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Sample records for kompleksy alkoholanow tiiv

  1. Ti(IV) and the Siderophore Desferrioxamine B: A Tight Complex Has Biological and Environmental Implications.

    Science.gov (United States)

    Jones, Kayleigh E; Batchler, Kathleen L; Zalouk, Célia; Valentine, Ann M

    2017-02-06

    The siderophore desferrioxamine B (DFOB) binds Ti(IV) tightly and precludes its hydrolytic precipitation under biologically and environmentally relevant conditions. This interaction of DFOB with Ti(IV) is investigated by using spectro-potentiometric and spectro-photometric titrations, mass spectrometry, isothermal titration calorimetry (ITC), and computational modeling. The data from pH 2-10 suggest two one-proton equilibria among three species, with one species predominating below pH 3.5, a second from pH 3.5 to 8, and a third above pH 8. The latter species is prone to slow hydrolytic precipitation. Electrospray mass spectrometry allowed the detection of [Ti(IV) (HDFOB)] 2+ and [Ti(DFOB)] + ; these species were assigned as the pH UV/vis-monitored competition with ethylenediaminetetraacetic acid (EDTA). Taking into consideration the available binding constant of Ti(IV) and EDTA, the data reveal values of log β 111 = 41.7, log β 110 = 38.1, and log β 11-1 = 30.1. The former value was supported by ITC, with the transfer of Ti(IV) from EDTA to DFOB determined to be both enthalpically and entropically favorable. Computational methods yielded a model of Ti-DFOB. The physiological and environmental implications of this tight interaction and the potential role of DFOB in solubilizing Ti(IV) are discussed.

  2. PVC Based Membrane of Ti(IV Iodovanadate for Pb(II Determination

    Directory of Open Access Journals (Sweden)

    Mu. Naushad

    2008-08-01

    Full Text Available Ti(IV iodovanadate has been synthesized by mixing a mixture of aqueous solutions of 0.1 M sodium vanadate and 0.1 M potassium iodate with 0.1 M solution of Ti(IV chloride at pH 1.0. Distribution coefficients (Kd of various metal ions were determined on the column of Ti(IV iodovanadate which showed the selectivity of Pb(II ions by this cation exchange material. So Ti(IV iodovanadate has been used as an electoactive material for the construction of Pb(II selective electrode. The main purpose of this study is to develop an inexpensive, simple and reliable ion-selective electrode for Pb(II determination. The sensor exhibit Nernstian response for Pb(II ions over a wide concentration range of 1 x 10-7 M to 1 x 10-1 M with a slope of 30±0.4 mV per decade of activity. The electrode is suitable for use in aqueous solution in a pH range of 2-7.2 with a response time of 10 second. The membrane electrode can be used at least for 4 months without any divergence in potential. The selectivity coefficients were determined by the mixed solution method and revealed that the electrode was selective for Pb(II ions in the presence of interfering cations. The sensor could be used as an indicator electrode in the potentiometric titration of Pb(II ions with EDTA. The practical applicability of the proposed sensor has been reported for Pb(II determination in a standard rock sample and water sample. The results are found to be in good agreement with those obtained by using conventional methods.

  3. Expanding the Therapeutic Potential of the Iron Chelator Deferasirox in the Development of Aqueous Stable Ti(IV) Anticancer Complexes.

    Science.gov (United States)

    Loza-Rosas, Sergio A; Vázquez-Salgado, Alexandra M; Rivero, Kennett I; Negrón, Lenny J; Delgado, Yamixa; Benjamín-Rivera, Josué A; Vázquez-Maldonado, Angel L; Parks, Timothy B; Munet-Colón, Charlene; Tinoco, Arthur D

    2017-07-17

    The recent X-ray structure of titanium(IV)-bound human serum transferrin (STf) exhibiting citrate as a synergistic anion reveals a difference in Ti(IV) coordination versus iron(III), the metal endogenously delivered by the protein to cells. This finding enriches our bioinspired drug design strategy for Ti(IV)-based anticancer therapeutics, which applies a family of Fe(III) chelators termed chemical transferrin mimetic (cTfm) ligands to inhibit Fe bioavailability in cancer cells. Deferasirox, a drug used for iron overload disease, is a cTfm ligand that models STf coordination to Fe(III), favoring Fe(III) binding versus Ti(IV). This metal affinity preference drives deferasirox to facilitate the release of cytotoxic Ti(IV) intracellularly in exchange for Fe(III). An aqueous speciation study performed by potentiometric titration from pH 4 to 8 with micromolar levels of Ti(IV) deferasirox at a 1:2 ratio reveals exclusively Ti(deferasirox) 2 in solution. The predominant complex at pH 7.4, [Ti(deferasirox) 2 ] 2- , exhibits the one of the highest aqueous stabilities observed for a potent cytotoxic Ti(IV) species, demonstrating little dissociation even after 1 month in cell culture media. UV-vis and 1 H NMR studies show that the stability is unaffected by the presence of biomolecular Ti(IV) binders such as citrate, STf, and albumin, which have been shown to induce dissociation or regulate cellular uptake and can alter the activity of other antiproliferative Ti(IV) complexes. Kinetic studies on [Ti(deferasirox) 2 ] 2- transmetalation with Fe(III) show that a labile Fe(III) source is required to induce this process. The initial step of this process occurs on the time scale of minutes, and equilibrium for the complete transmetalation is reached on a time scale of hours to a day. This work reveals a mechanism to deliver Ti(IV) compounds into cells and trigger Ti(IV) release by a labile Fe(III) species. Cellular studies including other cTfm ligands confirm the Fe(III) depletion

  4. Thermal decomposition and spectroscopic investigation of a new aqueous glycolato(-peroxo) Ti(IV) solution-gel precursor

    International Nuclear Information System (INIS)

    De Dobbelaere, Christopher; Mullens, Jules; Hardy, An; Van Bael, Marlies K.

    2011-01-01

    Highlights: → A totally water based glycolato-Ti(IV) precursor is presented and characterized. → The precursors' thermal decomposition profile depends on the ligand to metal ratio. → Titanium is coordinated in an unidentate fashion by the glycolate anion. → Smooth and uniform TiO 2 films can be prepared from the precursor solution. - Abstract: A new aqueous solution-gel precursor based on water soluble glycolato(-peroxo)-Ti(IV) complexes is developed for the preparation of TiO 2 films. With regard to the decomposition of complexes towards oxide formation, it is important to gain insight in the chemical transformations inside the precursor during thermal treatment. Therefore, the thermo-oxidative decomposition pathway of a gel obtained by slow evaporation of the precursor solution is described based on hyphenated thermogravimetric analysis with Fourier transform infrared spectroscopy (TGA-FTIR) and mass spectrometry (TGA-MS). Pure glycolic acid is used as a reference system for this study. By varying the molar glycolic acid to Ti(IV) ratio, the thermal decomposition of the gel can be drastically shortened and the profile's course changed. Gel structure and chemical changes in the gel upon heating are also studied by means of off-line FTIR. A unidentate coordination of the titanium(IV) ion by the carboxylate group of the glycolato ligands and the involvement of the hydroxyl group is confirmed. Phase formation at certain points in the thermal decomposition is studied by X-ray diffraction and Raman spectroscopy. Finally, it is proven that the new precursor is a valuable candidate for the deposition of low carbon containing solution-gel films which can ultimately be converted into smooth and uniform TiO 2 films.

  5. Thermal decomposition and spectroscopic investigation of a new aqueous glycolato(-peroxo) Ti(IV) solution-gel precursor

    Energy Technology Data Exchange (ETDEWEB)

    De Dobbelaere, Christopher, E-mail: christopher.dedobbelaere@uhasselt.be [Hasselt University, Institute for Materials Research, Inorganic and Physical Chemistry, Agoralaan Building D, B-3590 Diepenbeek (Belgium); Mullens, Jules, E-mail: jules.mullens@uhasselt.be [Hasselt University, Institute for Materials Research, Inorganic and Physical Chemistry, Agoralaan Building D, B-3590 Diepenbeek (Belgium); Hardy, An, E-mail: an.hardy@uhasselt.be [Hasselt University, Institute for Materials Research, Inorganic and Physical Chemistry, Agoralaan Building D, B-3590 Diepenbeek (Belgium); IMEC vzw, Division IMOMEC, Agoralaan Building D, B-3590 Diepenbeek (Belgium); Van Bael, Marlies K., E-mail: marlies.vanbael@uhasselt.be [Hasselt University, Institute for Materials Research, Inorganic and Physical Chemistry, Agoralaan Building D, B-3590 Diepenbeek (Belgium); IMEC vzw, Division IMOMEC, Agoralaan Building D, B-3590 Diepenbeek (Belgium)

    2011-06-10

    Highlights: {yields} A totally water based glycolato-Ti(IV) precursor is presented and characterized. {yields} The precursors' thermal decomposition profile depends on the ligand to metal ratio. {yields} Titanium is coordinated in an unidentate fashion by the glycolate anion. {yields} Smooth and uniform TiO{sub 2} films can be prepared from the precursor solution. - Abstract: A new aqueous solution-gel precursor based on water soluble glycolato(-peroxo)-Ti(IV) complexes is developed for the preparation of TiO{sub 2} films. With regard to the decomposition of complexes towards oxide formation, it is important to gain insight in the chemical transformations inside the precursor during thermal treatment. Therefore, the thermo-oxidative decomposition pathway of a gel obtained by slow evaporation of the precursor solution is described based on hyphenated thermogravimetric analysis with Fourier transform infrared spectroscopy (TGA-FTIR) and mass spectrometry (TGA-MS). Pure glycolic acid is used as a reference system for this study. By varying the molar glycolic acid to Ti(IV) ratio, the thermal decomposition of the gel can be drastically shortened and the profile's course changed. Gel structure and chemical changes in the gel upon heating are also studied by means of off-line FTIR. A unidentate coordination of the titanium(IV) ion by the carboxylate group of the glycolato ligands and the involvement of the hydroxyl group is confirmed. Phase formation at certain points in the thermal decomposition is studied by X-ray diffraction and Raman spectroscopy. Finally, it is proven that the new precursor is a valuable candidate for the deposition of low carbon containing solution-gel films which can ultimately be converted into smooth and uniform TiO{sub 2} films.

  6. Efficient generation of volatile cadmium species using Ti(III) and Ti(IV) and application to determination of cadmium by cold vapor generation inductively coupled plasma mass spectrometry (CVG-ICP-MS)†

    Science.gov (United States)

    Arslan, Zikri; Yilmaz, Vedat; Rose, LaKeysha

    2015-01-01

    In this study, a highly efficient chemical vapor generation (CVG) approach is reported for determination of cadmium (Cd). Titanium (III) and titanium (IV) were investigated for the first time as catalytic additives along with thiourea, L-cysteine and potassium cyanide (KCN) for generation of volatile Cd species. Both Ti(III) and Ti(IV) provided the highest enhancement with KCN. The improvement with thiourea was marginal (ca. 2-fold), while L-cysteine enhanced signal slightly only with Ti(III) in H2SO4. Optimum CVG conditions were 4% (v/v) HCl + 0.03 M Ti(III) + 0.16 M KCN and 2% (v/v) HNO3 + 0.03 M Ti(IV) + 0.16 M KCN with a 3% (m/v) NaBH4 solution. The sensitivity was improved about 40-fold with Ti(III) and 35-fold with Ti(IV). A limit of detection (LOD) of 3.2 ng L−1 was achieved with Ti(III) by CVG-ICP-MS. The LOD with Ti(IV) was 6.4 ng L−1 which was limited by the blank signals in Ti(IV) solution. Experimental evidence indicated that Ti(III) and Ti(IV) enhanced Cd vapor generation catalytically; for best efficiency mixing prior to reaction with NaBH4 was critical. The method was highly robust against the effects of transition metal ions. No significant suppression was observed in the presence of Co(II), Cr(III), Cu(II), Fe(III), Mn(II), Ni(II) and Zn(II) up to 1.0 μg mL−1. Among the hydride forming elements, no interference was observed from As(III) and Se(IV) at 0.5 μg mL−1 level. The depressive effects from Pb(II) and Sb(III) were not significant at 0.1 μg mL−1 while those from Bi(III) and Sn(II) were marginal. The procedures were validated with determination of Cd by CVG-ICP-MS in a number certified reference materials, including Nearshore seawater (CASS-4), Bone ash (SRM 1400), Dogfish liver (DOLT-4), Mussel tissue (SRM 2976) and Domestic Sludge (SRM 2781). PMID:26251554

  7. Studies of obtaining and stability in aqueous medium of new complex compounds of Ti(IV) and Zr(IV) used in ecological leather tanning

    Science.gov (United States)

    Crudu, Marian; Sibiescu, Doina; Rosca, Ioan; Sutiman, Daniel; Vizitiu, Mihaela

    2009-01-01

    In this paper, the study of obtaining new coordination compounds of Ti(IV) and Zr(IV) using as ligand: D,L-β-iso-butyric acid, is presented. Also, the stability of these compounds in aqueous medium is studied. The studies of obtaining and of stability of the new compounds were accomplished in aqueous solutions using methods characteristic for coordination compounds: conductance and pH measurements. The combination ratios and the stability were determined with methods characteristic for studies in solutions. From experimental data resulted that the combination ratio of central metallic atoms with the ligand derived from D,L-β-iso-butyric acid was 1:2. From experimental data resulted that in strong acid and strong basic mediums, the coordination compounds could not be obtained. The optimal stability of the studied compounds is limited between 3-6, pH - values. This fact is in accordance with the conditions of using these compounds in ecological leather tanning. Of great importance is that these compounds were used with very good results in tanning processes of different types of leather. This fact evidenced that the ecological alternative of tanning is better than non-ecological tanning using chrome compounds. The importance of this paper consists in obtaining new coordination compounds that can be used in ecological leather tanning.

  8. Enhanced adsorption of active brilliant red X-3B dye on chitosan molecularly imprinted polymer functionalized with Ti(IV) as Lewis acid.

    Science.gov (United States)

    Deng, Hui; Wei, Zhilai; Wang, XiaoNing

    2017-02-10

    A Ti(IV) functionalized chitosan molecularly imprinted polymer (Ti-CSMIP) was successfully prepared. Ti 4+ as Lewis acidic was used to modify chitosan MIP by producing metal hydroxyl group and protonated surface of adsorbent in aqueous solution to recognize X-3B molecule as a Lewis base. The adsorbent was characterized by FTIR, SEM, XRD, BET, elemental and zeta potential analysis. XRD illustrated Ti-CSMIP exhibited a weak anatase phase when Ti 4+ cross-linked with chitosan. Batch adsorption experiments were performed to evaluate adsorption condition, including sorption isotherm, kinetics and reusability. The maximum adsorption capacity of Ti-CSMIP for X-3B was 161.1mg/g at 293K when solution pH was in the range of 6.0-7.0. Equilibrium data was well analyzed by three-parameter isotherm model, and the kinetics of adsorption followed the pseudo-second kinetics equation. Regeneration experiments indicated a possible application as an effective sorbent for the selective removal of azo anionic dye in aqueous solutions. Copyright © 2016 Elsevier Ltd. All rights reserved.

  9. Formation of Ti(III) and Ti(IV) states in Ti{sub 3}O{sub 5} nano- and microfibers obtained from hydrothermal annealing of C-doped TiO{sub 2} on Si

    Energy Technology Data Exchange (ETDEWEB)

    Stem, Nair, E-mail: nairstem@hotmail.com [Laboratório de Sistemas Integráveis (LSI), Escola Politécnica, Universidade de São Paulo, Av. Prof. Luciano Gualberto 158, 05508900 São Paulo, SP (Brazil); Souza, Michele L.; Araújo de Faria, Dalva Lúcia Araújo [Laboratório de Espectroscopia Molecular (LEM), Instituto de Química, Universidade de São Paulo, Av. Prof. Lineu Prestes 748, 05508900 São Paulo, SP (Brazil); Santos Filho, Sebastião G. dos [Laboratório de Sistemas Integráveis (LSI), Escola Politécnica, Universidade de São Paulo, Av. Prof. Luciano Gualberto 158, 05508900 São Paulo, SP (Brazil)

    2014-05-02

    In this work, it is investigated the formation of Ti(III) and Ti(IV) states at the surface and in the bulk of the Ti{sub 3}O{sub 5} material grown as meshes of nano- and micro-fibers obtained from hydrothermal annealing of C-doped TiO{sub 2} on Si. The topography and distribution of the fibers in the meshes were characterized by atomic force microscopy. When the fiber distribution was more compact, a higher photoluminescence signal at 850 nm (1.46 eV) was obtained, indicating the presence of a higher number of defects corresponding to the Ti(III) sites. From X-ray photoelectron spectroscopy, it was obtained a Ti(III)/Ti(IV) ratio much lower than the expected value for the Ti{sub 3}O{sub 5} phase (2 Ti(III): 1 Ti(IV)). The discrepancy was mainly attributed to the reaction of surface Ti(III) states of the Ti{sub 3}O{sub 5} fibers with water during the hydrothermal annealing, resulting in surface Ti(IV) with -OH radicals. On the other hand, X-ray photoelectron spectroscopy also indicated that substitutional and interstitial carbon atoms coexist, elemental carbon exists in the samples due to the co-deposition process and, as a result, the carbon inside of the TiO{sub 2} rutile lattice is acting as one of the precursors for the formation of Ti{sub 3}O{sub 5}. - Highlights: • Ti(III) states are detected inside of Ti{sub 3}O{sub 5} nano- and microfibers. • Ti(IV) states are predominantly detected on the surface of Ti{sub 3}O{sub 5} nano- and microfibers. • Photoluminescence at 850 nm for Ti{sub 3}O{sub 5} is due to defects associated to Ti(III). • Rutile possibly changes to C2/m Ti{sub 3}O{sub 5} during the hydrothermal annealing of C-doped TiO{sub 2}.

  10. Liquid-liquid extraction (LLE) of Fe(III) and Ti(IV) by bis-(2-ethyl-hexyl) phosphoric acid (D2EHPA) in sulfuric acid medium; Extracao liquido-liquido de ferro (III) e titanio (IV) pelo acido bis-(2-etil-hexil) fosforico (D2EHPA) em meio de acido sulfurico

    Energy Technology Data Exchange (ETDEWEB)

    Silva, Glauco Correa da; Cunha, Jose Waldemar Silva Dias da [Instituto de Engenharia Nuclear (IEN), Rio de Janeiro, RJ (Brazil). Dept. de Quimica e Materiais Nucleares; Dweck, Jo [Universidade Federal do Rio de Janeiro (UFRJ), RJ (Brazil). Escola de Quimica. Dept. de Processos Inorganicos; Afonso, Julio Carlos [Universidade Federal do Rio de Janeiro (UFRJ), RJ (Brazil). Inst. de Quimica. Dept. de Quimica Analitica]. E-mail: julio@iq.ufrj.br

    2008-07-01

    This work presents a study on the separation of Fe(III) and Ti(IV) from sulfuric acid leaching solutions of ilmenite (FeTiO{sub 3}) using liquid-liquid extraction with D2EHPA in n-dodecane as extracting agent. The distribution coefficients (K{sub D}) of the elements related to free acidity and concentration of Fe(III) and Ti(IV) were determined. Free acidity was changed from 3x10{sup -2} to 11.88 mol L{sup -1} and D2EHPA concentration was fixed at 1.5 mol L{sup 1}. Recovery of final products as well as recycling of wastes generated in the process were also investigated. The LLE process as a feasible alternative to obtain high-purity TiO{sub 2}. (author)

  11. Kompleksi kujunemine ja tsaariaegsed ehitised / Karin Hallas-Murula

    Index Scriptorium Estoniae

    Hallas-Murula, Karin, 1957-

    2004-01-01

    20. sajandi alguse Tallinna arhitektuurist. Pangakvartali kujunemise algus: Eestimaa Aadli Mõisate Krediitseltsi (Aadlipanga) hoone Estonia pst. 11 (1902-1904, arhitekt August Reinberg, ehituse järelevalve: Carl Jacoby, stukitöö, reljeefid: August Volz, vitraaž, vapid: Ernst Tode). Venemaa Riigipanga Tallinna osakonna hoone Estonia pst 13 (1907-1908, ehituse järelevalve: Aleksandr Jaron). Panga teenistujate elamu Sakala 6

  12. Extração líquido-líquido de ferro(III e titânio(IV pelo ácido bis-(2-etil-hexil fosfórico (D2EHPA em meio de ácido sulfúrico Liquid-liquid extraction (LLE of Fe(III and Ti(IV by bis-(2-ethyl-hexyl phosphoric acid (D2EHPA in sulfuric acid medium

    Directory of Open Access Journals (Sweden)

    Glauco Corrêa da Silva

    2008-01-01

    Full Text Available This work presents a study on the separation of Fe(III and Ti(IV from sulfuric acid leaching solutions of ilmenite (FeTiO3 using liquid-liquid extraction with D2EHPA in n-dodecane as extracting agent. The distribution coefficients (K D of the elements related to free acidity and concentration of Fe(III and Ti(IV were determined. Free acidity was changed from 3x10-2 to 11.88 mol L-1 and D2EHPA concentration was fixed at 1.5 mol L-1. Recovery of final products as well as recycling of wastes generated in the process were also investigated. The LLE process as a feasible alternative to obtain high-purity TiO2.

  13. Molecular complexes of tungsten oxotetrachloride with azomethins. Molekulyarnye kompleksy oksotetrakhlorida vol'frama s azometinami

    Energy Technology Data Exchange (ETDEWEB)

    Abramenko, Yu V; Garnovskij, A D; Abramenko, V A; Medvedeva, T E [Rostovskij-na-Donu Gosudarstvennyj Univ., Rostov-na-Donu (Russian Federation). Nauchno-Issledovatel' skij Inst. Fizicheskoj i Organicheskoj Khimii

    1992-09-01

    Series of new molecular complexes of tungsten oxotetrachloride with benza- and salicylalimines of equimolar compositions obtained. Substances are studied using element analysis, IR spectroscopy and conductometry. Octahedral structure of complexes with central atom coordination of benzalaniline molecules via azomethin nitrogen atom, and salicylalimines - via carbonyl oxygen atom of quinoid tantometric form of ligand is assumed.

  14. Multiplexed Imaging of Protein Phosphorylation on Membranes Based on Ti(IV) Functionalized Nanopolymers.

    Science.gov (United States)

    Iliuk, Anton; Li, Li; Melesse, Michael; Hall, Mark C; Tao, W Andy

    2016-05-17

    Accurate protein phosphorylation analysis reveals dynamic cellular signaling events not evident from protein expression levels. The most dominant biochemical assay, western blotting, suffers from the inadequate availability and poor quality of phospho-specific antibodies for phosphorylated proteins. Furthermore, multiplexed assays based on antibodies are limited by steric interference between the antibodies. Here we introduce a multifunctionalized nanopolymer for the universal detection of phosphoproteins that, in combination with regular antibodies, allows multiplexed imaging and accurate determination of protein phosphorylation on membranes. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Nanomaterials based on carbon and Ti(IV) oxides: some aspects of their electrochemistry

    Czech Academy of Sciences Publication Activity Database

    Kavan, Ladislav

    2012-01-01

    Roč. 9, 8/9 (2012), s. 652-679 ISSN 1475-7435 R&D Projects: GA MŠk LC510; GA AV ČR IAA400400804; GA AV ČR KAN200100801 Institutional research plan: CEZ:AV0Z40400503 Keywords : carbon nanostructures * titanium oxide * electrochemistry Subject RIV: CG - Electrochemistry Impact factor: 1.087, year: 2012

  16. Chiral Diamine Bis(phenolate) Ti-IV and Zr-IV Complexes - Synthesis, Structures and Reactivity

    NARCIS (Netherlands)

    Barroso, Sonia; Adao, Pedro; Duarte, M. Teresa; Meetsma, Auke; Pessoa, Joao Costa; Bouwkamp, Marco W.; Martins, Ana M.

    Neutral and cationic titanium and zirconium diamine bis(phenolate) complexes supported by chiral ligands L-1 and L-2 are described [L-1 = (R)-6,6'-{1-(dimethylamino)propan-2-ylazanediyl}bis(methylene)-bis(2,4-di-tert-butylphenolate); L-2 =

  17. Supported Single-Site Ti(IV) on a Metal–Organic Framework for the Hydroboration of Carbonyl Compounds

    Energy Technology Data Exchange (ETDEWEB)

    Huang, Zhiyuan [College; amp, Molecular Sciences, Institute of Advanced Studies, Wuhan University, Wuhan 430072, PR China; Chemical; amp, Engineering Division, Argonne National Laboratory, Lemont, Illinois 60439, United States; Liu, Dong [College; amp, Molecular Sciences, Institute of Advanced Studies, Wuhan University, Wuhan 430072, PR China; Chemical; amp, Engineering Division, Argonne National Laboratory, Lemont, Illinois 60439, United States; Camacho-Bunquin, Jeffrey [Chemical; amp, Engineering Division, Argonne National Laboratory, Lemont, Illinois 60439, United States; Zhang, Guanghui [Department; Yang, Dali [College; amp, Molecular Sciences, Institute of Advanced Studies, Wuhan University, Wuhan 430072, PR China; Chemical; amp, Engineering Division, Argonne National Laboratory, Lemont, Illinois 60439, United States; López-Encarnación, Juan M. [Chemical; amp, Engineering Division, Argonne National Laboratory, Lemont, Illinois 60439, United States; Department; Xu, Yunjie [Department; Ferrandon, Magali S. [Chemical; amp, Engineering Division, Argonne National Laboratory, Lemont, Illinois 60439, United States; Niklas, Jens [Chemical; amp, Engineering Division, Argonne National Laboratory, Lemont, Illinois 60439, United States; Poluektov, Oleg G. [Chemical; amp, Engineering Division, Argonne National Laboratory, Lemont, Illinois 60439, United States; Jellinek, Julius [Chemical; amp, Engineering Division, Argonne National Laboratory, Lemont, Illinois 60439, United States; Lei, Aiwen [College; amp, Molecular Sciences, Institute of Advanced Studies, Wuhan University, Wuhan 430072, PR China; Chemical; amp, Engineering Division, Argonne National Laboratory, Lemont, Illinois 60439, United States; Bunel, Emilio E. [Chemical; amp, Engineering Division, Argonne National Laboratory, Lemont, Illinois 60439, United States; Delferro, Massimiliano [Chemical; amp, Engineering Division, Argonne National Laboratory, Lemont, Illinois 60439, United States

    2017-10-10

    ABSTRACT: A stable and structurally well-defined titanium alkoxide catalyst supported on a metal-organic-framework (MOF) of UiO-67 topology (ANL1-Ti(OiPr)2) was synthesized and fully characterized by a variety of analytical and spectroscopic techniques, including BET, TGA, PXRD, XAS, DRIFT, SEM, and DFT computations. The Ti-functionalized MOF was demonstrated active for the catalytic hydroboration of a wide range of aldehydes and ketones with HBpin as the boron source. Compared to traditional homogeneous and supported hydroboration catalysts, ANL1-Ti(OiPr)2 is completely recyclable and reusable, making it a promising hydroboration catalyst alternative for green and sustainable chemical synthesis. DFT calculations suggest that the catalytic hydroboration proceeds via a (1) hydride transfer between the active Ti-hydride species and a carbonyl moiety (rate determining step), and (2) alkoxide transfer (intramolecular σ-bond metathesis) to generate the boronate ester product.

  18. Different-ligand boron complexes with gluconate-ions and pentaerythritol and gluconatoborates with B-O-B bridge bond. Raznoligandnye kompleksy bora s glyukonat-ionami i pentaehritritom i glyukonatoboraty s mostikovoj V-O-V svyaz'yu

    Energy Technology Data Exchange (ETDEWEB)

    Tel' zhenskaya, P N; Shvarts, E M; Vitola, I M [AN Latvijskoj SSR, Riga (USSR). Inst. Neorganicheskoj Khimii

    1990-01-01

    Borogluconates differing in structure of the complex dimeric borogluconate ion from the described earlier have been synthesized. The results of physicochemical measurements (chemical and thermal analysis, IR-spectroscopy, titration according to Fisher, conductometry) allowed to propose formulas for the studied compounds.

  19. Sorption properties and reversibility of Ti(IV) and Nb(V)-fluoride doped-Ca(BH{sub 4}){sub 2}-MgH{sub 2} system

    Energy Technology Data Exchange (ETDEWEB)

    Bonatto Minella, Christian, E-mail: christian.minella@kit.edu [Institute for Metallic Materials, IFW Dresden, Helmholtzstrasse 20, D-01069 Dresden (Germany); Technische Universität Dresden, D-01062 Dresden (Germany); Garroni, Sebastiano [Dipartimento di Chimica e Farmacia, Universitá di Sassari and INSTM, Via Vienna 2, I-07100 Sassari (Italy); Pistidda, Claudio [Institute of Materials Research, Materials Technology, Helmholtz-Zentrum Geesthacht, Zentrum für Material- und Küstenforschung GmbH, Max Planck Str. 1, D-21502 Geesthacht (Germany); Baró, Maria Dolors [Departament de Física, Universitat Autònoma de Barcelona, E-08193 Bellaterra (Spain); Gutfleisch, Oliver [Materials Science, Technische Universität Darmstadt, Alarich-Weiss-Str. 16, 64287 Darmstadt (Germany); Klassen, Thomas; Dornheim, Martin [Institute of Materials Research, Materials Technology, Helmholtz-Zentrum Geesthacht, Zentrum für Material- und Küstenforschung GmbH, Max Planck Str. 1, D-21502 Geesthacht (Germany)

    2015-02-15

    Highlights: • Faster desorption reaction for doped materials vs. the pure composite system. • Kinetic improvement concerning re-hydrogenation reaction showed by the addition of NbF{sub 5}. • Full characterization of the de-hydrogenation reaction pathway by means of both SR-PXD and {sup 11}B{"1H} MAS-NMR. • Study of the evolution of the chemical state of the additives upon both milling and sorption reactions. - Abstract: In the last decade, alkaline and alkaline earth metal tetrahydroborates have been the focuses of the research due to their high gravimetric and volumetric hydrogen densities. Among them, Ca(BH{sub 4}){sub 2} and the Ca(BH{sub 4}){sub 2} + MgH{sub 2} reactive hydride composites (RHC), were calculated to have the ideal thermodynamic properties which fall within the optimal range for mobile applications. In this study, the addition of NbF{sub 5} or TiF{sub 4} to the Ca(BH{sub 4}){sub 2} + MgH{sub 2} reactive hydride composite system was attempted aiming to obtain a full reversible system with the simultaneous suppression of CaB{sub 12}H{sub 12}. Structural characterization of the specimens was performed by means of in-situ Synchrotron Radiation Powder X-ray diffraction (SR-PXD) and {sup 11}B{"1H} Solid State Magic Angle Spinning-Nuclear Magnetic Resonance (MAS-NMR). The evolution of the chemical state of the Nb- and Ti-based additives was monitored by X-ray Absorption Near Edge Structure (XANES). The addition of NbF{sub 5} or TiF{sub 4} to the Ca(BH{sub 4}){sub 2} + MgH{sub 2} system have not suppressed completely the formation of CaB{sub 12}H{sub 12} and only a slight improvement concerning the reversible reaction was displayed just in the case of Nb-doped composite material.

  20. Fluorophilic Properties of (Perfluorooctyl)ethyldimethylsilyl Substituted and Tetramethyl(perfluoroalkyl) Substituted Cyclopentadienes and Their Ti(IV), Rh(III), and Rh(I) Complexes

    Czech Academy of Sciences Publication Activity Database

    Červenková Šťastná, Lucie; Auerová, Kateřina; Kvíčala, J.; Čermák, Jan

    2007-01-01

    Roč. 692, č. 10 (2007), s. 1974-1982 ISSN 0022-328X R&D Projects: GA AV ČR(CZ) IAA4072203; GA MŠk(CZ) LC06070 Institutional research plan: CEZ:AV0Z40720504 Keywords : fluorophilicity * fluorous cyclopentadienes * partition coefficient Subject RIV: CC - Organic Chemistry Impact factor: 2.168, year: 2007

  1. Sorption properties and reversibility of Ti(IV) and Nb(V)-fluoride doped-Ca(BH4)2-MgH2 system

    International Nuclear Information System (INIS)

    Bonatto Minella, Christian; Garroni, Sebastiano; Pistidda, Claudio; Baró, Maria Dolors; Gutfleisch, Oliver; Klassen, Thomas; Dornheim, Martin

    2015-01-01

    Highlights: • Faster desorption reaction for doped materials vs. the pure composite system. • Kinetic improvement concerning re-hydrogenation reaction showed by the addition of NbF 5 . • Full characterization of the de-hydrogenation reaction pathway by means of both SR-PXD and 11 B{ 1 H} MAS-NMR. • Study of the evolution of the chemical state of the additives upon both milling and sorption reactions. - Abstract: In the last decade, alkaline and alkaline earth metal tetrahydroborates have been the focuses of the research due to their high gravimetric and volumetric hydrogen densities. Among them, Ca(BH 4 ) 2 and the Ca(BH 4 ) 2 + MgH 2 reactive hydride composites (RHC), were calculated to have the ideal thermodynamic properties which fall within the optimal range for mobile applications. In this study, the addition of NbF 5 or TiF 4 to the Ca(BH 4 ) 2 + MgH 2 reactive hydride composite system was attempted aiming to obtain a full reversible system with the simultaneous suppression of CaB 12 H 12 . Structural characterization of the specimens was performed by means of in-situ Synchrotron Radiation Powder X-ray diffraction (SR-PXD) and 11 B{ 1 H} Solid State Magic Angle Spinning-Nuclear Magnetic Resonance (MAS-NMR). The evolution of the chemical state of the Nb- and Ti-based additives was monitored by X-ray Absorption Near Edge Structure (XANES). The addition of NbF 5 or TiF 4 to the Ca(BH 4 ) 2 + MgH 2 system have not suppressed completely the formation of CaB 12 H 12 and only a slight improvement concerning the reversible reaction was displayed just in the case of Nb-doped composite material

  2. Moskva ehitab / Kusta Jõudu

    Index Scriptorium Estoniae

    Jõudu, Kusta, 1930-

    1999-01-01

    Teedest ja ristmikest. Luzhniki staadionist. Kompleksi autorid arhitekltid A. V. Vlassov, I. E. Pozin, N. N. Ullas, A. F. Hrjakov jt. Staadioni rekonstrueerimisest Moskva linna 850. aastapäevaks. 2 ill

  3. Audentese koolid kolivad väärikatesse majadesse / Marika Karo

    Index Scriptorium Estoniae

    Karo, Marika

    2002-01-01

    Tartu linnavalitsus otsustas 9. mail 2002.a. müüa Tartus Puiestee tänaval asuva ajaloolise koolikompleksi ASile Audentes, kes kavatseb kinnistul olevatest kahest muinsuskaitse alla kuuluvast koolimajast, tööõpetuse majast, abihoonetest ja spordiplatsist välja arendada campus-tüüpi tänapäevase koolide kompleksi. Hooneid hakkavad kasutama Audentes Mainor Ülikooli Tartu filiaal ja alg- ja põhiharidust pakkuv Audentese Erakool. Koolihoonete kompleksi ajaloost

  4. Crystal structures of lazulite-type oxidephosphates TiIIITiIV3O3(PO4)3 and MIII4TiIV27O24(PO4)24 (MIII=Ti, Cr, Fe)

    International Nuclear Information System (INIS)

    Schoeneborn, M.; Glaum, R.; Reinauer, F.

    2008-01-01

    Single crystals of the oxidephosphates Ti III Ti IV 3 O 3 (PO 4 ) 3 (black), Cr III 4 Ti IV 27 O 24 (PO 4 ) 24 (red-brown, transparent), and Fe III 4 Ti IV 27 O 24 (PO 4 ) 24 (brown) with edge-lengths up to 0.3 mm were grown by chemical vapour transport. The crystal structures of these orthorhombic members (space group F2dd ) of the lazulite/lipscombite structure family were refined from single-crystal data [Ti III Ti IV 3 O 3 (PO 4 ) 3 : Z=24, a=7.3261(9) A, b=22.166(5) A, c=39.239(8) A, R 1 =0.029, wR 2 =0.084, 6055 independent reflections, 301 variables; Cr III 4 Ti IV 27 O 24 (PO 4 ) 24 : Z=1, a=7.419(3) A, b=21.640(5) A, c=13.057(4) A, R 1 =0.037, wR 2 =0.097, 1524 independent reflections, 111 variables; Fe III 4 Ti IV 27 O 24 (PO 4 ) 24 : Z=1, a=7.4001(9) A, b=21.7503(2) A, c=12.775(3) A, R 1 =0.049, wR 2 =0.140, 1240 independent reflections, 112 variables). For Ti III Ti IV O 3 (PO 4 ) 3 a well-ordered structure built from dimers [Ti III,IV 2 O 9 ] and [Ti IV,IV 2 O 9 ] and phosphate tetrahedra is found. The metal sites in the crystal structures of Cr 4 Ti 27 O 24 (PO 4 ) 24 and Fe 4 Ti 27 O 24 (PO 4 ) 24 , consisting of dimers [M III Ti IV O 9 ] and [Ti IV,IV 2 O 9 ], monomeric [Ti IV O 6 ] octahedra, and phosphate tetrahedra, are heavily disordered. Site disorder, leading to partial occupancy of all octahedral voids of the parent lipscombite/lazulite structure, as well as splitting of the metal positions is observed. According to Guinier photographs Ti III 4 Ti IV 27 O 24 (PO 4 ) 24 (a=7.418(2) A, b=21.933(6) A, c=12.948(7) A) is isotypic to the oxidephosphates M III 4 Ti IV 27 O 24 (PO 4 ) 24 (M III : Cr, Fe). The UV/vis spectrum of Cr 4 Ti 27 O 24 (PO 4 ) 24 reveals a rather small ligand-field splitting Δ o =14,370 cm -1 and a very low nephelauxetic ratio β=0.72 for the chromophores [Cr III O 6 ] within the dimers [Cr III Ti IV O 9 ]. - Graphical abstract: Single crystals of the oxidephosphates Ti III Ti IV 3 O 3 (PO 4 ) 3 (black), Cr III 4 Ti IV 27 O 24 (PO 4 ) 24 (red-brown, transparent), and Fe III 4 Ti IV 27 O 24 (PO 4 ) 24 (brown) with edge-lengths up to 0.3 mm were grown by chemical vapour transport. The crystal structures of these orthorhombic members of the lazulite/lipscombite structure family were refined from single-crystal data

  5. Venemaa ja Valgevene hiiglaslikud spordikompleksid projekteeritakse Eestis / Signe Kalberg

    Index Scriptorium Estoniae

    Kalberg, Signe, 1959-

    2009-01-01

    Projekteerimisfirmast Ideab Project Eesti AS, firma suurprojektidest Valgevenes ja Venemaal. 2009. a. on sõlmitud lepingud energiasäästlike majade ehitamiseks Valgevenesse ja Sotši olümpiamängudeks laskesuusatamise kompleksi projekteerimiseks. Moskva kunstlumega suusalaskumisrajast, Norilski spordikompleksist jm.

  6. Sotsiaalne ilma shokita / Harry Liivrand

    Index Scriptorium Estoniae

    Liivrand, Harry, 1961-

    2007-01-01

    52. Veneetsia biennaalist, üldkuraator Robert Storr. Näitusest "Think with the Senses - Feel with the Mind" Arsenale kompleksis ning Itaalia paviljonis Giardini pargis. Aafrika kunsti ekspositsioonist. Biennaali peaauhinna Kuldse Lõvi pälvis mali fotograaf Malick Sidibe. Loetletud osavõtjaid

  7. Mustamäe haigla juurdeehitus läheb maksma 400 miljonit krooni / Aleksei Günter

    Index Scriptorium Estoniae

    Günter, Aleksei, 1979-

    2005-01-01

    Põhja-Eesti Regionaalhaigla koondab kõik oma raviteenused Mustamäe haiglasse ja ehitab selleks praeguse kompleksi juurde lisakorpuse. Uus korpus läheb maksma ligi 400 miljoni krooni, millest 170 miljonit saadakse Euroopa Liidu struktuurifondidest. Lisa: Uus korpus. Skeem

  8. Vaba aja keskus Tasku = Tasku centre

    Index Scriptorium Estoniae

    2009-01-01

    Tasku kompleksi Tartus Turu t. 2 projekteeris Arhitektuuribüroo Kalle Rõõmus. Tasku kaubandus- ja konverentsikeskuse sisekujundusest. Sisearhitektid Argo Vaikla, Katrin Vaikla, Mari-Liis Süld ja Liis Tarbe. Sisearhitektide tähtsamate tööde loetelu

  9. Biohuumus - looduslik, kuid tõhus lahendus mullaviljakuse tõstmiseks / Nadezda Knjazeva

    Index Scriptorium Estoniae

    Knjazeva, Nadezda

    2010-01-01

    Biohuumus "Green-PIK" on orgaaniliste jääkide tehnoloogiliste vihmaussidega "Staratel" ümbertöötlemise produkt. See kontsentreeritud väetis sisaldab tasakaalustatud kombinatsioonis tervet kompleksi vajalikke toitaineid ja mikroelemente, fermente, pinnasantibiootikume, vitamiine, taimede kasvu ja arengu hormoone. Väetamine muutub efektiivsemaks biohuumuse ja vedela kontsentraadi Gumistar "Grin-PIK" kompleksse kasutamise korral

  10. Hotell Bernhard, šveitsi miraaž Nuustakul / Anneliis Aunapuu

    Index Scriptorium Estoniae

    Aunapuu, Anneliis

    1998-01-01

    Hotell 'Bernhard' Otepääl. Arhitekt Andres Lunge, sisearhitekt Taisi Kadarik. Kompleksi läbib erksinise ja telliskivikarva värvikontrast, millele lisandub hall. Kogu hoones vahelduvad eurolikud güprokpinnad krobelistega ja annavad teed klaasile, pakkudes suurepärast vaadet. Hotellis on terrassile avanev restoran ning suure basseini ja saun

  11. Iskopajemõje tshlenistonogije v pomoshtsh japontsam / Kirill Smirnov

    Index Scriptorium Estoniae

    Smirnov, Kirill

    2008-01-01

    Eesti suurim põlevkivitöötleja AS Viru Keemia Grupp plaanib avada Ukrainas põlevkivi ümbertöötlemise kompleksi ja saada arvestatavaks ettevõtteks juuksevärvikomponentide tootmises. Kommenteerivad: Enno Reinsalu, Jaanus Purga ja Janek Parkman. Vt. samas: Viru Keemia Grupp

  12. Kuhu lähed, Kultuurikatel? / Thuur Caris, Renger Koning, Arne Lösekann ; interv. Katrin Koov, Regina Viljasaar

    Index Scriptorium Estoniae

    Caris, Thuur

    2008-01-01

    Endise Tallinna soojuselektrijaama kompleksis asuva Kultuurikatla ruumide võimalusi uuriv workshop, korraldajaks MTÜ Kultuurikatel koos Kavakava arhitektide Siiri Vallneri ja Katrin Kooviga. Hollandi meediakunstnik Thuur Caris ja helilooja ning helidisainer Renger Koning tutvustavad Groningeni Pudingivabrikut. Saksa arhitekt ja kunstnik Arne Lösekann tutvustab Kubasta kunstikeskust Hamburgis

  13. Synthesis and Isolation of the Titanium-Scandium Endohedral Fullerenes-Sc2 TiC@Ih -C80 , Sc2 TiC@D5h -C80 and Sc2 TiC2 @Ih -C80 : Metal Size Tuning of the Ti(IV) /Ti(III) Redox Potentials.

    Science.gov (United States)

    Junghans, Katrin; Ghiassi, Kamran B; Samoylova, Nataliya A; Deng, Qingming; Rosenkranz, Marco; Olmstead, Marilyn M; Balch, Alan L; Popov, Alexey A

    2016-09-05

    The formation of endohedral metallofullerenes (EMFs) in an electric arc is reported for the mixed-metal Sc-Ti system utilizing methane as a reactive gas. Comparison of these results with those from the Sc/CH4 and Ti/CH4 systems as well as syntheses without methane revealed a strong mutual influence of all key components on the product distribution. Whereas a methane atmosphere alone suppresses the formation of empty cage fullerenes, the Ti/CH4 system forms mainly empty cage fullerenes. In contrast, the main fullerene products in the Sc/CH4 system are Sc4 C2 @C80 (the most abundant EMF from this synthesis), Sc3 C2 @C80 , isomers of Sc2 C2 @C82 , and the family Sc2 C2 n (2 n=74, 76, 82, 86, 90, etc.), as well as Sc3 CH@C80 . The Sc-Ti/CH4 system produces the mixed-metal Sc2 TiC@C2 n (2 n=68, 78, 80) and Sc2 TiC2 @C2 n (2 n=80) clusterfullerene families. The molecular structures of the new, transition-metal-containing endohedral fullerenes, Sc2 TiC@Ih -C80 , Sc2 TiC@D5h -C80 , and Sc2 TiC2 @Ih -C80 , were characterized by NMR spectroscopy. The structure of Sc2 TiC@Ih -C80 was also determined by single-crystal X-ray diffraction, which demonstrated the presence of a short Ti=C double bond. Both Sc2 TiC- and Sc2 TiC2 -containing clusterfullerenes have Ti-localized LUMOs. Encapsulation of the redox-active Ti ion inside the fullerene cage enables analysis of the cluster-cage strain in the endohedral fullerenes through electrochemical measurements. © 2016 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

  14. Phase Content and Equilibrium Relationships in Ternary Systems MOx/VO2,5/PO2,5 (M = TiIV, ZrIV, NbV; x = 2 or 2,5) with Additions for Four-Component System Ti/Cr/P/O

    International Nuclear Information System (INIS)

    Titlbach, Sven

    2014-01-01

    In the systems TiO 2 / V 2 O 5 / P 2 O 5 , ZrO 2 / V 2 O 5 / P 2 O 5 and Nb 2 O 5 / V 2 O 5 / P 2 O 5 studies on phase composition and the equilibrium relations were performed in the context of the heterogeneously catalyzed gas-phase oxidation of n-butane to maleic anhydride. Here is a selection of the research findings: in the system TiO 2 / V 2 O 5 / P 2 O 5 the hitherto unknown orthophosphate (VO)Ti 6 (PO 4 ) 9 and the mixed crystal series Ti(P 1-x V x ) 2 O 7 (0 ≤ x ≤ 0,24; 0,30 ≤ x ≤ 0,43) with miscibility gap was detected. In the quasi-ternary system ZrO 2 / V 2 O 5 / P 2 O 5 the literature well described gapless solid solution Zr(P 1-x V x ) 2 O 7 was confirmed and investigated radiographically and by NMR spectroscopy. In the system Nb 2 O 5 / V 2 O 5 / P 2 O 5 the mixed crystal series Nb 1-x V x O(PO 4 ) (0 ≤ x ≤ 0,36), P 1-x V x Nb 9 O 25 (0 ≤ x ≤ 1) and NbOP 1-x V x O 4 (0 ≤ x ≤ 0,20) were found.

  15. SÄSI : kes on parim? / Karin Paulus

    Index Scriptorium Estoniae

    Paulus, Karin, 1975-

    2005-01-01

    Eesti parima noore disaineri auhinna SÄSI näitusest Eesti Kunstiakadeemia galeriis. Eksponeeritakse nominentide Anneli Tammiku, Monika Järgi, Riho Tiiveli, Sixten Heidmetsa, Igor Volkovi ja Björn Koopi töid

  16. Chemical nature of implant-derived titanium(IV) ions in synovial fluid

    International Nuclear Information System (INIS)

    Silwood, Christopher J.L.; Grootveld, Martin

    2005-01-01

    Previous investigations have indicated a deleterious leakage of Ti(III) and/or Ti(IV) species from Ti-Al-V alloy joint prostheses into adjacent tissue, synovium or synovial fluid (SF) in vivo. In view of the importance of the particular chemical nature of such complexes in determining their biological activity, we have employed high field proton ( 1 H) NMR spectroscopy to 'speciate' Ti(IV) in inflammatory SF. Treatment of osteoarthritic SF samples with increasing concentrations of Ti(IV) (0.10-1.03 mM [TiO(C 2 O 4 ) 2 ] 2- ) gave rise to a specific broadening of the citrate proton resonances, indicating that this bioavailable oxygen-donor ligand plays an important role in complexing implant-derived Ti(IV). 1 H NMR analysis of Ti(IV)-loaded SF samples subsequently treated with a large excess of ascorbate (0.05 M) showed that this added Ti(IV) chelator was only poorly effective in removing this metal ion from Ti(IV)-citrate/Ti(IV)-oxycitrate complexes. The results obtained here provide evidence for complexation of the low-molecular-mass (non-protein-bound) fraction of implant-derived Ti(IV) by citrate in vivo

  17. Simple and rapid spectrophotometric determination of trace titanium (IV) enriched by nanometer size zirconium dioxide in natural water

    International Nuclear Information System (INIS)

    Zheng Fengying; Li Shunxing; Lin Luxiu; Cheng Liqing

    2009-01-01

    A novel method for preconcentration of Ti(IV) with nanometer size ZrO 2 and determination by spectrophotometry has been developed. Ti(IV) was selectively adsorbed on 300 mg ZrO 2 from 500 mL solution at pH 6.0, then eluted by 5 mL 11.3 mol L -1 HF. The eluent added was diantipyrylmethane (DAPM, as chromogenic reagent) and ascorbic acid (as masking agent), used for the analysis of Ti(IV) by measuring the absorbance at 390 nm with spectrophotometry, based on the chromogenic reaction between the Ti(IV) and DAPM. This method gave a concentration enhancement of 100 for 500 mL sample, eliminated the sizable interferences on direct determination with spectrophotometry. Detection limit (3σ, n = 11) of 0.1 μg L -1 was obtained. The method was applied to determine the concentration of Ti(IV) in river water and seawater and the analytical recoveries of Ti(IV) added to samples were 97.6-101.3%.

  18. Electrochemistry of TiF4 in 1-butyl-2,3-dimethylimidazolium tetrafluoroborate

    International Nuclear Information System (INIS)

    Andriyko, Yuriy; Andriiko, Alexander; Babushkina, Olga B.; Nauer, Gerhard E.

    2010-01-01

    Electrochemical behaviour of Ti(IV) species in the ionic liquid (IL) 1-butyl-2,3-dimethylimidazolium tetrafluoroborate (BMMImBF 4 ) was studied by means of chronopotentiometry (CP) and cyclic voltammetry (CV) in melts with different concentrations of TiF 4 (2-35 mol%) within a temperature range of 65-180 deg. C. The electrochemical reduction of Ti(IV) was suggested to proceed via the sequence of one-electron steps with the formation of poorly soluble low valence intermediates (LVI). LVIs undergo further solid-state electrochemical reduction to Ti metal. Thin Ti coatings on a Pt substrate were thus obtained and characterized by ESEM method. FTIR spectroscopy was used for identification of the electrochemical active species of Ti(IV). The reaction 2BF 4 - + TiF 4 ↔ TiF 6 2- + 2BF 3 ↑ takes place in the concentrated solutions of TiF 4 at elevated temperatures.

  19. Archaeological excavations at a bronze age grave and a 6th - 10 th century cult site at Aunamägi in Tõnija-Põlluküla village, southern Saaremaa / Marika Mägi, Raili Allmäe, Riina Riiel ... [jt.

    Index Scriptorium Estoniae

    2015-01-01

    Kaevamised Saunamäel korraldati Tallinna Ülikooli üliõpilaste seminarkaevamistena. Kogu kaevamiste ala moodustas umbes 170 m2. Märkimisväärne Tuulingumäe ja Saunamäe kompleksi juures on see, et need olid mõeldud suhteliselt piiratud hulgale. Sellised väikesed pühapaigad viitavad rituaalidele, mida sooritasid üksikud valitud isikud. Kõik artiklis mainitud kultusekohad jäävad Läänemere põhjaosa rannikualadele, kus eelviikingiajal kujunes ühine kultuurisfäär

  20. Współczesna architektura wieżowców w stolicy Kataru – Dausze

    OpenAIRE

    Jerzy Szołomicki; Hanna Golasz-Szołomicka

    2017-01-01

    W artykule przedstawiono elementy analizy architektonicznej i konstrukcyjnej wybranych wieżowców ze stolicy Kataru Dohy zlokalizowanych w dzielnicy biznesowej West Bay oraz w kompleksie sportowym Aspire Zone. Analizując architekturę Dohy można stwierdzić, że obecnie jest to bardzo szybko rozwijająca się metropolia, która jest uznawana wraz z Dubajem za najbardziej zaawansowane technologicznie miasto świata w kategorii budynków inteligentnych. Koniunktura budowlana i rozwój konstrukcyjny spowo...

  1. Extractive properties of benzohydroxamic and N-benzoyl-benzohydroxamic acids as analytical reagents towards six transition metal ions

    International Nuclear Information System (INIS)

    Mohamed, Mohamed Rafie Hamid

    1999-06-01

    Two hydroxamic acids were prepared: benzohydroxamic and N-benzoyl benzohydroxamic acids. The former was prepared by coupling the free hydrox amine with benzoyl chloride with the ratio 1:1 in alkaline medium, where as the latter by the same procedure with the ratio 1:2 respectively, they were identified by their melting points, elemental analysis of their nitrogen contents. infra-red spectrophotometry, as well as their nitrogen using elevation of boiling point and the titration method to determine their molecular weights. The two hydroxamic acids were used as analytical reagents for the extraction of the metals Cr(vi), Fe(III), Ti(iv), Co(II) and U(vi). Benzohydroxamic acid has a maximum extraction 99.55% for Cr.(vi) 3M H 2 SO 4 , of 90.16% for Ti(iv) at pH 2.0,of 80.56% for Co(II) at pH 8.0 and 98.01% for U(vi) at pH 6.0. N-benzoyl benzohydroxamic acid has a maximum extraction of 96.45% for Cr(vi) at 3M H 2 So 4 , of 90.82% for Fe(III) at pH 4.0, of 97.02% for V(v) at 3M H 2 So 4 , of 83.56% for Ti(iv) at pH 2.0, of 89.82% for Co(II) at pH 8.0 and of 97.16% for U(vi) at pH 6.0. at the same pH of maximum extraction using heavy matrix, synthetic sea-water, benzohydroxamic acid has maximum values of 91.08%, of 77.99%, of 91.39%, of 87.50 and of 93.17% for Cr(vi), Fe(III), V(v), Ti(iv), Co9II) and U(vi) respectively whereas n-benzoyl benzohydroxamic acid has maximum values of 86.17%, of 77.78%, of 89.61%, of 75.66%, of 79.63% and of 91.18% for Cr(vi), Fe(III), V(v), Ti(iv), Co(II) and U(vi) respectively. The ratio of metal to ligand was determined utilizing the continuous variation method. It was 1 :2, 1: 1, 1 : 1, 1 : 2, 1: 2 and 1 : 2 with respect to Cr(vi), fe(III), Ti(iv), Co(II) and U(vi) respectively.(Author)

  2. Voltammetric determination of zirconium using azo compounds

    International Nuclear Information System (INIS)

    Orshulyak, O.O.; Levitskaya, G.D.

    2008-01-01

    The optimum conditions for zirconium complexation with azo compounds are found. The applicability of Eriochrome Red B, Calcon, and Calcion to the voltammetric determination of zirconium, total Zr(IV) and Hf(IV), and Zr(IV) in the presence of Zn(II), Cu(II), Cd(II), Ni(II), or Ti(IV) is demonstrated. The developed procedures are used to determine zirconium in a terbium alloy and in an alloy for airplane wheel drums [ru

  3. Spectral manifestation of substitution of out-of-plane ligands in metallophtalocyanines

    Directory of Open Access Journals (Sweden)

    Starukhin A.

    2017-01-01

    Full Text Available In our study, we demonstrate the splitting effect of long-wavelength bands in absorption spectra (excitation of fluorescence of the series of Zn(II, Ti(IV, Zr(IV and Hf(IV phthalocyanines at low temperatures. The effect has been explained by the shift of metal ion out of the plane of phthalocyanine macrocycle, the transformation of macrocycle to nonplanar “dome” conformation and additional loss the high symmetry of macrocycle.

  4. Spectroscopic studies on Titanium ion binding to the apo lactoferrin

    International Nuclear Information System (INIS)

    Moshtaghie, A.A.; Ani, M.; Arabi, M.H.

    2006-01-01

    Titanium is a relatively abundant element that has found growing applications in medical science and recently some of Titanium compounds are introduced as anticancer drugs. In spite of very limited data which exist on the Titanium metabolism, some proteins might be involved in the mechanism of action of Titanium up to our knowledge, there is not any report in the literature concerning binding of Titanium to apo lactoferrin. Binding of apo lactoferrin with Ti(IV)-citrate was studied by spectroflourimeterey and spectrophotometery techniques under physiological conditions. The spectroflourimeteric studies revealed a significant fluorescence quenching, that indicated binding of apo lactoferrin with Ti(IV). The same reaction was monitored through spectrophotometry technique; this represents a characteristic UV difference band at 267 nm, which is different from lac-Fe (III). Titration studies how that lactoferrin specifically binds two moles Ti(IV) as complex with citrate per mol protein. Spectroflourimeterey and spectrophotometery techniques indicated that Ti(IV) ions cause a reduction (13%-14%) in binding of Fe(III) to lactoferrin. In overall, we may come to this conclusion that this element might be involved in the iron metabolism

  5. Electrochemistry of TiF{sub 4} in 1-butyl-2,3-dimethylimidazolium tetrafluoroborate

    Energy Technology Data Exchange (ETDEWEB)

    Andriyko, Yuriy, E-mail: yuriy.andriyko@cest.a [Centre of Electrochemical Surface Technology (CEST), Viktor Kaplan-Strasse 2, A-2700 Wiener Neustadt (Austria); Andriiko, Alexander [National Technical University of Ukraine ' Kyiv Polytechnic Institute' , Prospect Peremogy 37, 03057 Kyiv (Ukraine); Babushkina, Olga B. [Centre of Electrochemical Surface Technology (CEST), Viktor Kaplan-Strasse 2, A-2700 Wiener Neustadt (Austria); Nauer, Gerhard E. [Centre of Electrochemical Surface Technology (CEST), Viktor Kaplan-Strasse 2, A-2700 Wiener Neustadt (Austria); Vienna University, Faculty of Chemistry, Waehringer Strasse 42, A-1090 Wien (Austria)

    2010-01-01

    Electrochemical behaviour of Ti(IV) species in the ionic liquid (IL) 1-butyl-2,3-dimethylimidazolium tetrafluoroborate (BMMImBF{sub 4}) was studied by means of chronopotentiometry (CP) and cyclic voltammetry (CV) in melts with different concentrations of TiF{sub 4} (2-35 mol%) within a temperature range of 65-180 deg. C. The electrochemical reduction of Ti(IV) was suggested to proceed via the sequence of one-electron steps with the formation of poorly soluble low valence intermediates (LVI). LVIs undergo further solid-state electrochemical reduction to Ti metal. Thin Ti coatings on a Pt substrate were thus obtained and characterized by ESEM method. FTIR spectroscopy was used for identification of the electrochemical active species of Ti(IV). The reaction 2BF{sub 4}{sup -} + TiF{sub 4} reversible TiF{sub 6}{sup 2-} + 2BF{sub 3}arrow up takes place in the concentrated solutions of TiF{sub 4} at elevated temperatures.

  6. RNA İNTERFERANS (RNAİ)

    OpenAIRE

    GÜNDOĞDU, Ramazan; ÇELİK, Venhar

    2009-01-01

    RNA interferans, uygun çift zincirli RNA’nın hücreye girdiği zaman, endojenik komplementer mRNA dizisinin parçalanmasına yol açan, transkripsiyon sonrası gen susturma mekanizmasıdır. RNA interferans, Dicer adı verilen bir RNase III enzimi tarafından çift zincirli RNA’nın küçük engelleyici RNA’lara (siRNA) kesilmesi ile başlamaktadır. Bu siRNA’lar daha sonra, bir multiprotein-RNA nükleaz kompleksi olan, RNA- indükleyici baskılama kompleksine (RISC) bağlanır. RISC, siRNA’ları komplementer mRNA’...

  7. Tarptautinis jūrų teisės tribunolas

    OpenAIRE

    Duobienė, Justina

    2013-01-01

    Tarptautinis jūrų teisės tribunolas- įsteigtas 1982 m. Jungtinių Tautų jūrų teisės konvencijos ir yra joje įtvirtinto kompleksiško ginčų sprendimų mechanizmo dalis. Naujos teisminės institucijos atsiradimo tarptautinėje teisėje poreikis analizuojamas pirmajame šio darbo skyriuje, kartu aptariant Tribunolo sudėtį ir struktūrą. Antrajame skyriuje nustatomos Tribunolo kompetencijos ribos. Aptariama Konvencijos privalomųjų ginčų sprendimo procedūrų pasirinkimo laisvė ir valstybių pareiškimų pa...

  8. Many-electron electrochemical processes. Reactions in molten salts, room-temperature ionic liquids and ionic solutions

    Energy Technology Data Exchange (ETDEWEB)

    Andriiko, Aleksandr A. [National Technical Univ. Ukraine, Kyiv (Ukraine). Kyiv Polytechnic Inst.; Andriyko, Yuriy O. [CEST Centre of Electrochemical Surface Technology, Wiener Neustadt (Austria); Nauer, Gerhard E. [Vienna Univ. (Austria). Inst. of Physical Chemistry

    2013-02-01

    The authors provide a unified concept for understanding multi-electron processes in electrochemical systems such as molten salts, ionic liquids, or ionic solutions. A major advantage of this concept is its independence of assumptions like one-step many-electron transfers or 'discrete' discharge of complex species. This book contains the following main topics: 1. Many-electron electrochemical systems: Concepts and definitions. 2. Many-electron systems at equilibrium. 3. Phenomenology of electrochemical kinetics. 4. Electrode film systems: experimental evidences. 5. Dynamics of a non-equilibrium electrochemical system. 6. Electrochemistry of Ti(IV) in ionic liquids.

  9. Synthesis and spectroscopic studies of mono- and dicyclopentadienyl titanium (IV)/zirconium (IV) derivatives with S-alkyl-β-N-(acetylferrocenyl) methylene dithiocarbazates

    International Nuclear Information System (INIS)

    Srivastava, B.K.; Srivastava, S.K.; Pandey, O.P.; Sengupta, S.K.

    1996-01-01

    The reactions of dicyclopentadienyl titanium (IV)/zirconium (IV) dichloride and monocyclopentadienyl titanium (IV) trichloride with thio-Schiff bases (LH), derived by the condensation of S-methyl/ethyl/propyl dithiocarbazic acid and acetylferrocene have been carried out under inert atmosphere and anhydrous conditions in different stoichiometric ratios. Complexes of the types Cp 2 M(L)Cl, CpM(L) 2 Cl (M= Ti(IV) or Zr(IV)), CpTi(L)Cl 2 , CpTi(L) 2 Cl are synthesised and characterized by elemental analysis, electrical conductance, magnetic moment and spectral (electronic, infrared, 1 H NMR) data. (author). 12 refs., 1 tab

  10. Eesti disaini uudised / Kai Lobjakas

    Index Scriptorium Estoniae

    Lobjakas, Kai, 1975-

    2006-01-01

    Eesti Kunstiakadeemia üliõpilaste Kadri Kruus-Laurimaa kott-jope, Riho Tiiveli lusikas "Spoon container" ja Ülle Jehe sisustuspadjad "Roll it!" valiti Prantsusmaal toimunud rahvusvahelisel kunsti-ja disainikõrgkoolide võrgustiku CUMULUS konkursil "European Ways of Life" nominentide hulka. EKA sisearhitektuuri eriala üliõpilaste toolide hindamisest. Mari Adamsoni nimelise noore tekstiilikunstniku preemia pälvis Kadri Klampe. Eesti Ajaloomuuseumis Maarjamäe lossis avatud moenäitusest "Paula, sul on poisipea!", mille koostas Helle Avila, konsulteeris Anu Ojavee, kujundasid Krista Lepland ja Malle Jürgenson büroost Laika, Belka ja Strelka

  11. Direct and indirect methods for the determination of vitamin K3 using differential pulse polarography and application to pharmaceuticals.

    Science.gov (United States)

    Somer, Güler; Doğan, Mehmet

    2008-11-01

    Two methods for the determination of vitamin K(3) have been developed. Vitamin K(3) in its oxidized form is determined by direct and indirect methods. Its standard solution was prepared by the indirect method using Ti(III) as reducing agent. For this purpose vitamin K(3) (menadion) in a clinical injection solution, which is in its hydroquinone form in the presence of sulfite, is oxidized with oxygen. In 0.2 M HAc and 0.02 M HCl electrolyte vitamin K(3) and Ti(IV) have reduction peaks at -0.58 V at -0.82 V respectively. The reaction between Ti(III) and vitamin takes place quantitatively in a medium of 0.2 M HAc and 0.002 M HCl. After the reduction, the reaction product Ti(IV) is followed from its polarographic peak at about -0.82 V. The most important result in this work is that, with this method vitamin K(3) can be standardized and after standardization this solution can be used for the direct determination in routine analysis with a very simple and fast method, using only the peak at -0.71 V in 0.2 M HAc medium. Both direct and indirect methods have been used for the determination of Vitamin K(3) in a clinical injection solution. The limit of quantification (LOQ) was 1.5x10(-6) M and in both methods the detection limit found was 7x10(-7) M.

  12. Solvent extraction of titanium (IV) from sulphuric acid media by cyanex 921 and tri-butylphosphate

    International Nuclear Information System (INIS)

    Nayl, A.A.; Aly, H.F.

    2009-01-01

    titanium and its compounds found different useful applications in the nuclear and radioactive waste treatment fields. extraction behavior of titanium (IV) from sulfuric acid by commercial tri-octylphosphine oxide (CYANEX 921) and tributylphosphate (TBP)has been investigated. effects of contact time, sulfuric acid concentration in the aqueous phase, the extractants concentration in the organic phase, and the temperature on the extraction of titanium by the two systems were studied. it is found that extraction equilibrium of titanium is reached after 10-15 min and 4 min for CYANEX 921 and TBP, respectively . the extraction of Ti(IV) by 0.15 M CYANEX 921 in kerosene increases with the increase in sulfuric acid concentration to reach a maximum extraction of 91% at 7.0 m acid concentration. for the TBP system, the maximum extraction of titanium was 79% using 1.0 M TBP in kerosene from 4.0 m H 2 SO 4 solution . the effect of temperature was also evaluated. Na 2 CO 3 was used as a good stripping agent compared with other reagents. the interaction of Ti(IV) in sulfate medium and different sulfate species in sulfuric acid are reviewed. within the literature survey together with analysis of the extraction results , it can be concluded that titanium extracted by CYANEX 921 as Ti O (HSO 4 ) 2 .2 CYANEX 921 whereby in case of TBP, the extracted species is TiOSO 4 .2 TBP

  13. Selective complexometric determination of titanium(IV) using sodium potassium tartrate or ascorbic acid as masking agent

    International Nuclear Information System (INIS)

    Sreekumar, N.V.; Bhat, N.G.; Narayana, B.; Nazareth, R.A.; Hegde, P.; Manjunatha, B.R.

    2003-01-01

    A simple, rapid and accurate complexometric method is proposed for the determination of titanium(IV) where sodium potassium tartrate or ascorbic acid were used as masking agents. In the presence of diverse metal ions, titanium is first complexed with excess of EDTA and surplus EDTA is then titrated at pH 5-6 with zinc sulfate, xylenol orange being used as indicator. An excess of 5 % aqueous sodium potassium tartrate is then added to displace the complexed EDTA from the Ti-EDTA complex quantitatively, which is titrated with zinc sulfate. Also, ascorbic acid may be used as the releasing agent. The methods work well in the range 1-53 mg of Ti(IV) for sodium potassium tartrate with relative errors ± 0.28 % and standard deviations 0.16 mg. For ascorbic acid the range is 1.00-30.00 mg of Ti(IV) with relative errors of ± 0.40 % and standard deviations of 0.05 mg. (author)

  14. Structure of titanium-doped goethite rust

    International Nuclear Information System (INIS)

    Nakayama, Takenori; Ishikawa, Tatsuo; Konno, Toyohiko J.

    2005-01-01

    To investigate the influence of titanium addition on the formation and structure of goethite (α-FeOOH) rust which is one of main corrosion products of weathering steel, the artificially synthesized α-FeOOH rusts were prepared by hydrolysis of aqueous solutions of Fe(III) containing Ti(IV) at different atomic ratios (Ti/Fe) in the range 0-0.1. The obtained rusts particles were observed by TEM. Characterization by XRD, N 2 absorption, Moessbauer spectroscopy was also done. TEM observation revealed that the α-FeOOH rust particle size increased with the increase of Ti/Fe, and that Ti-enriched poorly crystalline particles were formed around the rust particles. XRD confirmed that the crystallite size increased with the increase of Ti/Fe, while the XRD peaks decreased in intensity. Specific surface area obtained by N 2 absorption increased with the increase of Ti/Fe. It is deduced from the obtained results that the addition of Ti(IV) increases the crystallite size of α-FeOOH, and produces double domain particles consisting of the particle core and a porous poorly crystalline shell. It is thought that such unique rust structure produced by titanium addition contributes to the protective properties of rust layer of the weathering steel

  15. Współczesna architektura wieżowców w stolicy Kataru – Dausze

    Directory of Open Access Journals (Sweden)

    Jerzy Szołomicki

    2017-12-01

    Full Text Available W artykule przedstawiono elementy analizy architektonicznej i konstrukcyjnej wybranych wieżowców ze stolicy Kataru Dohy zlokalizowanych w dzielnicy biznesowej West Bay oraz w kompleksie sportowym Aspire Zone. Analizując architekturę Dohy można stwierdzić, że obecnie jest to bardzo szybko rozwijająca się metropolia, która jest uznawana wraz z Dubajem za najbardziej zaawansowane technologicznie miasto świata w kategorii budynków inteligentnych. Koniunktura budowlana i rozwój konstrukcyjny spowodowały wznoszenie ikonicznych wieżowców, obiektów widowiskowo-sportowych oraz muzeów. W pierwszej części artykułu zwrócono uwagę na to jak w ciągu kilkunastu lat Doha dołączyła do najciekawszych architektonicznie miast świata ze względu na gwałtowny rozwój gospodarczy wynikający ze znalezienia ogromnych złóż ropy naftowej i gazu ziemnego. Punktem zwrotnym była organizacja XV Igrzysk Azjatyckich w 2006 roku. W wyniku sukcesu ekonomicznego tych igrzysk ponad 100 budynków wysokich i wysokościowych było planowanych do budowy w dzielnicy biznesowej West Bay i przyległych dzielnicach. Oczywiście rozwój architektoniczny miasta nie mógłby się odbyć bez uczestnictwa w nim wybitnych zagranicznych architektów takich, jak na przykład Jean Nouvell, Ieoh Pei, czy Arata Isozaki. W drugiej części artykułu omówiono wieżowce w dzielnicy West Bay: Doha Tower, Al Bidda Tower, Tornado Tower oraz znajdującą się w kompleksie sportowym Aspire Tower. Budynki te stanowią obecnie znak rozpoznawczy Kataru na całym świecie.

  16. The Use of Copper- 64 in the Investigation of Reaction Mechanisms of Enzymes, Particularly as Related to Food Processing; Emploi de Cuivre-64 dans l'Etude des Mecanismes de Reaction des Enzymes, Notamment en Ce Qui Concerne la Preparation des Denrees Alimentaires; ПРИМЕНЕНИЕ МЕДИ-64 ДЛЯ ИССЛЕДОВАНИЯ МЕХАНИЗМОВ ФЕРМЕНТАТИВНЫХ РЕАКЦИЙ, СВЯЗАННЫХ С ОБРАБОТКОЙ ПИЛИ; Empleo de Cobre-64 en el Estudio de los Mecanismos de Reacciones Enzima Ticas de Interes para la Elaboracion de Alimentos

    Energy Technology Data Exchange (ETDEWEB)

    Arthur, Jr., J. C.; McLemore, T. A. [Southern Regional Research Laboratory, New Orleans, LA (United States)

    1963-03-15

    complejos del tipo Cu-p-quinona. Al afladir el ion a una solucion oxidante despues de iniciada la polimerizacion de los productos de reaccion del tipo o-quinona disminuyo la cantidad de ion cuprico complejado. La memoria examina matematicamente la cinetica del intercambio y de los procesos en virtud de los cuales se forman los complejos del ion cuprico con la enzima, asi como con los productos de reaccion. (author) [Russian] Okislitel'nye fermenty rastitel'nyh tkanej chasto ne aktivny ili lish' slabo aktivny v stadii pokoja, stanovjas' aktivnymi pri povrezhdenii tkanej ili pri otdelenii ot nee. pri obrabotke pishhi jeto privodit k uskoreniju okislenija estestvennyh substratov i polimerizacii produktov, chto menjaet cvet tkani. Katalizatorami jetih reakcij v osnovnom javljajutsja mednye oksidajen. Aktivacija fermenta vedet k ego reakcii inaktivacii. Odnoj ije prichin fenomena reakcii inaktivacii javljaetsja snizhenie jeffektivnoj koncentracii fermentov, vozmozhno, za schet udalenija ili svjazyvanija ego metallosoderzhashhej prosteticheskoj gruppy med'ju. S pomoshh'ju medi-64 in vitro, bylo pokazano, chto v pokojashhemsja rastvore ion dvuhvalentnoj medi mozhet obrazovyvat' kompleksy ili ob- yenivat'sja s med' fermenta, i chto v okisljajushhihsja rast.vorah dobavochnye kolichestva iona dvuhvalentnoj medi mogut obrazovyvat' kompleksy. Kompleksy medno-orto-hinonovogo tipa imejut bolee vysokuju konstantu obrazovanija, chem kompleksy medno-paro-hinonovogo tipa. Kolichestvo komplekse- obrazujushhego iona dvuhvalentnoj medi umen'shalos', esli ion dobavljalsja k okisljajushhemusja rastvoru posle nachala polimerizacii produktov reakcii orto-hinonovogo tipa. Obsuzhdaetsja s matematicheskoj tochki zrenija kinetiki processov obmena i kompleksoobrazovanija dlja ionov dvuhvalentnoj medi s fermentom i produkty reakcii. (author)

  17. Uus Eesti disain / Silvia Pärmann

    Index Scriptorium Estoniae

    Pärmann, Silvia

    2016-01-01

    Allan Prooso, Argo Männiku ja Kalmer Alliku (HOOG) disainitud riiulid. Liis Lindmaa ja Anatoli Tafitšuki disainitud kassimaja Juno. Anni Varmi puidust lõikelauad, Toivo Raidmetsa tool Arike, Maria Kalmu vineerist prossid, Jaanus Orgusaare kapp Rolling. Merili Sule ja Petrica Artene (StenCilit) disainitud seinašabloonid. Merlin Tiiveli (NION design) käsitsi valmistatud sisustuaksessuaarid (korvid, vaibad, kott-toolid). Margus Triibmanni toolvalgusti Cranberry, Stella Soomlaisi naturaalsest nahast käekotid. Kristjan Rabi, Janno Roodi, Veljo Viikanti (Aegaon) disainitud käekellad. Mari Saani, Mariana Laane (stuudio Nüüd) keraamika. Silver Tibbingi pakendikujundused Sõsara kosmeetikatoodetele, Elena Volki ja Eveliis Salaka Helge Kodu ruumiparfüümid. Kerly Kaljuste ja Anu Rajamäe (KOOSdisain) kodutekstiilid. Meelis Undi ja Mari Otsa (WolfBerry) lastemööbel

  18. Separation of some metal ions using coupled transport supported liquid membranes

    International Nuclear Information System (INIS)

    Chaudhary, M.A.

    1993-01-01

    Liquid membrane extraction processes has become very popular due to their superiority in many ways over other separation techniques. In coupled transport membranes the metal ions can be transported across the membrane against their concentration gradient under the influence of chemical potential difference. Liquid membranes consisting of a carrier-cum-diluent, supported in microporous polymeric hydrophobic films have been studied for transport of metal ions like U(VI), Cr(VI), Be(II), V(V), Ti(IV), Zn(II), Cd(II), Hf(IV), W(VI), and Co(II). The present paper presents basic data with respect to flux and permeabilities of these metal ions across membranes based on experimental results and theoretical equations, using different carriers and diluents and provides a brief reference to possibility of such membranes for large scale applications. (author)

  19. Bis(μ-2-hydroxymethyl-2-methylpropane-1,3-diolatobis[dichloridotitanium(IV] diethyl ether disolvate

    Directory of Open Access Journals (Sweden)

    Joyce M. Waters

    2013-12-01

    Full Text Available The title complex, [Ti2Cl4{CH3C(CH2O2(CH2OH}2], lies across a centre of symmetry with a diethyl ether solvent molecule hydrogen bonded to the –CH2OH groups on either side of it. The TiIV atom is coordinated in a distorted octahedral geometry by a tripodal ligand and two terminal chloride atoms. There are three coordination modes for the tripodal ligand distinguishable on the basis of their very different Ti—O bond lengths. For the terminal alkoxo ligand, the Ti—O distance is 1.760 (1 Å, the asymmetric bridge system has Ti—O bond lengths of 1.911 (1 and 2.048 (1 Å. The Ti—O bond length for the alcohol O atom is the longest at 2.148 (1 Å.

  20. Catalytic formal [2+2+1] synthesis of pyrroles from alkynes and diazenes via Ti(II)/Ti(IV) redox catalysis.

    Science.gov (United States)

    Gilbert, Zachary W; Hue, Ryan J; Tonks, Ian A

    2016-01-01

    Pyrroles are structurally important heterocycles. However, the synthesis of polysubstituted pyrroles is often challenging. Here, we report a multicomponent, Ti-catalysed formal [2+2+1] reaction of alkynes and diazenes for the oxidative synthesis of penta- and trisubstituted pyrroles: a nitrenoid analogue to classical Pauson-Khand-type syntheses of cyclopentenones. Given the scarcity of early transition-metal redox catalysis, preliminary mechanistic studies are presented. Initial stoichiometric and kinetic studies indicate that the mechanism of this reaction proceeds through a formally Ti(II)/Ti(IV) redox catalytic cycle, in which an azatitanacyclobutene intermediate, resulting from [2+2] alkyne + Ti imido coupling, undergoes a second alkyne insertion followed by reductive elimination to yield pyrrole and a Ti(II) species. The key component for catalytic turnover is the reoxidation of the Ti(II) species to a Ti(IV) imido via the disproportionation of an η(2)-diazene-Ti(II) complex.

  1. Metal Oxide Decomposition In Hydrothermal Alkaline Sodium Phosphate Solutions

    Energy Technology Data Exchange (ETDEWEB)

    S.E. Ziemniak

    2003-09-24

    Alkaline hydrothermal solutions of sodium orthophosphate (2.15 < Na/P < 2.75) are shown to decompose transition metal oxides into two families of sodium-metal ion-(hydroxy)phosphate compounds. Equilibria for these reactions are quantified by determining phosphate concentration-temperature thresholds for decomposition of five oxides in the series: Ti(IV), Cr(III), Fe(III, II), Ni(II) and Zn(II). By application of a computational chemistry method General Utility Lattice Program (GULP), it is demonstrated that the unique non-whole-number Na/P molar ratio of sodium ferric hydroxyphosphate is a consequence of its open-cage structure in which the H{sup +} and excess Na{sup +} ions are located.

  2. Asymmetric reduction of ketones with catecholborane using 2,6-BODOL complexes of titanium(IV) as catalysts.

    Science.gov (United States)

    Sarvary, I; Almqvist, F; Frejd, T

    2001-05-18

    Reductions performed with Ti(IV) complexes of ligands based on bicyclo[2.2.2]octane diols 5 and 6 are effective catalysts in the reduction of prochiral ketones to optically active alcohols, with catecholborane as the reducing agent. Methyl ketones are favored and enantiomeric excesses (ee) of octanone, which gave 2-octanol in 87% ee. Further details of the method were examined, for example, temperature, solvent composition, amount of molecular sieves (4 A), and catecholborane quality, as well as the sensitivity of the ligands towards acids. NMR spectroscopic methods were used to gain some insight into the complexes formed between the ligands and [Ti(OiPr)4]. A dimeric structure is proposed for the pre-catalyst.

  3. Determination of uranium (IV) by flow voltammetry

    International Nuclear Information System (INIS)

    Ding Anqing

    1987-01-01

    According to the quantitative reaction of U(IV) and Fe(III) in H 2 SO 4 as well as the relation between current and concentration of substance detected, U(IV) has been determined indirectly by measurement of the electrolysis current of residual Fe(III). The columniform electrode used is made of glass carbon particles. At the range of U(IV) from a few micrograms to 40 μg, the linear relation is excellent. The relative standard deviation is within ±4%. The interference of Fe(II), Ti(IV) and U(VI) is negligible but of Ti(III) is serious. This method has been successfully applied in the determination of actual samples (both out line and on line). Main advantages of this procedure are rapid, simple, small amount of sample (only at microgram level) and easy to realize automation, able to use for on line or process analysis

  4. Tailoring of transition metal alkoxides via complexation for the synthesis of hybrid organic-inorganic sols and gels

    International Nuclear Information System (INIS)

    Sanchez, C.; In, M.; Toledano, P.; Griesmar, P.

    1992-01-01

    This paper reports that the chemical control of hydrolysis-condensation reactions of transition metal alkoxides can be performed through the modification of the transition metal coordination sphere by using strong complexing ligands (SCL). Complexing organic groups can be bonded to the transition metal oxide network in two different ways, as network modifiers or network formers. Different illustrations of the role of complexing ligands on Ti(IV) and Zr(IV) alkoxides are presented. As a network modifier, SCL act as termination agents for condensation reactions allowing a control of particle growth. The complexing ligands being located at the periphery of the oxo core open many opportunities for colloid surface protection. SCL carrying organofunctional groups which exhibit non linear optical (NLO) properties have also been used as probes to study sol-gel transformations. SCL functionalized with organic polymerizable functions act as network formers

  5. Coordination compounds of titanium, zirconium, tin, thorium and uranium

    International Nuclear Information System (INIS)

    Deshpande, S.G.; Jain, S.C.

    1990-01-01

    Reactions of isatin, furoic acid and picolinic acid have been carried out with titanium tetrachloride, tin tetrachloride, thorium tetrachloride, zirconyl chloride and uranyl nitrate. While 2:3(metal:ligand) type compounds of isatin have been obtained with Ti(IV) and Sn(IV), zirconium(IV), thorium(IV), and uranium(VI) do not react with the ligand under similar experimental conditions. Furoic acid (FAH) and picolinic acid(PicH) form various chloro furoates and picolinates when reacted with TiCl 4 , ZrOCl 2 and ThCl 4 , but do not react with SnCl 4 . The various compounds synthesised have been characterised on the basis of elemental analysis, infrared studies, conductivity and thermogravimetric measurements. (author). 1 tab., 10 refs

  6. Separation of thorium and uranium by liquid-liquid extraction from mixed aqueous nitric acidic-methanolic solutions

    International Nuclear Information System (INIS)

    Schmid, E.R.; Kenndler, E.

    1976-01-01

    A method is described for the separation of Th and U from each other and from other elements, usually occuring in minerals, by liquid-liquid extraction with Aliquat Nitrate (tricaprylmethyl ammoniumnitrate, 6 vol%) in benzene from a mixed solution of 2.5 M HNO 3 and methanol (1:1 volume ratio). Permissible upper concentration ratios of interfering elements, such as Li, Na, K, Mg, Ca, Al, Cu, Co(II), Fe(III), Mn(II), Ti(IV), La(III), U(VI), Cl - , ClO 4 - , SO 4 2- , PO 4 3- , have been determined. Following the separation, Th has been determined by spectrophotometry using Thorin, and U by fluorometry. Results for yield under varying conditions, together with elemental concentrations in the ppm range for U and Th in minerals, are given. (B.T.)

  7. Kunstiakadeemia lõpetajad 2005 / Karin Paulus, Tanel Veenre, Tõnu Kaalep

    Index Scriptorium Estoniae

    Paulus, Karin, 1975-

    2005-01-01

    Valik Eesti Kunstiakadeemia bakalaureusetöid: Elize Hiiobi "Nimeta ehe", Anton Kooviti uued kirjatüübid, Raili Ilmsalu kipsskulptuur "Eva", Aleksei Aljoshini "Futuristlik spordirõivas", Merle Kasoneni töö "Võimalused", Leena Lüteri draakon "Isiklik kaitsja", Ave Maseri miniatuurid "Teised", Kärt Põldmani "Punased kingad", Riho Tiiveli vetelpäästesüsteem, Ester Kannelmäe rõivakollektsioon "Ahistab", töö "Eesti rahvalaulud", Helena Vaidla mosaiik "Veesilm", Merike Estna kineetiline maal "Punamütsike: I am the Prettiest Girl in the World", Eilve Mangluse käeobjektid, Annike Oldre maal "Üksi", Eliisa Ehini töö "Närviimpulsside liikumine ajus", Veiko Vaine terrassitool "Miinimum"

  8. The separation of trace elements in manganese dioxide

    International Nuclear Information System (INIS)

    Jones, E.A.; Dixon, K.

    1981-01-01

    Separations from manganese are discribed for (a)Al(III), Mo(VI), V(V), and Ti(IV), and (b)trace elements in general. In the first separation, a combined anion-cation exchange, the oxalate complexes are absorbed onto the anionic BIO.RAD 1-X8 resin. V(V) and Al(III) are then eluted into a cation-exchange column from which they are eluted successively, Mo(VI) and Ti(IV) then being eluted from the anionic resin. In the second separation, up to 2g of manganese is absorbed onto BIO.RAD AG 50W-X8 resin, from which V(V) is eluted with dilute hydrochloric acid prior to the elution of Co(II), Cu(II), Zn(II), Cd(II), Fe(III), As(III), Sb(III), Mo(VI), W(VI), and Sn(II) with a mixture of 1 M hydrochloric acid, 80 per cent acetone, and 0,1 per cent hydrogen peroxide. Mn(11) is eluted next with a mixture of 0,75M hydrochloric acid and 90 per cent acetone, after which the remaining cations are eluted with 4M hydrochloric acid. Satisfactory recoveries ranging from 0,8 to 60 mg/l were obtained for 18 of the 21 elements tested. After concentration by evaporation, final measurements were made by the use of atomic-absorption spectrophotometry, or direct-reading spectrometry with excitation from an inductively coupled plasma source. Comparative results were obtained with atomic-absorption procedures where the manganese was not separated. However, the separation procedure can reduce the time required for analysis by the direct method because it limits the number of dilutions necessary and eliminates the need for the use of the method of additions to compensate for interferences from manganese

  9. N2O2 Tipi Schiff Bazı Ligandı ile Sentezlenen Cu(II Kompleksinin X-Işını Yapısı ve Termal Özelliği

    Directory of Open Access Journals (Sweden)

    Ahmet Karahan

    2013-04-01

    Full Text Available Cu(II kompleksinin X-ışınları moleküler yapısı 293 K'de tayin edildi. Cu (II kompleksi monoklinik yapıda ve uzay grubu P21/n a= 12.4007(14, b= 8.4476(9, c= 20.0286(12 Ã…, β= 97.291(7°. Termal davranışları diferansiyel termal analiz ve termogravimetrik analiz ile incelendi. Ayrıca Schiff bazı ligandının karakterizasyonunda elementel analiz, IR, UV-vis spektroskopisi, termal analiz, 1H-NMR ve 13C-NMR yöntemlerinden faydalanıldı. Anahtar kelimeler: Schiff bazı, Tek Kristal, X-ışınları analizi, Termal analiz The X-Ray Molecular Structure and Thermal Behaviour of Cu (II Complex, Synthesis With N2O2 Type Schiff Base Ligand Abstract: The X-ray molecular structure of Cu (II complex at 293 K has been determined. The Cu (II complex, has been prepared and structurally and thermal characterized. The complex crystallizes in monoclinic space group P21/n with a= 12.407(14, b= 8.4476(9, c= 20.0286(12 Ã…, β= 97.291(7°. The thermal behavior of the compound was investigated by differential thermal analysis and thermogravimetry. Additionally, Schiff base ligand also characterized by elemental analysis, IR, UV-vis spectroscopy, thermal analysis, 1H-NMR and 13C-NMR. Key words: Schiff base, Single crystal, X-ray analysis, Thermal analysis

  10. A fresnoite-structure-related mixed valent titanium(III/IV) chlorosilicate, Ba{sub 3}Ti{sub 2}Si{sub 4}O{sub 14}Cl: A flux crystal growth route to Ti(III) containing oxides

    Energy Technology Data Exchange (ETDEWEB)

    Abeysinghe, Dileka; Smith, Mark D.; Loye, Hans-Conrad zur, E-mail: zurloye@mailbox.sc.edu

    2017-06-15

    Single crystals of mixed valent barium titanium(III/IV) chlorosilicate, Ba{sub 3}Ti{sub 2}Si{sub 4}O{sub 14}Cl{sub 0.91}O{sub 0.09}, were grown in a high temperature molten chloride flux involving an in situ reduction step. The fresnoite structure related Ba{sub 3}Ti{sub 2}Si{sub 4}O{sub 14}Cl{sub 0.91}O{sub 0.09} crystallizes in the tetragonal space group P4/mbm with lattice parameters of a=8.6717(2) Å, c=18.6492(5) Å. The title compound exhibits a 3D structure consisting of 2D layers of fused Ti{sub 2}O{sub 9} and Si{sub 4}O{sub 12} groups and 2D layers of fused Ti{sub 2}O{sub 9}Cl{sub 2} and Si{sub 2}O{sub 7} groups that are linked via barium atoms. The in situ reduction of Ti(IV) to Ti(III) is achieved via the addition of metallic Mg to the flux to function as the reducing agent. The temperature dependence of the magnetic susceptibility shows simple paramagnetism above 100 K. There is a discontinuity in the susceptibility data below 100 K, which might be due to a structural change that takes place resulting in charge ordering. - Graphical abstract: The fresnoite structure related novel reduced barium titanium chlorosilicate, Ba{sub 3}Ti{sub 2}Si{sub 4}O{sub 14}Cl{sub 0.91}O{sub 0.09}, were synthesized via flux method. An in situ reduction of Ti(IV) to Ti(III) achieved using Mg metal. The 3D structure consists 2D layers of fused Ti{sub 2}O{sub 9} and Si{sub 4}O{sub 12} and 2D layers of fused Ti{sub 2}O{sub 9}Cl{sub 2} and Si{sub 2}O{sub 7} connected via barium atoms. Compound shows simple paramagnetism above 100 K. - Highlights: • The fresnoite related Ba{sub 3}Ti{sub 2}Si{sub 4}O{sub 14}Cl{sub 0.91}O{sub 0.09} were grown via molten flux method. • The in situ reduction of Ti(IV) to Ti(III) is achieved using metallic Mg. • 2D layers of Ti{sub 2}O{sub 9} and Si{sub 4}O{sub 12} and Ti{sub 2}O{sub 9}Cl{sub 2} and Si{sub 2}O{sub 7} connect via Ba atoms. • The magnetic susceptibility shows simple paramagnetism above 100 K.

  11. 2,3,4-Trihydroxyflourones immobilized on cellulose matrices in test methods for determining rare elements

    International Nuclear Information System (INIS)

    Amelin, V.G.; Abramenkova, O.I.

    2008-01-01

    It was shown that 2,3,7-trihydroxyfluorones immobilized by adsorption on cellulose matrices can be used as reagents for the test determination of Mo(Vl), Ti(lV), Ge(lV), Hf(lV), Nb(V), Ta(V), W(VI), Bi(III), V(IV), and Zr(IV). The change of the protolytic and complexing properties of trihydroxyfluorones immobilized on cellulose matrices was considered in comparison to corresponding properties in a solution. It was found that the reactions of trihydroxyfluorones with rare elements on cellulose matrices and in a solution exhibit similar effects upon the addition of cetylpyridinium. These effects are the bathochromic shift of the absorption maxima of the reagents and their complexes with analytes and the extension of the range of optimum acidity for complex formation. The complexation of salicylfluorones with the titanium(IV) in solution and on cellulose paper was studied by IR spectrometry. Phenylfluorone immobilized on a mixed-fiber cloth as used in test determinations of (mg/L) 0.05-5 Ti(IV), V(IV), Hf(IV), Nb(V), and Mo(VI); 0.01-5 Ge(IV) and Zr(IV); 0.05-1 Bi(III) and W(VI); and 0.1-5 Ta(V) by the color intensity of the indicator matrix after passing through 20 mL of a analyzable solution. It was shown that phenylfluorone immobilized on cellulose paper can be used to determine (mg/L) 0.05-50 Ti(IV), 0.5-1000 Ge(IV), 0.5-500 Zr(IV), 5-200 Bi(III), 0.1-50 Mo(VI), 0.1-1000 V(IV), 0.1-100 Nb(V), 0.1-800 Hf(IV), 1-100 Ta(V), and 1-800 W(VI) by the length of the colored zone of a test strip after it was brought into contact with a test solution [ru

  12. DFT Study of Binding and Electron Transfer from a Metal-Free Dye with Carboxyl, Hydroxyl, and Sulfonic Anchors to a Titanium Dioxide Nanocluster

    Directory of Open Access Journals (Sweden)

    Corneliu I. Oprea

    2013-01-01

    Full Text Available We report results of density functional theory (DFT calculations of a metal-free dye, 5-(4-sulfophenylazosalicylic acid disodium salt, known as Mordant Yellow 10 (MY-10, used as sensitizer for TiO2 dye-sensitized solar cells (DSSCs. Given the need to better understand the behavior of the dyes adsorbed on the TiO2 nanoparticle, we studied various single and double deprotonated forms of the dye bound to a TiO2 cluster, taking advantage of the presence of the carboxyl, hydroxyl, and sulfonic groups as possible anchors. We discuss various binding configurations to the TiO2 substrate and the charge transfer from the pigment to the oxide by means of DFT calculations. In agreement with other reports, we find that the carboxyl group tends to bind in bidentate bridging configurations. The salicylate uses both the carboxyl and hydroxyl substituent groups for either a tridentate binding to adjacent Ti(IV ions or a bidentate Ti-O binding together with an O-H-O binding, due to the rotation of the carboxyl group out of the plane of the dye. The sulfonic group prefers a tridentate binding. We analyze the propensity for electron transfer of the various dyes and find that for MY-10, as a function of the anchor group, the DSSC performance decreases in the order hydroxyl + carboxyl > carboxyl > sulfonate.

  13. A Titanium–Organic Framework as an Exemplar of Combining the Chemistry of Metal– and Covalent–Organic Frameworks

    Energy Technology Data Exchange (ETDEWEB)

    Nguyen, Ha L.; Gándara, Felipe; Furukawa, Hiroyasu; Doan, Tan L. H.; Cordova, Kyle E.; Yaghi, Omar M.

    2016-04-06

    A crystalline material with a two-dimensional structure, termed metal–organic framework-901 (MOF-901), was prepared using a strategy that combines the chemistry of MOFs and covalent–organic frameworks (COFs). This strategy involves in situ generation of an amine-functionalized titanium oxo cluster, Ti6O6(OCH3)6(AB)6 (AB = 4-aminobenzoate), which was linked with benzene-1,4-dialdehyde using imine condensation reactions, typical of COFs. The crystal structure of MOF-901 is composed of hexagonal porous layers that are likely stacked in staggered conformation (hxl topology). This MOF represents the first example of combining metal cluster chemistry with dynamic organic covalent bond formation to give a new crystalline, extended framework of titanium metal, which is rarely used in MOFs. The incorporation of Ti(IV) units made MOF-901 useful in the photocatalyzed polymerization of methyl methacrylate (MMA). The resulting polyMMA product was obtained with a high-number-average molar mass (26 850 g mol–1) and low polydispersity index (1.6), which in many respects are better than those achieved by the commercially available photocatalyst (P-25 TiO2). Additionally, the catalyst can be isolated, reused, and recycled with no loss in performance.

  14. Synthesis, structure and photocatalytic activity of calcined Mg-Al-Ti-layered double hydroxides

    Energy Technology Data Exchange (ETDEWEB)

    Hosni, Khaled; Abdelkarim, Omar; Srasra, Ezzeddine [Centre National des Recherches en Sciences des Matériaux (CNRSM), Soliman (Turkey); Frini-Srasra, Najoua [Faculté des Sciences de Tunis (FST), Tunis (Turkey)

    2015-01-15

    Mg-Al-Ti layered double hydroxides (LDH), consisting of di-, tri- and tetra-valent cations with different Al{sup 3+}/Ti{sup 4+} ratio, have been synthesized by co-precipitation which was demonstrated as efficient visible-light photocatalysts. The structure and chemical composition of the compound were characterized by PXRD, FT-IR, SAA, N{sub 2} adsorption-desorption isotherms, and DSC techniques. It is found that no hydrotalcites structure were formed for Ti{sup 4+}/(Ti{sup 4+}+ Al{sup 3+})>0.5 and the substitution of Ti(IV) for Al(III) in the layer increases the thermal stability of the resulting LDH materials. The calcined sample containing titanium showed relatively high adsorption capacity for MB as compared to that without titanium. Results show that the pseudo-second-order kinetic model and the Langmuir were found to correlate the experimental data well. The photocatalytic activity was evaluated for the degradation of the methylene blue. The photocatalytic activity increased with the increase of the Al/Ti cationic ratio. 71% of the dye could be removed by the Mg/Al/Ti-LDH with the cationic ratio Al/Ti=0 : 1 and calcined at 500 .deg. C.

  15. NMR spectroscopic characterization and DFT calculations of zirconium(IV)-3,3'-Br2-BINOLate and related complexes used in an enantioselective Friedel-Crafts alkylation of indoles with α,β-unsaturated ketones.

    Science.gov (United States)

    Blay, Gonzalo; Cano, Joan; Cardona, Luz; Fernández, Isabel; Muñoz, M Carmen; Pedro, José R; Vila, Carlos

    2012-12-07

    Experimental and theoretical studies on the structure of several complexes based on (R)-3,3'-Br(2)-BINOL ligand and group (IV) metals used as catalysts in an enantioselective Friedel-Crafts alkylation of indoles with α,β-unsaturated ketones have been carried out. NMR spectroscopic studies of these catalysts have been performed, which suggested that at room temperature the catalysts would form a monomeric structure in the case of Ti(IV) and a dimeric structure in the cases of Zr(IV) and Hf(IV). Density functional theory (DFT) calculations clearly corroborate the conclusions of these experimental spectroscopic studies. The dimeric structure with a doubly bridged motif [Zr(IV)(2)(μ-(R)-3,3'-Br(2)-BINOL)(2)] where each binaphthol ligand acts as bridge between the metal centers (Novak's model) is more stable than the dimeric structure with a doubly bridged motif [Zr(IV)(2)(μ-O(t)Bu)(2)] where the tert-butoxide groups act as bridging ligands (Kobayashi's model). The scope of the Friedel-Crafts alkylation with regard to the indole structure has been studied. Finally a plausible mechanism for the Friedel-Crafts reaction and a stereomodel for the mode of action of the catalyst that explain the observed stereochemistry of the reaction products have been proposed.

  16. Aqueous Synthesis of Technetium-Doped Titanium Dioxide by Direct Oxidation of Titanium Powder, a Precursor for Ceramic Nuclear Waste Forms

    Energy Technology Data Exchange (ETDEWEB)

    Lukens, Wayne W. [Chemical; Saslow, Sarah A. [Earth

    2017-11-17

    Technetium-99 (Tc) is a problematic fission product that complicates the long-term disposal of nuclear waste due to its long half-life, high fission yield, and the environmental mobility of pertechnetate, its stable form in aerobic environments. One approach to preventing Tc contamination is through incorporation into durable waste forms based on weathering-resistant minerals such as rutile (titanium dioxide). Here, the incorporation of technetium into titanium dioxide by means of simple, aqueous chemistry is presented. X-ray absorption fine structure spectroscopy and diffuse reflectance spectroscopy indicate that Tc(IV) replaces Ti(IV) within the structure. Rather than being incorporated as isolated Tc(IV) ions, Tc is present as pairs of edge-sharing Tc(IV) octahedra similar to molecular Tc(IV) complexes such as [(H2EDTA)TcIV](u-O)2. Technetium-doped TiO2 was suspended in deionized water under aerobic conditions, and the Tc leached under these conditions was followed for 8 months. The normalized release rate of Tc (LRTc) from the TiO2 particles is low (3×10-6 g m-2 d-1), which illustrates the potential utility of TiO2 as waste form. However, the small size of the as-prepared TiO2 nanoparticles results in estimated retention of Tc for 104 years, which is only a fraction of the half-life of Tc (2×10-5 years).

  17. The characteristics of corrosion, radiation degradation and dissolution of titanium alloys

    International Nuclear Information System (INIS)

    Sung, K. W.; Na, J. W.; Choi, B. S.; Lee, D. J.; Chang, M. H.

    2001-12-01

    In order to establish the technical bases of water chemistry design requirement related titanium alloys, we investigated the characteristics of corrosion, activation, radiation degradation, radiation hydrogen embrittlement of titanium alloys and dissolution of titanium dioxide. Titanium alloys generally have high corrosion resistance. Corrosion product release from PT-7M and PT-3V titanium alloy surface for 18 months of operation is negligible, and the corrosion penetration for about 30 years is about 1 μm, while the corrosion rates is not higher than one third of that of austenitic steel. Titanium only converts into Sc-46 with 85 day halflife after neutron irradiation, and its radioactivity is not higher than one thousandth of that produced from nickel. Therefore, under the condition without any neutron irradiation, the radiation damage of titanium alloys would have no problem. Titanium dioxide, that protects the metals from the corrosion, has retrograde solubility in neutral solutions. It does not form any complexes with ligands such as ammonia, but Ti(IV) gets more stable by complexing with water molecules. In conclusion, it is estimated that titanium alloys such as PT-7M would be applicable to steam generator materials

  18. Preparation of Anatase TiO{sub 2} Thin Films with (O{sup i}Pr){sub 2}Ti(CH{sub 3}COCHCONEt{sub 2}){sub 2} Precursor by MOCVD

    Energy Technology Data Exchange (ETDEWEB)

    Bae, Byoung Jae; Seo, Won Seok; Miah, Arzu; Park, Joon T. [Korea Advanced Institute of Science and Technology, Daejeon (Korea, Republic of); Lee, Kwang Yeol [Korea University, Seoul (Korea, Republic of); Kim, Keun Chong [Hong-Ik University, Chochiwon (Korea, Republic of)

    2004-11-15

    The reaction of titanium tetraisopropoxide with 2 equiv of N,N-diethyl acetoacetamide affords Ti(O{sup i}Pr){sub 2}(CH{sub 3}COCHCONEt{sub 2}){sub 2} (1) as colorless crystals in 80% yield. Compound 1 is characterized by spectroscopic (Mass and {sup 1}H/{sup 13}C NMR) and microanalytical data. Molecular structure of 1 has been determined by a single crystal X-ray diffraction study, which reveals that it is a monomeric, cis-diisopropoxide and contains a six coordinate Ti(IV) atom with a cis(CONEt{sub 2}), trans(COCH{sub 3}) configuration (1a) in a distorted octahedral environment. Variable-temperature {sup 1}H NMR spectra of 1 indicate that it exists as an equilibrium mixture of cis, trans (1a) and cis, cis (1b) isomers in a 0.57 : 0.43 ratio at -20 .deg. C in toluene-d{sub 8} solution. Thermal properties of 1 as a MOCVD precursor for titanium dioxide films have been evaluated by thermal gravimetric analysis and vapor pressure measurement. Thin films of pure anatase titanium dioxide (after annealing above 500 .deg. C under oxygen) have been grown on Si(100) with precursor 1 in the substrate temperature range of 350- 500 .deg. C using a bubbler-based MOCVD method.

  19. Preparation of Anatase TiO2 Thin Films with (OiPr)2Ti(CH3COCHCONEt2)2 Precursor by MOCVD

    International Nuclear Information System (INIS)

    Bae, Byoung Jae; Seo, Won Seok; Miah, Arzu; Park, Joon T.; Lee, Kwang Yeol; Kim, Keun Chong

    2004-01-01

    The reaction of titanium tetraisopropoxide with 2 equiv of N,N-diethyl acetoacetamide affords Ti(O i Pr) 2 (CH 3 COCHCONEt 2 ) 2 (1) as colorless crystals in 80% yield. Compound 1 is characterized by spectroscopic (Mass and 1 H/ 13 C NMR) and microanalytical data. Molecular structure of 1 has been determined by a single crystal X-ray diffraction study, which reveals that it is a monomeric, cis-diisopropoxide and contains a six coordinate Ti(IV) atom with a cis(CONEt 2 ), trans(COCH 3 ) configuration (1a) in a distorted octahedral environment. Variable-temperature 1 H NMR spectra of 1 indicate that it exists as an equilibrium mixture of cis, trans (1a) and cis, cis (1b) isomers in a 0.57 : 0.43 ratio at -20 .deg. C in toluene-d 8 solution. Thermal properties of 1 as a MOCVD precursor for titanium dioxide films have been evaluated by thermal gravimetric analysis and vapor pressure measurement. Thin films of pure anatase titanium dioxide (after annealing above 500 .deg. C under oxygen) have been grown on Si(100) with precursor 1 in the substrate temperature range of 350- 500 .deg. C using a bubbler-based MOCVD method

  20. Tailoring the Synergistic Bronsted-Lewis acidic effects in Heteropolyacid catalysts: Applied in Esterification and Transesterification Reactions.

    Science.gov (United States)

    Tao, Meilin; Xue, Lifang; Sun, Zhong; Wang, Shengtian; Wang, Xiaohong; Shi, Junyou

    2015-09-16

    In order to investigate the influences of Lewis metals on acidic properties and catalytic activities, a series of Keggin heteropolyacid (HPA) catalysts, HnPW11MO39 (M = Ti(IV), Cu(II), Al(III), Sn(IV), Fe(III), Cr(III), Zr(IV) and Zn(II); for Ti and Zr, the number of oxygen is 40), were prepared and applied in the esterification and transesterification reactions. Only those cations with moderate Lewis acidity had a higher impact. Ti Substituted HPA, H5PW11TiO40, posse lower acid content compared with Ti(x)H(3-4x)PW12O40 (Ti partial exchanged protons in saturated H3PW12O40), which demonstrated that the Lewis metal as an addenda atom (H5PW11TiO40) was less efficient than those as counter cations (Ti(x)H(3-4x)PW12O40). On the other hand, the highest conversion reached 92.2% in transesterification and 97.4% in esterification. Meanwhile, a good result was achieved by H5PW11TiO40 in which the total selectivity of DAG and TGA was 96.7%. In addition, calcination treatment to H5PW11TiO40 make it insoluble in water which resulted in a heterogeneous catalyst feasible for reuse.

  1. Recovery of molybdenum using alumina microspheres and precipitation with selective organic reagents

    International Nuclear Information System (INIS)

    Carvalho, Fatima Maria Sequeira de; Abrao, Alcidio

    1998-01-01

    In this paper is presented a study for the optimization of dissolution of the UAL x plates used for irradiation and production of radiomolybdenum. The alloy is dissolved in nitric acid with mercury as catalyst. The separation and concentration of the molybdenum was achieved using a chromatographic grade alumina microspheres column. the purified eluted molybdenum is finally precipitated using one of the selective reagents: alizarine blue, α,α'- bipyridine and 1,10-phenanthroline. Any one of the obtained precipitate can be fired to the molybdenum trioxide. The interference of the following elements was studied: Re(VII), U(VI), Cr(VI), W(VI), V(V), Te(IV), Ti(IV), Zr(IV), Th(IV), Fe(III), Au(III), Ru(III), Al(III), Bi(III), Sb(III), Ce(IV), Pr(III), Sc(III), Y(III), Sm(III), Ba(II), Sr(II), Ni(II), Co(II), Cs(I). The molybdenum precipitates were characterized by gravimetric, CHN, TG, DTG, IR and X-ray diffraction analyses. (author)

  2. Suppression of the release of arsenic from arsenopyrite by carrier-microencapsulation using Ti-catechol complex.

    Science.gov (United States)

    Park, Ilhwan; Tabelin, Carlito Baltazar; Magaribuchi, Kagehiro; Seno, Kensuke; Ito, Mayumi; Hiroyoshi, Naoki

    2018-02-15

    Arsenopyrite is the most common arsenic-bearing sulfide mineral in nature, and its weathering contributes to acid mine drainage (AMD) formation and the release of toxic arsenic (As). To mitigate this problem, carrier-microencapsulation (CME) using titanium (Ti)-catechol complex (i.e., Ti-based CME) was investigated to passivate arsenopyrite by forming a protective coating. Ti 4+ ion dissolved in sulfuric acid and catechol were used to successfully synthesize Ti(IV) tris-catecholate complex, [Ti(Cat) 3 ] 2- , which was stable in the pH range of 5-12. Electrochemical studies on the redox properties of this complex indicate that its oxidative decomposition was a one-step, irreversible process. The leaching of As from arsenopyrite was suppressed by CME treatment using the synthesized Ti-catechol complex. Scanning electron microscopy with energy dispersive X-ray spectroscopy (SEM-EDX) and diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) indicate that this suppression was primarily due to the formation of an anatase (β-TiO 2 )-containing coating. Based on these results, a detailed 4-step mechanism to explain the decomposition of [Ti(Cat) 3 ] 2- and formation of TiO 2 coating in Ti-based CME is proposed: (1) adsorption, (2) partial oxidation-intermediate formation, (3) non electrochemical dissociation, and (4) hydrolysis-precipitation. Copyright © 2017 Elsevier B.V. All rights reserved.

  3. Epitaxial Fe{sub 3-x}Ti{sub x}O{sub 4} films from magnetite to ulvöspinel by pulsed laser deposition

    Energy Technology Data Exchange (ETDEWEB)

    Droubay, T.C.; Pearce, C.I.; Ilton, E.S.; Engelhard, M.H.; Engelhard, M.H.; Heald, S.M.; Arenholz, E.; Rosso, K.M.

    2011-07-21

    Epitaxial films along the Fe{sub 3-x}Ti{sub x}O{sub 4} (titanomagnetite) compositional series from pure end-members magnetite (Fe{sub 3}O{sub 4}) to ulvöspinel (Fe{sub 2}TiO{sub 4}) were successfully grown by pulsed laser deposition on MgO(100) substrates. Spectroscopic characterization including high resolution x-ray diffraction, x-ray photoelectron spectroscopy, and synchrotron-based x-ray absorption and magnetic circular dichroism consistently shows that Ti(IV) substitutes for Fe(III) in the inverse spinel lattice with a proportional increase in lattice Fe(II) concentration. No evidence of Ti interstitials, spinodal decomposition, or secondary phases was found in the bulk of the grown films. At the uppermost few nanometers of the Ti-bearing film surfaces, evidence suggests that Fe(II) is susceptible to facile oxidation, and that an associated lower Fe/Ti ratio in this region is consistent with surface compositional incompleteness or alteration to a titanomaghemite-like composition and structure. The surface of these films nonetheless appear to remain highly ordered and commensurate with the underlying structure despite facile oxidation, a surface condition that is found to be reversible to some extent by heating in low oxygen environments.

  4. Synthesis and Features of Luminescent Bromo- and Iodohectorite Nanoclay Materials

    Directory of Open Access Journals (Sweden)

    Hellen Silva Santos

    2017-11-01

    Full Text Available The smectites represent a versatile class of clay minerals with broad usage in industrial applications, e.g., cosmetics, drug delivery, bioimaging, etc. Synthetic hectorite Na0.7(Mg5.5Li0.3[Si8O20](OH4 is a distinct material from this class due to its low-cost production method that allows to design its structure to match better the applications. In the current work, we have synthesized for the first time ever nanoclay materials based on the hectorite structure but with the hydroxyl groups (OH− replaced by Br− or I−, yielding bromohectorite (Br-Hec and iodohectorite (I-Hec. It was aimed that these materials would be used as phosphors. Thus, OH− replacement was done to avoid luminescence quenching by multiphonon de-excitation. The crystal structure is similar to nanocrystalline fluorohectorite, having the d001 spacing of 14.30 Å and 3 nm crystallite size along the 00l direction. The synthetic materials studied here show strong potential to act as host lattices for optically active species, possessing mesoporous structure with high specific surface area (385 and 363 m2 g−1 for Br-Hec and I-Hec, respectively and good thermal stability up to 800 °C. Both materials also present strong blue-green emission under UV radiation and short persistent luminescence (ca. 5 s. The luminescence features are attributed to Ti3+/TiIV impurities acting as the emitting center in these materials.

  5. Spectrophotometric Determination of Chromium (III) in Egyptian 11 manite from phosphate solution using Ewes as a selective adsorbent

    International Nuclear Information System (INIS)

    Abdu, A. A.

    2012-12-01

    Egyptian white sand (EWS) was used as an adsorbent for the selective separation of Cr(III) from phosphate solution to be determined colorimetrically using 1,5-diphenylcarbazide. The experimental factors affecting maximum selective adsorption/desorption of Cr(III) on / from EWS were the amount of adsorption (g), pH of initial concentration of Cr(III) in solution, contact time temperature and initial concentration of Cr(III) in solution were investigated. No effect of [PO 4 ] 3- , Ti(IV) and Fe(III) on Cr(III) sorption were verified. Accuracy and relative standard deviations (RSD) were acceptable for all analyses. The maximum sorption capacity, Q e , of adsorbed Cr(III) per gram of sand was 93.5 mg/g, at EWS concentration 20 g/1, pH 0.8 contact time 120 min and temperature 30 o C for adsorption of Cr(III) on EWS and pH 0.4, contact time 6 min and temperature 25o C for desorption of Cr(III) from EWS. (Author)

  6. Synthesis and electrochemical evaluation of an amorphous titanium dioxide derived from a solid state precursor

    Science.gov (United States)

    Joyce, Christopher D.; McIntyre, Toni; Simmons, Sade; LaDuca, Holly; Breitzer, Jonathan G.; Lopez, Carmen M.; Jansen, Andrew N.; Vaughey, J. T.

    Titanium oxides are an important class of lithium-ion battery electrodes owing to their good capacity and stability within the cell environment. Although most Ti(IV) oxides are poor electronic conductors, new methods developed to synthesize nanometer scale primary particles have achieved the higher rate capability needed for modern commercial applications. In this report, the anionic water stable titanium oxalate anion [TiO(C 2O 4) 2] 2- was isolated in high yield as the insoluble DABCO (1,4-diazabicyclo[2.2.2]octane) salt. Powder X-ray diffraction studies show that the titanium dioxide material isolated after annealing in air is initially amorphous, converts to N-doped anatase above 400 °C, then to rutile above 600 °C. Electrochemical studies indicate that the amorphous titanium dioxide phase within a carbon matrix has a stable cycling capacity of ∼350 mAh g -1. On crystallizing at 400 °C to a carbon-coated anatase the capacity drops to 210 mAh g -1, and finally upon carbon burn-off to 50 mAh g -1. Mixtures of the amorphous titanium dioxide and Li 4Ti 5O 12 showed a similar electrochemical profile and capacity to Li 4Ti 5O 12 but with the addition of a sloping region to the end of the discharge curve that could be advantageous for determining state-of-charge in systems using Li 4Ti 5O 12.

  7. Rate and Selectivity Control in Thioether and Alkene Oxidation with H 2 O 2 over Phosphonate-Modified Niobium(V)-Silica Catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Thornburg, Nicholas E.; Notestein, Justin M. (NWU)

    2017-09-05

    Supported metal oxide catalysts are versatile materials for liquid-phase oxidations, including alkene epoxidation and thioether sulfoxidation with H2O2. Periodic trends in H2O2 activation was recently demonstrated for alkene epoxidation, highlighting Nb-SiO2 as a more active and selective catalyst than Ti-SiO2. Three representative catalysts are studied consisting of NbV, TiIV, and ZrIV on silica, each made through a molecular precursor approach that yields highly dispersed oxide sites, for thioanisole oxidation by H2O2. Initial rates trend Nb>Ti>>Zr, as for epoxidation, and Nb outperforms Ti for a number of other thioethers. In contrast, selectivity to sulfoxide vs. sulfone trends Ti>Nb>>Zr at all conversions. Modifying the Nb-SiO2 catalyst with phenylphosphonic acid does not completely remove sulfoxidation reactivity, as it did for photooxidation and epoxidation, and results in an unusual material active for sulfoxidation but neither epoxidation nor overoxidation to the sulfone.

  8. Determination of trace impurities in high-purity iron using salting-out of polyoxyethylene-type surfactants

    Energy Technology Data Exchange (ETDEWEB)

    Matsumiya, Hiroaki, E-mail: h-matsu@numse.nagoya-u.ac.jp [Department of Molecular Design and Engineering, Graduate School of Engineering, Nagoya University, Furo-cho, Chikusa-ku, Nagoya 464-8603 (Japan); Sakane, Yuto; Hiraide, Masataka [Department of Molecular Design and Engineering, Graduate School of Engineering, Nagoya University, Furo-cho, Chikusa-ku, Nagoya 464-8603 (Japan)

    2009-10-19

    To an iron sample solution was added polyoxyethylene-4-isononylphenoxy ether (PONPE, nonionic surfactant, average number of ethylene oxides 7.5) and the surfactant was aggregated by the addition of lithium chloride. The iron(III) matrix was collected into the condensed surfactant phase in >99.9% yields, leaving trace metals [e.g., Ti(IV), Cr(III), Mn(II), Co(II), Ni(II), Cu(II), Zn(II), Cd(II), Pb(II), and Bi(III)] in the aqueous phase. After removing the surfactant phase by centrifugation, the remaining trace metals were concentrated onto an iminodiacetic acid-type chelating resin. The trace metals were desorbed with dilute nitric acid for the determination by inductively coupled plasma-mass spectrometry or graphite-furnace atomic absorption spectrometry. The proposed separation method allowed the analysis of high-purity iron metals for trace impurities at low {mu}g g{sup -1} to ng g{sup -1} levels.

  9. Metal and ligand K-edge XAS of organotitanium complexes: metal 4p and 3d contributions to pre-edge intensity and their contributions to bonding.

    Science.gov (United States)

    George, Serena DeBeer; Brant, Patrick; Solomon, Edward I

    2005-01-19

    Titanium cyclopentadienyl (Cp) complexes play important roles as homogeneous polymerization catalysts and have recently received attention as potential anticancer agents. To systematically probe the contribution of the Cp to bonding in organotitanium complexes, Ti K-edge XAS has been applied to TiCl(4) and then to the mono- and bis-Cp complexes, TiCpCl(3) and TiCp(2)Cl(2). Ti K-edge XAS is used as a direct probe of metal 3d-4p mixing and provides insight into the contribution of the Cp to bonding. These data are complimented by Cl K-edge XAS data, which provide a direct probe of the effect of the Cp on the bonding to the spectator chloride ligand. The experimental results are correlated to DFT calculations. A model for metal 3d-4p mixing is proposed, which is based on covalent interactions with the ligands and demonstrates that metal K-pre-edge intensities may be used as a measure of ligand-metal covalency in molecular Ti(IV) systems in noncentrosymmetric environments.

  10. Gold sorption from aqueous solutions by hydroxides and oxides at conditions of complex formation and oxidation-reduction

    International Nuclear Information System (INIS)

    Novikov, A.I.; Shekoturova, E.K.; Ribalko, T.A.

    1986-01-01

    With using of radionuclide 198 Au 3+ at initial form 198 AuCl 4 - the sorption of Au 3+ at its concentrations from 1.27·10 3 till 1.9·10 -9 mol/l from solutions of NaClO 4 (0.1 and 1 mol/l), KHO 3 (0.1 and 1 mol/l), NaNO 3 (1 mol/l), NaCl(0.7-3 mol/l), KCl(0.01; 0.1 and 1 mol/l), NH 4 NO 3 (0.1 and 1 mol/l)NH 4 Cl(10 -3 ; 10 -2 ; 10 -1 and 1 mol/l) in a wide ph range (0+14) by hydroxides of Fe(III), Zr, oxides of Fe(III), Ti(IV), Mn(IV) and Sn(IV) is studied. The dependences of sorption value of Au 3+ on ph of medium, composition and concentrations of electrolytes in solution are defined. Calculations on condition of Au 3+ in aqueous solutions are conducted. Optimal conditions of gold concentration (including 198 Au) and its separation from carrier at sorption process are defined as well.

  11. Synthesis of Cr-doped CaTiSiO5 ceramic pigments by spray drying

    International Nuclear Information System (INIS)

    Lyubenova, T. Stoyanova; Matteucci, F.; Costa, A.L.; Dondi, M.; Ocana, M.; Carda, J.

    2009-01-01

    Cr-doped CaTiSiO 5 was synthesized by spray drying and conventional ceramic method in order to assess its potential as ceramic pigment. The evolution of the phase composition with thermal treatment was investigated by X-ray powder diffraction (XRPD) and thermal analyses (DTA-TGA-EGA). Powder morphology and particle size distribution were analyzed by scanning electron microscopy (SEM) and laser diffraction, respectively. The color efficiency of pigments was evaluated by optical spectroscopy (UV-vis-NIR) and colorimetric analysis (CIE Lab). Results proved that spray drying is an efficient procedure to prepare highly reactive pigment precursors. The spray-dried powders consist of hollow spherical particles with aggregate size in the 1-10 μm range, developing a brown coloration. Optical spectra reveal the occurrence of Cr(III) and Cr(IV), both responsible for the brown color of this pigment. The former occupies the octahedral site of titanite, in substitution of Ti(IV), while the latter is located at the tetrahedral site, where replaces Si(IV)

  12. The coordination and atom transfer chemistry of titanium porphyrin complexes

    Energy Technology Data Exchange (ETDEWEB)

    Hays, James Allen [Iowa State Univ., Ames, IA (United States)

    1993-11-05

    Preparation, characterization, and reactivity of (η2- alkyne)(meso-tetratolylpoprphrinato)titanium(II) complexes are described, along with inetermetal oxygen atom transfer reactions involving Ti(IV) and Ti(III) porphyrin complexes. The η2- alkyne complexes are prepared by reaction of (TTP)TiCl2 with LiAlH4 in presence of alkyne. Structure of (OEP)Ti(η2-Ph-C≡C-Ph) (OEP=octaethylporphryin) was determined by XRD. The compounds undergo simple substitution to displace the alkyne and produce doubly substituted complexes. Structure of (TTP)Ti(4-picoline)2 was also determined by XRD. Reaction of (TTP)Ti=O with (OEP)Ti-Cl yields intermetal O/Cl exchange, which is a one-electron redox process mediated by O atom transfer. Also a zero-electron redox process mediated by atom transfer is observed when (TTP)TiCl2 is reacted with (OEP)Ti=O.

  13. Analysis of dispersive interactions at polymer/TiAlN interfaces by means of dynamic force spectroscopy.

    Science.gov (United States)

    Wiesing, M; de Los Arcos, T; Gebhard, M; Devi, A; Grundmeier, G

    2017-12-20

    The structural and electronic origins of the interactions between polycarbonate and sputter deposited TiAlN were analysed using a combined electron and force spectroscopic approach. Interaction forces were measured by means of dynamic force spectroscopy and the surface polarizability was analysed by X-ray photoelectron valence band spectroscopy. It could be shown that the adhesive interactions between polycarbonate and TiAlN are governed by van der Waals forces. Different surface cleansing and oxidizing treatments were investigated and the effect of the surface chemistry on the force interactions was analysed. Intense surface oxidation resulted in a decreased adhesion force by a factor of two due to the formation of a 2 nm thick Ti 0.21 Al 0.45 O surface oxide layer. The origin of the residual adhesion forces caused by the mixed Ti 0.21 Al 0.45 O surface oxide was clarified by considering the non-retarded Hamaker coefficients as calculated by Lifshitz theory, based on optical data from Reflection Electron Energy Loss Spectroscopy. This disclosed increased dispersion forces of Ti 0.21 Al 0.45 O due to the presence of Ti(iv) ions and related Ti 3d band optical transitions.

  14. Synthesis of Thermally Switchable Chromatographic Materials with Immobilized Ti4+ for Enrichment of Phosphopeptides by Reversible Addition Fragmentation Chain Transfer Polymerization

    Science.gov (United States)

    Wang, Di; Cao, Zhihan; Pang, Xinzhu; Deng, Yulin; Li, Bo; Dai, Rongji

    2018-01-01

    Reversible phosphorylation of proteins is one of the most crucial types of post-translational modifications (PTMs). And it shows significant work in diversified biological processes. However, the separation technology of phosphorylated peptides is still an analytical challenge in phosphoproteomics, because phosphopeptides are alway in low stoichiometry. Thus, enrichment of phosphopeptides before detection is indispensable. In this study, a novel temperature regulated separation protocol was developed. Silica@p (NIPAAm-co-IPPA)-Ti4+, a new Ti(IV)-IMAC (Immobilized Metal Affinity chromatography) materials was synthesized by reversible addition fragmentation chain transfer polymerization (RAFT). By the unique thermally responsive properties of poly(N-isopropylacrylamide) (PNIPAAm), the captured phosphorylated peptides could be released by changing temperature only without applying any other eluant which could damage the phosphopeptides. We employed isopropanol phosphonic acid (IPPA) as an IMAC ligand for the immobilization of Ti(IV) which could increase the specific adsorption of phosphopeptides. The enrichment and release properties were examined by treatment with pyridoxal 5’-phosphate (PLP) and casein phosphopeptides (CPP). Two phosphorylated compounds above have temperature-stimulated binding to Ti4+. Finally, silica@p (NIPAAm-co-IPPA)-Ti4+ was successfully employed in pretreatment of phosphopeptides in a tryptic digest of a-casein and human serum albumin (HSA). The results indicated a great potential of this new temperature-responsive material in phosphoproteomics study.

  15. Possible Utilization of Nitronitrosylruthenium Complexes as Tracers in Hydrology; Note sur l'utilisation eventuelle des complexes de nitronitrosylruthenium comme traceurs en hydrologie; O vozmozhnom ispol'zovanii kompleksa nitronitrozilruteniya v kachestve indikatorov v gidrologii; Nota sobre el posible empleo de los complejos de nitronitrosilrutenio como indicadores en hidrologia

    Energy Technology Data Exchange (ETDEWEB)

    Gailledreau, C. [Commissariat a l' Energie Atomique (France)

    1963-08-15

    Ru{sup 106} might be a useful tracer in hydrology. Its half-life of about one year is in a range in which there are few radioisotopes which can be used as tracers. There are a great variety of complexes of Ru{sup 106}, the nitro-complexes of nitrosylruthenium being amongst the most stable. Percolation tests have been made with nitronitrosylruthenium diluted in water from the mains, on columns of aquilerous sand and a very argillaceous soil. (author) [French] Le {sup 106}Ru pourrait etre un traceur interessant en hydrologie. Sa vie moyenne, environ un an, se situe dans une gamme ou il existe peu d'autres radioisotopes susceptibles d'etre utilises comme traceurs. Il existe une grande variete de complexes du les complexes nitro de nitrosylruthenium etant parmi les plus stables. Des essais de percolation ont ete effectues avec du nitronitrosylruthenium dilue dans de l'eau de ville, sur des colonnes de sable aquifere et d'un sol tres argileux. (author) [Spanish] El ''1''0''6Ru podria emplearse en calidad de indicador en hidrologia. Tiene un periodo del orden de un ano que le situa en una gama en la que existen muy pocos radioisotopos utilisable: como indicadores. El {sup 106}Ru puede formar una gran variedad de complejos, siendo los mas estables los nitrocomplejos de nitrosilrutenio. El autor ha realizado ensayos de percolacion con nitronitrosilrutenio diluido en agua de grifo, en columnas de arena acuifera y de suelo muy arcilloso. (author) [Russian] Ru{sup 106} mozhet byt' ispol'zovan v kachestve indikatora, predstavlyayushchego opredelennyj interes dlya gidrologii. Ego period poluraspada (priblizitel'n o 1'god) raspolagaetsj v gamme, gde sushchestvuet malo drugikh radioizotopov, kotorye mogut byt' ispol'zovany v kachestve indikatorov. Sushchestvuet bol'shoe mnogoobrazie kompleksov Ru{sup 106}, prichem kompleksy nitronitrozilruteniya otnosyatsya k naibolee stabil'nym. Provodilis ' opyty po perkolyatsii s nitronitrozilruteniem, rastvorennym v vodoprovodnoj vode, na

  16. Preparative Radiation Chemistry of Transition Metal Complexes; Radiosynthese de complexes de metaux de transition; Radiatsionno-khimicheskij sintez kompleksnykh soedinenij perekhodnykh metallov; Radiosintesis de complejos de los metales de transicion

    Energy Technology Data Exchange (ETDEWEB)

    Gustorf, E. Koerner Von; Jun, M. -J.; Koller, H.; Schenck, G. O. [Max-Planck-Institut fuer Kohlenforschung, Abteilung Strahlenchemie, Muelheim-Ruhr, Federal Republic of Germany (Germany)

    1963-11-15

    halogenes et de methacrylate de methyie-fer tetracarbonyle, d'acetate de vinyle-fer tetracarbonyle, etc. 3. Radiosynthese de complexes {pi} et de composes carbonyles de metaux de transition. Exemple: exposition aux rayons gamma du cobalt-60 de [(C{sub 5}H{sub 5}){sub 2}Fe], [(C{sub 5}H{sub 5})2Ni], CH{sub 3}C{sub 5}H{sub 4}Mn(CO){sub 3}, (C{sub 5}H{sub 5}){sub 2}TiCl{sub 2}, Fe(CO){sub 5} et Ni(CO){sub 4} dans des hydrocarbures halogenes. (author) [Spanish] Los complejos {pi} y los compuestos carbonilo de los metales de transicion han adquirido cierta importancia tecnica en virtud de su reactividad especial y de su actividad catalitica. El autor ha llevado a cabo las siguientes investigaciones: 1. Radiointesis de complejos {pi} de metales de transicion. Como ejemplos, puede citarse la preparacion de los complejos anhidrido maleico-hierro tetracarbonilo; fumarato de dimetilo-hierro tetracarbonilo; metacrilato de metilo-hierro tetracarbonilo; acetato de vinilo-hierro tetracarbonilo, etc., por exposicion del Fe(CO){sub 5} y de los compuestos no saturados correspondientes a los rayos gamma del {sup 60}Co. 2. Reacciones quimicas con complejos {pi} formados por via radioquimica. Ejemplos: la polimerizacion de compuestos vinilicos a temperatura ambiente por accion de los compuestos organicos halogenados sobre complejos tales como el metacrilato de metilo-hierro tetracarbonilo, el acetato de vinilo-hierro tetracarbonilo, etc. 3. Radiosintesis de complejos {pi} y compuestos carbonilo de los metales de transicion. Como ejemplos, puede mencionarse la exposicion [(C{sub 5}H{sub 5}){sub 2}Fe], [(C{sub 5}H{sub 5}){sub 2}Ni], CH{sub 3}C{sub 5}H{sub 4}Mn(CO){sub 3}, (C{sub 5}H{sub 5}){sub 2}TiCl{sub 2}, Fe(CO){sub 5}, Ni(CO){sub 4} disueltos en hidrocarburos halogenados, a los rayos gamma del {sup 60}Co. (author) [Russian] {pi}-kompleksy i karbonil'nye' soedineniya perekhodnykh metallov imeyut bol'shoe znachenie v tekhnike iz-za ikh vysokoj reaktsionnoj sposobnosti i kataliticheskoj

  17. Use of magnesium-aluminium and zinc-aluminium hydroxycompounds as adsorbents of uranium ions in aqueous solutions

    International Nuclear Information System (INIS)

    Maki, Toshio

    1981-01-01

    It was found that precipitates formed by adding NaOH solution to the mixed solutions of MgSO 4 and Al 2 (SO 4 ) 3 with Mg/Al molar ratios of 2 to 4 and to the mixed solution of ZnSO 4 and Al 2 (SO 4 ) 3 with Zn/Al molar ratio of 2, respectively, can be used as efficient adsorbents of [UO 2 (CO 3 ) 3 ] 4- ions in aqueous alkaline carbonate solutions. The ideal structural formulas of the precipitates formed from the mixed Mg-Al solution with Mg/Al ratio of 2.0 and the mixed Zn-Al solution with Zn/Al ratio of 2.0 were estimated to be [Mg 4 Al 2 (OH) 12 ] 2+ [SO 4 .3H 2 O] 2- and [Zn 4 Al 2 (OH) 12 ] 2+ [SO 4 .3H 2 O] 2- , respectively. It has been shown that 0.1 g of the Mg-Al and Zn-Al double hydroxysulphate powders (particle size 70 - 170 μ uptake >97% of the U(VI) ions from 50 ml of an aqueous alkaline carbonate solution containing 100 ppm of U(VI) within 2 h at room temperature. The rates of adsorption of [UO 2 (CO 3 ) 3 ] 4- ions for the Mg-Al and Zn-Al double hydroxysulphate powders were both about 2 times that for the hydrous Ti(IV) oxide powders. Five weight percent sodium bicarbonate solution was found to be effective for the desorption of [UO 2 (CO 3 ) 3 ] 4- ions from the double hydroxysulphate powders. Adsorption capacity of the double hydroxysulphates was discussed in relation to their structure. (author)

  18. Flow injection spectrophotometric determination of Fe(III) and V(v)

    International Nuclear Information System (INIS)

    Elrahman, Azza Mohamed

    2000-01-01

    Phenylflourone was synthesized with the objective of developing a method for determining Fe(III) and V(V) in the pressence of micelles using flow injectoin technique. Phenylflourone showed a wavelength of maximum absorption at 412 nm which was not affected by the presence of miccelles i.e. n-hexadodecylpyridinum bromide and sodium n-dodecylsulphate, but they have different effects on the absorbance of PHF. The example of PHF-Fe(III) and PHF-V(V) showed the wavelength of the maximum absorption at 4428 nm and 412 nm, respectively. Presence of micelles shifted the wavelength of the two complexes to a lower one. Generally the addition of micelles increased the absorbance of phenylflourone metal ions complexes except for PHF-V(V) with hexadodecylpyridinum bromide. With flow injection technique two approaches were practiced the use of micelle as a carrier or water as a carrier. Sodium n-dodecylsulphate increased the absorbance of the two complexes when it was used as a carrier or added to the metal ions using water as carrier. On the other hand, the use of n-hexadodecylpyridinum bromide as carrieer increased the absorbance of the complexes but it decreased the absorbance when it was used in conjunction with metal ions and water as a carrier. After establishing the optimum FI conditions for PHF-Fe(III) and PHF-V(V) complexes, the calibration curves were construction and produced semiliner response in the concentration range studied. Ti(IV) III, Mo(VI) showed a positive interference in PHF-Fe(III) and PHF-V(V) complexes, respectively.(Author)

  19. Electron transfer. 93. Further reactions of transition-metal-center oxidants with vitamin B12s (Cob(I)alamin)

    International Nuclear Information System (INIS)

    Pillai, G.C.; Ghosh, S.K.; Gould, E.S.

    1988-01-01

    Vitamin B 12s (cob(I)alamin) reduces europium(III), titanium(IV) (TiO(C 2 O 4 ) 2 2- ), and uranium(VI) in aqueous solution. These oxidants undergo one-electron changes, leading in each case to the cobalt product cob(II)alamin (B 12r ). The reduction of Eu 3+ , which is inhibited by TES buffer, but not by glycine, is outer sphere. Its limiting specific rate (1 x 10 2 M -1 s -1 ), incorporated in the Marcus treatment, yields a B 12s ,B 12r self-exchange rate of 10 4.8±0.5 M -1 s -1 . Reductions of TiO(C 2 O 4 ) 2 2- are accelerated by H + and by acetic acid. Kinetic patterns suggest three competing reaction paths involving varying degrees of protonation of the Ti(IV) center or its association with acetic acid. The very rapid reduction of U(VI) (k = 4 x 10 6 M -1 s -1 ) yields U(V) in several buffering media, even when B 12s is taken in excess. The much slower conversion of U(V) to U(IV), although thermodynamically favored, appears to be retarded by the extensive reorganization of the coordination sphere of oxo-bound U(V) that must accompany its acceptance of an additional electron. The observed specific rate for the B 12s -U(VI) reaction is in reasonable agreement, in the framework of the Marcus formalism, with reported values of the formal potential and the self-exchange rate for U(V,VI). 37 references, 4 tables

  20. Surface and interlayer base-characters in lepidocrocite titanate: The adsorption and intercalation of fatty acid

    Science.gov (United States)

    Maluangnont, Tosapol; Arsa, Pornanan; Limsakul, Kanokporn; Juntarachairot, Songsit; Sangsan, Saithong; Gotoh, Kazuma; Sooknoi, Tawan

    2016-06-01

    While layered double hydroxides (LDHs) with positively-charged sheets are well known as basic materials, layered metal oxides having negatively-charged sheets are not generally recognized so. In this article, the surface and interlayer base-characters of O2- sites in layered metal oxides have been demonstrated, taking lepidocrocite titanate K0.8Zn0.4Ti1.6O4 as an example. The low basicity (0.04 mmol CO2/g) and low desorption temperature (50-300 °C) shown by CO2- TPD suggests that O2- sites at the external surfaces is weakly basic, while those at the interlayer space are mostly inaccessible to CO2. The liquid-phase adsorption study, however, revealed the uptake as much as 37% by mass of the bulky palmitic acid (C16 acid). The accompanying expansion of the interlayer space by ~0.1 nm was detected by PXRD and TEM. In an opposite manner to the external surfaces, the interlayer O2- sites can deprotonate palmitic acid, forming the salt (i.e., potassium palmitate) occluded between the sheets. Two types of basic sites are proposed based on ultrafast 1H MAS NMR and FTIR results. The interlayer basic sites in lepidocrocite titanate leads to an application of this material as a selective and stable two-dimensional (2D) basic catalyst, as demonstrated by the ketonization of palmitic acid into palmitone (C31 ketone). Tuning of the catalytic activity by varying the type of metal (Zn, Mg, and Li) substituting at TiIV sites was also illustrated.

  1. A simple preparation method and characterization of B and N co-doped TiO{sub 2} nanotube arrays with enhanced photoelectrochemical performance

    Energy Technology Data Exchange (ETDEWEB)

    Georgieva, J., E-mail: jenia@ipc.bas.bg [Rostislaw Kaischew Institute of Physical Chemistry, Bulgarian Academy of Sciences (Bulgaria); Valova, E.; Armyanov, S.; Tatchev, D. [Rostislaw Kaischew Institute of Physical Chemistry, Bulgarian Academy of Sciences (Bulgaria); Sotiropoulos, S. [Department of Chemistry, Aristotle University of Thessaloniki (Greece); Avramova, I. [Institute of General and Inorganic Chemistry, Bulgarian Academy of Sciences (Bulgaria); Dimitrova, N. [Rostislaw Kaischew Institute of Physical Chemistry, Bulgarian Academy of Sciences (Bulgaria); Hubin, A.; Steenhaut, O. [Research Group Electrochemical and Surface Engineering (SURF), Vrije Universiteit Brussel (Belgium)

    2017-08-15

    Highlights: • An environment-sparing method for preparation of B,N-co-doped TNTA is realized. • N and B promote additionally the reduction of Ti(IV) to Ti(III) during the crystallization annealing. • N and B dopants are predominantly in interstitial positions. • B,N-TNTA exhibited better photoelectrochemical performance and photoelectrocatalytic degradation of MO. - Abstract: Highly ordered TiO{sub 2} nanotube arrays (TNTA) have attracted much attention due to the excellent photocatalytic, optical and electrical properties. However, their absorption range is limited to ultraviolet (UV) spectrum only due to the wide band gap (3.2 eV). One of the strategies to overcome this problem is doping with boron and nitrogen. They are produced via titanium sheet anodization and subsequent electrochemical treatment of titania in an electrolyte containing boric acid. The as-prepared B-TNTA are annealed in N{sub 2} atmosphere at 500 °C for 2 h to obtain B,N-TNTA. The samples are characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), UV–vis diffuse reflectance spectroscopy (DRS) and X-ray photoelectron spectroscopy (XPS). The B,N-TNTA consist of uniform and well aligned nanotubes with an average inner diameter of 80–100 nm and a length not exceeding 1 μm. The photocurrent response measurements of undoped TNTA, N-doped and B,N-co-doped samples are performed under UV and visible light (Vis) illumination and a comparison is made. The obtained results show that the B,N-doping leads to remarkable photocurrent enhancement and better photocatalytic activity for methyl orange (MO) degradation due to the synergistic effects of B,N-co-doping and lower electron-hole recombination rates.

  2. Selective separation of uranium using alizarin red S (ARS)-modified anion-exchange resin or by flotation of U-ARS chelate

    International Nuclear Information System (INIS)

    Khalifa, M.E.

    1998-01-01

    An alizarin red S (ARS)-modified anion exchange resin was prepared by a simple reaction of ARS with the anion exchange Doulite A101 and used for the efficient sorption of uranium from aqueous media. The effect of various parameters on the sorption of U(VI) (pH effect, sorption kinetics, resin capacity and breakthrough curves) was investigated. The modified resin sorbs U(VI) over a wide range of pH (2.8--5) with a maximum sorption capacity of 0.68 mmol/g at pH 3.2 to 4.0. Iron(III), Zr(IV), Ti(IV), Cu(II), and Th(IV) ions are also sorbed to different extents, but Be(II), Bi(III), Ca(II), Mg(II), Pb(II), Hg(II), Zn(II), Cd(II), Al(III), Mn(II), Co(II) and Ni(II) are not sorbed; thus, conditions for separating U(VI) from these metal ions have been identified. For eluting U(VI) from the resin, 0.2 mol/L HCl was used and the recovery recorded was as high as 99.9%. The use of ARS is extended to float uranium quantitatively and selectively from aqueous media at pH ∼ 4 by using oleic acid as a surfactant. The different parameters affecting the flotation process have also been investigated. Uranium(VI) has been effectively separated from natural water samples and certified uranium ores using both procedures

  3. Biomolecule-free, selective detection of o-diphenol and its derivatives with WS2/TiO2-based photoelectrochemical platform.

    Science.gov (United States)

    Ma, Weiguang; Wang, Lingnan; Zhang, Nan; Han, Dongxue; Dong, Xiandui; Niu, Li

    2015-01-01

    Herein, a novel photoelectrochemical platform with WS2/TiO2 composites as optoelectronic materials was designed for selective detection of o-diphenol and its derivatives without any biomolecule auxiliary. First, catechol was chosen as a model compound for the discrimination from resorcinol and hydroquinone; then several o-diphenol derivatives such as dopamine, caffeic acid, and catechin were also detected by employing this proposed photoelectrochemical sensor. Finally, the mechanism of such a selective detection has been elaborately explored. The excellent selectivity and high sensitivity should be attributed to two aspects: (i) chelate effect of adjacent double oxygen atoms in the o-diphenol with the Ti(IV) surface site to form a five/six-atom ring structure, which is considered as the key point for distinction and selective detection. (ii) This selected WS2/TiO2 composites with proper band level between WS2 and TiO2, which could make the photogenerated electron and hole easily separated and results in great improvement of sensitivity. By employing such a photoelectrochemical platform, practical samples including commercial clinic drugs and human urine samples have been successfully performed for dopamine detection. This biomolecule-free WS2/TiO2 based photoelectrochemical platform demonstrates excellent stability, reproducibility, remarkably convenient, and cost-effective advantages, as well as low detection limit (e.g., 0.32 μmol L(-1) for dopamine). It holds great promise to be applied for detection of o-diphenol kind species in environment and food fields.

  4. Effects of adsorbed pyridine derivatives and ultrathin atomic-layer-deposited alumina coatings on the conduction band-edge energy of TiO2 and on redox-shuttle-derived dark currents.

    Science.gov (United States)

    Katz, Michael J; Vermeer, Michael J D; Farha, Omar K; Pellin, Michael J; Hupp, Joseph T

    2013-01-15

    Both the adsorption of t-butylpyridine and the atomic-layer deposition of ultrathin conformal coatings of insulators (such as alumina) are known to boost open-circuit photovoltages substantially for dye-sensitized solar cells. One attractive interpretation is that these modifiers significantly shift the conduction-edge energy of the electrode, thereby shifting the onset potential for dark current arising from the interception of injected electrons by solution-phase redox shuttle components such as Co(phenanthroline)(3)(3+) and triiodide. For standard, high-area, nanoporous photoelectrodes, band-edge energies are difficult to measure directly. In contrast, for flat electrodes they are readily accessible from Mott-Schottky analyses of impedance data. Using such electrodes (specifically TiO(2)), we find that neither organic nor inorganic electrode-surface modifiers shift the conduction-band-edge energy sufficiently to account fully for the beneficial effects on electrode behavior (i.e., the suppression of dark current). Additional experiments reveal that the efficacy of ultrathin coatings of Al(2)O(3) arises chiefly from the passivation of redox-catalytic surface states. In contrast, adsorbed t-butylpyridine appears to suppress dark currents mainly by physically blocking access of shuttle molecules to the electrode surface. Studies with other derivatives of pyridine, including sterically and/or electronically diverse derivatives, show that heterocycle adsorption and the concomitant suppression of dark current does not require the coordination of surface Ti(IV) or Al(III) atoms. Notably, the favorable (i.e., negative) shifts in onset potential for the flow of dark current engendered by organic and inorganic surface modifiers are additive. Furthermore, they appear to be largely insensitive to the identity of shuttle molecules.

  5. epoxidación de ésteres grasos

    Directory of Open Access Journals (Sweden)

    LUIS RIOS

    2006-01-01

    Full Text Available Centros discretos de TiIV dispersos en una matriz de SiO2 actúan como fuertes aceptores de electrones por lo cual son útiles para la activación de moléculas o funciones químicas densas en electrones. La cantidad de estos centros, su dispersión, accesibilidad y coordinación, determinan su eficiencia química; para determinar estas propiedades, varios materiales Ti-MCM-41 se caracterizaron mediante DRX, FTIR, UV-Vis e isotermas de adsorción de N2; también se determinaron la cristalinidad, porosidad y superficie específica de la matriz SiO2 permitiendo correlacionar el ambiente fisicoquímico del titanio y las propiedades texturales del catalizador, con su efectividad en la activación de enlaces O-O presentes en moléculas tipo peróxidos, usados en la epoxidación de aceites vegetales. Los resultados sugieren que la presencia de poros cristalinos, en la epoxidación del metiléster del ácido oleico con TBHP y catalizada con Ti-MCM-41, no es necesaria, puesto que la reacción ocurre principalmente en el área externa a los poros. Lo realmente importante es tener centros de Ti finamente dispersos sobre una área superficial alta y accesible. Por otro lado, la temperatura de reacción deber estar por debajo de 70°C para minimizar la formación de subproductos (cetona.

  6. Propozycja nowego podejścia metodycznego i interpretacji wyników oznaczeń przeciwciał przeciwko Borrelia burgdorferi – analiza składu przeciwciałowego krążących kompleksów immunologicznych

    Directory of Open Access Journals (Sweden)

    Karolina Miąskiewicz

    2011-10-01

    Full Text Available Borelioza z Lyme ma bogatą symptomatologię i w znacznym odsetkuprzypadków może przypominać wczesne stadia układowej chorobytkanki łącznej. Część pacjentów trafia po wizycie u lekarza POZdo reumatologa. Reumatolog może zlecić badania autoprzeciwciał„markerowych” oraz na obecność przeciwciał bakteryjnych (przeciwkoBorrelia burgdorferi. Odsetek wyników dodatnich w kierunku B. burgdorferijest znikomy (14,7%, istnieje zatem problem wiarygodnościtych wyników.Seronegatywność pod względem obecności swoistych przeciwciałdla B. burgdorferi dotyczy ok. 30���40% surowic pacjentów z podejrzeniemboreliozy, łącznie z pacjentami z potwierdzonymi w wywiadzieukąszeniami przez kleszcza i wystąpieniem objawu patognomonicznego(rumienia wędrującego. Mimo że dysponujemy licznymitestami bakteriologicznymi, serologicznymi czy molekularnymi(PCR, diagnostyka boreliozy nastręcza trudności i może prowadzić do uzyskiwania wyników fałszywie ujemnych lub fałszywie dodatnich.Autorzy pracy skupili się na surowicach pacjentów seronegatywnychpod względem przeciwciał dla B. burgdorferi, w których wolneprzeciwciała przeciwko B. burgdorferi zostały związane przezantygeny krętka i utworzyły krążące kompleksy immunologiczne (KKI.Celem pracy była analiza KKI pod kątem obecności przeciwciał przeciwkoB. burgdorferi w trudnych diagnostycznie surowicach pacjentów,u których obraz kliniczny wskazywał na obecność zakażenia krętkiemz rodzaju B. burgdorferi (ryc. 1–7. Badania przeprowadzono nasurowicach 54 chorych z wywiadem wskazującym na boreliozę. Zastosowanonowe metodyczne podejście do analizy obecności swoistychprzeciwciał dla B. burgdorferi – wytrącanie i dysocjację KKI, a następnieoznaczanie w uzyskanej frakcji γ z osadu PEG przeciwciał swoistychdla B. burgdorferi. W 41 surowicach ujemnych w teście ELISAwytrącono frakcję γ z osadu PEG i powtórnie oznaczono przeciwciaładla B. burgdorferi. W 82

  7. Ateities įžvalgos kaip e. valdžios plėtros strateginio planavimo sudedamoji dalis: siūlomas įžvalgų tyrimo proceso modelis

    Directory of Open Access Journals (Sweden)

    Rokas Grincevičius

    2013-01-01

    Full Text Available Tikslas – įvertinti įžvalgų poveikį e. valdžios strateginio planavimo procesui, atliekant šią temą nagrinėjančios literatūros bei skirtingų įžvalgų projektų metodikų analizę ir, sintezavus analizės rezultatus, parengti e. valdžios įžvalgų proceso modelį. Metodologija – tyrime taikyti metodai: literatūros apžvalga bei sisteminės analizės metodas. Rezultatai – išnagrinėtas įžvalgų poveikis e. valdžios plėtros procesams, nagrinėjant jį įvairių strateginio planavimo, politinių sprendimų priėmimo dimensijų kontekste, atlikta skirtingų įžvalgų metodikų analizė, remiantis ja, parengtas e. valdžios ateities įžvalgų tyrimo proceso modelis. Tyrimo ribotumas – nepaisant to, kad egzistuoja nemažai bandymų analizuoti e. valdžios strateginį planavimą ir ateities įžvalgas kaip du atskirus fenomenus, tvirtos teorijos, kompleksiškai apimančios abu reiškinius ir atskleidžiančios galimas jų sąveikos ribas, nėra, taigi nėra ir aiškios tyrimo metodologijos. Todėl egzistuoja tam tikra tikimybė, kad, nagrinėjant skirtingas įžvalgų metodikas, galėjo būti parinkti ne visi kintamieji, būtini tiksliam įžvalgų proceso įvertinimui. Praktinė reikšmė – tyrimo rezultatai gali būti taikomi kaip pagrindas organizuojamam įžvalgų proceso projektavimui, jau atlikto tyrimo proceso vertinimui ar siekiant geriau suprasti įžvalgų procesą sudarančius elementus bei jų tarpusavio ryšius. Vertingumas – nepaisant to, kad pasaulinėje prognozavimo praktikoje jau ne pirmus metus egzistuoja priemonės, leidžiančios tinkamai įvertinti ir padėti pasiruošti įvairaus pobūdžio ilgalaikiams iššūkiams, Lietuvoje bei daugelyje kitų Rytų Europos šalių planavimo procesas vis dar vyksta centralizuoto, penkmečiu paremto, planavimo tradicijomis. Dėl šios priežasties buvusio socialistinio bloko valstybės nuo kitų regionų atsilieka e. valdžios ir kitos tematikos ateities

  8. Optical properties of 3d transition metal ion-doped sodium borosilicate glass

    International Nuclear Information System (INIS)

    Wen, Hongli; Tanner, Peter A.

    2015-01-01

    Graphical abstract: Photographs of undoped (SiO 2 ) 50 (Na 2 O) 25 (B 2 O 3 ) 25 (SiNaB) glass and transition metal ion-doped (TM) 0.5 (SiO 2 ) 49.5 (Na 2 O) 25 (B 2 O 3 ) 25 glass samples. - Highlights: • 3d transition metal ion (from Ti to Zn) doped SiO 2 -Na 2 O-B 2 O 3 glasses. • Optical properties of doped glasses investigated. • V(IV,V); Cr(III, VI); Mn(II,III); Fe(II,III); Co(II); Ni(II); Cu(II) by XANES, DRS. • Strong visible absorption but only vanadium ion gives strong emission in glass. - Abstract: SiO 2 -Na 2 O-B 2 O 3 glasses doped with 3d-transition metal species from Ti to Zn were prepared by the melting-quenching technique and their optical properties were investigated. The X-ray absorption near edge spectra of V, Cr, and Mn-doped glasses indicate that the oxidation states of V(IV, V), Cr(III, VI) and Mn(II, III) exist in the studied glasses. The oxidation states revealed from the diffuse reflectance spectra of the glasses are V(IV, V), Cr(III, VI), Mn(III), Fe(II, III), Co(II), Ni(II), and Cu(II). Most of the 3d transition element ions exhibit strong absorption in the visible spectral region in the glass. Under ultraviolet excitation, the undoped sodium borosilicate glass produces weak and broad emission, while doping of vanadium introduces strong and broad emission due to the V(V) charge transfer transition. Only weak emission is observed from Ti(IV), Mn(II), Fe(III) and Cu(II), partly resulting from the strong electron–phonon coupling of the 3d-electrons and the relatively high phonon energy of the studied glass host, with the former leading to dominant nonradiative relaxation based on multiphonon processes for most of the 3d excited states

  9. Sandia octahedral molecular sieves (SOMS): structural and property effects of charge-balancing the M(IV)-substituted (M = Ti, Zr) Niobate framework.

    Science.gov (United States)

    Nyman, May; Tripathi, Akhilesh; Parise, John B; Maxwell, Robert S; Nenoff, Tina M

    2002-02-27

    Sandia octahedral molecular sieves (SOMS) is an isostructural, variable composition class of ion exchangers with the general formula Na(2)Nb(2-x)M(IV)(x)O (6-x)(OH)(x).H(2)O (M(IV) = Ti, Zr; x = 0.04-0.40) where up to 20% of the framework Nb(V) can be substituted with Ti(IV) or Zr(IV). This class of molecular sieves is easily converted to perovskite through low-temperature heat treatment (500-600 degrees C). This report provides a detailed account of how the charge imbalance of this Nb(V)-M(IV) substitution is compensated. X-ray powder diffraction with Rietveld refinement, infrared spectroscopy, thermogravimetric analysis, (23)Na MAS NMR, and (1)H MAS NMR were used to determine how the framework anionic charge is cation-balanced over a range of framework compositions. All spectroscopic evidence indicated a proton addition for each M(IV) substitution. Evidences for variable proton content included (1) increasing OH observed by (1)H MAS NMR with increasing M(IV) substitution, (2) increased infrared band broadening indicating increased H-bonding with increasing M(IV) substitution, (3) increased TGA weight loss (due to increased OH content) with increasing M(IV) substitution, (4) no variance in population on the sodium sites (indicated by Rietveld refinement) with variable composition, and (5) no change in the (23)Na MAS NMR spectra with variable composition. Also observed by infrared spectroscopy and (23)Na MAS NMR was increased disorder on the Nb(V)/M(IV) framework sites with increasing M(IV) substitution, evidenced by broadening of these spectral features. These spectroscopic studies, along with ion exchange experiments, also revealed the effect of the Nb(V)/M(IV) framework substitution on materials properties. Namely, the temperature of conversion to NaNb(1-x)M(IV)(x)O(3) (M = Ti, Zr) perovskite increased with increasing Ti in the framework and decreased with increasing Zr in the framework. This suggested that Ti stabilizes the SOMS framework and Zr destabilizes

  10. “Playing catch up”. The notion of needing to accelerate a country’s progress towards a civilised paradise – the Bulgarian version (a proposed entry for a dictionary of peregrinating ideas

    Directory of Open Access Journals (Sweden)

    Grażyna Szwat-Gyłybowa

    2014-11-01

    cultures which indulged in it, only to become doomed to dull, infantile repetition.   "Doganianie". Idea przyspieszonego rozwoju w drodze do cywilizacyjnego raju. Wersja bułgarska Artykuł poświęcony jest prezentacji głównych etapów procesu inkorporowania w tkankę bułgarskiej idei narodowej pojęcia doganiania (przyspieszonego rozwoju, które od połowy XIX wieku pozostaje narzędziem konceptualizacji przez Bułgarów ich (różnie wartościowanego miejsca wśród „narodów cywilizowanych”. „Doganianie” rozumiem jako kulturowo i politycz­nie funkcjonalny wzór rzeczy, który jest konceptem niesamodzielnym, należącym do różnych systemów idei, mającym swój aspekt ekonomiczny, geopolityczny, religijny, psychologiczny, kulturowy. Formuła opóźnienia, zintegrowana z ideą doganiania zagościła w dyskusjach nad statusem Bułgarów jeszcze przed zaistnieniem narodu politycznego. Wraz z rozwojem ruchu narodowego kompleksy otrzymały swój rewers w postaci wiary w możliwość zrównania poziomu cywilizacyjnego z europejskim. Ta linia rozumowania prowadziła od pierwszych fascynacji dorobkiem „oświeconych narodów” w ramach tzw. oświecenia prawosławnego, przez odwzorowywanie dyskursu rosyjskiego po myśl marksistowską (z jej propagandową dominantą w latach 1945–89 i polityki perswazyjne po 1989 roku. Wydaje się, że współcześnie mamy do czynienia z podzwonnym dla związanej z czasowością idei doganiania, która wyczerpała swój potencjał agoniczny a może nawet przyczyniła się do „samozatrucia” absorbujących ją kultur, skazujących się na infantylizację i nudę powtórzeń.

  11. Characteristics of the reindeer electrocardiogram

    Directory of Open Access Journals (Sweden)

    Jouni Timisjärvi

    1982-05-01

    ämen syketiheydestä, sähköisestä johtumisesta ja välillisesti jossain määrin myös sydänlihaksen toiminnallisesta tilasta. Suurin osa tämänkaltaista tietoa voidaan saada tavanomaisia skalaarisia kytkentöjäkäyttäen, ja usein yhdessä tasossa tapahtuva rekisteröinti on riittävä. Tässä työssä on tutkittu porojen normaalia sydänsähkökäyrää ja sen eri poikkeamien suuntautumista frontaalitasossa, kun rekisteröinnissä on käytetty Einthovenin postulaattien mukaisia raajakytkentöjä. P aalto suuntautui ylöspäin kythkennöissä II, III ja aVF, alaspäin kytkennässä aVL ja vaihteli kytkennöissä I ja aVR. P vektorin suunta oli 60 - 120°. QRS kompleksi vaihteli. Tavallisimmat muodot olivat R ja rS kytkennöissä I ja aVR; R, Rs ja rS kytkennässä aVL ja Qr tai qR muissa kytkennöissä. Tavallisin QRS vektorin suunta oli 240 - 300°. T aalto vaihteli. Poikkeaminen ja intervallien kesto riippui sydämen syketiheydestä.

  12. Analytical recovery of Cr (VI), Mo (VI), Ti (IV) and Co (II) by N-phenyl-meta-nitro-benzohydroxamic and N-P-tolyl-meta-nitro-benzohydroxamic acids

    International Nuclear Information System (INIS)

    Ahmed, Abdul Aziz Malik Mohamed

    2000-05-01

    , of 82.20% for Mo (VI) at pH 1.0, and of 78.47% for Co (II) at pH 8.0, whereas N-p-tolyl-m-nitro-benzohydroxamic acid was found to have a maximum extraction of 42.25% for Ti (IV) at pH 2.0, of 97.06 for Cr (VI) at 3MH 2 SO 4 , of 81.32% for Mo (VI) at pH 1.0, and of 71.13% for Co (II)) at pH 8.0. The two reagents developed yellow colour chelate with Cr(VI) which was found to have molar absorptivity equal to 9014 L.mole -1 .cm -1 at wave length 480 nm, whereas the chelate of Cr(VI) with 1,5 diphenyl-carbazide have molar absorptivity equal to 8694 L.mole -1 .cm -1 at the same wavelength. The two reagents developed colorless chelate with Ti(IV), Mo(VI) and Co(II). (Author)

  13. Group 4 Metalloporphyrin diolato Complexes and Catalytic Application of Metalloporphyrins and Related Transition Metal Complexes

    Energy Technology Data Exchange (ETDEWEB)

    Du, Guodong [Iowa State Univ., Ames, IA (United States)

    2003-01-01

    In this work, the first examples of group 4 metalloporphyrin 1,2-diolato complexes were synthesized through a number of strategies. In general, treatment of imido metalloporphyrin complexes, (TTP)M=NR, (M = Ti, Zr, Hf), with vicinal diols led to the formation of a series of diolato complexes. Alternatively, the chelating pinacolate complexes could be prepared by metathesis of (TTP)MCl2 (M = Ti, Hf) with disodium pinacolate. These complexes were found to undergo C-C cleavage reactions to produce organic carbonyl compounds. For titanium porphyrins, treatment of a titanium(II) alkyne adduct, (TTP)Ti(η2-PhC≡CPh), with aromatic aldehydes or aryl ketones resulted in reductive coupling of the carbonyl groups to produce the corresponding diolato complexes. Aliphatic aldehydes or ketones were not reactive towards (TTP)Ti(η2-PhC≡CPh). However, these carbonyl compounds could be incorporated into a diolato complex on reaction with a reactive precursor, (TTP)Ti[O(Ph)2C(Ph)2O] to provide unsymmetrical diolato complexes via cross coupling reactions. In addition, an enediolato complex (TTP)Ti(OCPhCPhO) was obtained from the reaction of (TTP)Ti(η2-PhC≡CPh) with benzoin. Titanium porphyrin diolato complexes were found to be intermediates in the (TTP)Ti=O-catalyzed cleavage reactions of vicinal diols, in which atmospheric oxygen was the oxidant. Furthermore, (TTP)Ti=O was capable of catalyzing the oxidation of benzyl alcohol and α-hydroxy ketones to benzaldehyde and α-diketones, respectively. Other high valent metalloporphyrin complexes also can catalyze the oxidative diol cleavage and the benzyl alcohol oxidation reactions with dioxygen. A comparison of Ti(IV) and Sn(IV) porphyrin chemistry was undertaken. While chelated diolato complexes were invariably obtained for titanium porphyrins on treatment with 1,2-diols, the reaction of vicinal diols with tin porphyrins gave a number of products, including mono

  14. Scanning electron microscopy and X-ray photoelectron studies of high temperature oxidation mechanism of a Fe-Cr-Al alloy; Etude par microscopie electronique a balayage et spectroscopie de photoelectrons des mecanismes d'oxydation a haute temperature d'un alliage Fe-Cr-Al

    Energy Technology Data Exchange (ETDEWEB)

    Delaunay, F.; Berthier, C.; Lameille, J.M. [CEA Saclay, Dept. d' Entreposage et de Stockage des Dechets (DCC/DPE/SPCP), 91 - Gif-sur-Yvette (France)

    2000-07-01

    The lifetime of high temperature materials is strongly dependent on their resistance to high temperature oxidation. Hence the technical applications of these materials require the formation of a protective, slow growing oxide scale. The efficiency of Cr{sub 2}O{sub 3}- forming alloys above 1100 deg C is limited because Cr{sub 2}O{sub 3} reacts with oxygen to form volatile CrO{sub 3}. It is known that doping alloys with small additions (< 0.1 wt %) can improve mechanical properties and/or alloy oxidation resistance. Fe{sub 20}Cr{sub 5}Al based alloys form protective scale of alumina with slow growth rates at temperatures above 1000 deg C. The alloy composition is given in Table 1. Various techniques have been used to determine the scale morphology, structure and composition of oxide scale, including Scanning Electron Microscopy coupled with Energy Dispersive X-ray Spectrometry, grazing incidence X-ray diffraction, and XPS. During heat treatment at 1150 C, ranging from 5 minutes to 24 hours, a parabolic regime is observed, leading to a protective layer against oxidation. The oxide scale structure mainly consists of thermodynamically stable {alpha}-Al{sub 2}O{sub 3}. After 1 hour, (Mg{sub 1-X}Fe{sub X})Al{sub 2}O{sub 4} appears and increases with treatment time. After 5 minutes at 1150 deg C, X ray maps indicating the location of the elements in the oxide scale were prepared with SEM-EDS. Figure 2 shows that the oxide scale mainly consists of alumina. The secondary electron image shows little islands consisting of yttrium and zirconium on the oxide scale. For longer oxidation time, I hour, XPS results reveal chemical species like Al{sub 2}O{sub 3}),Ti(IV) (TiO{sub 2}), Cr(III) that yttrium and zirconium are not detected. After 24 hours, scale thickness is about 2 {mu}m. Small islands of yttrium and zirconium (and to a lesser degree titanium) are still present. In Figure 4, magnesium and titanium are located on the alumina scale. X-ray maps on cross-sections in Figure

  15. Design and Development of Mixed-Metal Oxide Photocatalysts: the Band Engineering Approach

    Science.gov (United States)

    Boltersdorf, Jonathan Andrew

    (I), Pb(II), Sn(II), Bi(III); B = Ta, Nb), Pb3Ta 4O13, PbTa2O6, Bi7Ta 3O18, and Sn2TiO4. The impact of the dimensionality of the structural features on the photocatalytic activities of the metal-oxides will be examined. A comparison of the influence of Ag(I), Pb(II), Sn(II), and Bi(III) cations in combination with Ti(IV), Nb(V), and Ta(V) cations on the optical properties and photocatalytic rates of the mixed-metal oxides will be presented. The results of these investigations have led to new insights into synthetic strategies for the development of new metal-oxide photocatalysts, which have aided in understanding the effects of transition and post-transition metals, structural features, and flux-mediated synthesis methods on the optical and photocatalytic properties of metal oxides for solar fuel production.

  16. Imobilisasi TiO2 ke dalam Resin Penukar Kation dan Aplikasinya sebagai Fotokatalis dalam Proses Fotoreduksi Ion Hg2+

    Directory of Open Access Journals (Sweden)

    Rosyid Ridho

    2017-03-01

    Full Text Available Abstrak Dalam rangka mengembangkan bahan fotokatalitis TiO2 pada penelitian ini telah dilakukan preparasi fotokatalis TiO2-Resin yang disertai dengan karakterisasi dan uji aktivitas untuk proses fotoreduksi ion Hg(II. Preparasi imobilisasi ini dilakukan dengan metode pertukaran ion yang di ikuti dengan kalsinasi pada suhu tertentu. Pada preparasi telah dipelajari pengaruh konsentrasi Titanium Isopropoksida sebagai sumber ion Ti(IV terhadap TiO2-Resin yang dikarakterisasi dengan menggunakan Difraksi Sinar X (XRD dan Thermografimetri (TGA. Pada proses fotoreduksi ion Hg(II dipelajari pengaruh massa fotokatalis, kadar TiO2 yang terimobilisasi ke dalam resin, konsentrasi Ion Hg(II, dan pengaruh pH. Proses fotoreduksi dilakukan dalam suatu reaktor tertutup yang dilengkapi dengan lampu UV, yaitu dengan cara menyinari campuran yang terdiri dari larutan ion Hg(II dan serbuk fotokatalis TiO2-Resin, disertai dengan pengadukan selama waktu tertentu. Hasil fotoreduksi dihitung berdasarkan selisih antara konsentrasi ion Hg(II awal dengan ion Hg(II yang tak tereduksi. Penentuan konsentrasi ion Hg(II yang tak tereduksi dilakukan dengan menggunakan Spektrofotometer Serapan Atom (SSA teknik pembangkitan uap dingin atau Cold Vapor Atomic Absorption Spectrophotometry(CV-AAS. Hasil preparasi menunjukkan semakin tinggi konsentrasi Titanium Isopropoksida yang ditambahkan pada resin semakin tinggi juga kadar TiO2 yang terbentuk pada TiO2-Resin. Hasil uji fotokatalis menunjukkan bahwa penggunaan fotokatalis TiO¬2-Resin dapat meningkatkan hasil fotoreduksi ion Hg(II yang peningkatannya lebih tinggi dibandingkan TiO2 serbuk. Penambahan fotokatalis dengan massa yang semakin besar menambah efektivitas fotoreduksi terhadap ion Hg(II yang semakin besar, namun jika ditambahkan massa fotokatalis yang lebih tinggi lagi akan menurunkan efektivitas fotoreduksi terhadap ion Hg(II. Kenaikan konsentrasi Hg(II menyebabkan efektivitas fotoreduksi semakin rendah. Pada pH 1-4 terjadi

  17. Some factors influencing the absorption, retention and elimination of ruthenium; Facteurs agissant sur l'absorption, la retention et l'elimination du ruthenium; Nekotorye faktory, vliyakshchie na vsasyvanie, zaderzhku i vydelenie ruteniya; Factores que influyen sobre la absorcion, retencion y eliminacion de rutenio

    Energy Technology Data Exchange (ETDEWEB)

    Bruce, R. S. [Radiobiological Research Council, Medical Research Council, Harwell (United Kingdom)

    1963-02-15

    syvorotki. Zaderzhka ruteniya v drugikh tkanyakh takzhe mozhet opredelyat'sya skorost'yu katabolizma belkov. Poskol'ku pri reaktsii ruteniya s belkami obrazuyutsya ustojchivye kompleksy, trudno najti kakoelibo aek and rgtgennoe lechenie dlya snizheniya zaderzhki. Kompleksoobrazukhntsie veshchestva EDTA, DTRA i TTJA ne vliyayut na raspredelenie ili vydelenie ruteniya, vvedennogo krysam vnutrivenno. (author)