated in aqueous media using the polarizable continuum model (PCM) of the self-consistent reaction field theory. Zero-point energy (ZPE) correction to total energy and the corresponding thermal energy correction to enthalpy were made in each case. The reactant complexes of the keto form of guanine with methyl chloride and methyl bromide in water are appreciably more stable than the corresponding complexes involving the enol form of guanine. The nature of binding in the product complexes was found to be of the charge transfer type (O6mG+ · X-, X dbond Cl, Br). Binding of HCl, HBr, and H2O molecules to the PCs obtained with the keto form of guanine did not alter the positions of the halide anions in the PCs, and the charge transfer character of the PCs was also not modified due to this binding. Further, the complexes obtained due to the binding of HCl, HBr, and H2O molecules to the PCs had greater stability than the isolated PCs. The reaction barriers involved in the formation of PCs were found to be quite high (?50 kcal/mol). Mechanisms of genotoxicity, mutagenesis and carcinogenesis caused by the methyl halides appear to involve charge transfer-type complex formation. Thus the mechanisms of these processes involving the methyl halides appear to be quite different from those that involve the

  9. Kinetics of halide release of haloalkane dehalogenase : Evidence for a slow conformational change

    NARCIS (Netherlands)

    Schanstra, JP; Janssen, DB; Schanstra, Joost P.

    1996-01-01

    Haloalkane dehalogenase converts haloalkanes to their corresponding alcohols and halides, The reaction mechanism involves the formation of a covalent alkyl-enzyme complex which is hydrolyzed by water. The active site is a hydrophobic cavity buried between the main domain and the cap domain of the

  10. Synthesis, Reactivity and Stability of Aryl Halide Protecting Groups towards Di-Substituted Pyridines

    Directory of Open Access Journals (Sweden)

    Ptoton Mnangat Brian

    2016-03-01

    Full Text Available This paper reports the synthesis and reactivity of different Benzyl derivative protecting groups. The synthesis and stability of Benzyl halides, 4-methoxybenzyl halides, 3,5-dimethoxybenzyl halides, 3,4-dimethoxybenzyl halides, 3,4,5-trimethoxybenzyl halide protecting groups and their reactivity towards nitrogen atom of a di-substituted pyridine ring in formation of pyridinium salts is also reported.

  11. What a difference a 5f element makes: trivalent and tetravalent uranium halide complexes supported by one and two bis[2-(diisopropylphosphino)-4-methylphenyl]amido (PNP) ligands.

    Science.gov (United States)

    Cantat, Thibault; Scott, Brian L; Morris, David E; Kiplinger, Jaqueline L

    2009-03-02

    The coordination behavior of the bis[2-(diisopropylphosphino)-4-methylphenyl]amido ligand (PNP) toward UI3(THF)4 and UCl4 has been investigated to access new uranium(III) and uranium(IV) halide complexes supported by one and two PNP ligands. The reaction between (PNP)K (6) and 1 equiv of UI3(THF)4 afforded the trivalent halide complex (PNP)UI2(4-tBu-pyridine)2 (7) in the presence of 4-tert-butylpyridine. The same reaction carried out with UCl4 and no donor ligand gave [(PNP)UCl3]2 (8), in which the uranium coordination sphere in the (PNP)UCl3 unit is completed by a bridging chloride ligand. When UCl4 is reacted with 1 equiv (PNP)K (6) in the presence of THF, trimethylphosphine oxide (TMPO), or triphenylphosphineoxide (TPPO), the tetravalent halide complexes (PNP)UCl3(THF) (9), (PNP)UCl3(TMPO)2 (10), and (PNP)UCl3(TPPO) (11), respectively, are formed in excellent yields. The bis(PNP) complexes of uranium(III), (PNP)2UI (12), and uranium(IV), (PNP)2UCl2 (13), were easily isolated from the analogous reactions between 2 equiv of 6 and UI3(THF)4 or UCl4, respectively. Complexes 12 and 13 represent the first examples of complexes featuring two PNP ligands coordinated to a single metal center. Complexes 7-13 have been characterized by single-crystal X-ray diffraction and 1H and 31P NMR spectroscopy. The X-ray structures demonstrate the ability of the PNP ligand to adopt new coordination modes upon coordination to uranium. The PNP ligand can adopt both pseudo-meridional and pseudo-facial geometries when it is kappa3-(P,N,P) coordinated, depending on the steric demand at the uranium metal center. Additionally, its hemilabile character was demonstrated with an unusual kappa2-(P,N) coordination mode that is maintained in both the solid-state and in solution. Comparison of the structures of the mono(PNP) and bis(PNP) complexes 7, 9, 11-13 with their respective C5Me5 analogues 1-4 undoubtedly show that a more sterically congested environment is provided by the PNP ligand. The

  12. Synthesis and characterization of low-valence actinide phosphide tellurides and ternary selenium-halide iridium complexes; Synthese und Charakterisierung niedervalenter Actinoidphosphidtelluride und ternaerer Selen-Halogenid-Komplexe des Iridiums

    Energy Technology Data Exchange (ETDEWEB)

    Stolze, Karoline

    2016-04-07

    The thesis on the synthesis and characterization of low-valence actinide phosphide tellurides and ternary selenium-halide iridium complexes includes two parts: a description of the experimental synthesis of UPTe and U2PTe2O and ThPTe and the synthesis of selenium-chloride iridium complexes and selenium-bromide iridium complexes. The characterization included X-ray diffraction and phase studies.

  13. Formation of americium and europium humate complexes

    International Nuclear Information System (INIS)

    Minai, Y.; Tominaga, T.; Meguro, Y.

    1991-01-01

    Binding constants of americium and europium with a humic acid were determined to study if complex formation of trivalent actinide-humates affects dissolved species of the actinides in hydrosphere. The purified humic acid was characterized by means of UV-vis, IR, and pH titration, indicating high carboxylate capacity and low aromaticity. Binding constants of americium and europium humates were determined at pH 4.6 and 6.0 by solvent extraction using 241 Am or 152 Eu as a tracer. The binding constants for americium-humate obtained preliminarily suggest that complexes with humic acid are not negligible in speciation of trivalent actinides in hydrosphere. The obtained binding constants were nearly identical with those determined previously by the same procedures, but with humic acids of different origin and compositions. (author)

  14. Necessary conditions for the homogeneous formation of a volume avalanche discharge with specific applications to rare gas-halide excimer laser discharges

    International Nuclear Information System (INIS)

    Levatter, J.I.

    1979-01-01

    Self-sustained/avalanche discharges are an efficient method of rare gas-halide excimer laser excitation in small systems. However, with the exceptions of the work reported here, experiments attempting to increase the laser energy output by scaling up the discharge volume and/or pulse duration have not been successful. The major problem encountered in scaling experiments has been the formation of arc channels in the discharge volume. The presence of arcing can totally disrupt proper laser operation. This problem stems from a general lack of understanding of high pressure avalanche discharge phenomena. Therefore, clarifying the basic discharge formation process and establishing a set of criteria under which a homogeneous avalanche discharge can be obtained is of central importance in defining the scaling limits of avalanche discharge lasers. The work presented here reviews the phenomena involved in high E/n (electric field to gas number density ratio) breakdown and its relationship to the formation of spatially homogeneous discharges. This relationship was first explored by A.J. Palmer in 1974. The basic requirement of his model was that the preionization density be large enough to cause an appreciable overlap of the primary electron avalanches and hence smooth out the ensuing space-charge fields to the extent that individual streamer formation would be prevented. This is the same basic model used in the more detailed discharge formation analysis developed here except that the effects of a time varying electric field caused by a finite voltage rise time and the effects due to the various electrochemical properties of the gas mixture are property taken into consideration

  15. Physics of positronium acceptor complex formation reactions

    International Nuclear Information System (INIS)

    Gangopadhyay, Debarshi; Ganguly, Bichitra Nandi; Mukherjee, Tapas; Dutta-Roy, Binayak

    2002-01-01

    Positronium (P s ) reaction rates (κ) with weak Acceptors (Ac) leading to the formation of Ps-Ac complexes show several interesting features: non-monotonic temperature dependence of κ(departing from the usual Arrhenius behaviour), considerable variability of κ with respect to different solvents, and anomalies in response to external pressure at ambient temperature. The object of this work is to explain all these phenomena using a remarkably simple bubble model (the widely used model for the pick-off component of ortho-positronium decay in liquids), which has been revisited several times in the context and as a result smooth diffuse boundary of the bubble was suggested that yields reasonable agreement of the experimental data. The contractile force on the bubble relies much on the surface tension of the liquid, through our calculation the notion of critical surface tension emerges and enables us to explain the experimental observations satisfactorily. (author)

  16. Experimental and Theoretical Study of the Movement of the Wpd Flexible Loop of Human Protein Tyrosine Phosphatase PTP1B in Complex with Halide Ions

    Science.gov (United States)

    Katz, Aline; Saenz-Méndez, Patricia; Cousido-Siah, Alexandra; Podjarny, Alberto D.; Ventura, Oscar N.

    2012-11-01

    Protein tyrosine phosphorylation is a post-translational modification mechanism, crucial for the regulation of nearly all aspects of cell life. This dynamic, reversible process is regulated by the balanced opposing activity of protein tyrosine kinases and protein tyrosine phosphatases. In particular, the protein tyrosine phosphatase 1B (PTP1B) is implicated in the regulation of the insulin-receptor activity, leptin-stimulated signal transduction pathways and other clinically relevant metabolic routes, and it has been found overexpressed or overregulated in human breasts, colon and ovary cancers. The WPD loop of the enzyme presents an inherent flexibility, and it plays a fundamental role in the enzymatic catalysis, turning it into a potential target in the design of new efficient PTP1B inhibitors. In order to determine the interactions that control the spatial conformation adopted by the WPD loop, complexes between the enzyme and halide ions (Br- and I- in particular) were crystallized and their crystallographic structure determined, and the collective movements of the aforementioned complexes were studied through Molecular Dynamics (MD) simulations. Both studies yielded concordant results, indicating the existence of a relationship between the identity of the ion present in the complex and the strength of the interactions it establishes with the surrounding protein residues.

  17. Reactivity of halide and pseudohalide ligands

    International Nuclear Information System (INIS)

    Kukushkin, Yu.N.

    1987-01-01

    Reactivity of halide and pseudohalide (cyanide, azide, thiocyanate, cyanate) ligands tending to form bridge bonds in transition metal (Re, Mo, W) complexes is considered. Complexes where transition metal salts are ligands of other, complex-forming ion, are described. Transformation of innerspheric pseudohalide ligands is an important way of directed synthesis of these metal coordination compounds

  18. Quantum-chemical ab initio and B3LYP study of donor-acceptor complexes of gallium halides with pyridine

    International Nuclear Information System (INIS)

    Timoshkin, A.Yu.; Suvorov, A.V.; Shefer, G.F.

    1999-01-01

    By the ab initio and density functional methods the structural characteristics and vibrational spectra of gallium iodide donor-acceptor complexes with pyridine have been calculated. The standard thermodynamic characteristics of GaI 3 Py complex dissociation in gaseous phase have been calculated, as well. Short I-H intramolecular distances suggest that hydrogen iodide elimination with Ga-N chemical bond retention is the first stage of the complex pyrolysis [ru

  19. Complex formation of p-carboxybenzeneboronic acid with fructose

    International Nuclear Information System (INIS)

    Bulbul Islam, T.M.; Yoshino, K.

    2000-01-01

    To increase the solubility of p-caboxybenzeneboronic acid (PCBA) in physiological pH 7.4, the complex formation of PCBA with fructose has been studied by 11 B-NMR. PCBA formed complex with fructose and the complex increased the solubility of PCBA. The complex formation constant (log K) was obtained in pH 7.4 as 2.75 from the 11 B-NMR spectra. Based on this result the complex formation ability of PCBA with fructose has been discussed. (author)

  20. Controlled Radical Polymerisation of Styrene in the Presence of Lithium Molybdate(V) Complexes and Benzylic Halides

    NARCIS (Netherlands)

    Koten, G. van; Brandts, J.A.M.; Geijn, P. van de; Faassen, E.E.H. van; Boersma, J.

    1999-01-01

    The new lithium molybdate(V) complexes [LiMo(NAr){2}(C-N)R] (C-N=C{6}H{4}(CH{2}NMe{2})-2; R=(C-N) (5), Me (6), CH{2}SiMe{3} (7), p-tolyl (8)), have been generated in situ from reaction of the corresponding molybdenum(VI) complexes [Mo(NAr){2}(C-N)R] (C-N=C{6}H{4}(CH{2}NMe{2})-2; R=(C-N) (1), Me (2),

  1. Quantum chemical study of halophilic interactions. Communication 3. Non-empirical study of the ways of tetrachloromethane attack by halide ions

    International Nuclear Information System (INIS)

    Kobychev, V.B.; Vitkovskaya, N.M.; Abramov, A.V.; Timokhin, B.V.

    1999-01-01

    It has been shown by means of non-empirical calculations of model reactions between tetrachloromethane and chlorine/iodine anions that in case of attack via carbon atom according to mechanism S N 2 formation of weakly-bound CCl 4 complexes with halide ions is observed at initial state. Further transformation of the complexes is restricted by considerable potential barriers. Attack of nucleophil via chlorine atom with formation of stable complexes CCl 3 -Cl-Hlg - is preferable [ru

  2. Photofragmentation of metal halides

    International Nuclear Information System (INIS)

    Veen, N.J.A. van.

    1980-01-01

    The author deals with photodissociation of molecules of alkali halides. It is shown that the total absorption cross section consists of two contributions arising from transitions to excited states of total electronic angular momentum Ω=0 + and Ω=1. From the inversion of the absorption continua potential energy curves of the excited states can be constructed in the Franck-Condon region. It is found that for all alkali halides the 0 + state is higher in energy than the Ω=1 state. Extensive studies are reported on three thallium halides, TlI, TlBr and TlCl at various wavelengths covering the near ultraviolet region. (Auth.)

  3. Entropy in halide perovskites

    Science.gov (United States)

    Katan, Claudine; Mohite, Aditya D.; Even, Jacky

    2018-05-01

    Claudine Katan, Aditya D. Mohite and Jacky Even discuss the possible impact of various entropy contributions (stochastic structural fluctuations, anharmonicity and lattice softness) on the optoelectronic properties of halide perovskite materials and devices.

  4. New antimony(III) halide complexes with dithiocarbamate ligands derived from thiuram degradation: The effect of the molecule's close contacts on in vitro cytotoxic activity

    International Nuclear Information System (INIS)

    Urgut, O.S.; Ozturk, I.I.; Banti, C.N.; Kourkoumelis, N.; Manoli, M.; Tasiopoulos, A.J.; Hadjikakou, S.K.

    2016-01-01

    ABSTRACT: Antimony(III) halide complexes of the formulae {[SbBr(Me 2 DTC) 2 ] n } (1), {[SbI(Me 2 DTC) 2 ] n } (2) and {[(Me 2 DTC) 2 Sb(μ 2 -I)Sb(Me 2 DTC) 2 ] + .I 3 − } (3) (Me 2 DTC = dimethyldithiocarbomate) were synthesized from SbX 3 , (X = Br or I) and tetramethylthiuram monosulfide (Me 4 tms) or tetramethylthiuram disulfide (Me 4 tds). The complexes were characterized by melting point (m.p.), elemental analysis (e.a.), Fourier-transform Infra-Red (FT-IR), Fourier-transform Raman (FT-Raman), Nuclear Magnetic Resonance ( 1 H, 13 C-NMR) spectroscopy and Thermogravimetric-Differential Thermal Analysis (TG-DTA). Crystal structures of complexes 1–3 were determined with single crystal X-ray diffraction analysis. Complexes 1 and 2 are polymers with distorted square pyramidal (SP) geometry in each monomeric unit, whereas complex 3 is ionic, containing an iodonium linkage Sb–I + –Sb and an I 3 − counter anion; to the best of our knowledge, this is the first ionic antimony(III) iodide complex. The in vitro cytotoxic activity of 1–3 against human adenocarcinoma cells: breast (MCF-7) and cervix (HeLa) cells and non-cancerous cells: MRC-5 (normal human fetal lung fibroblast cells) was evaluated with trypan blue (TB) and sulforhodamine B (SRB) assays. Among antimony(III) compounds with sulfur containing ligand, those of dithiocarbamates exhibit significant cytotoxic activity. Hirshfeld surface volumes were analyzed to clarify the nature of the intermolecular interactions by the 2D fingerprint plot. Molecules with lower H-all atoms inter-molecular interactions exhibit the higher activity against MCF-7 cells. The in vivo genotoxicity of 1–3 was evaluated by the mean of Allium cepa test. Alterations in the mitotic index values due to the chromosomal aberrations were observed in the case of complexes 2 and 3. Since, no such alteration is caused by 1, it makes this compound candidate for further study as potential drug. - Graphical abstract: The in vitro

  5. New antimony(III) halide complexes with dithiocarbamate ligands derived from thiuram degradation: The effect of the molecule's close contacts on in vitro cytotoxic activity

    Energy Technology Data Exchange (ETDEWEB)

    Urgut, O.S. [Department of Chemistry, Namık Kemal University, 59030, Tekirdag (Turkey); Ozturk, I.I., E-mail: iiozturk@nku.edu.tr [Department of Chemistry, Namık Kemal University, 59030, Tekirdag (Turkey); Banti, C.N., E-mail: cbanti@cc.uoi.gr [Section of Inorganic and Analytical Chemistry, Department of Chemistry, University of Ioannina, 45110 Ioannina (Greece); Kourkoumelis, N., E-mail: nkourkou@uoi.gr [Medical Physics Laboratory, Medical School, University of Ioannina, Ioannina, 45110 (Greece); Manoli, M.; Tasiopoulos, A.J. [Department of Chemistry, University of Cyprus, Nicosia (Cyprus); Hadjikakou, S.K., E-mail: shadjika@uoi.gr [Section of Inorganic and Analytical Chemistry, Department of Chemistry, University of Ioannina, 45110 Ioannina (Greece)

    2016-01-01

    ABSTRACT: Antimony(III) halide complexes of the formulae {[SbBr(Me_2DTC)_2]_n} (1), {[SbI(Me_2DTC)_2]_n} (2) and {[(Me_2DTC)_2Sb(μ_2-I)Sb(Me_2DTC)_2]"+.I_3"−} (3) (Me{sub 2}DTC = dimethyldithiocarbomate) were synthesized from SbX{sub 3}, (X = Br or I) and tetramethylthiuram monosulfide (Me{sub 4}tms) or tetramethylthiuram disulfide (Me{sub 4}tds). The complexes were characterized by melting point (m.p.), elemental analysis (e.a.), Fourier-transform Infra-Red (FT-IR), Fourier-transform Raman (FT-Raman), Nuclear Magnetic Resonance ({sup 1}H,{sup 13}C-NMR) spectroscopy and Thermogravimetric-Differential Thermal Analysis (TG-DTA). Crystal structures of complexes 1–3 were determined with single crystal X-ray diffraction analysis. Complexes 1 and 2 are polymers with distorted square pyramidal (SP) geometry in each monomeric unit, whereas complex 3 is ionic, containing an iodonium linkage Sb–I{sup +}–Sb and an I{sub 3}{sup −} counter anion; to the best of our knowledge, this is the first ionic antimony(III) iodide complex. The in vitro cytotoxic activity of 1–3 against human adenocarcinoma cells: breast (MCF-7) and cervix (HeLa) cells and non-cancerous cells: MRC-5 (normal human fetal lung fibroblast cells) was evaluated with trypan blue (TB) and sulforhodamine B (SRB) assays. Among antimony(III) compounds with sulfur containing ligand, those of dithiocarbamates exhibit significant cytotoxic activity. Hirshfeld surface volumes were analyzed to clarify the nature of the intermolecular interactions by the 2D fingerprint plot. Molecules with lower H-all atoms inter-molecular interactions exhibit the higher activity against MCF-7 cells. The in vivo genotoxicity of 1–3 was evaluated by the mean of Allium cepa test. Alterations in the mitotic index values due to the chromosomal aberrations were observed in the case of complexes 2 and 3. Since, no such alteration is caused by 1, it makes this compound candidate for further study as potential drug. - Graphical

  6. Ternary complex formation at mineral/solution interfaces

    International Nuclear Information System (INIS)

    Leckie, J.O.

    1995-01-01

    Adsorption of trace concentrations of radionuclides and heavy metals from aqueous solution is dependent on pH, absorbent and adsorbate concentration, and speciation of the metal in solution. In particular, complexation of metal ions by organic and inorganic ligands can dramatically alter adsorption behavior compared to ligand-free systems. The presence of complexing ligands can cause the formation of ''metal like'' or ''ligand like'' ternary surface complexes depending on whether adsorption of the ternary complex increases or decreases with increasing pH, respectively. Examples of ternary surface complexes behaving ''metal like'' include uranyl-EDTA surface complexes on goethite, neptunyl-EDTA surface complexes on hematite and neptunyl-humic surface complexes on gibbsite. Examples of ''ligand like'' ternary surface complexes include uranyl-carbonato and neptunyl-carbonato surface complexes on iron oxides. The effects of complex solutions and multimineralic systems are discussed. (authors). 39 refs., 16 figs., 8 tabs

  7. Positron life time and annihilation Doppler broadening measurements on transition metal complexes

    International Nuclear Information System (INIS)

    Levay, B.; Burger, K.

    1982-01-01

    Positron life time and annihilation Doppler broadening measurements have been carried out on 44 solid coordination compounds. Several correlations have been found between the annihilation life time (tau 1 ) and line shape parameters (L) and the chemical structure of the compounds. Halide ligands were the most active towards positrons. This fact supports the assumption on the possible formation of [e + X - ] positron-halide bound state. The life time was decreasing and the annihilation energy spectra were broadening with the increasing negative character of the halides. The aromatic base ligands affected the positron-halide interaction according to their basicity and space requirement and thus they indirectly affected the annihilation parameters, too. In the planar and tetrahedral complexes the electron density on the central met--al ion affected directly the annihilation parameters, while in the octahedral mixed complexes it had only an ind--irect effect through the polarization of the halide ligands. (author)

  8. Synthesis of iridacarborane halide complexes [(η-9-SMe2-7,8-C2B9H10)IrX2]2 (X=Cl, Br, I)

    International Nuclear Information System (INIS)

    Kudinov, A.R.; Perekalin, D.S.; Petrovskij, P.V.

    2001-01-01

    By interaction between Na[9-SMe 2 -7,8-C 2 B 9 H 10 ] and [(Cod)IrCl] 2 (Cod - cycloocta-1,5-diene) iridium complex (η-9-SMe 2 -7,8-C 2 B 9 H 10 )Ir(Cod), which under the action of anhydrous hydrohalogenic acids HX (X=Cl, Br, I) yields iridacarborane halide complexes [(η-9-SMe 2 -7,8-C 2 B 9 H 10 )IrX 2 ] 2 , being analogs of cyclopentadienyl complexes [(C 5 Me 5 )IrX 2 ] 2 . The complexes prepared were characterized on the basis of data of elementary analysis and 1 H, 11 B NMR spectra [ru

  9. Reversibility and Relaxation Behavior of Polyelectrolyte Complex Micelle Formation

    NARCIS (Netherlands)

    Lindhoud, Saskia; Norde, Willem; Stuart, Martien A. Cohen

    2009-01-01

    In this study, the formation and disintegration of polyelectrolyte complex micelles is studied by dynamic light scattering titrations with the aim to assess the extent to which these complexes equilibrate. Also, the time evolution of samples at fixed (electroneutral) composition was followed to

  10. Investigation of formation constant of complex of a new synthesized ...

    African Journals Online (AJOL)

    The complex formation between a newly synthesized tripodal ligand and the cation Cu2+ in water and surfactant media was studied spectrophotometrically using rank annihilation factor analysis (RAFA). According to molar ratio data the stoichiometry of complexation between the ligand and the cation Cu2+ was 1:1.

  11. Complex Formation Control of Large-Scale Intelligent Autonomous Vehicles

    Directory of Open Access Journals (Sweden)

    Ming Lei

    2012-01-01

    Full Text Available A new formation framework of large-scale intelligent autonomous vehicles is developed, which can realize complex formations while reducing data exchange. Using the proposed hierarchy formation method and the automatic dividing algorithm, vehicles are automatically divided into leaders and followers by exchanging information via wireless network at initial time. Then, leaders form formation geometric shape by global formation information and followers track their own virtual leaders to form line formation by local information. The formation control laws of leaders and followers are designed based on consensus algorithms. Moreover, collision-avoiding problems are considered and solved using artificial potential functions. Finally, a simulation example that consists of 25 vehicles shows the effectiveness of theory.

  12. Sonogashira Reaction of Aryl and Heteroaryl Halides with Terminal Alkynes Catalyzed by a Highly Efficient and Recyclable Nanosized MCM-41 Anchored Palladium Bipyridyl Complex

    Directory of Open Access Journals (Sweden)

    Chung-Yuan Mou

    2010-12-01

    Full Text Available A heterogeneous catalyst, nanosized MCM-41-Pd, was used to catalyze the Sonogashira coupling of aryl and heteroaryl halides with terminal alkynes in the presence of CuI and triphenylphosphine. The coupling products were obtained in high yields using low Pd loadings to 0.01 mol%, and the nanosized MCM-41-Pd catalyst was recovered by centrifugation of the reaction solution and re-used in further runs without significant loss of reactivity.

  13. Curcumin complexation with cyclodextrins by the autoclave process: Method development and characterization of complex formation.

    Science.gov (United States)

    Hagbani, Turki Al; Nazzal, Sami

    2017-03-30

    One approach to enhance curcumin (CUR) aqueous solubility is to use cyclodextrins (CDs) to form inclusion complexes where CUR is encapsulated as a guest molecule within the internal cavity of the water-soluble CD. Several methods have been reported for the complexation of CUR with CDs. Limited information, however, is available on the use of the autoclave process (AU) in complex formation. The aims of this work were therefore to (1) investigate and evaluate the AU cycle as a complex formation method to enhance CUR solubility; (2) compare the efficacy of the AU process with the freeze-drying (FD) and evaporation (EV) processes in complex formation; and (3) confirm CUR stability by characterizing CUR:CD complexes by NMR, Raman spectroscopy, DSC, and XRD. Significant differences were found in the saturation solubility of CUR from its complexes with CD when prepared by the three complexation methods. The AU yielded a complex with expected chemical and physical fingerprints for a CUR:CD inclusion complex that maintained the chemical integrity and stability of CUR and provided the highest solubility of CUR in water. Physical and chemical characterizations of the AU complexes confirmed the encapsulated of CUR inside the CD cavity and the transformation of the crystalline CUR:CD inclusion complex to an amorphous form. It was concluded that the autoclave process with its short processing time could be used as an alternate and efficient methods for drug:CD complexation. Copyright © 2017 Elsevier B.V. All rights reserved.

  14. Relation between the electroforming voltage in alkali halide-polymer diodes and the bandgap of the alkali halide

    International Nuclear Information System (INIS)

    Bory, Benjamin F.; Wang, Jingxin; Janssen, René A. J.; Meskers, Stefan C. J.; Gomes, Henrique L.; De Leeuw, Dago M.

    2014-01-01

    Electroforming of indium-tin-oxide/alkali halide/poly(spirofluorene)/Ba/Al diodes has been investigated by bias dependent reflectivity measurements. The threshold voltages for electrocoloration and electroforming are independent of layer thickness and correlate with the bandgap of the alkali halide. We argue that the origin is voltage induced defect formation. Frenkel defect pairs are formed by electron–hole recombination in the alkali halide. This self-accelerating process mitigates injection barriers. The dynamic junction formation is compared to that of a light emitting electrochemical cell. A critical defect density for electroforming is 10 25 /m 3 . The electroformed alkali halide layer can be considered as a highly doped semiconductor with metallic transport characteristics

  15. The creation of defects in ammonium halides by excitons

    International Nuclear Information System (INIS)

    Kim, L.M.

    2002-01-01

    The ammonium halides crystals and alkali halides crystals are analogous by kind chemical bonds and crystalline lattices. The anionic sublattice is identical in this crystals. It is known the main mechanism of defect creation by irradiation is radiationless decay of excitons in alkali halides crystals. The F-, H-centers are formation in this processes. However, F, H-centres are not detected in ammonium halides. The goal of this work is investigation the creation of defects in ammonium halides by excitons. We established that excitons in ammonium chlorides and bromides are similar to excitons in alkali halides. It is known excitons are self-trapped and have identical parameters of the exciton-phonon interaction in both kind crystals. It is supposed, that processes of radiationless disintegration of excitons are identical in ammonium and alkali halides. It is necessary to understand why F-, H-centers are absent in ammonium halides. V k -centres are created by the excitation of the ammonium halides crystals in the absorption band of excitons. It was established by thermoluminescence and spectrums of absorption. The V k -centers begin to migrate at 110-120 K in ammonium chlorides and bromides. The curve of thermoluminescence have peak with maximum at this temperatures. It is known V k -centers in ammonium chlorides have the absorption band at 380 nm. We discovered this absorption band after irradiation of crystals by ultra-violet. In alkali halides F-center is anionic vacancy with electron. The wave function of electron are spread ed at the cations around anionic vacancy. We established the cation NH 4 + in ammonium halides can to capture electron. The ion NH 4 2+ is unsteady. It is disintegrated to NH 3 + and H + . We suppose that excitons in ammonium and alkali halides are disintegrated identically. When cation NH 4 + capture electron, in the anionic sublattice the configuration are created in a direction (100) The indicated configuration is unsteady in relation to a

  16. INTERRELATION OF ACIDITY-BASICITY, SOLUBILITY AND ABILITY TO INTERACTION OF HALIDES OF MX AND M'X2 (M - Li ÷ Cs, M' - Be ÷ Ba, X - Cl ÷ I TYPES

    Directory of Open Access Journals (Sweden)

    V. F. Zinchenko

    2015-11-01

    Full Text Available The size-charge factor of basicity for definition of the acid-base properties of alkaline both alkaline-earth metals and Be halides is offered. The certain interrelation of the specified factor, and also the magnitudes connected with energy of a crystal lattice (temperature of boiling and enthalpy of evaporation of salt with its solubility in water, and also with enthalpy of hydration is established. It is shown that the minimum solubility possess alkaline metals halides (KCl for chlorides, RbBr for Rubidium halides and CsI for alkaline metals halides as a whole at which value of the factor of basicity is equal to 0.83, i.e. it is slightly less than 1. Among alkaline-earth metals halides the lowest solubility has BaCl2 with the highest value of the factor of basicity (0.4. An absolute value of enthalpy of hydration for salts crystal-hydrates possesses tens kJ/mol H2O and increases with reduction of the factor of basicity at transition from metals chlorides to iodides, and also at cationic substitution by easier analogue. Qualitative correlation between a difference of basicity of binary halides and their ability to interaction with formation of complex compounds of various degree of durability is established. At an average difference of basicities 0.4 in halide systems are formed incongruently melting, and at 0.6-0.8 and more – congruently melting compounds. Forecasting of solubility of complex halide of CsSrCl3 composition on the basis of its value of equalized basicity is carried out.

  17. Geology of the Biwabik Iron Formation and Duluth Complex.

    Science.gov (United States)

    Jirsa, Mark A; Miller, James D; Morey, G B

    2008-10-01

    The Biwabik Iron Formation is a approximately 1.9 billion year-old sequence of iron-rich sedimentary rocks that was metamorphosed at its eastern-most extent by approximately 1.1 billion year-old intrusions of the Duluth Complex. The metamorphic recrystallization of iron-formation locally produced iron-rich amphiboles and other fibrous iron-silicate minerals. The presence of these minerals in iron-formation along the eastern part of what is known as the Mesabi Iron Range, and their potential liberation by iron mining has raised environmental health concerns. We describe here the geologic setting and mineralogic composition of the Biwabik Iron Formation in and adjacent to the contact metamorphic aureole of the Duluth Complex. The effects of metamorphism are most pronounced within a few kilometers of the contact, and decrease progressively away from it. The contact aureole has been divided into four metamorphic zones-each characterized by the composition and crystal structure of the metamorphic minerals it contains. The recrystallization of iron-formation to iron-rich amphibole minerals (grunerite and cummingtonite) and iron-pyroxene minerals (hedenbergite and ferrohypersthene) is best developed in zones that are most proximal to the Duluth Complex contact.

  18. Zein/caseinate/pectin complex nanoparticles: Formation and characterization.

    Science.gov (United States)

    Chang, Chao; Wang, Taoran; Hu, Qiaobin; Luo, Yangchao

    2017-11-01

    In this study, pectin was used as coating material to form zein/caseinate/pectin complex nanoparticles through pH adjustment and heating treatment for potential oral delivery applications. The preparation conditions were studied by applying heating treatment at different pHs, either the isoelectric point of zein (pH 6.2) or caseinate (pH 4.6), or consecutively at both pHs. The particulate characteristics, including particle size, polydispersity index, and zeta potential were monitored for complex nanoparticles formed under different preparation conditions. The complex nanoparticles generally exhibited particle size smaller than 200nm with narrow distribution, spherical shape, and strong negative charge. Fourier transform infrared and fluorescence spectroscopy revealed that hydrophobic interactions and hydrogen bonds were involved in the formation of complex nanoparticles, in addition to electrostatic interactions. Fresh colloidal dispersion and freeze-dried powders varied in their morphology, depending on their preparation conditions. Our results suggested that heating pH and sequence significantly affected the morphology of complex nanoparticles, and pectin coating exerted stabilization effect under simulated gastrointestinal conditions. The present study provides insight into the formation of protein/polysaccharide complex nanoparticles under different preparation conditions. Copyright © 2017 Elsevier B.V. All rights reserved.

  19. Positronium formation studies in crystalline molecular complexes: Triphenylphosphine oxide - Acetanilide

    Science.gov (United States)

    Oliveira, F. C.; Denadai, A. M. L.; Guerra, L. D. L.; Fulgêncio, F. H.; Windmöller, D.; Santos, G. C.; Fernandes, N. G.; Yoshida, M. I.; Donnici, C. L.; Magalhães, W. F.; Machado, J. C.

    2013-04-01

    Hydrogen bond formation in the triphenylphosphine oxide (TPPO), acetanilide (ACN) supramolecular heterosynton system, named [TPPO0.5·ACN0.5], has been studied by Positron Annihilation Lifetime Spectroscopy (PALS) and supported by several analytical techniques. In toluene solution, Isothermal Titration Calorimetry (ITC) presented a 1:1 stoichiometry and indicated that the complexation process is driven by entropy, with low enthalpy contribution. X-ray structure determination showed the existence of a three-dimensional network of hydrogen bonds, allowing also the confirmation of the existence of a 1:1 crystalline molecular complex in solid state. The results of thermal analysis (TGA, DTA and DSC) and FTIR spectroscopy showed that the interactions in the complex are relatively weaker than those found in pure precursors, leading to a higher positronium formation probability at [TPPO0.5·ACN0.5]. These weak interactions in the complex enhance the possibility of the n- and π-electrons to interact with positrons and consequently, the probability of positronium formation is higher. Through the present work is shown that PALS is a sensible powerful tool to investigate intermolecular interactions in solid heterosynton supramolecular systems.

  20. complex formation of americium (III) with humic acid

    International Nuclear Information System (INIS)

    Zhang Yingjie; Zhao Xin; Wei Liansheng; Lin Zhangji

    1998-01-01

    The presence of humic substances in natural waters will modify the migration behavior of actinides in the geosphere due to the strong reaction properties of these ligands with actinides. Therefore, the possible reactions of humic acid with actinides have been studied widely in recent years. The complex formation of Am(III) with humic acid is studied with solvent extraction technique. The experiments are performed in the pH range from 4.0 to 8.0 in 0.1 mol/kg NaClO 4 solution at ambient temperature. Experimental results show that the complex formation constants of Am(III) with humic acid are varied with the variation of pH value in solution. 1:2 complex is obtained in the experiments and the complex formation constants determined at each pH are: lgβ 1 = 6.56 +- 0.05, lgβ 2 = 10.77 +- 0.31 at pH 4.0. lgβ 1 = 7.94 +- 0.11, lgβ 2 = 11.80 +- 0.21 at pH = 5.0. lgβ 1 = 10.74 +- 0.28, lgβ 2 = 12.88 +- 0.49 at pH = 6.0. lgβ 1 = 12.85 +- 0.30, lgβ 2 = 14.80 +- 0.62 at pH = 7.0. lgβ 1 = 14.88 +- 0.48, lgβ 2 = 15.65 +- 0.69 at pH = 8.0, respectively. The dependence of the complex formation constant on pH is: lgβ 1 = 2.16 (+-0.98)pH-2.34(+-0.93),lgβ 2 1.28(+-1.04)pH+5.52(+-1.21), respectively

  1. SPECTROPHOTOMETRIC STUDIES OF SANGUINARINE-Β-CYCLODEXTRIN COMPLEX FORMATION

    Directory of Open Access Journals (Sweden)

    Veaceslav Boldescu

    2008-06-01

    Full Text Available The main aim of this study was to investigate the influence of pH and the presence of hydrophilic polymer polyvinylpyrrolidone on the formation of sanguinarine-β-cyclodextrin (SANG-β-CD inclusion complex. Spectrophotometric studies of the SANG-β-CD systems in the presence and without 0.1 % PVP at the pH 5.0 did not show any evidence of the complex formation. However, the same systems showed several obvious evidences at the pH 8.0: the hyperchromic and the hypochromic effects and the presence of the isosbestic point in the region of 200 – 210 nm. The association constants calculated by three linear methods: Benesi-Hildebrand, Scott and Scatchard, were two times higher for the systems with addition of 0.1% PVP than for the systems without it.

  2. Gel phase formation in dilute triblock copolyelectrolyte complexes

    Science.gov (United States)

    Srivastava, Samanvaya; Andreev, Marat; Levi, Adam E.; Goldfeld, David J.; Mao, Jun; Heller, William T.; Prabhu, Vivek M.; de Pablo, Juan J.; Tirrell, Matthew V.

    2017-02-01

    Assembly of oppositely charged triblock copolyelectrolytes into phase-separated gels at low polymer concentrations (simulations. Here we show that in contrast to uncharged, amphiphilic block copolymers that form discrete micelles at low concentrations and enter a phase of strongly interacting micelles in a gradual manner with increasing concentration, the formation of a dilute phase of individual micelles is prevented in polyelectrolyte complexation-driven assembly of triblock copolyelectrolytes. Gel phases form and phase separate almost instantaneously on solvation of the copolymers. Furthermore, molecular models of self-assembly demonstrate the presence of oligo-chain aggregates in early stages of copolyelectrolyte assembly, at experimentally unobservable polymer concentrations. Our discoveries contribute to the fundamental understanding of the structure and pathways of complexation-driven assemblies, and raise intriguing prospects for gel formation at extraordinarily low concentrations, with applications in tissue engineering, agriculture, water purification and theranostics.

  3. Tunable light emission by exciplex state formation between hybrid halide perovskite and core/shell quantum dots: Implications in advanced LEDs and photovoltaics.

    Science.gov (United States)

    Sanchez, Rafael S; de la Fuente, Mauricio Solis; Suarez, Isaac; Muñoz-Matutano, Guillermo; Martinez-Pastor, Juan P; Mora-Sero, Ivan

    2016-01-01

    We report the first observation of exciplex state electroluminescence due to carrier injection between the hybrid lead halide perovskite (MAPbI3-xClx) and quantum dots (core/shell PbS/CdS). Single layers of perovskite (PS) and quantum dots (QDs) have been produced by solution processing methods, and their photoluminescent properties are compared to those of bilayer samples in both PS/QD and QD/PS configurations. Exciplex emission at lower energies than the band gap of both PS and QD has been detected. The exciplex emission wavelength of this mixed system can be simply tuned by controlling the QD size. Light-emitting diodes (LEDs) have been fabricated using those configurations, which provide light emission with considerably low turn-on potential. The "color" of the LED can also be tuned by controlling the applied bias. The presence of the exciplex state PS and QDs opens up a broad range of possibilities with important implications not only in tunable LEDs but also in the preparation of intermediate band gap photovoltaic devices with the potentiality of surpassing the Shockley-Queisser limit.

  4. Tunable light emission by exciplex state formation between hybrid halide perovskite and core/shell quantum dots: Implications in advanced LEDs and photovoltaics

    Science.gov (United States)

    Sanchez, Rafael S.; de la Fuente, Mauricio Solis; Suarez, Isaac; Muñoz-Matutano, Guillermo; Martinez-Pastor, Juan P.; Mora-Sero, Ivan

    2016-01-01

    We report the first observation of exciplex state electroluminescence due to carrier injection between the hybrid lead halide perovskite (MAPbI3–xClx) and quantum dots (core/shell PbS/CdS). Single layers of perovskite (PS) and quantum dots (QDs) have been produced by solution processing methods, and their photoluminescent properties are compared to those of bilayer samples in both PS/QD and QD/PS configurations. Exciplex emission at lower energies than the band gap of both PS and QD has been detected. The exciplex emission wavelength of this mixed system can be simply tuned by controlling the QD size. Light-emitting diodes (LEDs) have been fabricated using those configurations, which provide light emission with considerably low turn-on potential. The “color” of the LED can also be tuned by controlling the applied bias. The presence of the exciplex state PS and QDs opens up a broad range of possibilities with important implications not only in tunable LEDs but also in the preparation of intermediate band gap photovoltaic devices with the potentiality of surpassing the Shockley-Queisser limit. PMID:26844299

  5. Single-stranded nucleic acids promote SAMHD1 complex formation.

    Science.gov (United States)

    Tüngler, Victoria; Staroske, Wolfgang; Kind, Barbara; Dobrick, Manuela; Kretschmer, Stefanie; Schmidt, Franziska; Krug, Claudia; Lorenz, Mike; Chara, Osvaldo; Schwille, Petra; Lee-Kirsch, Min Ae

    2013-06-01

    SAM domain and HD domain-containing protein 1 (SAMHD1) is a dGTP-dependent triphosphohydrolase that degrades deoxyribonucleoside triphosphates (dNTPs) thereby limiting the intracellular dNTP pool. Mutations in SAMHD1 cause Aicardi-Goutières syndrome (AGS), an inflammatory encephalopathy that mimics congenital viral infection and that phenotypically overlaps with the autoimmune disease systemic lupus erythematosus. Both disorders are characterized by activation of the antiviral cytokine interferon-α initiated by immune recognition of self nucleic acids. Here we provide first direct evidence that SAMHD1 associates with endogenous nucleic acids in situ. Using fluorescence cross-correlation spectroscopy, we demonstrate that SAMHD1 specifically interacts with ssRNA and ssDNA and establish that nucleic acid-binding and formation of SAMHD1 complexes are mutually dependent. Interaction with nucleic acids and complex formation do not require the SAM domain, but are dependent on the HD domain and the C-terminal region of SAMHD1. We finally demonstrate that mutations associated with AGS exhibit both impaired nucleic acid-binding and complex formation implicating that interaction with nucleic acids is an integral aspect of SAMHD1 function.

  6. A study on complex formation of cadmium (II) ions, 9

    International Nuclear Information System (INIS)

    Matsui, Haruo

    1984-01-01

    Formation constants of cadmium (11) complexes with dicarboxylic acids such as oxalic, malonic, methylmalonic, succinic, and glutaric acids were determined in aqueous solutions containing 3 mol.dm -3 LiClO 4 as a constan ionic medium at 25 0 C by potentiometric titrations. It was reported in the previous works that cadmium (11)- aspartic acid complexes contained two chelate rings. However, a problem remained whether the second chelate ring could be formed by six membered-ring containing -O-Cd-N- bond or by seven membered-ring containing -O-Cd-O- bond. The results of the present work suggested that it would be formed by a six membered ring. Cadmium (11) ions were coordinated with a carboxylic group of the dicarboxylic acids studied, and formed no chelate ring within the complexes. The white precipitate appeared in the solution containing cadmium (11) ion and oxalic acid, in the pH range below 3.0, therefore, the chelate formation was not ascertained in this case. The formation constants, log βsub(pr)= log([Cdsub(p)Lsub(r)sup((2p-2r)+)]/([Cd 2+ ]sup(p)[L 2- ]sup(r))), of the complexes were: log β 11 = 1.98, log β 12 = 3.05 for cadmium (11)-malonic acid; log β 11 = 2.28, log β 12 = 3.06 for cadmium (11)-methylmalonic acid; log β 11 = 1.78, log β 12 = 3.08 for cadmium (11)-succinic acid; log β 11 = 1.85, log β 12 = 3.28 for cadmium (11)-glutaric acid complexes. (author)

  7. Complex formation of americium (III) with humic acid

    International Nuclear Information System (INIS)

    Zhang Yingjie; Zhao Xin; Wen Liansheng; Lin Zhangji

    2004-01-01

    The presence of humic substances in natural waters will modify the migration behavior of actinides in the geosphere due to the strong reaction properties of these ligands with actinides. Therefore, the possible reactions of humic acid with actinides have been studied widely in recent years. The complex formation of Am (III) with humic acid is studied with solvent extraction technique in this paper. The experiments are performed in the pH range from 4.0 to 8.0 in 0.1 M NaClO 4 solution at ambient temperature. Experimental results show that the complex formation constants of Am (III) with humic acid are varied with the variation of pH value in solution. 1:2 complex is obtained in the experiments and the complex formation constants determined at each pH are: lgβ 1 =6.56±0.05, lgβ 2 =10.77±0.31 at pH=4.0; lgβ 1 =7.94±0.11, lgβ 2 =11.80±0.21 at pH=5.0; lgβ 1 =10.74±0.28, lgβ 2 =12.88±0.49 at pH=6.0; lgβ 1 =12.85±0.30, lgβ 2 =14.80±0.62 at pH=7.0; lgβ 1 =14.88±0.48, lgβ 2 =15.65±0.69 at pH=8.0, respectively. The dependence of the complex of the complex formation constant on pH is: lgβ 1 =2.16(±0.98)pH-2.34(±1.03), lgβ 2 =1.28(±1.04)pH+5.52(±1.21), respectively. (author)

  8. Resonant halide perovskite nanoparticles

    Science.gov (United States)

    Tiguntseva, Ekaterina Y.; Ishteev, Arthur R.; Komissarenko, Filipp E.; Zuev, Dmitry A.; Ushakova, Elena V.; Milichko, Valentin A.; Nesterov-Mueller, Alexander; Makarov, Sergey V.; Zakhidov, Anvar A.

    2017-09-01

    The hybrid halide perovskites is a prospective material for fabrication of cost-effective optical devices. Unique perovskites properties are used for solar cells and different photonic applications. Recently, perovskite-based nanophotonics has emerged. Here, we consider perovskite like a high-refractive index dielectric material, which can be considered to be a basis for nanoparticles fabrication with Mie resonances. As a result, we fabricate and study resonant perovskite nanoparticles with different sizes. We reveal, that spherical nanoparticles show enhanced photoluminescence signal. The achieved results lay a cornerstone in the field of novel types of organic-inorganic nanophotonics devices with optical properties improved by Mie resonances.

  9. Large polarons in lead halide perovskites

    OpenAIRE

    Miyata, Kiyoshi; Meggiolaro, Daniele; Trinh, M. Tuan; Joshi, Prakriti P.; Mosconi, Edoardo; Jones, Skyler C.; De Angelis, Filippo; Zhu, X.-Y.

    2017-01-01

    Lead halide perovskites show marked defect tolerance responsible for their excellent optoelectronic properties. These properties might be explained by the formation of large polarons, but how they are formed and whether organic cations are essential remain open questions. We provide a direct time domain view of large polaron formation in single-crystal lead bromide perovskites CH3NH3PbBr3 and CsPbBr3. We found that large polaron forms predominantly from the deformation of the PbBr3 ? framewor...

  10. The ribosome-associated complex antagonizes prion formation in yeast.

    Science.gov (United States)

    Amor, Alvaro J; Castanzo, Dominic T; Delany, Sean P; Selechnik, Daniel M; van Ooy, Alex; Cameron, Dale M

    2015-01-01

    The number of known fungal proteins capable of switching between alternative stable conformations is steadily increasing, suggesting that a prion-like mechanism may be broadly utilized as a means to propagate altered cellular states. To gain insight into the mechanisms by which cells regulate prion formation and toxicity we examined the role of the yeast ribosome-associated complex (RAC) in modulating both the formation of the [PSI(+)] prion - an alternative conformer of Sup35 protein - and the toxicity of aggregation-prone polypeptides. The Hsp40 RAC chaperone Zuo1 anchors the RAC to ribosomes and stimulates the ATPase activity of the Hsp70 chaperone Ssb. We found that cells lacking Zuo1 are sensitive to over-expression of some aggregation-prone proteins, including the Sup35 prion domain, suggesting that co-translational protein misfolding increases in Δzuo1 strains. Consistent with this finding, Δzuo1 cells exhibit higher frequencies of spontaneous and induced prion formation. Cells expressing mutant forms of Zuo1 lacking either a C-terminal charged region required for ribosome association, or the J-domain responsible for Ssb ATPase stimulation, exhibit similarly high frequencies of prion formation. Our findings are consistent with a role for the RAC in chaperoning nascent Sup35 to regulate folding of the N-terminal prion domain as it emerges from the ribosome.

  11. Multi-Level Formation of Complex Software Systems

    Directory of Open Access Journals (Sweden)

    Hui Li

    2016-05-01

    Full Text Available We present a multi-level formation model for complex software systems. The previous works extract the software systems to software networks for further studies, but usually investigate the software networks at the class level. In contrast to these works, our treatment of software systems as multi-level networks is more realistic. In particular, the software networks are organized by three levels of granularity, which represents the modularity and hierarchy in the formation process of real-world software systems. More importantly, simulations based on this model have generated more realistic structural properties of software networks, such as power-law, clustering and modularization. On the basis of this model, how the structure of software systems effects software design principles is then explored, and it could be helpful for understanding software evolution and software engineering practices.

  12. Simulations of photochemical smog formation in complex urban areas

    Science.gov (United States)

    Muilwijk, C.; Schrijvers, P. J. C.; Wuerz, S.; Kenjereš, S.

    2016-12-01

    In the present study we numerically investigated the dispersion of photochemical reactive pollutants in complex urban areas by applying an integrated Computational Fluid Dynamics (CFD) and Computational Reaction Dynamics (CRD) approach. To model chemical reactions involved in smog generation, the Generic Reaction Set (GRS) approach is used. The GRS model was selected since it does not require detailed modeling of a large set of reactive components. Smog formation is modeled first in the case of an intensive traffic emission, subjected to low to moderate wind conditions in an idealized two-dimensional street canyon with a building aspect ratio (height/width) of one. It is found that Reactive Organic Components (ROC) play an important role in the chemistry of smog formation. In contrast to the NOx/O3 photochemical steady state model that predicts a depletion of the (ground level) ozone, the GRS model predicts generation of ozone. Secondly, the effect of direct sunlight and shadow within the street canyon on the chemical reaction dynamics is investigated for three characteristic solar angles (morning, midday and afternoon). Large differences of up to one order of magnitude are found in the ozone production for different solar angles. As a proof of concept for real urban areas, the integrated CFD/CRD approach is applied for a real scale (1 × 1 km2) complex urban area (a district of the city of Rotterdam, The Netherlands) with high traffic emissions. The predicted pollutant concentration levels give realistic values that correspond to moderate to heavy smog. It is concluded that the integrated CFD/CRD method with the GRS model of chemical reactions is both accurate and numerically robust, and can be used for modeling of smog formation in complex urban areas.

  13. Theoretical study about L-arginine complexes formation with thiotriazolin

    Directory of Open Access Journals (Sweden)

    L. I. Kucherenko

    2017-02-01

    Full Text Available Brain vascular diseases are one of the leading causes of morbidity, mortality and disability of population in the industrialized countries of the world. An important element of this problem’s solution is the creation of new highly effective and safe drugs, which would lead to mortality reduction, to increase in life expectancy and quality of life. Therefore it is interesting to create a new combined drug based on L-arginine and thiotriazolin. Purpose of the study: to consider the possible structure and energy characteristics of complexes formed by L-arginine, 3-methyl-1,2,4-triazolyl-5-thioacetate (MTTA and morpholine. Calculation method. The initial approximation to the complex geometry was obtained using molecular docking with the help of AutoDock Vina program. The obtained ternary complexes were pre-optimized by semi-empirical PM7 method with modeling the impact of the environment by COSMO method. The calculations were carried out using MOPAC2012 program. Then they were optimized by B97-D3/SVP + COSMO (Water dispersion-corrected DFT-D with geometrical spreading correction on insufficiency of gCP basis set. A more accurate calculation of the solvation energy was conducted by SMD. The calculations by density functional method were carried out using the ORCA 3.0.3 software. Energy complex formation in solution was calculated as the difference of the Gibbs free energy of the solvated complex and its individual components. Results. Quantum chemical calculations show, that thiotriazolin and L-arginine are able to form ternary complexes, where molecules are linked by multiple hydrogen bonds. The calculation data suggest, that studied complexes are thermodynamically unstable in solution. The energies of them are positive, but rather low despite charge gain of a number of intermolecular hydrogen bonds. Finding. Based on the results of the conducted quantum-chemical study of a three components system (MTTA, morpholine, and L-arginine it is possible

  14. Complex formation between uranyl and various thiosemicarbazide derivatives

    International Nuclear Information System (INIS)

    Chuguryan, D.G.; Dzyubenko, V.I.

    1987-01-01

    Complex formation between hexavalent uranium and salicylaldehyde thiosemicarbazone (H 2 L), salicylaldehyde S-methyl-isothiosemicarbazone (H 2 Q), S-methyl-N 1 ,N 4 -bis(salicylidene)isothiosemicarbazide(H 2 Z), and thiosemicarbazidodiacetic acid (H 2 R) has been studied spectrophotometrically in solution. Stability constants for complexes having the composition UO 2 A have been calculated. Solid uranyl derivatives having the composition UO 2 L x 2H 2 O, UO 2 Q x 2H 2 O, UO 2 Z x 2H 2 O, and UO 2 R x 2H 2 O have been obtained. These derivatives were isolated and their IR spectroscopic behavior and thermal properties were investigated

  15. Impact of the organic halide salt on final perovskite composition for photovoltaic applications

    KAUST Repository

    Moore, David T.

    2014-08-01

    The methylammonium lead halide perovskites have shown significant promise as a low-cost, second generation, photovoltaic material.Despite recent advances, however, there are still a number of fundamental aspects of their formation as well as their physical and electronic behavior that are not well understood. In this letter we explore the mechanism by which these materials crystallize by testing the outcome of each of the reagent halide salts. We find that components of both salts, lead halide and methylammonium halide, are relatively mobile and can be readily exchanged during the crystallization process when the reaction is carried out in solution or in the solid state. We exploit this fact by showing that the perovskite structure is formed even when the lead salt\\'s anion is a non-halide, leading to lower annealing temperature and time requirements for film formation. Studies into these behaviors may ultimately lead to improved processing conditions for photovoltaic films. © 2014 Author(s).

  16. Impact of the organic halide salt on final perovskite composition for photovoltaic applications

    Directory of Open Access Journals (Sweden)

    David T. Moore

    2014-08-01

    Full Text Available The methylammonium lead halide perovskites have shown significant promise as a low-cost, second generation, photovoltaic material. Despite recent advances, however, there are still a number of fundamental aspects of their formation as well as their physical and electronic behavior that are not well understood. In this letter we explore the mechanism by which these materials crystallize by testing the outcome of each of the reagent halide salts. We find that components of both salts, lead halide and methylammonium halide, are relatively mobile and can be readily exchanged during the crystallization process when the reaction is carried out in solution or in the solid state. We exploit this fact by showing that the perovskite structure is formed even when the lead salt's anion is a non-halide, leading to lower annealing temperature and time requirements for film formation. Studies into these behaviors may ultimately lead to improved processing conditions for photovoltaic films.

  17. Complex formation in aqueous trimethylamine-N-oxide (TMAO) solutions.

    Science.gov (United States)

    Hunger, Johannes; Tielrooij, Klaas-Jan; Buchner, Richard; Bonn, Mischa; Bakker, Huib J

    2012-04-26

    We study aqueous solutions of the amphiphilic osmolyte trimethylamine-N-oxide (TMAO) using broadband dielectric spectroscopy and femtosecond mid-infrared spectroscopy. Both experiments provide strong evidence for distinctively slower rotation dynamics for water molecules interacting with the hydrophobic part of the TMAO molecules. Further, water is found to interact more strongly at the hydrophilic site of the TMAO molecules: we find evidence for the formation of stable, TMAO·2H2O and/or TMAO·3H2O complexes. While this coordination structure seems obvious, the lifetime of these complexes is found to be extraordinarily long (>50 ps). The existence of these long-lived complexes leads to pronounced parallel dipole correlations between water and TMAO, reflected in enhanced amplitudes in the dielectric spectra. The strong interaction between water and TMAO also results in a red-shifted band for the O-D stretching vibration of HDO molecules in an isotopically diluted aqueous TMAO solution. This O-D stretching vibration has a vibrational lifetime of 670 fs, which is significantly shorter than the lifetime of the O-D stretch vibration of bulk-like HDO molecules, presumably due to efficient coupling to vibrational modes of TMAO. The rotational dynamics of these O-D groups are slowed down dramatically, and are limited by the rotation of the whole complex, while the O-D vector oriented away from TMAO probably shows an accelerated reorientation.

  18. Characterization of Hydrogen Complex Formation in III-V Semiconductors

    Energy Technology Data Exchange (ETDEWEB)

    Williams, Michael D

    2006-09-28

    Atomic hydrogen has been found to react with some impurity species in semiconductors. Hydrogenation is a methodology for the introduction of atomic hydrogen into the semiconductor for the express purpose of forming complexes within the material. Efforts to develop hydrogenation as an isolation technique for AlGaAs and Si based devices failed to demonstrate its commercial viability. This was due in large measure to the low activation energies of the formed complexes. Recent studies of dopant passivation in long wavelength (0.98 - 1.55m) materials suggested that for the appropriate choice of dopants much higher activation energies can be obtained. This effort studied the formation of these complexes in InP, This material is extensively used in optoelectronics, i.e., lasers, modulators and detectors. The experimental techniques were general to the extent that the results can be applied to other areas such as sensor technology, photovoltaics and to other material systems. The activation energies for the complexes have been determined and are reported in the scientific literature. The hydrogenation process has been shown by us to have a profound effect on the electronic structure of the materials and was thoroughly investigated. The information obtained will be useful in assessing the long term reliability of device structures fabricated using this phenomenon and in determining new device functionalities.

  19. Unraveling halide hydration: A high dilution approach.

    Science.gov (United States)

    Migliorati, Valentina; Sessa, Francesco; Aquilanti, Giuliana; D'Angelo, Paola

    2014-07-28

    The hydration properties of halide aqua ions have been investigated combining classical Molecular Dynamics (MD) with Extended X-ray Absorption Fine Structure (EXAFS) spectroscopy. Three halide-water interaction potentials recently developed [M. M. Reif and P. H. Hünenberger, J. Chem. Phys. 134, 144104 (2011)], along with three plausible choices for the value of the absolute hydration free energy of the proton (ΔG [minus sign in circle symbol]hyd[H+]), have been checked for their capability to properly describe the structural properties of halide aqueous solutions, by comparing the MD structural results with EXAFS experimental data. A very good agreement between theory and experiment has been obtained with one parameter set, namely LE, thus strengthening preliminary evidences for a ΔG [minus sign in circle symbol]hyd[H] value of -1100 kJ mol(-1) [M. M. Reif and P. H. Hünenberger, J. Chem. Phys. 134, 144104 (2011)]. The Cl(-), Br(-), and I(-) ions have been found to form an unstructured and disordered first hydration shell in aqueous solution, with a broad distribution of instantaneous coordination numbers. Conversely, the F(-) ion shows more ordered and defined first solvation shell, with only two statistically relevant coordination geometries (six and sevenfold complexes). Our thorough investigation on the effect of halide ions on the microscopic structure of water highlights that the perturbation induced by the Cl(-), Br(-), and I(-) ions does not extend beyond the ion first hydration shell, and the structure of water in the F(-) second shell is also substantially unaffected by the ion.

  20. Interference-mediated synaptonemal complex formation with embedded crossover designation

    Science.gov (United States)

    Zhang, Liangran; Espagne, Eric; de Muyt, Arnaud; Zickler, Denise; Kleckner, Nancy E.

    2014-01-01

    Biological systems exhibit complex patterns at length scales ranging from the molecular to the organismic. Along chromosomes, events often occur stochastically at different positions in different nuclei but nonetheless tend to be relatively evenly spaced. Examples include replication origin firings, formation of chromatin loops along chromosome axes and, during meiosis, localization of crossover recombination sites (“crossover interference”). We present evidence in the fungus Sordaria macrospora that crossover interference is part of a broader pattern that includes synaptonemal complex (SC) nucleation. This pattern comprises relatively evenly spaced SC nucleation sites, among which a subset are crossover sites that show a classical interference distribution. This pattern ensures that SC forms regularly along the entire length of the chromosome as required for the maintenance of homolog pairing while concomitantly having crossover interactions locally embedded within the SC structure as required for both DNA recombination and structural events of chiasma formation. This pattern can be explained by a threshold-based designation and spreading interference process. This model can be generalized to give diverse types of related and/or partially overlapping patterns, in two or more dimensions, for any type of object. PMID:25380597

  1. Large polarons in lead halide perovskites

    Science.gov (United States)

    Miyata, Kiyoshi; Meggiolaro, Daniele; Trinh, M. Tuan; Joshi, Prakriti P.; Mosconi, Edoardo; Jones, Skyler C.; De Angelis, Filippo; Zhu, X.-Y.

    2017-01-01

    Lead halide perovskites show marked defect tolerance responsible for their excellent optoelectronic properties. These properties might be explained by the formation of large polarons, but how they are formed and whether organic cations are essential remain open questions. We provide a direct time domain view of large polaron formation in single-crystal lead bromide perovskites CH3NH3PbBr3 and CsPbBr3. We found that large polaron forms predominantly from the deformation of the PbBr3− frameworks, irrespective of the cation type. The difference lies in the polaron formation time, which, in CH3NH3PbBr3 (0.3 ps), is less than half of that in CsPbBr3 (0.7 ps). First-principles calculations confirm large polaron formation, identify the Pb-Br-Pb deformation modes as responsible, and explain quantitatively the rate difference between CH3NH3PbBr3 and CsPbBr3. The findings reveal the general advantage of the soft [PbX3]− sublattice in charge carrier protection and suggest that there is likely no mechanistic limitations in using all-inorganic or mixed-cation lead halide perovskites to overcome instability problems and to tune the balance between charge carrier protection and mobility. PMID:28819647

  2. Radiation damage in the alkali halide crystals

    International Nuclear Information System (INIS)

    Diller, K.M.

    1975-10-01

    A general review is given of the experimental data on radiation damage in the alkali halide crystals. A report is presented of an experimental investigation of irradiation produced interstitial dislocation loops in NaCl. These loops are found to exhibit the usual growth and coarsening behaviour during thermal annealing which operates by a glide and self-climb mechanism. It is shown that the recombination of defects in these crystals is a two stage process, and that the loss of interstitials stabilized at the loops is caused by extrinsic vacancies. The theoretical techniques used in simulating point defects in ionic crystals are described. Shell model potentials are derived for all the alkali halide crystals by fitting to bulk crystal data. The fitting is supplemented by calculations of the repulsive second neighbour interactions using methods based on the simple electron gas model. The properties of intrinsic and substitutional impurity defects are calculated. The HADES computer program is used in all the defect calculations. Finally the report returns to the problems of irradiation produced interstitial defects. The properties of H centres are discussed; their structure, formation energies, trapping at impurities and dimerization. The structure, formation energies and mobility of the intermediate and final molecular defects are then discussed. The thermodynamics of interstitial loop formation is considered for all the alklai halide crystals. The nucleation of interstitial loops in NaCl and NaBr is discussed, and the recombination of interstitial and vacancy defects. The models are found to account for all the main features of the experimental data. (author)

  3. The effect of temperature and time on the formation of amylose- lysophosphatidylcholine inclusion complexes

    NARCIS (Netherlands)

    Ahmadi-Abhari, S.; Woortman, A.J.J.; Oudhuis, A.A.C.M.; Hamer, R.J.; Loos, K.

    2014-01-01

    The formation of amylose inclusion complexes could help to decrease the susceptibility of starch granules against amylase digestion. We studied the formation of amyloselysophosphatidylcholine (LPC) inclusion complexes at temperatures at and below the gelatinization temperature of starch, using DSC,

  4. Theoretical approach of complex DNA lesions: from formation to repair

    International Nuclear Information System (INIS)

    Bignon, Emmanuelle

    2017-01-01

    This thesis work is focused on the theoretical modelling of DNA damages, from formation to repair. Several projects have been led in this framework, which can be sorted into three different parts. One on hand, we studied complex DNA reactivity. It included a study about 8-oxo-7,8-dihydro-guanine (8oxoG) mechanisms of formation, a project concerning the UV-induced pyrimidine 6-4 pyrimidone (6-4PP) endogenous photo-sensitizer features, and another one about DNA photo-sensitization by nonsteroidal anti-inflammatory drugs (i.e. ketoprofen and ibuprofen). On the other hand, we investigated mechanical properties of damaged DNA. The structural signature of a DNA lesion is of major importance for their repair, unfortunately only few NMR and X-ray structures of such systems are available. In order to gain insights into their dynamical structure, we investigated a series of complex damages: clustered abasic sites, interstrand cross-links, and the 6-4PP photo-lesion. Likewise, we studied the interaction modes DNA with several polyamines, which are well known to interact with the double helix, but also with the perspective to model DNA-protein cross-linking. The third part concerned the study of DNA interactions with repair enzymes. In line with the structural study about clustered abasic sites, we investigated the dynamics of the same system, but this time interacting with the APE1 endonuclease. We also studied interactions between the Fpg glycosylase with an oligonucleotides containing tandem 8-oxoG on one hand and 8-oxoG - abasic site as multiply damaged sites. Thus, we shed new lights on damaged DNA reactivity, structure and repair, which provides perspectives for biomedicine and life's mechanisms understanding as we begin to describe nucleosomal DNA. (author)

  5. Impact of the organic halide salt on final perovskite composition for photovoltaic applications

    KAUST Repository

    Moore, David T.; Sai, Hiroaki; Wee Tan, Kwan; Estroff, Lara A.; Wiesner, Ulrich

    2014-01-01

    The methylammonium lead halide perovskites have shown significant promise as a low-cost, second generation, photovoltaic material.Despite recent advances, however, there are still a number of fundamental aspects of their formation as well

  6. MECHANISM OF FINANCIAL SAFETY FORMATION OF ENTERPRISES OF AGROINDUSTRIAL COMPLEX

    Directory of Open Access Journals (Sweden)

    Aleksandr Khomenko

    2016-11-01

    answer their aims. As a result, depending on the worked out strategy of financial safety, it is possible to draw basic directions of guaranteeing his financial safety activity of enterprises of agro-industrial complex. Organizational-economic principles of forming of mechanism of financial safety of agricultural enterprises must be built on the basis of realization of its expressly certain strategy. It, in same queue, must go out from present of their production potential. This strategy is the basic internal reference-point of forming of financial safety of agricultural enterprise that sets the parameters of all her development. Practical implications. On financial safety of enterprises of agro-industrial complex testifies the conducted analysis of scientific researches, that without regard to the wide list of existing in economic literature researches on the mechanism of forming of enterprises’ financial safety, among scientific circles until now there is not a general idea. It requires forming of new knowledge’s in relation to forming of mechanism of enterprise financial safety, where not only the certain state of subject but also dynamic constituent of development must come forward as a priority lever, what is considered in this article. Value/originality. Creation of valuable mechanism of forming of financial safety of agro-industrial enterprises foresees formulation of criteria and principles of providing of financial safety of every enterprise, determinations of priority national interests in a financial sphere, realization of the permanent watching of factors, which cause a threat financial safety, and also acceptance of measures in relation to their warning and overcoming. The formed mechanism of financial safety of the agricultural formations is pre-condition of prevention of financial threats and negative financial phenomena in production activity of the agricultural formations, defence of their financial losses, and in future stabilizing of activity of the

  7. The Smart Residential Complex Effect on Personality Formation of Children

    Directory of Open Access Journals (Sweden)

    Seyed Kasra Mirpadyab

    2017-06-01

    Full Text Available The interaction between human beings and the environment has been a question of all times; however, the Industrial Revolution has begun to change its way. It can be seen that the human beings were a part of their environment in the past, but now with the advancement of knowledge and technology, the man can dominate in their environment. But today, the man’s needs should be well known about the interaction with the natural environment and with respect to the position of the residential complexes in the modern society, these buildings are designed to create the psychological comfort and the formation of the personality. The authors of this paper believe the mentioned event will be happening in the future generation of the buildings. These buildings will be equipped with smart automation system for all their activities. This research conducted by grounded theories about the explanation of the smart residential complexes equipped with the BMS, which can be effective for shaping the managerial character of the children in their future.

  8. Spectroscopic Studies on Complex Formation of U(VI)-thiosalicylate

    Energy Technology Data Exchange (ETDEWEB)

    Cha, Wan Sik; Cho, Hye Ryun; Park, Kyoung Kyun; Jung, Euo Chang [Korea Atomic Energy Research Institute, Daejeon (Korea, Republic of)

    2011-05-15

    The dynamic interaction between radionuclides and organic ligands is largely dependent on the composition of functional groups in a ligand chemical structure. Therefore, the structural mimics of natural ligands possessing specific functional groups, such as hydroxy, phenol, carboxyl, thiol and amine groups, have been studied to understand their influence on the migration of radionuclides including actinide species under geological groundwater conditions. In previous studies, we demonstrated that the fraction of hydrolyzed U(VI) species occurring in weak acidic solutions (pH {approx}4.5) is significantly influenced by the presence of salicylate (Sal) ligand due to the simultaneous participation of both phenol and carboxyl groups in the formation of U(VI)-complexes. Thiosalicylic acid (TSalH{sub 2}) is a good model compound for studying the effects of both carboxyl and thiol (-SH) groups. The fraction of di-anionic ligand form (TSal{sup 2-}) is higher at near neutral pH due to the lower pKa ({approx} 8) of the thiol group than the case of salicylic acid (pKa, {approx}13 for salicylic -OH), despite the structural similarity. In addition, the redox capability of the thiol group is expected to influence the reducible radiouclides and the chemical structures of natural ligands by creating cross-linkage (-S-S-) upon oxidation. The goal of the present study is to investigate aqueous U(VI)-TSal complexation equilibrium via laser-based spectroscopic techniques including time resolved laser-induced fluorescence spectroscopy (TRLFS). In this preliminary work, we report the results of spectroscopic studies using conventional UVVis absorbance and fluorescence (FL) measurement methods. The photo-stability of U(VI)-TSal complex or ligand itself upon exposure to a series of laser pulses is estimated by monitoring the change in their absorption bands. Additionally, TSal FL-quenching effect by U(VI) ions is discussed in comparison with that of Sal FL-quenching

  9. Demixing in a metal halide lamp, results from modeling

    NARCIS (Netherlands)

    Beks, M.L.; Hartgers, A.; Mullen, van der J.J.A.M.; Veldhuizen, van E.M.

    2005-01-01

    Metal Halide (MH) lamps are high pressure discharge devices, containing a complex chemical mixture, to emit light on a broad spectrum while maintaining good efficacies. Lamps of this type were first exhibited by General Electric at the 1964 World Fair in New York [1]. They typically consist of an

  10. Making and Breaking of Lead Halide Perovskites

    KAUST Repository

    Manser, Joseph S.; Saidaminov, Makhsud I.; Christians, Jeffrey A.; Bakr, Osman; Kamat, Prashant V.

    2016-01-01

    To date, improvements in perovskite solar cell efficiency have resulted primarily from better control over thin film morphology, manipulation of the stoichiometry and chemistry of lead halide and alkylammonium halide precursors, and the choice

  11. On determination of enthalpies of complex formation reactions by means of temperature coefficient of complexing degree

    International Nuclear Information System (INIS)

    Povar, I.G.

    1995-01-01

    Equations describing the relation between temperature coefficient of ∂lnα/∂T complexing degree and the sum of changes in the enthalpy of complex formation of the composition M m L n δH mn multiplied by the weight coefficients k mm , are presented. A method to determine changes in the enthalpy of certain ΔH mm reactions from ∂lnα/∂T derivatives has been suggested. The best approximating equation from lnα/(T) dependence has been found. Errors of thus determined δH mm values are estimated and the results of calculation experiment for the system In 3+ -F - are provided. 10 refs., 2 figs., 3 tabs

  12. Reversible photo-induced trap formation in mixed-halide hybrid perovskites for photovoltaics† †Electronic supplementary information (ESI) available: Experimental details, PL, PDS spectra and XRD patterns. See DOI: 10.1039/c4sc03141e Click here for additional data file.

    Science.gov (United States)

    Hoke, Eric T.; Slotcavage, Daniel J.; Dohner, Emma R.; Bowring, Andrea R.

    2015-01-01

    We report on reversible, light-induced transformations in (CH3NH3)Pb(BrxI1–x)3. Photoluminescence (PL) spectra of these perovskites develop a new, red-shifted peak at 1.68 eV that grows in intensity under constant, 1-sun illumination in less than a minute. This is accompanied by an increase in sub-bandgap absorption at ∼1.7 eV, indicating the formation of luminescent trap states. Light soaking causes a splitting of X-ray diffraction (XRD) peaks, suggesting segregation into two crystalline phases. Surprisingly, these photo-induced changes are fully reversible; the XRD patterns and the PL and absorption spectra revert to their initial states after the materials are left for a few minutes in the dark. We speculate that photoexcitation may cause halide segregation into iodide-rich minority and bromide-enriched majority domains, the former acting as a recombination center trap. This instability may limit achievable voltages from some mixed-halide perovskite solar cells and could have implications for the photostability of halide perovskites used in optoelectronics. PMID:28706629

  13. Asymmetric synthesis of α-amino acids via homologation of Ni(II) complexes of glycine Schiff bases; Part 1: alkyl halide alkylations.

    Science.gov (United States)

    Sorochinsky, Alexander E; Aceña, José Luis; Moriwaki, Hiroki; Sato, Tatsunori; Soloshonok, Vadim A

    2013-10-01

    Alkylations of chiral or achiral Ni(II) complexes of glycine Schiff bases constitute a landmark in the development of practical methodology for asymmetric synthesis of α-amino acids. Straightforward, easy preparation as well as high reactivity of these Ni(II) complexes render them ready available and inexpensive glycine equivalents for preparing a wide variety of α-amino acids, in particular on a relatively large scale. In the case of Ni(II) complexes containing benzylproline moiety as a chiral auxiliary, their alkylation proceeds with high thermodynamically controlled diastereoselectivity. Similar type of Ni(II) complexes derived from alanine can also be used for alkylation providing convenient access to quaternary, α,α-disubstituted α-amino acids. Achiral type of Ni(II) complexes can be prepared from picolinic acid or via recently developed modular approach using simple secondary or primary amines. These Ni(II) complexes can be easily mono/bis-alkylated under homogeneous or phase-transfer catalysis conditions. Origin of diastereo-/enantioselectivity in the alkylations reactions, aspects of practicality, generality and limitations of this methodology is critically discussed.

  14. Halide-Dependent Electronic Structure of Organolead Perovskite Materials

    KAUST Repository

    Buin, Andrei

    2015-06-23

    © 2015 American Chemical Society. Organometal halide perovskites have recently attracted tremendous attention both at the experimental and theoretical levels. These materials, in particular methylammonium triiodide, are still limited by poor chemical and structural stability under ambient conditions. Today this represents one of the major challenges for polycrystalline perovskite-based photovoltaic technology. In addition to this, the performance of perovskite-based devices is degraded by deep localized states, or traps. To achieve better-performing devices, it is necessary to understand the nature of these states and the mechanisms that lead to their formation. Here we show that the major sources of deep traps in the different halide systems have different origin and character. Halide vacancies are shallow donors in I-based perovskites, whereas they evolve into a major source of traps in Cl-based perovskites. Lead interstitials, which can form lead dimers, are the dominant source of defects in Br-based perovskites, in line with recent experimental data. As a result, the optimal growth conditions are also different for the distinct halide perovskites: growth should be halide-rich for Br and Cl, and halide-poor for I-based perovskites. We discuss stability in relation to the reaction enthalpies of mixtures of bulk precursors with respect to final perovskite product. Methylammonium lead triiodide is characterized by the lowest reaction enthalpy, explaining its low stability. At the opposite end, the highest stability was found for the methylammonium lead trichloride, also consistent with our experimental findings which show no observable structural variations over an extended period of time.

  15. Energetics of the ruthenium-halide bond in olefin metathesis (pre)catalysts

    KAUST Repository

    Falivene, Laura; Poater, Albert; Cazin, Catherine S J; Slugovc, Christian; Cavallo, Luigi

    2013-01-01

    A DFT analysis of the strength of the Ru-halide bond in a series of typical olefin metathesis (pre)catalysts is presented. The calculated Ru-halide bond energies span the rather broad window of 25-43 kcal mol-1. This indicates that in many systems dissociation of the Ru-halide bond is possible and is actually competitive with dissociation of the labile ligand generating the 14e active species. Consequently, formation of cationic Ru species in solution should be considered as a possible event. © 2013 The Royal Society of Chemistry.

  16. Complex formation of calcium with humic acid and polyacrylic acid

    Energy Technology Data Exchange (ETDEWEB)

    Kirishima, A.; Tanaka, K.; Niibori, Y.; Tochiyama, O. [Dept. of Quantum Science and Energy Engineering, Graduate School of Engineering, Tohoku Univ., Sendai (Japan)

    2002-07-01

    In order to understand the migration behavior of radionuclides in the underground, it is also important to estimate the effect of the competing cations originally present in the groundwater. In this connection, the complexation of Ca(II) with Aldrich humic acid has been examined. For the study at trace concentrations ({proportional_to} 10{sup -10} M) of Ca(II), the solvent extraction of {sup 45}Ca with TTA and TOPO in cyclohexane has been used. At macro concentrations (10{sup -4} M) of Ca(II), the measurement of the free Ca{sup 2+} ion concentration with a calcium selective electrode has been conducted. To estimate the polyelectrolyte effect of humic acid separately from its heterogeneous composition effect, polyacrylic acid ([-CH{sub 2}CH(COOH)-]{sub n}) has been selected as a representative of the homogeneous polymeric weak acids and its complexation with Ca(II) has also been examined. The values of log {beta}{sub {alpha}} have been obtained at pH 5 {proportional_to} 7 in 0.1, 0.4 and 1.0 M NaCl, where {beta}{sub {alpha}} is the apparent formation constants defined by {beta}{sub {alpha}} = [ML]/([M][R]). In this definition, [ML] and [M] are the concentrations of bound and free Ca{sup 2+} respectively, [R] is the concentration of dissociated proton exchanging sites. log {beta}{sub {alpha}} of humate decreases from 2.19 {proportional_to} 2.92 (depending on pH and ionic strength 1.0 < I < 0.4) at pCa = 10 to 1.98 {proportional_to} 2.44 at pCa = 4, while the variation of pCa has no appreciable influence on the log {beta}{sub {alpha}} of polyacrylate (1.36 {proportional_to} 3.24 for I = 0.1 {proportional_to} 1.0). For both humate and polyacrylate, log {beta}{sub {alpha}} decreases linearly with log[Na{sup +}], where [Na{sup +}] is the bulk concentration of sodium ion. Their dependences of log {beta}{sub {alpha}} on ionic strength are stronger than those of log {beta} of monomeric carboxylates such as oxalate and EDTA, indicating the large electrostatic effect of

  17. Formation and stabilization of anionic metal complexes in concentrated aqueous quaternary ammonium salt solutions

    International Nuclear Information System (INIS)

    Aronson, F.L.; Hwang, L.L.Y.; Ronca, N.; Solomon, N.A.; Steigman, J.

    1985-01-01

    Anionic complexes of transition metals were stabilized in aqueous solutions containing high concentrations of various short-chain quaternary ammonium salts. Compounds with longer paraffin chains were effective in much less concentrated solution. Complex ions were detected spectrophotometrically. FeCl 4 - , which is usually formed in concentrated HCl, was the predominant Fe(III) complex in 30 m choline chloride containing only 0.12 M HCl. A yellow transitory Tc(VII) chloro-addition intermediate, formed in the reduction of TcO 4 - by concentrated HCl, was stabilized when the solution also contained 25 m choline chloride. Its spectrum, as well as the isolation of an already known Tc(VII) bipyridyl complex, is reported. Concentrated organic electrolytes also stabilized Tc(V) oxide halides against disproportionation and Tc(IV) hexahalides against hydrolysis. Halochromates of Cr(VI) were formed and stabilized in dilute acid containing quaternary ammonium salts. Their UV spectra showed the well-resolved vibronic fine structure associated with the symmetric chromium-to-oxygen charge-transfer band. It is known that these progressions are resolved in aprotic solvents, but not in aqueous acidic solution alone, and that the loss of fine structure in aqueous media is due to hydrogen bonding. The stabilization of anionic metal complexes and the resolution of vibronic structure in halochromates are probably consequences of water-structure-enforced ion paring. The present work suggests that the water molecules in immediate contact with the complex anions are more strongly hydrogen bonded to each other than to the complex. 21 references, 4 figures

  18. Refined global methyl halide budgets with respect to rapeseed (Brassica napus) by life-cycle measurements

    Science.gov (United States)

    Jiao, Y.; Acdan, J.; Xu, R.; Deventer, M. J.; Rhew, R. C.

    2017-12-01

    A precise quantification of global methyl halide budgets is needed to evaluate the ozone depletion potential of these compounds and to predict future changes of stratospheric ozone. However, the global budgets of methyl halides are not balanced between currently identified and quantified sources and sinks. Our study re-evaluated the methyl bromide budget from global cultivated rapeseed (Brassica napus) through life-cycle flux measurements both in the greenhouse and in the field, yielding a methyl bromide emission rate that scales globally to 1.0 - 1.2 Gg yr-1. While this indicates a globally significant source, it is much smaller than the previously widely cited value of 5 - 6 Gg yr-1(Mead et al., 2008), even taking into account the near tripling of annual global yield of rapeseed since the previous evaluation was conducted. Our study also evaluated the methyl chloride and methyl iodide emission levels from rapeseed, yielding emission rates that scale to 5.4 Gg yr-1 for methyl chloride and 1.8 Gg yr-1 of methyl iodide. The concentrations of the methyl donor SAM (S-adenosyl methionine) and the resultant product SAH (S-Adenosyl-L-homocysteine) were also analyzed to explore their role in biogenic methyl halide formation. Halide gradient incubations showed that the magnitude of methyl halide emissions from rapeseed is highly correlated to soil halide levels, thus raising the concern that the heterogeneity of soil halide contents geographically should be considered when extrapolating to global budget.

  19. Starch-lipid inclusion complexes for aerogel formation

    Science.gov (United States)

    Recently we reported that aqueous slurries of starch can be excess steam jet-cooked and blended with aqueous solutions of fatty acid salts to produce inclusion complexes between amylose and the fatty acid salt. These complexes can be simply prepared on large scale using commercially available steam ...

  20. Miscellaneous Lasing Actions in Organo-Lead Halide Perovskite Films.

    Science.gov (United States)

    Duan, Zonghui; Wang, Shuai; Yi, Ningbo; Gu, Zhiyuan; Gao, Yisheng; Song, Qinghai; Xiao, Shumin

    2017-06-21

    Lasing actions in organo-lead halide perovskite films have been heavily studied in the past few years. However, due to the disordered nature of synthesized perovskite films, the lasing actions are usually understood as random lasers that are formed by multiple scattering. Herein, we demonstrate the miscellaneous lasing actions in organo-lead halide perovskite films. In addition to the random lasers, we show that a single or a few perovskite microparticles can generate laser emissions with their internal resonances instead of multiple scattering among them. We experimentally observed and numerically confirmed whispering gallery (WG)-like microlasers in polygon shaped and other deformed microparticles. Meanwhile, owing to the nature of total internal reflection and the novel shape of the nanoparticle, the size of the perovskite WG laser can be significantly decreased to a few hundred nanometers. Thus, wavelength-scale lead halide perovskite lasers were realized for the first time. All of these laser behaviors are complementary to typical random lasers in perovskite film and will help the understanding of lasing actions in complex lead halide perovskite systems.

  1. Development of Halide and Oxy-Halides for Isotopic Separations

    Energy Technology Data Exchange (ETDEWEB)

    Martin, Leigh R. [Idaho National Lab. (INL), Idaho Falls, ID (United States); Johnson, Aaron T. [Idaho National Lab. (INL), Idaho Falls, ID (United States); Pfeiffer, Jana [Idaho National Lab. (INL), Idaho Falls, ID (United States); Finck, Martha R. [Idaho National Lab. (INL), Idaho Falls, ID (United States)

    2014-10-01

    The goal of this project was to synthesize a volatile form of Np for introduction into mass spectrometers at INL. Volatile solids of the 5f elements are typically those of the halides (e.g. UF6), however fluorine is highly corrosive to the sensitive internal components of the mass separator, and the other volatile halides exist as several different stable isotopes in nature. However, iodide is both mono-isotopic and volatile, and as such presents an avenue for creation of a form of Np suitable for introduction into the mass separator. To accomplish this goal, the technical work in the project sought to establish a novel synthetic route for the conversion NpO2+ (dissolved in nitric acid) to NpI3 and NpI4.

  2. The effect of temperature and time on the formation of amylose- lysophosphatidylcholine inclusion complexes

    NARCIS (Netherlands)

    Ahmadiabhari, Salomeh; Woortman, Albert J. J.; Oudhuis, A. A. C. M. (Lizette); Hamer, Rob J.; Loos, Katja

    The formation of amylose inclusion complexes could help to decrease the susceptibility of starch granules against amylase digestion. We studied the formation of amylose-lysophosphatidylcholine (LPC) inclusion complexes at temperatures at and below the gelatinization temperature of starch, using DSC,

  3. The effect of temperature and time on the formation of amylose–lysophosphatidylcholine inclusion complexes

    NARCIS (Netherlands)

    Ahmadi-Abhari, S.; Woortman, A.J.J.; Oudhuis, A.A.C.M.; Hamer, R.J.; Loos, K.

    2014-01-01

    The formation of amylose inclusion complexes could help to decrease the susceptibility of starch granules against amylase digestion. We studied the formation of amylose–lysophosphatidylcholine (LPC) inclusion complexes at temperatures at and below the gelatinization temperature of starch, using DSC,

  4. Electrolytic formation of technetium complexes with π-acceptor ligands

    International Nuclear Information System (INIS)

    Cerda, F.; Kremer, C.; Gambino, D.; Kremer, E.

    1994-01-01

    Electrolytic reduction of pertechnetate was performed in aqueous solution containing π-acceptor ligands. Cyanide and 1,10-phenanthroline were the selected ligands. In both cases, electrolyses produced a cathodic TcO 2 deposit and soluble Tc complexes. When cyanide was the ligand, the complexes formed were [Tc(CN) 6 ] 5- and [TcO 2 (CN) 4 ] 3- . When working with the amine, [Tc(phen) 3 ] 2+ and another positively charged species were found after reaction. Results are compared with previous studies with amines, and the usefulness of the electrolytic route to obtain Tc complexes is evaluated. (author) 11 refs.; 2 figs.; 1 tab

  5. Studies on cluster, salt and molecular complex of zinc-quinolinate

    Indian Academy of Sciences (India)

    Reactions of zinc halides with 8-hydroxyquinoline (hydroxQ) in equimolar ratio were carried out in different solvents. ... determination of surface area. We prepared a ..... resulted in the formation of de-solvated complex, which on standing at ...

  6. Coexistence facilitates interspecific biofilm formation in complex microbial communities

    DEFF Research Database (Denmark)

    Madsen, Jonas Stenløkke; Røder, Henriette Lyng; Russel, Jakob

    2016-01-01

    Social interactions in which bacteria respond to one another by modifying their phenotype are central determinants of microbial communities. It is known that interspecific interactions influence the biofilm phenotype of bacteria; a phenotype that is central to the fitness of bacteria. However......, the underlying role of fundamental ecological factors, specifically coexistence and phylogenetic history, in biofilm formation remains unclear. This study examines how social interactions affect biofilm formation in multi-species co-cultures from five diverse environments. We found prevalence of increased...

  7. Influence of the Hydrophobicity of Polyelectrolytes on Polyelectrolyte Complex Formation and Complex Particle Structure and Shape

    Directory of Open Access Journals (Sweden)

    Gudrun Petzold

    2011-08-01

    Full Text Available Polyelectrolyte complexes (PECs were prepared by structural uniform and strongly charged cationic and anionic modified alternating maleic anhydride copolymers. The hydrophobicity of the polyelectrolytes was changed by the comonomers (ethylene, isobutylene and styrene. Additionally, the n−/n+ ratio of the molar charges of the polyelectrolytes and the procedure of formation were varied. The colloidal stability of the systems and the size, shape, and structure of the PEC particles were investigated by turbidimetry, dynamic light scattering (DLS and atomic force microscopy (AFM. Dynamic light scattering indicates that beside large PEC particle aggregates distinct smaller particles were formed by the copolymers which have the highest hydrophobicity (styrene. These findings could be proved by AFM. Fractal dimension (D, root mean square (RMS roughness and the surface profiles of the PEC particles adsorbed on mica allow the following conclusions: the higher the hydrophobicity of the polyelectrolytes, the broader is the particle size distribution and the minor is the swelling of the PEC particles. Hence, the most compact particles are formed with the very hydrophobic copolymer.

  8. TRANSURANIC METAL HALIDES AND A PROCESS FOR THE PRODUCTION THEREOF

    Science.gov (United States)

    Fried, S.

    1951-03-20

    Halides of transuranic elements are prepared by contacting with aluminum and a halogen, or with an aluminum halide, a transuranic metal oxide, oxyhalide, halide, or mixture thereof at an elevated temperature.

  9. Inner-sphere and outer-sphere complexes of yttrium(III), lanthanum (III), neodymium(III), terbium(III) and thulium(III) with halide ions in N,N-dimethylformamide

    International Nuclear Information System (INIS)

    Takahashi, Ryouta; Ishiguro, Shin-ichi

    1991-01-01

    The formation of chloro, bromo and iodo complexes of yttrium(III), and bromo and iodo complexes of lanthanum(III), neodymium(III), terbium(III) and thulium(III) has been studied by precise titration calorimetry in N,N-dimethylformamide (DMF) at 25 o C. The formation of [YCl] 2+ , [YCl 2 ] + , [YCl 3 ] and [YCl 4 ] - , and [MBr] 2+ and [MBr 2 ] + (M = Y, La, Nd, Tb, Tm) was revealed, and their formation constants, enthalpies and entropies were determined. It is found that the formation enthalpies change in the sequence ΔH o (Cl) > ΔH o (l), which is unusual for hard metal (III) ions. This implies that, unlike the chloride ion, the bromide ion forms outer-sphere complexes with the lanthanide(III) and yttrium(III) ions in DMF. Evidence for either an inner- or outer-sphere complex was obtained from 89 Y NMR spectra for Y(ClO 4 ) 3 , YCl 3 and YBr 3 DMF solutions at room temperature. (author)

  10. Quality Enhancement by Inclusion Complex Formation of Simvastatin Tablets

    Directory of Open Access Journals (Sweden)

    Emőke Rédai

    2013-08-01

    Full Text Available Introduction: Simvastatin is an inhibitor of hydroxy-methyl-glutaryl-coenzyme A reductase, used in the treatment of hypercholesterolemia. To enhance its bioavailability by inclusion complexation, as host molecule randommethyl-β-cyclodextrin had been used. After evaluating the complexes we chose the kneading product in 1:2 molar ratio for incorporation of 10 mg simvastatin tablets. Materials and methods: We prepared homogenous mixtures of the inclusion complex and some excipients. The tablets were prepared by direct compression. The tablets were evaluated in regard to: weight uniformity, thickness, diameter, hardness, friability, disintegration and dissolution profile. Results: Weights are in the range of 196-208 mg, diameter 6.83-6.86 mm, height 3.86-4.01 mm, hardness 78.3-113.1 N, friability 0.75- 1.19 %, disintegration above 15 minutes. The dissolved amounts of simvastatin from the tablets are higher compared to the dissolution of pure simvastatin, but lower than the dissolution of the complex itself. Excipients, like disintegrants and lubricants greatly influence the dissolution properties of the tablets. Conclusions: According to our results, tablets containing inclusion complex of simvastatin exhibit better solubility, according to the dissolved amount of simvastatin, than pure drug alone. Proper physical parameters of the tablets are obtained by application of 5 % Primellose

  11. Structure of the mercury(II mixed-halide (Br/Cl complex of 2,2′-(5-tert-butyl-1,3-phenylenebis(1-pentyl-1H-benzo[d]imidazole

    Directory of Open Access Journals (Sweden)

    Varsha Rani

    2017-03-01

    Full Text Available The mercury(II complex of 2,2′-(5-tert-butyl-1,3-phenylenebis(1-pentyl-1H-benzimidazole, namely catena-poly[[dihalogenidomercury(II]-μ-2,2′-(5-tert-butyl-1,3-phenylenebis(1-pentyl-1H-benzimidazole-κ2N3:N3′], [HgBr1.52Cl0.48(C34H42N4], 2, has a polymeric structure bridging via the N atoms from the benzimidazole moieties of the ligand. The compound crystallizes in the orthorhombic space group Pca21 and is a racemic twin [BASF = 0.402 (9]. The geometry around the HgII atom is distorted tetrahedral, with the HgII atom coordinated to two N atoms, one Br atom, and a fourth coordination site is occupied by a mixed halide (Br/Cl. For the two ligands in the asymmetric unit, there is disorder with one of the two tert-butyl groups and benzimidazole moieties showing twofold disorder, with occupancy factors of 0.57 (2:0.43 (2 for the tert-butyl group and 0.73 (3:0.27 (3 for the benzimidazole group. In addition, there is threefold disorder for two of the four n-pentyl groups, with occupancy factors of 0.669 (4:0.177 (4:0.154 (4 and 0.662 (4:0.224 (4:0.154 (4, respectively. The molecules form a one-dimensional helical polymer propagating in the b-axis direction. The helices are held together by intra-strand C—H...Br and C—H...Cl interactions. Each strand is further linked by inter-strand C—H...Br and C—H...Cl interactions. In addition, there are weak C—H...N inter-strand interactions which further stabilize the structural arrangement.

  12. Formation of a Tc(III)-adenosine diphosphate complex

    International Nuclear Information System (INIS)

    Torres, J.; Kremer, C.; Kremer, E.

    1995-01-01

    A 99 Tc-ADP complex was prepared when KTcO 4 was reduced in aqueous medium by SnCl 2 , Na 2 S 2 O 4 , NaBH 4 or Zn in the presence of ADP in excess. The resulting solution was studied by chromatography and spectrophotometry. Electrochemical reduction and substitution on [Tc III (tu) 6 ] 3+ were investigated as alternative synthetic routes. The anionic Tc-ADP complex was isolated as a solid. Cerimetric titrations confirmed the oxidation state +3 for the central atom. IR and 1 H-NMR data showed that the purine base is bonded to the Tc central atom but not the ribose moiety. No oxo groups seemed to be directly bonded to the Tc atom. The complex is rather stable in neutral solutions. However, it decomposes to pertechnetate and TcO 2 at extreme pH values. (author). 16 refs., 2 figs., 3 tabs

  13. Crystal structures of complexes of NAD+-dependent formate dehydrogenase from methylotrophic bacterium Pseudomonas sp. 101 with formate

    International Nuclear Information System (INIS)

    Filippova, E. V.; Polyakov, K. M.; Tikhonova, T. V.; Stekhanova, T. N.; Boiko, K. M.; Sadykhov, I. G.; Tishkov, V. I.; Popov, V. O.; Labru, N.

    2006-01-01

    Formate dehydrogenase (FDH) from the methylotrophic bacterium Pseudomonas sp. 101 catalyzes oxidation of formate to NI 2 with the coupled reduction of nicotinamide adenine dinucleotide (NAD + ). The three-dimensional structures of the apo form (the free enzyme) and the holo form (the ternary FDH-NAD + -azide complex) of FDH have been established earlier. In the present study, the structures of FDH complexes with formate are solved at 2.19 and 2.28 A resolution by the molecular replacement method and refined to the R factors of 22.3 and 20.5%, respectively. Both crystal structures contain four protein molecules per asymmetric unit. These molecules form two dimers identical to the dimer of the apo form of FDH. Two possible formatebinding sites are found in the active site of the FDH structure. In the complexes the sulfur atom of residue Cys354 exists in the oxidized state

  14. Dynamics of Research Team Formation in Complex Networks

    Science.gov (United States)

    Sun, Caihong; Wan, Yuzi; Chen, Yu

    Most organizations encourage the formation of teams to accomplish complicated tasks, and vice verse, effective teams could bring lots benefits and profits for organizations. Network structure plays an important role in forming teams. In this paper, we specifically study the dynamics of team formation in large research communities in which knowledge of individuals plays an important role on team performance and individual utility. An agent-based model is proposed, in which heterogeneous agents from research communities are described and empirically tested. Each agent has a knowledge endowment and a preference for both income and leisure. Agents provide a variable input (‘effort’) and their knowledge endowments to production. They could learn from others in their team and those who are not in their team but have private connections in community to adjust their own knowledge endowment. They are allowed to join other teams or work alone when it is welfare maximizing to do so. Various simulation experiments are conducted to examine the impacts of network topology, knowledge diffusion among community network, and team output sharing mechanisms on the dynamics of team formation.

  15. INVESTIGATION OF FORMATION CONSTANT OF COMPLEX OF A ...

    African Journals Online (AJOL)

    Preferred Customer

    Theory. For the first time Abdollahi used RAFA for determination of complex ... measure of the lack of fit of a principal component model to a data set. ..... Cantor, C.R.; Schimmel, P.R. Biophysical Chemistry, Freeman, W.H. Company: San.

  16. The Formation of the Self. Nietzsche and Complexity | Cilliers ...

    African Journals Online (AJOL)

    Our inquiry takes place from two perspectives: the first derived from the Nietzschean analysis of how one becomes what one is; the other from current developments in complexity theory. This two-angled approach opens up different, yet related dimensions of a non-essentialist understanding of the self that is none the less ...

  17. Complex Formation Between Iron(III) and Isonicotinohydroxamic ...

    African Journals Online (AJOL)

    acer

    as a consequence of their biological importance which is related ... complexes with a series of metal ions via co- ordination ... water was added with stirring to a solution of ... Evaluation of the antimicrobial activity ... All are regarded as pathogenic to ... each agar dish and fresh bacteria suspension was .... Copper(II) Mixed.

  18. Complex formation between glutamic acid and molybdenum (VI)

    International Nuclear Information System (INIS)

    Gharib, Farrokh; Khorrami, S.A.; Sharifi, Sasan

    1997-01-01

    Equilibria of the reaction of molybdenum (VI) with L-glutamic acid have been studied in aqueous solution in the pH range 2.5 to 9.5, using spectrophotometric and optical rotation methods at constant ionic strength (0.15 mol dm -3 sodium perchlorate) and temperature 25 ± 0.1 degC. Our studies have shown that glutamic acid forms a mononuclear complex with Mo(VI) of the type MoO 3 L 2- at pH 5.5. The stability constant of this complexation and the dissociation constants of L-glutamic acid have been determined. (author). 17 refs., 2 figs., 4 tabs

  19. Tube formation by complex cellular processes in Ciona intestinalis notochord.

    Science.gov (United States)

    Dong, Bo; Horie, Takeo; Denker, Elsa; Kusakabe, Takehiro; Tsuda, Motoyuki; Smith, William C; Jiang, Di

    2009-06-15

    In the course of embryogenesis multicellular structures and organs are assembled from constituent cells. One structural component common to many organs is the tube, which consists most simply of a luminal space surrounded by a single layer of epithelial cells. The notochord of ascidian Ciona forms a tube consisting of only 40 cells, and serves as a hydrostatic "skeleton" essential for swimming. While the early processes of convergent extension in ascidian notochord development have been extensively studied, the later phases of development, which include lumen formation, have not been well characterized. Here we used molecular markers and confocal imaging to describe tubulogenesis in the developing Ciona notochord. We found that during tubulogenesis each notochord cell established de novo apical domains, and underwent a mesenchymal-epithelial transition to become an unusual epithelial cell with two opposing apical domains. Concomitantly, extracellular luminal matrix was produced and deposited between notochord cells. Subsequently, each notochord cell simultaneously executed two types of crawling movements bi-directionally along the anterior/posterior axis on the inner surface of notochordal sheath. Lamellipodia-like protrusions resulted in cell lengthening along the anterior/posterior axis, while the retraction of trailing edges of the same cell led to the merging of the two apical domains. As a result, the notochord cells acquired endothelial-like shape and formed the wall of the central lumen. Inhibition of actin polymerization prevented the cell movement and tube formation. Ciona notochord tube formation utilized an assortment of common and fundamental cellular processes including cell shape change, apical membrane biogenesis, cell/cell adhesion remodeling, dynamic cell crawling, and lumen matrix secretion.

  20. Reactivity of paraquat with sodium salicylate: Formation of stable complexes

    International Nuclear Information System (INIS)

    Dinis-Oliveira, Ricardo Jorge; Guedes de Pinho, Paula; Ferreira, Antonio Cesar Silva; Silva, Artur M.S.; Afonso, Carlos; Bastos, Maria de Lourdes; Remiao, Fernando; Duarte, Jose Alberto; Carvalho, Felix

    2008-01-01

    Sodium salicylate (NaSAL) has been shown to be a promising antidote for the treatment of paraquat (PQ) poisonings. The modulation of the pro-oxidant and pro-inflammatory pathways, as well as the anti-thrombogenic properties of NaSAL are probably essential features for the healing effects provided by this drug. Nevertheless, a possible direct chemical reactivity between PQ and NaSAL is also a putative pathway to be considered, this hypothesis being the ground of the present study. In accordance, it is shown, for the first time that PQ and NaSAL react immediately in aqueous medium and within 2-3 min in the solid state. Photographs and scanning electron photomicrographs indicated that a new chemical entity is formed when both compounds are mixed. This assumption was corroborated by the evaluation of the melting point, and through several analytical techniques, namely ultraviolet/visible spectroscopy, nuclear magnetic resonance spectroscopy, gas chromatography/mass spectrometry/mass spectrometry (GC/MS/MS), liquid chromatography/electrospray ionization/mass spectrometry/mass spectrometry (LC/ESI/MS/MS) and infrared spectroscopy, which revealed that stable charge-transfer complexes are formed when PQ is mixed with NaSAL. LC/ESI/MS/MS allowed obtaining the stoichiometry of the charge-transfer complexes. In order to increase resolution, single value decomposition, acting as a filter, showed that the charge-transfer complexes with m/z 483, 643 and 803 correspond to the pseudo-molecular ions, respectively 1:2, 1:3 and 1:4 (PQ:NaSAL). In conclusion, these results provided a new and important mechanism of action of NaSAL against the toxicity mediated by PQ

  1. Social power and opinion formation in complex networks

    Science.gov (United States)

    Jalili, Mahdi

    2013-02-01

    In this paper we investigate the effects of social power on the evolution of opinions in model networks as well as in a number of real social networks. A continuous opinion formation model is considered and the analysis is performed through numerical simulation. Social power is given to a proportion of agents selected either randomly or based on their degrees. As artificial network structures, we consider scale-free networks constructed through preferential attachment and Watts-Strogatz networks. Numerical simulations show that scale-free networks with degree-based social power on the hub nodes have an optimal case where the largest number of the nodes reaches a consensus. However, given power to a random selection of nodes could not improve consensus properties. Introducing social power in Watts-Strogatz networks could not significantly change the consensus profile.

  2. Hybrid lead halide perovskites for light energy conversion: Excited state properties and photovoltaic applications

    Science.gov (United States)

    Manser, Joseph S.

    The burgeoning class of metal halide perovskites constitutes a paradigm shift in the study and application of solution-processed semiconductors. Advancements in thin film processing and our understanding of the underlying structural, photophysical, and electronic properties of these materials over the past five years have led to development of perovskite solar cells with power conversion efficiencies that rival much more mature first and second-generation commercial technologies. It seems only a matter of time before the real-world impact of these compounds is put to the test. Like oxide perovskites, metal halide perovskites have ABX3 stoichiometry, where typically A is a monovalent cation, B a bivalent post-transition metal, and X a halide anion. Characterizing the behavior of photogenerated charges in metal halide perovskites is integral for understanding the operating principles and fundamental limitations of perovskite optoelectronics. The majority of studies outlined in this dissertation involve fundamental study of the prototypical organic-inorganic compound methylammonium lead iodide (CH3NH3PbI 3). Time-resolved pump-probe spectroscopy serves as a principle tool in these investigations. Excitation of a semiconductor can lead to formation of a number different excited state species and electronic complexes. Through analysis of excited state decay kinetics and optical nonlinearities in perovskite thin films, we identify spontaneous formation of a large fraction of free electrons and holes, whose presence is requisite for efficient photovoltaic operation. Following photogeneration of charge carriers in a semiconductor absorber, these species must travel large distances across the thickness of the material to realize large external quantum efficiencies and efficient carrier extraction. Using a powerful technique known as transient absorption microscopy, we directly image long-range carrier diffusion in a CH3NH3PbI 3 thin film. Charges are unambiguously shown to

  3. Complex formation of transferrin with tetravalent plutonium and cerium

    International Nuclear Information System (INIS)

    Subramanian, M.S.; Oomen, I.K.

    1981-01-01

    Gel filtration experiments with 239 Pu labelled In Vitro bovine serum showed that the metal ion is bound to the transferrin of the serum proteins as in the case of iron labelled serum. This was confirmed by polyacrylamide gel electrophoresis. The ovotransferrin prepared from chicken egg white which was devoid of hemopexin contaminant was found to complex both tetravalent plutonium and cerium giving visible absorption peak at 365 and 435 nm respectively. The binding capacity of ovotransferrin with tetravalent plutonium and cerium, determined by spectrophotometric titration indicates that two metal ions are bound to each protein molecule as in the case of iron. The average molecular weight computed from this binding capacity measurements was found to be 71,000-75,000. The number of protons liberated for each metal ion bound was found to be three as in the case of iron. (author)

  4. Investigation of complex formation processes of hydroxypropylmethylcellulose and polymethacrylic acid in aqueous solutions

    Directory of Open Access Journals (Sweden)

    M. Katayeva

    2012-12-01

    Full Text Available The complex formation process of hydroxypropylcellulose (HPC with polymethacrylic acid (PMA have been studied using methods of turbidimetric and viscosimetric titration. Position of maximum depending on polymer concentration and molecular mass of polysaccharide have different values.

  5. Investigation of complex formation processes of hydroxypropylmethylcellulose and polymethacrylic acid in aqueous solutions

    OpenAIRE

    M. Katayeva; R. Mangazbayeva; R. Abdykalykova

    2012-01-01

    The complex formation process of hydroxypropylcellulose (HPC) with polymethacrylic acid (PMA) have been studied using methods of turbidimetric and viscosimetric titration. Position of maximum depending on polymer concentration and molecular mass of polysaccharide have different values.

  6. Heterofacial alkylation of alkylenediamines by higher alkyl halides

    International Nuclear Information System (INIS)

    Semenov, V.A.; Kryshko, G.M.; Sokal'skaya, L.I.; Zhukova, N.G.

    1985-01-01

    A study of the physiochemical properties of alkylenediamines substituted by lower alkyls, showed that they possess increased complex-forming ability with respect to salts of different metals as titanium, niobium, zirconium, molybdenum, and zinc. To create a simpler method of synthesis of higher tetraaklyalkylalklyenediamines, based on the use of the accessible domestic raw material, the authors investigated the reaction of alkylenediamines with various alkyl halides. It was established that the best reagents can be obtained using alkyl bromides. It is concluded that the procedure of alkylation of alkylenediamines by higher alkyl halides in the presence of water developed permits the production of terraalkylalkylenediamines in one step with good yield and with purity acceptable for use as extraction reagents

  7. OTDM-to-WDM Conversion of Complex Modulation Formats by Time-Domain Optical Fourier Transformation

    DEFF Research Database (Denmark)

    Palushani, Evarist; Richter, T.; Ludwig, R.

    2012-01-01

    We demonstrate the utilization of the optical Fourier transform technique for serial-to-parallel conversion of 64×10-GBd OTDM data tributaries with complex modulation formats into 50-GHz DWDM grid without loss of phase and amplitude information.......We demonstrate the utilization of the optical Fourier transform technique for serial-to-parallel conversion of 64×10-GBd OTDM data tributaries with complex modulation formats into 50-GHz DWDM grid without loss of phase and amplitude information....

  8. Complex formation between uranium(VI) and α-D-glucose 1-phosphate

    International Nuclear Information System (INIS)

    Koban, A.; Geipel, G.; Bernhard, G.

    2003-01-01

    The complex formation of uranium(VI) with α-D-glucose 1-phosphate (C 6 H 11 O 6 PO 3 2- , G1P) was determined by time-resolved laser-induced fluorescence spectroscopy (TRLFS) at pH 4 and potentiometric titration in the pH range from 3 to 10. Both measurements show the formation of a 1 : 1 complex at lower pH values. The formation constant of UO 2 (C 6 H 11 O 6 PO 3 ) was calculated from TRLFS measurements to be log β 11 = 5.72±0.12, and from potentiometric titration log β 11 = 5.40±0.25, respectively. It was found by potentiometric titration that at higher pH values the complexation changes to a 1 : 2 complex. The stability constant for this complex was calculated to be log β 12 = 8.96±0.18. (orig.)

  9. Determination of stability constants of lanthanide nitrate complex formation using a solvent extraction technique

    International Nuclear Information System (INIS)

    Andersson, S.; Ekberg, C.; Liljenzin, J.O.; Nilsson, M.; Skarnemark, G.; Eberhardt, K.

    2006-01-01

    For lanthanides and actinides, nitrate complex formation is an important factor with respect to the reprocessing of nuclear fuels and in studies that treat partitioning and transmutation/conditioning. Different techniques, including microcalorimetry, various kinds of spectroscopy, ion-exchange and solvent extraction, can be used to determine stability constants of nitrate complex formation. However, it is uncommon that all lanthanides are studied at the same time, using the same experimental conditions and technique. The strengths of the complexes are different for lanthanides and actinides, a feature that may assist in the separation of the two groups. This paper deals with nitrate complex formation of lanthanides using a solvent extraction technique. Trace amounts of radioactive isotopes of lanthanides were produced at the TRIGA Mainz research reactor and at the Institutt for Energiteknikk in Kjeller, Norway (JEEP II reactor). The extraction of lanthanide ions into an organic phase consisting of 2, 6-bis-(benzoxazolyl)-4-dodecyloxylpyridine, 2-bromodecanoic acid and tert-butyl benzene as a function of nitrate ion concentration in the aqueous phase was studied in order to estimate the stability constants of nitrate complex formation. When the nitrate ion concentration is increased in the aqueous phase, the nitrate complex formation starts to compete with the extraction of metal ions. Thus the stability constants of nitrate complex formation can be estimated by measuring the decrease in extraction and successive fitting of an appropriate model. Extraction curves for La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Dy, Ho and Er were obtained and stability constants for their nitrate complex formation were estimated. Tb, Tm, Yb and Lu were also investigated, but no stability constants could be determined. The distribution ratios for the metal ions at low nitrate ion concentration were obtained at the same time, showing the effect of lanthanide contraction resulting in decreasing

  10. Structural characterization of Am(III) formate complexes. Combining EXAFS spectroscopy with DFT and thermodynamical calculations

    Energy Technology Data Exchange (ETDEWEB)

    Rossberg, Andre [Helmholtz-Zentrum Dresden-Rossendorf e.V., Dresden (Germany). Molecular Structures; Froehlich, D.R. [Heidelberg Univ. (Germany). Physikalisch-Chemisches Inst.

    2017-06-01

    We used iterative transformation factor analysis (ITFA) in order to isolate the EXAFS spectral contributions of the complexing ligand from a Am(III)/formate pH-series. Thermodynamic calculations were used as constraint for ITFA and for density functional theory (DFT) calculations to identify the coordination mode within the formed complexes.

  11. Trans-complex formation by proteolipid channels in the terminal phase of membrane fusion

    DEFF Research Database (Denmark)

    Peters, C; Bayer, M J; Bühler, S

    2001-01-01

    -complex formation occurs downstream from trans-SNARE pairing, and depends on both the Rab-GTPase Ypt7 and calmodulin. The maintenance of existing complexes and completion of fusion are independent of trans-SNARE pairs. Reconstituted proteolipids form sealed channels, which can expand to form aqueous pores in a Ca2...

  12. Complex formation of technetium with the methyl esters of MAG2 and MAG1

    International Nuclear Information System (INIS)

    Noll, B.; Noll, S.; Grosse, B.; Johannsen, B.; Spies, H.

    1993-01-01

    Mercaptoacetylglycine methyl ester (MAG 2 ester) and mercaptoacetyldiglycine methyl ester (MAG 1 ester) were included to investigate complex formation of SH/amide ligands with technetium. The studies are aimed at finding out how blocking the carboxylic groups influences the complexation reaction, with a view to finding an approach to new lipophilic species. (orig./BBR)

  13. FORMATION AND ELECTROCHEMICAL BEHAVIOUR OF POLYION COMPLEXES FOR ELECTROCHROMIC DISPLAY MATERIAL

    Institute of Scientific and Technical Information of China (English)

    WAN Guoxiang; WANG Bing; DENG Zhenghua; LUO Chunqiao

    1988-01-01

    Formation of intermacromolecular complexes containing viologen and electron-transfer reaction occurred on the electrode modified by the complex films were studied. Compositions and morphology of the complexes depend on the properties of polyanion and chemical environment of complexation. The analytical results of cyclic voltammetry (CV) and rotating disk voltammetry(RDV) indicated: (1) active sites of viologen in network of complexes transferred single electron reversibly; (2) the redox peak currents showed excellent symmetry and stability; (3) redox potentials were related to properties of polyanions, varying from -0.4 to -0.6V (vs. SCE). Electrochromic materials with different displaying colors could be obtained by changing the structure of polyviologen.

  14. Complex formation between menadione and cetylethylmorpholinium ethosulfate: effect on uv photodegradation of menadione

    International Nuclear Information System (INIS)

    Kowarski, C.R.; Ghandi, H.I.

    1975-01-01

    The process of menadione photodegradation can be enhanced or diminished by other compounds. The presence of the quaternary ammonium compound cetylethylmorpholinium ethosulfate (I) in solutions of menadione was found to slow the rate of photodegradation by uv light (253.7 nm). The mechanism of this effect may be due to complex formation between menadione and I. Complex formation was demonstrated by a shift in the absorption peaks of menadione from 245 and 260 nm to 251.5 and 261.5 nm, respectively. The equilibrium constant of this complex was calculated to be 1.647 M

  15. Study of the formation of soluble complexes of sodium caseinate and xanthan in solution.

    Science.gov (United States)

    Bouhannache, Bouchra; HadjSadok, Abdelkader; Touabet, Abdelkrim

    2017-09-01

    The main objective of this work was to determinate the optimum conditions for the formation of soluble complexes between sodium caseinate and xanthan in solution at neutral pH, in the presence of the NaCl. The study of the influence of the concentrations of these three substances showed that salt was the most influent factor. It worsens the thermodynamic incompatibility of the two biopolymers in solution, when they are present at large amounts. However, it contributes to soluble complexes formation, when sodium caseinate concentration is below 5.5%. In this case, gels with enhanced rheological properties were obtained. Infrared spectroscopy confirmed that the complexes formation within these gels involves hydrophobic interactions. On the other hand, dynamic light scattering revealed that dilution cause their dissociation. These soluble complexes are promising ingredients to ensure new texturing properties.

  16. Palladium(II-catalyzed Heck reaction of aryl halides and arylboronic acids with olefins under mild conditions

    Directory of Open Access Journals (Sweden)

    Tanveer Mahamadali Shaikh

    2013-08-01

    Full Text Available A series of general and selective Pd(II-catalyzed Heck reactions were investigated under mild reaction conditions. The first protocol has been developed employing an imidazole-based secondary phosphine oxide (SPO ligated palladium complex (6 as a precatalyst. The catalytic coupling of aryl halides and olefins led to the formation of the corresponding coupled products in excellent yields. A variety of substrates, both electron-rich and electron-poor olefins, were converted smoothly to the targeted products in high yields. Compared with the existing approaches employing SPO–Pd complexes in a Heck reaction, the current strategy features mild reaction conditions and broad substrate scope. Furthermore, we described the coupling of arylboronic acids with olefins, which were catalyzed by Pd(OAc2 and employed N-bromosuccinimide as an additive under ambient conditions. The resulted biaryls have been obtained in moderate to good yields.

  17. Structure of polyvalent metal halide melts

    International Nuclear Information System (INIS)

    Tosi, M.P.

    1990-12-01

    A short review is given of recent progress in determining and understanding the structure of molten halide salts involving polyvalent metal ions. It covers the following three main topics: (i) melting mechanisms and types of liquid structure for pure polyvalent-metal chlorides; (ii) geometry and stability of local coordination for polyvalent metal ions in molten mixtures of their halides with alkali halides; and (iii) structure breaking and electron localization on addition of metal to the melt. (author). 28 refs, 3 figs, 1 tab

  18. Structure and energetics of trivalent metal halides

    International Nuclear Information System (INIS)

    Hutchinson, F.

    1999-01-01

    Metal trihalide (MX 3 ) systems represent a stern challenge in terms of constructing transferable potential models. Starting from a previously published set of potentials, 'extended' ionic models are developed which, at the outset, include only anion polarization. Deficiencies in these models, particularly for smaller (highly polarizing) cations, axe shown to be significant. For example, crystal structures different to those observed experimentally axe adopted. The potentials axe improved upon by reference to ab initio information available for alkali halides with the 'constraint' that the parameters transfer systematically in a physically transparent manner, for example, in terms of ion radii. The possible influence of anion compression ('breathing') and the relative abundance of anion-anion interactions are considered. Simulation techniques axe developed to allow for the effective simulation of any system symmetry and for the study of transitions between different crystals (constant stress). The developed models are fully tested for a large range of metal trichloride (MCl 3 ) systems. Particular attention is paid to the comparison with recent neutron and X-ray diffraction data on the liquid state. Polarization effects axe shown to be vital in reproducing strong experimental features. The excellent agreement between simulation and experiment allows for differences in experimental procedures to be highlighted. The transferability is further tested by modelling mixtures of the lanthanides with alkali halides with potentials unchanged from the pure systems. The complex evolution of the melt structure is highlighted as the concentration of MCl 3 increases. The effectiveness of the models is tested by reference to dynamical properties. Particular attention is paid to the comparison with Raman scattering data available for a wide range of systems and mixture concentrations. The simulated spectra are generated both by a simple molecular picture of the underlying

  19. Complex 3D Vortex Lattice Formation by Phase-Engineered Multiple Beam Interference

    Directory of Open Access Journals (Sweden)

    Jolly Xavier

    2012-01-01

    Full Text Available We present the computational results on the formation of diverse complex 3D vortex lattices by a designed superposition of multiple plane waves. Special combinations of multiples of three noncoplanar plane waves with a designed relative phase shift between one another are perturbed by a nonsingular beam to generate various complex 3D vortex lattice structures. The formation of complex gyrating lattice structures carrying designed vortices by means of relatively phase-engineered plane waves is also computationally investigated. The generated structures are configured with both periodic as well as transversely quasicrystallographic basis, while these whirling complex lattices possess a long-range order of designed symmetry in a given plane. Various computational analytical tools are used to verify the presence of engineered geometry of vortices in these complex 3D vortex lattices.

  20. Asymmetry of limbic structure (hippocampal formation and amygdaloidal complex at PTSD

    Directory of Open Access Journals (Sweden)

    Aida Sarač-Hadžihalilović

    2003-05-01

    Full Text Available Defining exact position of weak anatomic function which is find in a base of neurological and psychiatric disorder is just became the subject of intensive research interest. For this purposes it is important to implement structural and functional MRI techniques, also for further lightening and seeing subject of this work, more concretely connected to PTSD. Therefore, exactly MRI gives most sensitive volumetric measuring of hippocampal formation and amygdaloidal complex.The goal of this work was to research asymmetry of hippocampal formation and amygdaloidal complex to the PTSD patients.Results showed that at the axial slice length of hippocampal formation on the left and right side of all patients are significantly asymmetric. At the sagittal slice from the left side of hippocampal formation is in many cases longer than right about 50 %. At the coronal slice, there are no significant differences toward patient proportion according to symm. / asymm. of the hippocampal formation width at the right and left side. Difference in volume average of hippocampal formation between right and left side for axial and coronal slice is not statistically significant, but it is significant for sagittal slice. In about amygdaloidal complex patients with PTSD toward symm. / asymm. Amygdaloidal complex at the right and left side of axial and sagittal slice in all three measurement shows asymmetry, what is especially shown at sagittal slice. Difference in average length of amygdaloidal complex at the right and left side is not statistically significant for no one slice.Therefore, results of a new research that are used MRI, showed smaller hippocampal level at PTSD (researched by Van der Kolka 1996, Pitman 1996, Bremner et al., 1995.. Application of MRI technique in research of asymmetry of hippocampal formation and amygdaloidal complex, which we used in our research, we recommend as a template for future researches in a sense of lightening anatomic function that is

  1. Fullerenes doped with metal halides

    International Nuclear Information System (INIS)

    Martin, T.P.; Heinebrodt, M.; Naeher, U.; Goehlich, H.; Lange, T.; Schaber, H.

    1993-01-01

    The cage-like structure of fullerenes is a challenge to every experimental to put something inside - to dope the fullerenes. In fact, the research team that first identified C 60 as a football-like molecule quickly succeeded in trapping metal atoms inside and in shrinking the cage around this atom by photofragmentation. In this paper we report the results of ''shrink-wrapping'' the fullerenes around metal halide molecules. Of special interest is the critical size (the minimum number of carbon atoms) that can still enclose the dopant. A rough model for the space available inside a carbon cage gives good agreement with the measured shrinking limits. (author). 8 refs, 6 figs

  2. Cleavage and formation of molecular dinitrogen in a single system assisted by molybdenum complexes bearing ferrocenyldiphosphine.

    Science.gov (United States)

    Miyazaki, Takamasa; Tanaka, Hiromasa; Tanabe, Yoshiaki; Yuki, Masahiro; Nakajima, Kazunari; Yoshizawa, Kazunari; Nishibayashi, Yoshiaki

    2014-10-20

    The N≡N bond of molecular dinitrogen bridging two molybdenum atoms in the pentamethylcyclopentadienyl molybdenum complexes that bear ferrocenyldiphosphine as an auxiliary ligand is homolytically cleaved under visible light irradiation at room temperature to afford two molar molybdenum nitride complexes. Conversely, the bridging molecular dinitrogen is reformed by the oxidation of the molybdenum nitride complex at room temperature. This result provides a successful example of the cleavage and formation of molecular dinitrogen induced by a pair of two different external stimuli using a single system assisted by molybdenum complexes bearing ferrocenyldiphosphine under ambient conditions. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Control of cell fate by the formation of an architecturally complex bacterial community.

    Science.gov (United States)

    Vlamakis, Hera; Aguilar, Claudio; Losick, Richard; Kolter, Roberto

    2008-04-01

    Bacteria form architecturally complex communities known as biofilms in which cells are held together by an extracellular matrix. Biofilms harbor multiple cell types, and it has been proposed that within biofilms individual cells follow different developmental pathways, resulting in heterogeneous populations. Here we demonstrate cellular differentiation within biofilms of the spore-forming bacterium Bacillus subtilis, and present evidence that formation of the biofilm governs differentiation. We show that motile, matrix-producing, and sporulating cells localize to distinct regions within the biofilm, and that the localization and percentage of each cell type is dynamic throughout development of the community. Importantly, mutants that do not produce extracellular matrix form unstructured biofilms that are deficient in sporulation. We propose that sporulation is a culminating feature of biofilm formation, and that spore formation is coupled to the formation of an architecturally complex community of cells.

  4. Complexometric determination: Part I - EDTA and complex formation with the Cu2+ ion

    Directory of Open Access Journals (Sweden)

    Rajković Miloš B.

    2002-01-01

    Full Text Available Compounds forming very stable complexes - chelates, have a wide field of application in analytical chemistry. The most famous group of these compounds are complexons. Complexons represent organic polyaminocarbonic acids as for example ethylenediaminetetraacetic acid (EDTA and its salts. The EDTA molecule has six coordinative sites. It is a hexadentate ligands i.e. it has two binding nitrogen atoms and four oxygen atoms from carboxyl groups and it forms complexes with almost all metal ions. EDTA as a tetraprotonic acid, H4Y disociates through four steps, yielding the ions HsY-, H2Y2-, HY3- and Y4-. Which of the EDTA forms will be encountered in a solution, depends on the pH. Due to the poor solubility of EDTA in pure water, as well as in most organic solvents, the disodium salt of EDTA Na2H2Y-2H2O, under the commercial name complexon III, is utilized for analytical determinations. In water, EDTA forms soluble, stabile chelate complexes with all cations, at the molar ratio 1:1, regardless of the charge of the metal ion. In contrast to other equilibria, which are mainly defined by Le Chatellier's principle, equilibria related to metal-EDTA complex formation are also dependent on the influence of the secondary equilibria of EDTA complex formation. Complexing reactions, which are equilibrium reactions, are simultaneously influenced by the following factors: solution pH and the presence of complexing agents which may also form a stabile complex with metal ions. The secondary reaction influence may be viewed and monitored through conditional stability constants. In the first part of the paper, the reaction of the formation of the Cu2+-ion complex with EDTA is analyzed beginning from the main reaction through various influences of secondary reactions on the complex Cu2+-EDTA: pH effect, complexation effect and hydrolysis effect. The equations are given for conditional stability constants, which include equilibrium reactions under actual conditions.

  5. Mechanisms Underlying the Formation of Complexes between Maize Starch and Lipids.

    Science.gov (United States)

    Chao, Chen; Yu, Jinglin; Wang, Shuo; Copeland, Les; Wang, Shujun

    2018-01-10

    This study aimed to reveal the mechanism of formation of complexes between native maize starch (NMS) and different types of lipids, namely palmitic acid (PA), monopalmitate glycerol (MPG), dipalmitate glycerol (DPG), and tripalmitate glycerol (TPG). The complexing index followed the order of MPG (96.3%) > PA (41.8%) > TPG (8.3%) > DPG (1.1%), indicating that MPG formed more complexes with NMS than PA, and that few complexes were formed between NMS and DPG and TPG. The NMS-PA complex presented higher thermal transition temperatures and lower enthalpy change than the NMS-MPG complex, indicating that although MPG formed more starch complexes, they had less stable crystalline structures than the complex between NMS and PA. X-ray diffraction (XRD) and Raman spectroscopy showed that both MPG and PA formed V-type crystalline structures with NMS, and confirmed that no complexes were formed between NMS and DPG and TPG. We conclude that the monoglyceride formed more starch-lipid complex with maize starch than PA, but that the monoglyceride complex had a less stable structure than that formed with PA. The di- and triglycerides did not form complexes with maize starch.

  6. Formation of mixed ligand complexes of UO22+ involving some nitrogen and oxygen donor ligands

    International Nuclear Information System (INIS)

    Singh, Mamta; Ram Nayan

    1996-01-01

    The complexation reactions of UO 2 2+ ion with nitrogen and oxygen donor ligands, 1-amino-2-naphthol-4-sulphonic acid, o-aminophenol (ap), 2-hydroxybenzoic acid (sa), 3-carboxy-4-hydroxybenzenesulphonic acid (ss) and 1,2-dihydroxybenzene (ca) have been investigated in aqueous solution employing the pH-titration technique. Analysis of the experimental data recorded at 25 degC and at an ionic strength of 0.10 M KNO 3 indicates formation of binary, hydroxo and ternary complexes of uranium. Formation constant values of the existing species have been evaluated and the results have been discussed. (author). 21 refs., 2 figs., 2 tabs

  7. 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...

  8. Generating functional analysis of complex formation and dissociation in large protein interaction networks

    International Nuclear Information System (INIS)

    Coolen, A C C; Rabello, S

    2009-01-01

    We analyze large systems of interacting proteins, using techniques from the non-equilibrium statistical mechanics of disordered many-particle systems. Apart from protein production and removal, the most relevant microscopic processes in the proteome are complex formation and dissociation, and the microscopic degrees of freedom are the evolving concentrations of unbound proteins (in multiple post-translational states) and of protein complexes. Here we only include dimer-complexes, for mathematical simplicity, and we draw the network that describes which proteins are reaction partners from an ensemble of random graphs with an arbitrary degree distribution. We show how generating functional analysis methods can be used successfully to derive closed equations for dynamical order parameters, representing an exact macroscopic description of the complex formation and dissociation dynamics in the infinite system limit. We end this paper with a discussion of the possible routes towards solving the nontrivial order parameter equations, either exactly (in specific limits) or approximately.

  9. The importance of moisture in hybrid lead halide perovskite thin film fabrication

    NARCIS (Netherlands)

    Eperon, G.E.; Habisreutinger, S.N.; Leijtens, T.; Bruijnaers, B.J.; van Franeker, J.J.; deQuilettes, D.W.; Pathak, S.; Sutton, R.J.; Grancini, G.; Ginger, D.S.; Janssen, R.A.J.; Petrozza, A.; Snaith, H.J.

    2015-01-01

    Moisture, in the form of ambient humidity, has a significant impact on methylammonium lead halide perovskite films. In particular, due to the hygroscopic nature of the methylammonium component, moisture plays a significant role during film formation. This issue has so far not been well understood

  10. Theoretical study of the possibility of glycin with thiotriazoline complexes formation

    Directory of Open Access Journals (Sweden)

    L. I. Kucherenko

    2017-10-01

    Full Text Available Brain strokes are widely spread all over the world and are among the most dangerous for the population. Often it leads to death, complete or partial loss of ability to work. The correction of imbalance of Excitatory and inhibitory neurotransmitter systems by activation of natural inhibitory processes is a promising direction of primary neuroprotection in cerebral ischemia. Particular attention is drawn to the natural inhibitory neurotransmitter – glycine and its role in the mechanisms of acute cerebral ischemia. There are data on the ability of the thiotriazoline antioxidant to potentiate the therapeutic effect of neurometabolic cerebroprotectors. Therefore, the creation of new combined preparation based on glycine with thiotriazoline is important today. Objective: to study the structure, and estimate the energy of formation and geometric characteristics of the intermolecular hydrogen bonds for complexes which are formed with glycine, 3-methyl-1,2,4-triazolyl-5-thioacetate (MTTA and morpholine. Method of calculation. The initial approximation to the structure of the complexes was obtained with the help of molecular docking procedure using the AutoDock Vina program. The resulting three-component complexes were preliminarily optimized by the semiempirical PM7 method, taking into account the outward influences, which was simulated by the COSMO method. The calculations were carried out using the MOPAC2012 program. The complexes were optimized using the density functional method with the empirical dispersion correction B97-D3/SVP+COSMO (Water using geometric correction for the incompleteness of the gCP basic set. A more accurate calculation of the solvation energy was carried out by SMD method. Calculations by the density functional method were carried out using the ORCA 3.0.3 program. The energy of formation of complexes in solution was calculated as the difference between the free Gibbs energies of the solvated complex and its individual solvated

  11. Complex formation constant and hydration number change of aqua-rare earth ions

    International Nuclear Information System (INIS)

    Kanno, H.

    1998-01-01

    Full text: It is now well established that the inner-sphere hydration number of aqua-rare earth ions changes from nine to eight in the middle of the rare earth series. This hydration number change greatly affects the complex formation of rare earth ions as we observe irregular variations in most series behaviours of the complex formation constant (K) in aqueous solution systems when K being plotted against 1/r or r (r is ionic radius of rare earth ion). Furthermore, it shows very anomalous concentration dependence in the sense that nona-aqua Ln 3+ ion increases in number with increase in salt concentration in aqueous rare earth salt solution (salt chloride, perchlorate). In this report, a theoretical derivation of the formation constant (K) for the inner-sphere complex formation of rare earth ions with a monodentate ligand was made by taking account of both the hydration number change in the middle of the series and its anomalous salt concentration dependence. The series behaviour of the formation constant against 1/r (or r) is successfully explained with using the empirical finding that K varies almost linearly with 1/r (or r) in the region where only one hydration number dominates. This success is also taken as evidence that the anomalous salt concentration dependence of the hydration number change is caused by the outer-sphere complex formation of rare earth ions with the condition that nona-aqua rare earth ions form outer-sphere complexes more easily than octa-aqua ions

  12. Holographic Optical Elements Recorded in Silver Halide Sensitized Gelatin Emulsions. Part I. Transmission Holographic Optical Elements

    Science.gov (United States)

    Kim, Jong Man; Choi, Byung So; Kim, Sun Il; Kim, Jong Min; Bjelkhagen, Hans I.; Phillips, Nicholas J.

    2001-02-01

    Silver halide sensitized gelatin (SHSG) holograms are similar to holograms recorded in dichromated gelatin (DCG), the main recording material for holographic optical elements (HOE s). The drawback of DCG is its low sensitivity and limited spectral response. Silver halide materials can be processed in such a way that the final hologram will have properties like a DCG hologram. Recently this technique has become more interesting since the introduction of new ultra-high-resolution silver halide emulsions. An optimized processing technique for transmission HOE s recorded in these materials is introduced. Diffraction efficiencies over 90% can be obtained for transmissive diffraction gratings. Understanding the importance of the selective hardening process has made it possible to obtain results similar to conventional DCG processing. The main advantage of the SHSG process is that high-sensitivity recording can be performed with laser wavelengths anywhere within the visible spectrum. This simplifies the manufacturing of high-quality, large-format HOE s.

  13. The influence of atomic number on the complex formation constants by visible spectrophotometric method

    International Nuclear Information System (INIS)

    Samin; Kris-Tri-Basuki; Farida-Ernawati

    1996-01-01

    The influence of atomic number on the complex formation constants and it's application by visible spectrophotometric method has been carried out. The complex compound have been made of Y, Nd, Sm and Gd with alizarin red sulfonic in the mole fraction range of 0.20 - 0.53 and pH range of 3.5 - 5. The optimum condition of complex formation was found in the mole fraction range of 0.30 - 0.53, range of pH 3.75 - 5, and the total concentration was 0.00030 M. It was found that the formation constant (β) of alizarin red S. complex by continued variation and matrix disintegration techniques were β : (7.00 ± 0.64).10 9 of complex 3 9γ,β : (4.09±0.34).10 8 of 6 0Nd, β : (7.26 ± 0.42).10 8 of 62 S m and β : (8.38 ± 0.70).10 8 of 64 G d. It can be concluded that the atomic number of Nd is bigger than Sm which is bigger than Gd. The atomic number of Y is the smallest. (39) and the complex formation constant is a biggest. The complex compound can be used for sample analysis with limit detection of Y : 2.2 .10 -5 M, Nd : 2.9 .10 -5 M, Sm : 2.6 .10 -5 M and Gd : 2.4 .10 -5 M. The sensitivity of analysis are Y>Gd>Sm>Nd. The Y 2 O 3 sample of product result from xenotime sand contains Y 2 O 3 : 98.96 ± 1.40 % and in the filtrate (product of monazite sand) contains Nd : 0.27 ± 0.002 M

  14. Current state and perspectives for organo-halide perovskite solar cells. Part 1. Crystal structures and thin film formation, morphology, processing, degradation, stability improvement by carbon nanotubes. A review

    Directory of Open Access Journals (Sweden)

    Nigmat Ashurov

    2017-03-01

    Full Text Available The fundamental problems of the modern state of the studies of organic–inorganic organo-halide perovskites (OHP as basis for high efficiency thin film solar cells are discussed. Perovskite varieties and background properties are introduced. The chronology of development of the studies in this direction has been presented – structural aspects of these OHP perovskites, from early 2D to recent 3D MAPbI3 perovskites and important technological aspects of smooth thin film structure creation by various techniques, such as solvent engineering, spin- and dip - coating, vacuum deposition, cation exchange approach, nanoimprinting (particularly, a many-sided role of polymers. The most important theoretical problems such as electronic structure of lattice, impurity and defect states in pure and mixed perovskites, suppressed electron-hole recombination, extra-long lifetimes, and diffusion lengths are analyzed. Degradation effects associated with moisture and photo irradiation, as well as degradation of metallic electrodes to OHP solar cells have been considered. The application of carbon nanostructures: carbon nanotubes (CNT and graphene as stable semitransparent charge collectors to OHP perovskites is demonstrated on the example of original results of authors.

  15. Study of factors that influence complex-formation of n-alkanes with crystal carbamide

    Energy Technology Data Exchange (ETDEWEB)

    Dorodnova, V.S.; Korzhov, Yu.A.; Martynenko, A.G.

    1982-01-01

    Studies effect of temperature, solid phase content in the suspension and amount of MeOH on extent of n-alkane extraction during carbamide deparaffinization. A most thorough extraction of n-alkanes is achieved with a graduated temperature regimen of complex-formation.

  16. Computer analysis of potentiometric data of complexes formation in the solution

    Science.gov (United States)

    Jastrzab, Renata; Kaczmarek, Małgorzata T.; Tylkowski, Bartosz; Odani, Akira

    2018-02-01

    The determination of equilibrium constants is an important process for many branches of chemistry. In this review we provide the readers with a discussion on computer methods which have been applied for elaboration of potentiometric experimental data generated during complexes formation in solution. The review describes both: general basis of modeling tools and examples of the use of calculated stability constants.

  17. Proton transfer and complex formation of angiotensin I ions with gaseous molecules at various temperature

    International Nuclear Information System (INIS)

    Nonose, Shinji; Yamashita, Kazuki; Sudo, Ayako; Kawashima, Minami

    2013-01-01

    Highlights: • Proton transfer from angiotensin I ions (z = 2, 3) to gaseous molecules was studied. • Temperature dependence of absolute reaction rate constants was measured. • Remarkable changes were obtained for distribution of product ions and reaction rate constants. • Proton transfer reaction was enhanced and reduced by complex formation. • Conformation changes are induced by complex formation and or by thermal collision with He. - Abstract: Proton transfer reactions of angiotensin I ions for +2 charge state, [M + 2H] 2+ , to primary, secondary and aromatic amines were examined in the gas phase. Absolute reaction rate constants for proton transfer were determined from intensities of parent and product ions in the mass spectra. Temperature dependence of the reaction rate constants was measured. Remarkable change was observed for distribution of product ions and reaction rate constants. Proton transfer reaction was enhanced or reduced by complex formation of [M + 2H] 2+ with gaseous molecules. The results relate to conformation changes of [M + 2H] 2+ with change of temperature, which are induced by complex formation and or by thermal collision with He. Proton transfer reactions of angiotensin I ions for +3 charge state, [M + 3H] 3+ , were also studied. The reaction rates did not depend on temperature so definitely

  18. High-Frequency Promoter Firing Links THO Complex Function to Heavy Chromatin Formation

    DEFF Research Database (Denmark)

    Mouaikel, John; Causse, Sébastien Z; Rougemaille, Mathieu

    2013-01-01

    The THO complex is involved in transcription, genome stability, and messenger ribonucleoprotein (mRNP) formation, but its precise molecular function remains enigmatic. Under heat shock conditions, THO mutants accumulate large protein-DNA complexes that alter the chromatin density of target genes...... (heavy chromatin), defining a specific biochemical facet of THO function and a powerful tool of analysis. Here, we show that heavy chromatin distribution is dictated by gene boundaries and that the gene promoter is necessary and sufficient to convey THO sensitivity in these conditions. Single......-molecule fluorescence insitu hybridization measurements show that heavy chromatin formation correlates with an unusually high firing pace of the promoter with more than 20 transcription events per minute. Heavy chromatin formation closely follows the modulation of promoter firing and strongly correlates with polymerase...

  19. Quantum statistical vibrational entropy and enthalpy of formation of helium-vacancy complex in BCC W

    Energy Technology Data Exchange (ETDEWEB)

    Wen, Haohua [Sino-French Institute of Nuclear Engineering and Technology, Sun Yat-Sen University, 519082, Zhuhai (China); Woo, C.H., E-mail: chung.woo@polyu.edu.hk [ME Department, The Hong Kong Polytechnic University, Hong Kong SAR (China)

    2016-12-15

    High-temperature advance-reactor design and operation require knowledge of in-reactor materials properties far from the thermal ground state. Temperature-dependence due to the effects of lattice vibrations is important to the understanding and formulation of atomic processes involved in irradiation-damage accumulation. In this paper, we concentrate on the formation of He-V complex. The free-energy change in this regard is derived via thermodynamic integration from the phase-space trajectories generated from MD simulations based on the quantum fluctuation-dissipation relation. The change of frequency distribution of vibration modes during the complex formation is properly accounted for, and the corresponding entropy change avoids the classical ln(T) divergence that violates the third law. The vibrational enthalpy and entropy of formation calculated this way have significant effects on the He kinetics during irradiation.

  20. Manganese-Catalyzed Cross-Coupling of Aryl Halides and Grignard Reagents by a Radical Mechanism

    DEFF Research Database (Denmark)

    Antonacci, Giuseppe; Ahlburg, Andreas; Fristrup, Peter

    2017-01-01

    The substrate scope and the mechanism have been investigated for the MnCl2-catalyzed cross-coupling reaction between aryl halides and Grignard reagents. The transformation proceeds rapidly and in good yield when the aryl halide component is an aryl chloride containing a cyano or an ester group....... Two radical-clock experiments were carried out, and in both cases an intermediate aryl radical was successfully trapped. The cross-coupling reaction is therefore believed to proceed by an SRN1 mechanism, with a triorganomanganate complex serving as the most likely nucleophile and single-electron donor...

  1. Star-formation complexes in the `galaxy-sized' supergiant shell of the galaxy Holmberg I

    Science.gov (United States)

    Egorov, Oleg V.; Lozinskaya, Tatiana A.; Moiseev, Alexei V.; Smirnov-Pinchukov, Grigory V.

    2018-05-01

    We present the results of observations of the galaxy Holmberg I carried out at the Russian 6-m telescope in the narrow-band imaging, long-slit spectroscopy, and scanning Fabry-Perot interferometer modes. A detailed analysis of gas kinematics, ionization conditions, and metallicity of star-forming regions in the galaxy is presented. The aim of the paper is to analyse the propagation of star formation in the galaxy and to understand the role of the ongoing star formation in the evolution of the central `galaxy-sized' supergiant H I shell (SGS), where all regions of star formation are observed. We show that star formation in the galaxy occurs in large unified complexes rather than in individual giant H II regions. Evidence of the triggered star formation is observed both on scales of individual complexes and of the whole galaxy. We identified two supernova-remnant candidates and one late-type WN star and analysed their spectrum and surrounding-gas kinematics. We provide arguments indicating that the SGS in Holmberg I is destructing by the influence of star formation occurring on its rims.

  2. Complex formation between neptunium(V) and various thiosemicarbazide derivatives in aqueous solution

    International Nuclear Information System (INIS)

    Chuguryan, D.G.; Dzyubenko, V.I.; Gerbeleu, N.V.

    1987-01-01

    Complex formation between neptunium(V) and various thiosemicarbazide derivatives in solution has been studied spectrophotometrically in the pH range 4-10. Stepwise formation of three types of complexes, with composition NpO 2 HA, NpO 2 A - , and NpOHA 2- , has been demonstrated with salicylaldehyde thiosemicarbazone (H 2 L) and salicylaldehyde S-methyl-isothiosemicarbazone (H 2 Q) at t = 25 +/- 1 0 C and μ = 0.05. The logarithmic stability constants of the first two complexes are 5.14 +/- 0.06, 11.85 +/- 0.04 and 8.42 +/- 0.09, 13.33 +/- 0.015 for H 2 L and H 2 Q, respectively; equilibrium constants for the formation of hydroxo complexes of the form NpO 2 OHL 2- and NpO 2 OHQ 2- were also determined, and found to be equal to (2.23 +/-0.37) x 10 -5 and (5.02 +/- 0.9) x 10 -5 , respectively. In the case of S-methyl-N 1 ,N 4 -bis(salicylidene)isothiosemicarbazide (H 2 Z), only one type of complex is formed under these experimental conditions, namely, NpO 2 Z - , with a logarithmic stability constant of 4.78 +/- 0.03. Dissociation constants for H 2 Q and H 2 Z were also determined

  3. Formation of nitridotechnetium(VI) μ-oxo dimer complexes with EDTA and EDDA

    International Nuclear Information System (INIS)

    Takayama, T.; Kani, Y.; Sekine, T.; Kudo, H.; Yoshihara, K.

    1995-01-01

    Reactions of [ 99 TcNCl 4 ] - with ethylenediaminetetraacetic acid 4 (ETDA) and ethylenediamine-N,N'-diacetic acid (EDDA) in a mixture of water and acetone gave Tc VI N-EDTA and Tc VI N-EDTA complexes. The infrared spectra of both reaction products showed the existence of the Tc≡N and C=O groups. The elemental analysis indicated the 1:1 TcN-ligand ratio in the EDTA and EDDA complexes. Electrophoresis showed that the Tc VI -EDTA complex was an anionic species in a perchlorate solution. For the Tc VI N-EDDA complex, neutral and anionic species were formed, depending on the pH of the solution. Formation of the μ-oxo dimer complexes was suggested from the UV-Vis absorption spectra. (author) 11 refs.; 4 figs.; 1 tab

  4. The role of plasma proteins in formation of obstructive protamine complexes

    International Nuclear Information System (INIS)

    De Paulis, R.; Mohammad, S.F.; Chiariello, L.; Morea, M.; Olsen, D.B.

    1991-01-01

    Formation of complexes between heparin and protamine (in saline), or heparin, plasma proteins, and protamine (in plasma) was assessed by measurements of light transmission through different test solutions. To examine the formation of these complexes, 125I-labeled protamine was used. Addition of 125I-protamine to plasma or blood resulted in the sedimentation of 125I-protamine in the form of insoluble complexes. This complex formation was not affected by the presence of heparin, suggesting that protamine-plasma protein interaction may be primarily responsible for precipitation of 125I-protamine. To assess the capability of these complexes to obstruct the pulmonary circulation, an in vitro experimental model was developed. Citrated serum, plasma, blood, or saline were allowed to flow through a glass bead column with the help of a peristaltic pump. A pressure transducer positioned before the column allowed pressure measurements at a constant flow rate during the experiment. Mixing of protamine with plasma or blood prior to their passage through the glass bead column resulted in a significant increase in pressure suggesting that the column was being clogged with insoluble complexes. The increase in pressure occurred both in the presence and absence of heparin in plasma or blood. Under identical experimental conditions, the increase in pressure was insignificant when protamine was added to saline or serum regardless of whether heparin was present or absent. This was further confirmed by the use of 125I-protamine. These observations suggest that protamine forms insoluble complexes with certain plasma proteins. Based on these observations, it is hypothesized that following intravenous administration, protamine immediately forms complexes in circulating blood

  5. The role of halide ions on the electrochemical behaviour of iron in alkali solutions

    Science.gov (United States)

    Begum, S. Nathira; Muralidharan, V. S.; Basha, C. Ahmed

    2008-02-01

    Active dissolution and passivation of transition metals in alkali solutions is of technological importance in batteries. The performance of alkaline batteries is decided by the presence of halides as they influence passivation. Cyclic voltammetric studies were carried out on iron in different sodium hydroxide solutions in presence of halides. In alkali solutions iron formed hydroxo complexes and their polymers in the interfacial diffusion layer. With progress of time they formed a cation selective layer. The diffusion layer turned into bipolar ion selective layer consisted of halides, a selective inner sublayer to the metal side and cation selective outer layer to the solution side. At very high anodic potentials, dehydration and deprotonation led to the conversion of salt layer into an oxide.

  6. A model for additive transport in metal halide lamps containing mercury and dysprosium tri-iodide

    NARCIS (Netherlands)

    Beks, M.L.; Haverlag, M.; Mullen, van der J.J.A.M.

    2008-01-01

    The distribution of additives in a metal halide lamp is examined through numerical modelling. A model for a lamp containing sodium iodide additives has been modified to study a discharge containing dysprosium tri-iodide salts. To study the complex chemistry the method of Gibbs minimization is used

  7. A spectrophotometric investigation of the complex formation between lanthanum (III) and eriochrome cyanine R

    International Nuclear Information System (INIS)

    Boodts, J.F.C.; Saffioti, W.

    1979-01-01

    The complex formation between La(III) and Eriochrome Cyanine R has been investigated. Three complexes have been detected. A first one (Complex I) in the pH range of 5.3-5.5 with lambda sub(max) = 460nm. a second one (Complex II) in the pH range of 6.2-6.5 with lambda sub(max) = 490nm and a third one (complex III) in the pH range of 8.2 - 9.0 with lambda sub(max) = 545nm and a shoulder between 570-580nm. The composition and stability constants of the complexes, respectively: complex I: La(ECR) 2 and 4.9 x 10 7 , complex II: La(ECR) 2 and 7.0 x 10 7 , complex III: La.ECR and 1.0 x 10 4 . All measurements were taken at 25.0 +- 0.1 0 C and μ = 0.2 (NaClO 4 ). (Author) [pt

  8. Thermochromic halide perovskite solar cells

    Science.gov (United States)

    Lin, Jia; Lai, Minliang; Dou, Letian; Kley, Christopher S.; Chen, Hong; Peng, Fei; Sun, Junliang; Lu, Dylan; Hawks, Steven A.; Xie, Chenlu; Cui, Fan; Alivisatos, A. Paul; Limmer, David T.; Yang, Peidong

    2018-03-01

    Smart photovoltaic windows represent a promising green technology featuring tunable transparency and electrical power generation under external stimuli to control the light transmission and manage the solar energy. Here, we demonstrate a thermochromic solar cell for smart photovoltaic window applications utilizing the structural phase transitions in inorganic halide perovskite caesium lead iodide/bromide. The solar cells undergo thermally-driven, moisture-mediated reversible transitions between a transparent non-perovskite phase (81.7% visible transparency) with low power output and a deeply coloured perovskite phase (35.4% visible transparency) with high power output. The inorganic perovskites exhibit tunable colours and transparencies, a peak device efficiency above 7%, and a phase transition temperature as low as 105 °C. We demonstrate excellent device stability over repeated phase transition cycles without colour fade or performance degradation. The photovoltaic windows showing both photoactivity and thermochromic features represent key stepping-stones for integration with buildings, automobiles, information displays, and potentially many other technologies.

  9. Thermochromic halide perovskite solar cells.

    Science.gov (United States)

    Lin, Jia; Lai, Minliang; Dou, Letian; Kley, Christopher S; Chen, Hong; Peng, Fei; Sun, Junliang; Lu, Dylan; Hawks, Steven A; Xie, Chenlu; Cui, Fan; Alivisatos, A Paul; Limmer, David T; Yang, Peidong

    2018-03-01

    Smart photovoltaic windows represent a promising green technology featuring tunable transparency and electrical power generation under external stimuli to control the light transmission and manage the solar energy. Here, we demonstrate a thermochromic solar cell for smart photovoltaic window applications utilizing the structural phase transitions in inorganic halide perovskite caesium lead iodide/bromide. The solar cells undergo thermally-driven, moisture-mediated reversible transitions between a transparent non-perovskite phase (81.7% visible transparency) with low power output and a deeply coloured perovskite phase (35.4% visible transparency) with high power output. The inorganic perovskites exhibit tunable colours and transparencies, a peak device efficiency above 7%, and a phase transition temperature as low as 105 °C. We demonstrate excellent device stability over repeated phase transition cycles without colour fade or performance degradation. The photovoltaic windows showing both photoactivity and thermochromic features represent key stepping-stones for integration with buildings, automobiles, information displays, and potentially many other technologies.

  10. Deficiency of PHB complex impairs respiratory supercomplex formation and activates mitochondrial flashes.

    Science.gov (United States)

    Jian, Chongshu; Xu, Fengli; Hou, Tingting; Sun, Tao; Li, Jinghang; Cheng, Heping; Wang, Xianhua

    2017-08-01

    Prohibitins (PHBs; prohibitin 1, PHB1 or PHB, and prohibitin 2, PHB2) are evolutionarily conserved and ubiquitously expressed mitochondrial proteins. PHBs form multimeric ring complexes acting as scaffolds in the inner mitochondrial membrane. Mitochondrial flashes (mitoflashes) are newly discovered mitochondrial signaling events that reflect electrical and chemical excitations of the organelle. Here, we investigate the possible roles of PHBs in the regulation of mitoflash signaling. Downregulation of PHBs increases mitoflash frequency by up to 5.4-fold due to elevated basal reactive oxygen species (ROS) production in the mitochondria. Mechanistically, PHB deficiency impairs the formation of mitochondrial respiratory supercomplexes (RSCs) without altering the abundance of individual respiratory complex subunits. These impairments induced by PHB deficiency are effectively rescued by co-expression of PHB1 and PHB2, indicating that the multimeric PHB complex acts as the functional unit. Furthermore, downregulating other RSC assembly factors, including SCAFI (also known as COX7A2L), RCF1a (HIGD1A), RCF1b (HIGD2A), UQCC3 and SLP2 (STOML2), all activate mitoflashes through elevating mitochondrial ROS production. Our findings identify the PHB complex as a new regulator of RSC formation and mitoflash signaling, and delineate a general relationship among RSC formation, basal ROS production and mitoflash biogenesis. © 2017. Published by The Company of Biologists Ltd.

  11. Improved catalytic properties of halohydrin dehalogenase by modification of the halide-binding site.

    Science.gov (United States)

    Tang, Lixia; Torres Pazmiño, Daniel E; Fraaije, Marco W; de Jong, René M; Dijkstra, Bauke W; Janssen, Dick B

    2005-05-03

    Halohydrin dehalogenase (HheC) from Agrobacterium radiobacter AD1 catalyzes the dehalogenation of vicinal haloalcohols by an intramolecular substitution reaction, resulting in the formation of the corresponding epoxide, a halide ion, and a proton. Halide release is rate-limiting during the catalytic cycle of the conversion of (R)-p-nitro-2-bromo-1-phenylethanol by the enzyme. The recent elucidation of the X-ray structure of HheC showed that hydrogen bonds between the OH group of Tyr187 and between the Odelta1 atom of Asn176 and Nepsilon1 atom of Trp249 could play a role in stabilizing the conformation of the halide-binding site. The possibility that these hydrogen bonds are important for halide binding and release was studied using site-directed mutagenesis. Steady-state kinetic studies revealed that mutant Y187F, which has lost both hydrogen bonds, has a higher catalytic activity (k(cat)) with two of the three tested substrates compared to the wild-type enzyme. Mutant W249F also shows an enhanced k(cat) value with these two substrates, as well as a remarkable increase in enantiopreference for (R)-p-nitro-2-bromo-1-phenylethanol. In case of a mutation at position 176 (N176A and N176D), a 1000-fold lower catalytic efficiency (k(cat)/K(m)) was obtained, which is mainly due to an increase of the K(m) value of the enzyme. Pre-steady-state kinetic studies showed that a burst of product formation precedes the steady state, indicating that halide release is still rate-limiting for mutants Y187F and W249F. Stopped-flow fluorescence experiments revealed that the rate of halide release is 5.6-fold higher for the Y187F mutant than for the wild-type enzyme and even higher for the W249F enzyme. Taken together, these results show that the disruption of two hydrogen bonds around the halide-binding site increases the rate of halide release and can enhance the overall catalytic activity of HheC.

  12. Uranium (VI) complexing by macrocyclic or chelating ligands in aqueous solutions stability, formation kinetics, polarographic properties

    International Nuclear Information System (INIS)

    Brighli, M.

    1984-07-01

    Stability of chelates (with EDTA,N,N ethylenediamine diacetic acid EDDA nitrilotriacetic acid NTA and iminodiacetic acid) of UO 2 2+ and UO 4 species of uranium VI is studied in aqueous solution (NaClO 4 3M at 25 deg celcius). Structure in solution are proposed and discussed for mononuclear species. Only complexing kinetics (formation and acid hydrolysis) of UO 4 with EDDA and NTA are studied by spectrophotometry (other reactions are too fast). Besides UO 2 2+ complexes are formed with crown ethers I5C5 and I8C6 in aqueous solution (TEA ClO 4 M/10 at 25 deg celcius. Complexes are probably stabilized by solvation. Results are confirmed by voltametry and reduction mechanisms of UO 2 2+ and its complexes on mercury drop are proposed. 143 refs [fr

  13. Thermodynamics of complex formation of natural iron(III)porphyrins with neutral ligands

    International Nuclear Information System (INIS)

    Lebedeva, Nataliya Sh.; Yakubov, Sergey P.; Vyugin, Anatoly I.; Parfenyuk, Elena V.

    2003-01-01

    Calorimetric titrations in benzene and chloroform at 298.15 K have been performed to give the complexes stability constants and the thermodynamic parameters for the complex formation of nature iron(III)porphyrins with pyridine. Stoichimetry of the complexes formed has been determined. It has been found that the thermodynamic parameters obtained depend on nature of peripheral substituents of the porphyrins. The estimation of the influence of Cl - and Ac - ions on the processes studied has been carried out. Using thermodynamic analysis method, the crystallsolvates of nature iron(III)porphyrins with benzene have been studied. Stoichiometry, thermal and energetic stability of the π-π-complexes formed have been determined. The data obtained have been used to the estimate solvent effect on the thermodynamic parameters of axial coordination of pyridine on the iron(III)porphyrins in benzene

  14. Halide-Dependent Electronic Structure of Organolead Perovskite Materials

    KAUST Repository

    Buin, Andrei; Comin, Riccardo; Xu, Jixian; Ip, Alexander H.; Sargent, Edward H.

    2015-01-01

    -based perovskites, in line with recent experimental data. As a result, the optimal growth conditions are also different for the distinct halide perovskites: growth should be halide-rich for Br and Cl, and halide-poor for I-based perovskites. We discuss stability

  15. Kinetic and mechanism formation reaction of complex compound Cu with di-n-buthildithiocarbamate (dbdtc) ligand

    Science.gov (United States)

    Haryani, S.; Kurniawan, C.; Kasmui

    2018-04-01

    Synthesis of complex compound is one field of research which intensively studied. Metal-dithiocarbamate complexes find wide-ranging applications in nanomaterial and metal separation science, and have potential use as chemotherapeutic, pesticides, and as additives to lubricants. However, the information about is reaction kinetic and mechanism are very much lacking. The research and analyzes results show that reaction synthesis ligand DBDTC and complex compounds Cu-DBDTC. Optimum reaction condition of formation of complex compounds Cu with DBDTC at pH=3, [DBDTC] = 4.10-3 M, and the time of reaction 5 minutes. Based the analysis varian reaction of complex compounds at pH 3 and 4, diffrence significance at the other pH: 5; 5,5; 6; 6,5 ; 7; and 8. The various of mole with reactants comosition difference sigbificance, those the time reaction for 5 and 6 minutes diffrence by significance with the other time, it is 3,4,8, and 10 minutes. The great product to at condition pH 6, the time optimum at 5 minutes and molar ratio of logam: ligand = 1:2. The reaction kinetic equation of complex compound Cu with chelathing ligand DBDTC is V=0.917106 [Cu2+]0.87921 [DBDTC]2.03021. Based on the kinetic data, and formed complex compounds estimation, the mechanism explaining by 2 stages. In the first stage formation of [Cu(DBDTC)], and then [Cu(DBDTC)2] with the last structure geomethry planar rectangle. The result of this research will be more useful if an effort is being done in reaction mechanism by chemical computation method for obtain intermediate, and for constant “k” in same stage, k1.k2. and compound complex constanta (β).

  16. Spectroscopic studies on U(VI)-salicylate complex formation with multiple equilibria

    Energy Technology Data Exchange (ETDEWEB)

    Cha, W.; Cho, H.R.; Jung, E.C.; Park, K.K.; Kim, W.H.; Song, K. [Korea Atomic Energy Research Institute, Daejeon (Korea, Republic of). Nuclear Chemistry Research Div.

    2012-07-01

    This study investigates multiple equilibria related to the formation of the U(VI)-salicylate complex in a pH range of 3.0-5.5 using UV-Vis absorption and fluorescence measurement techniques. The absorbance changes at the characteristic charge-transfer bands of the complex were monitored, and the results indicated the presence of multiple equilibria and the formation of both 1:1 and 1:2 (U(VI):salicylate) complexes possessing bi-dentate chelate structures. The determined step-wise formation constants (log K{sub 1:1} and log K{sub 1:2}) are as follows: 12.5 {+-} 0.1 and 11.4 {+-} 0.2 for salicylate, 11.2 {+-} 0.1 and 10.1 {+-} 0.2 for 5-sulfosalicylate, and 12.4 {+-} 0.1 and 11.4 {+-} 0.1 for 2,6-dihydroxybenzoate, respectively. The molar absorptivities of the complexes are also provided. Furthermore, time-resolved laser-induced luminescence spectra of U(VI) species demonstrate the presence of both a dynamic and static quenching process upon the addition of a salicylate ligand. Particularly for the luminescent hydroxouranyl species, a strong static quenching effect is observed. The results suggest that both the UO{sub 2}(HSal){sup +} and the U(VI)-Sal chelate complexes serve as ground-state complexes that induce static quenching. The Stern-Volmer parameters were derived based on the measured luminescent intensity and lifetime data. The static quenching constants (log K{sub S}) obtained are 3.3 {+-} 0.1, 4.9 {+-} 0.1, and 4.4 {+-} 0.1 for UO{sub 2}{sup 2+}, (UO{sub 2}){sub 2}(OH){sub 2}{sup 2+} and (UO{sub 2}){sub 3}(OH){sub 5}{sup +}, respectively. (orig.)

  17. Spectroscopic studies on U(VI)-salicylate complex formation with multiple equilibria

    International Nuclear Information System (INIS)

    Cha, W.; Cho, H.R.; Jung, E.C.; Park, K.K.; Kim, W.H.; Song, K.

    2012-01-01

    This study investigates multiple equilibria related to the formation of the U(VI)-salicylate complex in a pH range of 3.0-5.5 using UV-Vis absorption and fluorescence measurement techniques. The absorbance changes at the characteristic charge-transfer bands of the complex were monitored, and the results indicated the presence of multiple equilibria and the formation of both 1:1 and 1:2 (U(VI):salicylate) complexes possessing bi-dentate chelate structures. The determined step-wise formation constants (log K 1:1 and log K 1:2 ) are as follows: 12.5 ± 0.1 and 11.4 ± 0.2 for salicylate, 11.2 ± 0.1 and 10.1 ± 0.2 for 5-sulfosalicylate, and 12.4 ± 0.1 and 11.4 ± 0.1 for 2,6-dihydroxybenzoate, respectively. The molar absorptivities of the complexes are also provided. Furthermore, time-resolved laser-induced luminescence spectra of U(VI) species demonstrate the presence of both a dynamic and static quenching process upon the addition of a salicylate ligand. Particularly for the luminescent hydroxouranyl species, a strong static quenching effect is observed. The results suggest that both the UO 2 (HSal) + and the U(VI)-Sal chelate complexes serve as ground-state complexes that induce static quenching. The Stern-Volmer parameters were derived based on the measured luminescent intensity and lifetime data. The static quenching constants (log K S ) obtained are 3.3 ± 0.1, 4.9 ± 0.1, and 4.4 ± 0.1 for UO 2 2+ , (UO 2 ) 2 (OH) 2 2+ and (UO 2 ) 3 (OH) 5 + , respectively. (orig.)

  18. Computational screening of mixed metal halide ammines

    DEFF Research Database (Denmark)

    Jensen, Peter Bjerre; Lysgaard, Steen; Quaade, Ulrich

    2013-01-01

    Metal halide ammines, e.g. Mg(NH3)6Cl2 and Sr(NH3)8Cl2, can reversibly store ammonia, with high volumetric hydrogen storage capacities. The storage in the halide ammines is very safe, and the salts are therefore highly relevant as a carbon-free energy carrier in future transportation infrastructure...... selection. The GA is evolving from an initial (random) population and selecting those with highest fitness, a function based on e.g. stability, release temperature and storage capacity. The search space includes all alkaline, alkaline earth, 3d and 4d metals and the four lightest halides. In total...... the search spaces consists of millions combinations, which makes a GA ideal, to reduce the number of necessary calculations. We are screening for a one step release from either a hexa or octa ammine, and we have found promising candidates, which will be further investigated ? both computationally...

  19. Muonium centers in the alkali halides

    International Nuclear Information System (INIS)

    Baumeler, H.; Kiefl, R.F.; Keller, H.; Kuendig, W.; Odermatt, W.; Patterson, B.D.; Schneider, J.W.; Savic, I.M.

    1986-01-01

    Muonium centers (Mu) in single crystals and powdered alkali halides have been studied using the high-timing-resolution transverse field μSR technique. Mu has been observed and its hyperfine parameter (HF) determined in every alkali halide. For the rocksalt alkali halides, the HF parameter A μ shows a systematic dependence on the host lattice constant. A comparison of the Mu HF parameter with hydrogen ESR data suggests that the Mu center is the muonic analogue of the interstitial hydrogen H i 0 -center. The rate of Mu diffusion can be deduced from the motional narrowing of the nuclear hyperfine interaction. KBr shows two different Mu states, a low-temperature Mu I -state and a high-temperature Mu II -state. (orig.)

  20. Thermodynamics of mixed-ligand complex formation of mercury (II) ethylenediaminetetraacetate with amino acids in solution

    Energy Technology Data Exchange (ETDEWEB)

    Pyreu, Dmitrii, E-mail: pyreu@mail.ru [Department of Inorganic and Analytic Chemistry, Ivanovo State University, Ermak 39, Ivanovo 153025 (Russian Federation); Kozlovskii, Eugenii [Department of Inorganic and Analytic Chemistry, Ivanovo State University, Ermak 39, Ivanovo 153025 (Russian Federation); Gruzdev, Matvei; Kumeev, Roman [Institute of Solution Chemistry, Ivanovo (Russian Federation)

    2012-11-20

    Highlights: Black-Right-Pointing-Pointer Stable mixed ligand complexes of HgEdta with amino acids at physiological pH value. Black-Right-Pointing-Pointer The thermodynamic and NMR data evident the ambidentate coordination mode of arginine. Black-Right-Pointing-Pointer Participation of the guanidinic group of Arg in coordination process. Black-Right-Pointing-Pointer Binuclear complexes (HgEdta){sub 2}L with the bridging function of amino acid. - Abstract: The mixed-ligand complex formation in the systems Hg{sup 2+} - Edta{sup 4-} - L{sup -}(L = Arg, Orn, Ser) has been studied by means of calorimetry, pH-potentiometry and NMR spectroscopy in aqueous solution at 298.15 K and the ionic strength of I = 0.5 (KNO{sub 3}). The thermodynamic parameters of formation of the HgEdtaL, HgEdtaHL and (HgEdta){sub 2}L complexes have been determined. The most probable coordination mode for the complexone and the amino acid in the mixed-ligand complexes was discussed.

  1. Polarografic study about the complex formation between indium (III) and sodium azide, in aqueous media

    International Nuclear Information System (INIS)

    Tokoro, R.; Bertotti, M.

    1988-01-01

    The present work is a branch of the main work concerned with the complex formation between several metal cations and azide ligand in aqueous media. The polarographic behavior of indium in azide system showed the tendency of complexation. Using polarographic method to determine the half potential of indium at each analytical concentration afforded experimental data to evaluate the constants. The azide concentrations was modified from 1 m to 100 m , the ionic strength held at 2,0 M with sodium perchlorate, indium concentration 7.892 x 10 -4 M, and temperature kept constant at 25,0 0 C. (author) [pt

  2. Formation of multiple focal spots using a high NA lens with a complex spiral phase mask

    Science.gov (United States)

    Lalithambigai, K.; Anbarasan, P. M.; Rajesh, K. B.

    2014-07-01

    The formation of a transversally polarized beam by transmitting a tightly focused double-ring-shaped azimuthally polarized beam through a complex spiral phase mask and high numerical aperture lens is presented based on vector diffraction theory. The generation of transversally polarized focal spot segment splitting and multiple focal spots is illustrated numerically. Moreover, we found that a properly designed complex spiral phase mask can move the focal spots along the optical axis in the z direction. Therefore, one can achieve a focal segment of two, three or multiple completely transversely polarized focal spots, which finds applications in optical trapping and in material processing technologies.

  3. Regularity in the changes of the thermodynamic functions associated with the formation of mononuclear complexes

    International Nuclear Information System (INIS)

    Mihailov, M.H.; Mihailova, V.T.; Strezov, A.S.; Taskaeva, M.I.

    1979-01-01

    Regularities for the changes of the free energy ΔG, enthalpy ΔH enthropy ΔS have been derived, associated with the complex formation processes in metal-ligand systems whose stability constants of the consecutive mononuclear compelxes ML, ML 2 , ML 3 , ML 4 ...MLsub(n) satisfy the relation βn = A an/n (n = 1,2,3... N) where βn is the overall stability constant of the MLsub(n) complex, n is the number of ligands (1 [de

  4. Electrochemical specific adsorption of halides on Cu 111, 100, and 211: A Density Functional Theory study

    International Nuclear Information System (INIS)

    McCrum, Ian T.; Akhade, Sneha A.; Janik, Michael J.

    2015-01-01

    The specific adsorption of ions onto electrode surfaces can affect electrocatalytic reactions. Density functional theory is used to investigate the specific adsorption of aqueous F − , Cl − , Br − , and I − onto Cu (111), (100), and (211) surfaces. The adsorption is increasingly favorable in the order of F − < Cl − < Br − < I − . The adsorption has a weak dependence on the surface facet, with adsorption most favorable on Cu (100) and least favorable on Cu (111). Potential ranges where specific adsorption would be expected on each facet are reported. The thermodynamics of bulk copper halide (CuX, CuX 2 ) formation are also investigated as a function of potential. CuX formation occurs at potentials slightly more positive of halide specific adsorption and of copper oxidation in aqueous electrolytes. Specifically adsorbed halides and bulk CuX may be present during a variety of electrochemical reactions carried out over a Cu electrode in halide containing electrolyte solutions

  5. Green synthesis of ZnO nanoparticles via complex formation by using Curcuma longa extract

    Energy Technology Data Exchange (ETDEWEB)

    Fatimah, Is, E-mail: isfatimah@uii.ac.id; Yudha, Septian P.; Mutiara, Nur Afisa Lintang [Chemistry Department, Islamic University of Indonesia Kampus Terpadu UII, Jl. Kaliurang Km 14, Sleman, Yogyakarta (Indonesia)

    2016-02-08

    Synthesis of ZnO nanoparticles(NPs) were conducted via Zn(II) complex formation by using Curcuma longa extract as template. Curcuma longa extract has the ability to form zinc ions complex with curcumin as ligating agent. Study on synthesis was conducted by monitoring thermal degradation of the material. Successful formation of zinc oxide nanoparticles was confirmed by employing x-ray diffraction, surface area analysis and transmission electron microscopy(TEM) studies. From the XRD analysis it is denoted that ZnO in hexagonal wurtzite phase was formed and particle size was varied as varied temperature. The data are also confirmed by TEM analysis which shows the particle sie at the range 20-80nm. The NPs exhibited excelent photocatalytic activity for methylene blue degradation and also significant antibacterial activity for Eschericia coli. The activity in methylene blue degradation was also confirmed from fast chemical oxygen demand (COD) reduction.

  6. Role of complex formation in the photosensitized degradation of DNA induced by N'-formylkynurenine

    International Nuclear Information System (INIS)

    Walrant, P.; Santus, R.; Charlier, M.

    1976-01-01

    N'-Formylkynurenine derivatives efficiently bind to DNA or polynucleotides. Homopolynucleotides and DNA displayed marked differences in the binding process. Association constants were derived which indicated that the oxidized indole ring is more strongly bound to DNA than the unoxidized one. Irradiation of such complexes with wavelengths greater than 320 nm induced pyrimidine dimer formation as well as DNA chain breaks. Complex formation is shown to play an important role in these photosensitized reactions. The photodynamic action of N-formylkynurenine on DNA constituents was negligible at neutral pH but guanine and xanthine derivatives were sensitizable at higher pH. Thymine dimer splitting can occur in aggregated frozen aqueous solutions of N'-formylkynurenine and thymine dimer but this photosensitized splitting was negligible in liquid solutions at room temperature. (author)

  7. Green synthesis of ZnO nanoparticles via complex formation by using Curcuma longa extract

    International Nuclear Information System (INIS)

    Fatimah, Is; Yudha, Septian P.; Mutiara, Nur Afisa Lintang

    2016-01-01

    Synthesis of ZnO nanoparticles(NPs) were conducted via Zn(II) complex formation by using Curcuma longa extract as template. Curcuma longa extract has the ability to form zinc ions complex with curcumin as ligating agent. Study on synthesis was conducted by monitoring thermal degradation of the material. Successful formation of zinc oxide nanoparticles was confirmed by employing x-ray diffraction, surface area analysis and transmission electron microscopy(TEM) studies. From the XRD analysis it is denoted that ZnO in hexagonal wurtzite phase was formed and particle size was varied as varied temperature. The data are also confirmed by TEM analysis which shows the particle sie at the range 20-80nm. The NPs exhibited excelent photocatalytic activity for methylene blue degradation and also significant antibacterial activity for Eschericia coli. The activity in methylene blue degradation was also confirmed from fast chemical oxygen demand (COD) reduction

  8. Green synthesis of ZnO nanoparticles via complex formation by using Curcuma longa extract

    Science.gov (United States)

    Fatimah, Is; Yudha, Septian P.; Mutiara, Nur Afisa Lintang

    2016-02-01

    Synthesis of ZnO nanoparticles(NPs) were conducted via Zn(II) complex formation by using Curcuma longa extract as template. Curcuma longa extract has the ability to form zinc ions complex with curcumin as ligating agent. Study on synthesis was conducted by monitoring thermal degradation of the material. Successful formation of zinc oxide nanoparticles was confirmed by employing x-ray diffraction, surface area analysis and transmission electron microscopy(TEM) studies. From the XRD analysis it is denoted that ZnO in hexagonal wurtzite phase was formed and particle size was varied as varied temperature. The data are also confirmed by TEM analysis which shows the particle sie at the range 20-80nm. The NPs exhibited excelent photocatalytic activity for methylene blue degradation and also significant antibacterial activity for Eschericia coli. The activity in methylene blue degradation was also confirmed from fast chemical oxygen demand (COD) reduction.

  9. Formation constants of binary complexes of lanthanides with 2-hydroxymethyl-benzimidazole

    Energy Technology Data Exchange (ETDEWEB)

    Nagendram, A; Omprakash, K L; Chandra Pal, A V; Reddy, M L.N.

    1988-03-01

    Proton-ligand and metal-ligand formation constants of binary complexes of La(III), Pr(III), Nd(III), Gd(III), Dy(III) and Y(III) with 2-hydroxymethylbenzimidazole have been determined pH-metrically in 50 per cent v/v aq dioxane medium at 30deg, 40deg and 50degC and I=0.1 M (NaClO/sub 4/). The theromdynamic parameters of complex formation have been evaluated. Stabilities (log ..beta../sub 2/ values) of the chelates increase with decrease in ionic radius of the metal (Dy(III) > Gd(III) > Y(III) > Nd(III) > Pr(III) > La(III)). (author). 7 refs.

  10. Conformation-Directed Formation of Self-Healing Diblock Copolypeptide Hydrogels via Polyion Complexation.

    Science.gov (United States)

    Sun, Yintao; Wollenberg, Alexander L; O'Shea, Timothy Mark; Cui, Yanxiang; Zhou, Z Hong; Sofroniew, Michael V; Deming, Timothy J

    2017-10-25

    Synthetic diblock copolypeptides were designed to incorporate oppositely charged ionic segments that form β-sheet-structured hydrogel assemblies via polyion complexation when mixed in aqueous media. The observed chain conformation directed assembly was found to be required for efficient hydrogel formation and provided distinct and useful properties to these hydrogels, including self-healing after deformation, microporous architecture, and stability against dilution in aqueous media. While many promising self-assembled materials have been prepared using disordered or liquid coacervate polyion complex (PIC) assemblies, the use of ordered chain conformations in PIC assemblies to direct formation of new supramolecular morphologies is unprecedented. The promising attributes and unique features of the β-sheet-structured PIC hydrogels described here highlight the potential of harnessing conformational order derived from PIC assembly to create new supramolecular materials.

  11. Formation of Polyelectrolyte Complex Colloid Particles between Chitosan and Pectin with Different Degree of Esterification

    Science.gov (United States)

    Wang, Hui; Sun, Hongyuan; He, Jieyu

    2017-12-01

    The effects of degree of esterification, pectin/chitosan ratio and pH on the formation of polyelectrolyte complex colloid particles between chitosan (CS) and pectin (PE) were investigated. Low methoxyl pectin (LPE) was achieved by de-esterifying high methoxyl pectin (HPE) with pectin methyl esterase. Turbidity titration and colorimetric method was used to determine the stability of complex colloid particles. The structure and morphology of complex particles were characterized by FTIR and TEM. When pectin solution was dropped into chitosan solution, complex colloidal dispersion was stable as PE/CS mass ratio was no more than 3:2. Colloidal particles of HPE-CS complex coagulated at larger ratio of PE/CS than LPE-CS. The maximum complex occurred at pH 6.1 for HPE-CS and pH 5.7 for LPE-CS, and decreasing pH leaded to the dissociation of complex particles. Electrostatic interactions between carboxyl groups on pectin and amino groups on chitosan were confirmed by FTIR. Colloidal particle sizes ranged from about 100 nm to 400 nm with spherical shape.

  12. EPR study of complex formation between copper (II) ions and sympathomimetic amines in aqueous solution

    Energy Technology Data Exchange (ETDEWEB)

    Preoteasa, E.A. [Inst. of Atomic Physics, IFIN, Bucharest (Romania); Duliu, O.G.; Grecu, V.V. [Bucharest, Univ. (Romania). Dept. of Atomic and Nuclear Physics

    1997-07-01

    The complex formation between sympathomimetic amines (SA): adrenaline (AD), noradrenaline (NA), dopamine (DA), ephedrine (ED) and p-tyramine (pTA), and Cu(II) ion in aqueous solution has been studied by X-band EPR at room temperature. Excepting pTA, all investigated SA yielded two types of complexes in different pH domains. All complexes consistent with a ligand fields having a distorted octahedral symmetry, i.e., hexacoordination of Cu(II). The covalence coefficient calculated from the isotropic g and A values has shown strong ionic sigma-type ligand bonds. A structural model with the Cu(II) ion bound by four catecholic O(hydroxy) atoms for the low pH complexes of AD, NA and DA is proposed. For the high pH complexes of the former compounds as well as for both Ed complexes, the authors suppose Cu(II) bound by two N (amino) and two O (hydroxy) atoms. The spectra are consistent to water binding on the longitudinal octahedron axis in all compounds excepting the high pH complex of Ed, where OH2- ions are bound. Possible implications for the SA-cell receptors interactions are discussed.

  13. Peculiarities of litter invertebrates’ multispecies complexes formation on the Khortitsa island (Zaporizhzhya province

    Directory of Open Access Journals (Sweden)

    D. О. Fedorchenko

    2008-02-01

    Full Text Available Peculiarities of litter invertebrates’ complexes formation under conditions of the Khortitsa National Reserve (Zaporizhzhya province are studied. The dispersion of taxonomic groups of different levels (families and species in litter mesofauna is swayed by the inter- and intrasystem factors; the largest influence has the power of litter and its humidity. The rate of ecological factors’ influence at different taxonomic levels may diverge.

  14. Cytochrome P-450 complex formation in rat liver by the antibiotic tiamulin.

    OpenAIRE

    Witkamp, R F; Nijmeijer, S M; van Miert, A S

    1996-01-01

    Tiamulin is a semisynthetic diterpene antibiotic frequently used in farm animals. The drug has been shown to produce clinically important--often lethal--interactions with other compounds. It has been suggested that this is caused by a selective inhibition of oxidative drug metabolism via the formation of a cytochrome P-450 metabolic intermediate complex. In the present study, rats were treated orally for 6 days with tiamulin at two different doses: 40 and 226 mg/kg of body weight. For compari...

  15. Simultaneous measurement of amyloid fibril formation by dynamic light scattering and fluorescence reveals complex aggregation kinetics.

    Directory of Open Access Journals (Sweden)

    Aaron M Streets

    Full Text Available An apparatus that combines dynamic light scattering and Thioflavin T fluorescence detection is used to simultaneously probe fibril formation in polyglutamine peptides, the aggregating subunit associated with Huntington's disease, in vitro. Huntington's disease is a neurodegenerative disorder in a class of human pathologies that includes Alzheimer's and Parkinson's disease. These pathologies are all related by the propensity of their associated protein or polypeptide to form insoluble, β-sheet rich, amyloid fibrils. Despite the wide range of amino acid sequence in the aggregation prone polypeptides associated with these diseases, the resulting amyloids display strikingly similar physical structure, an observation which suggests a physical basis for amyloid fibril formation. Thioflavin T fluorescence reports β-sheet fibril content while dynamic light scattering measures particle size distributions. The combined techniques allow elucidation of complex aggregation kinetics and are used to reveal multiple stages of amyloid fibril formation.

  16. Electrochemically reduced titanocene dichloride as a catalyst of reductive dehalogenation of organic halides

    International Nuclear Information System (INIS)

    Magdesieva, Tatiana V.; Graczyk, Magdalena; Vallat, Alain; Nikitin, Oleg M.; Demyanov, Petr I.; Butin, Kim P.; Vorotyntsev, Mikhail A.

    2006-01-01

    We have studied a reaction between the reduced form of titanocene dichloride (Cp 2 TiCl 2 ) and a group of organic halides: benzyl derivatives (4-X-C 6 H 4 CH 2 Cl, X = H, NO 2 , CH 3 ; 4-X-C 6 H 4 CH 2 Br, X = H, NO 2 , PhC(O); 4-X-C 6 H 4 CH 2 SCN, X = H, NO 2 ) as well as three aryl halides (4-NO 2 C 6 H 4 Hal, Hal = Cl, Br; 4-CH 3 O-C 6 H 4 Cl). It has been shown that the electrochemical reduction of Cp 2 TiCl 2 in the presence of these benzyl halides leads to a catalytic cycle resulting in the reductive dehalogenation of these organic substrates to yield mostly corresponding toluene derivatives as the main product. No dehalogenation has been observed for aryl derivatives. Based on electrochemical data and digital simulation, possible schemes of the catalytic process have been outlined. For non-substituted benzyl halides halogen atom abstraction is a key step. For the reaction of nitrobenzyl halides the complexation of Ti(III) species with the nitro group takes place, with the electron transfer from Ti(III) to this group (owing to its highest coefficient in LUMO of the nitro benzyl halide) followed by an intramolecular dissociative electron redistribution in the course of the heterolytic C-Hal bond cleavage. The results for reduced titanocene dichloride centers immobilized inside a polymer film showed that the catalytic reductive dehalogenation of the p-nitrobenzyl chloride does occur but with a low efficiency because of the partial deactivation of the film due to the blocking of the electron charge transport between the electrode and catalytic centers

  17. Nephrin regulates lamellipodia formation by assembling a protein complex that includes Ship2, filamin and lamellipodin.

    Directory of Open Access Journals (Sweden)

    Madhusudan Venkatareddy

    Full Text Available Actin dynamics has emerged at the forefront of podocyte biology. Slit diaphragm junctional adhesion protein Nephrin is necessary for development of the podocyte morphology and transduces phosphorylation-dependent signals that regulate cytoskeletal dynamics. The present study extends our understanding of Nephrin function by showing in cultured podocytes that Nephrin activation induced actin dynamics is necessary for lamellipodia formation. Upon activation Nephrin recruits and regulates a protein complex that includes Ship2 (SH2 domain containing 5' inositol phosphatase, Filamin and Lamellipodin, proteins important in regulation of actin and focal adhesion dynamics, as well as lamellipodia formation. Using the previously described CD16-Nephrin clustering system, Nephrin ligation or activation resulted in phosphorylation of the actin crosslinking protein Filamin in a p21 activated kinase dependent manner. Nephrin activation in cell culture results in formation of lamellipodia, a process that requires specialized actin dynamics at the leading edge of the cell along with focal adhesion turnover. In the CD16-Nephrin clustering model, Nephrin ligation resulted in abnormal morphology of actin tails in human podocytes when Ship2, Filamin or Lamellipodin were individually knocked down. We also observed decreased lamellipodia formation and cell migration in these knock down cells. These data provide evidence that Nephrin not only initiates actin polymerization but also assembles a protein complex that is necessary to regulate the architecture of the generated actin filament network and focal adhesion dynamics.

  18. The Effect of Radiation "Memory" in Alkali-Halide Crystals

    Science.gov (United States)

    Korovkin, M. V.; Sal'nikov, V. N.

    2017-01-01

    The exposure of the alkali-halide crystals to ionizing radiation leads to the destruction of their structure, the emergence of radiation defects, and the formation of the electron and hole color centers. Destruction of the color centers upon heating is accompanied by the crystal bleaching, luminescence, and radio-frequency electromagnetic emission (REME). After complete thermal bleaching of the crystal, radiation defects are not completely annealed, as the electrons and holes released from the color centers by heating leave charged and locally uncompensated defects. Clusters of these "pre centers" lead to electric microheterogeneity of the crystal, the formation of a quasi-electret state, and the emergence of micro-discharges accompanied by radio emission. The generation of REME associated with residual defectiveness, is a manifestation of the effect of radiation "memory" in dielectrics.

  19. FORMATION AND RECONDENSATION OF COMPLEX ORGANIC MOLECULES DURING PROTOSTELLAR LUMINOSITY OUTBURSTS

    International Nuclear Information System (INIS)

    Taquet, Vianney; Wirström, Eva S.; Charnley, Steven B.

    2016-01-01

    During the formation of stars, the accretion of surrounding material toward the central object is thought to undergo strong luminosity outbursts followed by long periods of relative quiescence, even at the early stages of star formation when the protostar is still embedded in a large envelope. We investigated the gas-phase formation and recondensation of the complex organic molecules (COMs) di-methyl ether and methyl formate, induced by sudden ice evaporation processes occurring during luminosity outbursts of different amplitudes in protostellar envelopes. For this purpose, we updated a gas-phase chemical network forming COMs in which ammonia plays a key role. The model calculations presented here demonstrate that ion–molecule reactions alone could account for the observed presence of di-methyl ether and methyl formate in a large fraction of protostellar cores without recourse to grain-surface chemistry, although they depend on uncertain ice abundances and gas-phase reaction branching ratios. In spite of the short outburst timescales of about 100 years, abundance ratios of the considered species higher than 10% with respect to methanol are predicted during outbursts due to their low binding energies relative to water and methanol which delay their recondensation during cooling. Although the current luminosity of most embedded protostars would be too low to produce complex organics in the hot-core regions that are observable with current sub-millimetric interferometers, previous luminosity outburst events would induce the formation of COMs in extended regions of protostellar envelopes with sizes increasing by up to one order of magnitude

  20. Formation and Recondensation of Complex Organic Molecules during Protostellar Luminosity Outbursts

    Science.gov (United States)

    Taquet, Vianney; Wirström, Eva S.; Charnley, Steven B.

    2016-04-01

    During the formation of stars, the accretion of surrounding material toward the central object is thought to undergo strong luminosity outbursts followed by long periods of relative quiescence, even at the early stages of star formation when the protostar is still embedded in a large envelope. We investigated the gas-phase formation and recondensation of the complex organic molecules (COMs) di-methyl ether and methyl formate, induced by sudden ice evaporation processes occurring during luminosity outbursts of different amplitudes in protostellar envelopes. For this purpose, we updated a gas-phase chemical network forming COMs in which ammonia plays a key role. The model calculations presented here demonstrate that ion-molecule reactions alone could account for the observed presence of di-methyl ether and methyl formate in a large fraction of protostellar cores without recourse to grain-surface chemistry, although they depend on uncertain ice abundances and gas-phase reaction branching ratios. In spite of the short outburst timescales of about 100 years, abundance ratios of the considered species higher than 10% with respect to methanol are predicted during outbursts due to their low binding energies relative to water and methanol which delay their recondensation during cooling. Although the current luminosity of most embedded protostars would be too low to produce complex organics in the hot-core regions that are observable with current sub-millimetric interferometers, previous luminosity outburst events would induce the formation of COMs in extended regions of protostellar envelopes with sizes increasing by up to one order of magnitude.

  1. FORMATION AND RECONDENSATION OF COMPLEX ORGANIC MOLECULES DURING PROTOSTELLAR LUMINOSITY OUTBURSTS

    Energy Technology Data Exchange (ETDEWEB)

    Taquet, Vianney [Leiden Observatory, Leiden University, P.O. Box 9513, 2300-RA Leiden (Netherlands); Wirström, Eva S. [Department of Earth and Space Sciences, Chalmers University of Technology, Onsala Space Observatory, SE-439 92 Onsala (Sweden); Charnley, Steven B. [Astrochemistry Laboratory and The Goddard Center for Astrobiology, Mailstop 691, NASA Goddard Space Flight Center, 8800 Greenbelt Road, Greenbelt, MD 20770 (United States)

    2016-04-10

    During the formation of stars, the accretion of surrounding material toward the central object is thought to undergo strong luminosity outbursts followed by long periods of relative quiescence, even at the early stages of star formation when the protostar is still embedded in a large envelope. We investigated the gas-phase formation and recondensation of the complex organic molecules (COMs) di-methyl ether and methyl formate, induced by sudden ice evaporation processes occurring during luminosity outbursts of different amplitudes in protostellar envelopes. For this purpose, we updated a gas-phase chemical network forming COMs in which ammonia plays a key role. The model calculations presented here demonstrate that ion–molecule reactions alone could account for the observed presence of di-methyl ether and methyl formate in a large fraction of protostellar cores without recourse to grain-surface chemistry, although they depend on uncertain ice abundances and gas-phase reaction branching ratios. In spite of the short outburst timescales of about 100 years, abundance ratios of the considered species higher than 10% with respect to methanol are predicted during outbursts due to their low binding energies relative to water and methanol which delay their recondensation during cooling. Although the current luminosity of most embedded protostars would be too low to produce complex organics in the hot-core regions that are observable with current sub-millimetric interferometers, previous luminosity outburst events would induce the formation of COMs in extended regions of protostellar envelopes with sizes increasing by up to one order of magnitude.

  2. Thermodynamics of formation for the 18-crown-6-triglycine molecular complex in water-dimethylsulfoxide solvents

    Science.gov (United States)

    Usacheva, T. R.; Lan, Pham Thi; Sharnin, V. A.

    2014-06-01

    The effect of a water-dimethylsulfoxide (DMSO) solvent on the formation of a molecular complex of 18-crown-6 (18C6) with triglycine (diglycylglycine, 3Gly) is studied via calorimetric titration. It is found that switching from water to an H2O-DMSO mixture with DMSO mole fraction of 0.30 is accompanied by a monotonic increase in the stability of [3Gly18C6] complex, from log K ∘ = 1.10 to log K ∘ = 2.44, and an increase in the exothermicity of the reaction of its formation, from -5.9 to -16.9 kJ/mol. It is shown that the [3Gly18C6] complex exhibits enthalpy stabilization with negative values of enthalpy and entropy over the investigated range of H2O-DMSO solvents. Analysis of the reagents' solvation characteristics reveals that the increase in the reaction's exothermicity of transfer is due to differences in the solvation of [3Gly18C6] and 18C6 with a small solvation contribution from 3Gly. It is concluded that the change in the Gibbs energy of the reaction 3Glysolv + 18C6solv ↔ [3Gly18C6]solv is due to differences in the change in the solvation state of the complex and the peptide (Δtr G ∘([3Gly18C6])-Δtr G ∘(3Gly)).

  3. Accessibility of tyrosyl residues altered by formation of the histone 2A/2B complex

    International Nuclear Information System (INIS)

    Callaway, J.E.; Ho, Y.S.; DeLange, R.J.

    1985-01-01

    The availability of tyrosyl residues to surface iodination was analyzed for histone 2A (H2A), histone 2B (H2B), and the H2A/H2B complex. When H2A is free in solution (200 mM NaCl, pH 7.4) tyrosine-39 and one or both tyrosines-50 and -57 were readily iodinated. Tyrosines-83 and -121 of H2B were iodinated, both when the histone was free in solution and when it was associated with H2A, while tyrosines-37, -40, and -42 of H2B were not iodinated under either condition. When H2A and H2B were associated or covalently cross-linked, all tyrosyl residues of H2A were unavailable for iodination. The authors also found that the iodination of nondenatured H2A and H2B did not inhibit formation of the H2A/H2B complex. These results indicate that the amino-terminal regions of the hydrophobic portions of H2A and H2B undergo significant conformational changes upon formation of the H2A/H2B complex. These conformational shifts occur in the same region of the H2A/H2B complex that contains a contact site between H2A and H2B in the nucleosome, thus indicating an involvement of this region in chromatin assembly

  4. Interdependency of formation and localisation of the Min complex controls symmetric plastid division.

    Science.gov (United States)

    Maple, Jodi; Møller, Simon G

    2007-10-01

    Plastid division represents a fundamental biological process essential for plant development; however, the molecular basis of symmetric plastid division is unclear. AtMinE1 plays a pivotal role in selection of the plastid division site in concert with AtMinD1. AtMinE1 localises to discrete foci in chloroplasts and interacts with AtMinD1, which shows a similar localisation pattern. Here, we investigate the importance of Min protein complex formation during the chloroplast division process. Dissection of the assembly of the Min protein complex and determination of the interdependency of complex assembly and localisation in planta allow us to present a model of the molecular basis of selection of the division site in plastids. Moreover, functional analysis of AtMinE1 in bacteria demonstrates the level of functional conservation and divergence of the plastidic MinE proteins.

  5. Self-trapped holes in alkali silver halide crystals

    International Nuclear Information System (INIS)

    Awano, T.; Ikezawa, M.; Matsuyama, T.

    1995-01-01

    γ-Ray irradiation at 77 K induces defects in M 2 AgX 3 (M=Rb, K and NH 4 ; X=Br and I) crystals. The irradiation induces self-trapped holes of the form of I 0 in the case of alkali silver iodides, and (halogen) 2 - and (halogen) 0 in the case of ammonium silver halides. The (halogen) 0 is weakly coupled with the nearest alkali metal ion or ammonium ion. It is able to be denoted as RbI + , KI + , NH 4 I + or NH 4 Br + . The directions of hole distribution of (halogen) 2 - and (halogen) 0 were different in each case of the alkali silver iodides, ammonium silver halides and mixed crystal of them. The (halogen) 0 decayed at 160 K in annealing process. The (halogen) 2 - was converted into another form of (halogen) 2 - at 250 K and this decayed at 310 K. A formation of metallic layers was observed on the crystal surface parallel with the c-plane of (NH 4 ) 2 AgI 3 irradiated at room temperature. (author)

  6. The influence of the formation pitching angle on the area for employing the KM-103 complex

    Energy Technology Data Exchange (ETDEWEB)

    Shulga, A I; Teryanik, V I

    1982-01-01

    Mining sections in which the KM-103 powered complexes are used should be selected and planned on the basis of the actual pitching angle of the formation, and the anticipated vertical and lateral rock displacement in the workings. With the shapes and dimensions characteristic of galley cross-sections which are reinforced by arched 3 and 5-arm supports, and with the anticipated values of rock displacement, a maximum pitching angle exists, above which it is difficult to facilitate the drives of stope face conveyors. For arch-shaped galleys, which are reinforced by an arched 5-arm support, the maximum pitching angle of the formation is greater than in galleys which are reinforced by arched three-arm supports, with equal cross-sections even with large rock displacements. An increase in the cross-section of upwards of 13 square meters does not result in an increase in the maximum pitching angle of the formation due to the extension of the support roof timber. In the trapezoidal workings which are supported by the KPS-3 supports and are worked without employing roof blasting, the maximum pitching angle of the formation is 12 degrees. The thickness of the formation worked must be less than 1.1 meter.

  7. Study of inclusion complex formation between chlorpromazine hydrochloride, as an antiemetic drug, and β-cyclodextrin, using conductometric technique

    International Nuclear Information System (INIS)

    Rafati, Amir Abbas; Hamnabard, Nazanin; Ghasemian, Ensieh; Nojini, Zabiolah Bolboli

    2009-01-01

    The behavior of micellization of chlorpromazine hydrochloride (CPH) as an antiemetic drug and its inclusion complex formation with β-cyclodextrin (β-CD) was studied using conductometric technique. The binding or association constant of the complexation equilibrium is evaluated from conductometric measurements by using a nonlinear regression method. The resulting K values for micellization as well as complexation are analyzed. The experiments were carried out at different temperatures. It has been found that CPH form only the 1:1 complex. The association constant values are used for evaluation of thermodynamic parameters of complexation, such as ΔG complex o , ΔH complex o and ΔS complex o .

  8. Functional cooperation between FACT and MCM is coordinated with cell cycle and differential complex formation

    Directory of Open Access Journals (Sweden)

    Lin Chih-Li

    2010-02-01

    Full Text Available Abstract Background Functional cooperation between FACT and the MCM helicase complex constitutes an integral step during DNA replication initiation. However, mode of regulation that underlies the proper functional interaction of FACT and MCM is poorly understood. Methods & Results Here we present evidence indicating that such interaction is coordinated with cell cycle progression and differential complex formation. We first demonstrate the existence of two distinct FACT-MCM subassemblies, FACT-MCM2/4/6/7 and FACT-MCM2/3/4/5. Both complexes possess DNA unwinding activity and are subject to cell cycle-dependent enzymatic regulation. Interestingly, analysis of functional attributes further suggests that they act at distinct, and possibly sequential, steps during origin establishment and replication initiation. Moreover, we show that the phosphorylation profile of the FACT-associated MCM4 undergoes a cell cycle-dependent change, which is directly correlated with the catalytic activity of the FACT-MCM helicase complexes. Finally, at the quaternary structure level, physical interaction between FACT and MCM complexes is generally dependent on persistent cell cycle and further stabilized upon S phase entry. Cessation of mitotic cycle destabilizes the complex formation and likely leads to compromised coordination and activities. Conclusions Together, our results correlate FACT-MCM functionally and temporally with S phase and DNA replication. They further demonstrate that enzymatic activities intrinsically important for DNA replication are tightly controlled at various levels, thereby ensuring proper progression of, as well as exit from, the cell cycle and ultimately euploid gene balance.

  9. cAMP prevents TNF-induced apoptosis through inhibiting DISC complex formation in rat hepatocytes

    International Nuclear Information System (INIS)

    Bhattacharjee, Rajesh; Xiang, Wenpei; Wang, Yinna; Zhang, Xiaoying; Billiar, Timothy R.

    2012-01-01

    Highlights: ► cAMP blocks cell death induced by TNF and actinomycin D in cultured hepatocytes. ► cAMP blocks NF-κB activation induced by TNF and actinomycin D. ► cAMP blocks DISC formation following TNF and actinomycin D exposure. ► cAMP blocks TNF signaling at a proximal step. -- Abstract: Tumor necrosis factor α (TNF) is a pleiotropic proinflammatory cytokine that plays a role in immunity and the control of cell proliferation, cell differentiation, and apoptosis. The pleiotropic nature of TNF is due to the formation of different signaling complexes upon the binding of TNF to its receptor, TNF receptor type 1 (TNFR1). TNF induces apoptosis in various mammalian cells when the cells are co-treated with a transcription inhibitor like actinomycin D (ActD). When TNFR1 is activated, it recruits an adaptor protein, TNF receptor-associated protein with death domain (TRADD), through its cytoplasmic death effector domain (DED). TRADD, in turn, recruits other signaling proteins, including TNF receptor-associated protein 2 (TRAF2) and receptor-associated protein kinase (RIPK) 1, to form a complex. Subsequently, this complex combines with FADD and procaspase-8, converts into a death-inducing signaling complex (DISC) to induce apoptosis. Cyclic AMP (cAMP) is a second messenger that regulates various cellular processes such as cell proliferation, gene expression, and apoptosis. cAMP analogues are reported to act as anti-apoptotic agents in various cell types, including hepatocytes. We found that a cAMP analogue, dibutyryl cAMP (db-cAMP), inhibits TNF + ActD-induced apoptosis in rat hepatocytes. The protein kinase A (PKA) inhibitor KT-5720 reverses this inhibitory effect of cAMP on apoptosis. Cytoprotection by cAMP involves down-regulation of various apoptotic signal regulators like TRADD and FADD and inhibition of caspase-8 and caspase-3 cleavage. We also found that cAMP exerts its affect at the proximal level of TNF signaling by inhibiting the formation of the DISC

  10. cAMP prevents TNF-induced apoptosis through inhibiting DISC complex formation in rat hepatocytes

    Energy Technology Data Exchange (ETDEWEB)

    Bhattacharjee, Rajesh [Department of Surgery, University of Pittsburgh Medical Center, Pittsburgh, PA 15213 (United States); Xiang, Wenpei [Department of Surgery, University of Pittsburgh Medical Center, Pittsburgh, PA 15213 (United States); Family Planning Research Institute, Tongji Medical College, Huazhong University of Science and Technology, Wuhan 430030, People' s Republic of China (China); Wang, Yinna [Vascular Medicine Institute, University of Pittsburgh School of Medicine, 10051-5A BST 3, 3501 Fifth Avenue, Pittsburgh, PA 15261 (United States); Zhang, Xiaoying [Department of Medicine/Endocrinology Division, University of Pittsburgh Medical Center, 200 Lothrop St., Pittsburgh, PA 15213 (United States); Billiar, Timothy R., E-mail: billiartr@upmc.edu [Department of Surgery, University of Pittsburgh Medical Center, Pittsburgh, PA 15213 (United States)

    2012-06-22

    Highlights: Black-Right-Pointing-Pointer cAMP blocks cell death induced by TNF and actinomycin D in cultured hepatocytes. Black-Right-Pointing-Pointer cAMP blocks NF-{kappa}B activation induced by TNF and actinomycin D. Black-Right-Pointing-Pointer cAMP blocks DISC formation following TNF and actinomycin D exposure. Black-Right-Pointing-Pointer cAMP blocks TNF signaling at a proximal step. -- Abstract: Tumor necrosis factor {alpha} (TNF) is a pleiotropic proinflammatory cytokine that plays a role in immunity and the control of cell proliferation, cell differentiation, and apoptosis. The pleiotropic nature of TNF is due to the formation of different signaling complexes upon the binding of TNF to its receptor, TNF receptor type 1 (TNFR1). TNF induces apoptosis in various mammalian cells when the cells are co-treated with a transcription inhibitor like actinomycin D (ActD). When TNFR1 is activated, it recruits an adaptor protein, TNF receptor-associated protein with death domain (TRADD), through its cytoplasmic death effector domain (DED). TRADD, in turn, recruits other signaling proteins, including TNF receptor-associated protein 2 (TRAF2) and receptor-associated protein kinase (RIPK) 1, to form a complex. Subsequently, this complex combines with FADD and procaspase-8, converts into a death-inducing signaling complex (DISC) to induce apoptosis. Cyclic AMP (cAMP) is a second messenger that regulates various cellular processes such as cell proliferation, gene expression, and apoptosis. cAMP analogues are reported to act as anti-apoptotic agents in various cell types, including hepatocytes. We found that a cAMP analogue, dibutyryl cAMP (db-cAMP), inhibits TNF + ActD-induced apoptosis in rat hepatocytes. The protein kinase A (PKA) inhibitor KT-5720 reverses this inhibitory effect of cAMP on apoptosis. Cytoprotection by cAMP involves down-regulation of various apoptotic signal regulators like TRADD and FADD and inhibition of caspase-8 and caspase-3 cleavage. We also found

  11. Studies on coordination and addition compounds and anti microbial activity of some mixed ligand complexes of Au(III), Mo(II), Co(II) and Cd(II) with dibasic acid and heterocyclic amines and addition compounds of As(III) and Sb(III) halides with benzamide and acetophenon

    International Nuclear Information System (INIS)

    Hossain, M.; Sultana, C.; Saidul Islam, M.; Zakaria, C.M.

    2008-06-01

    Three new mixed ligand complexes of Au(III) and Mo(II) with dibasic acid e.g., homophthalic acid, oxalic acid and heterocylic amines e.g., quinonine, iso-quinonine, bipyridine, Phenylanaline and the two new addition compounds of As(III) and Sb(III) halides with N-donor ligands viz. benzamide and acetophenone and one complex [Cd(DPH)(IQ) 2 ], where IQ = Iso-quinoline and DPH = Deprotonated phthalic acid have been prepared according to the procedure in the literature. Their conventional physical and chemical analyses have been done. Their antibacterial studies against nine gram positive and five gram negative pathogenic bacteria and antifungal activities against eight plant and three human fungi have been evaluated. Kanamycin and Nystatin have been used as a standard for carrying out experiments of antibacterial and antifungal activities, respectively. The minimum inhibitory concentration (MIC) values of these compounds, as antibiotic against two gram positive and two gram negative pathogenic bacteria, have also been carried out and in this case, Amoxacilin antibiotic has been used as a standard antibiotic. (author)

  12. Formation constants of lanthanide(III)- aminopolycarboxylate- ATP mixed ligand complexes and their systematics

    International Nuclear Information System (INIS)

    Verma, Sangeeta; Limaye, S.N.; Saxena, M.C.

    1993-01-01

    Formation constants (log Ksub(MAL)sup(MA), log Ksub(ML)sup(M) and log Ksub(ML)sup(ML) of mixed ligand lanthanide(III) complexes of the type [Ln(III).A.ATP[ 2 , where LN(III)=La 3+ , Ce 3+ , Pr 3+ , Nd 3+ , Sm 3+ , Eu 3+ , Gd 3+ , Tb 3+ or Dy 3+ ' A=NTA(nitrilotriacetate) or HEDTA (2-hydroxyethylethylenediamine triacetate) and ATP=adenosine 5'-triphosphate (L), and of the binary [Ln(III).ATP[ and [Ln(III).(ATP) 2 [ complexes have been determined by potentiometric pH titrations using the Irving-Rossotti approach at three temperatures 20, 30 and 40 degC and at a fixed ionic strength, I=0.2 mol dm -3 (NAclO 4 ). The solution stabilities (log Ksub(MAL)sup(MA) values) are influenced by the electrostatic effect involved in ternary complexation and increase with temperature. The enthalpy factor (ΔH) has been found to be small but unfavourable and the entropy factor (ΔS) large and favourable. The log Ksub(MAL)sup(MA) values lie in the order NTA>HEDTA with respect to A and La 3+ 3+ 3+ 3+ 3+ 3+ >Gd 3+ 3+ 3+ with respect to lanthanides. Tetrad effect is present in the formation constant values; its magnitude has been found to lie in the sequence f 7 >f 3 -f 4 ≅ f 10 -f 11 for the Ln(III) ions. Systematics in the formation constant values has been further studied by evaluating changes in the inter-electronic repulsion Racah parameters, extra stabilisation of specific 4f 9 -configurations and nephelauxetic ratio using experimental values of the formation constants. (author). 24 refs., 2 figs., 3 tabs

  13. Reaction of aromatic diazonium salts with carrier-free radioiodine and astatine, evidence for complex formation

    International Nuclear Information System (INIS)

    Meyer, G.J.; Roessler, K.; Stoecklin, G.

    1979-01-01

    Systematic studies of the astatodiazoniation reaction and a comparison with iododediazoniation under comparable conditions are reported. The yields for all astatohalobenzenes and -toluenes were nearly constant and unaffected by the nature of the diazonium compound, its isomeric form, and the number of isomers used at the same time. Only astatofluorobenzenes were obtained at higher yields. An electron-transfer mechanism is proposed for dediazoniation at these low halide concentration levels. At sufficient thermal excitation levels the electron transfer leads to the dissociation of nitrogen, while the phenyl and halogen radicals recombine. The isomer distribution found for some of the derivatives from dediazoniation may also be due to steric effects

  14. luminescence in coloured alkali halide crystals

    Indian Academy of Sciences (India)

    have studied the effect of annealing in chlorine gas on the ML of X-rayed KCl crystals. ..... high temperature because of the thermal bleaching of the coloration in alkali halide ..... [31] J Hawkins, Ph.D. Thesis (University of Reading, 1976).

  15. Monocrystalline halide perovskite nanostructures for optoelectronic applications

    NARCIS (Netherlands)

    Khoram, P.

    2018-01-01

    Halide perovskites are a promising class of materials for incorporation in optoelectronics with higher efficiency and lower cost. The solution processability of these materials provides unique opportunities for simple nanostructure fabrication. In the first half of the thesis (chapter 2 and 3) we

  16. An air-stable copper reagent for nucleophilic trifluoromethylthiolation of aryl halides

    KAUST Repository

    Weng, Zhiqiang; He, Weiming; Chen, Chaohuang; Lee, Richmond; Tan, Davin; Lai, Zhiping; Kong, Dedao; Yuan, Yaofeng; Huang, Kuo-Wei

    2012-01-01

    A series of copper(I) trifluoromethyl thiolate complexes have been synthesized from the reaction of CuF2 with Me3SiCF 3 and S8 (see scheme; Cu red, F green, N blue, S yellow). These air-stable complexes serve as reagents for the efficient conversion of a wide range of aryl halides into the corresponding aryl trifluoromethyl thioethers in excellent yields. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. An air-stable copper reagent for nucleophilic trifluoromethylthiolation of aryl halides

    KAUST Repository

    Weng, Zhiqiang

    2012-12-12

    A series of copper(I) trifluoromethyl thiolate complexes have been synthesized from the reaction of CuF2 with Me3SiCF 3 and S8 (see scheme; Cu red, F green, N blue, S yellow). These air-stable complexes serve as reagents for the efficient conversion of a wide range of aryl halides into the corresponding aryl trifluoromethyl thioethers in excellent yields. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. The History and Rate of Star Formation within the G305 Complex

    Science.gov (United States)

    Faimali, Alessandro Daniele

    2013-07-01

    Within this thesis, we present an extended multiwavelength analysis of the rich massive Galactic star-forming complex G305. We have focused our attention on studying the both the embedded massive star-forming population within G305, while also identifying the intermediate-, to lowmass content of the region also. Though massive stars play an important role in the shaping and evolution of their host galaxies, the physics of their formation still remains unclear. We have therefore set out to studying the nature of star formation within this complex, and also identify the impact that such a population has on the evolution of G305. We firstly present a Herschel far-infrared study towards G305, utilising PACS 70, 160 micron and SPIRE 250, 350, and 500 micron observations from the Hi-GAL survey of the Galactic plane. The focus of this study is to identify the embedded massive star-forming population within G305, by combining far-infrared data with radio continuum, H2O maser, methanol maser, MIPS, and Red MSX Source survey data available from previous studies. From this sample we identify some 16 candidate associations are identified as embedded massive star-forming regions, and derive a two-selection colour criterion from this sample of log(F70/F500) >= 1 and log(F160/F350) >= 1.6 to identify an additional 31 embedded massive star candidates with no associated star-formation tracers. Using this result, we are able to derive a star formation rate (SFR) of 0.01 - 0.02 Msun/yr. Comparing this resolved star formation rate, to extragalactic star formation rate tracers (based on the Kennicutt-Schmidt relation), we find the star formation activity is underestimated by a factor of >=2 in comparison to the SFR derived from the YSO population. By next combining data available from 2MASS and VVV, Spitzer GLIMPSE and MIPSGAL, MSX, and Herschel Hi-GAL, we are able to identify the low-, to intermediate-mass YSOs present within the complex. Employing a series of stringent colour

  19. CARBON DIOXIDE INFLUENCE ON THE THERMAL FORMATION OF COMPLEX ORGANIC MOLECULES IN INTERSTELLAR ICE ANALOGS

    Energy Technology Data Exchange (ETDEWEB)

    Vinogradoff, V.; Fray, N.; Bouilloud, M.; Cottin, H. [LISA Laboratoire Interuniversitaire des Systèmes Atmosphériques, UMR CNRS 7583, Université Paris Est Créteil (UPEC), Université Paris Diderot (UPD), Institut Pierre Simon Laplace, Labex ESEP, Paris (France); Duvernay, F.; Chiavassa, T., E-mail: vvinogradoff@mnhn.fr [PIIM, Laboratoire de Physique des Interactions Ioniques et Moléculaires, Université Aix-Marseille, UMR CNRS 7345, Marseille (France)

    2015-08-20

    Interstellar ices are submitted to energetic processes (thermal, UV, and cosmic-ray radiations) producing complex organic molecules. Laboratory experiments aim to reproduce the evolution of interstellar ices to better understand the chemical changes leading to the reaction, formation, and desorption of molecules. In this context, the thermal evolution of an interstellar ice analogue composed of water, carbon dioxide, ammonia, and formaldehyde is investigated. The ice evolution during the warming has been monitored by IR spectroscopy. The formation of hexamethylenetetramine (HMT) and polymethylenimine (PMI) are observed in the organic refractory residue left after ice sublimation. A better understanding of this result is realized with the study of another ice mixture containing methylenimine (a precursor of HMT) with carbon dioxide and ammonia. It appears that carbamic acid, a reaction product of carbon dioxide and ammonia, plays the role of catalyst, allowing the reactions toward HMT and PMI formation. This is the first time that such complex organic molecules (HMT, PMI) are produced from the warming (without VUV photolysis or irradiation with energetic particles) of abundant molecules observed in interstellar ices (H{sub 2}O, NH{sub 3}, CO{sub 2}, H{sub 2}CO). This result strengthens the importance of thermal reactions in the ices’ evolution. HMT and PMI, likely components of interstellar ices, should be searched for in the pristine objects of our solar system, such as comets and carbonaceous chondrites.

  20. CARBON DIOXIDE INFLUENCE ON THE THERMAL FORMATION OF COMPLEX ORGANIC MOLECULES IN INTERSTELLAR ICE ANALOGS

    International Nuclear Information System (INIS)

    Vinogradoff, V.; Fray, N.; Bouilloud, M.; Cottin, H.; Duvernay, F.; Chiavassa, T.

    2015-01-01

    Interstellar ices are submitted to energetic processes (thermal, UV, and cosmic-ray radiations) producing complex organic molecules. Laboratory experiments aim to reproduce the evolution of interstellar ices to better understand the chemical changes leading to the reaction, formation, and desorption of molecules. In this context, the thermal evolution of an interstellar ice analogue composed of water, carbon dioxide, ammonia, and formaldehyde is investigated. The ice evolution during the warming has been monitored by IR spectroscopy. The formation of hexamethylenetetramine (HMT) and polymethylenimine (PMI) are observed in the organic refractory residue left after ice sublimation. A better understanding of this result is realized with the study of another ice mixture containing methylenimine (a precursor of HMT) with carbon dioxide and ammonia. It appears that carbamic acid, a reaction product of carbon dioxide and ammonia, plays the role of catalyst, allowing the reactions toward HMT and PMI formation. This is the first time that such complex organic molecules (HMT, PMI) are produced from the warming (without VUV photolysis or irradiation with energetic particles) of abundant molecules observed in interstellar ices (H 2 O, NH 3 , CO 2 , H 2 CO). This result strengthens the importance of thermal reactions in the ices’ evolution. HMT and PMI, likely components of interstellar ices, should be searched for in the pristine objects of our solar system, such as comets and carbonaceous chondrites

  1. Young stellar population and star formation history ofW4 HII region/Cluster Complex

    Science.gov (United States)

    Panwar, Neelam

    2018-04-01

    The HII region/cluster complex has been a subject of numerous investigations to study the feedback effect of massive stars on their surroundings. Massive stars not only alter the morphology of the parental molecular clouds, but also influence star formation, circumstellar disks and the mass function of low-mass stars in their vicinity. However, most of the studies of low-mass stellar content of the HII regions are limited only to the nearby regions. We study the star formation in the W4 HII region using deep optical observations obtained with the archival data from Canada - France - Hawaii Telescope, Two-Micron All Sky Survey, Spitzer, Herschel and Chandra. We investigate the spatial distribution of young stellar objects in the region, their association with the remnant molecular clouds, and search for the clustering to establish the sites of recent star formation. Our analysis suggests that the influence of massive stars on circumstellar disks is significant only to thei! r immediate neighborhood. The spatial correlation of the young stars with the distribution of gas and dust of the complex indicate that the clusters would have formed in a large filamentary cloud. The observing facilities at the 3.6-m Devasthal Optical Telescope (DOT), providing high-resolution spectral and imaging capabilities, will fulfill the major objectives in the study of HII regions.

  2. Young stellar population and ongoing star formation in the H II complex Sh2-252

    Science.gov (United States)

    Jose, Jessy; Pandey, A. K.; Samal, M. R.; Ojha, D. K.; Ogura, K.; Kim, J. S.; Kobayashi, N.; Goyal, A.; Chauhan, N.; Eswaraiah, C.

    2013-07-01

    In this paper, an extensive survey of the star-forming complex Sh2-252 has been undertaken with an aim to explore its hidden young stellar population as well as to understand the structure and star formation history for the first time. This complex is composed of five prominent embedded clusters associated with the subregions A, C, E, NGC 2175s and Teu 136. We used Two Micron All Sky Survey-near-infrared and Spitzer-Infrared Array Camera, Multiband Imaging Photometer for Spitzer photometry to identify and classify the young stellar objects (YSOs) by their infrared (IR) excess emission. Using the IR colour-colour criteria, we identified 577 YSOs, of which, 163 are Class I, 400 are Class II and 14 are transition disc YSOs, suggesting a moderately rich number of YSOs in this complex. Spatial distribution of the candidate YSOs shows that they are mostly clustered around the subregions in the western half of the complex, suggesting enhanced star formation activity towards its west. Using the spectral energy distribution and optical colour-magnitude diagram-based age analyses, we derived probable evolutionary status of the subregions of Sh2-252. Our analysis shows that the region A is the youngest (˜0.5 Myr), the regions B, C and E are of similar evolutionary stage (˜1-2 Myr) and the clusters NGC 2175s and Teu 136 are slightly evolved (˜2-3 Myr). Morphology of the region in the 1.1 mm map shows a semicircular shaped molecular shell composed of several clumps and YSOs bordering the western ionization front of Sh2-252. Our analyses suggest that next generation star formation is currently under way along this border and that possibly fragmentation of the matter collected during the expansion of the H II region as one of the major processes is responsible for such stars. We observed the densest concentration of YSOs (mostly Class I, ˜0.5 Myr) at the western outskirts of the complex, within a molecular clump associated with water and methanol masers and we suggest that it

  3. Thermodynamics of the complex formation between thorium(IV) and some polydentate ligands in aqueous solution

    International Nuclear Information System (INIS)

    Di Bernado, P.; Cassol, A.; Tomat, G.; Bismondo, A.; Magon, L.

    1983-01-01

    The changes in free energy, enthalpy, and entropy for the formation of thorium(IV)-oxydiacetate, -iminodiacetate, -thiodiacetate, and -succinate complexes have been determined by potentiometric and calorimetric titrations at 25 deg C in aqueous 1 mol dm - 3 sodium perchlorate. All the ligands form 1:1 chelate complexes with the thorium(IV) ion the stability of which is dependent on both the chelate ring dimensions and the nature of the donor group in the chain. The order of the relative stabilities (iminodiacetate > oxydiacetate > thiodiacetate > succinate) is mainly dependent on the reaction enthalpies, since the δS values are close to each other. In the thorium(IV)-oxydiacetate system the maximum number of three ligands for every metal ion was reached. Because of precipitation of solid compounds in the other systems, it was only possible to define complexes with a lower number of co-ordinated ligands: two for succinate and thiodiacetate, and one for iminodiacetate. Owing to the lower stability of the chelate ring of thiodiacetate and succinate complexes and the high basicity of the amino-group of iminodiacetate, these ligands form also unchelated protonated complexes. (author)

  4. Ternary complex formation of lanthanides and radiolanthanides with phosphate and serum proteins

    International Nuclear Information System (INIS)

    Neumaier, B.; Roesch, F.

    1999-01-01

    Radioyttrium was recently reported to form ternary complexes with phosphate and serum proteins in blood. In the present work it was investigated whether the trivalent radiolanthanides react in a chemically similar way. In systematic binding studies using gel filtration a ternary complex formation between different lanthanides, phosphate and serum proteins could be identified. The tendency to build a ternary compound of the type Ln III - phosphate - serum protein, however, is dependent on the ionic radii of the lanthanides. Whereas the light and transition lanthanides have a strong inclination to build a ternary complex, this tendency is weaker for the heavier ones. Taking into account the high content of phosphate in human blood, the corresponding ternary complexes of radiolanthanides represent an important transport form of these elements in blood. This finding may contribute to an understanding of the nuclear medical observation on the biodistribution of radiolanthanides. The heavy radiolanthanides can be classified as bone seeking metals, whereas the light and transition lanthanide elements accumulate mainly in the liver and the spleen. For the lighter radiolanthanides the corresponding ternary complexes thus represent an important transport form in blood. This physicochemical form of lanthanides mainly results in reticulo endothelial accumulation; on the other hand, the lower tendency of heavier lanthanides leads to preferential skeletal deposition. (orig.)

  5. Influence of structural features of carrageenan on the formation of polyelectrolyte complexes with chitosan.

    Science.gov (United States)

    Volod'ko, A V; Davydova, V N; Glazunov, V P; Likhatskaya, G N; Yermak, I M

    2016-03-01

    The polyelectrolyte complexes (PEC) of carrageenans (CG)-κ-, κ/β-, λ-and x-CG with chitosan were obtained. The formation of PEC was detected by Fourier-transform infrared (FTIR) spectroscopy and by centrifugation in a Percoll gradient. The influence of the structural peculiarities of CG on its interaction with chitosan was studied. The results of centrifugation showed that x-CG with a high degree of sulphation (SD) was completely bound to chitosan, unlike low SD κ-CG and κ/β-CG. Binding constant values showed there was a high affinity of CG for chitosan. CG with flexible macromolecule conformation and high SD exhibited the greatest binding affinity for chitosan. The full-atomic 3D-structures of the PEC κ-CG: chitosan in solution have been obtained by the experiments in silico for the first time. The amino groups of chitosan make the largest contribution to the energy of the complex formation by means of hydrogen and ionic bonds. The most probable complexes have stoichiometries of 1:1 and 1:1.5. Copyright © 2015 Elsevier B.V. All rights reserved.

  6. Effect of halide-mixing on the switching behaviors of organic-inorganic hybrid perovskite memory

    Science.gov (United States)

    Hwang, Bohee; Gu, Chungwan; Lee, Donghwa; Lee, Jang-Sik

    2017-03-01

    Mixed halide perovskite materials are actively researched for solar cells with high efficiency. Their hysteresis which originates from the movement of defects make perovskite a candidate for resistive switching memory devices. We demonstrate the resistive switching device based on mixed-halide organic-inorganic hybrid perovskite CH3NH3PbI3-xBrx (x = 0, 1, 2, 3). Solvent engineering is used to deposit the homogeneous CH3NH3PbI3-xBrx layer on the indium-tin oxide-coated glass substrates. The memory device based on CH3NH3PbI3-xBrx exhibits write endurance and long retention, which indicate reproducible and reliable memory properties. According to the increase in Br contents in CH3NH3PbI3-xBrx the set electric field required to make the device from low resistance state to high resistance state decreases. This result is in accord with the theoretical calculation of migration barriers, that is the barrier to ionic migration in perovskites is found to be lower for Br- (0.23 eV) than for I- (0.29-0.30 eV). The resistive switching may be the result of halide vacancy defects and formation of conductive filaments under electric field in the mixed perovskite layer. It is observed that enhancement in operating voltage can be achieved by controlling the halide contents in the film.

  7. Quantum-chemical analysis of formation reactions of Со2+ complexes

    Directory of Open Access Journals (Sweden)

    Viktor F. Vargalyuk

    2017-11-01

    Full Text Available Based on the analysis of quantum chemical calculations results (GAMESS, density functional theory, B3LYP method as to coordination compounds of Co2+ions with H2O, NH3, OH–, F–, Cl–, Br–, I–, CN–, Ac–, Ak– generally given by [Co(H2O6–nLn]2+nx, it has been demonstrated that within the selected series of ligands, there is no correlation between the amount of energy of monosubstituted cobalt aqua complexes formation(∆Е and pK1,just like between the effective nuclear charge of the central atom (z*Со and pK1. According to the behavior of ∆Е and z*Со,we identified two groups of ligands. The first group (OH–, F–, Ac–, Ak–, CN–, NH3 demonstrates logical ∆Е decrease caused by the growth of z*Со. On the contrary, the second group (Cl–, Br–, I– demonstrates ∆Е increase caused by the growth of z*Со. This phenomenon is explained by the change in electronegativity and polarizability of donor atoms in groups and periods of the periodic table. It is established that linear correlations given by lgK = A + B·z*Со can be actualized only for complexes having ligands with similar donor atoms. Referring to the literature on stepwise complex formation of hydroxide, amine and chloride cobalt complexes in combination with z*Со calculations results, we determined A and B constants of lgK, z*Со-correlations for the atoms of oxygen (30.2, –17.7; nitrogen (125.4, –69.9 and chlorine (–6.3, 5.8. The existence of the detected correlation series enables us to lean on lgK,z*М–dependence parameters for the fixed donor atom and to determine Kn values for various complexes with complex-based ligands using calculations and z*М data. This applies to complexes having central atoms of the same nature as well as simple monodentate ligands. The mentioned approach was used to calculate the stability constants for acrylate cobalt complexes (lgK1 = 1.2 и lgК2 = 4.3, which are not covered in literature.

  8. Cloud fluid compression and softening in spiral arms and the formation of giant molecular cloud complexes

    International Nuclear Information System (INIS)

    Cowie, L.L.

    1981-01-01

    In this, the second paper of a series on the galactodynamics of the cloudy interstellar medium, we consider the response of such a gas to a forcing potential in the tight-winding density wave theory. The cloud fluid is treated in the hydrodynamic limit with an equation of state which softens at high densities. It is shown that in the inner regions of the galaxy, cooling of the cloud fluid in the arms can result in gravitational instability and the formation of large bound complexes of clouds which we identify with the giant molecular clouds (GMCs). Masses dimensions, distributions, and scale heights of the GMCs are predicted by the theory. It is suggested that the interstellar gas density in the disk is regulated by the gravitational instability mechanism in the arms which siphons material into star formation. Implications for the evolution of individual GMCs and for galactic morphology are discussed

  9. High-throughput metagenomic technologies for complex microbial community analysis: open and closed formats.

    Science.gov (United States)

    Zhou, Jizhong; He, Zhili; Yang, Yunfeng; Deng, Ye; Tringe, Susannah G; Alvarez-Cohen, Lisa

    2015-01-27

    Understanding the structure, functions, activities and dynamics of microbial communities in natural environments is one of the grand challenges of 21st century science. To address this challenge, over the past decade, numerous technologies have been developed for interrogating microbial communities, of which some are amenable to exploratory work (e.g., high-throughput sequencing and phenotypic screening) and others depend on reference genes or genomes (e.g., phylogenetic and functional gene arrays). Here, we provide a critical review and synthesis of the most commonly applied "open-format" and "closed-format" detection technologies. We discuss their characteristics, advantages, and disadvantages within the context of environmental applications and focus on analysis of complex microbial systems, such as those in soils, in which diversity is high and reference genomes are few. In addition, we discuss crucial issues and considerations associated with applying complementary high-throughput molecular technologies to address important ecological questions. Copyright © 2015 Zhou et al.

  10. Radiation accelerated formation of oxygen and carbon related complexes in silicon

    International Nuclear Information System (INIS)

    Lazrak, A.; Magnea, N.; Pautrat, J.L.

    1984-06-01

    During the pulling of silicon monocrystals by the Czochralsky method, oxygen is incorporated into the lattice. It is known from early works that low temperature annealings (400-1000 0 C) make this oxygen to precipitate and a number of different defects to be generated. In order to check whether the fast diffusivity of an oxygen silicon interstitial complex has to be taken in consideration it was interesting to examinate the possible role of radiation damage on the formation of oxygen related defects. Experimental results of an experiment are presented and discussed

  11. Electrochemistry of metal complexes applications from electroplating to oxide layer formation

    CERN Document Server

    Survila, Arvydas

    2015-01-01

    This book aims to sequentially cover all the major stages of electrochemical processes (mass transport, adsorption, charge transfer), with a special emphasis on their deep interrelation. Starting with general considerations on equilibria in solutions and at interfaces as well as on mass transport, the text acquaints readers with the theory and common experimental practice for studying electrochemical reactions of metals complexes. The core part of the book deals with all important aspects of electroplating, including a systematic discussion of co-deposition of metals and formation of alloys.

  12. The formation of super-dislocation/micropipe complexes in 6H-SiC

    Energy Technology Data Exchange (ETDEWEB)

    Giocondi, J.; Rohrer, G.S.; Skowronski, M. [Carnegie Mellon Univ., Pittsburgh, PA (United States). Dept. of Materials Science and Engineering; Balakrishna, V.; Augustine, G.; Hobgood, H.McD.; Hopkins, R.H. [Northrop Grumman Science and Technology Center, Pittsburgh PA (United States)

    1998-06-01

    Atomic force microscope images of surface/micropipe intersections on the (0001) growth surface of a 6H-SiC single crystal grown by the physical vapor transport method indicate that micropipes are associated with super-dislocations and that micron-scale deposits of a heterogeneous phase are frequently found in the vicinity of the defect. Based on our observations, we propose a model for the formation of super-dislocation/micropipe complexes that involves the coalescence of unit screw dislocations. The unit dislocations are forced together as large steps grow around heterogeneous material on the surface. (orig.) 5 refs.

  13. A Solution Study of Complex Formation of Some Diamines with Lanthanones

    Directory of Open Access Journals (Sweden)

    J. J. Vora

    2009-01-01

    Full Text Available To study the metal ligand equilibrium in aqueous solution, the well known Irving-Rossotti titration method was used. The temperature selected is 30±0.10C at ionic strength 0.2 M (NaClO4 which was maintained constant through out the work. The binary metal complex (ML2 formation was studied. The metals selected are Sm3+, Gd3+, Dy3+ and Yb3+. The diamine ligands taken are ethylenediamine, 1,2 diamino propane, 1,3 diamino propane, N-N diethyl ethylenediamine and N-N -dimethyl ethylenediamine. Factors that affected the stability of the complexes are size and ionic potential of lanthanone ions, basicity of ligands, ring size and steric effect of ligands.

  14. Determination of the structural phase and octahedral rotation angle in halide perovskites

    Science.gov (United States)

    dos Reis, Roberto; Yang, Hao; Ophus, Colin; Ercius, Peter; Bizarri, Gregory; Perrodin, Didier; Shalapska, Tetiana; Bourret, Edith; Ciston, Jim; Dahmen, Ulrich

    2018-02-01

    A key to the unique combination of electronic and optical properties in halide perovskite materials lies in their rich structural complexity. However, their radiation sensitive nature limits nanoscale structural characterization requiring dose efficient microscopic techniques in order to determine their structures precisely. In this work, we determine the space-group and directly image the Br halide sites of CsPbBr3, a promising material for optoelectronic applications. Based on the symmetry of high-order Laue zone reflections of convergent-beam electron diffraction, we identify the tetragonal (I4/mcm) structural phase of CsPbBr3 at cryogenic temperature. Electron ptychography provides a highly sensitive phase contrast measurement of the halide positions under low electron-dose conditions, enabling imaging of the elongated Br sites originating from the out-of-phase octahedral rotation viewed along the [001] direction of I4/mcm persisting at room temperature. The measurement of these features and comparison with simulations yield an octahedral rotation angle of 6.5°(±1.5°). The approach demonstrated here opens up opportunities for understanding the atomic scale structural phenomena applying advanced characterization tools on a wide range of radiation sensitive halide-based all-inorganic and hybrid organic-inorganic perovskites.

  15. Formation of stable nanoparticles via electrostatic complexation between sodium caseinate and gum arabic.

    Science.gov (United States)

    Ye, Aiqian; Flanagan, John; Singh, Harjinder

    2006-06-05

    The formation of electrostatic complexes between sodium caseinate and gum arabic (GA) was studied as a function of pH (2.0-7.0), using slow acidification in situ with glucono-delta-lactone (GDL) or titration with HCl. The colloidal behavior of the complexes under specific conditions was investigated using absorbance measurements (at 515 or 810 nm) and dynamic light scattering (DLS). In contrast to the sudden increase in absorbance and subsequent precipitation of sodium caseinate solutions at pH sodium caseinate and GA increased to a level that was dependent on GA concentration at pH 5.4 (pH(c)). The absorbance values remained constant with further decreases in pH until a sudden increase in absorbance was observed (at pH(phi)). The pH(phi) was also dependent upon the GA concentration. Dynamic light scattering (DLS) data showed that the sizes of the particles formed by the complexation of sodium caseinate and GA between pH(c) and pH(phi) were between 100 and 150 nm and these nanoparticles were visualized using negative staining transmission electron microscopy (TEM). Below pH(phi), the nanoparticles associated to form larger particles, causing phase separation. zeta-Potential measurements of the nanoparticles and chemical analysis after phase separation showed that phase separation was a consequence of charge neutralization. The formation of complexes between sodium caseinate and GA was inhibited at high ionic strength (>50 mM NaCl). It is postulated that the structure of the nanoparticles comprises an aggregated caseinate core, protected from further aggregation by steric repulsion of one, or more, electrostatically attached GA molecules. Copyright 2005 Wiley Periodicals, Inc.

  16. Radiation increases the cellular uptake of exosomes through CD29/CD81 complex formation

    International Nuclear Information System (INIS)

    Hazawa, Masaharu; Tomiyama, Kenichi; Saotome-Nakamura, Ai; Obara, Chizuka; Yasuda, Takeshi; Gotoh, Takaya; Tanaka, Izumi; Yakumaru, Haruko; Ishihara, Hiroshi; Tajima, Katsushi

    2014-01-01

    Highlights: • Radiation increases cellular uptake of exosomes. • Radiation induces colocalization of CD29 and CD81. • Exosomes selectively bind the CD29/CD81 complex. • Radiation increases the cellular uptake of exosomes through CD29/CD81 complex formation. - Abstract: Exosomes mediate intercellular communication, and mesenchymal stem cells (MSC) or their secreted exosomes affect a number of pathophysiologic states. Clinical applications of MSC and exosomes are increasingly anticipated. Radiation therapy is the main therapeutic tool for a number of various conditions. The cellular uptake mechanisms of exosomes and the effects of radiation on exosome–cell interactions are crucial, but they are not well understood. Here we examined the basic mechanisms and effects of radiation on exosome uptake processes in MSC. Radiation increased the cellular uptake of exosomes. Radiation markedly enhanced the initial cellular attachment to exosomes and induced the colocalization of integrin CD29 and tetraspanin CD81 on the cell surface without affecting their expression levels. Exosomes dominantly bound to the CD29/CD81 complex. Knockdown of CD29 completely inhibited the radiation-induced uptake, and additional or single knockdown of CD81 inhibited basal uptake as well as the increase in radiation-induced uptake. We also examined possible exosome uptake processes affected by radiation. Radiation-induced changes did not involve dynamin2, reactive oxygen species, or their evoked p38 mitogen-activated protein kinase-dependent endocytic or pinocytic pathways. Radiation increased the cellular uptake of exosomes through CD29/CD81 complex formation. These findings provide essential basic insights for potential therapeutic applications of exosomes or MSC in combination with radiation

  17. Zeaxanthin Radical Cation Formation in Minor Light-Harvesting Complexes of Higher Plant Antenna

    Energy Technology Data Exchange (ETDEWEB)

    Avenson, Thomas H.; Ahn, Tae Kyu; Zigmantas, Donatas; Niyogi, Krishna K.; Li, Zhirong; Ballottari, Matteo; Bassi, Roberto; Fleming, Graham R.

    2008-01-31

    Previous work on intact thylakoid membranes showed that transient formation of a zeaxanthin radical cation was correlated with regulation of photosynthetic light-harvesting via energy-dependent quenching. A molecular mechanism for such quenching was proposed to involve charge transfer within a chlorophyll-zeaxanthin heterodimer. Using near infrared (880-1100 nm) transient absorption spectroscopy, we demonstrate that carotenoid (mainly zeaxanthin) radical cation generation occurs solely in isolated minor light-harvesting complexes that bind zeaxanthin, consistent with the engagement of charge transfer quenching therein. We estimated that less than 0.5percent of the isolated minor complexes undergo charge transfer quenching in vitro, whereas the fraction of minor complexes estimated to be engaged in charge transfer quenching in isolated thylakoids was more than 80 times higher. We conclude that minor complexes which bind zeaxanthin are sites of charge transfer quenching in vivo and that they can assume Non-quenching and Quenching conformations, the equilibrium LHC(N)<--> LHC(Q) of which is modulated by the transthylakoid pH gradient, the PsbS protein, and protein-protein interactions.

  18. Formation of protein-birnessite complex: XRD, FTIR, and AFM analysis.

    Science.gov (United States)

    Naidja, A; Liu, C; Huang, P M

    2002-07-01

    Limited information is available on formation chemistry of enzyme-Mn oxide complexes. Adsorption isotherm of protein molecules (tyrosinase) on birnessite (delta-MnO(2)) at pH 6.0 and room temperature (23 degrees C) was of H type, indicating a very high affinity of the enzyme protein molecules to the birnessite mineral surfaces. After thorough washing of the protein-mineral complex with deionized-distilled water, up to 89% of adsorbed protein molecules remained bound to the mineral surfaces. When a high amount of the protein was immobilized, the X-ray diffractogram shows a significant decrease in the intensity of characteristic d-spacings of birnessite. No shift to higher values of the d-spacings of protein-birnessite complex was observed, indicating that the enzyme molecules were not intercalated in the mineral structure but immobilized at the external surfaces and the edges of the mineral oxide. By comparison to the free enzyme, infrared absorption spectra of the protein-birnessite complexes show a shift by up to 11 cm(-1) to lower frequencies in the absorption bands characteristic of amide I and II modes of the polypeptides chains. The mineral surfaces exerted some strain on the protein structure, resulting in an alteration of the protein molecular conformation after binding to the mineral colloid surfaces. In the free state, the globular protein molecules had a spheroid shape with an average cross-sectional diameter of 70+/-6 nm. The unfolding and flattening of the protein molecules after immobilization is clearly shown in atomic force micrographs. Compared to the tyrosinase-birnessite complex, similar FTIR spectra and atomic force micrographs were observed for the pure protein, bovine serum albumin (BSA), after immobilization on birnessite. The information obtained in this study is of fundamental significance for understanding birnessite as an adsorbent of biopolymers and the catalytic role of the enzyme-birnessite complex.

  19. Hormad1 mutation disrupts synaptonemal complex formation, recombination, and chromosome segregation in mammalian meiosis.

    Directory of Open Access Journals (Sweden)

    Yong-Hyun Shin

    2010-11-01

    Full Text Available Meiosis is unique to germ cells and essential for reproduction. During the first meiotic division, homologous chromosomes pair, recombine, and form chiasmata. The homologues connect via axial elements and numerous transverse filaments to form the synaptonemal complex. The synaptonemal complex is a critical component for chromosome pairing, segregation, and recombination. We previously identified a novel germ cell-specific HORMA domain encoding gene, Hormad1, a member of the synaptonemal complex and a mammalian counterpart to the yeast meiotic HORMA domain protein Hop1. Hormad1 is essential for mammalian gametogenesis as knockout male and female mice are infertile. Hormad1 deficient (Hormad1(-/ (- testes exhibit meiotic arrest in the early pachytene stage, and synaptonemal complexes cannot be visualized by electron microscopy. Hormad1 deficiency does not affect localization of other synaptonemal complex proteins, SYCP2 and SYCP3, but disrupts homologous chromosome pairing. Double stranded break formation and early recombination events are disrupted in Hormad1(-/ (- testes and ovaries as shown by the drastic decrease in the γH2AX, DMC1, RAD51, and RPA foci. HORMAD1 co-localizes with γH2AX to the sex body during pachytene. BRCA1, ATR, and γH2AX co-localize to the sex body and participate in meiotic sex chromosome inactivation and transcriptional silencing. Hormad1 deficiency abolishes γH2AX, ATR, and BRCA1 localization to the sex chromosomes and causes transcriptional de-repression on the X chromosome. Unlike testes, Hormad1(-/ (- ovaries have seemingly normal ovarian folliculogenesis after puberty. However, embryos generated from Hormad1(-/ (- oocytes are hyper- and hypodiploid at the 2 cell and 8 cell stage, and they arrest at the blastocyst stage. HORMAD1 is therefore a critical component of the synaptonemal complex that affects synapsis, recombination, and meiotic sex chromosome inactivation and transcriptional silencing.

  20. M-center growth in alkali halides: computer simulation

    International Nuclear Information System (INIS)

    Aguilar, M.; Jaque, F.; Agullo-Lopez, F.

    1983-01-01

    The heterogeneous interstitial nucleation model previously proposed to explain F-center growth curves in irradiated alkali halides has been extended to account for M-center kinetics. The interstitials produced during the primary irradiation event are assumed to be trapped at impurities and interstitial clusters or recombine with F and M centers. For M-center formation two cases have been considered: (a) diffusion and aggregation of F centers, and (b) statistical generation and pairing of F centers. Process (b) is the only one consistent with the quadratic relationship between M and F center concentrations. However, to account for the F/M ratios experimentally observed as well as for the role of dose-rate, a modified statistical model involving random creation and association of F + -F pairs has been shown to be adequate. (author)

  1. Irradiation damage of alkali halide crystals during positron bombardment

    International Nuclear Information System (INIS)

    Arefiev, K.P.; Arefiev, V.P.; Vorobiev, S.A.

    1978-01-01

    The bleaching effect of positron irradiation of KCl and KBr single crystals previously coloured with electrons or protons was investigated. Positrons injection in the coloured alkali halide samples reduced the F-centres concentration considerably. For KCl crystals thicker than the positrons range the appearance of additional bands in the absorption spectra is noticeable. The experimental data show that the bleaching phenomenon should be observed merely throughout the positron exposure both for irradiated and non-irradiated regions of the sample. Irradiation effects, due to positron source, on the peak counting rate of (γ-γ) angular correlation in KCl crystals under applied magnetic field were also investigated. The growth of peak counting rate shows the increase of positronium-like states formation near defects of cation sublattice. (author)

  2. Photoinduced, copper-catalyzed alkylation of amides with unactivated secondary alkyl halides at room temperature.

    Science.gov (United States)

    Do, Hien-Quang; Bachman, Shoshana; Bissember, Alex C; Peters, Jonas C; Fu, Gregory C

    2014-02-05

    The development of a mild and general method for the alkylation of amides with relatively unreactive alkyl halides (i.e., poor substrates for SN2 reactions) is an ongoing challenge in organic synthesis. We describe herein a versatile transition-metal-catalyzed approach: in particular, a photoinduced, copper-catalyzed monoalkylation of primary amides. A broad array of alkyl and aryl amides (as well as a lactam and a 2-oxazolidinone) couple with unactivated secondary (and hindered primary) alkyl bromides and iodides using a single set of comparatively simple and mild conditions: inexpensive CuI as the catalyst, no separate added ligand, and C-N bond formation at room temperature. The method is compatible with a variety of functional groups, such as an olefin, a carbamate, a thiophene, and a pyridine, and it has been applied to the synthesis of an opioid receptor antagonist. A range of mechanistic observations, including reactivity and stereochemical studies, are consistent with a coupling pathway that includes photoexcitation of a copper-amidate complex, followed by electron transfer to form an alkyl radical.

  3. Evaluation of thermodynamic data on zirconium and hafnium halides and oxyhalides by means of transport experiments

    International Nuclear Information System (INIS)

    Dittmer, G.; Niemann, U.

    1987-01-01

    A consistent set of thermodynamic data for zirconium and hafnium halides, oxides and oxyhalides was achieved. It was found that formation enthalpies of gaseous compounds could be derived from solubility measurements together with theoretical estimations and a revision of literature data. Free energy functions were calculated employing statistical mechanics. Data for liquid and solid compounds were obtained via sublimation and vaporization data. Chemical equilibria of zirconium and hafnium with halogens are discussed. 51 refs.; 16 figs.; 14 tabs

  4. The Possibility of Ce3+ and Mn2+ Complex Ions Formation With Iodine Species in a Dushman Reaction

    Directory of Open Access Journals (Sweden)

    Iurie Ungureanu

    2018-06-01

    Full Text Available This contribution presents investigations into possible effects of Ce3+ and Mn2+ on the reduction of UV-spectral signal for I3- observed e.g. in the Dushman reaction. The potential of the metal ions to form complexes with iodine-containing species was analysed. It was shown that no complex ions are formed between Ce3+ and Mn2+ metals ions with IO3-, I-, I2 species. Only the formation of a very weak CeI32+ complex ion was found to occur. An effect of a complex formation on the studied systems could be excluded.

  5. Study of the formation of complexes of nitrosyl-rhutenium nitrates with thiourea

    International Nuclear Information System (INIS)

    Floh, B.

    1977-01-01

    A method for the treatment of spent uranium fuel is presented, based on the Purex process using thiourea to increase the ruthenium decontamination factor. Thiourea exhibits a strong tendency for the formation of coordination compounds in acidic media. This tendency serves as a basis to transform nitrosyl-ruthenium species into Ru/SC(NH)(NH 2 )/ 2+ and Ru/SC(NH)(NH 2 )/ 3 complexes which are unextractable by TBP-varsol. The best conditions for the ruthenium-thiourea complex formation were found to be: thiourea-ruthenium ratio (mass/mass) close to 42, at 75 0 C, 30 minutes reaction time and aging period of 60 minutes. The ruthenium decontamination factor for a single uranium extraction are ca. 80-100, not interfering with extraction of actinides. These values are rather high in comparison to those obtained using the conventional Purex process (e.g. F.D. sub(Ru)=10). For this reason, the method developed here is suitable for the treatment of spent uranium fuels. Thiourea (100 g/l) scrubbing experiments of ruthenium, partially co-extracted with actinides, confirmed the possibility of its removal from the extract. With this procedure a decontamination greater than 83,5% for ruthenium as fission product is obtained in two stages [pt

  6. Thermodynamics of HEDPA protonation in different media and complex formation with Mg2+ and Ca2+

    International Nuclear Information System (INIS)

    Foti, Claudia; Giuffrè, Ottavia; Sammartano, Silvio

    2013-01-01

    Highlights: • Acid–base properties of etidronic acid in different ionic media and at different ionic strengths. • Complex formation of etidronate with Na + , K + , Ca 2+ and Mg 2+ . • Dependence on ionic strength analysed by a Debye–Hückel type equation and the SIT approach. • Suggested protonation constants calculated at I = 0.1 mol · L −1 and t = 25 °C, in different ionic media. -- Abstract: Acid–base properties of etidronic acid [(1-Hydroxyethane-1,1-diyil)bis(phosphonic acid), HEDPA] in different ionic media and at different ionic strengths (NaCl, KCl: I ⩽ 2 mol · L −1 ; (C 2 H 5 ) 4 NI: I ⩽ 1 mol · L −1 ) were studied at t = 25 °C, determining, by potentiometric and calorimetric techniques, protonation constants and enthalpy changes. The differences in the protonation constants in the different supporting electrolytes were also interpreted in terms of weak complex formation with M i L (with i = 1, 2), MLH j (with j = 1, 2, 3) and M 2 LH species (with L = HEDPA; M = Na + , K + ). The formation constants for the species of Ca 2+ and Mg 2+ , were determined by potentiometric titrations at different ionic strengths (0.1 ⩽ I/mol · L −1 ⩽ 1) in NaCl at t = 25 °C. The stability of these species is fairly high, as an example, at I = 0.1 mol · L −1 and t = 25 °C, for ML species, log β = 6.52 and 6.86, for Ca 2+ and Mg 2+ , respectively, obtained by considering simultaneously HEDPA–Na + interactions. The dependence on ionic strength was analysed by a Debye–Hückel type equation and the SIT (Specific ion Interaction Theory) approach for protonation thermodynamic parameters and by a Debye–Hückel type equation for Mg 2+ and Ca 2+ complex formation. The sequestering ability of HEDPA toward Ca 2+ and Mg 2+ was also analysed. A comparison with literature data is given

  7. Discovery of Multiseeded Multimode Formation of Embedded Clusters in the Rosette Molecular Complex

    Science.gov (United States)

    Li, Jin Zeng; Smith, Michael D.

    2005-02-01

    An investigation based on data from the spatially complete Two Micron All Sky Survey (2MASS) reveals that a remarkable burst of clustered star formation is taking place throughout the southeast quadrant of the Rosette Molecular Cloud. Compact clusters are forming in a multiseeded mode, in parallel and at various places. In addition, sparse aggregates of embedded young stars are extensively distributed. In this study we report the primary results and implications for high-mass and clustered star formation in giant molecular clouds. In particular, we incorporate for the first time the birth of medium- to low-mass stars into the scenario of sequential formation of OB clusters. Following the emergence of the young OB cluster NGC 2244, a variety of manifestations of forming clusters of medium to high mass appears in the vicinity of the swept-up layer of the H II region as well as farther into the molecular cloud. The embedded clusters appear to form in a structured manner, which suggests they follow tracks laid out by the decay of macroturbulence. We address the possible origins of the turbulence. This leads us to propose a tree model to interpret the neat spatial distribution of clusters within a large section of the Rosette complex. Prominent new-generation OB clusters are identified at the root of the tree pattern.

  8. Effect of fat type in baked bread on amylose-lipid complex formation and glycaemic response.

    Science.gov (United States)

    Lau, Evelyn; Zhou, Weibiao; Henry, Christiani Jeyakumar

    2016-06-01

    The formation of amylose-lipid complexes (ALC) had been associated with reduced starch digestibility. A few studies have directly characterised the extent of ALC formation with glycaemic response. The objectives of this study were to investigate the effect of using fats with varying degree of saturation and chain length on ALC formation as well as glycaemic and insulinaemic responses after consumption of bread. Healthy men consumed five test breads in a random order: control bread without any added fats (CTR) and breads baked with butter (BTR), coconut oil (COC), grapeseed oil (GRP) or olive oil (OLV). There was a significant difference in glycaemic response between the different test breads (P=0·002), primarily due to COC having a lower response than CTR (P=0·016), but no significant differences between fat types were observed. Insulinaemic response was not altered by the addition of fats/oils. Although BTR was more insulinotropic than GRP (Pfats/oils, with coconut oil showing the greatest attenuation of glycaemic response.

  9. Morphology-Controlled Synthesis of Organometal Halide Perovskite Inverse Opals.

    Science.gov (United States)

    Chen, Kun; Tüysüz, Harun

    2015-11-09

    The booming development of organometal halide perovskites in recent years has prompted the exploration of morphology-control strategies to improve their performance in photovoltaic, photonic, and optoelectronic applications. However, the preparation of organometal halide perovskites with high hierarchical architecture is still highly challenging and a general morphology-control method for various organometal halide perovskites has not been achieved. A mild and scalable method to prepare organometal halide perovskites in inverse opal morphology is presented that uses a polystyrene-based artificial opal as hard template. Our method is flexible and compatible with different halides and organic ammonium compositions. Thus, the perovskite inverse opal maintains the advantage of straightforward structure and band gap engineering. Furthermore, optoelectronic investigations reveal that morphology exerted influence on the conducting nature of organometal halide perovskites. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Remarkable fluorescence enhancement versus complex formation of cationic porphyrins on the surface of ZnO nanoparticles

    KAUST Repository

    Aly, Shawkat Mohammede; Eita, Mohamed Samir; Khan, Jafar Iqbal; Alarousu, Erkki; Mohammed, Omar F.

    2014-01-01

    the first experimental measurements demonstrating a clear transition from pronounced fluorescence enhancement to charge transfer (CT) complex formation by simply changing the nature and location of the positive charge of the meso substituent of the cationic

  11. Neckteeth formation in two species of the Daphnia curvirostris complex (Crustacea: Cladocera

    Directory of Open Access Journals (Sweden)

    Petr Jan JURAČKA

    2011-08-01

    Full Text Available Cladocerans of the genus Daphnia show different morphological adaptations against invertebrate predation. Among those, the formation of neckteeth has attracted substantial attention. Morphotypes exhibiting neckteeth better resist predation from larvae of phantom midges Chaoborus (Diptera. These morphological structures are known from several species of the Daphnia longispina and D. pulex complexes; recently they have also been reported in the D. curvirostris complex, within which they are well documented from the Far East species D. sinevi and from Central European D. hrbaceki. Much scarcer are indications of the formation of these structures in the widespread species D. curvirostris. Careful inspection of samples from pools with Chaoborus larvae nevertheless revealed that a small necktooth in the first few instars of D. curvirostris is not uncommon, but probably has been mostly overlooked in the past. Occasionally, even adult D. curvirostris males may carry this feature. We provide documentation, particularly by scanning electron micrographs, of neckteeth in field-collected D. curvirostris, and in juvenile individuals of its sister species D. hrbaceki. In addition, we tested the response of three clones each of D. curvirostris and D. hrbaceki to Chaoborus kairomones in laboratory experiments. Two clones of the former species and all three of the latter responded to this predator cue with neckteeth formation. First-instar juveniles of D. hrbaceki also occasionally carried neckteeth in control treatments without Chaoborus kairomones, but second and third instars did not. We also observed strong interclonal variation in neonate length in the presence of kairomones in this species. We provide a summary table listing all Daphnia species presently known to exhibit neckteeth, and propose that the ability to form these structures may be more widespread among common Daphnia species than previously assumed.

  12. Papillae formation on trichome cell walls requires the function of the mediator complex subunit Med25.

    Science.gov (United States)

    Fornero, Christy; Suo, Bangxia; Zahde, Mais; Juveland, Katelyn; Kirik, Viktor

    2017-11-01

    Glassy Hair 1 (GLH1) gene that promotes papillae formation on trichome cell walls was identified as a subunit of the transcriptional mediator complex MED25. The MED25 gene is shown to be expressed in trichomes. The expression of the trichome development marker genes GLABRA2 (GL2) and Ethylene Receptor2 (ETR2) is not affected in the glh1 mutant. Presented data suggest that Arabidopsis MED25 mediator component is likely involved in the transcription of genes promoting papillae deposition in trichomes. The plant cell wall plays an important role in communication, defense, organization and support. The importance of each of these functions varies by cell type. Specialized cells, such as Arabidopsis trichomes, exhibit distinct cell wall characteristics including papillae. To better understand the molecular processes important for papillae deposition on the cell wall surface, we identified the GLASSY HAIR 1 (GLH1) gene, which is necessary for papillae formation. We found that a splice-site mutation in the component of the transcriptional mediator complex MED25 gene is responsible for the near papillae-less phenotype of the glh1 mutant. The MED25 gene is expressed in trichomes. Reporters for trichome developmental marker genes GLABRA2 (GL2) and Ethylene Receptor2 (ETR2) were not affected in the glh1 mutant. Collectively, the presented results show that MED25 is necessary for papillae formation on the cell wall surface of leaf trichomes and suggest that the Arabidopsis MED25 mediator component is likely involved in the transcription of a subset of genes that promote papillae deposition in trichomes.

  13. Studies on chalcone derivatives: Complex formation, thermal behavior, stability constant and antioxidant activity

    Science.gov (United States)

    El-Sayed, Yusif S.; Gaber, M.

    2015-02-01

    The chalcone 3-[4‧-dimethylaminophenyl]-1-(2-pyridyl) prop-2-en-1-one (DMAPP) and 3-(4‧-diethylaminophenyl)-1-(2-pyridinyl) prop-2-en-1-one abbreviated as DEAPP have been synthesized and characterized with IR, 1H NMR, 13C NMR spectroscopic techniques as described previously (El-Daly et al., 2008; Gaber et al., 2009; El-Sayed, 2013). By using UV visible spectroscopy method the mole fraction ratio for copper with DMAPP and DEAPP complexes were determined and it was found to be 1:1. The stability constants of this complex have been determined by Job's method. The stability constant (Kf) of copper with DMAPP and DEAPP complexes in universal buffer pH = 3.2 was determined to be 9.9 × 104 and 5.2 × 104 respectively. The effect of Cu(II) ion on the emission spectrum of the free chalcone is also assigned. Adherence to Beer's law and Ringbom optimum concentration ranges are determined. The thermal decomposition of the metal complexes is studied by TGA technique. The kinetic parameters like activation energy, pre-exponential factor and entropy of activation are estimated. The structure of complexes was energetically optimized through molecular mechanics applying MM+ force field coupled with molecular dynamics simulation. The bond lengths and bond angles have been calculated to confirm the geometry of the ligands and their Cu(II) complexes. The mode of interaction of the chalcone to copper nanoparticles was studied. The apparent association constants of the colloidal copper nanoparticles:chalcone complexes in solution were evaluated using the spectral method and compared with the formation constant of the Cu(II) chalcone complexes. Antioxidant activity of these chalcones was evaluated by using 1,1‧-diphenyl-2-picrylhydrazyl (DPPHrad) radicals scavenging method, which showed that the antioxidant activity of DMAPP has higher value than the DEAPP. Semi-empirical study results showed that DMAPP have higher dipole moment than DEAPP [1].

  14. Binuclear trivalent and tetravalent uranium halides and cyanides supported by cyclooctatetraene ligands

    International Nuclear Information System (INIS)

    Wang, Cong-Zhi; Wu, Qun-Yan; Lan, Jian-Hui; Shi, Wei-Qun; Gibson, John K.

    2017-01-01

    Although the first organoactinide chloride Cp_3UCl (Cp = η"5-C_5H_5) was synthesized more than 50 years ago, binuclear uranium halides remain very rare in organoactinide chemistry. Herein, a series of binuclear trivalent and tetravalent uranium halides and cyanides with cyclooctatetraene ligands, (COT)_2U_2X_n (COT = η"8-C_8H_8; X=F, Cl, CN; n=2, 4), have been systematically studied using scalar-relativistic density functional theory (DFT). The structures with bridging halide or cyanide ligands were predicted to be the most stable complexes of (COT)_2U_2X_n, and all the complexes show weak antiferromagnetic interactions between the uranium centers. However, for each species, there is no significant uranium-uranium bonding interaction. The bonding between the metal and the ligands shows some degree of covalent character, especially between the metal and terminal halide or cyanide ligands. The U-5f and 6d orbitals are predominantly involved in the metal-ligand bonding. All the (COT)_2U_2X_n species were predicted to be more stable compared to the mononuclear half-sandwich complexes at room temperature in the gas phase such that (COT)_2U_2X_4 might be accessible through the known (COT)_2U complex. The tetravalent derivatives (COT)_2U_2X_4 are more energetically favorable than the trivalent (COT)_2U_2X_2 analogs, which may be attributed to the greater number of strong metal-ligand bonds in the former complexes.

  15. Binuclear trivalent and tetravalent uranium halides and cyanides supported by cyclooctatetraene ligands

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Cong-Zhi; Wu, Qun-Yan; Lan, Jian-Hui; Shi, Wei-Qun [Chinese Academy of Sciences, Beijing (China). Laboratory of Nuclear Energy Chemistry and Key Laboratory for Biomedical Effects of Nanomaterials and Nanosafety; Chai, Zhi-Fang [Chinese Academy of Sciences, Beijing (China). Laboratory of Nuclear Energy Chemistry and Key Laboratory for Biomedical Effects of Nanomaterials and Nanosafety; Soochow Univ., Suzhou (China). School of Radiological and Interdisciplinary Sciences (RAD-X); Gibson, John K. [Lawrence Berkeley National Laboratory, CA (United States). Chemical Sciences Division

    2017-03-01

    Although the first organoactinide chloride Cp{sub 3}UCl (Cp = η{sup 5}-C{sub 5}H{sub 5}) was synthesized more than 50 years ago, binuclear uranium halides remain very rare in organoactinide chemistry. Herein, a series of binuclear trivalent and tetravalent uranium halides and cyanides with cyclooctatetraene ligands, (COT){sub 2}U{sub 2}X{sub n} (COT = η{sup 8}-C{sub 8}H{sub 8}; X=F, Cl, CN; n=2, 4), have been systematically studied using scalar-relativistic density functional theory (DFT). The structures with bridging halide or cyanide ligands were predicted to be the most stable complexes of (COT){sub 2}U{sub 2}X{sub n}, and all the complexes show weak antiferromagnetic interactions between the uranium centers. However, for each species, there is no significant uranium-uranium bonding interaction. The bonding between the metal and the ligands shows some degree of covalent character, especially between the metal and terminal halide or cyanide ligands. The U-5f and 6d orbitals are predominantly involved in the metal-ligand bonding. All the (COT){sub 2}U{sub 2}X{sub n} species were predicted to be more stable compared to the mononuclear half-sandwich complexes at room temperature in the gas phase such that (COT){sub 2}U{sub 2}X{sub 4} might be accessible through the known (COT){sub 2}U complex. The tetravalent derivatives (COT){sub 2}U{sub 2}X{sub 4} are more energetically favorable than the trivalent (COT){sub 2}U{sub 2}X{sub 2} analogs, which may be attributed to the greater number of strong metal-ligand bonds in the former complexes.

  16. Cytochrome P-450 complex formation in rat liver by the antibiotic tiamulin.

    Science.gov (United States)

    Witkamp, R F; Nijmeijer, S M; van Miert, A S

    1996-01-01

    Tiamulin is a semisynthetic diterpene antibiotic frequently used in farm animals. The drug has been shown to produce clinically important--often lethal--interactions with other compounds. It has been suggested that this is caused by a selective inhibition of oxidative drug metabolism via the formation of a cytochrome P-450 metabolic intermediate complex. In the present study, rats were treated orally for 6 days with tiamulin at two different doses: 40 and 226 mg/kg of body weight. For comparison, another group received 300 mg of triacetyloleandomycin (TAO) per kg, which is equivalent to the 226-mg/kg tiamulin group. Subsequently, microsomal P-450 contents, P-450 enzyme activities, metabolic intermediate complex spectra, and P-450 apoprotein concentrations were assessed. In addition, effects on individual microsomal P-450 activities were studied in control microsomes at different tiamulin and substrate concentrations. In the rats treated with tiamulin, a dose-dependent complex formation as evidenced by its absorption spectrum and an increase in cytochrome P-4503A1/2 contents as assessed by Western blotting (immunoblotting) were found. The effects were comparable to those of TAO. Tiamulin induced microsomal P-450 content, testosterone 6 beta-hydroxylation rate, erythromycin N-demethylation rate, and the ethoxyresorufin O-deethylation activity. Other activities were not affected or decreased. When tiamulin was added to microsomes of control rats, the testosterone 6 beta-hydroxylation rate and the erythromycin N-demethylation were strongly inhibited. It is concluded that tiamulin is a potent and selective inducer-inhibitor of cytochrome P-450. Though not belonging to the macrolides, the compound produces an effect on P-450 similar to those of TAO and related compounds.

  17. Physicochemical properties of mixed phosphorus halides

    International Nuclear Information System (INIS)

    Sladkov, I.B.; Tugarinova, N.S.

    1996-01-01

    Certain physicochemical properties (thermodynamic characteristics at boiling point, critical constants, density of liquid on the saturation line) of mixed phosphorus halides (PI 3 , PI 2 F, PIF 2 , PI 2 Cl, PICl 2 , PI 1 Br, PIBr 2 , PIClF, PIBrCl, etc.) are determined by means of approximate methods. Reliability of the results obtained is confirmed by comparison of calculated and experimental data for phosphorus compounds of the same type. 7 refs., 3 figs., 4 tabs

  18. Thermomechanical measurements of lead halide single crystals

    Czech Academy of Sciences Publication Activity Database

    Nitsch, Karel; Rodová, Miroslava

    2002-01-01

    Roč. 234, č. 2 (2002), s. 701-709 ISSN 0370-1972 R&D Projects: GA AV ČR IAA2010926 Institutional research plan: CEZ:AV0Z1010914 Keywords : PbX 2 (X=Cl, Br, I) * coefficients of linear thermal expansion * polymorphism in lead halides Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 0.930, year: 2002

  19. Formation and Atmosphere of Complex Organic Molecules of the HH 212 Protostellar Disk

    Energy Technology Data Exchange (ETDEWEB)

    Lee, Chin-Fei; Ho, Paul T. P.; Hirano, Naomi; Shang, Hsien [Academia Sinica Institute of Astronomy and Astrophysics, P.O. Box 23-141, Taipei 106, Taiwan (China); Li, Zhi-Yun [Astronomy Department, University of Virginia, Charlottesville, VA 22904 (United States); Zhang, Qizhou, E-mail: cflee@asiaa.sinica.edu.tw [Harvard-Smithsonian Center for Astrophysics, 60 Garden Street, Cambridge, MA 02138 (United States)

    2017-07-01

    HH 212 is a nearby (400 pc) Class 0 protostellar system recently found to host a “hamburger”-shaped dusty disk with a radius of ∼60 au, deeply embedded in an infalling-rotating flattened envelope. We have spatially resolved this envelope-disk system with the Atacama Large Millimeter/submillimeter Array at up to ∼16 au (0.″04) resolution. The envelope is detected in HCO{sup +} J = 4–3 down to the dusty disk. Complex organic molecules (COMs) and doubly deuterated formaldehyde (D{sub 2}CO) are detected above and below the dusty disk within ∼40 au of the central protostar. The COMs are methanol (CH{sub 3}OH), deuterated methanol (CH{sub 2}DOH), methyl mercaptan (CH{sub 3}SH), and formamide (NH{sub 2}CHO, a prebiotic precursor). We have modeled the gas kinematics in HCO{sup +} and COMs and found a centrifugal barrier (CB) at a radius of ∼44 au, within which a Keplerian rotating disk is formed. This indicates that HCO{sup +} traces the infalling-rotating envelope down to the CB and COMs trace the atmosphere of a Keplerian rotating disk within the CB. The COMs are spatially resolved for the first time, both radially and vertically, in the atmosphere of a disk in the earliest, Class 0 phase of star formation. Our spatially resolved observations of COMs favor their formation in the disk rather than a rapidly infalling (warm) inner envelope. The abundances and spatial distributions of the COMs provide strong constraints on models of their formation and transport in low-mass star formation.

  20. Voltammetric investigation of avidin-biotin complex formation using an electroactive bisbiotinyl compound

    International Nuclear Information System (INIS)

    Sugawara, Kazuharu; Shirotori, Tatsuya; Hirabayashi, George; Kamiya, Naoto; Kuramitz, Hideki; Tanaka, Shunitz

    2004-01-01

    Formation of avidin-biotin complex was investigated using bisbiotinyl thionine (BBT) by means of voltammetric techniques. Thionine is an electroactive compound and has two amino groups that are necessary for the reaction with a biotinylation reagent. The biotinylation of thionine produces a new reagent with two biotin moieties at each end of thionine. Three BBTs of different lengths of the spacer that connects the biotin moiety to the thionine moiety were prepared. The avidin-biotin binding assay was achieved by measuring the electrode response of the thionine moiety in BBT. The binding affinity and the conformation of complex, which depended on the length of spacer, are discussed. BBT in which the spacer is shortest (BBT-S, distance between carbonyl group of the two biotin moieties: 11 A) binds with only one avidin molecule. BBT with medium length of spacer (BBT-M, 28.8 A) forms the complex with two avidin molecules. BBT with the longest spacer (BBT-L, 46.6 A) allows binding with two avidin molecules as well as intramolecular binding within one avidin molecule. The affinity constants of BBT-S, BBT-M and BBT-L for avidin were estimated to be 7.0 x 10 12 M -1 , 3.2 x 10 12 M -1 and 4.0 x 10 12 M -1 , respectively

  1. Substrate-Na{sup +} complex formation: Coupling mechanism for {gamma}-aminobutyrate symporters

    Energy Technology Data Exchange (ETDEWEB)

    Pallo, Anna; Simon, Agnes [Department of Neurochemistry, Institute of Biomolecular Chemistry, Chemical Research Center, Hungarian Academy of Sciences (Hungary); Bencsura, Akos [Department of Theoretical Chemistry, Institute of Structural Chemistry, Chemical Research Center, Hungarian Academy of Sciences, Budapest (Hungary); Heja, Laszlo [Department of Neurochemistry, Institute of Biomolecular Chemistry, Chemical Research Center, Hungarian Academy of Sciences (Hungary); Kardos, Julianna, E-mail: jkardos@chemres.hu [Department of Neurochemistry, Institute of Biomolecular Chemistry, Chemical Research Center, Hungarian Academy of Sciences (Hungary)

    2009-07-24

    Crystal structures of transmembrane transport proteins belonging to the important families of neurotransmitter-sodium symporters reveal how they transport neurotransmitters across membranes. Substrate-induced structural conformations of gated neurotransmitter-sodium symporters have been in the focus of research, however, a key question concerning the mechanism of Na{sup +} ion coupling remained unanswered. Homology models of human glial transporter subtypes of the major inhibitory neurotransmitter {gamma}-aminobutyric acid were built. In accordance with selectivity data for subtype 2 vs. 3, docking and molecular dynamics calculations suggest similar orthosteric substrate (inhibitor) conformations and binding crevices but distinguishable allosteric Zn{sup 2+} ion binding motifs. Considering the occluded conformational states of glial human {gamma}-aminobutyric acid transporter subtypes, we found major semi-extended and minor ring-like conformations of zwitterionic {gamma}-aminobutyric acid in complex with Na{sup +} ion. The existence of the minor ring-like conformation of {gamma}-aminobutyric acid in complex with Na{sup +} ion may be attributed to the strengthening of the intramolecular H-bond by the electrostatic effect of Na{sup +} ion. Coupling substrate uptake into cells with the thermodynamically favorable Na{sup +} ion movement through substrate-Na{sup +} ion complex formation may be a mechanistic principle featuring transmembrane neurotransmitter-sodium symporter proteins.

  2. Incorporation of polyoxotungstate complexes in silica spheres and in situ formation of tungsten trioxide nanoparticles.

    Science.gov (United States)

    Zhao, Yuanyuan; Fan, Haimei; Li, Wen; Bi, Lihua; Wang, Dejun; Wu, Lixin

    2010-09-21

    In this paper, we demonstrated a new convenient route for in situ fabrication of well separated small sized WO(3) nanoparticles in silica spheres, through a predeposition of surfactant encapsulated polyoxotungates as tungsten source, and followed by a calcination process. In a typical procedure, selected polyoxotungates with different charges were enwrapped with dioctadecyldimethylammonium cations through electrostatic interaction. Elemental analysis, thermogravimetric analysis, and spectral characterization confirmed the formation of prepared complexes with the anticipated chemical structure. The complexes were then phase-transferred into aqueous solution that predissolved surfactant cetyltrimethylammonium bromide, and finally incorporated into silica spheres through a joint sol-gel reaction with tetraethyl orthosilicate in a well dispersed state under the protection of organic layer for polyoxotungates from the alkaline reaction condition. Transmission electron microscopic images illustrated the well dispersed WO(3) nanoparticles in the size range of ca. 2.2 nm in the silica spheres after the calcination at 465 °C. The sizes of both the silica spheres and WO(3) nanoparticles could be adjusted independently through changing the doping content to a large extent. Meanwhile, the doped polyoxotungate complexes acted as the template for the mesoporous structure in silica spheres after the calcination. Along with the increase of doping content and surfactant, the mesopore size changed little (2.0-2.9 nm), but the specific surface areas increased quite a lot. Importantly, the WO(3)-nanoparticle-doped silica spheres displayed an interesting photovoltaic property, which is favorable for the funtionalization of these nanomaterials.

  3. Colorimetric method for enzymatic screening assay of ATP using Fe(III)-xylenol orange complex formation.

    Science.gov (United States)

    Ishida, Akihiko; Yamada, Yasuko; Kamidate, Tamio

    2008-11-01

    In hygiene management, recently there has been a significant need for screening methods for microbial contamination by visual observation or with commonly used colorimetric apparatus. The amount of adenosine triphosphate (ATP) can serve as the index of a microorganism. This paper describes the development of a colorimetric method for the assay of ATP, using enzymatic cycling and Fe(III)-xylenol orange (XO) complex formation. The color characteristics of the Fe(III)-XO complexes, which show a distinct color change from yellow to purple, assist the visual observation in screening work. In this method, a trace amount of ATP was converted to pyruvate, which was further amplified exponentially with coupled enzymatic reactions. Eventually, pyruvate was converted to the Fe(III)-XO complexes through pyruvate oxidase reaction and Fe(II) oxidation. As the assay result, yellow or purple color was observed: A yellow color indicates that the ATP concentration is lower than the criterion of the test, and a purple color indicates that the ATP concentration is higher than the criterion. The method was applied to the assay of ATP extracted from Escherichia coli cells added to cow milk.

  4. A Natural Mutation Involving both Pathogenicity and Perithecium Formation in the Fusarium graminearum Species Complex

    Directory of Open Access Journals (Sweden)

    Haruhisha Suga

    2016-12-01

    Full Text Available Members of the Fusarium graminearum species complex (Fg complex or FGSC are the primary pathogens causing Fusarium head blight in wheat and barley worldwide. A natural pathogenicity mutant (strain 0225022 was found in a sample of the Fg complex collected in Japan. The mutant strain did not induce symptoms in wheat spikes beyond the point of inoculation, and did not form perithecia. No segregation of phenotypic deficiencies occurred in the progenies of a cross between the mutant and a fully pathogenic wild-type strain, which suggested that a single genetic locus controlled both traits. The locus was mapped to chromosome 2 by using sequence-tagged markers; and a deletion of ∼3 kb was detected in the mapped region of the mutant strain. The wild-type strain contains the FGSG_02810 gene, encoding a putative glycosylphosphatidylinositol anchor protein, in this region. The contribution of FGSG_02810 to pathogenicity and perithecium formation was confirmed by complementation in the mutant strain using gene transfer, and by gene disruption in the wild-type strain.

  5. BAG3 regulates formation of the SNARE complex and insulin secretion

    Science.gov (United States)

    Iorio, V; Festa, M; Rosati, A; Hahne, M; Tiberti, C; Capunzo, M; De Laurenzi, V; Turco, M C

    2015-01-01

    Insulin release in response to glucose stimulation requires exocytosis of insulin-containing granules. Glucose stimulation of beta cells leads to focal adhesion kinase (FAK) phosphorylation, which acts on the Rho family proteins (Rho, Rac and Cdc42) that direct F-actin remodeling. This process requires docking and fusion of secretory vesicles to the release sites at the plasma membrane and is a complex mechanism that is mediated by SNAREs. This transiently disrupts the F-actin barrier and allows the redistribution of the insulin-containing granules to more peripheral regions of the β cell, hence facilitating insulin secretion. In this manuscript, we show for the first time that BAG3 plays an important role in this process. We show that BAG3 downregulation results in increased insulin secretion in response to glucose stimulation and in disruption of the F-actin network. Moreover, we show that BAG3 binds to SNAP-25 and syntaxin-1, two components of the t-SNARE complex preventing the interaction between SNAP-25 and syntaxin-1. Upon glucose stimulation BAG3 is phosphorylated by FAK and dissociates from SNAP-25 allowing the formation of the SNARE complex, destabilization of the F-actin network and insulin release. PMID:25766323

  6. Spectrophotometric determination of tizanidine and orphenadrine via ion pair complex formation using eosin Y

    Directory of Open Access Journals (Sweden)

    Eid Manal I

    2011-10-01

    Full Text Available Abstract A simple, sensitive and rapid spectrophotometric method was developed and validated for the determination of two skeletal muscle relaxants namely, tizanidine hydrochloride (I and orphenadrine citrate (II in pharmaceutical formulations. The proposed method is based on the formation of a binary complex between the studied drugs and eosin Y in aqueous buffered medium (pH 3.5. Under the optimum conditions, the binary complex showed absorption maxima at 545 nm for tizanidine and 542 nm for orphenadrine. The calibration plots were rectilinear over concentration range of 0.5-8 μg/mL and 1-12 μg/mL with limits of detection of 0.1 μg/mL and 0.3 μg/mL for tizanidine and orphenadrine respectively. The different experimental parameters affecting the development and stability of the complex were studied and optimized. The method was successfully applied for determination of the studied drugs in their dosage forms; and to the content uniformity test of tizanidine in tablets.

  7. Electrochemistry of plutonium in molten halides

    International Nuclear Information System (INIS)

    McCurry, L.E.; Moy, G.M.M.; Bowersox, D.F.

    1987-01-01

    The electrochemistry of plutonium in molten halides is of technological importance as a method of purification of plutonium. Previous authors have reported that plutonium can be purified by electrorefining impure plutonium in various molten haldies. Work to eluciate the mechanism of the plutonium reduction in molten halides has been limited to a chronopotentiometric study in LiCl-KCl. Potentiometric studies have been carried out to determine the standard reduction potential for the plutonium (III) couple in various molten alkali metal halides. Initial cyclic voltammetric experiments were performed in molten KCL at 1100 K. A silver/silver chloride (10 mole %) in equimolar NaCl-KCl was used as a reference electrode. Working and counter electrodes were tungsten. The cell components and melt were contained in a quartz crucible. Background cyclic voltammograms of the KCl melt at the tungsten electrode showed no evidence of electroactive impurities in the melt. Plutonium was added to the melt as PuCl/sub 3/, which was prepared by chlorination of the oxide. At low concentrations of PuCl/sub 3/ in the melt (0.01-0.03 molar), no reduction wave due to the reduction of Pu(III) was observed in the voltammograms up to the potassium reduction limit of the melt. However on scan reversal after scanning into the potassium reduction limit a new oxidation wave was observed

  8. Investigation of surface halide modification of nitrile butadiene rubber

    Science.gov (United States)

    Sukhareva, K. V.; Mikhailov, I. A.; Andriasyan, Yu O.; Mastalygina, E. E.; Popov, A. A.

    2017-12-01

    The investigation is devoted to the novel technology of surface halide modification of rubber samples based on nitrile butadiene rubber (NBR). 1,1,2-trifluoro-1,2,2-trichlorethane was used as halide modifier. The developed technology is characterized by production stages reduction to one by means of treating the rubber compound with a halide modifier. The surface halide modification of compounds based on nitrile butadiene rubber (NBR) was determined to result in increase of resistance to thermal oxidation and aggressive media. The conducted research revealed the influence of modification time on chemical resistance and physical-mechanical properties of rubbers under investigation.

  9. Lanthanide doped strontium-barium cesium halide scintillators

    Science.gov (United States)

    Bizarri, Gregory; Bourret-Courchesne, Edith; Derenzo, Stephen E.; Borade, Ramesh B.; Gundiah, Gautam; Yan, Zewu; Hanrahan, Stephen M.; Chaudhry, Anurag; Canning, Andrew

    2015-06-09

    The present invention provides for a composition comprising an inorganic scintillator comprising an optionally lanthanide-doped strontium-barium, optionally cesium, halide, useful for detecting nuclear material.

  10. Complex formation of uranium(VI) with fructose and glucose phosphates

    International Nuclear Information System (INIS)

    Koban, A.; Geipel, G.; Bernhard, G.; Fanghaenel, T.

    2002-01-01

    scale, we obtain: log [UO 2 (lig) x (2-y)+ ]/ [UO 2 2+ ] = x log [lig(noncomplexed)] - y log [H + ] + log K. From this we conclude that the 1:1 uranyl sugar phosphate species UO 2 (ROPO 3 ) (R is either glucose or fructose) has formed. Using these data, the complex formation constants for the complexes were calculated to lie in the range of log K=3.7 for G6P and 3.2 for F6P. (author)

  11. Theoretical predictions of hydrolysis and complex formation of group-4 elements Zr, Hf and Rf in HF and HCl solutions

    International Nuclear Information System (INIS)

    Pershina, V.; Trubert, D.; Le Naour, C.; Kratz, J.V.

    2002-01-01

    Fully relativistic molecular density-functional calculations of the electronic structures of hydrated, hydrolyzed and fluoride/chloride complexes have been performed for group-4 elements Zr, Hf, and element 104, Rf. Using the electronic density distribution data, relative values of the free energy change for hydrolysis and complex formation reactions were defined. The results show the following trend for the first hydrolysis step of the cationic species: Zr>Hf>Rf in agreement with experiments. For the complex formation in HF solutions, the trend to a decrease from Zr to Hf is continued with Rf, provided no hydrolysis takes place. At pH>0, further fluorination of hydrolyzed species or fluoro-complexes has an inversed trend in the group Rf≥Zr>Hf, with the difference between the elements being very small. For the complex formation in HCl solutions, the trend is continued with Rf, so that Zr>Hf>Rf independently of pH. A decisive energetic factor in hydrolysis or complex formation processes proved to be a predominant electrostatic metal-ligand interaction. Trends in the K d (distribution coefficient) values for the group-4 elements are expected to follow those of the complex formation

  12. Polysaccharide charge density regulating protein adsorption to air/water interfaces by protein/polysaccharide complex formation

    NARCIS (Netherlands)

    Ganzevles, R.A.; Kosters, H.; Vliet, T. van; Stuart, M.A.C.; Jongh, H.H.J. de

    2007-01-01

    Because the formation of protein/polysaccharide complexes is dominated by electrostatic interaction, polysaccharide charge density is expected to play a major role in the adsorption behavior of the complexes. In this study, pullulan (a non-charged polysaccharide) carboxylated to four different

  13. Unprecedented Carbonato Intermediates in Cyclic Carbonate Synthesis Catalysed by Bimetallic Aluminium(Salen) Complexes.

    Science.gov (United States)

    Castro-Osma, José A; North, Michael; Offermans, Willem K; Leitner, Walter; Müller, Thomas E

    2016-04-21

    The mechanism by which [Al(salen)]2 O complexes catalyse the synthesis of cyclic carbonates from epoxides and carbon dioxide in the absence of a halide cocatalyst has been investigated. Density functional theory (DFT) studies, mass spectrometry and (1) H NMR, (13) C NMR and infrared spectroscopies provide evidence for the formation of an unprecedented carbonato bridged bimetallic aluminium complex which is shown to be a key intermediate for the halide-free synthesis of cyclic carbonates from epoxides and carbon dioxide. Deuterated and enantiomerically-pure epoxides were used to study the reaction pathway. Based on the experimental and theoretical results, a catalytic cycle is proposed. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Formation of quinones, indanones and furans by the reaction of molybdenum carbene complexes with alkynes

    International Nuclear Information System (INIS)

    Doetz, K.H.; Larbig, H.

    1992-01-01

    (Alkoxy)carbene complexes of molybdenum react with terminal alkynes to give carbene annulation of cycloaddition products, the skeleton of which depends on the carbene substitution pattern and the alkyne used. (CO) 5 Mo=C(OMe)-p-tol undergoes carbene annulation upon reaction with trimethylsilylacetylene leading to naphthoquinone after oxidative work-up. Similar products are obtained from (CO) 5 Mo=C(OMe)2-furyl and hex-1-yne or oct-1-yne. The reaction of these alkynes results in the formation of indanones as five-membered annulation products. In the presence of 3.3-dimethylbut-1-yne the (phenyl) carbene ligands act as a C 1 -synthon, which is incorporated into the furan cycloaddition products

  15. Dimerisation, rhodium complex formation and rearrangements of N-heterocyclic carbenes of indazoles

    Directory of Open Access Journals (Sweden)

    Zong Guan

    2014-04-01

    Full Text Available Deprotonation of indazolium salts at low temperatures gives N-heterocyclic carbenes of indazoles (indazol-3-ylidenes which can be trapped as rhodium complexes (X-ray analysis. In the absence of Rh, the indazol-3-ylidenes spontaneously dimerize under ring cleavage of one of the N,N-bonds and ring closure to an indazole–indole spiro compound which possesses an exocyclic imine group. The E/Z isomers of the imines can be separated by column chromatography when methanol is used as eluent. We present results of a single crystal X-ray analysis of one of the E-isomers, which equilibrate in solution as well as in the solid state. Heating of the indazole–indole spiro compounds results in the formation of quinazolines by a ring-cleavage/ring-closure sequence (X-ray analysis. Results of DFT calculations are presented.

  16. Complex formation of hypoxanthine and 6-mercaptopurine with Cd(II) ion

    International Nuclear Information System (INIS)

    Perello, L.; Borras, J.; Soto, L.; Gordo, F.J.; Gordo, J.C.

    1984-01-01

    Reaction of Cd(II) ion with hypoxanthine (H 2 Y) and with 6-mercaptopurine (H 2 MP) in dioxane-water (50%) leads to the formation of CdY x 2H 2 O and Cd(HMP) 2 x 2H 2 O, respectively. In methanolic medium Cd(II) and H 2 MP give Cd(MP) x H 2 O. These compounds have been characterized by chemical analysis, IR spectra and thermogravimetric analysis. The stability constant of CdY complex at 25 +- 0.1 0 C and 1M ionic strength with NaClO 4 in dioxane-water medium is logβ = 10.25 +- 0.05. (Author)

  17. Complex formation of hypoxanthine and 6-mercaptopurine with Cd(II) ion

    Energy Technology Data Exchange (ETDEWEB)

    Perello, L.; Borras, J.; Soto, L.; Gordo, F.J.; Gordo, J.C. (Valencia Univ. (Spain))

    1984-01-01

    Reaction of Cd(II) ion with hypoxanthine (H/sub 2/Y) and with 6-mercaptopurine (H/sub 2/MP) in dioxane-water (50%) leads to the formation of CdY x 2H/sub 2/O and Cd(HMP)/sub 2/ x 2H/sub 2/O, respectively. In methanolic medium Cd(II) and H/sub 2/MP give Cd(MP) x H/sub 2/O. These compounds have been characterized by chemical analysis, IR spectra and thermogravimetric analysis. The stability constant of CdY complex at 25 +- 0.1/sup 0/C and 1M ionic strength with NaClO/sub 4/ in dioxane-water medium is log..beta.. = 10.25 +- 0.05.

  18. Formation of ammonia complexes of alkaline earth elements in aqueous solutions

    International Nuclear Information System (INIS)

    Padar, T.G.; Stupko, T.V.; Isaev, I.D.; Pashkov, G.L.; Mironov, V.E.

    1990-01-01

    Coefficients of ammonia distribution between aqueous solutions of calcium, strontium, barium and ammonium perchlorate mixtures at ionic strength - 0.50; 1.0 and 1.5 at 298.2 K and ammonia concentrations 0.2-10 mol/dm 3 are measured. Formation of ammonia complexes of M(NH 3 ) n 2+ composition is shown. Logarithms of stepped stability constants for solutions with zero ionic strength for Ca 2+ are: -0.13; -0.25; -0.52 and -0.77, where n=1-4; for Sr 2+ : -0.04; -0.42 and -0.70, where n=1-3 and for Ba 2+ : -0.11; -0.50 and 0.76, where n=1-3

  19. Hydration of the sulfuric acid-methylamine complex and implications for aerosol formation.

    Science.gov (United States)

    Bustos, Danielle J; Temelso, Berhane; Shields, George C

    2014-09-04

    The binary H2SO4-H2O nucleation is one of the most important pathways by which aerosols form in the atmosphere, and the presence of ternary species like amines increases aerosol formation rates. In this study, we focus on the hydration of a ternary system of sulfuric acid (H2SO4), methylamine (NH2CH3), and up to six waters to evaluate its implications for aerosol formation. By combining molecular dynamics (MD) sampling with high-level ab initio calculations, we determine the thermodynamics of forming H2SO4(NH2CH3)(H2O)n, where n = 0-6. Because it is a strong acid-base system, H2SO4-NH2CH3 quickly forms a tightly bound HSO4(-)-NH3CH3(+) complex that condenses water more readily than H2SO4 alone. The electronic binding energy of H2SO4-NH2CH3 is -21.8 kcal mol(-1) compared with -16.8 kcal mol(-1) for H2SO4-NH3 and -12.8 kcal mol(-1) for H2SO4-H2O. Adding one to two water molecules to the H2SO4-NH2CH3 complex is more favorable than adding to H2SO4 alone, yet there is no systematic difference for n ≥ 3. However, the average number of water molecules around H2SO4-NH2CH3 is consistently higher than that of H2SO4, and it is fairly independent of temperature and relative humidity.

  20. Formation of polyelectrolyte complexes with diethylaminoethyl dextran: charge ratio and molar mass effect.

    Science.gov (United States)

    Le Cerf, Didier; Pepin, Anne Sophie; Niang, Pape Momar; Cristea, Mariana; Karakasyan-Dia, Carole; Picton, Luc

    2014-11-26

    The formation of polyelectrolyte complexes (PECs) between carboxymethyl pullulan and DEAE Dextran, was investigated, in dilute solution, with emphasis on the effect of charge density (molar ratio or pH) and molar masses. Electrophoretic mobility measurements have evidenced that insoluble PECs (neutral electrophoretic mobility) occurs for charge ratio between 0.6 (excess of polycation) and 1 (stoichiometry usual value) according to the pH. This atypical result is explained by the inaccessibility of some permanent cationic charge when screened by pH dependant cationic ones (due to the Hoffman alkylation). Isothermal titration calorimetry (ITC) indicates an endothermic formation of PEC with a binding constant around 10(5) L mol(-1). Finally asymmetrical flow field flow fractionation coupled on line with static multi angle light scattering (AF4/MALS) evidences soluble PECs with very large average molar masses and size around 100 nm, in agreement with scrambled eggs multi-association between various polyelectrolyte chains. Copyright © 2014 Elsevier Ltd. All rights reserved.

  1. Teacher formation related to socio-scientific issues: complexity, contributions and limitations of an educational practice

    Directory of Open Access Journals (Sweden)

    Mariuce Campos de Moraes

    2015-12-01

    Full Text Available This reflection refers to teacher formation related to socio-scientific issues. Whereas such matters take into account the impact of scientific development in society, including ethical aspects and encompass dilemmas involving a wide range of prospects for its resolution, we propose analysis of the complexity that is inherent in their teaching. Thus, we aimed to analyze different spaces and teaching time that produce and are produced in close linkage between theory and practice, as well as their contributions and limitations. The study required a dynamic conversation system that led to the analysis indicators. The issue of sustainability was shown to be feasible for educational planning as cover technical and scientific knowledge, ethical, social and economic pressures. The collective production allowed understand arguments and reflective-creative processes. The lived relations in schools has accompanied and limited the ideas expressed on the socio-scientific issues. We understand that the simultaneity of research and reflection in the sociocultural context has strengthened teacher formation.

  2. Star Formation and Young Population of the H II Complex Sh2-294

    Science.gov (United States)

    Samal, M. R.; Pandey, A. K.; Ojha, D. K.; Chauhan, N.; Jose, J.; Pandey, B.

    2012-08-01

    The Sh2-294 H II region ionized by a single B0V star features several infrared excess sources, a photodissociation region, and also a group of reddened stars at its border. The star formation scenario in this region seems to be quite complex. In this paper, we present follow-up results of Sh2-294 H II region at 3.6, 4.5, 5.8, and 8.0 μm observed with the Spitzer Space Telescope Infrared Array Camera (IRAC), coupled with H2 (2.12 μm) observation, to characterize the young population of the region and to understand its star formation history. We identified 36 young stellar object (YSO, Class I, Class II, and Class I/II) candidates using IRAC color-color diagrams. It is found that Class I sources are preferentially located at the outskirts of the H II region and associated with enhanced H2 emission; none of them are located near the central cluster. Combining the optical to mid-infrared (MIR) photometry of the YSO candidates and using the spectral energy distribution fitting models, we constrained stellar parameters and the evolutionary status of 33 YSO candidates. Most of them are interpreted by the model as low-mass (<4 M ⊙) YSOs; however, we also detected a massive YSO (~9 M ⊙) of Class I nature, embedded in a cloud of visual extinction of ~24 mag. Present analysis suggests that the Class I sources are indeed a younger population of the region relative to Class II sources (age ~ 4.5 × 106 yr). We suggest that the majority of the Class I sources, including the massive YSOs, are second-generation stars of the region whose formation is possibly induced by the expansion of the H II region powered by a ~4 × 106 yr B0 main-sequence star.

  3. STAR FORMATION AND YOUNG POPULATION OF THE H II COMPLEX Sh2-294

    International Nuclear Information System (INIS)

    Samal, M. R.; Pandey, A. K.; Chauhan, N.; Jose, J.; Ojha, D. K.; Pandey, B.

    2012-01-01

    The Sh2-294 H II region ionized by a single B0V star features several infrared excess sources, a photodissociation region, and also a group of reddened stars at its border. The star formation scenario in this region seems to be quite complex. In this paper, we present follow-up results of Sh2-294 H II region at 3.6, 4.5, 5.8, and 8.0 μm observed with the Spitzer Space Telescope Infrared Array Camera (IRAC), coupled with H 2 (2.12 μm) observation, to characterize the young population of the region and to understand its star formation history. We identified 36 young stellar object (YSO, Class I, Class II, and Class I/II) candidates using IRAC color-color diagrams. It is found that Class I sources are preferentially located at the outskirts of the H II region and associated with enhanced H 2 emission; none of them are located near the central cluster. Combining the optical to mid-infrared (MIR) photometry of the YSO candidates and using the spectral energy distribution fitting models, we constrained stellar parameters and the evolutionary status of 33 YSO candidates. Most of them are interpreted by the model as low-mass ( ☉ ) YSOs; however, we also detected a massive YSO (∼9 M ☉ ) of Class I nature, embedded in a cloud of visual extinction of ∼24 mag. Present analysis suggests that the Class I sources are indeed a younger population of the region relative to Class II sources (age ∼ 4.5 × 10 6 yr). We suggest that the majority of the Class I sources, including the massive YSOs, are second-generation stars of the region whose formation is possibly induced by the expansion of the H II region powered by a ∼4 × 10 6 yr B0 main-sequence star.

  4. Thermodynamic Investigation and Mixed Ligand Complex Formation of 1,4-Bis-(3-aminopropyl)-piperazine and Biorelevant Ligands.

    Science.gov (United States)

    El-Sherif, Ahmed A; Shehata, Mohamed R; Shoukry, Mohamed M; Barakat, Mohammad H

    2012-01-01

    Thermodynamic parameters for protonation of 1,4-bis(3-aminopropyl)-piperazine (BAPP) and its metal complexation with some divalent metal ions were determined in aqueous solution at constant ionic strength (0.1 M NaNO(3)) using a potentiometric technique. The order of -ΔG(0) and -ΔH(0) was found to obey Co(2+) Zn(2+), in accordance with the Irving-Williams order. The formation equilibria of zinc (II) complexes and the ternary complexes Zn(BAPP)L, where L = amino acid, amides, or DNA constituents), have been investigated. Ternary complexes are formed by a simultaneous mechanism. The concentration distribution of the complexes in solution was evaluated as a function of pH. Stoichiometry and stability constants for the complexes formed are reported and discussed. The stability of ternary complexes was quantitatively compared with their corresponding binary complexes in terms of the parameter Δlog K.

  5. Spectrophotometric Determination of Gemifloxacin Mesylate in Pharmaceutical Formulations Through Ion-Pair Complex Formation

    Directory of Open Access Journals (Sweden)

    Marothu Vamsi Krishna

    2008-01-01

    Full Text Available Four simple and sensitive ion-pairing spectrophotometric methods have been described for the assay of gemifloxacin mesylate (GFX either in pure form or in pharmaceutical formulations. The developed methods involve formation of colored chloroform extractable ion-pair complexes of the drug with safranin O (SFN O and methylene blue (MB in basic medium; Napthol blue 12BR (NB 12BR and azocaramine G (AG in acidic medium. The extracted complexes showed absorbance maxima at 525, 650, 620 and 540 nm for SFN O, MB, NB 12BR and AG, respectively.Beer's law is obeyed in the concentration ranges 3-15, 4-20, 2-10 and 2-10 μg/mL with molar absorptivity of 2.81 × 104, 2.20 x 104, 4.02 × 104 and 4.15 × 104 L mole−1 cm−1 and relative standard deviation of 0.077, 0.104, 0.080 and 0.103% for SFN O, MB, NB 12BR and AG, respectively. These methods have been successfully applied for the assay of drug in pharmaceutical formulations. No interference was observed from common pharmaceutical adjuvants. Results of analysis were validated statistically and through recovery studies.

  6. Enhanced conformational sampling to visualize a free-energy landscape of protein complex formation.

    Science.gov (United States)

    Iida, Shinji; Nakamura, Haruki; Higo, Junichi

    2016-06-15

    We introduce various, recently developed, generalized ensemble methods, which are useful to sample various molecular configurations emerging in the process of protein-protein or protein-ligand binding. The methods introduced here are those that have been or will be applied to biomolecular binding, where the biomolecules are treated as flexible molecules expressed by an all-atom model in an explicit solvent. Sampling produces an ensemble of conformations (snapshots) that are thermodynamically probable at room temperature. Then, projection of those conformations to an abstract low-dimensional space generates a free-energy landscape. As an example, we show a landscape of homo-dimer formation of an endothelin-1-like molecule computed using a generalized ensemble method. The lowest free-energy cluster at room temperature coincided precisely with the experimentally determined complex structure. Two minor clusters were also found in the landscape, which were largely different from the native complex form. Although those clusters were isolated at room temperature, with rising temperature a pathway emerged linking the lowest and second-lowest free-energy clusters, and a further temperature increment connected all the clusters. This exemplifies that the generalized ensemble method is a powerful tool for computing the free-energy landscape, by which one can discuss the thermodynamic stability of clusters and the temperature dependence of the cluster networks. © 2016 The Author(s).

  7. RIT1 controls actin dynamics via complex formation with RAC1/CDC42 and PAK1.

    Science.gov (United States)

    Meyer Zum Büschenfelde, Uta; Brandenstein, Laura Isabel; von Elsner, Leonie; Flato, Kristina; Holling, Tess; Zenker, Martin; Rosenberger, Georg; Kutsche, Kerstin

    2018-05-01

    RIT1 belongs to the RAS family of small GTPases. Germline and somatic RIT1 mutations have been identified in Noonan syndrome (NS) and cancer, respectively. By using heterologous expression systems and purified recombinant proteins, we identified the p21-activated kinase 1 (PAK1) as novel direct effector of RIT1. We found RIT1 also to directly interact with the RHO GTPases CDC42 and RAC1, both of which are crucial regulators of actin dynamics upstream of PAK1. These interactions are independent of the guanine nucleotide bound to RIT1. Disease-causing RIT1 mutations enhance protein-protein interaction between RIT1 and PAK1, CDC42 or RAC1 and uncouple complex formation from serum and growth factors. We show that the RIT1-PAK1 complex regulates cytoskeletal rearrangements as expression of wild-type RIT1 and its mutant forms resulted in dissolution of stress fibers and reduction of mature paxillin-containing focal adhesions in COS7 cells. This effect was prevented by co-expression of RIT1 with dominant-negative CDC42 or RAC1 and kinase-dead PAK1. By using a transwell migration assay, we show that RIT1 wildtype and the disease-associated variants enhance cell motility. Our work demonstrates a new function for RIT1 in controlling actin dynamics via acting in a signaling module containing PAK1 and RAC1/CDC42, and highlights defects in cell adhesion and migration as possible disease mechanism underlying NS.

  8. Labeled EF-Tus for rapid kinetic studies of pretranslocation complex formation

    DEFF Research Database (Denmark)

    Liu, Wei; Kavaliauskas, Darius; Schrader, Jared

    2014-01-01

    The universally conserved translation elongation factor EF-Tu delivers aminoacyl(aa)-tRNA in the form of an aa-tRNA·EF-Tu·GTP ternary complex (TC) to the ribosome where it binds to the cognate mRNA codon within the ribosomal A-site, leading to formation of a pretranslocation (PRE) complex. Here we...... describe preparation of QSY9 and Cy5 derivatives of the variant E348C-EF-Tu that are functional in translation elongation. Together with fluorophore derivatives of aa-tRNA and of ribosomal protein L11, located within the GTPase associated center (GAC), these labeled EF-Tus allow development of two new FRET...... assays that permit the dynamics of distance changes between EF-Tu and both L11 (Tu-L11 assay) and aa-tRNA (Tu-tRNA assay) to be determined during the decoding process. We use these assays to examine: (i) the relative rates of EF-Tu movement away from the GAC and from aa-tRNA during decoding, (ii...

  9. Spectrophotometric Determination of Terbutaline Sulphate and Tetracycline Hydrochloride via ion pair Complex Formation Using Eosin Y

    Directory of Open Access Journals (Sweden)

    Mohamed Y. Dhamra

    2014-06-01

    Full Text Available A simple, sensitive and rapid spectrophotometric method was developed and validated for the determination of terbutaline sulphate and tetracycline hydrochloride drugs in pure form and pharmaceutical formulations. The proposed method is based on the formation of binary complexes between these drugs and eosin Y in aqueous acetate buffered medium. Under the optimum conditions, the binary complexes showed absorption maxima at 545 nm. Beer's law was rectilinear over concentration range of 0.5-10 and 5-45 μg/mL, R2 were 0.9984 and 0.9988, RSD were ≤ 0.72 and ≤ 0.19 (n=5 with average recovery % 101.42 % and 100.08 % and the average recovery values of pharmaceutical formulations 101.48 and 98.01 for above drugs respectively. The limit of detection (LOD were 0.030 and 0.613 μg/mL and limit of quantitation (LOQ were 0.103 and 2.00 μg/mL with molar absorptivity values 3.169  103 and 6.347  103 l. mol-1. cm-1 and the relative standard deviation values ≤0.720 and ≤ 0.19 for both drugs respectively. No interference was observed from the excipients that are commonly present in pharmaceutical formulations. The proposed method was successfully applied to the analysis of terbutaline sulphate tablet and tetracycline hydrochloride capsule in their dosage forms.

  10. Spectrophotometric determination of terbutaline sulphate and tetracycline hydrochloride via ion pair complex formation using eosin y

    International Nuclear Information System (INIS)

    Dhamra, M.Y.; Sabha, T.N.A.; Ghabsha, T.S.A.

    2014-01-01

    A simple, sensitive and rapid spectrophotometric method was developed and validated for the determination of terbutaline sulphate and tetracycline hydrochloride drugs in pure form and pharmaceutical formulations. The proposed method is based on the formation of binary complexes between these drugs and eosin Y in aqueous acetate buffered medium. Under the optimum conditions, the binary complexes showed absorption maxima at 545 nm. Beer's law was rectilinear over concentration range of 0.5-10 and 5-45 micro g/mL, R/sub 2/ were 0.9984 and 0.9988, RSD were 0.72 and 0.19 (n=5) with average recovery 101.42 % and 100.08 % and the average recovery values of pharmaceutical formulations 101.48 and 98.01 for above drugs respectively. The limit of detection (LOD) were 0.030 and 0.613 micro g/mL and limit of quantitation (LOQ) were 0.103 and 2.00 micro g/mL with molar absorptivity values 3.169 10/sup 3/ and 6.347 10/sup 3/l. mol/sup -1/. Cm/sup -1/ and the relative standard deviation values 0.720 and 0.19 for both drugs respectively. No interference was observed from the excipients that are commonly present in pharmaceutical formulations. The proposed method was successfully applied to the analysis of terbutaline sulphate tablet and tetracycline hydrochloride capsule in their dosage forms. (author)

  11. Preparation and evaluation of periodontal films based on polyelectrolyte complex formation.

    Science.gov (United States)

    Kassem, Abeer Ahmed; Ismail, Fatma Ahmed; Naggar, Viviane Fahim; Aboulmagd, Elsayed

    2015-05-01

    Local intra-pocket drug delivery devices can provide an effective concentration of the antimicrobial agent at the site of action with avoidance of undesirable side effects. This study explored the application of chitosan-alginate and chitosan-pectin polyelectrolyte complex (PEC) films as drug release regulators for tetracycline HCl (Tc) to treat periodontal pockets. Periodontal films with 1:1 Tc:PEC ratio were prepared using 1:1 chitosan (Ch) to sodium alginate (A) or 1:3 Ch to pectin (P). The scanning electron microscope showed acceptable film appearance and differential scanning calorimetry analysis confirmed complex formation. The in vitro release studies for both films showed a burst drug release, followed by prolonged release for 70 h. A prolonged antibacterial activity of both films against Staphylococcus aureus ATCC 6538 was observed over a period of 21 days. Aging studies indicated that the five months storage period in freezer did not significantly influence the drug release profile or the antibacterial activity of both films. Clinical evaluation showed a significant reduction in pocket depth (p < 0.0001) to their normal values (≤3 mm). PEC films could be exploited as a prolonged drug release devices for treatment of periodontal pockets.

  12. NMR and luminescence spectroscopy study of formation of mixed β-diketonate europium complexes

    International Nuclear Information System (INIS)

    Kavun, V.Ya.; Kalinovskaya, I.V.; Karasev, V.E.; Chernyshov, B.N.; Steblevskaya, N.I.

    1987-01-01

    Methods of NMR ('H, 19 F) and luminescent spectroscopy were applied to study ligand substitution in Eu(β-dik) 3 phen-CDCl 3 -(β-dik)' systems, where β-dik-acetylacetone (AA) and hexafluoroacetyl-acetone (HFAA), phen-1.10-phenathroline at different mole ratio (m) of competing ligands (m=AA/HFAA). Formation of mixed Eu(AA) 2 (HFAA)phen and Eu(AA)(HFAA) 2 phen complexes is proved; calculation of the stark structure of 5 D 0 - 7 F j (j=0,1,2) transitions in low-temperature luminescence spectra is conducted for these complexes. It is stated that at minimum HFAA concentration in the solution the latter replaces AA from europium coordination sphere. It is shown that depending on the value in substitution of acidoligands proceeds successfully by the equations Eu(AA) 3 phen+(NHFAA) n → Eu(AA) 3-n → (HFAA) n phen+(NAA) n ; (n=1,2,3)

  13. Influence of RNA Strand Rigidity on Polyion Complex Formation with Block Catiomers.

    Science.gov (United States)

    Hayashi, Kotaro; Chaya, Hiroyuki; Fukushima, Shigeto; Watanabe, Sumiyo; Takemoto, Hiroyasu; Osada, Kensuke; Nishiyama, Nobuhiro; Miyata, Kanjiro; Kataoka, Kazunori

    2016-03-01

    Polyion complexes (b-PICs) are prepared by mixing single- or double-stranded oligo RNA (aniomer) with poly(ethylene glycol)-b-poly(L-lysine) (PEG-PLL) (block catiomer) to clarify the effect of aniomer chain rigidity on association behaviors at varying concentrations. Here, a 21-mer single-stranded RNA (ssRNA) (persistence length: 1.0 nm) and a 21-mer double-stranded RNA (small interfering RNA, siRNA) (persistence length: 62 nm) are compared. Both oligo RNAs form a minimal charge-neutralized ionomer pair with a single PEG-PLL chain, termed unit b-PIC (uPIC), at low concentrations (<≈ 0.01 mg mL(-1)). Above the critical association concentration (≈ 0.01 mg mL(-1)), ssRNA b-PICs form secondary associates, PIC micelles, with sizes up to 30-70 nm, while no such multimolecular assembly is observed for siRNA b-PICs. The entropy gain associated with the formation of a segregated PIC phase in the multimolecular PIC micelles may not be large enough for rigid siRNA strands to compensate with appreciably high steric repulsion derived from PEG chains. Chain rigidity appears to be a critical parameter in polyion complex association. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Reaction between aminoalkyl radicals and akyl halides: Dehalogenation by electron transfer?

    Science.gov (United States)

    Lalevée, J.; Fouassier, J. P.; Blanchard, N.; Ingold, K. U.

    2011-07-01

    Aminoalkyl radicals, such as Et2NCrad HCH3, have low oxidation potentials and are therefore powerful reducing agents. We have found that Et2NCrad HCH3 reacts with CCl4 and CBr4 in di-tert-butyl peroxide with bimolecular rate constants (measured by LFP) close, or equal, to the diffusion-controlled limit. For the less reactive halide, CH2Br2, the reaction rate is increased substantially by the addition of acetonitrile as a co-solvent. It is tentatively concluded that these reactions occur by electron-transfer from the aminoalkyl to the organohalide with formation of the iminium ion, Et2N+dbnd CHCH3 (NMR detection), halide ion and a halomethyl radical, e.g., rad CCl3 and rad CHCl2 (ESR, spin-trapping detection).

  15. Lateral Fluid Percussion Injury Impairs Hippocampal Synaptic Soluble N-Ethylmaleimide Sensitive Factor Attachment Protein Receptor Complex Formation

    Directory of Open Access Journals (Sweden)

    Shaun W. Carlson

    2017-10-01

    Full Text Available Traumatic brain injury (TBI and the activation of secondary injury mechanisms have been linked to impaired cognitive function, which, as observed in TBI patients and animal models, can persist for months and years following the initial injury. Impairments in neurotransmission have been well documented in experimental models of TBI, but the mechanisms underlying this dysfunction are poorly understood. Formation of the soluble N-ethylmaleimide-sensitive factor attachment protein receptor (SNARE complex facilitates vesicular docking and neurotransmitter release in the synaptic cleft. Published studies highlight a direct link between reduced SNARE complex formation and impairments in neurotransmitter release. While alterations in the SNARE complex have been described following severe focal TBI, it is not known if deficits in SNARE complex formation manifest in a model with reduced severity. We hypothesized that lateral fluid percussion injury (lFPI reduces the abundance of SNARE proteins, impairs SNARE complex formation, and contributes to impaired neurobehavioral function. To this end, rats were subjected to lFPI or sham injury and tested for acute motor performance and cognitive function at 3 weeks post-injury. lFPI resulted in motor impairment between 1 and 5 days post-injury. Spatial acquisition and spatial memory, as assessed by the Morris water maze, were significantly impaired at 3 weeks after lFPI. To examine the effect of lFPI on synaptic SNARE complex formation in the injured hippocampus, a separate cohort of rats was generated and brains processed to evaluate hippocampal synaptosomal-enriched lysates at 1 week post-injury. lFPI resulted in a significant reduction in multiple monomeric SNARE proteins, including VAMP2, and α-synuclein, and SNARE complex abundance. The findings in this study are consistent with our previously published observations suggesting that impairments in hippocampal SNARE complex formation may contribute to

  16. Thermodynamic study on salt effects on complex formation of α-, β- and γ-cyclodextrins with p-aminobenzoic acid

    International Nuclear Information System (INIS)

    Chibunova, E.S.; Kumeev, R.S.; Terekhova, I.V.

    2015-01-01

    Highlights: • Thermodynamic study on salt effects in CD/pABA complex formation was performed. • Effects of KCl, KH 2 PO 4 and K 2 SO 4 are insignificant and nonspecific. • Specific influence of KBr is caused by the ability of Br − to penetrate into CD cavity. • Coexistence of two complexation equilibria is accompanied by solvent reorganization. - Abstract: The aim of this work was to gain a deeper understanding of salt effects in the inclusion complex formation of cyclodextrins. For this purpose, thermodynamic study of complex formation of α-, β- and γ-cyclodextrins with p-aminobenzoic acid was carried out in water and solutions of KCl, KBr, KH 2 PO 4 and K 2 SO 4 (0.2 mol/kg). Stability constants were calculated from the binding isotherms obtained on the basis of 1 H NMR measurements. Enthalpy and entropy of complex formation were estimated from the van’t Hoff plots. It was found that effects of KCl, KH 2 PO 4 and K 2 SO 4 are insignificant, while the influence of KBr on complex formation of cyclodextrins with p-aminobenzoic acid is more pronounced and results in a decrease of the stability constants. Specific action of Br − is caused by the ability of these anions to penetrate into macrocyclic cavity. Coexistence of two complexation equilibria in KBr solution is accompanied by significant solvent reorganization originated from more intensive dehydration of the interacting species. This results in an increase of the enthalpy and entropy of complex formation. Manifestation of Br − effect was found to be the same in the binding of p-aminobenzoic acid with α-, β- and γ-cyclodextrins.

  17. Thermal decomposition of rhenium (5) complexes with 1,2,4-triazole

    International Nuclear Information System (INIS)

    Amindzhanov, A.A.; Gagieva, S.Ch.; Kotegov, K.V.

    1991-01-01

    Processes of thermal decomposition of rhenium (5) complexes with 1,2,4-triazole were studied. Thermolysis products were identified on the basis of data of the element analysis, IR spectra, conductometry and other methods. It is ascertained that at the first stage of thermolysis of hydroxyl-containing monomer complexes removal of water molecules occurs, and at the second one - dimerization process with formation of Re-O-Re group. It is shown that the nature of halide ion practically does not affect the temperature of the start of intensive thermal decomposition of the complexes

  18. MECHANISMS OF THE COMPLEX FORMATION BY d-METALS ON POROUS SUPPORTS AND THE CATALYTIC ACTIVITY OF THE FORMED COMPLEXES IN REDOX REACTIONS

    Directory of Open Access Journals (Sweden)

    T. L. Rakitskaya

    2015-11-01

    Full Text Available The catalytic activity of supported complexes of d metals in redox reactions with participation of gaseous toxicants, PH3, CO, O3, and SO2, depends on their composition. Owing to the variety of physicochemical and structural-adsorption properties of available supports, their influence on complex formation processes, the composition and catalytic activity of metal complexes anchored on them varies over a wide range. The metal complex formation on sup-ports with weak ion-exchanging properties is similar to that in aqueous solutions. In this case, the support role mainly adds up to the ability to reduce the activity of water adsorbed on them. The interaction between a metal complex and a support surface occurs through adsorbed water molecules. Such supports can also affect complex formation processes owing to protolytic reactions on account of acidic properties of sorbents used as supports. The catalytic activity of metal complexes supported on polyphase natural sorbents considerably depends on their phase relationship. In the case of supports with the nonsimple structure and pronounced ion-exchanging properties, for instance, zeolites and laminar silicates, it is necessary to take into account the variety of places where metal ions can be located. Such location places determine distinctions in the coordination environment of the metal ions and the strength of their bonding with surface adsorption sites and, therefore, the catalytic activity of surface complexes formed by theses metal ions. Because of the energy surface inhomogeneity, it is important to determine a relationship between the strength of a metal complex bonding with a support surface and its catalytic activity. For example, bimetallic complexes are catalytically active in the reactions of oxidation of the above gaseous toxicants. In particular, in the case of carbon monoxide oxidation, the most catalytic activity is shown by palladium-copper complexes in which copper(II is strongly

  19. Modelling current transfer to cathodes in metal halide plasmas

    International Nuclear Information System (INIS)

    Benilov, M S; Cunha, M D; Naidis, G V

    2005-01-01

    This work is concerned with investigation of the main features of current transfer to cathodes under conditions characteristic of metal halide (MH) lamps. It is found that the presence of MHs in the gas phase results in a small decrease of the cathode surface temperature and of the near-cathode voltage drop in the diffuse mode of current transfer; the range of stability of the diffuse mode expands. Effects caused by a variation of the work function of the cathode surface owing to formation of a monolayer of alkali metal atoms on the surface are studied for particular cases where the monolayer is composed of sodium or caesium. It is found that the formation of the sodium monolayer affects the diffuse mode of current transfer only moderately and in the same direction that the presence of metal atoms in the gas phase affects it. Formation of the caesium monolayer produces a dramatic effect: the cathode surface temperature decreases very strongly, the diffuse-mode current-voltage characteristic becomes N-S-shaped

  20. Unveiling the Shape Evolution and Halide-Ion-Segregation in Blue-Emitting Formamidinium Lead Halide Perovskite Nanocrystals Using an Automated Microfluidic Platform.

    Science.gov (United States)

    Lignos, Ioannis; Protesescu, Loredana; Emiroglu, Dilara Börte; Maceiczyk, Richard; Schneider, Simon; Kovalenko, Maksym V; deMello, Andrew J

    2018-02-14

    Hybrid organic-inorganic perovskites and in particular formamidinium lead halide (FAPbX 3 , X = Cl, Br, I) perovskite nanocrystals (NCs) have shown great promise for their implementation in optoelectronic devices. Specifically, the Br and I counterparts have shown unprecedented photoluminescence properties, including precise wavelength tuning (530-790 nm), narrow emission linewidths (photoluminescence quantum yields (70-90%). However, the controlled formation of blue emitting FAPb(Cl 1-x Br x ) 3 NCs lags behind their green and red counterparts and the mechanism of their formation remains unclear. Herein, we report the formation of FAPb(Cl 1-x Br x ) 3 NCs with stable emission between 440 and 520 nm in a fully automated droplet-based microfluidic reactor and subsequent reaction upscaling in conventional laboratory glassware. The thorough parametric screening allows for the elucidation of parametric zones (FA-to-Pb and Br-to-Cl molar ratios, temperature, and excess oleic acid) for the formation of nanoplatelets and/or NCs. In contrast to CsPb(Cl 1-x Br x ) 3 NCs, based on online parametric screening and offline structural characterization, we demonstrate that the controlled synthesis of Cl-rich perovskites (above 60 at% Cl) with stable emission remains a challenge due to fast segregation of halide ions.

  1. Evolution of multi-mineral formation evaluation using LWD data in complex carbonates offshore Brazil

    Energy Technology Data Exchange (ETDEWEB)

    Ferraris, Paolo; Borovskaya, Irina [Schlumberger, Houston, TX (United States)

    2012-07-01

    Petrophysical Formation Evaluation using Logging While Drilling (LWD) measurements is a new requisite when drilling in carbonates reservoirs offshore Brazil. These reservoirs are difficult to characterize due to an unusual mixture of the minerals constituting the matrix and affecting rock texture. As wells are getting deeper and more expensive, an early identification of the drilled targets potential is necessary for valuable decisions. Brazil operators have been especially demanding towards service providers, pushing for development of suitable services able to positively identify and quantify not only the presence of hydrocarbons but also their flowing capability. In addition to the standard gamma ray / resistivity / porosity and density measurements, three new measurements have proven to be critical to evaluate complex carbonate formations: Nuclear Magnetic Resonance (NMR), Spectroscopy and Capture Cross-Section (sigma). Under appropriate logging conditions, NMR data provides lithology independent porosity, bound and free fluids fractions, reservoir texture and permeability. Capture Spectroscopy allows assessment of mineral composition in terms of calcite, dolomite, quartz and clay fractions, and in addition highlights presence of other heavier minerals. Finally, sigma allows performing a volumetric formation evaluation without requiring custom optimization of the classical exponents used in all forms of resistivity saturation equations. All these new measurements are inherently statistical and if provided by wireline after drilling the well they may result in significant usage of rig time. When acquired simultaneously while drilling they have three very clear advantages: 1) no extra rig time, 2) improved statistics due to long formation exposure (drilling these carbonates is a slow process and rate of penetration (ROP) rarely exceeds 10 m/hr), 3) less invasion effect and better hole condition. This paper describes the development of two LWD tools performing the

  2. Phosphole complexes of Gold(I) halides: Comparison of solution and solid-state structures by a combination of solution and CP/MAS 31P NMR spectroscopy and x-ray crystallography

    International Nuclear Information System (INIS)

    Attar, S.; Nelson, J.H.; Bearden, W.H.; Alcock, N.W.; Alyea, E.C.

    1990-01-01

    A series of complexes of 1-phenyldibenzophosphole (DBP), 1-phenyl-3,4,-dimethylphosphole (DMPP), and triphenylphosphine of the type L n AuX (n = 1, L = DBP, DMPP, Ph 3 P, X = Cl, Br, I; n = 3, L = DBP, X = Cl, Br, I; n = 3, L = Ph 3 P, X = Cl; n = 4, L = DBP, DMPP, X = PF 6 ) have been prepared and characterized. The structures of (DBP)AuCl (1), (DBP) 3 AuCl (2), and (DMPP)AuCl (3) have been determined from three-dimensional x-ray data collected by counter methods. Crystal structure of the complexes is reported. The CP/MAS 31 P( 1 H) NMR spectrum of complex 1 shows two resonances in a 1:1 intensity ratio, and the CP/MAS 31 P( 1 H) NMR spectrum of complex 3 shows three resonances in a 1:1:1 intensity ratio for reasons that are not yet understood. Though the three phospholes are crystallographically inequivalent (d(AuP) = 2.359 (1), 2.382 (1), and 2.374 (2) angstrom) the molecule has effective C s symmetry as evidenced by the observation of two 31 P resonances in a 2:1 intensity ratio in its CP/MAS 31 P( 1 H) NMR spectrum. Variable-temperature 31 P( 1 H) NMR spectra obtained on solutions of LAuCl + L in various ratios were analyzed to determine the nature of the species present in solution and to gain information regarding their relative stabilities as a function of the nature of the phosphine. 79 refs., 8 figs., 9 tabs

  3. The coacervation of aqueous solutions of tetraalkylammonium halides

    International Nuclear Information System (INIS)

    Mugnier de Trobriand, Anne.

    1979-09-01

    The coacervation of aqueous solutions of tatraalkylammonium halides in the presence of not of inorganic halides and acids has been studied, considering thermodynamic and spectroscopic aspects. The importance of dispersion forces as well as forces resulting from hydrophobic hydration has been assessed. The analogy between these systems and anionic ion exchange resins has been shown especially for Uranium VI extraction [fr

  4. Definition of a high intensity metal halide discharge reference lamp

    NARCIS (Netherlands)

    Stoffels, W.W.; Baede, A.H.F.M.; Mullen, van der J.J.A.M.; Haverlag, M.; Zissis, G.

    2006-01-01

    The design of a ref. metal halide discharge lamp is presented. This lamp is meant as a common study object for researchers working on metal halide discharge lamps, who by using the same design will be able to compare results between research groups, diagnostic techniques and numerical models. The

  5. Potentiometric and spectral studies of complex formation of La(3), Pr(3) and Lu(3) with aspartic acid and asparagine

    International Nuclear Information System (INIS)

    Wojciechowska, A.; Lomozik, L.; Zielinski, S.

    1987-01-01

    The composition and stability of La 3+ , Pr 3+ and Lu 3+ complexes with aspartic acid and asparagine were analysed. The formation of complexes of the type ML and MHL was determined for La 3+ and Pr 3+ with aspartic acid, and of the type MHL for Lu 3+ with aspartic acid. For La 3+ , Pr 3+ and Lu 3+ with asparagine the formation of ML(OH) complexes was observed. By means of 1 HNMR and 13 CNMR studies the participation in the coordination of both -COOH groups was determined for aspartic acid, whereas for asparagine the participation of the -COOH group was determined in complexes with La 3+ , Pr 3+ , and of the -COOH and the -NH 2 groups in the complex with Lu 3+ . (Author)

  6. Quantum chemical and thermodynamic calculations of fulvic and humic copper complexes in reactions of malachite and azurite formation

    International Nuclear Information System (INIS)

    Fomin, Vitaliy N.; Gogol, Daniil B.; Rozhkovoy, Ivan E.; Ponomarev, Dmitriy L.

    2017-01-01

    This article provides a thermodynamic evaluation of the reactions of humic and fulvic acids in the process of malachite and azurite mineralogenesis. Semi-empirical methods AM/1, MNDO, PM3, PM5, PM6 and PM7 were used to compute the heat of formation, enthalpy and entropy for thermodynamic calculations of the reactions performed on the basis of Hess's law. It is shown that methods PM6 and PM7 in the MOPAC software package provide good compliance with experimental and calculated heats of formation for copper complexes and alkaline earth metal complexes with organic acids. It is found that the malachite and azurite formation processes involving humus complexing substances are thermodynamically possible. - Highlights: • Copper and alkali-earth metal complexes with humic and fulvic acids are considered. • Quantum chemical calculation of thermodynamics for the structures was performed. • Semi-empirical methods PM6 and PM7 provide best correlation for the properties. • Parameters of basic copper carbonate formation reactions were obtained by Hess's law. • Processes of malachite and azurite formation from humus complexes are possible.

  7. Double-decker phthalocyanine complex: Scanning tunneling microscopy study of film formation and spin properties

    Science.gov (United States)

    Komeda, Tadahiro; Katoh, Keiichi; Yamashita, Masahiro

    2014-05-01

    interesting spin configuration. The center metal atom, including a lanthanoid metal of Tb, tends to be 3+ cation, while the Pc ligand to be 2- anion. This realizes two-spin system, in which spins from 4f electrons and π radical coexist. Though the spins of 4f orbitals of those molecules have been studied, the importance of the π radicals has been highlighted recently from the measurement of electronic conductance properties of these molecules. In this article, recent researches on multi-decker Pc molecules are reviewed. The manuscript is organized with groups of chapters as follows: (1) Film formation, (2) Spin of TbPc2 film and Kondo resonance observation, (3) Rotation of double-decker Pc complex and chemical modification for spin control, (4) Device formation using double-decker Pc complex.

  8. Structure Formation of Ultrathin PEO Films at Solid Interfaces—Complex Pattern Formation by Dewetting and Crystallization

    Science.gov (United States)

    Braun, Hans-Georg; Meyer, Evelyn

    2013-01-01

    The direct contact of ultrathin polymer films with a solid substrate may result in thin film rupture caused by dewetting. With crystallisable polymers such as polyethyleneoxide (PEO), molecular self-assembly into partial ordered lamella structures is studied as an additional source of pattern formation. Morphological features in ultrathin PEO films (thickness dewetting patterns and diffusion limited growth pattern of ordered lamella growing within the dewetting areas. Besides structure formation of hydrophilic PEO molecules, n-alkylterminated (hydrophobic) PEO oligomers are investigated with respect to self-organization in ultrathin films. Morphological features characteristic for pure PEO are not changed by the presence of the n-alkylgroups. PMID:23385233

  9. From PII signaling to metabolite sensing: a novel 2-oxoglutarate sensor that details PII-NAGK complex formation.

    Directory of Open Access Journals (Sweden)

    Jan Lüddecke

    Full Text Available The widespread PII signal transduction proteins are known for integrating signals of nitrogen and energy supply and regulating cellular behavior by interacting with a multitude of target proteins. The PII protein of the cyanobacterium Synechococcus elongatus forms complexes with the controlling enzyme of arginine synthesis, N-acetyl-L-glutamate kinase (NAGK in a 2-oxoglutarate- and ATP/ADP-dependent manner. Fusing NAGK and PII proteins to either CFP or YFP yielded a FRET sensor that specifically responded to 2-oxoglutarate. The impact of the fluorescent tags on PII and NAGK was evaluated by enzyme assays, surface plasmon resonance spectroscopy and isothermal calorimetric experiments. The developed FRET sensor provides real-time data on PII - NAGK interaction and its modulation by the effector molecules ATP, ADP and 2-oxoglutarate in vitro. Additionally to its utility to monitor 2-oxoglutarate levels, the FRET assay provided novel insights into PII - NAGK complex formation: (i It revealed the formation of an encounter-complex between PII and NAGK, which holds the proteins in proximity even in the presence of inhibitors of complex formation; (ii It revealed that the PII T-loop residue Ser49 is neither essential for complex formation with NAGK nor for activation of the enzyme but necessary to form a stable complex and efficiently relieve NAGK from arginine inhibition; (iii It showed that arginine stabilizes the NAGK hexamer and stimulates PII - NAGK interaction.

  10. Stabilization and activation of alpha-chymotrypsin in water-organic solvent systems by complex formation with oligoamines.

    Science.gov (United States)

    Kudryashova, Elena V; Artemova, Tatiana M; Vinogradov, Alexei A; Gladilin, Alexander K; Mozhaev, Vadim V; Levashov, Andrey V

    2003-04-01

    Formation of enzyme-oligoamine complexes was suggested as an approach to obtain biocatalysts with enhanced resistance towards inactivation in water-organic media. Complex formation results in broadening (by 20-40% v/v ethanol) of the range of cosolvent concentrations where the enzyme retains its catalytic activity (stabilization effect). At moderate cosolvent concentrations (20-40% v/v) complex formation activates the enzyme (by 3-6 times). The magnitude of activation and stabilization effects increases with the number of possible electrostatic contacts between the protein surface and the molecules of oligoamines (OA). Circular dichroism spectra in the far-UV region show that complex formation stabilizes protein conformation and prevents aggregation in water-organic solvent mixtures. Two populations of the complexes with different thermodynamic stabilities were found in alpha-chymotrypsin (CT)-OA systems depending on the CT/OA ratio. The average dissociation constants and stoichiometries of both low- and high-affinity populations of the complexes were estimated. It appears that it is the low-affinity sites on the CT surface that are responsible for the activation effect.

  11. Development of alkali halide-optics for high power-IR laser

    International Nuclear Information System (INIS)

    Pohl, L.

    1989-01-01

    In this work 'Development of Alkali Halide-Optics for High Power-IR Laser' we investigated the purification of sodiumchloride-, potassiumchloride- and potassiumbromide-raw materials. We succeeded to reduce the content of impurities like Cu, Pb, V, Cr, Mn, Fe, Co and Ni in these raw materials to the lower of ppb's by a Complex-Adsorption-Method (CAM). Crystals were grown from purified substances by 'Kyropoulos' method'. Windows were cur thereof, polished and measured by FTIR-spectroscopy. Analytical data showed, that the resulting crystals were of lower quality than the raw materials. Because of this fact crystal-growing-conditions have to undergo a special improvement. Alkali halide windows from other sources on the market had been tested. (orig.) [de

  12. Theoretical studies of the nucleophilic substitution of halides and amine at a sulfonyl center.

    Science.gov (United States)

    Sung, Dae Dong; Kim, Tae Joon; Lee, Ikchoon

    2009-06-25

    Gas-phase nucleophilic substitution reactions, F(-) + CH(3)SO(2)F, Cl(-) + CH(3)SO(2)Cl, Cl(-) + CH(3)SO(2)F, and NH(3) + CH(3)SO(2)Cl, have been investigated at the B3LYP/6-311+G** and MP2/6-31+G* levels of theory. A very shallow well for the reaction intermediate in a triple-well potential energy surface (PES) was observed for the identity fluoride exchange, but double well PESs were obtained for the other three reactions with three different PES profiles. NBO analyses of the transition states showed substantial charge transfer interactions in all cases which provided a much larger amount of stabilization energy compared with the corresponding species at the carbon center of methyl halides. This difference is primarily caused by the strong electropositive nature of the sulfur center. The F-S-F axial linkage in the distorted TBP type intermediate in the identity fluoride exchange reaction exhibited a weak three-center, four-electron omega-bonding, which is considered to provide stability of the intermediate. All the reactant (RC) and product complexes (PC) have Cs symmetry. The symmetry plane bisects angles HCH (of methyl group), OSO (of sulfonyl group), and HNH (of ammonia). Vicinal charge transfer interactions between the two out-of-plane C-H, S-O, and N-H bonds provide extra stabilization to the ion-dipole complexes together with H-bond formation of in-plane H atom with the nucleophile and/or leaving group.

  13. Research Update: Luminescence in lead halide perovskites

    Directory of Open Access Journals (Sweden)

    Ajay Ram Srimath Kandada

    2016-09-01

    Full Text Available Efficiency and dynamics of radiative recombination of carriers are crucial figures of merit for optoelectronic materials. Following the recent success of lead halide perovskites in efficient photovoltaic and light emitting technologies, here we review some of the noted literature on the luminescence of this emerging class of materials. After outlining the theoretical formalism that is currently used to explain the carrier recombination dynamics, we review a few significant works which use photoluminescence as a tool to understand and optimize the operation of perovskite based optoelectronic devices.

  14. Exciton-relaxation dynamics in lead halides

    International Nuclear Information System (INIS)

    Iwanaga, Masanobu; Hayashi, Tetsusuke

    2003-01-01

    We survey recent comprehensive studies of exciton relaxation in the crystals of lead halides. The luminescence and electron-spin-resonance studies have revealed that excitons in lead bromide spontaneously dissociate and both electrons and holes get self-trapped individually. Similar relaxation has been also clarified in lead chloride. The electron-hole separation is ascribed to repulsive correlation via acoustic phonons. Besides, on the basis of the temperature profiles of self-trapped states, we discuss the origin of luminescence components which are mainly induced under one-photon excitation into the exciton band in lead fluoride, lead chloride, and lead bromide

  15. Shock-induced kelyphite formation in the core of a complex impact crater

    Science.gov (United States)

    Deseta, Natalie; Boonsue, Suporn; Gibson, Roger L.; Spray, John G.

    2017-10-01

    We present a compositional and textural analysis of shock-induced microtextures in garnet porphyroblasts in migmatitic garnet-cordierite-biotite paragneisses from the centre of the Vredefort impact structure, South Africa. Detailed imaging and major element analysis of deformation features in, and adjacent to, the garnet porphyroblasts record a complex, heterogeneous distribution of shock effects at the microscale. As the most competent silicate mineral in the assemblage, with the highest Hugoniot Elastic Limit and a wide pressure-temperature stability field, the porphyroblastic garnet preserves a more diverse shock deformation response compared to minerals such as quartz and feldspar, which underwent more comprehensive shock metamorphism and subsequent annealing. The garnet porphyroblasts display pre-impact fractures that are overprinted by later intra-granular Hertzian and distinctive planar fractures associated with the impact event. Shock-induced strain localization occurred along internal slip planes and defects, including pre-existing fractures and inclusion boundaries in the garnet. Symplectitic (kelyphitic) coronas commonly enclose the garnet porphyroblasts, and inhabit intra-granular fractures. The kelyphite assemblage in fractures with open communication beyond garnet grain boundaries is characterized by orthopyroxene—cordierite—sapphirine. Conversely, the kelyphite assemblage in closed-off intra-granular fractures is highly variable, comprising spatially restricted combinations of a secondary garnet phase with a majoritic component, Al-rich orthopyroxene, sapphirine and cordierite. The impedance contrast between garnet porphyroblasts and their inclusions further facilitated the formation of shock-induced features (Al-rich orthopyroxene coronas). Together, the textural and mineralogical data suggest that these features provide a record of oscillatory shock perturbations initiated under confining pressure beneath the transient crater floor. This

  16. Formation of nano-hydroxyapatite crystal in situ in chitosan-pectin polyelectrolyte complex network

    International Nuclear Information System (INIS)

    Li Junjie; Zhu Dunwan; Yin Jianwei; Liu Yuxi; Yao Fanglian; Yao Kangde

    2010-01-01

    Hydroxyapatite (HA)/polysaccharide composites have been widely used in bone tissue engineering due to their chemical similarity to natural bone. Polymer matrix-mediated synthesis of nano-hydroxyapatite is one of the simplest models for biomimetic. In this article, the nano-hydroxyapatite/chitosan-pectin (nHCP) composites were prepared through in situ mineralization of hydroxyapatite in chitosan-pectin polyelectrolyte complex (PEC) network. The formation processes of nHCP were investigated by X-ray diffraction (XRD) analysis. The interactions between nHA crystal and chitosan-pectin PEC networks were studied using Fourier Transform Infrared Spectroscopy (FTIR) and Differential Scanning Calorimetry (DSC). The morphology and structure of nHA crystal were characterized by XRD and Transmission Electron Microscope (TEM). Results suggested that the interfacial interactions between nano-hydroxyapatite crystal and chitosan-pectin PEC network assist the site specific nucleation and growth of nHA nanoparticles. The nHA crystals grow along the c-axis. In this process, pH value is the main factor to control the nucleation and growth of nHA crystal in chitosan-pectin PEC networks, because both the interactions' strength between nHA crystal and chitosan-pectin and diffusion rate of inorganic ions depend on the pH value of the reaction system. Apart from the pH value, the chitosan/pectin ratio and [Ca 2+ ] also take important effects on the formation of nHA crystal. An effective way to control the size of nHA crystal is to adjust the content of pectin and [Ca 2+ ]. It is interesting that the Zeta potential of nHCP composites is about - 30 mV when the chitosan/pectin ratio ≤ 1:1, and the dispersion solution of nHCP composites has higher stability, which provides the possibility to prepare 3D porous scaffolds with nHCP for bone tissue engineering.

  17. The alkali halide disk technique in infra-red spectrometry : Anomalous behaviour of some samples dispersed in alkali halide disks

    NARCIS (Netherlands)

    Tolk, A.

    1961-01-01

    Some difficulties encountered in the application of the alkali halide disk technique in infra-red spectrometry are discussed. Complications due to interaction of the sample with the alkali halide have been studied experimentally. It was found that the anomalous behaviour of benzoic acid, succinic

  18. Swarming and complex pattern formation in Paenibacillus vortex studied by imaging and tracking cells

    Directory of Open Access Journals (Sweden)

    Jacob Eshel

    2008-02-01

    Full Text Available Abstract Background Swarming motility allows microorganisms to move rapidly over surfaces. The Gram-positive bacterium Paenibacillus vortex exhibits advanced cooperative motility on agar plates resulting in intricate colonial patterns with geometries that are highly sensitive to the environment. The cellular mechanisms that underpin the complex multicellular organization of such a simple organism are not well understood. Results Swarming by P. vortex was studied by real-time light microscopy, by in situ scanning electron microscopy and by tracking the spread of antibiotic-resistant cells within antibiotic-sensitive colonies. When swarming, P. vortex was found to be peritrichously flagellated. Swarming by the curved cells of P. vortex occurred on an extremely wide range of media and agar concentrations (0.3 to 2.2% w/v. At high agar concentrations (> 1% w/v rotating colonies formed that could be detached from the main mass of cells by withdrawal of cells into the latter. On lower percentage agars, cells moved in an extended network composed of interconnected "snakes" with short-term collision avoidance and sensitivity to extracts from swarming cells. P. vortex formed single Petri dish-wide "supercolonies" with a colony-wide exchange of motile cells. Swarming cells were coupled by rapidly forming, reversible and non-rigid connections to form a loose raft, apparently connected via flagella. Inhibitors of swarming (p-Nitrophenylglycerol and Congo Red were identified. Mitomycin C was used to trigger filamentation without inhibiting growth or swarming; this facilitated dissection of the detail of swarming. Mitomycin C treatment resulted in malcoordinated swarming and abortive side branch formation and a strong tendency by a subpopulation of the cells to form minimal rotating aggregates of only a few cells. Conclusion P. vortex creates complex macroscopic colonies within which there is considerable reflux and movement and interaction of cells. Cell

  19. A Biomimetic Nickel Complex with a Reduced CO2 Ligand Generated by Formate Deprotonation and its Behaviour towards CO2.

    Science.gov (United States)

    Limberg, Christian; Zimmermann, Philipp; Hoof, Santina; Braun-Cula, Beatrice; Herwig, Christian

    2018-04-10

    Reduced CO2 species are key intermediates in a variety of natural and synthetic processes. In the majority of systems, however, they elude isolation or characterisation due to high reactivity or limited accessibility (heterogeneous systems) and thus formulations often remain uncertain or based on calculations only. We herein report on a Ni-CO22- complex that is unique in many ways. While its structural and electronic features help understanding the CO2 bound state in Ni,Fe carbon monoxide dehydrogenases, its reactivity sheds light on how CO2 can be converted into CO/CO32- by nickel complexes. In addition, the complex has been generated via a rare example of formate β deprotonation, a mechanistical step relevant to nickel catalysed conversion of HxCOyz- at electrodes and formate oxidation in formate dehydrogenases. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. Band registration of tuneable frame format hyperspectral UAV imagers in complex scenes

    Science.gov (United States)

    Honkavaara, Eija; Rosnell, Tomi; Oliveira, Raquel; Tommaselli, Antonio

    2017-12-01

    A recent revolution in miniaturised sensor technology has provided markets with novel hyperspectral imagers operating in the frame format principle. In the case of unmanned aerial vehicle (UAV) based remote sensing, the frame format technology is highly attractive in comparison to the commonly utilised pushbroom scanning technology, because it offers better stability and the possibility to capture stereoscopic data sets, bringing an opportunity for 3D hyperspectral object reconstruction. Tuneable filters are one of the approaches for capturing multi- or hyperspectral frame images. The individual bands are not aligned when operating a sensor based on tuneable filters from a mobile platform, such as UAV, because the full spectrum recording is carried out in the time-sequential principle. The objective of this investigation was to study the aspects of band registration of an imager based on tuneable filters and to develop a rigorous and efficient approach for band registration in complex 3D scenes, such as forests. The method first determines the orientations of selected reference bands and reconstructs the 3D scene using structure-from-motion and dense image matching technologies. The bands, without orientation, are then matched to the oriented bands accounting the 3D scene to provide exterior orientations, and afterwards, hyperspectral orthomosaics, or hyperspectral point clouds, are calculated. The uncertainty aspects of the novel approach were studied. An empirical assessment was carried out in a forested environment using hyperspectral images captured with a hyperspectral 2D frame format camera, based on a tuneable Fabry-Pérot interferometer (FPI) on board a multicopter and supported by a high spatial resolution consumer colour camera. A theoretical assessment showed that the method was capable of providing band registration accuracy better than 0.5-pixel size. The empirical assessment proved the performance and showed that, with the novel method, most parts of

  1. RIT1 controls actin dynamics via complex formation with RAC1/CDC42 and PAK1.

    Directory of Open Access Journals (Sweden)

    Uta Meyer Zum Büschenfelde

    2018-05-01

    Full Text Available RIT1 belongs to the RAS family of small GTPases. Germline and somatic RIT1 mutations have been identified in Noonan syndrome (NS and cancer, respectively. By using heterologous expression systems and purified recombinant proteins, we identified the p21-activated kinase 1 (PAK1 as novel direct effector of RIT1. We found RIT1 also to directly interact with the RHO GTPases CDC42 and RAC1, both of which are crucial regulators of actin dynamics upstream of PAK1. These interactions are independent of the guanine nucleotide bound to RIT1. Disease-causing RIT1 mutations enhance protein-protein interaction between RIT1 and PAK1, CDC42 or RAC1 and uncouple complex formation from serum and growth factors. We show that the RIT1-PAK1 complex regulates cytoskeletal rearrangements as expression of wild-type RIT1 and its mutant forms resulted in dissolution of stress fibers and reduction of mature paxillin-containing focal adhesions in COS7 cells. This effect was prevented by co-expression of RIT1 with dominant-negative CDC42 or RAC1 and kinase-dead PAK1. By using a transwell migration assay, we show that RIT1 wildtype and the disease-associated variants enhance cell motility. Our work demonstrates a new function for RIT1 in controlling actin dynamics via acting in a signaling module containing PAK1 and RAC1/CDC42, and highlights defects in cell adhesion and migration as possible disease mechanism underlying NS.

  2. Theory Meets Experiment: Metal Ion Effects in HCV Genomic RNA Kissing Complex Formation

    Directory of Open Access Journals (Sweden)

    Li-Zhen Sun

    2017-12-01

    Full Text Available The long-range base pairing between the 5BSL3. 2 and 3′X domains in hepatitis C virus (HCV genomic RNA is essential for viral replication. Experimental evidence points to the critical role of metal ions, especially Mg2+ ions, in the formation of the 5BSL3.2:3′X kissing complex. Furthermore, NMR studies suggested an important ion-dependent conformational switch in the kissing process. However, for a long time, mechanistic understanding of the ion effects for the process has been unclear. Recently, computational modeling based on the Vfold RNA folding model and the partial charge-based tightly bound ion (PCTBI model, in combination with the NMR data, revealed novel physical insights into the role of metal ions in the 5BSL3.2-3′X system. The use of the PCTBI model, which accounts for the ion correlation and fluctuation, gives reliable predictions for the ion-dependent electrostatic free energy landscape and ion-induced population shift of the 5BSL3.2:3′X kissing complex. Furthermore, the predicted ion binding sites offer insights about how ion-RNA interactions shift the conformational equilibrium. The integrated theory-experiment study shows that Mg2+ ions may be essential for HCV viral replication. Moreover, the observed Mg2+-dependent conformational equilibrium may be an adaptive property of the HCV genomic RNA such that the equilibrium is optimized to the intracellular Mg2+ concentration in liver cells for efficient viral replication.

  3. Bacillus subtilis δ Factor Functions as a Transcriptional Regulator by Facilitating the Open Complex Formation.

    Science.gov (United States)

    Prajapati, Ranjit Kumar; Sengupta, Shreya; Rudra, Paulami; Mukhopadhyay, Jayanta

    2016-01-15

    Most bacterial RNA polymerases (RNAP) contain five conserved subunits, viz. 2α, β, β', and ω. However, in many Gram-positive bacteria, especially in fermicutes, RNAP is associated with an additional factor, called δ. For over three decades since its identification, it had been thought that δ functioned as a subunit of RNAP to enhance the level of transcripts by recycling RNAP. In support of the previous observations, we also find that δ is involved in recycling of RNAP by releasing the RNA from the ternary complex. We further show that δ binds to RNA and is able to recycle RNAP when the length of the nascent RNA reaches a critical length. However, in this work we decipher a new function of δ. Performing biochemical and mutational analysis, we show that Bacillus subtilis δ binds to DNA immediately upstream of the promoter element at A-rich sequences on the abrB and rrnB1 promoters and facilitates open complex formation. As a result, δ facilitates RNAP to initiate transcription in the second scale, compared with minute scale in the absence of δ. Using transcription assay, we show that δ-mediated recycling of RNAP cannot be the sole reason for the enhancement of transcript yield. Our observation that δ does not bind to RNAP holo enzyme but is required to bind to DNA upstream of the -35 promoter element for transcription activation suggests that δ functions as a transcriptional regulator. © 2016 by The American Society for Biochemistry and Molecular Biology, Inc.

  4. Stated Choice Experiments with Complex Ecosystem Changes: The Effect of Information Formats on Estimated Variances and Choice Parameters

    OpenAIRE

    Hoehn, John P.; Lupi, Frank; Kaplowitz, Michael D.

    2010-01-01

    Stated choice experiments about ecosystem changes involve complex information. This study examines whether the format in which ecosystem information is presented to respondents affects stated choice outcomes. Our analysis develops a utility-maximizing model to describe respondent behavior. The model shows how alternative questionnaire formats alter respondents’ use of filtering heuristics and result in differences in preference estimates. Empirical results from a large-scale stated choice e...

  5. Structure Formation of Ultrathin PEO Films at Solid Interfaces—Complex Pattern Formation by Dewetting and Crystallization

    Directory of Open Access Journals (Sweden)

    Hans-Georg Braun

    2013-02-01

    Full Text Available The direct contact of ultrathin polymer films with a solid substrate may result in thin film rupture caused by dewetting. With crystallisable polymers such as polyethyleneoxide (PEO, molecular self-assembly into partial ordered lamella structures is studied as an additional source of pattern formation. Morphological features in ultrathin PEO films (thickness < 10 nm result from an interplay between dewetting patterns and diffusion limited growth pattern of ordered lamella growing within the dewetting areas. Besides structure formation of hydrophilic PEO molecules, n-alkylterminated (hydrophobic PEO oligomers are investigated with respect to self-organization in ultrathin films. Morphological features characteristic for pure PEO are not changed by the presence of the n-alkylgroups.

  6. Electrochemically reduced titanocene dichloride as a catalyst of reductive dehalogenation of organic halides

    Energy Technology Data Exchange (ETDEWEB)

    Magdesieva, Tatiana V. [Department Chemistry, M.V. Lomonosov Moscow State University, Moscow 119992 (Russian Federation)]. E-mail: tvm@org.chem.msu.ru; Graczyk, Magdalena [LSEO-UMR 5188 CNRS, Universite de Bourgogne, Dijon (France); Vallat, Alain [LSEO-UMR 5188 CNRS, Universite de Bourgogne, Dijon (France); Nikitin, Oleg M. [Department Chemistry, M.V. Lomonosov Moscow State University, Moscow 119992 (Russian Federation); Demyanov, Petr I. [Department Chemistry, M.V. Lomonosov Moscow State University, Moscow 119992 (Russian Federation); Butin, Kim P. [Department Chemistry, M.V. Lomonosov Moscow State University, Moscow 119992 (Russian Federation); Vorotyntsev, Mikhail A. [LSEO-UMR 5188 CNRS, Universite de Bourgogne, Dijon (France)]. E-mail: MV@u-bourgogne.fr

    2006-11-12

    We have studied a reaction between the reduced form of titanocene dichloride (Cp{sub 2}TiCl{sub 2}) and a group of organic halides: benzyl derivatives (4-X-C{sub 6}H{sub 4}CH{sub 2}Cl, X = H, NO{sub 2}, CH{sub 3}; 4-X-C{sub 6}H{sub 4}CH{sub 2}Br, X = H, NO{sub 2}, PhC(O); 4-X-C{sub 6}H{sub 4}CH{sub 2}SCN, X = H, NO{sub 2}) as well as three aryl halides (4-NO{sub 2}C{sub 6}H{sub 4}Hal, Hal = Cl, Br; 4-CH{sub 3}O-C{sub 6}H{sub 4}Cl). It has been shown that the electrochemical reduction of Cp{sub 2}TiCl{sub 2} in the presence of these benzyl halides leads to a catalytic cycle resulting in the reductive dehalogenation of these organic substrates to yield mostly corresponding toluene derivatives as the main product. No dehalogenation has been observed for aryl derivatives. Based on electrochemical data and digital simulation, possible schemes of the catalytic process have been outlined. For non-substituted benzyl halides halogen atom abstraction is a key step. For the reaction of nitrobenzyl halides the complexation of Ti(III) species with the nitro group takes place, with the electron transfer from Ti(III) to this group (owing to its highest coefficient in LUMO of the nitro benzyl halide) followed by an intramolecular dissociative electron redistribution in the course of the heterolytic C-Hal bond cleavage. The results for reduced titanocene dichloride centers immobilized inside a polymer film showed that the catalytic reductive dehalogenation of the p-nitrobenzyl chloride does occur but with a low efficiency because of the partial deactivation of the film due to the blocking of the electron charge transport between the electrode and catalytic centers.

  7. Formation of Mixed-Ligand Complexes of Metals(II) with Monoamine Complexones and Amino Acids in Solution

    Science.gov (United States)

    Pyreu, D. F.; Gridchin, S. N.

    2018-05-01

    The formation of mixed-ligand complexes in the M(II)-Nta, Ida-L (M = Cu(II), Ni, Zn, Co(II), L = Ser, Thr, Asp, Arg, Asn) systems, where Ida and Nta are the residues of iminodiacetic and nitrilotriacetic acids, respectively, is studied using pH measurements, calorimetry and spectrophotometry. The thermodynamic parameters (log K, Δr G 0, Δr H, Δr S) of their formation at 298.15 K and ionic strength I = 0.5 (KNO3) are determined. The most likely scenario of amino acid residue coordination in the composition of mixed complexes is discussed.

  8. Apatite formation behaviour during metasomatism in the Bathtub Intrusion (Babbitt deposit, Duluth Complex, USA)

    Science.gov (United States)

    Raič, Sara; Mogessie, Aberra; Krenn, Kurt; Hauzenberger, Christoph A.; Tropper, Peter

    2016-04-01

    The mineralized troctolitic Bathtub intrusion (Duluth Complex, NE-Minnesota) is known for its famous Cu-Ni-Sulfide±PGM Babbitt deposit, where platinum group minerals (PGMs) are either hosted by primary magmatic sulfides (base metal sulfides) or associated with hydrothermally altered portions. This secondary generation of PGMs is present in alteration patches and suggests the involvement of hydrothermal fluids in the mobilization of platinum-group elements (PGEs). Accessory fluorapatite in these samples reveals besides H2O- and CO2-rich primary fluid inclusions, textural and compositional variations that also record magmatic and metasomatic events. Based on detailed back-scattered electron imaging (BSE) and laser ablation-inductively coupled plasma-mass spectrometry (LA-ICPMS), a primary magmatic origin is reflected by homogeneous or zoned grains, where zoning patterns are either concentric or oscillatory, with respect to LREE. Late magmatic to hydrothermal processes are indicated by grains with bright LREE-enriched rims or conversion textures with REE-enriched patches in the interior of the apatite. A metasomatic formation of monazite from apatite is documented by the presence of monazite inclusions in apatite and newly grown monazite at altered apatite rims. They formed by the release of REEs from the apatite during a fluid-induced alteration, based on the coupled substitution Ca2+ + P5+ = REE3+ + Si4+ (Rønsbo 1989; Rønsbo 2008). Samples with monazite inclusions in apatite further display occurrences of PGMs associated with hydrothermal alteration patches (chlorite + amphibole). The presence of H2O- and CO2-rich fluid inclusions in apatite, the metasomatically induced monazite growth, as well as the occurrence of PGMs in hydrothermally alteration zones, also suggest the involvement of aqueous chloride complexes in a H2O dominated fluid in the transportation of LREE and redistribution of the second generation of PGEs. Rønsbo, J.G. (1989): Coupled substitutions

  9. Formation of giant cloud complexes by the Parker-Jeans instability

    International Nuclear Information System (INIS)

    Elmegreen, B.G.

    1982-01-01

    The Parker-Jeans instability is considered as a possible mechanism for forming the giant cloud complexes observed near OB associations. We use a previously derived dispersion relation to evaluate the masses and growth times of the dominant modes in this instability. The results show that massive clouds (Mroughly-equal10 6 M/sub sun/) can form quickly (roughly-equal12 million yr) in the high density environments (5 cm -3 ) associated with spiral density wave shocks. For densities larger than about 3 cm -3 , these clouds form primarily as a result of the self-graviational forces in the interstellar medium. Lower mass clouds (Mroughly-equal10 5 M/sub sun/) can form in lower density environments as a result of the pure Parker instability. The masses of the clouds that form when the density exceeds about 3 cm -3 are insensitive to the magnetic field strength, cosmic ray pressure, and ambient density (even in compressed media.). These masses are essentially the Jeans mass in a magnetic interstellar medium. The occurrence of a characteristic mass may explain the similarity of the local OB associations. The role of the Parker-Jeans instability as part of a complete theory of cloud formation is summarized

  10. Modification of the SERS spectrum of cyanide traces due to complex formation between cyanide and silver

    Science.gov (United States)

    Cao Dao, Tran; Kieu, Ngoc Minh; Quynh Ngan Luong, Truc; Cao, Tuan Anh; Hai Nguyen, Ngoc; Le, Van Vu

    2018-06-01

    It is well known that cyanide is an extremely toxic lethal poison with human death within minutes after exposure to only 300 ppm cyanide. On the other hand, cyanide is released into the environment (mainly through waste water) every day from various human activities. Therefore, rapid, sensitive and cost-effective cyanide trace detection is an urgent need. Surface-enhanced Raman scattering (SERS) is a method that meets these requirements. It should be noted, however, that in this technique SERS substrates, which are usually made of gold or silver, will be leached with aqueous cyanide by the formation of complexes between gold or silver with cyanide. This will cause the SERS spectrum of cyanide to be modified. When determining cyanide concentrations by SERS analysis, this spectral modification should be taken into account. This report presents the SERS spectral modification of aqueous cyanide traces (in ppm and lower concentration range) when the SERS substrates used are flower-like silver micro-structures.

  11. Accelerated fluctuation analysis by graphic cards and complex pattern formation in financial markets

    International Nuclear Information System (INIS)

    Preis, Tobias; Virnau, Peter; Paul, Wolfgang; Schneider, Johannes J

    2009-01-01

    The compute unified device architecture is an almost conventional programming approach for managing computations on a graphics processing unit (GPU) as a data-parallel computing device. With a maximum number of 240 cores in combination with a high memory bandwidth, a recent GPU offers resources for computational physics. We apply this technology to methods of fluctuation analysis, which includes determination of the scaling behavior of a stochastic process and the equilibrium autocorrelation function. Additionally, the recently introduced pattern formation conformity (Preis T et al 2008 Europhys. Lett. 82 68005), which quantifies pattern-based complex short-time correlations of a time series, is calculated on a GPU and analyzed in detail. Results are obtained up to 84 times faster than on a current central processing unit core. When we apply this method to high-frequency time series of the German BUND future, we find significant pattern-based correlations on short time scales. Furthermore, an anti-persistent behavior can be found on short time scales. Additionally, we compare the recent GPU generation, which provides a theoretical peak performance of up to roughly 10 12 floating point operations per second with the previous one.

  12. Planktonic growth and biofilm formation profiles in Candida haemulonii species complex.

    Science.gov (United States)

    Ramos, Lívia S; Oliveira, Simone S C; Souto, Xênia M; Branquinha, Marta H; Santos, André L S

    2017-10-01

    Candida haemulonii species complex have emerged as multidrug-resistant yeasts able to cause fungemia worldwide. However, very little is known regarding their physiology and virulence factors. In this context, planktonic growth and biofilm formation of Brazilian clinical isolates of Candida haemulonii (n = 5), Candida duobushaemulonii (n = 4), and Candida haemulonii var. vulnera (n = 3) were reported. Overall, the fungal planktonic growth curves in Sabouraud dextrose broth reached the exponential phase in 48 h at 37°C. All the clinical isolates formed biofilm on polystyrene in a time-dependent event, as judged by the parameters evaluated: biomass (crystal violet staining), metabolic activity (XTT reduction), and extracellular matrix (safranin incorporation). No statistically significant differences were observed when the average measurements among the three Candida species were compared regarding both planktonic and biofilm lifestyles; however, typical isolate-specific differences were clearly noticed in fungal growth kinetics. © The Author 2017. Published by Oxford University Press on behalf of The International Society for Human and Animal Mycology. All rights reserved. For permissions, please e-mail: journals.permissions@oup.com.

  13. Formation of wood secondary cell wall may involve two type cellulose synthase complexes in Populus.

    Science.gov (United States)

    Xi, Wang; Song, Dongliang; Sun, Jiayan; Shen, Junhui; Li, Laigeng

    2017-03-01

    Cellulose biosynthesis is mediated by cellulose synthases (CesAs), which constitute into rosette-like cellulose synthase complexe (CSC) on the plasma membrane. Two types of CSCs in Arabidopsis are believed to be involved in cellulose synthesis in the primary cell wall and secondary cell walls, respectively. In this work, we found that the two type CSCs participated cellulose biosynthesis in differentiating xylem cells undergoing secondary cell wall thickening in Populus. During the cell wall thickening process, expression of one type CSC genes increased while expression of the other type CSC genes decreased. Suppression of different type CSC genes both affected the wall-thickening and disrupted the multilaminar structure of the secondary cell walls. When CesA7A was suppressed, crystalline cellulose content was reduced, which, however, showed an increase when CesA3D was suppressed. The CesA suppression also affected cellulose digestibility of the wood cell walls. The results suggest that two type CSCs are involved in coordinating the cellulose biosynthesis in formation of the multilaminar structure in Populus wood secondary cell walls.

  14. Modulation of Correlated Segment Fluctuations in IDPs upon Complex Formation as an Allosteric Regulatory Mechanism.

    Science.gov (United States)

    Beier, Andreas; Schwarz, Thomas C; Kurzbach, Dennis; Platzer, Gerald; Tribuzio, Francesca; Konrat, Robert

    2018-05-05

    Molecular recognition of and by intrinsically disordered proteins (IDPs) is an intriguing and still largely elusive phenomenon. Typically, protein recognition involving IDPs requires either folding upon binding or, alternatively, the formation of "fuzzy complexes." Here we show via correlation analyses of paramagnetic relaxation enhancement data unprecedented and striking alterations of the concerted fluctuations within the conformational ensemble of IDPs upon ligand binding. We study the binding of α-synuclein to calmodulin, a ubiquitous calcium-binding protein, and the binding of the extracellular matrix IDP osteopontin to heparin, a mimic of the extracellular matrix ligand hyaluronic acid. In both cases, binding leads to reduction of correlated long-range motions in these two IDPs and thus indicates a loosening of structural compaction upon binding. Most importantly, however, the simultaneous presence of correlated and anti-correlated fluctuations in IDPs suggests the prevalence of "energetic frustration" and provides an explanation for the puzzling observation of disordered allostery in IDPs. Copyright © 2018. Published by Elsevier Ltd.

  15. Computation of infinite dilute activity coefficients of binary liquid alloys using complex formation model

    Energy Technology Data Exchange (ETDEWEB)

    Awe, O.E., E-mail: draweoe2004@yahoo.com; Oshakuade, O.M.

    2016-04-15

    A new method for calculating Infinite Dilute Activity Coefficients (γ{sup ∞}s) of binary liquid alloys has been developed. This method is basically computing γ{sup ∞}s from experimental thermodynamic integral free energy of mixing data using Complex formation model. The new method was first used to theoretically compute the γ{sup ∞}s of 10 binary alloys whose γ{sup ∞}s have been determined by experiments. The significant agreement between the computed values and the available experimental values served as impetus for applying the new method to 22 selected binary liquid alloys whose γ{sup ∞}s are either nonexistent or incomplete. In order to verify the reliability of the computed γ{sup ∞}s of the 22 selected alloys, we recomputed the γ{sup ∞}s using three other existing methods of computing or estimating γ{sup ∞}s and then used the γ{sup ∞}s obtained from each of the four methods (the new method inclusive) to compute thermodynamic activities of components of each of the binary systems. The computed activities were compared with available experimental activities. It is observed that the results from the method being proposed, in most of the selected alloys, showed better agreement with experimental activity data. Thus, the new method is an alternative and in certain instances, more reliable approach of computing γ{sup ∞}s of binary liquid alloys.

  16. Decamethylytterbocene Complexes of Bipyridines and Diazabutadienes: Multiconfigurational Ground States and Open-Shell Singlet Formation

    Energy Technology Data Exchange (ETDEWEB)

    Booth, Corwin H.; Walter, Marc D.; Kazhdan, Daniel; Hu, Yung-Jin; Lukens, Wayne W.; Bauer, Eric D.; Maron, Laurent; Eisenstein, Odile; Andersen, Richard A.

    2009-04-22

    Partial ytterbium f-orbital occupancy (i.e., intermediate valence) and open-shell singlet formation are established for a variety of bipyridine and diazabutadiene adducts with decamethylytterbocene, (C5Me5)2Yb, abbreviated as Cp*2Yb. Data used to support this claim include ytterbium valence measurements using Yb LIII-edge X-ray absorption near-edge structure spectroscopy, magnetic susceptibility, and complete active space self-consistent field (CASSCF) multiconfigurational calculations, as well as structural measurements compared to density functional theory calculations. The CASSCF calculations indicate that the intermediate valence is the result of a multiconfigurational ground-state wave function that has both an open-shell singlet f13(?*)1, where pi* is the lowest unoccupied molecular orbital of the bipyridine or dpiazabutadiene ligands, and a closed-shell singlet f14 component. A number of other competing theories for the unusual magnetism in these materials are ruled out by the lack of temperature dependence of the measured intermediate valence. These results have implications for understanding chemical bonding not only in organolanthanide complexes but also for f-element chemistry in general, as well as understanding magnetic interactions in nanoparticles and devices.

  17. Decamethylytterbocene complexes of bipyridines and diazabutadines: multiconfigurational ground states and open-shell singlet formation

    Energy Technology Data Exchange (ETDEWEB)

    Bauer, Eric D [Los Alamos National Laboratory; Booth, C H [LBNL; Walter, M D [LBNL; Kazhdan, D [LBNL; Hu, Y - J [LBNL; Lukens, Wayne [LBNL; Maron, Laurent [INSA TOULOUSE; Eisentein, Odile [UNIV MONTPELLIER 2; Anderson, Richard [LBNL

    2009-01-01

    Partial ytterbium f-orbital occupancy (i.e. intermediate valence) and open-shell singlet Draft 12/formation are established for a variety of bipyridine and diazabutadiene adducts to decamethylytterbocene, (C{sub 5}Me{sub 5}){sub 2}Yb or Cp*{sub 2}Yb. Data used to support this claim includes ytterbium valence measurements using Yb Lm-edge x-ray absorption near-edge structure (XANES) spectroscopy, magnetic susceptibility and Complete Active Space Self-Consistent Field (CASSCF) multi configurational calculations, as well as structural measurements compared to density-functional theory (DFT) calculations. The CASSCF calculations indicate that the intermediate valence is the result of a multiconfigurational ground state wave function that has both an open-shell singlet f{sup 13} and a closed-shell singlet f{sup 14} component. A number of other competing theories for the unusual magnetism in these materials are ruled out by the presence of intermediate valence and its lack of any significant temperature dependence. These results have implications for understanding chemical bonding not only in organolanthanide complexes, but also for organometallic chemistry in general, as well as understanding magnetic interactions in nanopartic1es and devices.

  18. Effect of ultrasonic waves on the water turbidity during the oxidation of phenol. Formation of (hydro)peroxo complexes.

    Science.gov (United States)

    Villota, Natalia; Lomas, Jose M; Camarero, Luis M

    2017-11-01

    Analysis of the kinetics of aqueous phenol oxidation by a sono-Fenton process reveals that the via involving ortho-substituted intermediates prevails: catechol (25.0%), hydroquinone (7.7%) and resorcinol (0.6%). During the oxidation, water rapidly acquires color that reaches its maximum intensity at the maximum concentration of p-benzoquinone. Turbidity formation occurs at a slower rate. Oxidant dosage determines the nature of the intermediates, being trihydroxylated benzenes (pyrogallol, hydroxyhydroquinone) and muconic acid the main precursors causing turbidity. It is found that the concentration of iron species and ultrasonic waves affects the intensity of the turbidity. The pathway of (hydro)peroxo-iron(II) complexes formation is proposed. Operating with 20.0-27.8mgFe 2+ /kW rates leads to formation of (hydro)peroxo-iron(II) complexes, which induce high turbidity levels. These species would dissociate into ZZ-muconic acid and ferrous ions. Applying relationships around 13.9mgFe 2+ /kW, the formation of (hydro)peroxo-iron(III) complexes would occur, which could react with carboxylic acids (2,5-dioxo-3-hexenedioic acid). That reaction induces turbidity slower. This is due to the organic substrate reacting with two molecules of the (hydro)peroxo complex. Therefore, it is necessary to accelerate the iron regeneration, intensifying the ultrasonic irradiation. Afterwards, this complex would dissociate into maleic acid and ferric ions. Copyright © 2017 Elsevier B.V. All rights reserved.

  19. Synthesis, characterization and computational studies of zinc(ii)-halide complexes with a bidentate Schiff base ligand (2,5-MeO-ba).sub.2./sub.En: the crystal structure of (2,5-MeO-ba).sub.2./sub.En

    Czech Academy of Sciences Publication Activity Database

    Khalaji, A.D.; Mighani, H.; Gholinejad, M.; Grivani, G.; Jalali Akerdi, S.; Fejfarová, Karla; Dušek, Michal

    2013-01-01

    Roč. 54, č. 4 (2013), s. 766-773 ISSN 0022-4766 Institutional research plan: CEZ:AV0Z10100521 Keywords : zinc(II) halides * Schiff base * crystal structure * density functional theory Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 0.501, year: 2013

  20. Determination of the stability constants of a number of metal fluoride complexes and their rates of formation

    International Nuclear Information System (INIS)

    Hammer, R.R.

    1979-08-01

    The stability constants of the fluoride complexes of Al +3 , H 3 BO 3 , Cr +3 , Cr +6 , Fe +3 , Gd +3 , Nb +5 , UO 2 +2 , and Zr +4 were determined in 0.96 and 2.88 M HNO 3 solutions in the temperature range 25 to 60 0 C with a fluoride specific ion electrode. These data can be used to calculate the concentration of chemical species in solution and will be used to correlate solution properties with solution composition. The solubilities of some fluoride precipitates were also measured in nitric acid solutions. The rates of formation of the fluoborates, aluminum fluoride, and zirconium fluoride complexes were measured with a fluoride specific ion electrode at 25, 35, and 45 0 C. The rates of formation of all complexes, except BF 4 - , AlF +2 , and a fluoride complex with aluminum containing more than three fluorides associated with it, were too fast to measure with the instrumentation used

  1. The effect of ligand efficacy on the formation and stability of a GPCR-G protein complex

    DEFF Research Database (Denmark)

    Yao, Xiao Jie; Vélez Ruiz, Gisselle; Whorton, Matthew R

    2009-01-01

    G protein-coupled receptors (GPCRs) mediate the majority of physiologic responses to hormones and neurotransmitters. However, many GPCRs exhibit varying degrees of agonist-independent G protein activation. This phenomenon is referred to as basal or constitutive activity. For many of these GPCRs...... of an agonist, the beta(2)AR and Gs can be trapped in a complex by enzymatic depletion of guanine nucleotides. Formation of the complex is enhanced by the agonist isoproterenol, and it rapidly dissociates on exposure to concentrations of GTP and GDP found in the cytoplasm. The inverse agonist ICI prevents...... formation of the beta(2)AR-Gs complex, but has little effect on preformed complexes. These results provide insights into G protein-induced conformational changes in the beta(2)AR and the structural basis for ligand efficacy....

  2. Silver nanoparticles from silver halide photography to plasmonics

    CERN Document Server

    Tani, Tadaaki

    2015-01-01

    This book provides systematic knowledge and ideas on nanoparticles of Ag and related materials. While Ag and metal nanoparticles are essential for plasmonics, silver halide (AgX) photography relies to a great extent on nanoparticles of Ag and AgX which have the same crystal structure and have been studied extensively for many years. This book has been written to combine the knowledge of nanoparticles of Ag and related materials in plasmonics and AgX photography in order to provide new ideas for metal nanoparticles in plasmonics. Chapters 1–3 of this book describe the structure and formation of nanoparticles of Ag and related materials. Systematic descriptions of the structure and preparation of Ag, Au, and noble-metal nanoparticles for plasmonics are followed by and related to those of nanoparticles of Ag and AgX in AgX photography. Knowledge of the structure and preparation of Ag and AgX nanoparticles in photography covers nanoparticles with widely varying sizes, shapes, and structures, and formation proce...

  3. Photography: enhancing sensitivity by silver-halide crystal doping

    International Nuclear Information System (INIS)

    Belloni, Jacqueline

    2003-01-01

    The physical chemistry of the silver photography processes, exposure, development and fixing, is briefly summarized. The mechanism of the autocatalytic development by the developer of the clusters produced in silver bromide crystals during the exposure which is controlled by the critical nuclearity of these clusters was understood from pulse radiolysis studies. The effective quantum yield PHI eff of photoinduced silver cluster formation in silver halide microcrystals is usually much lower than the photoionization theoretical limit PHI theor =1 electron-hole pair per photon absorbed, owing to a subsequent very fast intra-crystal recombination of a part of the electron-hole pairs. In order to inhibit this recombination and favor the silver reduction by photo-electrons, the AgX crystals were doped with the formate HCO 2 - as a specific hole scavenger. First, the dopant scavenges the photoinduced hole, thus enhancing the electron escape from the pair recombination. Second, the CO 2 ·- radical so formed transfers an electron to another silver cation, so that the PHI eff limit may be of 2Ag 0 per photon. This Photoinduced Bielectronic Transfer mechanism is strictly proportional to the light quanta absorbed and induces an exceptional efficiency for enhancing the radio- or photographic sensitivity insofar as it totally suppresses the electron-hole recombination

  4. Finding New Perovskite Halides via Machine learning

    Directory of Open Access Journals (Sweden)

    Ghanshyam ePilania

    2016-04-01

    Full Text Available Advanced materials with improved properties have the potential to fuel future technological advancements. However, identification and discovery of these optimal materials for a specific application is a non-trivial task, because of the vastness of the chemical search space with enormous compositional and configurational degrees of freedom. Materials informatics provides an efficient approach towards rational design of new materials, via learning from known data to make decisions on new and previously unexplored compounds in an accelerated manner. Here, we demonstrate the power and utility of such statistical learning (or machine learning via building a support vector machine (SVM based classifier that uses elemental features (or descriptors to predict the formability of a given ABX3 halide composition (where A and B represent monovalent and divalent cations, respectively, and X is F, Cl, Br or I anion in the perovskite crystal structure. The classification model is built by learning from a dataset of 181 experimentally known ABX3 compounds. After exploring a wide range of features, we identify ionic radii, tolerance factor and octahedral factor to be the most important factors for the classification, suggesting that steric and geometric packing effects govern the stability of these halides. The trained and validated models then predict, with a high degree of confidence, several novel ABX3 compositions with perovskite crystal structure.

  5. Finding New Perovskite Halides via Machine learning

    Science.gov (United States)

    Pilania, Ghanshyam; Balachandran, Prasanna V.; Kim, Chiho; Lookman, Turab

    2016-04-01

    Advanced materials with improved properties have the potential to fuel future technological advancements. However, identification and discovery of these optimal materials for a specific application is a non-trivial task, because of the vastness of the chemical search space with enormous compositional and configurational degrees of freedom. Materials informatics provides an efficient approach towards rational design of new materials, via learning from known data to make decisions on new and previously unexplored compounds in an accelerated manner. Here, we demonstrate the power and utility of such statistical learning (or machine learning) via building a support vector machine (SVM) based classifier that uses elemental features (or descriptors) to predict the formability of a given ABX3 halide composition (where A and B represent monovalent and divalent cations, respectively, and X is F, Cl, Br or I anion) in the perovskite crystal structure. The classification model is built by learning from a dataset of 181 experimentally known ABX3 compounds. After exploring a wide range of features, we identify ionic radii, tolerance factor and octahedral factor to be the most important factors for the classification, suggesting that steric and geometric packing effects govern the stability of these halides. The trained and validated models then predict, with a high degree of confidence, several novel ABX3 compositions with perovskite crystal structure.

  6. Local polar fluctuations in lead halide perovskites

    Science.gov (United States)

    Tan, Liang; Yaffe, Omer; Guo, Yinsheng; Brus, Louis; Rappe, Andrew; Egger, David; Kronik, Leeor

    The lead halide perovskites have recently attracted much attention because of their large and growing photovoltaic power conversion efficiencies. However, questions remain regarding the temporal and spatial correlations of the structural fluctuations, their atomistic nature, and how they affect electronic and photovoltaic properties. To address these questions, we have performed a combined ab initio molecular dynamics (MD) and density functional theory (DFT) study on CsPbBr3. We have observed prevalent anharmonic motion in our MD trajectories, with local polar fluctuations involving head-to-head motion of A-site Cs cations coupled with Br window opening. We calculate Raman spectra from the polarizability auto-correlation functions obtained from these trajectories and show that anharmonic A-site cation motion manifests as a broad central peak in the Raman spectrum, which increases in intensity with temperature. A comparison of the experimental Raman spectrum of hybrid organometallic MAPbBr3 and fully inorganic CsPbBr3 suggests that structural fluctuations in lead-halide perovskites is more general than rotation of polar organic cations and is intimately coupled to the inorganic framework.

  7. Formation mechanism of a silane-PVA/PVAc complex film on a glass fiber surface.

    Science.gov (United States)

    Repovsky, Daniel; Jane, Eduard; Palszegi, Tibor; Slobodnik, Marek; Velic, Dusan

    2013-10-21

    Mechanical properties of glass fiber reinforced composite materials are affected by fiber sizing. A complex film formation, based on a silane film and PVA/PVAc (polyvinyl alcohol/polyvinyl acetate) microspheres on a glass fiber surface is determined at 1) the nanoscale by using atomic force microscopy (AFM), and 2) the macroscale by using the zeta potential. Silane groups strongly bind through the Si-O-Si bond to the glass surface, which provides the attachment mechanism as a coupling agent. The silane groups form islands, a homogeneous film, as well as empty sites. The average roughness of the silanized surface is 6.5 nm, whereas it is only 0.6 nm for the non-silanized surface. The silane film vertically penetrates in a honeycomb fashion from the glass surface through the deposited PVA/PVAc microspheres to form a hexagonal close pack structure. The silane film not only penetrates, but also deforms the PVA/PVAc microspheres from the spherical shape in a dispersion to a ellipsoidal shape on the surface with average dimensions of 300/600 nm. The surface area value Sa represents an area of PVA/PVAc microspheres that are not affected by the silane penetration. The areas are found to be 0.2, 0.08, and 0.03 μm(2) if the ellipsoid sizes are 320/570, 300/610, and 270/620 nm for silane concentrations of 0, 3.8, and 7.2 μg mL(-1), respectively. The silane film also moves PVA/PVAc microspheres in the process of complex film formation, from the low silane concentration areas to the complex film area providing enough silane groups to stabilize the structure. The values for the residual silane honeycomb structure heights (Ha ) are 6.5, 7, and 12 nm for silane concentrations of 3.8, 7.2, and 14.3 μg mL(-1), respectively. The pH-dependent zeta-potential results suggest a specific role of the silane groups with effects on the glass fiber surface and also on the PVA/PVAc microspheres. The non-silanized glass fiber surface and the silane film have similar zeta potentials ranging

  8. Preparation of gold microparticles using halide ions in bulk block copolymer phases via photoreduction

    International Nuclear Information System (INIS)

    Cha, Sang-Ho; Kim, Ki-Hyun; Lee, Won-Ki; Lee, Jong-Chan

    2009-01-01

    Gold microparticles were prepared from the gold salt in the solid bulk phase of a poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) block copolymer via a photoreduction process in the presence of halide ions. The shapes and sizes of the gold microparticles were found to be dependent on the types and amount of halide ions as well as the types of cations used due to the combined effects of the adsorption power and oxidative dissolution ability of the additives on gold surfaces. Gold nanorods were obtained when poly(ethylene oxide) was used instead of the block copolymer. This suggests that the poly(propylene oxide) (PPO) parts in the block copolymer are essential for the formation of gold microparticles, even though the degree of the direct interaction between the PPO blocks and gold salt is not significant. - Graphical abstract: Gold microparticles were successfully prepared using halide ions as additives in the polymeric bulk phase via photoreduction with the glow lamp irradiation.

  9. Holographic Optical Elements Recorded in Silver Halide Sensitized Gelatin Emulsions. Part 2. Reflection Holographic Optical Elements

    Science.gov (United States)

    Kim, Jong Man; Choi, Byung So; Choi, Yoon Sun; Kim, Jong Min; Bjelkhagen, Hans I.; Phillips, Nicholas J.

    2002-03-01

    Silver halide sensitized gelatin (SHSG) holograms are similar to holograms recorded in dichromated gelatin (DCG), the main recording material for holographic optical elements (HOEs). The drawback of DCG is its low energetic sensitivity and limited spectral response. Silver halide materials can be processed in such a way that the final hologram will have properties like a DCG hologram. Recently this technique has become more interesting since the introduction of new ultra-fine-grain silver halide (AgHal) emulsions. In particular, high spatial-frequency fringes associated with HOEs of the reflection type are difficult to construct when SHSG processing methods are employed. Therefore an optimized processing technique for reflection HOEs recorded in the new AgHal materials is introduced. Diffraction efficiencies over 90% can be obtained repeatably for reflection diffraction gratings. Understanding the importance of a selective hardening process has made it possible to obtain results similar to conventional DCG processing. The main advantage of the SHSG process is that high-sensitivity recording can be performed with laser wavelengths anywhere within the visible spectrum. This simplifies the manufacturing of high-quality, large-format HOEs, also including high-quality display holograms of the reflection type in both monochrome and full color.

  10. First-principles study of γ-ray detector materials in perovskite halides

    Science.gov (United States)

    Im, Jino; Jin, Hosub; Stoumpos, Constantinos; Chung, Duck; Liu, Zhifu; Peters, John; Wessels, Bruce; Kanatzidis, Mercouri; Freeman, Arthur

    2013-03-01

    In an effort to search for good γ-ray detector materials, perovskite halide compounds containing heavy elements were investigated. Despite the three-dimensional network of the corner shared octahedra and the extended nature of the outermost shell, its strong ionic character leads to a large band gap, which is one of the essential criteria for γ-ray detector materials. Thus, considering high density and high atomic number, these pervoskite halides are possible candidate for γ-ray detector materials. We performed first-principles calculations to investigate electronic structures and thermodynamic properties of intrinsic defects in the selected perovskite halide, CsPbBr3. The screened-exchange local density approximation scheme was employed to correct the underestimation of the band gap in the LDA method. As a result, the calculated band gap of CsPbBr3 is found to be suitable for γ-ray detection. Furthermore, defect formation energy calculations allow us to predict thermodynamic and electronic properties of possible intrinsic defects, which affect detector efficiency and energy resolution. Supported by the office of Nonproliferation and Verification R &D under Contract No. DE-AC02-06CH11357

  11. Formation of aqueous complexes of metal ions formed during the reprocessing of nuclear fuels with ortho-phenanthroline and dibutylphosphate

    International Nuclear Information System (INIS)

    Musikas, C.; Le Marois, G.; Racinoux, J.

    1979-01-01

    In this work the formation of aqueous complexes of metalions (lanthanides, actinides) was investigated that occurs during reprocessing of nuclear combustibles with ortho-phenanthroline and dibutylphosphate. Complexes with different ligand numbers and solubility are formed. Cationic and anionic forms according to the DBP concentration in the extraction solution. Acid-base titrations, absorption spectra and solubility determinations were used for the characterization. (RB) [de

  12. Thermodynamics of mixed-ligand complex formation of zinc nitrilotriacetate with amino acids and dipeptides in solution

    International Nuclear Information System (INIS)

    Pyreu, Dmitrii; Gruzdev, Matvey; Kumeev, Roman; Gridchin, Sergei

    2014-01-01

    Highlights: • Stable mixed ligand complexes of ZnNta with amino acids and dipeptides. • Histamine-like coordination mode of His in the complex ZnNtaHis. • Glycine-like coordination of Lys and Orn in the complexes ZnNtaL and ZnNtaHL • NH 2 , CO-coordination mode of GlyGly in the complex ZnNtaGG. • NH 2 , N − or NH2, N − , COO-coordination modes of GlyGly in the complex ZnNtaGGH −1 . - Abstract: The isothermal calorimetry, pH-potentiometric titration and 1 H and 13 C NMR methods has been used to study the mixed-ligand complex formation in the systems Zn 2+ –Nta 3– –L − (L = His, Orn, Lys, GlyGly, AlaAla) in aqueous solution at 298.15 K and the ionic strength of I = 0.5 (KNO 3 ). The thermodynamic parameters of formation of the mixed complexes have been determined. The relationship between the probable coordination modes of the complexone and amino acid or dipeptide molecules in the mixed-ligand complex and the thermodynamic parameters has been discussed

  13. Thermodynamics of mixed-ligand complex formation of zinc nitrilotriacetate with amino acids and dipeptides in solution

    Energy Technology Data Exchange (ETDEWEB)

    Pyreu, Dmitrii, E-mail: pyreu@mail.ru [Department of Inorganic and Analytic Chemistry, Ivanovo State UniversityErmak 39, Ivanovo 153025 (Russian Federation); Gruzdev, Matvey; Kumeev, Roman [G.A. Krestov Institute of Solution Chemistry of the Russian Academy of Sciences, Ivanovo (Russian Federation); Gridchin, Sergei [Ivanovo State University of Chemistry and Technology, Ivanovo (Russian Federation)

    2014-10-20

    Highlights: • Stable mixed ligand complexes of ZnNta with amino acids and dipeptides. • Histamine-like coordination mode of His in the complex ZnNtaHis. • Glycine-like coordination of Lys and Orn in the complexes ZnNtaL and ZnNtaHL • NH{sub 2}, CO-coordination mode of GlyGly in the complex ZnNtaGG. • NH{sub 2}, N{sup −} or NH2, N{sup −}, COO-coordination modes of GlyGly in the complex ZnNtaGGH{sub −1}. - Abstract: The isothermal calorimetry, pH-potentiometric titration and {sup 1}H and {sup 13}C NMR methods has been used to study the mixed-ligand complex formation in the systems Zn{sup 2+}–Nta{sup 3–}–L{sup −} (L = His, Orn, Lys, GlyGly, AlaAla) in aqueous solution at 298.15 K and the ionic strength of I = 0.5 (KNO{sub 3}). The thermodynamic parameters of formation of the mixed complexes have been determined. The relationship between the probable coordination modes of the complexone and amino acid or dipeptide molecules in the mixed-ligand complex and the thermodynamic parameters has been discussed.

  14. A peroxynitrite complex of copper: formation from a copper-nitrosyl complex, transformation to nitrite and exogenous phenol oxidative coupling or nitration.

    Science.gov (United States)

    Park, Ga Young; Deepalatha, Subramanian; Puiu, Simona C; Lee, Dong-Heon; Mondal, Biplab; Narducci Sarjeant, Amy A; del Rio, Diego; Pau, Monita Y M; Solomon, Edward I; Karlin, Kenneth D

    2009-11-01

    Reaction of nitrogen monoxide with a copper(I) complex possessing a tridentate alkylamine ligand gives a Cu(I)-(*NO) adduct, which when exposed to dioxygen generates a peroxynitrite (O=NOO(-))-Cu(II) species. This undergoes thermal transformation to produce a copper(II) nitrito (NO(2) (-)) complex and 0.5 mol equiv O(2). In the presence of a substituted phenol, the peroxynitrite complex effects oxidative coupling, whereas addition of chloride ion to dissociate the peroxynitrite moiety instead leads to phenol ortho nitration. Discussions include the structures (including electronic description) of the copper-nitrosyl and copper-peroxynitrite complexes and the formation of the latter, based on density functional theory calculations and accompanying spectroscopic data.

  15. Collectin-11/MASP complex formation triggers activation of the lectin complement pathway--the fifth lectin pathway initiation complex

    DEFF Research Database (Denmark)

    Ma, Ying Jie; Skjoedt, Mikkel-Ole; Garred, Peter

    2013-01-01

    Collectins and ficolins are important in the clearance of endogenous and exogenous danger materials. A new human collectin-11 was recently identified in low concentration in serum in complex with mannose-binding lectin (MBL)/ficolin-associated serine proteases. Collectin-11 binds to carbohydrate...... complement complex on C. albicans. Moreover, spiking collectin-11-depleted serum, which did not mediate complement activation, with recombinant collectin-11 restored the complement activation capability. These results define collectin-11 as the fifth recognition molecule in the lectin complement pathway...

  16. Methodological basis for formation of uniterruptible education content for future specialists of atomic-nuclear complex

    International Nuclear Information System (INIS)

    Burtebayev, N.; Burtebayeva, J.T.; Basharuly, R.; Altynsarin, Y.

    2009-01-01

    content for future specialists of atomic-nuclear complex at the particular science methodological level. It should be highlighted that the so called 'methods system' of teaching is the inseparable link of its subsequent backbone elements: aim, content, forms, methods and techniques of teaching. The creation of such methods system, consisting of above five elements assures the functional adequacy of specialists teaching, including nuclear profile personnel. Thereby, as the system methodological analysis shows, the determination of the content of uninterrupted education for nuclear profile specialists is only one of the tasks of united teaching methods system formation. Consequently, the development of other its backbone elements is the vital task of the training of atomic-nuclear complex specialists. These are the main approaches in general of theoretical-methodological provision of the training for future competitive capable specialists of nuclear profile in the national system of uninterrupted education in the Republic of Kazakhstan. Reference: 1. Basharuly R. Methodology of poly-cultural education development in Kazakhstan. Almaty: G ylym , 2002, p. 236.; 2. Sedov E.A. Again dialectics: truth and myths. // Pedagogic, 1993, No.3, pp.113-117.; 3. Lednev V.S. Education content. M.: High school. 1989, p.362. (authors)

  17. Formation of nano-hydroxyapatite crystal in situ in chitosan-pectin polyelectrolyte complex network

    Energy Technology Data Exchange (ETDEWEB)

    Li Junjie [Department of Polymer Science and Key Laboratory of Systems Bioengineering of Ministry of Education, School of Chemical Engineering and Technology, Tianjin University, Tianjin, 300072 (China); Research Institute of Polymeric Materials, Tianjin University, Tianjin, 300072 (China); Zhu Dunwan [Institute of Biomedical Engineering, Chinese Academy of Medical Sciences and Peking Union Medical College, Tianjin, 300072 (China); Yin Jianwei; Liu Yuxi [Department of Polymer Science and Key Laboratory of Systems Bioengineering of Ministry of Education, School of Chemical Engineering and Technology, Tianjin University, Tianjin, 300072 (China); Yao Fanglian, E-mail: yaofanglian@tju.edu.cn [Department of Polymer Science and Key Laboratory of Systems Bioengineering of Ministry of Education, School of Chemical Engineering and Technology, Tianjin University, Tianjin, 300072 (China); Yao Kangde [Research Institute of Polymeric Materials, Tianjin University, Tianjin, 300072 (China)

    2010-07-20

    Hydroxyapatite (HA)/polysaccharide composites have been widely used in bone tissue engineering due to their chemical similarity to natural bone. Polymer matrix-mediated synthesis of nano-hydroxyapatite is one of the simplest models for biomimetic. In this article, the nano-hydroxyapatite/chitosan-pectin (nHCP) composites were prepared through in situ mineralization of hydroxyapatite in chitosan-pectin polyelectrolyte complex (PEC) network. The formation processes of nHCP were investigated by X-ray diffraction (XRD) analysis. The interactions between nHA crystal and chitosan-pectin PEC networks were studied using Fourier Transform Infrared Spectroscopy (FTIR) and Differential Scanning Calorimetry (DSC). The morphology and structure of nHA crystal were characterized by XRD and Transmission Electron Microscope (TEM). Results suggested that the interfacial interactions between nano-hydroxyapatite crystal and chitosan-pectin PEC network assist the site specific nucleation and growth of nHA nanoparticles. The nHA crystals grow along the c-axis. In this process, pH value is the main factor to control the nucleation and growth of nHA crystal in chitosan-pectin PEC networks, because both the interactions' strength between nHA crystal and chitosan-pectin and diffusion rate of inorganic ions depend on the pH value of the reaction system. Apart from the pH value, the chitosan/pectin ratio and [Ca{sup 2+}] also take important effects on the formation of nHA crystal. An effective way to control the size of nHA crystal is to adjust the content of pectin and [Ca{sup 2+}]. It is interesting that the Zeta potential of nHCP composites is about - 30 mV when the chitosan/pectin ratio {<=} 1:1, and the dispersion solution of nHCP composites has higher stability, which provides the possibility to prepare 3D porous scaffolds with nHCP for bone tissue engineering.

  18. Formation of different-ligand complexes of neodymium,-holmium- and erbium ions with diantipyrylmethane and gallic acid

    International Nuclear Information System (INIS)

    Gerasimenko, G.I.; Tishchenko, M.A.; Poluehktov, N.S.

    1978-01-01

    Spectrometry has been used for studying the formation of different-ligand complexes of Nd 3+ , Ho 3+ , and Er 3+ with diantipyrylmethane (DAM) and gallic aicd (GA) at pH 10.0-12.0. It has been found that in the complex being formed one ion of rare earth element interacts with one molecule of DAM and three molecules of GA. The oscillator forces grow when passing from aquaions to compounds with gallic acid and then with DAM and GA. The oscillator forces of Nd 3+ and Er 3+ depend linearly on those of Ho 3+ in the solutions of complexes with DAM and GA

  19. Formative assessment in an online learning environment to support flexible on-the-job learning in complex professional domains

    NARCIS (Netherlands)

    Tamara van Gog; Desirée Joosten-ten Brinke; F. J. Prins; Dominique Sluijsmans

    2010-01-01

    This article describes a blueprint for an online learning environment that is based on prominent instructional design and assessment theories for supporting learning in complex domains. The core of this environment consists of formative assessment tasks (i.e., assessment for learning) that center on

  20. The role of territorial marketing in the formation of Russian Far East social and economic development complex

    Directory of Open Access Journals (Sweden)

    Bacherikova M. L.

    2016-11-01

    Full Text Available the article describes those areas of marketing tools which used in the complex of measures on Far East development. The role of territory marketing in formation of conditions for social and economic development of Far East macroregion is determinated; proposals on marketing approach to territory management in order to increase its competitiveness and attractiveness are formulated.

  1. Treatment of alcaline metals halides for developing crystals

    International Nuclear Information System (INIS)

    Spurney, R.W.

    1974-01-01

    A process is described whereby crystals of an alkaline metal halide may be dried and placed in a crucible for development by the Bridgeman-Stockbarger method. Purified alkaline halides from a suspension are dried and formed into dense cakes of transverse section slightly smaller than that of the crucible, where they are packed, melted and grown into crystals according to the Bridgeman-Stockbarger technique. This method applies to the preparation of alkaline halide crystals, particularly sodium iodide for optical elements or scintillation counters [fr

  2. Alkali metal and alkali earth metal gadolinium halide scintillators

    Science.gov (United States)

    Bourret-Courchesne, Edith; Derenzo, Stephen E.; Parms, Shameka; Porter-Chapman, Yetta D.; Wiggins, Latoria K.

    2016-08-02

    The present invention provides for a composition comprising an inorganic scintillator comprising a gadolinium halide, optionally cerium-doped, having the formula A.sub.nGdX.sub.m:Ce; wherein A is nothing, an alkali metal, such as Li or Na, or an alkali earth metal, such as Ba; X is F, Br, Cl, or I; n is an integer from 1 to 2; m is an integer from 4 to 7; and the molar percent of cerium is 0% to 100%. The gadolinium halides or alkali earth metal gadolinium halides are scintillators and produce a bright luminescence upon irradiation by a suitable radiation.

  3. THE FORMATION OF THE COMPETITIVENESS OF THE ENTERPRISES OF MACHINE-BUILDING COMPLEX OF UKRAINE

    Directory of Open Access Journals (Sweden)

    Oksana Zbyrannyk

    2016-11-01

    Full Text Available The purpose is to analyse the existing approaches to determine the value of the production of innovative products and innovation in enterprises of machine-building complex of Ukraine in order to improve their level of competitiveness. Methodology. Statistical analysis and generalization of scientific approaches to the formation of the competitiveness of machine-building enterprises. Results of the of the analyzed approaches allowed to identify the cause of the imperfection of innovation policy in engineering. According to the research, the number of machine-building enterprises engaged in innovation activity, constantly shrinks; the share of innovative products in the total is only 3.5-4%, and the volume of imports of high-tech products exceeding the size of own production; the level of knowledge-intensive industrial production is only 0.3%. All this slows down the process of creating competitive products and as a result, the failure to provide highly own products to other industries, take a niche world of mechanical engineering. Practical implications. Ensure accelerated economic growth of the country as the defining condition for implementation of the European integration aspirations of Ukraine in the short term requires the intensification of innovative activity of the machine-building enterprises. The current state of innovation activity of enterprises in Ukraine is characterized by a number of negative factors: the internal environment of the majority of machine-building enterprises does not correspond to the market conditions of managing: high energy productions, the growth of the degree of wear and tear of fixed assets and reduce investment to update them, the lack of introduction of advanced production and resource-saving technologies, reducing innovation activity due to lack of financial resources significantly affect the level of the competitive machine-building enterprises. Value/ originality systematic approaches to determining the

  4. Formation of atoll garnets in the UHP eclogites of the Tso Morari Complex, Ladakh, Himalaya

    Science.gov (United States)

    Jonnalagadda, Mallika K.; Karmalkar, Nitin R.; Duraiswami, Raymond A.; Harshe, Shivani; Gain, Sarah; Griffin, William L.

    2017-12-01

    The eclogites of the Tso Morari Complex, Ladakh, NW Himalayas preserve both garnets with spectacular atoll textures, as well as whole porphyroblastic garnets. Whole garnets are euhedral, idiomorphic and enclose inclusions of amphibole, phengite and zoisite within the cores, and omphacite and quartz/coesite towards the rims. Detailed electron microprobe analyses and back-scattered electron images show well-preserved prograde zoning in the whole garnets with an increase in Mg and decrease in Ca and Mn contents from the core to the rim. The atoll garnets commonly consist of euhedral ring over island/peninsular core containing inclusions of phengite, omphacite and rarely amphibole between the core and ring. Compositional profiles across the studied atoll grains show elemental variations with higher concentrations of Ca and Mn with low Mg at the peninsula/island cores; contrary to this low Ca, Mn and high Mg is observed at the outer rings. Temperature estimates yield higher values at the Mg-rich atoll garnet outer rings compared to the atoll cores. Atoll garnet formation was favoured by infiltration of fluid formed due to breakdown of hydrous phases, and/or the release of structurally bounded OH from nominally anhydrous minerals at the onset of exhumation. Infiltration of fluids along pre-existing fracture pathways and along mineral inclusion boundaries triggered breakdown of the original garnet cores and released elements which were subsequently incorporated into the newly-grown garnet rings. This breakdown of garnet cores and inward re-growth at the outer ring produced the atoll structure. Calibrated geo-thermobarometers and mineral equilibria reflect that the Tso Morari eclogites attain peak pressures prior to peak temperatures representing a clockwise path of evolution.

  5. Formation and past evolution of the showers of 96P/Machholz complex

    Science.gov (United States)

    Abedin, Abedin; Wiegert, Paul; Janches, Diego; Pokorný, Petr; Brown, Peter; Hormaechea, Jose Luis

    2018-01-01

    In this work we model the dynamical evolution of meteoroid streams of comet 96P/Machholz, and the largest member of the Marsden sunskirters, comet P/1999 J6. We simultaneously fit the characteristics of eight meteor showers which have been proposed to be linked to the complex, using observations from a range of techniques - visual, video, TV and radar. The aim is to obtain a self-consistent scenario of past capture of a large comet into a short-period orbit, and its subsequent fragmentation history. Moreover, we also aim to constrain the dominant parent of these showers. The fit of our simulated shower characteristics to observations is consistent with the scenario of a capture of a proto-comet 96P/Machholz by Jupiter circa 20000 BCE, and a subsequent major breakup around 100-950 CE which resulted in the formation of the Marsden group of comets. We find that the Marsden group of comets are not the immediate parents of the daytime Arietids and Northern and Southern δ-Aquariids, as previously suggested. In fact, the hypothesis that the Northern δ-Aquariids are related to the Marsden group of comets is not supported by this study. The bulk of the observational characteristics of all eight showers can be explained by meteoroid ejection primarily from comet 96P/Machholz between 10000 BCE and 20000 BCE. Assuming the Marsden group of comets originated between 100 CE-950 CE, we conclude that sunskirting comets contribute mainly to the meteoroid stream near the time of the peak of the daytime Arietids, Southern δ-Aquariids, κ-Velids. Finally, we find that the meteor showers identified by Babadzhanov and Obrubov (1992) as the α-Cetids, the Ursids and Carinids correspond to the daytime λ-Taurids, the November ι-Draconids or December α-Draconids and the θ-Carinids.

  6. Protection of metal artefacts with the formation of metal-oxalates complexes by Beauveria bassiana.

    Directory of Open Access Journals (Sweden)

    Edith eJoseph

    2012-01-01

    Full Text Available Several fungi present high tolerance to toxic metals and some are able to transform metals into metal-oxalate complexes. In this study, the ability of Beauveria bassiana to produce copper oxalates was evaluated in vitro. Growth performance was tested on various copper-containing media. B. bassiana proved highly resistant to copper, tolerating concentrations of up to 20 g.L-1, and precipitating copper oxalates on all media tested. Chromatographic analyses showed that this species produced oxalic acid as sole metal chelator. The production of metal-oxalates can be used in the restoration and conservation of archaeological and modern metal artefacts. The production of copper-oxalates was confirmed directly using metallic pieces (both archaeological and modern. The conversion of corrosion products into copper oxalates was demonstrated as well. In order to assess whether the capability of B. bassiana to produce metal-oxalates could be applied to other metals, iron and silver were tested as well. Iron appears to be directly sequestered in the wall of the fungal hyphae forming oxalates and probably goethite. However, the formation of a homogeneous layer on the object is not yet optimal. Silver nitrate was extracellularly reduced into nanoparticles of elemental silver by an unknown mechanism. The production of copper oxalates is immediately applicable for the conservation of copper-based artefacts. For iron and silver this is not yet the case. However, the vast ability of B. bassiana to transform toxic metals using different immobilization mechanisms seems to offer considerable possibilities for industrial applications, such as the bioremediation of contaminated soils or the green synthesis of chemicals.

  7. Characterizing Extragalactic Star Formation with GALEX Legacy Photometric Analysis of UV-Bright Stellar Complexes

    Science.gov (United States)

    Thilker, David

    At the close of nearly a decade of observing, GALEX has accumulated an unprecedented archive of ultraviolet (UV) images revealing both the scope and intricacy of star formation (SF) in many thousands of galaxies inhabiting the local universe. If the observed hierarchical SF morphology can be quantified systematically, and physically interpreted with multi-wavelength ancillary data and modeling, then the low redshift GALEX legacy will approach completion. However, the GALEX GR6 pipeline database contains a highly incomplete census of young stellar complexes even for very well-studied galaxies. We propose to apply a dedicated photometry algorithm that has been optimized for measuring the properties of irregularly shaped sources in crowded galaxy images containing spatially variant, diffuse intra-clump emission. Structures will be selected in the UV, but we will compile UV-visible-MIR SEDs for each detection utilizing Pan-STARRS1+SDSS and WISE data. These SEDs will then be fit using population-synthesis models to derive estimated stellar mass, age, and extinction. Processing will be completed for the entire diameter-limited GALEX Large Galaxy Atlas (GLGA) sample of 20,000+ galaxies, at a variety of standardized spatial resolutions. Although the precise categorization of the cataloged substructures will depend on galaxy distance, the outcome of our analysis will be a catalog similar to the stellar association surveys of past decades for very nearby galaxies based on resolved stars (e.g. van den Bergh 1964, Hodge 1986, Efremov et al. 1987), except that our investigation will probe a galaxy sample of dramatically larger size using the integrated UV light from such groupings of young stars. Our algorithm is multi-scale in nature and will thus preserve the hierarchical properties of the stellar distribution, by linking sub-clumps to their larger-scale parent feature(s). The resulting database will be a fundamental resource for follow-up multi-wavelength studies probing SF

  8. Nuclear magnetic resonance study of charge transfer complex formation between Silver Nitrate and Benzylcyanide in Solvent Ethylene Glycol

    CERN Document Server

    Modarress, H

    2003-01-01

    The formation constant for charge transfer complexes between electron acceptor (AgNo sub 3) and electron donor benzylcyanide (C sub 6 H sub 5 -CH sub 2 -C ident to N) in solvent ethyleneglycol [(CH sub 2 OH) sub 2] has been evaluated by using the nuclear magnetic resonance chemical shifts of aromatic group of benzylcyanide measured against external references, tetramethylsilane, hexamethyldisilane and cyclohexane at 20 sup d ig sup C. The external referencing procedure eliminated the interference of internal reference in the course of complexation. The necessary bulk magnetic susceptibility corrections on the measured chemical shifts have been made. The solution nationalised and their effects on the formation constant have been considered and a new equation has been suggested to obtain the main ionic activity coefficient of AgNO sub 3 from nuclear magnetic resonance results. The mean ionic activity coefficient has been taken into account in the formation constant calculations. The results indicated that the a...

  9. Hemolymph Melanization in the Silkmoth Bombyx mori Involves Formation of a High Molecular Mass Complex That Metabolizes Tyrosine*

    Science.gov (United States)

    Clark, Kevin D.; Strand, Michael R.

    2013-01-01

    The phenoloxidase (PO) cascade regulates the melanization of blood (hemolymph) in insects and other arthropods. Most studies indicate that microbial elicitors activate the PO cascade, which results in processing of the zymogen PPO to PO. PO is then thought to oxidize tyrosine and o-diphenols to quinones, which leads to melanin. However, different lines of investigation raise questions as to whether these views are fully correct. Here we report that hemolymph from the silkmoth, Bombyx mori, rapidly melanizes after collection from a wound site. Prior studies indicated that in vitro activated PPO hydroxylates Tyr inefficiently. Measurement of in vivo substrate titers, however, suggested that Tyr was the only PO substrate initially present in B. mori plasma and that it is rapidly metabolized by PO. Fractionation of plasma by gel filtration chromatography followed by bioassays indicated that melanization activity was primarily associated with a high mass complex (∼670 kDa) that contained PO. The prophenoloxidase-activating protease inhibitor Egf1.0 blocked formation of this complex and Tyr metabolism, but the addition of phenylthiourea to plasma before fractionation enhanced complex formation and Tyr metabolism. Mass spectrometry analysis indicated that the complex contained PO plus other proteins. Taken together, our results indicate that wounding alone activates the PO cascade in B. mori. They also suggest that complex formation is required for efficient use of Tyr as a substrate. PMID:23553628

  10. Post-synthetic halide conversion and selective halogen capture in hybrid perovskites† †Electronic supplementary information (ESI) available. CCDC 1048945–1048947. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c5sc01135c

    Science.gov (United States)

    Solis-Ibarra, D.; Smith, I. C.

    2015-01-01

    Reaction with halogen vapor allows us to post-synthetically exchange halides in both three- (3D) and two-dimensional (2D) organic–inorganic metal-halide perovskites. Films of 3D Pb–I perovskites cleanly convert to films of Pb–Br or Pb–Cl perovskites upon exposure to Br2 or Cl2 gas, respectively. This gas–solid reaction provides a simple method to produce the high-quality Pb–Br or Pb–Cl perovskite films required for optoelectronic applications. Reactivity with halogens can be extended to the organic layers in 2D metal-halide perovskites. Here, terminal alkene groups placed between the inorganic layers can capture Br2 gas through chemisorption to form dibromoalkanes. This reaction's selectivity for Br2 over I2 allows us to scrub Br2 to obtain high-purity I2 gas streams. We also observe unusual halogen transfer between the inorganic and organic layers within a single perovskite structure. Remarkably, the perovskite's crystallinity is retained during these massive structural rearrangements. PMID:29218171

  11. Determination of complex formation constants by phase sensitive alternating current polarography: Cadmium-polymethacrylic acid and cadmium-polygalacturonic acid.

    Science.gov (United States)

    Garrigosa, Anna Maria; Gusmão, Rui; Ariño, Cristina; Díaz-Cruz, José Manuel; Esteban, Miquel

    2007-10-15

    The use of phase sensitive alternating current polarography (ACP) for the evaluation of complex formation constants of systems where electrodic adsorption is present has been proposed. The applicability of the technique implies the previous selection of the phase angle where contribution of capacitive current is minimized. This is made using Multivariate Curve Resolution by Alternating Least Squares (MCR-ALS) in the analysis of ACP measurements at different phase angles. The method is checked by the study of the complexation of Cd by polymethacrylic (PMA) and polygalacturonic (PGA) acids, and the optimal phase angles have been ca. -10 degrees for Cd-PMA and ca. -15 degrees for Cd-PGA systems. The goodness of phase sensitive ACP has been demonstrated comparing the determined complex formation constants with those obtained by reverse pulse polarography, a technique that minimizes the electrode adsorption effects on the measured currents.

  12. Formation and characterization of zein-propylene glycol alginate-surfactant ternary complexes: Effect of surfactant type.

    Science.gov (United States)

    Dai, Lei; Sun, Cuixia; Wei, Yang; Zhan, Xinyu; Mao, Like; Gao, Yanxiang

    2018-08-30

    In this study, zein, propylene glycol alginate (PGA) and surfactant ternary complexes were fabricated by antisolvent co-precipitation method. Two types of surfactants (rhamnolipid and lecithin) were applied to generate zein-PGA-rhamnolipid (Z-P-R) and zein-PGA-lecithin (Z-P-L) ternary complexes, respectively. Results showed that the surfactant types significantly affected the properties of ternary complexes. The formation of ternary complexes was mainly due to the non-covalent interactions such as hydrogen bonding, electrostatic interaction and hydrophobic interactions among zein, PGA and surfactants. Moreover, the thermal stability of ternary complexes was enhanced with increasing the levels of both surfactants. Notably, ternary complex dispersions exhibited better stability against pH from 2 to 8. Furthermore, a compact network structure was observed in Z-P-R ternary complex, while Z-P-L ternary complex remained the spherical structure. These findings would provide new insights into the development of novel delivery system and expand the options, when zein-based complexes were utilized under different environment conditions. Copyright © 2018 Elsevier Ltd. All rights reserved.

  13. Radiation chemistry of the alkali halides

    International Nuclear Information System (INIS)

    Robinson, V.J.; Chandratillake, M.R.

    1987-01-01

    By far the most thoroughly investigated group of compounds in solid-state radiation chemistry are the alkali halides. Some of the reasons are undoubtedly practical: large single crystals of high purity are readily prepared. The crystals are transparent over a wide range of wavelengths. They are more sensitive to radiation damage than most other ionic solids. The crystals have simple well-defined structures, and the products of radiolysis have also in many cases been clearly identified by a variety of experimental techniques, the most important being optical methods and electron paramagnetic resonance (EPR). In recent years the application of pulse techniques-radiolysis and laser photolysis-has yielded a wealth of information concerning the mechanisms of the primary processes of radiation damage, on the one hand, and of thermal and photolytic reactions that the radiolysis products undergo, on the other

  14. Catalytic effect of halide additives ball milled with magnesium hydride

    Energy Technology Data Exchange (ETDEWEB)

    Malka, I.E.; Bystrzycki, J. [Department of Advanced Materials and Technologies, Military University of Technology, Kaliskiego 2, 00-908 Warsaw (Poland); Czujko, T. [Department of Advanced Materials and Technologies, Military University of Technology, Kaliskiego 2, 00-908 Warsaw (Poland); CanmetENERGY, Hydrogen Fuel Cells and Transportation Energy, Natural Resources (Canada)

    2010-02-15

    The influence of various halide additives milled with magnesium hydride (MgH{sub 2}) on its decomposition temperature was studied. The optimum amount of halide additive and milling conditions were evaluated. The MgH{sub 2} decomposition temperature and energy of activation reduction were measured by temperature programmed desorption (TPD) and differential scanning calorimetry (DSC). The difference in catalytic efficiency between chlorides and fluorides of the various metals studied is presented. The effects of oxidation state, valence and position in the periodic table for selected halides on MgH{sub 2} decomposition temperature were also studied. The best catalysts, from the halides studied, for magnesium hydride decomposition were ZrF{sub 4}, TaF{sub 5}, NbF{sub 5}, VCl{sub 3} and TiCl{sub 3}. (author)

  15. Single Crystals of Organolead Halide Perovskites: Growth, Characterization, and Applications

    KAUST Repository

    Peng, Wei

    2017-01-01

    Despite their outstanding charge transport characteristics, organolead halide perovskite single crystals grown by hitherto reported crystallization methods are not suitable for most optoelectronic devices due to their small aspect ratios

  16. Dipole-dipole van der Waals interaction in alkali halides

    International Nuclear Information System (INIS)

    Thakur, B.N.; Thakur, K.P.

    1978-01-01

    Values of van der Waals dipole-dipole constants and interaction energetics of alkali halides are reported using the recent data. The values obtained are somewhat larger than those of earlier workers. (orig.) [de

  17. High temperature reactions between molybdenum and metal halides

    International Nuclear Information System (INIS)

    Boeroeczki, A.; Dobos, G.; Josepovits, V.K.; Hars, Gy.

    2006-01-01

    Good colour rendering properties, high intensity and efficacy are of vital importance for high-end lighting applications. These requirements can be achieved by high intensity discharge lamps doped with different metal halide additives (metal halide lamps). To improve their reliability, it is very important to understand the different failure processes of the lamps. In this paper, the corrosion reactions between different metal halides and the molybdenum electrical feed-through electrode are discussed. The reactions were studied in the feed-through of real lamps and on model samples too. X-ray photoelectron spectroscopy (XPS) was used to establish the chemical states. In case of the model samples we have also used atomic absorption spectroscopy (AAS) to measure the reaction product amounts. Based on the measurement results we were able to determine the most corrosive metal halide components and to understand the mechanism of the reactions

  18. Dislocation unpinning model of acoustic emission from alkali halide ...

    Indian Academy of Sciences (India)

    The present paper reports the dislocation unpinning model of acoustic emis- sion (AE) from ... Acoustic emission; dislocation; alkali halide crystals; plastic deformation. ..... [5] T Nishimura, A Tahara and T Kolama, Jpn. Metal Inst. 64, 339 (2000).

  19. A new fundamental hydrogen defect in alkali halides

    International Nuclear Information System (INIS)

    Morato, S.P.; Luety, F.

    1978-01-01

    Atom hydrogen in neutral (H 0 ) and negative (H - ) form on substitutional and interstitial lattice sites gives rise to well characterized model defects in alkali-halides (U,U 1 ,U 2 ,U 3 centers), which have been extensively investigated in the past. When studying the photo-decomposition of OH - defects, a new configuration of atomic charged hidrogen was discovered, which can be produced in large quantities in the crystal and is apparently not connected to any other impurity. This new hidrogen defect does not show any pronounced electronic absorption, but displays a single sharp local mode band (at 1114cm -1 in KCl) with a perfect isotope shift. The defect can be produced by various UV or X-ray techniques in crystais doped with OH - , Sh - or H - defects. A detailed study of its formation kinetics at low temperature shows that it is primarily formed by the reaction of a mobile CI 2 - crowdion (H-center) with hidrogen defects [pt

  20. Thermodynamic model of Ni(II) solubility, hydrolysis and complex formation with ISA

    Energy Technology Data Exchange (ETDEWEB)

    Gonzalez-Siso, Maria Rosa; Duro, Lara; Bruno, Jordi [Amphos21, Barcelona (Spain); Gaona, Xavier; Altmaier, Marcus [Karlsruhe Institute of Technology (KIT), Karlsruhe (Germany). Inst. for Nuclear Waste Disposal

    2018-04-01

    The solubility of β-Ni(OH){sub 2}(cr) was investigated at T=(22±2) C in the absence and presence of α-isosaccharinic acid (ISA), the main degradation product of cellulose under alkaline pH conditions. Batch solubility experiments were performed from undersaturation conditions under inert gas (Ar) atmosphere. Solubility experiments in the absence of ISA were conducted in 0.5 and 3.0 M NaCl-NaOH solutions at 7.5 ≤ pH{sub m} ≤ 13 (with pH{sub m} = -log{sub 10}[H{sup +}]). XRD analyses of selected solid phases collected after completing the solubility experiments (∼300 days) confirmed that β-Ni(OH){sub 2}(cr) remains as solid phase controlling the solubility of Ni(II) in all investigated conditions. Based on the slope analysis (log{sub 10}[Ni] vs. pH{sub m}) of the solubility data and solid phase characterization, the equilibrium reactions β-Ni(OH){sub 2}(cr)+2 H{sup +} <=> Ni{sup 2+}+2 H{sub 2}O(l) and β-Ni(OH){sub 2}(cr) <=> Ni(OH){sub 2}(aq) were identified as controlling the solubility of Ni(II) within the investigated pH{sub m} region. The conditional equilibrium constants determined from the solubility experiments at different ionic strengths were evaluated with the specific ion interaction theory (SIT). In contrast to the current thermodynamic selection in the NEA-TDB, solubility data collected in the present work does not support the formation of the anionic hydrolysis species Ni(OH){sub 3}{sup -} up to pH{sub m} ≤ 13.0. Solubility experiments in the presence of ISA were conducted in 0.5 M NaCl-NaOH-NaISA solutions with 0.01 M ≤ [NaISA] ≤ 0.2 M and 9 ≤ pH{sub m} ≤ 13. XRD analyses confirmed that β-Ni(OH){sub 2}(cr) is also the solid phase controlling the solubility of Ni(II) in the presence of ISA. Solubility data of all investigated systems can be properly explained with chemical and thermodynamic models including the formation of the complexes NiOHISA(aq), Ni(OH){sub 2}ISA{sup -} and Ni(OH){sub 3}ISA{sup 2-}. The reported data confirm

  1. Systemic analysis of thermodynamic properties of lanthanide halides

    International Nuclear Information System (INIS)

    Mirsaidov, U.; Badalov, A.; Marufi, V.K.

    1992-01-01

    System analysis of thermodynamic characteristics of lanthanide halides was carried out. A method making allowances for the influence of spin and orbital moments of momentum of the main states of lanthanide trivalent ions in their natural series was employed. Unknown in literature thermodynamic values were calculated and corrected for certain compounds. The character of lanthanide halide thermodynamic parameter change depending on ordinal number of the metals was ascertained. Pronouncement of tetrad-effect in series of compounds considered was pointed out

  2. Nuclear magnetic resonance study of charge transfer complex formation between Silver Nitrate and Benzylcyanide in Solvent Ethylene Glycol

    International Nuclear Information System (INIS)

    Modarress, H.; Shekaari, H.

    2003-01-01

    The formation constant for charge transfer complexes between electron acceptor (AgNo 3 ) and electron donor benzylcyanide (C 6 H 5 -CH 2 -C≡N) in solvent ethyleneglycol [(CH 2 OH) 2 ] has been evaluated by using the nuclear magnetic resonance chemical shifts of aromatic group of benzylcyanide measured against external references, tetramethylsilane, hexamethyldisilane and cyclohexane at 20 d ig C . The external referencing procedure eliminated the interference of internal reference in the course of complexation. The necessary bulk magnetic susceptibility corrections on the measured chemical shifts have been made. The solution nationalised and their effects on the formation constant have been considered and a new equation has been suggested to obtain the main ionic activity coefficient of AgNO 3 from nuclear magnetic resonance results. The mean ionic activity coefficient has been taken into account in the formation constant calculations. The results indicated that the appropriate formation constant should be expressed in terms of activities. Also an equation have been derived to eliminate the undesirable effects on the nuclear magnetic resonance measured chemical shifts in calculating the constant. The selection of concentration domains and its effect on the calculated formation constant has been discussed and the new equation is modified to be independent of the concentration domains. In this equation the solution nationalised, by considering coefficients, have been taken in to account

  3. THE FORMATION OF DESIGN AND ORGANIZATIONAL AND TECHNOLOGICAL DECISIONS OF THE CONSTRUCTION OF HIGH-RISE MULTIPURPOSE COMPLEXES

    Directory of Open Access Journals (Sweden)

    BOLSHAKOV V. I.

    2016-05-01

    Full Text Available Purpose. The formation of the many ways the construction of high-rise multipurpose complexes. Methodology. The formation of system implementation variants of creation and functioning of high-rise multipurpose complexes using combinatorial morphological analysis and synthesis. Findings. Many life cycle options of high-rise multipurpose complexes. Originality. The developed method of formation of organizational and technological solutions adapted to the conditions of the construction of high-rise multipurpose complexes, which provides the opportunity for multi-variant conditions, taking into account regulatory requirements for fire safety, insolation of buildings and premises, protection against noise and vibration, energy efficiency, infrastructure and population density of a residential district with a full range of institutions and enterprises of local significance, within existing resource constraints, to ensure the commissioning of objects with specified technical and economic characteristics. Practical value. The proposed model and the methodology allow to determine a rational variant of high-rise building according to specified criteria and constraints.

  4. Basic mechanisms of color centres production by excitons in activated alkali halides

    International Nuclear Information System (INIS)

    Vale, G.

    1981-01-01

    The paper deals with some peculiarities of colour centers formation which are caused by introduction of the activator in alkali halide crystals. The crystals of KBr and KI activated with Tl + , In + , Sn ++ in concentrations 10 17 -10 18 cm -3 and irradiated with ultraviolet light are studied. Excitation spectra of photostimulated activator luminescence and thermoluminescence were measured. The kinetics of the photostimulated activator luminescence is studied. The conclusion is made that the activator does not affect the primary reaction of exciton decay with F-H pair generation, but only the secondary reactions of colour center production [ru

  5. Organizational-economic model of formation of socio-commercial multifunctional complex in the construction of high-rise buildings

    Science.gov (United States)

    Kirillova, Ariadna; Prytkova, Oksana O.

    2018-03-01

    The article is devoted to the features of the formation of the organizational and economic model of the construction of a socio-commercial multifunctional complex for high-rise construction. Authors have given examples of high-altitude multifunctional complexes in Moscow, analyzed the advantages and disadvantages in the implementation of multifunctional complexes, stressed the need for a holistic strategic approach, allowing to take into account the prospects for the development of the city and the creation of a comfortable living environment. Based on the analysis of multifunctional complexes features, a matrix of SWOT analysis was compiled. For the development of cities and improving the quality of life of the population, it is proposed to implement a new type of multifunctional complexes of a joint social and commercial direction, including, along with the implementation of office areas - schools, polyclinics, various sports facilities and cultural and leisure centers (theatrical, dance, studio, etc.). The approach proposed in the article for developing the model is based on a comparative evaluation of the multifunctional complex project of a social and commercial direction implemented at the expense of public-private partnership in the form of a concession agreement and a commercial multifunctional complex being built at the expense of the investor. It has been proved by calculations that the obtained indicators satisfy the conditions of expediency of the proposed organizational-economic model and the project of the social and commercial multifunctional complex is effective.

  6. Organizational-economic model of formation of socio-commercial multifunctional complex in the construction of high-rise buildings

    Directory of Open Access Journals (Sweden)

    Kirillova Ariadna

    2018-01-01

    Full Text Available The article is devoted to the features of the formation of the organizational and economic model of the construction of a socio-commercial multifunctional complex for high-rise construction. Authors have given examples of high-altitude multifunctional complexes in Moscow, analyzed the advantages and disadvantages in the implementation of multifunctional complexes, stressed the need for a holistic strategic approach, allowing to take into account the prospects for the development of the city and the creation of a comfortable living environment. Based on the analysis of multifunctional complexes features, a matrix of SWOT analysis was compiled. For the development of cities and improving the quality of life of the population, it is proposed to implement a new type of multifunctional complexes of a joint social and commercial direction, including, along with the implementation of office areas - schools, polyclinics, various sports facilities and cultural and leisure centers (theatrical, dance, studio, etc.. The approach proposed in the article for developing the model is based on a comparative evaluation of the multifunctional complex project of a social and commercial direction implemented at the expense of public-private partnership in the form of a concession agreement and a commercial multifunctional complex being built at the expense of the investor. It has been proved by calculations that the obtained indicators satisfy the conditions of expediency of the proposed organizational-economic model and the project of the social and commercial multifunctional complex is effective.

  7. Entropy-driven complex formation of malvidin-3- O-glucoside with common polyphenols in ethanol-water binary solutions

    Science.gov (United States)

    Kunsági-Máté, Sándor; Ortmann, Erika; Kollár, László; Nikfardjam, Martin Pour

    2008-09-01

    The complex formation of malvidin-3- O-glucoside with several polyphenols, the so-called "copigmentation" phenomenon, was studied in aqueous solutions. To simulate the copigmentation process during fermentation, the stability of the formed complexes was examined in dependence of the ethanol content of the aqueous solution. Results indicate that stronger and larger complexes are formed, when the ethanol content exceeds a critical margin of 8 vol.% However, the size of complexes of malvidin/procyanidin and malvidin/epicatechin is drastically reduced above this critical concentration. Fluorescence lifetime and solvent relaxation measurements give insight into the particular processes at molecular level and will help us comprehend the first important steps during winemaking in order to recommend an optimized winemaking technology to ensure extraordinary colour stability in red wines.

  8. [Complex formation between alpha-chymotrypsin and block copolymers based on ethylene and propylene oxide, induced by high pressure].

    Science.gov (United States)

    Topchieva, I N; Sorokina, E M; Kurganov, B I; Zhulin, V M; Makarova, Z G

    1996-06-01

    A new method of formation of non-covalent adducts based on an amphiphilic diblock copolymer of ethylene and propylene oxides with molecular mass of 2 kDa and alpha-chymotrypsin (ChT) under high pressure, has been developed. The composition of the complexes corresponds to seven polymer molecules per one ChT molecule in the pressure range of 1.1 to 400 MPa. The complexes fully retain the catalytic activity. Kinetic constants (Km and kcat) for enzymatic hydrolysis of N-benzoyl-L-tyrosine ethyl ester catalyzed by the complexes are identical with the corresponding values for native ChT. Analysis of kinetics of thermal inactivation of the complexes revealed that the constant of the rate of the slow inactivation step is markedly lower than for ChT.

  9. Thermodynamic Characteristics of Reactions of the Formation of Complexes between Triglycine and Ni2+ Ions in Aqueous Solution

    Science.gov (United States)

    Gorboletova, G. G.; Metlin, A. A.; Bychkova, S. A.

    2018-05-01

    Thermal effects of reactions of the formation of complexes between Ni(II) and triglycine are determined via direct calorimetry in aqueous solutions at 298.15 K and ionic strengths of 0.2, 0.5, and 1.0 (KNO3). Standard thermodynamic characteristics (Δr H°, Δr G°, Δr S°) of complexing processes in the investigated systems are calculated. The structures of triglycinate complexes NiL+, NiH-1L, NiL2, NiH-2L2- 2, NiL- 3, and NiH-3L4- 3 are introduced to compare the obtained values and data on the thermodynamics of triglycinate complexes of Ni(II).

  10. Formation of W(3)A(1) electron-transferring flavoprotein (ETF) hydroquinone in the trimethylamine dehydrogenase x ETF protein complex.

    Science.gov (United States)

    Jang, M H; Scrutton, N S; Hille, R

    2000-04-28

    The electron-transferring flavoprotein (ETF) from Methylophilus methylotrophus (sp. W(3)A(1)) exhibits unusual oxidation-reduction properties and can only be reduced to the level of the semiquinone under most circumstances (including turnover with its physiological reductant, trimethylamine dehydrogenase (TMADH), or reaction with strong reducing reagents such as sodium dithionite). In the present study, we demonstrate that ETF can be reduced fully to its hydroquinone form both enzymatically and chemically when it is in complex with TMADH. Quantitative titration of the TMADH x ETF protein complex with sodium dithionite shows that a total of five electrons are taken up by the system, indicating that full reduction of ETF occurs within the complex. The results indicate that the oxidation-reduction properties of ETF are perturbed upon binding to TMADH, a conclusion further supported by the observation of a spectral change upon formation of the TMADH x ETF complex that is due to a change in the environment of the FAD of ETF. The results are discussed in the context of ETF undergoing a conformational change during formation of the TMADH x ETF electron transfer complex, which modulates the spectral and oxidation-reduction properties of ETF such that full reduction of the protein can take place.

  11. Excitonic and electron-hole mechanisms of the creation of Frenkel defect in alkali halides

    International Nuclear Information System (INIS)

    Lushchik, A.; Kirm, M.; Lushchik, Ch.; Vasil'chenko, E.

    2000-01-01

    Excitonic and electron-hole (e-h) mechanisms of stable F centre creation by VUV radiation in alkali halide crystals are discussed. In KCl at 4.2 K, the efficiency of stable F-H pair creation is especially high at the direct optical formation of triplet excitons with n=1. At 200-400 K, the creation processes of stable F centres in KCl are especially efficient at the formation of one-halide exciton in the Urbach tail of an exciton absorption. In KCl and KBr, the decay of a cation exciton (∼20 eV) causes the formation of two e-h pairs, while in NaCl a cation exciton (33.5 eV) decays into two e-h and an anion exciton. An elastic uniaxial stress of a crystal excited by VUV radiation decreases the mean free path of excitons before their self-trapping (KI) and increases the mean free path of hot holes before self-trapping (NaCl)

  12. In Situ Preparation of Metal Halide Perovskite Nanocrystal Thin Films for Improved Light-Emitting Devices.

    Science.gov (United States)

    Zhao, Lianfeng; Yeh, Yao-Wen; Tran, Nhu L; Wu, Fan; Xiao, Zhengguo; Kerner, Ross A; Lin, YunHui L; Scholes, Gregory D; Yao, Nan; Rand, Barry P

    2017-04-25

    Hybrid organic-inorganic halide perovskite semiconductors are attractive candidates for optoelectronic applications, such as photovoltaics, light-emitting diodes, and lasers. Perovskite nanocrystals are of particular interest, where electrons and holes can be confined spatially, promoting radiative recombination. However, nanocrystalline films based on traditional colloidal nanocrystal synthesis strategies suffer from the use of long insulating ligands, low colloidal nanocrystal concentration, and significant aggregation during film formation. Here, we demonstrate a facile method for preparing perovskite nanocrystal films in situ and that the electroluminescence of light-emitting devices can be enhanced up to 40-fold through this nanocrystal film formation strategy. Briefly, the method involves the use of bulky organoammonium halides as additives to confine crystal growth of perovskites during film formation, achieving CH 3 NH 3 PbI 3 and CH 3 NH 3 PbBr 3 perovskite nanocrystals with an average crystal size of 5.4 ± 0.8 nm and 6.4 ± 1.3 nm, respectively, as confirmed through transmission electron microscopy measurements. Additive-confined perovskite nanocrystals show significantly improved photoluminescence quantum yield and decay lifetime. Finally, we demonstrate highly efficient CH 3 NH 3 PbI 3 red/near-infrared LEDs and CH 3 NH 3 PbBr 3 green LEDs based on this strategy, achieving an external quantum efficiency of 7.9% and 7.0%, respectively, which represent a 40-fold and 23-fold improvement over control devices fabricated without the additives.

  13. The Mechanism of Redox Reaction between Palladium(II Complex Ions and Potassium Formate in Acidic Aqueous Solution

    Directory of Open Access Journals (Sweden)

    Wojnicki M.

    2017-06-01

    Full Text Available The kinetics studies of redox reaction between palladium(II chloride complex ions and potassium formate in acidic aqueous solutions was investigated. It was shown, that the reduction reaction of Pd(II is selective in respect to Pd(II complex structure. The kinetic of the process was monitored spectrophotometrically. The influence of chloride ions concentration, Pd(II initial concentration, reductant concentration, ionic strength as well as the temperature were investigated in respect to the process dynamics. Arrhenius equation parameters were determined and are equal to 65.8 kJ/mol, and A = 1.12×1011 s−1.

  14. Some regularities in formation and solvent extraction of complexes in metal-salicylic acid or its derivative- organic base systems

    International Nuclear Information System (INIS)

    Alimarin, I.P.; Fadeeva, V.I.; Tikhomirova, T.I.

    1982-01-01

    The influence of concentrations of the reagents, pH and solvent on the conditions for the formation and extraction of Sc, Ti, Zr, Hf, Th complexes has been examined in salicylic acid (H 2 Sal)-heterocyclic amine systems. The extraction chemism and factors, which affect the reactions between the metal ions and the ligands, are discussed. It has been shown that Zr, Hf, Ti form species of ion associate type, Sc and Th form different-ligand complexes under conditions for interphase equilibrium in a Me-H 2 Sal-heterocyclic amine system

  15. Predicted formation constants using the unified theory of metal ion complexation

    International Nuclear Information System (INIS)

    Brown, P.L.; Wanner, H.

    1987-01-01

    Formation constants are listed for standard conditions, i.e., 298.15K (25 0 C), 10 5 Pa, and zero ionic strength for a number of species containing selected elements (Am, Cs, Np, Pa, Pb, Pd, Pu, Ra, Sn, Sr, Tc, Th, U) and ligands (hydroxide, fluoride, chloride, bromide, iodide, iodate, sulphate, ammonia, nitrate, hydrogen phosphate, dihydrogen phosphate, carbonate, bicarbonate, oxalate, formate, thiocyanate, acetate, benzoate, catecholate, ethylenediamine, glycinate, glycollate and phenolate) that have been considered important for nuclear technology. 16 refs

  16. Microbial Adhesion and Biofilm Formation on Microfiltration Membranes: A Detailed Characterization Using Model Organisms with Increasing Complexity

    Directory of Open Access Journals (Sweden)

    L. Vanysacker

    2013-01-01

    Full Text Available Since many years, membrane biofouling has been described as the Achilles heel of membrane fouling. In the present study, an ecological assay was performed using model systems with increasing complexity: a monospecies assay using Pseudomonas aeruginosa or Escherichia coli separately, a duospecies assay using both microorganisms, and a multispecies assay using activated sludge with or without spiked P. aeruginosa. The microbial adhesion and biofilm formation were evaluated in terms of bacterial cell densities, species richness, and bacterial community composition on polyvinyldifluoride, polyethylene, and polysulfone membranes. The data show that biofouling formation was strongly influenced by the kind of microorganism, the interactions between the organisms, and the changes in environmental conditions whereas the membrane effect was less important. The findings obtained in this study suggest that more knowledge in species composition and microbial interactions is needed in order to understand the complex biofouling process. This is the first report describing the microbial interactions with a membrane during the biofouling development.

  17. Microbial Adhesion and Biofilm Formation on Microfiltration Membranes: A Detailed Characterization Using Model Organisms with Increasing Complexity

    Science.gov (United States)

    Vanysacker, L.; Denis, C.; Declerck, P.; Piasecka, A.; Vankelecom, I. F. J.

    2013-01-01

    Since many years, membrane biofouling has been described as the Achilles heel of membrane fouling. In the present study, an ecological assay was performed using model systems with increasing complexity: a monospecies assay using Pseudomonas aeruginosa or Escherichia coli separately, a duospecies assay using both microorganisms, and a multispecies assay using activated sludge with or without spiked P. aeruginosa. The microbial adhesion and biofilm formation were evaluated in terms of bacterial cell densities, species richness, and bacterial community composition on polyvinyldifluoride, polyethylene, and polysulfone membranes. The data show that biofouling formation was strongly influenced by the kind of microorganism, the interactions between the organisms, and the changes in environmental conditions whereas the membrane effect was less important. The findings obtained in this study suggest that more knowledge in species composition and microbial interactions is needed in order to understand the complex biofouling process. This is the first report describing the microbial interactions with a membrane during the biofouling development. PMID:23986906

  18. Co-adsorption of NH3 and SO2 on quartz : Formation of a stabilized complex

    NARCIS (Netherlands)

    Grecea, M.L.; Gleeson, M.A.; van Schaik, W.; Kleyn, A.W.; Bijkerk, Frederik

    2011-01-01

    We have investigated the co-adsorption of NH3 and SO2 on the quartz(0 0 0 1) surface by TPD and RAIRS. A surface complex is formed as a result of various relative exposures of NH3 and SO2, irrespective of dosage order. However, the relative molecular composition of the complex is dependent on the

  19. Formation of inclusion complexes between high amylose starch and octadecyl ferulate via steam jet cooking

    Science.gov (United States)

    Amylose can form inclusion complexes with guest molecules and represents an interesting approach to deliver bioactive molecules. However, ferulic acid has been shown not to form single helical inclusion complexes with amylose. To overcome this problem a ferulic acid ester, octadecyl ferulate, posses...

  20. Complex Formation by the mrpABCDEFG Gene Products, Which Constitute a Principal Na+/H+ Antiporter in Bacillus subtilis▿

    OpenAIRE

    Kajiyama, Yusuke; Otagiri, Masato; Sekiguchi, Junichi; Kosono, Saori; Kudo, Toshiaki

    2007-01-01

    The Bacillus subtilis Mrp (also referred to as Sha) is a particularly unusual Na+/H+ antiporter encoded by mrpABCDEFG. Using His tagging of Mrp proteins, we showed complex formation by the mrpABCDEFG gene products by pull-down and blue native polyacrylamide gel electrophoresis analyses. This is the first molecular evidence that the Mrp is a multicomponent antiporter in the cation-proton antiporter 3 family.

  1. X-ray crystallography, electrochemistry, spectral and thermal analysis of some tetradentate schiff base complexes and formation constant measurements

    Czech Academy of Sciences Publication Activity Database

    Asadi, Z.; Savarypour, N.; Dušek, Michal; Eigner, Václav

    2017-01-01

    Roč. 47, č. 11 (2017), s. 1501-1508 ISSN 2470-1556 R&D Projects: GA ČR(CZ) GA15-12653S Institutional support: RVO:68378271 Keywords : X-ray crystallography * transition metal Schiff base complexes * thermogravimetry * electrochemistry * formation constant measurements Subject RIV: BM - Solid Matter Physics ; Magnetism OBOR OECD: Condensed matter physics (including formerly solid state physics, supercond.)

  2. Thermal decomposition of rhenium (5) complexes with 1,2,4-triazole. Termicheskoe razlozhenie kompleksov reniya (5) s 1,2,4-triazolom

    Energy Technology Data Exchange (ETDEWEB)

    Amindzhanov, A A; Gagieva, S Ch; Kotegov, K V [Tadzhikskij Gosudarstvennyj Univ., Dushanbe (Tajikistan)

    1991-01-01

    Processes of thermal decomposition of rhenium (5) complexes with 1,2,4-triazole were studied. Thermolysis products were identified on the basis of data of the element analysis, IR spectra, conductometry and other methods. It is ascertained that at the first stage of thermolysis of hydroxyl-containing monomer complexes removal of water molecules occurs, and at the second one - dimerization process with formation of Re-O-Re group. It is shown that the nature of halide ion practically does not affect the temperature of the start of intensive thermal decomposition of the complexes.

  3. Shatter Complex Formation in the Twin Craters Lava Flow, Zuni-Bandera Field, New Mexico

    Science.gov (United States)

    von Meerscheidt, H. C.; Bleacher, J. E.; Brand, B. D.; deWet, A.; Samuels, R.; Hamilton, C.; Garry, W. B.; Bandfield, J. L.

    2013-12-01

    . Prominent ';a';a channels travel around the bluff, leaving a 'wake' of uncovered ground on the downstream side. We interpret this shatter area to have been a branching tube network within an active sheet. The limestone bluff acted as an obstacle that caused a backup of lava within the tubes, driving episodes of shattering. The mounds likely represent earlier solidified sections between active, possibly braided, tube branches, which remained as mounds within the shatter area after the adjacent crust subsided. When lava broke out from the pressurized sheet-like lobe, it formed the ';a';a channels. This section of the flow field is interpreted using inferences from shatter ring formation, but is perhaps better termed a shatter sheet or shatter complex. This study has implications for understanding lava flow dynamics at constriction points, as well as the evolution and morphology of shatter rings.

  4. Oxo-group-14-element bond formation in binuclear uranium(V) pacman complexes

    International Nuclear Information System (INIS)

    Jones, Guy M.; Arnold, Polly L.; Love, Jason B.

    2013-01-01

    Simple and versatile routes to the functionalization of uranyl-derived U"V-oxo groups are presented. The oxo-lithiated, binuclear uranium(V)-oxo complexes [{(py)_3LiOUO}_2(L)] and [{(py)_3LiOUO}(OUOSiMe_3)(L)] were prepared by the direct combination of the uranyl(VI) silylamide ''ate'' complex [Li(py)_2][(OUO)(N'')_3](N''=N(SiMe_3)_2) with the polypyrrolic macrocycle H_4L or the mononuclear uranyl (VI) Pacman complex [UO_2(py)(H_2L)], respectively. These oxo-metalated complexes display distinct U-O single and multiple bonding patterns and an axial/equatorial arrangement of oxo ligands. Their ready availability allows the direct functionalization of the uranyl oxo group leading to the binuclear uranium(V) oxo-stannylated complexes [{(R_3Sn)OUO}_2(L)] (R=nBu, Ph), which represent rare examples of mixed uranium/tin complexes. Also, uranium-oxo-group exchange occurred in reactions with [TiCl(OiPr)_3] to form U-O-C bonds [{(py)_3LiOUO}(OUOiPr)(L)] and [(iPrOUO)_2(L)]. Overall, these represent the first family of uranium(V) complexes that are oxo-functionalised by Group 14 elements. (Copyright copyright 2013 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  5. Formation of inclusion complexes between high amylose starch and octadecyl ferulate via steam jet cooking.

    Science.gov (United States)

    Kenar, James A; Compton, David L; Little, Jeanette A; Peterson, Steve C

    2016-04-20

    Amylose-ligand inclusion complexes represent an interesting approach to deliver bioactive molecules. However, ferulic acid has been shown not to form single helical inclusion complexes with amylose from high amylose maize starch. To overcome this problem a lipophilic ferulic acid ester, octadecyl ferulate, was prepared and complexed with amylose via excess steam jet cooking. Jet-cooking octadecyl ferulate and high amylose starch gave an amylose-octadecyl ferulate inclusion complex in 51.0% isolated yield. X-ray diffraction (XRD) and differential scanning calorimetry (DSC) confirmed that a 61 V-type inclusion complex was formed. Amylose and extraction assays showed the complex to be enriched in amylose (91.9±4.3%) and contain 70.6±5.6mgg(-1) octadecyl ferulate, although, minor hydrolysis (∼4%) of the octadecyl ferulate was observed under the excess steam jet-cooking conditions utilized. This study demonstrates that steam jet cooking is a rapid and scalable process in which to prepare amylose-octadecyl ferulate inclusion complexes. Published by Elsevier Ltd.

  6. In vitro complex formation and inhibition of hepatic cytochrome P450 activity by different macrolides and tiamulin in goats and cattle

    NARCIS (Netherlands)

    Zweers-Zeilmaker, W.M.; Miert, A.S.J.P.A.M. van; Horbach, G.J.; Witkamp, R.F.

    1998-01-01

    In humans, clinically relevant drug–drug interactions occur with some macrolide antibiotics via the formation of stable metabolic intermediate (MI) complexes with enzymes of the cytochrome P4503A (CYP3A) subfamily. The formation of such complexes can result in a decreased biotransformation rate of

  7. Hydrogen exchange kinetics changes upon formation of the soybean trypsin inhibitor: trypsin complex

    International Nuclear Information System (INIS)

    Woodward, C.K.; Ellis, L.M.

    1975-01-01

    The hydrogen exchange kinetics of the complex of trypsin--soybean trypsin inhibitor (Kunitz) have been compared to the calculated sum of the exchange kinetics for the inhibitor and trypsin measured separately. The exchange rates observed for the complex are substantially less than the sum of the exchange rates in the two individual proteins. These results cannot be accounted for by changes in intermolecular or intramolecular hydrogen bonding. The decrease in exchange rates in the complex are ascribed to changes in solvent accessibility in the component proteins. (U.S.)

  8. Nitrosothiol formation and protection against Fenton chemistry by nitric oxide-induced dinitrosyliron complex formation from anoxia-initiated cellular chelatable iron increase.

    Science.gov (United States)

    Li, Qian; Li, Chuanyu; Mahtani, Harry K; Du, Jian; Patel, Aashka R; Lancaster, Jack R

    2014-07-18

    Dinitrosyliron complexes (DNIC) have been found in a variety of pathological settings associated with (•)NO. However, the iron source of cellular DNIC is unknown. Previous studies on this question using prolonged (•)NO exposure could be misleading due to the movement of intracellular iron among different sources. We here report that brief (•)NO exposure results in only barely detectable DNIC, but levels increase dramatically after 1-2 h of anoxia. This increase is similar quantitatively and temporally with increases in the chelatable iron, and brief (•)NO treatment prevents detection of this anoxia-induced increased chelatable iron by deferoxamine. DNIC formation is so rapid that it is limited by the availability of (•)NO and chelatable iron. We utilize this ability to selectively manipulate cellular chelatable iron levels and provide evidence for two cellular functions of endogenous DNIC formation, protection against anoxia-induced reactive oxygen chemistry from the Fenton reaction and formation by transnitrosation of protein nitrosothiols (RSNO). The levels of RSNO under these high chelatable iron levels are comparable with DNIC levels and suggest that under these conditions, both DNIC and RSNO are the most abundant cellular adducts of (•)NO. © 2014 by The American Society for Biochemistry and Molecular Biology, Inc.

  9. Nitrosothiol Formation and Protection against Fenton Chemistry by Nitric Oxide-induced Dinitrosyliron Complex Formation from Anoxia-initiated Cellular Chelatable Iron Increase*

    Science.gov (United States)

    Li, Qian; Li, Chuanyu; Mahtani, Harry K.; Du, Jian; Patel, Aashka R.; Lancaster, Jack R.

    2014-01-01

    Dinitrosyliron complexes (DNIC) have been found in a variety of pathological settings associated with •NO. However, the iron source of cellular DNIC is unknown. Previous studies on this question using prolonged •NO exposure could be misleading due to the movement of intracellular iron among different sources. We here report that brief •NO exposure results in only barely detectable DNIC, but levels increase dramatically after 1–2 h of anoxia. This increase is similar quantitatively and temporally with increases in the chelatable iron, and brief •NO treatment prevents detection of this anoxia-induced increased chelatable iron by deferoxamine. DNIC formation is so rapid that it is limited by the availability of •NO and chelatable iron. We utilize this ability to selectively manipulate cellular chelatable iron levels and provide evidence for two cellular functions of endogenous DNIC formation, protection against anoxia-induced reactive oxygen chemistry from the Fenton reaction and formation by transnitrosation of protein nitrosothiols (RSNO). The levels of RSNO under these high chelatable iron levels are comparable with DNIC levels and suggest that under these conditions, both DNIC and RSNO are the most abundant cellular adducts of •NO. PMID:24891512

  10. Interaction of phosphorus dendrimers with HIV peptides—Fluorescence studies of nano-complexes formation

    Energy Technology Data Exchange (ETDEWEB)

    Ciepluch, Karol, E-mail: ciepluch@biol.uni.lodz.pl [Department of General Biophysics, Faculty of Biology and Environmental Protection, University of Lodz, Pomorska Street 141/143, 90-236 Lodz (Poland); Ionov, Maksim [Department of General Biophysics, Faculty of Biology and Environmental Protection, University of Lodz, Pomorska Street 141/143, 90-236 Lodz (Poland); Majoral, Jean-Pierre [Laboratoire de Chimie de Coordination du CNRS (LCC), 205 Route de Narbonne, F-31077 Toulouse cedex 4 (France); Muñoz-Fernández, Maria Angeles [Laboratorio InmunoBiología Molecular, Hospital General Universitario Gregorio Marañón, Madrid (Spain); Bryszewska, Maria [Department of General Biophysics, Faculty of Biology and Environmental Protection, University of Lodz, Pomorska Street 141/143, 90-236 Lodz (Poland)

    2014-04-15

    In this study, dendrimers emerge as an alternative approach for delivery of HIV peptides to dendritic cells. Gp160, NH-EIDNYTNTIYTLLEE-COOH; P24, NH-DTINEEAAEW-COOH and Nef, NHGMDDPEREVLEWRFDSRLAF-COOH peptides were complexed with two types of positively charged phosphorus-containing dendrimers (CPD). Fluorescence polarization, dynamic light scattering, transmission and electron microscopy (TEM) techniques were chosen to evaluate the dendriplexes stability. We were able to show that complexes were stable in time and temperature. This is crucial for using these peptide/dendrimer nano-complexes in a new vaccine against HIV-1 infection. -- Highlights: • The phosphorus dendrimers as nanocarriers of HIV-peptides are proposed. • The complexes of dendrimers and HIV-peptides were stable in time, temperature. • The results convince that phosphorus dendrimers could be consider as anti-HIV vaccine candidates.

  11. Interaction of phosphorus dendrimers with HIV peptides—Fluorescence studies of nano-complexes formation

    International Nuclear Information System (INIS)

    Ciepluch, Karol; Ionov, Maksim; Majoral, Jean-Pierre; Muñoz-Fernández, Maria Angeles; Bryszewska, Maria

    2014-01-01

    In this study, dendrimers emerge as an alternative approach for delivery of HIV peptides to dendritic cells. Gp160, NH-EIDNYTNTIYTLLEE-COOH; P24, NH-DTINEEAAEW-COOH and Nef, NHGMDDPEREVLEWRFDSRLAF-COOH peptides were complexed with two types of positively charged phosphorus-containing dendrimers (CPD). Fluorescence polarization, dynamic light scattering, transmission and electron microscopy (TEM) techniques were chosen to evaluate the dendriplexes stability. We were able to show that complexes were stable in time and temperature. This is crucial for using these peptide/dendrimer nano-complexes in a new vaccine against HIV-1 infection. -- Highlights: • The phosphorus dendrimers as nanocarriers of HIV-peptides are proposed. • The complexes of dendrimers and HIV-peptides were stable in time, temperature. • The results convince that phosphorus dendrimers could be consider as anti-HIV vaccine candidates

  12. THE ROLE OF EDUCATIONAL COMPLEXES IN THE IMPLEMENTATION OF THE PARTNERSHIP MODEL FORMATION OF THE NATIONAL QUALIFICATIONS FRAMEWORK

    Directory of Open Access Journals (Sweden)

    Kristina V. Gileva

    2015-01-01

    Full Text Available The aim of the study is to define potential of modern educational complexes in the field of formation of national system of qualifications on the basis of interpretation of procedures changes in regulation of social and labour relations. Methods. The methods involve analysis, generalisation, ordering and a technique of modelling of processes.Results. The authors describe key positions of the theory of the continuous education that provides rapprochement of requirements of employers with quality of vocational training and the content of educational process in the branch educational institutions. The possible contribution of educational complexes to creation of national system of qualifications and professional standards is considered. In this connection various forms of partnership of the given complexes with public authorities, public structures, and also employers are described.Scientific novelty. The concept of business competence characterising ability of system of vocational training is offered to satisfy the requirement of a labour market by means of active integration of educational, innovative and labour processes.Practical significance. The presented model of interaction of educational complexes and subjects of a labour market can be realised by working out of professional standards, creation of the expert centers and the innovative platforms intended to realisation of advisory activity on the basis of high schools; and also organizational-methodical support of processes of professional certification system formation. According to authors, this model will help to co-ordinate the content of professional and Federal State Educational Standards (FSES. 

  13. Formation of poly(ethylene glycol) inclusion complexes in aqueous solutions of mixed cyclodextrins

    Czech Academy of Sciences Publication Activity Database

    Horský, Jiří; Walterová, Zuzana

    2003-01-01

    Roč. 203, - (2003), s. 259-264 ISSN 1022-1360. [International Conference on Polymer-Solvent Complexes and Intercalates /4./. Prague, 22.07.2002-25.07.2002] R&D Projects: GA AV ČR IAA1050101 Institutional research plan: CEZ:AV0Z4050913 Keywords : cyclodextrins * inclusion complexes * phase separation Subject RIV: BO - Biophysics Impact factor: 0.895, year: 2003

  14. In vitro formation of metabolic-intermediate cytochrome P450 complexes in rabbit liver microsomes by tiamulin and various macrolides.

    Science.gov (United States)

    Carletti, Monica; Gusson, Federica; Zaghini, Anna; Dacasto, Mauro; Marvasi, Luigi; Nebbia, Carlo

    2003-01-01

    Tiamulin and a number of macrolides were evaluated as to their ability in forming metabolic-intermediate (MI) complexes with cytochrome P450 in liver microsomes from rabbits bred for meat production. Complex formation, which occurred only in preparations where the expression of P450 3A was increased as the result of rifampicin pre-treatment and with different kinetics, was in the order tiamulin > erythromycin > TAO approximately roxithromycin approximately tylosin and did not take place with tilmicosin and spiramycin. Most of the tested compounds underwent an oxidative N-dealkylation and a good relationship could be found between the rate of N-dealkylase activity in induced preparations and the aptitude in generating MI complexes. Although the results from in vitro studies should be interpreted with caution, it is suggested that the potential for in vivo drug interactions also exists in the rabbit for tiamulin and for four out of the six tested macrolides.

  15. Complex formation of blueberry (Vaccinium angustifolium) anthocyanins during freeze-drying and its influence on their biological activity.

    Science.gov (United States)

    Correa-Betanzo, Julieta; Padmanabhan, Priya; Corredig, Milena; Subramanian, Jayasankar; Paliyath, Gopinadhan

    2015-03-25

    Biological activity of polyphenols is influenced by their uptake and is highly influenced by their interactions with the food matrix. This study evaluated the complex formation of blueberry polyphenols with fruit matrixes such as pectin and cellulose and their effect on the biological and antiproliferative properties of human colon cell lines HT-29 and CRL 1790. Free or complexed polyphenols were isolated by dialyzing aqueous or methanolic blueberry homogenates. Seven phenolic compounds and thirteen anthocyanins were identified in blueberry extracts. Blueberry extracts showed varying degrees of antioxidant and antiproliferative activities, as well as α-glucosidase activity. Fruit matrix containing cellulose and pectin, or purified polygalacturonic acid and cellulose, did not retain polyphenols and showed very low antioxidant or antiproliferative activities. These findings suggest that interactions between polyphenols and the food matrix may be more complex than a simple association and may play an important role in the bioefficacy of blueberry polyphenols.

  16. An Efficient Synthesis of Substituted Furans by Cupric Halide-Mediated Intramolecular Halocyclization of 2-(1-Alkynyl)-2-alken-1-ones

    International Nuclear Information System (INIS)

    Fu, Weijun; Guo, Wenbo; Zhu, Mei; Xu, Chen; Xu, Fengjuan

    2013-01-01

    An efficient synthesis of 3-halofurans by the intramolecular cyclization of 2-(1-alkynyl)-2-alken-1-ones with cupric halide has been developed. A broad range of 3-chloro- and 3-bromofuran derivatives could be obtained in the present method in moderate to good yields. The 3-halofuran derivatives are potential synthetic intermediates for amplification of molecular complexity

  17. Junction Propagation in Organometal Halide Perovskite-Polymer Composite Thin Films.

    Science.gov (United States)

    Shan, Xin; Li, Junqiang; Chen, Mingming; Geske, Thomas; Bade, Sri Ganesh R; Yu, Zhibin

    2017-06-01

    With the emergence of organometal halide perovskite semiconductors, it has been discovered that a p-i-n junction can be formed in situ due to the migration of ionic species in the perovskite when a bias is applied. In this work, we investigated the junction formation dynamics in methylammonium lead tribromide (MAPbBr 3 )/polymer composite thin films. It was concluded that the p- and n- doped regions propagated into the intrinsic region with an increasing bias, leading to a reduced intrinsic perovskite layer thickness and the formation of an effective light-emitting junction regardless of perovskite layer thicknesses (300 nm to 30 μm). The junction propagation also played a major role in deteriorating the LED operation lifetime. Stable perovskite LEDs can be achieved by restricting the junction propagation after its formation.

  18. High Defect Tolerance in Lead Halide Perovskite CsPbBr3.

    Science.gov (United States)

    Kang, Jun; Wang, Lin-Wang

    2017-01-19

    The formation energies and charge-transition levels of intrinsic point defects in lead halide perovskite CsPbBr 3 are studied from first-principles calculations. It is shown that the formation energy of dominant defect under Br-rich growth condition is much lower than that under moderate or Br-poor conditions. Thus avoiding the Br-rich condition can help to reduce the defect concentration. Interestingly, CsPbBr 3 is found to be highly defect-tolerant in terms of its electronic structure. Most of the intrinsic defects induce shallow transition levels. Only a few defects with high formation energies can create deep transition levels. Therefore, CsPbBr 3 can maintain its good electronic quality despite the presence of defects. Such defect tolerance feature can be attributed to the lacking of bonding-antibonding interaction between the conduction bands and valence bands.

  19. In vitro formation of the Merkel cell-neurite complex in embryonic mouse whiskers using organotypic co-cultures.

    Science.gov (United States)

    Ishida, Kentaro; Saito, Tetsuichiro; Mitsui, Toshiyuki

    2018-06-01

    A Merkel cell-neurite complex is a touch receptor composed of specialized epithelial cells named Merkel cells and peripheral sensory nerves in the skin. Merkel cells are found in touch-sensitive skin components including whisker follicles. The nerve fibers that innervate Merkel cells of a whisker follicle extend from the maxillary branch of the trigeminal ganglion. Whiskers as a sensory organ attribute to the complicated architecture of the Merkel cell-neurite complex, and therefore it is intriguing how the structure is formed. However, observing the dynamic process of the formation of a Merkel cell-neurite complex in whiskers during embryonic development is still difficult. In this study, we tried to develop an organotypic co-culture method of a whisker pad and a trigeminal ganglion explant to form the Merkel cell-neurite complex in vitro. We initially developed two distinct culture methods of a single whisker row and a trigeminal ganglion explant, and then combined them. By dissecting and cultivating a single row from a whisker pad, the morphogenesis of whisker follicles could be observed under a microscope. After the co-cultivation of the whisker row with a trigeminal ganglion explant, a Merkel cell-neurite complex composed of Merkel cells, which were positive for both cytokeratin 8 and SOX2, Neurofilament-H-positive trigeminal nerve fibers and Schwann cells expressing Nestin, SOX2 and SOX10 was observed via immunohistochemical analyses. These results suggest that the process for the formation of a Merkel cell-neurite complex can be observed under a microscope using our organotypic co-culture method. © 2018 Japanese Society of Developmental Biologists.

  20. Professional Motivation Formation of Future Specialists under the Conditions of Regional Educational Complex

    Science.gov (United States)

    Kargina, Elena Mikhaylovna

    2015-01-01

    Motivation plays the leading role in the organization of the personality structure. It is a driving force of the activity. Motivation accounts for the behavior and activity and has a great impact on professional self-determination and person's satisfaction with the work. The problem of professional motivation formation of a future specialist is…

  1. A First Step Towards Synthesising Rubrics and Video for the Formative Assessment of Complex Skills

    NARCIS (Netherlands)

    Ackermans, Kevin; Rusman, Ellen; Brand-Gruwel, Saskia; Specht, Marcus

    2016-01-01

    Abstract. The performance objectives used for the formative assessment of com- plex skills are generally set through text-based analytic rubrics[1]. Moreover, video modeling examples are a widely applied method of observational learning, providing students with context-rich modeling examples of

  2. Complex formation in mixtures of lysozyme-stabilized emulsions and human saliva

    NARCIS (Netherlands)

    Silletti, E.; Vingerhoeds, M.H.; Norde, W.; Aken, van G.A.

    2007-01-01

    In this paper, we studied the interaction between human unstimulated saliva and lysozyme-stabilized oil-in-water emulsions (10 wt/wt% oil phase, 10 mM NaCl, pH 6.7), to reveal the driving force for flocculation of these emulsions. Confocal scanning laser microscopy (CSLM) showed formation of

  3. Oxo-group-14-element bond formation in binuclear uranium(V) pacman complexes

    Energy Technology Data Exchange (ETDEWEB)

    Jones, Guy M.; Arnold, Polly L.; Love, Jason B. [EaStCHEM School of Chemistry, University of Edinburgh (United Kingdom)

    2013-07-29

    Simple and versatile routes to the functionalization of uranyl-derived U{sup V}-oxo groups are presented. The oxo-lithiated, binuclear uranium(V)-oxo complexes [{(py)_3LiOUO}{sub 2}(L)] and [{(py)_3LiOUO}(OUOSiMe{sub 3})(L)] were prepared by the direct combination of the uranyl(VI) silylamide ''ate'' complex [Li(py){sub 2}][(OUO)(N''){sub 3}](N''=N(SiMe{sub 3}){sub 2}) with the polypyrrolic macrocycle H{sub 4}L or the mononuclear uranyl (VI) Pacman complex [UO{sub 2}(py)(H{sub 2}L)], respectively. These oxo-metalated complexes display distinct U-O single and multiple bonding patterns and an axial/equatorial arrangement of oxo ligands. Their ready availability allows the direct functionalization of the uranyl oxo group leading to the binuclear uranium(V) oxo-stannylated complexes [{(R_3Sn)OUO}{sub 2}(L)] (R=nBu, Ph), which represent rare examples of mixed uranium/tin complexes. Also, uranium-oxo-group exchange occurred in reactions with [TiCl(OiPr){sub 3}] to form U-O-C bonds [{(py)_3LiOUO}(OUOiPr)(L)] and [(iPrOUO){sub 2}(L)]. Overall, these represent the first family of uranium(V) complexes that are oxo-functionalised by Group 14 elements. (Copyright copyright 2013 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  4. Excitonic Effects in Methylammonium Lead Halide Perovskites

    Energy Technology Data Exchange (ETDEWEB)

    Beard, Matthew C [National Renewable Energy Laboratory (NREL), Golden, CO (United States); Chen, Xihan [National Renewable Energy Laboratory (NREL), Golden, CO (United States); Lu, Haipeng [National Renewable Energy Laboratory (NREL), Golden, CO (United States); Yang, Ye [National Renewable Energy Laboratory (NREL), Golden, CO (United States)

    2018-05-01

    The exciton binding energy in methylammonium lead iodide (MAPbI3) is about 10 meV, around 1/3 of the available thermal energy (kBT ~ 26 meV) at room temperature. Thus, exciton populations are not stable at room temperature at moderate photoexcited carrier densities. However, excitonic resonances dominate the absorption onset. Furthermore, these resonances determine the transient absorbance and transient reflectance spectra. The exciton binding energy is a reflection of the Coulomb interaction energy between photoexcited electrons and holes. As such, it serves as a marker for the strength of electron/hole interactions and impacts a variety of phenomena, such as, absorption, radiative recombination, and Auger recombination. In this Perspective, we discuss the role of excitons and excitonic resonances in the optical properties of lead-halide perovskite semiconductors. Finally, we discuss how the strong light-matter interactions induce an optical stark effect splitting the doubly spin degenerate ground exciton states and are easily observed at room temperature.

  5. Structured alkali halides for medical applications

    International Nuclear Information System (INIS)

    Schmitt, B.; Fuchs, M.; Hell, E.; Knuepfer, W.; Hackenschmied, P.; Winnacker, A.

    2002-01-01

    Image plates based on storage phosphors are a major application of radiation defects in insulators. Storage phosphors absorb X-ray quanta creating trapped electron-hole pairs in the material. Optical stimulation of the electron causes recombination leading to light emission. Application of image plates requires an optimal compromise between resolution (represented by the modulation transfer function (MTF)) and sensitivity. In our paper we present a new solution of the problem of combining a high MTF with a high sensitivity by structuring the image plates in form of thin needles acting as light guides. This suppresses the lateral spread of light which is detrimental to resolution. As doped CsBr, e.g. CsBr:Ga [Physica Medica XV (1999) 301], can pose a good storage phosphor evaporated layers are of interest in computed radiography. Needle structured CsI:Tl is used as scintillator in direct radiography [IEEE Trans. Nucl. Sci. 45 (3) (1998)]. CsBr layers have been produced by evaporation in vacuum and in inert gas atmosphere varying pressure and temperature. The resulting structures are of fibrous or columnar nature being in good agreement with the zone model of Thornton [Ann. Rev. Mater. Sci. 7 (1977) 239]. A zone model for CsBr has been developed. Measurements on doped alkali halide image plates having needle structure show good MTF at high sensitivity making a significant progress in image plate technology

  6. Regulation of Botulinum Neurotoxin Synthesis and Toxin Complex Formation by Arginine and Glucose in Clostridium botulinum ATCC 3502.

    Science.gov (United States)

    Fredrick, Chase M; Lin, Guangyun; Johnson, Eric A

    2017-07-01

    Botulinum neurotoxin (BoNT), produced by neurotoxigenic clostridia, is the most potent biological toxin known and the causative agent of the paralytic disease botulism. The nutritional, environmental, and genetic regulation of BoNT synthesis, activation, stability, and toxin complex (TC) formation is not well studied. Previous studies indicated that growth and BoNT formation were affected by arginine and glucose in Clostridium botulinum types A and B. In the present study, C. botulinum ATCC 3502 was grown in toxin production medium (TPM) with different levels of arginine and glucose and of three products of arginine metabolism, citrulline, proline, and ornithine. Cultures were analyzed for growth (optical density at 600 nm [OD 600 ]), spore formation, and BoNT and TC formation by Western blotting and immunoprecipitation and for BoNT activity by mouse bioassay. A high level of arginine (20 g/liter) repressed BoNT production approximately 1,000-fold, enhanced growth, slowed lysis, and reduced endospore production by greater than 1,000-fold. Similar effects on toxin production were seen with equivalent levels of citrulline but not ornithine or proline. In TPM lacking glucose, levels of formation of BoNT/A1 and TC were significantly decreased, and extracellular BoNT and TC proteins were partially inactivated after the first day of culture. An understanding of the regulation of C. botulinum growth and BoNT and TC formation should be valuable in defining requirements for BoNT formation in foods and clinical samples, improving the quality of BoNT for pharmaceutical preparations, and elucidating the biological functions of BoNTs for the bacterium. IMPORTANCE Botulinum neurotoxin (BoNT) is a major food safety and bioterrorism concern and is also an important pharmaceutical, and yet the regulation of its synthesis, activation, and stability in culture media, foods, and clinical samples is not well understood. This paper provides insights into the effects of critical

  7. Roles of mono-ubiquitinated Smad4 in the formation of Smad transcriptional complexes

    International Nuclear Information System (INIS)

    Wang Bei; Suzuki, Hiroyuki; Kato, Mitsuyasu

    2008-01-01

    TGF-β activates receptor-regulated Smad (R-Smad) through phosphorylation by type I receptors. Activated R-Smad binds to Smad4 and the complex translocates into the nucleus and stimulates the transcription of target genes through association with co-activators including p300. It is not clear, however, how activated Smad complexes are removed from target genes. In this study, we show that TGF-β enhances the mono-ubiquitination of Smad4. Smad4 mono-ubiquitination was promoted by p300 and suppressed by the c-Ski co-repressor. Smad4 mono-ubiquitination disrupted the interaction with Smad2 in the presence of constitutively active TGF-β type I receptor. Furthermore, mono-ubiquitinated Smad4 was not found in DNA-binding Smad complexes. A Smad4-Ubiquitin fusion protein, which mimics mono-ubiquitinated Smad4, enhanced localization to the cytoplasm. These results suggest that mono-ubiquitination of Smad4 occurs in the transcriptional activator complex and facilitates the turnover of Smad complexes at target genes

  8. Formation of stable and functional HIV-1 nucleoprotein complexes in vitro.

    Science.gov (United States)

    Tanchou, V; Gabus, C; Rogemond, V; Darlix, J L

    1995-10-06

    HIV genomic RNA resides within the nucleocapsid, in the interior of the virus, which serves to protect the RNA against nuclease degradation and to promote its reverse transcription. To investigate the role of nucleocapsid protein (NCp7) in the stability and replication of genomic RNA within the nucleocapsid, we used NCp7, reverse transcriptase (RT) and RNAs representing the 5' and 3' regions of the genome to reconstitute functional HIV-1 nucleocapsids. The nucleoprotein complexes generated in vitro were found to be stable, which, according to biochemical and genetic data, probably results from the tight binding of NCp7 molecules to the RNA and strong NCp7/NCp7 interactions. The nucleoprotein complexes efficiently protected viral RNA against RNase degradation and, at the same time, promoted viral DNA synthesis by RT. DNA strand transfer from the 5' to the 3' RNA template was very efficient in nucleoprotein complexes formed in the presence of both RNAs, but not when the RNAs were in separate complexes. These results indicate that the in vitro reconstituted HIV-1 nucleoprotein complexes function like virion nucleocapsids and thus provide a way to study at the molecular level this viral substructure and the synthesis of proviral DNA, and to search for new anti-HIV agents.

  9. Solar cells, structures including organometallic halide perovskite monocrystalline films, and methods of preparation thereof

    KAUST Repository

    Bakr, Osman; Peng, Wei; Wang, Lingfei

    2017-01-01

    Embodiments of the present disclosure provide for solar cells including an organometallic halide perovskite monocrystalline film (see fig. 1.1B), other devices including the organometallic halide perovskite monocrystalline film, methods of making

  10. Trivalent metallocene chemistry of some uranium, titanium, and zirconium complexes

    International Nuclear Information System (INIS)

    Lukens, W.W. Jr.

    1995-05-01

    Dicyclopentadienyluranium halide dimers have been prepared and their solution behavior examined. These molecules exist as dimers in solution, and the halide ligands undergo rapid site exchange on the NMR timescale above 50 C. Analogous dicyclopentadienyluranium hydroxide dimers have also been prepared; they oxidatively eliminate hydrogen to give the corresponding oxide dimers. Mechanism of this reaction is consistent with αmigration of one of the hydroxide hydrogen atoms to a uranium center followed by elimination of hydrogen. Ground state of [(Me 3 Si) 2 C 5 H 3 ] 3 M M = Nd, U and their base adducts has been examined by variable temperature magnetic susceptibility and EPR spectroscopy. The ground state is found to be 4 I 9/2 with a crystal field state consisting largely of J z = 1/2 lowest, in agreement with previous studies on tris-cyclopentadienylneodymium complexes. The zirconium metallocene Cp 3 Zr has been prepared, characterized crystallographically, and its reactivity studied. Its chemical behavior is controlled by presence of an electron in the non-bonding, d z 2 orbital which prevents formation of base adducts Of Cp 3 Zr, but allows Cp 3 Zr to abstract atoms from other molecules. Electonic and EPR spectra of Cp* 2 TiX complexes, where Cp* is Me 5 C 5 and X is a monodentate, anionic ligand such as halide, have been studied. A π-bonding spectrochemical series is developed, and trends in π-bonding ability are found similar to those in other inorganic complexes. The β-agostic interactions in Cp* 2 TiN(Me)Ph have been examined using variable temperature EPR spectroscopy, and the enthalpy/entropy of the interaction determined. In Cp* 2 TiEt, enthalpy of the β-agostic interaction is -1.9 kcal/mol. The titanocene anion, Cp* 2 TiLi(TMEDA) (TMEDA is N,N,N',N'-tetramethylethylenediamine), has been prepared and its structure determined

  11. Directed formation of micro- and nanoscale patterns of functional light-harvesting LH2 complexes.

    Science.gov (United States)

    Reynolds, Nicholas P; Janusz, Stefan; Escalante-Marun, Maryana; Timney, John; Ducker, Robert E; Olsen, John D; Otto, Cees; Subramaniam, Vinod; Leggett, Graham J; Hunter, C Neil

    2007-11-28

    The precision placement of the desired protein components on a suitable substrate is an essential prelude to any hybrid "biochip" device, but a second and equally important condition must also be met: the retention of full biological activity. Here we demonstrate the selective binding of an optically active membrane protein, the light-harvesting LH2 complex from Rhodobacter sphaeroides, to patterned self-assembled monolayers at the micron scale and the fabrication of nanometer-scale patterns of these molecules using near-field photolithographic methods. In contrast to plasma proteins, which are reversibly adsorbed on many surfaces, the LH2 complex is readily patterned simply by spatial control of surface polarity. Near-field photolithography has yielded rows of light-harvesting complexes only 98 nm wide. Retention of the native optical properties of patterned LH2 molecules was demonstrated using in situ fluorescence emission spectroscopy.

  12. The complex formation-partition and partition-association models of solvent extraction of ions

    International Nuclear Information System (INIS)

    Siekierski, S.

    1976-01-01

    Two models of the extraction process have been proposed. In the first model it is assumed that the partitioning neutral species is at first formed in the aqueous phase and then transferred into the organic phase. The second model is based on the assumption that equivalent amounts of cations are at first transferred from the aqueous into the organic phase and then associated to form a neutral molecule. The role of the solubility parameter in extraction and the relation between the solubility of liquid organic substances in water and the partition of complexes have been discussed. The extraction of simple complexes and complexes with organic ligands has been discussed using the first model. Partition coefficients have been calculated theoretically and compared with experimental values in some very simple cases. The extraction of ion pairs has been discussed using the partition-association model and the concept of single-ion partition coefficients. (author)

  13. Complex formation of trivalent americium with salicylic acid at very low concentrations

    International Nuclear Information System (INIS)

    Melanie Mueller; Margret Acker; Steffen Taut; Gert Bernhard; Forschungszentrum Dresden-Rossendorf, Dresden

    2010-01-01

    For the first time, the complexation of americium(III) with salicylic acid was studied at trace metal concentrations using a 2.0 m Long Path Flow Cell for UV-vis spectroscopy. The detection limit of Am(III) in aqueous solution at pH 3.0 was found to be 5 x 10 -9 M. Two Am(III)-salicylate complexes were formed at pH 5.0 in 0.1 M NaClO 4 , indicated by a clear red shift of the absorption maximum. The absorption spectra obtained from spectrophotometric titration were analyzed by means of factor analysis and complex stabilities were calculated to be log β 110 = 2.56 ± 0.08 and log β 120 = 3.93 ± 0.19. (author)

  14. Thermodynamics of formation of cadmium dicarboxylate and carboxylate mixed complexes with benzimidazole

    Energy Technology Data Exchange (ETDEWEB)

    Kharitonov, G V; Bolotov, V M; Kharitonova, R I [Voronezhskij Tekhnologicheskij Inst. (USSR)

    1980-01-01

    Thermodynamic parameters of the mixed complexing of cadmium propionate, butyrate, valerate, succinate, maleinate and malate with benzimidazole in 20 % aqUeous-ethanol solution of 0.1 M KNO/sub 3/ are studied using polarographic method. It is shown that stability of mixed complexes of cadmium carboxylates with benzimidazole is connected with the process enthalpy and is determined by covalency of the metal-carboxylate bond. Increasing length of hydrocarbon chain of acyl group of monobasic acids hampers amine coordination with central complexing agent (..delta..S<0). The presence of dicarboxylate-ion in the inner coordination sphere decreases the enthalpy and increases the entropy of the process (..delta..S>0).

  15. Formation of a dinuclear complex in collisions between light nuclei and entrance channel limitations to fusion

    International Nuclear Information System (INIS)

    Shapira, D.; Shivakumar, B.; Ayik, S.; Harmon, B.A.

    1986-01-01

    A model for fusion of light nuclei has been proposed recently wherein fusion progresses through nucleus-nucleus capture via a dinuclear stage which acts as a doorway to fusion. While this model accounts for the fusion cross sections, it makes no attempt at predicting observables associated with the non-fusion part of the captured flux. A study of products from the decay of the dinuclear complex into non-fusion channels can provide a stringent test for such a model. In this contribution a model which addresses both the binary decay and the fusion of a dinuclear complex formed in the collision is described and model predictions are compared with data. Accompanying contributions discuss the formalism which is used to describe the evolution of the dinuclear complex and present new data which provide information that helps justify the approximations made in applying this model

  16. Kinetics of cesium lead halide perovskite nanoparticle growth; focusing and de-focusing of size distribution

    Science.gov (United States)

    Koolyk, Miriam; Amgar, Daniel; Aharon, Sigalit; Etgar, Lioz

    2016-03-01

    In this work we study the kinetics of cesium lead halide perovskite nanoparticle (NP) growth; the focusing and de-focusing of the NP size distribution. Cesium lead halide perovskite NPs are considered to be attractive materials for optoelectronic applications. Understanding the kinetics of the formation of these all-inorganic perovskite NPs is critical for reproducibly and reliably generating large amounts of uniformly sized NPs. Here we investigate different growth durations for CsPbI3 and CsPbBr3 NPs, tracking their growth by high-resolution transmission electron microscopy and size distribution analysis. As a result, we are able to provide a detailed model for the kinetics of their growth. It was observed that the CsPbI3 NPs exhibit focusing of the size distribution in the first 20 seconds of growth, followed by de-focusing over longer growth durations, while the CsPbBr3 NPs show de-focusing of the size distribution starting from the beginning of the growth. The monomer concentration is depleted faster in the case of CsPbBr3 than in the case of CsPbI3, due to faster diffusion of the monomers, which increases the critical radius and results in de-focusing of the population. Accordingly, focusing is not observed within 40 seconds of growth in the case of CsPbBr3. This study provides important knowledge on how to achieve a narrow size distribution of cesium lead halide perovskite NPs when generating large amounts of these promising, highly luminescent NPs.In this work we study the kinetics of cesium lead halide perovskite nanoparticle (NP) growth; the focusing and de-focusing of the NP size distribution. Cesium lead halide perovskite NPs are considered to be attractive materials for optoelectronic applications. Understanding the kinetics of the formation of these all-inorganic perovskite NPs is critical for reproducibly and reliably generating large amounts of uniformly sized NPs. Here we investigate different growth durations for CsPbI3 and CsPbBr3 NPs, tracking

  17. Excited-state complex formation between aqua-uranyl (VI) and thallous ion

    International Nuclear Information System (INIS)

    Deschaux, M.; Marcantonatos, M.D.

    1981-01-01

    The formation of the non-radiative *(UO 2 Tl) 3+ exciplex occurs in aqueous solution by a less involved mechanism than that of the *(UO 2 Ag) 3+ exciplex. This is shown to be due to the absence of a primary hydration shell for Tl + and to the energy and expansion of its 6s 2 pair, which are more suitable for electron transfer than Ag + . (author)

  18. Mixed ligand complex formation of Fe with boric acid and typical N ...

    Indian Academy of Sciences (India)

    Unknown

    diethylenetriamine and triethylenetetramine (L) in different molar ratios provides ... the complexes at 25 ± 0⋅1°C in aqueous solution at a fixed ionic strength,. I = 0⋅1 mol ... acid–base, ion exchange and complexometric titrations5. ... concentrations of H+ ion corresponding to the pH-meter readings were obtained by the.

  19. Formation of competitive potential of the machine-building complex of the region

    Directory of Open Access Journals (Sweden)

    Oleg Ivanovich Botkin

    2014-03-01

    Full Text Available The article describes the features of competitive potential of regional machine-building complex in a globalized world economy. The purpose of the research is the development of theoretically reasonable economic basis of the machine-building complex considering  the  features of business in the conditions of the WTO. In the work, the hypothesis of a special role of the external economic factors locates in development of the enterprises of regional industrial complexes. The study of the theoretical provisions defining the development of the region revealed the factors determining influence of the international trade agreements on spatial localization of the industry. The main attention is paid to an analytical assessment of the current state and the trends, which have developed in the period of post-crisis economic recovery. Analysis of the main indicators of attractiveness has revealed the weak position of local industrial enterprises in the WTO. The directions of strengthening of the competitive capacity of the local industrial enterprises are defined. The obtained results allow us to increase the sustainability of the industry by means of effective management mechanism improvements and to create favorable operating conditions of a machine-building complex of the region

  20. A pulse radiolysis study of the formation and reactions of reduced metal EDTA complexes

    International Nuclear Information System (INIS)

    Buitenhuis, R.

    1977-01-01

    The construction of a computerized pulse radiolysis system with available means appropriate for the wavelength interval between 300 and 1000 nm is described. The investigation of the radiolysis of aqueous solutions of EDTA complexes in the presence of alcohols is discussed

  1. Study of the competitive reaction ability of harmine and harmaline during complex formation with transition metals

    International Nuclear Information System (INIS)

    Chepulsky, S.A.; Kadirova, Z.Ch.; Parpiev, N.A.

    2006-01-01

    New coordination compounds of d-metals (Zn(II), Co(II), Mn(II), Mo(VI), Cr(VI)) β-carboline alkaloids were synthesized. The structure of obtained substances was established by IR, PMR spectroscopy. The quantum-chemical assessment of the harmine and harmaline reactivity in complexation reactions with d-metals was carried out. (author)

  2. Copper(II) complex as a precursor for formation of cyano-bridged ...

    Indian Academy of Sciences (India)

    chemsci

    structural similarities to the natural hexaazamacrocyclic complexes such as heme in human red blood cell, chlorophyll A and B, and vitamin B12.1 ...... and phenolic contents of medicinal plants used by the. Venda people for conditions related ...

  3. Viewbrics: Formative Assessment of Complex Skills with Video-Enhanced Rubrics (VER) in Dutch Secondary Education

    NARCIS (Netherlands)

    Rusman, Ellen; Nadolski, Rob; Boon, Jo; Ackermans, Kevin

    2016-01-01

    To learn complex skills, like collaboration, learners need to acquire a concrete and consistent mental model of what it means to master this skill. If learners know their current mastery level and know their targeted mastery level, they can better determine their subsequent learning activities.

  4. Mixed-ligand complex formation equilibria of Cu with biguanide in ...

    Indian Academy of Sciences (India)

    Unknown

    by potentiometric investigation on the decomposi- tion of the corresponding complexes with acid.16–18. Literature ... the molecular mechanism of actions of biguanide derivatives as drugs. Results of such investigation .... tems, higher values may be possible. For the ternary. 1 : 1 : 1 CuII : Bg : HG system, p = q = r = 1 and for.

  5. MOOC design analysis - Constructive alignment, interactions, task complexity, formative assessment & feedback

    NARCIS (Netherlands)

    Kasch, Julia; Van Rosmalen, Peter; Kalz, Marco

    2016-01-01

    Massive Open Online Courses (MOOCs) hold the potential of providing education at large scale. However, the challenge lies in the scalability of their educational design. It is unclear whether and to what extent MOOCs to provide active and complex learning activities, support and feedback to large

  6. Formation of lactoferrin/sodium caseinate complexes and their adsorption behaviour at the air/water interface.

    Science.gov (United States)

    Li, Quanyang; Zhao, Zhengtao

    2017-10-01

    This research investigated the complexation behaviour between lactoferrin (Lf) and sodium caseinate (NaCas) before and after heat treatment. The results showed that heating facilitated their interaction and different complexes were formed at different Lf/NaCas ratios. The presence of low concentrations of NaCas resulted in the rapid precipitation of Lf, while no precipitation was observed at the NaCas concentrations higher than Lf/NaCas ratio of 2:1. The formed complexes at the ratio of 2:1 have an average diameter of 194±9.0nm and they exhibited a great capacity in lowering the air/water interfacial tension. Further increase of NaCas concentration to ratios of 1:1 and 1:2 resulted in the formation of smaller complexes with average diameters of 60±2.5nm. The complexes formed at these two ratios showed similar adsorption behaviour at the air/water interface and they exhibited lower capacity in decreasing the interfacial tension than the ratio of 2:1. Copyright © 2017 Elsevier Ltd. All rights reserved.

  7. Thermodynamics of inclusion complex formation of β-cyclodextrin with a variety of surfactants differing in the nature of headgroup

    International Nuclear Information System (INIS)

    Benkő, Mária; Király, Zoltán

    2012-01-01

    Highlights: ► Inclusion complexation of β-cyclodextrins with various surfactants. ► Thermodynamic parameters determined by titration microcalorimetry. ► Stoichiometry of complexation is 1:1. ► The binding constant decreases linearly with increasing temperature. ► Enthalpy–entropy compensation is independent of the nature of the headgroup. - Abstract: The inclusion complexation of β-cyclodextrin with various surfactants, possessing the same alkyl chain length but differing in the hydrophilic headgroup, was investigated by isothermal titration microcalorimetry. Sodium dodecyl sulfate, sodium dodecyl sulfonate, dodecyltrimethylammonium bromide and dodecyl(dimethyl)amine oxide were investigated. The major aim of this study was to elucidate the effects of temperature and the nature of the headgroup on the complex formation. Thermometric titrations were effected between the temperatures (288 and 348) K. The results provided the stoichiometry, the equilibrium constant and the reaction enthalpy of complexation. Changes in Gibbs energy, entropy and van’t Hoff enthalpy were additionally calculated.

  8. Studies on Ternary Complex Formation of U(VI)-salicylate by Using Time-resolved Fluorescence Spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Cha, Wan Sik; Cho, H. R.; Park, K. K.; Kim, W. H.; Jung, E. C. [Korea Atomic Energy Research Institute, Daejeon (Korea, Republic of)

    2010-05-15

    Organic ligands containing carboxylic and phenolic functional groups naturally occur in groundwater environment, particularly in forms of polyelectrolytes such as humic and fulvic acids, from microbial degradation of biomass, e.g., plant and animal tissues. These ligands play important roles in dissolution and migration of actinide radionuclide species since they can form stable ternary actinide complexes with common inorganic ions like hydroxides and carbonates. Therefore, model ternary complexes of lanthanides and actinides have been targets of studies to understand their chemical behaviors under near-neutral pH groundwater conditions. Previous model carboxylic ligands include phthalates, maleic acids, or alpha- substituted carboxylic acids. However, majority of previous studies investigated binary systems or used potentiometric titration method that requires high ligand concentration in mM levels. Recently, highly sensitive time-resolved laserinduced fluorescence spectroscopy (TRLFS) has been used to investigate lower concentration (e.g., a few {mu}M levels) reactions of binary complexes between of ligands and metal ions. This technique provides information regarding electronic structures and complexation constants as well as fluorescence quenching mechanism. In the present study, we studied the U(VI)-OH-salicylate (SA) ternary complex formation at higher pH (> 4) via TRLF spectrum and UV-Vis absorbance measurement. Preliminary studies show that the fluorescence (FL) intensity of hydroxouranyl species at pH 4.5 decreases as SA concentration elevates in aqueous solution. Fluorescence quenching mechanism by SA is suggested based on FL intensity (I) and lifetime (tau) measurement via TRLFS

  9. Molecular dynamics of formation of TD lesioned DNA complexed with repair enzyme - onset of the enzymatic repair process

    Energy Technology Data Exchange (ETDEWEB)

    Pinak, Miroslav [Japan Atomic Energy Research Inst., Tokai, Ibaraki (Japan). Tokai Research Establishment

    1999-12-01

    To describe the first step of the enzymatic repair process (formation of complex enzyme-DNA), in which the thymine dimer (TD) part is removed from DNA, the 500 picosecond (ps) molecular dynamics (MD) simulation of TD lesioned DNA and part of repair enzyme cell (inclusive of catalytic center - Arg-22, Glu-23, Arg-26 and Thr-2) was performed. TD is UV originated lesion in DNA and T4 Endonuclease V is TD specific repair enzyme. Both molecules were located in the same simulation cell and their relative movement was examined. During the simulation the research was focused on the role of electrostatic energy in formation of complex enzyme-DNA. It is found, that during the first 100 ps of MD, the part of enzyme approaches the DNA surface at the TD lesion, interacts extensively by electrostatic and van der Walls interactions with TD part of DNA and forms complex that lasts stabile for 500 ps of MD. In the beginning of MD, the positive electrostatic interaction energy between part of enzyme and TD ({approx} +10 kcal/mol) drives enzyme towards the DNA molecule. Water-mediated hydrogen bonds between enzyme and DNA help to keep complex stabile. As a reference, the MD simulation of the identical system with native DNA molecule (two native thymines (TT) instead of TD) was performed. In this system the negative electrostatic interaction energy between part of enzyme and TT ({approx} -11 kcal/mol), in contrary to the positive one in the system with TD, doesn't drive enzyme towards DNA and complex is not formed. (author)

  10. Molecular dynamics of formation of TD lesioned DNA complexed with repair enzyme - onset of the enzymatic repair process

    International Nuclear Information System (INIS)

    Pinak, Miroslav

    1999-12-01

    To describe the first step of the enzymatic repair process (formation of complex enzyme-DNA), in which the thymine dimer (TD) part is removed from DNA, the 500 picosecond (ps) molecular dynamics (MD) simulation of TD lesioned DNA and part of repair enzyme cell (inclusive of catalytic center - Arg-22, Glu-23, Arg-26 and Thr-2) was performed. TD is UV originated lesion in DNA and T4 Endonuclease V is TD specific repair enzyme. Both molecules were located in the same simulation cell and their relative movement was examined. During the simulation the research was focused on the role of electrostatic energy in formation of complex enzyme-DNA. It is found, that during the first 100 ps of MD, the part of enzyme approaches the DNA surface at the TD lesion, interacts extensively by electrostatic and van der Walls interactions with TD part of DNA and forms complex that lasts stabile for 500 ps of MD. In the beginning of MD, the positive electrostatic interaction energy between part of enzyme and TD (∼ +10 kcal/mol) drives enzyme towards the DNA molecule. Water-mediated hydrogen bonds between enzyme and DNA help to keep complex stabile. As a reference, the MD simulation of the identical system with native DNA molecule (two native thymines (TT) instead of TD) was performed. In this system the negative electrostatic interaction energy between part of enzyme and TT (∼ -11 kcal/mol), in contrary to the positive one in the system with TD, doesn't drive enzyme towards DNA and complex is not formed. (author)

  11. Understanding the Slow Transient Optoelectronic Response of Hybrid Organic-Inorganic Halide Perovskites

    Science.gov (United States)

    Jacobs, Daniel Louis

    Hybrid organic-inorganic halide perovskites, particularly methylammonium lead triiodide (MAPbI3), have emerged within the past decade as an exciting class of photovoltaic materials. In less than ten years, MAPbI3-based photovoltaic devices have seen unprecedented performance growth, with photoconversion efficiency increasing from 3% to over 22%, making it competitive with traditional high-efficiency solar cells. Furthermore, the fabrication of MAPbI3 devices utilize low-temperature solution processing, which could facilitate ultra low cost manufacturing. However, MAPbI3 suffers from significant instabilities under working conditions that have limited their applications outside of the laboratory. The instability of the MAPbI3 material can be generalized as a complex, slow transient optoelectronic response (STOR). The mechanism of the generalized STOR is dependent on the native defects of MAPbI3, but detailed understanding of the material defect properties is complicated by the complex ionic bonding of MAPbI3. Furthermore, characterization of the intrinsic material's response is complicated by the diverse approach to material processing and device architecture across laboratories around the world. In order to understand and mitigate the significant problems of MAPbI3 devices, a new approach focused on the material response, rather than the full device response, must be pursued. This dissertation highlights the work to analyze and mitigate the STOR intrinsic to MAPbI3. An experimental platform was developed based on lateral interdigitated electrode (IDE) arrays capable of monitoring the current and photoluminescence response simultaneously. By correlating the dynamics of the current and photoluminescence (PL) responses, both charge trapping and ion migration mechanisms were identified to contribute to the STOR. Next, a novel fabrication technique is introduced that is capable of reliably depositing MAPbI3 thin films with grain sizes at least an order of magnitude

  12. Heteroprotein Complex Formation of Bovine Lactoferrin and Pea Protein Isolate: A Multiscale Structural Analysis.

    Science.gov (United States)

    Adal, Eda; Sadeghpour, Amin; Connell, Simon; Rappolt, Michael; Ibanoglu, Esra; Sarkar, Anwesha

    2017-02-13

    Associative electrostatic interactions between two oppositely charged globular proteins, lactoferrin (LF) and pea protein isolate (PPI), the latter being a mixture of vicilin, legumin, and convicilin, was studied with a specific PPI/LF molar ratio at room temperature. Structural aspects of the electrostatic complexes probed at different length scales were investigated as a function of pH by means of different complementary techniques, namely, with dynamic light scattering, small-angle X-ray scattering (SAXS), turbidity measurements, and atomic force microscopy (AFM). Irrespective of the applied techniques, the results consistently displayed that complexation between LF and PPI did occur. In an optimum narrow range of pH 5.0-5.8, a viscous liquid phase of complex coacervate was obtained upon mild centrifugation of the turbid LF-PPI mixture with a maximum R h , turbidity and the ζ-potential being close to zero observed at pH 5.4. In particular, the SAXS data demonstrated that the coacervates were densely assembled with a roughly spherical size distribution exhibiting a maximum extension of ∼80 nm at pH 5.4. Equally, AFM image analysis showed size distributions containing most frequent cluster sizes around 40-80 nm with spherical to elliptical shapes (axis aspect ratio ≤ 2) as well as less frequent elongated to chainlike structures. The most frequently observed compact complexes, we identify as mainly leading to LF-PPI coacervation, whereas for the less frequent chain-like aggregates, we hypothesize that additionally PPI-PPI facilitated complexes exist.

  13. Concomitant carboxylate and oxalate formation from the activation of CO{sub 2} by a thorium(III) complex

    Energy Technology Data Exchange (ETDEWEB)

    Formanuik, Alasdair; Ortu, Fabrizio; Mills, David P. [School of Chemistry, The University of Manchester (United Kingdom); Inman, Christopher J. [Department of Chemistry and Biochemistry, School of Life Sciences, University of Sussex, Brighton (United Kingdom); Kerridge, Andrew [Department of Chemistry, Lancaster University (United Kingdom); Castro, Ludovic; Maron, Laurent [LPCNO, CNRA et INSA, Universite Paul Sabatier, Toulouse (France)

    2016-12-12

    Improving our comprehension of diverse CO{sub 2} activation pathways is of vital importance for the widespread future utilization of this abundant greenhouse gas. CO{sub 2} activation by uranium(III) complexes is now relatively well understood, with oxo/carbonate formation predominating as CO{sub 2} is readily reduced to CO, but isolated thorium(III) CO{sub 2} activation is unprecedented. We show that the thorium(III) complex, [Th(Cp''){sub 3}] (1, Cp''={C_5H_3(SiMe_3)_2-1,3}), reacts with CO{sub 2} to give the mixed oxalate-carboxylate thorium(IV) complex [{Th(Cp'')_2[κ"2-O_2C{C_5H_3-3,3'-(SiMe_3)_2}]}{sub 2}(μ-κ{sup 2}:κ{sup 2}-C{sub 2}O{sub 4})] (3). The concomitant formation of oxalate and carboxylate is unique for CO{sub 2} activation, as in previous examples either reduction or insertion is favored to yield a single product. Therefore, thorium(III) CO{sub 2} activation can differ from better understood uranium(III) chemistry. (copyright 2016 The Authors. Published by Wiley-VCH Verlag GmbH and Co. KGaA.)

  14. Formation of Shc-Grb2 complexes is necessary to induce neoplastic transformation by overexpression of Shc proteins

    DEFF Research Database (Denmark)

    Salcini, A E; McGlade, J; Pelicci, G

    1994-01-01

    The mammalian SHC gene encodes three overlapping proteins which all contain a carboxy-terminal SH2 domain. Shc proteins are phosphorylated on tyrosine by a variety of receptor and cytoplasmic tyrosine kinases. Phosphorylated Shc proteins form a complex with the SH2-SH3 containing Grb2 protein which...... of Grb2 to Shc proteins requires phosphorylation of Shc at Tyr317, which lies within the high affinity binding motif for the Grb2 SH2 domain, pYVNV, where Asn at the +2 position is crucial for complex formation. In vivo, Tyr317 is the major, but not the only, site for Shc phosphorylation, and is the sole...... aminoterminal deletion, but retain the Tyr317 site and the SH2 domain conserve the capacity to be phosphorylated, to bind to Grb2 and to induce cell transformation. These data indicate that the formation of the Shc-Grb2 complex is a crucial event in the transformation induced by overexpression of Shc...

  15. 78 FR 51463 - Energy Conservation Program: Energy Conservation Standards for Metal Halide Lamp Fixtures

    Science.gov (United States)

    2013-08-20

    ... merging the metal halide lamp fixture and the high-intensity discharge (HID) lamp rulemakings. This NOPR... Conservation Program: Energy Conservation Standards for Metal Halide Lamp Fixtures; Proposed Rule #0;#0;Federal...: Energy Conservation Standards for Metal Halide Lamp Fixtures AGENCY: Office of Energy Efficiency and...

  16. Solvated Positron Chemistry. Competitive Positron Reactions with Halide Ions in Water

    DEFF Research Database (Denmark)

    Christensen, Palle; Pedersen, Niels Jørgen; Andersen, J. R.

    1979-01-01

    It is shown by means of the angular correlation technique that the binding of positrons to halides is strongly influenced by solvation effects. For aqueous solutions we find increasing values for the binding energies between the halide and the positron with increasing mass of the halide...

  17. Solar cells, structures including organometallic halide perovskite monocrystalline films, and methods of preparation thereof

    KAUST Repository

    Bakr, Osman M.

    2017-03-02

    Embodiments of the present disclosure provide for solar cells including an organometallic halide perovskite monocrystalline film (see fig. 1.1B), other devices including the organometallic halide perovskite monocrystalline film, methods of making organometallic halide perovskite monocrystalline film, and the like.

  18. Studies on radiation-sensitive nonsilver halide materials, (1)

    International Nuclear Information System (INIS)

    Komizu, Hideo; Honda, Koichi; Yabe, Akira; Kawasaki, Masami; Fujii, Etsuo

    1978-01-01

    In order to discover new radiation-sensitive nonsilver halide materials, the coloration based on the formation of Stenhouse salts was studied in the following three systems: (a) furfural-amine/HCl aq/methanol solution, (b) furfural-amine/polyhalogenide/PMMA matrix, (c) furfural-amine/PVC matrix. Firstly, forty-five aromatic amines were surveyed to find out the amines suitable for the color precursors (reactant from furfural and amine) in the system (a). As a result, the five amines, which gave the precursors in good yields by the reaction with furfural, were selected: m-nitroaniline, N-methylaniline, m-methyl-N-methylaniline, aniline, and o-methoxyaniline. Secondly, the coloration induced by electron beam bombardment was studied in the systems (b) and (c) containing the color precursors (the reactants from these amines and furfural). Although the PMMA films containing the color precursors and polyhalogenides were sensitive to electron beam, they were not stable when standing under daylight at room temperature. The PVC films containing the color precursors were very stable and colored to reddish yellow (lambda sub(max) 498 - 545 nm) by electron beam bombardment. The PVC film containing N-methylaniline-furfural was the most sensitive and the increase in absorbance at 498 nm was 0.78 by electron beam bombardment of 60 kV - 7.5 x 10 -7 C/cm 2 . A good linear relationship existed between the degree of coloration and the amounts of electron beam bombardment in the range from 0 to 10 -6 C/cm 2 . (author)

  19. Formation of Hg(II) Tetrathiolate Complexes with Cysteine at Neutral pH.

    Science.gov (United States)

    Warner, Thomas; Jalilehvand, Farideh

    2016-04-01

    Mercury(II) ions precipitate from aqueous cysteine (H 2 Cys) solutions containing H 2 Cys/Hg(II) mole ratio ≥ 2.0 as Hg( S -HCys) 2 . In absence of additional cysteine, the precipitate dissolves at pH ~12 with the [Hg( S,N -Cys) 2 ] 2- complex dominating. With excess cysteine (H 2 Cys/Hg(II) mole ratio ≥ 4.0), higher complexes form and the precipitate dissolves at lower pH values. Previously, we found that tetrathiolate [Hg( S -Cys) 4 ] 6- complexes form at pH = 11.0; in this work we extend the investigation to pH values of physiological interest. We examined two series of Hg(II)-cysteine solutions in which C Hg(II) varied between 8 - 9 mM and 80 - 100 mM, respectively, with H 2 Cys/Hg(II) mole ratios from 4 to ~20. The solutions were prepared in the pH range 7.1 - 8.8, at the pH at which the initial Hg( S -HCys) 2 precipitate dissolved. The variations in the Hg(II) speciation were followed by 199 Hg NMR, X-ray absorption and Raman spectroscopic techniques. Our results show that in the dilute solutions ( C Hg(II) = 8 - 9 mM), mixtures of di-, tri- (major) and tetrathiolate complexes exist at moderate cysteine excess ( C H2Cys ~ 0.16 M) at pH 7.1. In the more concentrated solutions ( C Hg(II) = 80 - 100 mM) with high cysteine excess ( C H2Cys > 0.9 M), tetrathiolate [Hg( S -cysteinate) 4 ] m -6 ( m = 0 - 4) complexes dominate in the pH range 7.3 - 7.8, with lower charge than for the [Hg( S -Cys) 4 ] 6- complex due to protonation of some ( m ) of the amino groups of the coordinated cysteine ligands. The results of this investigation could provide a key to the mechanism of biosorption and accumulation of Hg(II) ions in biological / environmental systems.

  20. Tetrapeptide-coumarin conjugate 3D networks based on hydrogen-bonded charge transfer complexes: gel formation and dye release.

    Science.gov (United States)

    Guo, Zongxia; Gong, Ruiying; Jiang, Yi; Wan, Xiaobo

    2015-08-14

    Oligopeptide-based derivatives are important synthons for bio-based functional materials. In this article, a Gly-(L-Val)-Gly-(L-Val)-coumarin (GVGV-Cou) conjugate was synthesized, which forms 3D networks in ethanol. The gel nanostructures were characterized by UV-vis spectroscopy, FT-IR spectroscopy, X-ray diffraction (XRD), SEM and TEM. It is suggested that the formation of charge transfer (CT) complexes between the coumarin moieties is the main driving force for the gel formation. The capability of the gel to encapsulate and release dyes was explored. Both Congo Red (CR) and Methylene Blue (MB) can be trapped in the CT gel matrix and released over time. The present gel might be used as a functional soft material for guest encapsulation and release.

  1. A Low-Complexity Subgroup Formation with QoS-Aware for Enhancing Multicast Services in LTE Networks

    Science.gov (United States)

    Algharem, M.; Omar, M. H.; Rahmat, R. F.; Budiarto, R.

    2018-03-01

    The high demand of Multimedia services on in Long Term Evolution (LTE) and beyond networks forces the networks operators to find a solution that can handle the huge traffic. Along with this, subgroup formation techniques are introduced to overcome the limitations of the Conventional Multicast Scheme (CMS) by splitting the multicast users into several subgroups based on the users’ channels quality signal. However, finding the best subgroup configuration with low complexity is need more investigations. In this paper, an efficient and simple subgroup formation mechanisms are proposed. The proposed mechanisms take the transmitter MAC queue in account. The effectiveness of the proposed mechanisms is evaluated and compared with CMS in terms of throughput, fairness, delay, Block Error Rate (BLER).

  2. Quaternary oxide halides of group 15 with zinc and cadmium

    International Nuclear Information System (INIS)

    Rueck, Nadia

    2014-01-01

    The present thesis ''Quaternary oxide halides of group 15 with zinc and cadmium'' deals with the chemical class of oxide halides, which contain d-block element cations and pnicogens. Over the past few years compounds containing pnicogene cations are intensively investigated. The reason for this is the free electron pair of the Pn"3"+ cation, which is responsible for some interesting properties. Free electron pairs do not only impact the spatial structure of molecules but also the properties of materials. The object of this work was the synthesis and characterization of compounds containing Pn"3"+ cations with free electron pairs. Due to the structure-determining effect of these free electron pairs and in combination with halides it is possible to synthesize compounds with low-dimensional structures like chains and layers. In these compounds the structure is separated into halophilic and chalcophilic sub-structures, which are held together only by weak Van der Waals forces.

  3. Two-Dimensional Halide Perovskites for Emerging New- Generation Photodetectors

    DEFF Research Database (Denmark)

    Tang, Yingying; Cao, Xianyi; Chi, Qijin

    2018-01-01

    Compared to their conventional three-dimensional (3D) counterparts, two-dimensional (2D) halide perovskites have attracted more interests recently in a variety of areas related to optoelectronics because of their unique structural characteristics and enhanced performances. In general, there are two...... distinct types of 2D halide perovskites. One represents those perovskites with an intrinsic layered crystal structure (i.e. MX6 layers, M = metal and X = Cl, Br, I), the other defines the perovskites with a 2D nanostructured morphology such as nanoplatelets and nanosheets. Recent studies have shown that 2D...... halide perovskites hold promising potential for the development of new-generation photodetectors, mainly arising from their highly efficient photoluminescence and absorbance, color tunability in the visible-light range and relatively high stability. In this chapter, we present the summary and highlights...

  4. Local Polar Fluctuations in Lead Halide Perovskite Crystals

    Science.gov (United States)

    Yaffe, Omer; Guo, Yinsheng; Tan, Liang Z.; Egger, David A.; Hull, Trevor; Stoumpos, Constantinos C.; Zheng, Fan; Heinz, Tony F.; Kronik, Leeor; Kanatzidis, Mercouri G.; Owen, Jonathan S.; Rappe, Andrew M.; Pimenta, Marcos A.; Brus, Louis E.

    2017-03-01

    Hybrid lead-halide perovskites have emerged as an excellent class of photovoltaic materials. Recent reports suggest that the organic molecular cation is responsible for local polar fluctuations that inhibit carrier recombination. We combine low-frequency Raman scattering with first-principles molecular dynamics (MD) to study the fundamental nature of these local polar fluctuations. Our observations of a strong central peak in the cubic phase of both hybrid (CH3 NH3 PbBr3 ) and all-inorganic (CsPbBr3 ) lead-halide perovskites show that anharmonic, local polar fluctuations are intrinsic to the general lead-halide perovskite structure, and not unique to the dipolar organic cation. MD simulations indicate that head-to-head Cs motion coupled to Br face expansion, occurring on a few hundred femtosecond time scale, drives the local polar fluctuations in CsPbBr3 .

  5. ON MAGNETIC ACTIVITY BAND OVERLAP, INTERACTION, AND THE FORMATION OF COMPLEX SOLAR ACTIVE REGIONS

    Energy Technology Data Exchange (ETDEWEB)

    McIntosh, Scott W. [High Altitude Observatory, National Center for Atmospheric Research, P.O. Box 3000, Boulder, CO 80307 (United States); Leamon, Robert J., E-mail: mscott@hao.ucar.edu [Department of Physics, Montana State University, Bozeman, MT 59717 (United States)

    2014-11-20

    Recent work has revealed a phenomenological picture of the how the ∼11 yr sunspot cycle of the Sun arises. The production and destruction of sunspots is a consequence of the latitudinal-temporal overlap and interaction of the toroidal magnetic flux systems that belong to the 22 yr magnetic activity cycle and are rooted deep in the Sun's convective interior. We present a conceptually simple extension of this work, presenting a hypothesis on how complex active regions can form as a direct consequence of the intra- and extra-hemispheric interaction taking place in the solar interior. Furthermore, during specific portions of the sunspot cycle, we anticipate that those complex active regions may be particularly susceptible to profoundly catastrophic breakdown, producing flares and coronal mass ejections of the most severe magnitude.

  6. Spectrophotometric Determination of Metoprolol Tartrate in Pharmaceutical Dosage Forms on Complex Formation with Cu(II

    Directory of Open Access Journals (Sweden)

    Mustafa Cesme

    2011-06-01

    Full Text Available A new, simple, sensitive and accurate spectrophotometric method has been developed for the assay of metoprolol tartrate (MPT, which is based on the complexation of drug with copper(II [Cu(II] at pH 6.0, using Britton-Robinson buffer solution, to produce a blue adduct. The latter has a maximum absorbance at 675 nm and obeys Beer’s law within the concentration range 8.5-70 mg/mL. Regression analysis of the calibration data showed a good correlation coefficient (r = 0.998 with a limit of detection of 5.56 mg/mL. The proposed procedure has been successfully applied to the determination of this drug in its tablets. In addition, the spectral data and stability constant for the binuclear copper(II complex of MPT (Cu2MPT2Cl2 have been reported.

  7. Diastereoselective formation of metallamacrocyclic (arene)Ru(II) and CpRh(III) complexes.

    Science.gov (United States)

    Lehaire, Marie-Line; Scopelliti, Rosario; Herdeis, Lorenz; Polborn, Kurt; Mayer, Peter; Severin, Kay

    2004-03-08

    The reaction of [(arene)RuCl(2)](2) (arene = cymene, 1,3,5-C(6)H(3)Me(3)) and [CpRhCl(2)](2) half-sandwich complexes with tridentate heterocyclic ligands in the presence of base has been investigated. In all cases, the chloro-ligands were substituted to give metallacyclic products with ring sizes between 4 and 18 atoms. The cyclization occurs in a highly diastereoselective fashion with chiral recognition between the different metal fragments. The complexes were comprehensively characterized by elemental analysis, NMR spectroscopy, and single crystal X-ray crystallography. For 2-hydroxy-nicotinic acid and 2-amino-nicotinic acid, dinuclear structures were obtained (15-17) whereas for 2,3-dihydroxyquinoline, 2,3-dihydroxyquinoxaline, and 6-methyl-2,3-phenazinediol, trimeric assemblies were found (19-22), and for 4-imidazolecarboxylic acid, a tetrameric assembly (18) was found.

  8. Formation and stability of calcium complexes of dimethyl sulfoxide in water

    Czech Academy of Sciences Publication Activity Database

    Jakl, M.; Straka, Michal; Jaklová Dytrtová, Jana; Roithová, J.

    2014-01-01

    Roč. 360, č. 1 (2014), s. 8-14 ISSN 1387-3806 R&D Projects: GA ČR GP13-21409P Grant - others:GA ČR(CZ) GAP206/12/0539 Institutional support: RVO:61388963 Keywords : bonding energies * DFT * ESI-MS * complexation * speciation Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 1.972, year: 2014

  9. Chabazite and dolomite formation in a dolocrete profile: An example of a complex alkaline paragenesis in Lanzarote, Canary Islands

    Science.gov (United States)

    Alonso-Zarza, Ana M.; Bustamante, Leticia; Huerta, Pedro; Rodríguez-Berriguete, Álvaro; Huertas, María José

    2016-05-01

    This paper studies the weathering and soil formation processes operating on detrital sediments containing alkaline volcanic rock fragments of the Mirador del Río dolocrete profile. The profile consists of a lower horizon of removilised weathered basalts, an intermediate red sandy mudstones horizon with irregular carbonate layers and a topmost horizon of amalgamated carbonate layers with root traces. Formation occurred in arid to semiarid climates, giving place to a complex mineralogical association, including Mg-carbonates and chabazite, rarely described in cal/dolocretes profiles. Initial vadose weathering processes occurred in the basalts and in directly overlying detrital sediments, producing (Stage 1) red-smectites and dolomicrite. Dominant phreatic (Stage 2) conditions allowed precipitation of coarse-zoned dolomite and chabazite filling porosities. In Stages 3 and 4, mostly pedogenic, biogenic processes played an important role in dolomite and calcite accumulation in the profile. Overall evolution of the profile and its mineralogical association involved initial processes dominated by alteration of host rock, to provide silica and Mg-rich alkaline waters, suitable for chabazite and dolomite formation, without a previous carbonate phase. Dolomite formed both abiogenically and biogenically, but without a previous carbonate precursor and in the absence of evaporites. Dominance of calcite towards the profile top is the result of Mg/Ca decrease in the interstitial meteoric waters due to decreased supply of Mg from weathering, and increased supply of Ca in aeolian dust. Meteoric origin of the water is confirmed by C and O isotope values, which also indicate lack of deep sourced CO2. The dolocrete studied and its complex mineral association reveal the complex interactions that occur at surface during weathering and pedogenesis of basalt-sourced rocks.

  10. Application of rank annihilation factor analysis to the spectrophotometric determination of the formation constant of complex of a new synthesized tripodal ligand with Co2+

    Directory of Open Access Journals (Sweden)

    Reza Golbedaghi

    2017-05-01

    Full Text Available The complex formation between a new synthesized tripodal ligand (L22py and the cation Co2+ in water was studied spectrophotometrically using rank annihilation factor analysis (RAFA. According to molar ratio data the stoichiometry of complexation between the ligand and the cation Co2+ was 1:1. Formation constant of this complex was derived using RAFA on spectrophotometric data. In this process the contribution of ligand is removed from the absorbance data matrix when the complex stability constant acts as an optimizing object and simply combined with the pure spectrum of ligand, the rank of original data matrix can be reduced by one by annihilating the information of the ligand from the original data matrix. The effect of ethanol, dimethylformamide (DMF and acetonitrile (AN was investigated on the formation constant of the Co2+ complex. Complex formation constant in water was estimated as log Kf = 5.09 ± 0.02. In mixtures of solvents of water and DMF and water and AN, the formation constant of the complex was increased because of lowering donor number of the solvent and in mixture of water and ethanol, the complex formation constant was decreased because of lowering of dielectric constant of the solvent.

  11. Analysis of the complex formation of heparin with protamine by light scattering and analytical ultracentrifugation: implications for blood coagulation management.

    Science.gov (United States)

    Maurer, Jürgen; Haselbach, Stephanie; Klein, Oliver; Baykut, Doan; Vogel, Vitali; Mäntele, Werner

    2011-02-02

    Heparin, a linear glycosaminoglycan, is used in different forms in anticoagulation treatment. Protamine, a highly positive charged peptide containing about 32 amino acids, acts as an antagonist for heparin to restore normal blood coagulation. The complex formation of protamine with heparin was analyzed by a combination of analytical ultracentrifugation and light scattering. Titration of heparin with protamine in blood plasma preparations results in a drastic increase of turbidity, indicating the formation of nanoscale particles. A similar increase of turbidity was observed in physiological saline solution with or without human serum albumin (HSA). Particle size analysis by analytical ultracentrifugation revealed a particle radius of approximately 30 nm for unfractionated heparin and of approximately 60 nm for low molecular weight heparin upon complexation with excess protamine, in agreement with atomic force microscopy data. In the absence of HSA, larger and more heterogeneous particles were observed. The particles obtained were found to be stable for hours. The particle formation kinetics was analyzed by light scattering at different scattering angles and was found to be complete within several minutes. The time course of particle formation suggests a condensation reaction, with sigmoidal traces for low heparin concentrations and quasi-first-order reaction for high heparin concentrations. Under all conditions, the final scattering intensity reached after several minutes was found to be proportional to the amount of heparin in the blood plasma or buffer solution, provided that excess protamine was available and no multiple scattering occurred. On the basis of a direct relation between particle concentration and the heparin concentration present before protaminization, a light scattering assay was developed which permits the quantitative analysis of the heparin concentration in blood plasma and which could complement or even replace the activated clotting time test

  12. Ammonia formation by a thiolate-bridged diiron amide complex as a nitrogenase mimic

    Science.gov (United States)

    Li, Yang; Li, Ying; Wang, Baomin; Luo, Yi; Yang, Dawei; Tong, Peng; Zhao, Jinfeng; Luo, Lun; Zhou, Yuhan; Chen, Si; Cheng, Fang; Qu, Jingping

    2013-04-01

    Although nitrogenase enzymes routinely convert molecular nitrogen into ammonia under ambient temperature and pressure, this reaction is currently carried out industrially using the Haber-Bosch process, which requires extreme temperatures and pressures to activate dinitrogen. Biological fixation occurs through dinitrogen and reduced NxHy species at multi-iron centres of compounds bearing sulfur ligands, but it is difficult to elucidate the mechanistic details and to obtain stable model intermediate complexes for further investigation. Metal-based synthetic models have been applied to reveal partial details, although most models involve a mononuclear system. Here, we report a diiron complex bridged by a bidentate thiolate ligand that can accommodate HN=NH. Following reductions and protonations, HN=NH is converted to NH3 through pivotal intermediate complexes bridged by N2H3- and NH2- species. Notably, the final ammonia release was effected with water as the proton source. Density functional theory calculations were carried out, and a pathway of biological nitrogen fixation is proposed.

  13. Snapin mediates insulin secretory granule docking, but not trans-SNARE complex formation

    Energy Technology Data Exchange (ETDEWEB)

    Somanath, Sangeeta [Blizard Institute, Barts and the London School of Medicine and Dentistry, Queen Mary University of London, London, E1 2AT (United Kingdom); Partridge, Christopher J. [Diabetes Research Laboratories, Oxford Centre for Diabetes, Endocrinology and Churchill Hospital, University of Oxford, Oxford, OX3 7LJ (United Kingdom); Marshall, Catriona [Blizard Institute, Barts and the London School of Medicine and Dentistry, Queen Mary University of London, London, E1 2AT (United Kingdom); Rowe, Tony [CSL Limited, 45 Poplar Road, Parkville, Victoria 3052 (Australia); Turner, Mark D., E-mail: mark.turner@ntu.ac.uk [Interdisciplinary Biomedical Research Centre, School of Science and Technology, Nottingham Trent University, Nottingham, NG11 8NS (United Kingdom)

    2016-04-29

    Secretory granule exocytosis is a tightly regulated process requiring granule targeting, tethering, priming, and membrane fusion. At the heart of this process is the SNARE complex, which drives fusion through a coiled-coil zippering effect mediated by the granule v-SNARE protein, VAMP2, and the plasma membrane t-SNAREs, SNAP-25 and syntaxin-1A. Here we demonstrate that in pancreatic β-cells the SNAP-25 accessory protein, snapin, C-terminal H2 domain binds SNAP-25 through its N-terminal Sn-1 domain. Interestingly whilst snapin binds SNAP-25, there is only modest binding of this complex with syntaxin-1A under resting conditions. Instead synataxin-1A appears to be recruited in response to secretory stimulation. These results indicate that snapin plays a role in tethering insulin granules to the plasma membrane through coiled coil interaction of snapin with SNAP-25, with full granule fusion competency only resulting after subsequent syntaxin-1A recruitment triggered by secretory stimulation. - Highlights: • Snapin mediates granule docking. • Snapin binds SNAP-25. • SNARE complex forms downstream.

  14. Metamorphic core complex formation by density inversion and lower-crust extrusion.

    Science.gov (United States)

    Martinez, F; Goodliffe, A M; Taylor, B

    2001-06-21

    Metamorphic core complexes are domal uplifts of metamorphic and plutonic rocks bounded by shear zones that separate them from unmetamorphosed cover rocks. Interpretations of how these features form are varied and controversial, and include models involving extension on low-angle normal faults, plutonic intrusions and flexural rotation of initially high-angle normal faults. The D'Entrecasteaux islands of Papua New Guinea are actively forming metamorphic core complexes located within a continental rift that laterally evolves to sea-floor spreading. The continental rifting is recent (since approximately 6 Myr ago), seismogenic and occurring at a rapid rate ( approximately 25 mm yr-1). Here we present evidence-based on isostatic modelling, geological data and heat-flow measurements-that the D'Entrecasteaux core complexes accommodate extension through the vertical extrusion of ductile lower-crust material, driven by a crustal density inversion. Although buoyant extrusion is accentuated in this region by the geological structure present-which consists of dense ophiolite overlaying less-dense continental crust-this mechanism may be generally applicable to regions where thermal expansion lowers crustal density with depth.

  15. Snapin mediates insulin secretory granule docking, but not trans-SNARE complex formation

    International Nuclear Information System (INIS)

    Somanath, Sangeeta; Partridge, Christopher J.; Marshall, Catriona; Rowe, Tony; Turner, Mark D.

    2016-01-01

    Secretory granule exocytosis is a tightly regulated process requiring granule targeting, tethering, priming, and membrane fusion. At the heart of this process is the SNARE complex, which drives fusion through a coiled-coil zippering effect mediated by the granule v-SNARE protein, VAMP2, and the plasma membrane t-SNAREs, SNAP-25 and syntaxin-1A. Here we demonstrate that in pancreatic β-cells the SNAP-25 accessory protein, snapin, C-terminal H2 domain binds SNAP-25 through its N-terminal Sn-1 domain. Interestingly whilst snapin binds SNAP-25, there is only modest binding of this complex with syntaxin-1A under resting conditions. Instead synataxin-1A appears to be recruited in response to secretory stimulation. These results indicate that snapin plays a role in tethering insulin granules to the plasma membrane through coiled coil interaction of snapin with SNAP-25, with full granule fusion competency only resulting after subsequent syntaxin-1A recruitment triggered by secretory stimulation. - Highlights: • Snapin mediates granule docking. • Snapin binds SNAP-25. • SNARE complex forms downstream.

  16. Weak bases and formation of a less soluble lauryl sulfate salt/complex in sodium lauryl sulfate (SLS) containing media.

    Science.gov (United States)

    Bhattachar, Shobha N; Risley, Donald S; Werawatganone, Pornpen; Aburub, Aktham

    2011-06-30

    This work reports on the solubility of two weakly basic model compounds in media containing sodium lauryl sulfate (SLS). Results clearly show that the presence of SLS in the media (e.g. simulated gastric fluid or dissolution media) can result in an underestimation of solubility of some weak bases. We systematically study this phenomenon and provide evidence (chromatography and pXRD) for the first time that the decrease in solubility is likely due to formation of a less soluble salt/complex between the protonated form of the weak base and lauryl sulfate anion. Copyright © 2011 Elsevier B.V. All rights reserved.

  17. Formation and uranium explorating prospect of sub-volcanic granitic complex and rich uranium ore deposit in South China

    International Nuclear Information System (INIS)

    Wang Yusheng

    1997-01-01

    The rich uranium ore deposits are all closely related to tecto-magmatism of late-magmatic cycle whether volcanic types or granitic types in south China. Volcanic type rich uranium deposit has closely relationship with sub-volcanic activity, and granitic type rich uranium deposit is also closely related to mid-fine, unequal particle small massif in late main invasion stage. Based on characteristics of magmatism, we name the rock sub-volcanic granite complex, which is a unique style and closely related to the formation of rich uranium ore deposit

  18. Unusual C-C bond cleavage in the formation of amine-bis(phenoxy) group 4 benzyl complexes: Mechanism of formation and application to stereospecific polymerization

    KAUST Repository

    Gowda, Ravikumar R.

    2014-08-11

    Group 4 tetrabenzyl compounds MBn4 (M = Zr, Ti), upon protonolysis with an equimolar amount of the tetradentate amine-tris(phenol) ligand N[(2,4-tBu2C6H2(CH 2)OH]3 in toluene from -30 to 25 °C, unexpectedly lead to amine-bis(phenoxy) dibenzyl complexes, BnCH2N[(2,4- tBu2C6H2(CH2)O] 2MBn2 (M = Zr (1), Ti (2)) in 80% (1) and 75% (2) yields. This reaction involves an apparent cleavage of the >NCH2-ArOH bond (loss of the phenol in the ligand) and formation of the >NCH 2-CH2Bn bond (gain of the benzyl group in the ligand). Structural characterization of 1 by X-ray diffraction analysis confirms that the complex formed is a bis(benzyl) complex of Zr coordinated by a newly derived tridentate amine-bis(phenoxy) ligand arranged in a mer configuration in the solid state. The abstractive activation of 1 and 2 with B(C6F 5)3·THF in CD2Cl2 at room temperature generates the corresponding benzyl cations {BnCH2N[(2,4- tBu2C6H2(CH2)O] 2MBn(THF)}+[BnB(C6F5) 3]- (M = Zr (3), Ti, (4)). These cationic complexes, along with their analogues derived from (imino)phenoxy tri- and dibenzyl complexes, [(2,6-iPr2C6H3)N=C(3,5- tBu2C6H2)O]ZrBn3 (5) and [2,4-Br2C6H2(O)(6-CH2(NC 5H9))CH2N=CH(2-adamantyl-4-MeC 6H2O)]ZrBn2 (6), have been found to effectively polymerize the biomass-derived renewable β-methyl-α-methylene- γ-butyrolactone (βMMBL) at room temperature into the highly stereoregular polymer PβMMBL with an isotacticity up to 99% mm. A combined experimental and DFT study has yielded a mechanistic pathway for the observed unusual C-C bond cleavage in the present protonolysis reaction between ZrBn4 and N[(2,4-tBu2C 6H2(CH2)OH]3 for the formation of complex 1, which involves the benzyl radical and the Zr(III) species, resulting from thermal and photochemical decomposition of ZrBn4, followed by a series of reaction sequences consisting of protonolysis, tautomerization, H-transfer, oxidation, elimination, and radical coupling. © 2014 American Chemical Society.

  19. Thymidine phosphorylase exerts complex effects on bone resorption and formation in myeloma.

    Science.gov (United States)

    Liu, Huan; Liu, Zhiqiang; Du, Juan; He, Jin; Lin, Pei; Amini, Behrang; Starbuck, Michael W; Novane, Nora; Shah, Jatin J; Davis, Richard E; Hou, Jian; Gagel, Robert F; Yang, Jing

    2016-08-24

    Myelomatous bone disease is characterized by the development of lytic bone lesions and a concomitant reduction in bone formation, leading to chronic bone pain and fractures. To understand the underlying mechanism, we investigated the contribution of myeloma-expressed thymidine phosphorylase (TP) to bone lesions. In osteoblast progenitors, TP up-regulated the methylation of RUNX2 and osterix, leading to decreased bone formation. In osteoclast progenitors, TP up-regulated the methylation of IRF8 and thereby enhanced expression of NFATc1 (nuclear factor of activated T cells, cytoplasmic 1 protein), leading to increased bone resorption. TP reversibly catalyzes thymidine into thymine and 2-deoxy-d-ribose (2DDR). Myeloma-secreted 2DDR bound to integrin αVβ3/α5β1 in the progenitors, activated PI3K (phosphoinositide 3-kinase)/Akt signaling, and increased DNMT3A (DNA methyltransferase 3A) expression, resulting in hypermethylation of RUNX2, osterix, and IRF8 This study elucidates an important mechanism for myeloma-induced bone lesions, suggesting that targeting TP may be a viable approach to healing resorbed bone in patients. Because TP overexpression is common in bone-metastatic tumors, our findings could have additional mechanistic implications. Copyright © 2016, American Association for the Advancement of Science.

  20. Ising-based model of opinion formation in a complex network of interpersonal interactions

    Science.gov (United States)

    Grabowski, A.; Kosiński, R. A.

    2006-03-01

    In our work the process of opinion formation in the human population, treated as a scale-free network, is modeled and investigated numerically. The individuals (nodes of the network) are characterized by their authorities, which influence the interpersonal interactions in the population. Hierarchical, two-level structures of interpersonal interactions and spatial localization of individuals are taken into account. The effect of the mass media, modeled as an external stimulation acting on the social network, on the process of opinion formation is investigated. It was found that in the time evolution of opinions of individuals critical phenomena occur. The first one is observed in the critical temperature of the system TC and is connected with the situation in the community, which may be described by such quantifiers as the economic status of people, unemployment or crime wave. Another critical phenomenon is connected with the influence of mass media on the population. As results from our computations, under certain circumstances the mass media can provoke critical rebuilding of opinions in the population.