Science.gov

Sample records for acid zirconium complex

  1. 40 CFR 721.10089 - Modified salicylic acid, zirconium complex (generic).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Modified salicylic acid, zirconium... Specific Chemical Substances § 721.10089 Modified salicylic acid, zirconium complex (generic). (a) Chemical... as modified salicylic acid, zirconium complex (PMN P-00-552) is subject to reporting under...

  2. 40 CFR 721.10089 - Modified salicylic acid, zirconium complex (generic).

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Modified salicylic acid, zirconium... Specific Chemical Substances § 721.10089 Modified salicylic acid, zirconium complex (generic). (a) Chemical... as modified salicylic acid, zirconium complex (PMN P-00-552) is subject to reporting under...

  3. 40 CFR 721.10089 - Modified salicylic acid, zirconium complex (generic).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Modified salicylic acid, zirconium... Specific Chemical Substances § 721.10089 Modified salicylic acid, zirconium complex (generic). (a) Chemical... as modified salicylic acid, zirconium complex (PMN P-00-552) is subject to reporting under...

  4. 40 CFR 721.10089 - Modified salicylic acid, zirconium complex (generic).

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Modified salicylic acid, zirconium... Specific Chemical Substances § 721.10089 Modified salicylic acid, zirconium complex (generic). (a) Chemical... as modified salicylic acid, zirconium complex (PMN P-00-552) is subject to reporting under...

  5. 40 CFR 721.10089 - Modified salicylic acid, zirconium complex (generic).

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Modified salicylic acid, zirconium... Specific Chemical Substances § 721.10089 Modified salicylic acid, zirconium complex (generic). (a) Chemical... as modified salicylic acid, zirconium complex (PMN P-00-552) is subject to reporting under...

  6. Zirconium complexes with lactic acid in the solution and solid states

    NASA Astrophysics Data System (ADS)

    Demkowicz, Paul Andrew

    Lactic acid complexes of zirconium are used in a great number of industrial applications. Among these is their use as crosslinking agents for hydraulic fracturing fluids used in secondary oil recovery operations. Because of a poor understanding of zirconium lactate complex chemistry and crosslinking reactions, however, the design of superior fluid systems is often not guided by sound chemical principles and leads to empirical guesswork. Zirconium lactate solutions were characterized using Fourier transform infrared (FT-IR) spectroscopy, 1H, 13C, and 17O nuclear magnetic resonance (NMR) spectroscopy, and potentiometry. The results indicate that lactic acid is coordinated bidentate to zirconium via the alcohol and carboxylate groups. The average number of lactate ligands per zirconium ion is approximately 2 and is demonstrated to be relatively constant from pH 4--9. The lability of the lactate complexes increases as the pH is decreased. The NMR data reveal that there are both large and small complex molecules present in solution, with the size of the complex depending on the extent of zirconium hydrolysis. Large complexes consist of lactic acid coordinated to polynuclear zirconium hydroxy ions. The molecular size of these complexes is sufficient to hinder their tumbling in solution and cause broadening of the measured NMR signals. Small complexes involve lactic acid coordinated to hydroxylated species containing fewer zirconium ions, such that the rotational motion in solution is sufficiently rapid to result in narrow NMR signals. Zirconium lactate complexes were precipitated from solution and analyzed in the solid state using FT-IR spectroscopy, 13C magic angle spinning (MAS) NMR spectroscopy, elemental analysis, thermal gravitational analysis, and x-ray diffraction. Two distinct types of crystalline compounds were synthesized with four lactate ligands per zirconium ion. The coordination of lactic acid to zirconium is different in the two compounds, with one showing

  7. Modification in band gap of zirconium complexes

    NASA Astrophysics Data System (ADS)

    Sharma, Mayank; Singh, J.; Chouhan, S.; Mishra, A.; Shrivastava, B. D.

    2016-05-01

    The optical properties of zirconium complexes with amino acid based Schiff bases are reported here. The zirconium complexes show interesting stereo chemical features, which are applicable in organometallic and organic synthesis as well as in catalysis. The band gaps of both Schiff bases and zirconium complexes were obtained by UV-Visible spectroscopy. It was found that the band gap of zirconium complexes has been modified after adding zirconium compound to the Schiff bases.

  8. Defluoridation of water using dicarboxylic acids mediated chitosan-polyaniline/zirconium biopolymeric complex.

    PubMed

    Muthu Prabhu, Subbaiah; Meenakshi, Sankaran

    2016-04-01

    The present investigation describes the preparation of hydrogen bonded chitosan-polyaniline/zirconium biopolymeric matrix by grafting method under dicarboxylic acid medium for the removal of fluoride, first time. Herein, the dicarboxylic acids, oxalic acid, malonic acid, succinic acid were used as medium. The synthesized complex was characterized by usual analytical techniques like FTIR, XRD, SEM and EDAX analysis. From the batch equilibrium experiments, the maximum defluoridation capacity (DC) was found to be 8.713 mg/g at room temperature with the minimum contact time of 24 min at 100mg of the sorbent dosage. The temperature study results of adsorption kinetics showed the adsorption behavior could be better described by the pseudo-second-order equation than pseudo-first-order kinetic model. The adsorption isotherm was well fitted by the Freundlich equation rather than Langmuir and D-R isotherms. The mechanism of fluoride removal was ligand exchange at neutral pH and electrostatic attraction at acidic pH of the medium. Regeneration studies were carried out to identify the best regenerant which makes the process cost-effective. Conclusions of this work demonstrate the potential applicability of the dicarboxylic acid mediated chitosan-polyaniline/zirconium complex as an effective adsorbent for fluoride removal from water. PMID:26706844

  9. Novel one-pot synthesis of dicarboxylic acids mediated alginate-zirconium biopolymeric complex for defluoridation of water.

    PubMed

    Prabhu, Subbaiah Muthu; Meenakshi, Sankaran

    2015-04-20

    The present investigation explains the fluoride removal from aqueous solution using alginate-zirconium complex prepared with respective dicarboxylic acids like oxalic acid (Ox), malonic acid (MA) and succinic acid (SA) as a medium. The complexes viz., alginate-oxalic acid-zirconium (Alg-Ox-Zr), alginate-malonic acid-zirconium (Alg-MA-Zr) and alginate-succinic acid-zirconium (Alg-SA-Zr) were synthesized and studied for fluoride removal. The synthesized complexes were characterized by FTIR, XRD, SEM with EDAX and mapping images. The effects of various operating parameters were optimized. The result showed that the maximum removal of fluoride 9653mgF(-)/kg was achieved by Alg-Ox-Zr complex at acidic pH in an ambient atmospheric condition. Equilibrium data of Alg-Ox-Zr complex was fitted well with Freundlich isotherm. The calculated values of thermodynamic parameters indicated that the fluoride adsorption is spontaneous and endothermic in nature. The mechanism of fluoride removal behind Alg-Ox-Zr complex has been proposed in detail. The suitability of the Alg-Ox-Zr complex has been tested with the field sample collected in a nearby fluoride endemic area. PMID:25662688

  10. Zirconium in a sulfuric acid pickling application

    SciTech Connect

    Yau, T.L.

    1988-01-01

    In 1972, Goodyear discovered that zirconium was an ideal material to construct heating coils for sulfuric acid picking tanks. Recently, localized corrosion and high uniform corrosion were reported with certain zirconium coils. The problems could be attributed to the contamination of chloride and/or fluoride ions. Results of electrochemical and immersion tests are used to discuss the effects of acid concentration and acid impurities, such as iron, chloride and fluoride ions, on zirconium's corrosion properties in H/sub 2/SO/sub 4/. Possible sources for acid impurities are identified. Recommendations are made for steel picking when zirconium equipment is used.

  11. Synthesis, Structural Characterization and Biological Activity of Peroxo Complexes of Zirconium (IV) Containing Organic Acid and Amine Bases

    NASA Astrophysics Data System (ADS)

    Nasrin, Jahanara; Saidul Islam, M.

    The study was extended to isolate the peroxo complexes of Zr (IV) containing organic acid and amine bases. The Zr (IV) complexes have been found to oxidize allyl alcohol and triphenylphosphine as well as triphenylarsine to their respective oxides. The analytical data are in good agreement with the proposed empirical formulae of the present complexes. The complexes display v(C = O) bands at ~1630 cm-1 and v(C-O) bands at ~1412 cm-1 significantly lower than the values of amino acid (~1650 and ~1450 cm-1). These indicate the coordination of amino acid through their carboxylate anion. The broad band observed at about 3217-3350 cm-1 for v (N-H) modes indicate the coordination of amino group through nitrogen atom of amino acid. The metal peroxo grouping gives rise to three IR active vibrational modes. These are predominantly O-O stretching v1, the symmetric M-O stretch v2 and the antisymmetric M-O stretch v3. The magnetic moment values indicated that these complexes were diamagnetic in nature suggesting no changes in their oxidation states of the metal ions upon complexation. These data also consistent with six fold coordination of Zr (IV). The electronic spectral data of the complexes showed bands in the region 230-372 nm due to the charge transfer band only. All the complexes of Zr (IV) did not show any remarkable antibacterial activity. It is interesting to note that these complexes were found to be fully inactive against the three pathogenic fungi A. niger, A. fumigatus and A. flarus. Moreover, all the complexes of Zr (IV) metals showed toxic effect against the brine shrimp.

  12. 40 CFR 721.10250 - Zirconium lysine complex (generic).

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Zirconium lysine complex (generic... Specific Chemical Substances § 721.10250 Zirconium lysine complex (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as...

  13. 40 CFR 721.10250 - Zirconium lysine complex (generic).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Zirconium lysine complex (generic... Specific Chemical Substances § 721.10250 Zirconium lysine complex (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as...

  14. 40 CFR 721.10250 - Zirconium lysine complex (generic).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Zirconium lysine complex (generic... Specific Chemical Substances § 721.10250 Zirconium lysine complex (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as...

  15. Evaluation of localized corrosion of zirconium in acidic chloride solutions

    SciTech Connect

    Fahey, J.; Holmes, D.; Yau, T.L.

    1997-01-01

    Zirconium is prone to localized corrosion in acidic chloride (Cl{sup {minus}}) solutions contaminated by oxidizing ions, such as ferric or cupric ions. This tendency can be reduced by ensuring that the zirconium surface is clean and smooth. The effect of surface condition on localized corrosion of zirconium in acidic chloride solutions was predicted using potentiodynamic polarization scans. Predictions were confirmed by mass-loss tests on various combinations of surface finish and acid concentrations. A real-time indication of localized corrosion was derived by monitoring electrochemical noise produced between two similar electrodes immersed in an acidic chloride solution. Electrochemical noise monitoring correlated well with predictions from the potentiodynamic polarization and mass-loss experiments. Electrochemical noise results showed a more anodic potential caused by ferric ion (Fe{sup 3+}) contamination might be necessary for localized corrosion but that it was not a sufficient condition. A clean zirconium surface reduced localized corrosion of zirconium.

  16. Theoretical stusy of the reaction between 2,2',4' - trihydroxyazobenzene-5-sulfonic acid and zirconium

    USGS Publications Warehouse

    Fletcher, Mary H.

    1960-01-01

    Zirconium reacts with 2,2',4'-trihydroxyazobenzene-5-sulfonic acid in acid solutions to Form two complexes in which the ratios of dye to zirconium are 1 to 1 and 2 to 1. Both complexes are true chelates, with zirconium acting as a bridge between the two orthohydroxy dye groups. Apparent equilibrium constants for the reactions to form each of the complexes are determined. The reactions are used as a basis for the determination of the active component in the dye and a graphical method for the determination of reagent purity is described. Four absorption spectra covering the wave length region from 350 to 750 mu are given, which completely define the color system associated with the reactions in solutions where the hydrochloric acid concentration ranges from 0.0064N to about 7N.

  17. Stress corrosion cracking of zirconium in nitric acid

    SciTech Connect

    Beavers, J A; Griess, J C; Boyd, W K

    1980-01-01

    The susceptibility of zirconium and its common alloys to stress corrosion cracking (SCC) in nitric acid was investigated by slow strain-rate and constant deflection techniques. Cracking occurred at 25/sup 0/C over a wide range of acid concentrations and electrochemical potentials. The crack velocity increased slightly with increasing temperature. The failure mode was transgranular and the morphology was similar to SCC failures of zirconium alloys in other environments. The fracture was very orientation-dependent suggesting that it occurs on a single crystallographic plane in the material. The results of the study are not consistent with a hydrogen mechanism for cracking.

  18. Comparative behavior of titanium and zirconium in hydrofluoric-nitric acid pickling solutions

    SciTech Connect

    Sutter, E.M.M.; Hlawka, F.; Cornet, A. )

    1990-07-01

    The different behavior of titanium and zirconium in HF-HNO{sub 3} pickling solutions has been studied using electrochemical methods and Raman spectrometry. In each case, the depleting of the solutions during a pickling experiment could be correlated with the consumption of HF to form metal oxo or oxofluoro complexes. However, the mechanism of metal dissolution is quite different for the two metals. The titanium dissolution process in such solutions can be interpreted using a passivation model in which dissolution and passivation are two competing reactions at the surface of the bare metal. On the other hand, zirconium dissolution occurs through formation of an oxide film with ionic diffusion through the film being a rate-determining step. The particular role of strong acid added to the HF solution for pickling of titanium and zirconium is also discussed.

  19. Zirconium

    USGS Publications Warehouse

    Bedinger, G.M.

    2013-01-01

    Zirconium is the 20th most abundant element in the Earth’s crust. It occurs in a variety of rock types and geologic environments but most often in igneous rocks in the form of zircon (ZrSiO4). Zircon is recovered as a coproduct of the mining and processing of heavy mineral sands for the titanium minerals ilmenite and rutile. The sands are formed by the weathering and erosion of rock containing zircon and titanium heavy minerals and their subsequent concentration in sedimentary systems, particularly in coastal environments. A small quantity of zirconium, less than 10 kt/a (11,000 stpy), compared with total world production of 1.4 Mt (1.5 million st) in 2012, was derived from the mineral baddeleyite (ZrO2), produced from a single source in Kovdor, Russia.

  20. Stress corrosion cracking of zirconium in hot nitric acid

    SciTech Connect

    Kajimura, H.; Nagano, H. )

    1992-05-01

    Zirconium (Zr) has excellent general corrosion resistance in nitric acid. However, stress corrosion cracking (SCC) has been reported in concentrated nitric acid. The purpose of this paper is to evaluate the SCC susceptibility of Zr as a function of HNO[sub 3] concentration, from 6 to 94%, and temperature. The SCC mechanism was also investigated in relation to the electrochemical behavior. The slow strain rate test technique, under constant potential conditions, was mainly adopted for SCC testing. SCC did not occur in the boiling HNO[sub 3] at concentrations less than 70% unless an anodic potential was applied. The critical SCC potential, which coincides with the transient potential from passive to transpassive behavior in the polarization curve, decreased with an increase in HNO[sub 3] concentration. In boiling 94% HNO[sub 3] Zr exhibited SCC even under open-circuit potential conditions.

  1. Control and monitoring of the localized corrosion of zirconium in acidic chloride solutions

    SciTech Connect

    Fahey, J.; Holmes, D.; Yau, T.L.

    1995-09-01

    Zirconium in acidic chloride solutions which are contaminated with ferric or cupric cations is prone to localized corrosion. This tendency can be reduced by ensuring that the zirconium surface is clean and smooth. In this paper, the effect of surface condition on the localized corrosion of zirconium in acidic chloride solutions is predicted with potentiodynamic scans. These predictions are confirmed by weight loss tests on various combinations of surface finish and acid concentrations. A real time indication of localized corrosion is seen by monitoring the electrochemical noise produced between two similar electrodes immersed in an acidic chloride solutions. Electrochemical noise monitoring correlates well with the predictions from potentiodynamic and weight loss experiments. The electrochemical noise results show that while an elevated (more anodic) potential caused by ferric ion contamination may be a necessary condition for localized corrosion, it is not a sufficient condition: A smooth, clean zirconium surface reduces the localized corrosion of zirconium.

  2. Electrochemical protection of zirconium in oxidizing hydrochloric acid solutions

    SciTech Connect

    Yuu, T-L.; Maguire, M.

    1984-06-01

    An electrochemical protection technique using cathodic polarization to maintain zirconium below its critical repassivation potential was used to avoid pitting and stress corrosion cracking (SCC) in hydrochloric acid (HCI) containing ferric ions (Fe/sup +3/). Corrosion and pit penetration rates are reported for pickled, abraded, and as-received surface conditions in 10, 20, and 37% HCI containing 50, 100, or 500 ppm Fe/sup +3/ at temperatures to boiling. The pickled surface was the least susceptible to pitting in the 64 day tests. Electrochemical protection is then evaluated for total immersion, partial immersion, U-bend, and constant strain rate tensile tests. Protection is effective in eliminating pitting and SCC in 10 and 20% HCI containing Fe/sup +3/.

  3. Isomerization of Cyclooctadiene to Cyclooctyne with a Zinc/Zirconium Heterobimetallic Complex.

    PubMed

    Butler, Michael J; White, Andrew J P; Crimmin, Mark R

    2016-06-01

    Reaction of a zinc/zirconium heterobimetallic complex with 1,5-cyclooctadiene (1,5-COD) results in slow isomerization to 1,3-cyclooctadiene (1,3-COD), along with the formation of a new complex that includes a cyclooctyne ligand bridging two metal centers. While analogous magnesium/zirconium and aluminum/zirconium heterobimetallic complexes are competent for the catalytic isomerization of 1,5-COD to 1,3-COD, only in the case of the zinc species is the cyclooctyne adduct observed. PMID:27071992

  4. Factors affecting the stress corrosion cracking susceptibility of zirconium in 90% nitric acid

    SciTech Connect

    Yau, T.L.

    1988-10-01

    U-band, C-ring, and slow strain rate tests were performed to evaluate the effects of texture, stress, surface condition, heat treatments electrochemical potential, and strain rate on stress corrosion cracking (SCC) of zirconium in 90% nitric acid at room temperature. Careful control of texture, surface condition (scratching, cleaning, and oxide coating), and/or applied stress was shown to effectively lead to the prevention of SCC of zirconium in 90% HNO/sub 3/. Heat treating at 760, 880, or 1000 C does not seem to improve the SCC resistance. However, if the potential of zirconium is maintained at 500 mV/sub SCE/ or lower, or 200 ppm of HF is added, zirconium's SCC susceptibility in 90% HNO/sub 3/ is eliminated. When adding HF, zirconium sponge must also be added to avoid corrosion rates.

  5. Determination of trace amount of oxalic acid with zirconium(IV)-(DBS-arsenazo) by spectrophotometry

    NASA Astrophysics Data System (ADS)

    Zhai, Qing-Zhou

    2008-11-01

    A novel method is proposed for the determination of trace amount of oxalic acid in the present article. In 1.0 M hydrochloric acid medium, oxalic acid can react with the zirconium(IV) in Zr(IV)-(DBS-arsenazo) complex and replaces the DBS-arsenazo to produce a hyperchromic effect at 520 nm. The hyperchromic degree is proportional to the concentration of the oxalic acid added over a defined range. Based on this property, a new method for the spectrophotometric determination of trace oxalic acid was developed. Beer's law is held over the concentration range of 9.0 × 10 -6 to 5.0 × 10 -4 M for oxalic acid with a correlation coefficient of 0.9995. The apparent molar absorptivity of the method is ɛ520 nm = 1.16 × 10 3 L mol -1 cm -1 and the detection limit for oxalic acid is 0.815 μg/mL. The developed method was directly applied to the determination of oxalic acid in tomato samples with satisfactory results.

  6. Trivalent metallocene chemistry of some uranium, titanium, and zirconium complexes

    SciTech Connect

    Lukens, W.W. Jr.

    1995-05-01

    Dicyclopentadienyluranium halide dimers have been prepared and their solution behavior examined. These molecules exist as dimers in solution, and the halide ligands undergo rapid site exchange on the NMR timescale above 50 C. Analogous dicyclopentadienyluranium hydroxide dimers have also been prepared; they oxidatively eliminate hydrogen to give the corresponding oxide dimers. Mechanism of this reaction is consistent with {alpha}migration of one of the hydroxide hydrogen atoms to a uranium center followed by elimination of hydrogen. Ground state of [(Me{sub 3}Si){sub 2}C{sub 5}H{sub 3}]{sub 3}M M = Nd, U and their base adducts has been examined by variable temperature magnetic susceptibility and EPR spectroscopy. The ground state is found to be {sup 4}I{sub 9/2} with a crystal field state consisting largely of J{sub z} = 1/2 lowest, in agreement with previous studies on tris-cyclopentadienylneodymium complexes. The zirconium metallocene Cp{sub 3}Zr has been prepared, characterized crystallographically, and its reactivity studied. Its chemical behavior is controlled by presence of an electron in the non-bonding, d{sub z}2 orbital which prevents formation of base adducts Of Cp{sub 3}Zr, but allows Cp{sub 3}Zr to abstract atoms from other molecules. Electonic and EPR spectra of Cp*{sub 2}TiX complexes, where Cp* is Me{sub 5}C{sub 5} and X is a monodentate, anionic ligand such as halide, have been studied. A {pi}-bonding spectrochemical series is developed, and trends in {pi}-bonding ability are found similar to those in other inorganic complexes. The {beta}-agostic interactions in Cp*{sub 2}TiN(Me)Ph have been examined using variable temperature EPR spectroscopy, and the enthalpy/entropy of the interaction determined. In Cp*{sub 2}TiEt, enthalpy of the {beta}-agostic interaction is {minus}1.9 kcal/mol. The titanocene anion, Cp*{sub 2}TiLi(TMEDA) (TMEDA is N,N,N`,N`-tetramethylethylenediamine), has been prepared and its structure determined.

  7. Synthesis of zirconium carbide nanosized powders by pursed wire discharge in oleic acid

    NASA Astrophysics Data System (ADS)

    Sugashima, Kenta; Suzuki, Kazuma; Suzuki, Tsuneo; Nakayama, Tadachika; Suematsu, Hisayuki; Niihara, Koichi

    2016-01-01

    In this study, we propose novel PWD methods in inert gas mixed organic vapor and organic liquid which work as harmless carbon sources. Metal zirconium wire evaporation by PWD in organic vapor or liquid media was investigated. It was confirmed that in the PWD process using oleic acid liquid, single phase zirconium carbide nanopowders were synthesized by a reaction between Zr vapor and oleic acid. A new method for synthesis of carbide nanopowders was developed using the PWD in organic liquid. Therefore, the present result suggested that PWD method in oleic acid liquids is effective for the synthesis of carbide nanopowders.

  8. Factors affecting the stress corrosion cracking susceptibility of zirconium in 90% nitric acid

    SciTech Connect

    Yau, T.L.

    1987-01-01

    U-bend, C-ring, and slow strain-rate tests have been performed to evaluate the effects of texture, stress, surface conditions, heat treatment, electrochemical potential, and strain rate on stress corrosion cracking (SCC) of zirconium in 90% nitric acid at room temperatures. It has been shown that careful control of texture, surface condition (scratching, cleaning and oxide coating), and/or applied stress can effectively lead to the prevention of SCC of zirconium in 90% HNO/sub 3/. Heat treating at 760/sup 0/C, 880/sup 0/C, or 1000/sup 0/C does not seem to improve the SCC resistance. However, if the potential of zirconium is maintained at 500 mV/sub SCE/ or lower, or 200 ppm of HF is added, zirconium's SCC susceptibility in 90% HNO/sub 3/ is eliminated. In the case of adding HF, zirconium sponge must also be added in order to avoid high corrosion rates. The mechanism for SCC of zirconium in 90% HNO/sub 3/ appears to be stress assisted local anodic dissolution, since the highest susceptibility is observed at strain rate = 7.5 x 10/sup -7//sec, and, at a higher or lower strain rate the susceptibility decreases. There is additional evidence to support this mechanism.

  9. FTIR studies on the acidity of sulfated zirconia prepared by thermolysis of zirconium sulfate

    SciTech Connect

    Platero, E.E.; Mentruit, M.P.; Arean, C.O.; Zecchina, A.

    1996-09-01

    Sulfated zirconia having a BET surface area of 90 m{sup 2}g{sup -1} and a temperature-resistant mesoporous texture was prepared by thermolysis (at 1000 K) of zirconium sulfate. Infrared studies of surface sulfates, CO adsorption at 77 K, and room temperature adsorption of pyridine showed close similarity to sulfated zirconias prepared by impregnation of doping from the gas phase. Four main families of Lewis acid centers were found, which gave CO adducts characterized by stretching frequencies of 2212, 2202, 2196, and 2188 cm{sup -1}. Interaction of CO (at liquid nitrogen temperature) with surface hydroxyls (in partially hydroxylated samples) was found to shift the O-H stretching frequency from 3650 to 3510 cm{sup -1}, due to formation of hydrogen-bonded OH{center_dot}{center_dot}CO complexes. This downward shift, {Delta}{nu}{sub OH} = 140 cm{sup -1}, is significantly larger than the corresponding value for pure zirconia ({Delta}{nu}{sub OH} = 90 cm{sup -1}), which strongly suggests enhancement of the Bronsted acidity. Samples showing the acidic OH group at 3650 cm{sup -1} were found to contain also disulfate groups and traces of molecular water. Surface hydroxyls is sulfated zirconia still appear, however, to be weaker Bronsted acid sites than are bridging OH groups in zeolites. 49 refs., 7 figs., 2 tabs.

  10. Evaluation of the acid properties of porous zirconium-doped and undoped silica materials

    SciTech Connect

    Fuentes-Perujo, D.; Santamaria-Gonzalez, J.; Merida-Robles, J.; Rodriguez-Castellon, E.; Jimenez-Lopez, A.; Maireles-Torres, P. . E-mail: maireles@uma.es; Moreno-Tost, R.

    2006-07-15

    A series of porous silica and Zr-doped silica molecular sieves, belonging to the MCM-41 and MSU families, were prepared and characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and N{sub 2} adsorption at 77 K. Their acid properties have been evaluated by NH{sub 3}-TPD, adsorption of pyridine and deuterated acetonitrile coupled to FT-IR spectroscopy and the catalytic tests of isopropanol decomposition and isomerization of 1-butene. The acidity of purely siliceous solids were, in all cases, very low, while the incorporation of Zr(IV) into the siliceous framework produced an enhancement of the acidity. The adsorption of basic probe molecules and the catalytic behaviour revealed that Zr-doped MSU-type silica was more acidic than the analogous Zr-MCM-41 solid, with a similar Zr content. This high acidity observed in the case of Zr-doped silica samples is due to the presence of surface zirconium atoms with a low coordination, mainly creating Lewis acid sites. - Graphical abstract: The adsorption of basic probe molecules and the catalytic behaviour have revealed that MSU-type materials are more acidic than the analogous MCM-41 solids, mainly after the incorporation of zirconium into the silica framework.

  11. Distribution of zirconium in petroleum sulfoxides during extraction and sorption from nitric and hydrochloric acid solutions

    SciTech Connect

    Turanov, A.N.

    1988-11-20

    Petroleum sulfoxides (PSO) are effective extractants for several metals. We discussed the distribution of petroleum sulfoxides and zirconium between aqueous solutions of hydrochloric and nitric acid and organic solvents, and also the macroporous sorbent impregnated with PSO. For the investigation we used a macroposous copolymer of styrene with divinylbenzene. Our investigation showed a noticeable decrease in the contamination of the raffinates by petroleum sulfoxides and their more complete utilization as extractant of metals from solutions of acids when PSO is deposited on a macroporous copolymer of styrene with divinylbenzene.

  12. The formation and study of titanium, zirconium, and hafnium complexes

    NASA Technical Reports Server (NTRS)

    Wilson, Bobby; Sarin, Sam; Smith, Laverne; Wilson, Melanie

    1989-01-01

    Research involves the preparation and characterization of a series of Ti, Zr, Hf, TiO, and HfO complexes using the poly(pyrazole) borates as ligands. The study will provide increased understanding of the decomposition of these coordination compounds which may lead to the production of molecular oxygen on the Moon from lunar materials such as ilmenite and rutile. The model compounds are investigated under reducing conditions of molecular hydrogen by use of a high temperature/pressure stainless steel autoclave reactor and by thermogravimetric analysis.

  13. Hydrogenation and cleavage of dinitrogen to ammonia with a zirconium complex.

    PubMed

    Pool, Jaime A; Lobkovsky, Emil; Chirik, Paul J

    2004-02-01

    Molecular nitrogen is relatively inert owing to the strength of its triple bond, nonpolarity and high ionization potential. As a result, the fixation of atmospheric nitrogen to ammonia under mild conditions has remained a challenge to chemists for more than a century. Although the Haber-Bosch process produces over 100 million tons of ammonia annually for the chemical industry and agriculture, it requires high temperature and pressure, in addition to a catalyst, to induce the combination of hydrogen (H2) and nitrogen (N2). Coordination of molecular nitrogen to transition metal complexes can activate and even rupture the strong N-N bond under mild conditions, with protonation yielding ammonia in stoichiometric and even catalytic yields. But the assembly of N-H bonds directly from H2 and N2 remains challenging: adding H2 to a metal-N2 complex results in the formation of N2 and metal-hydrogen bonds or, in the case of one zirconium complex, in formation of one N-H bond and a bridging hydride. Here we extend our work on zirconium complexes containing cyclopentadienyl ligands and show that adjustment of the ligands allows direct observation of N-H bond formation from N2 and H2. Subsequent warming of the complex cleaves the N-N bond at 45 degrees C, and continued hydrogenation at 85 degrees C results in complete fixation to ammonia. PMID:14765191

  14. Modulation by Amino Acids: Toward Superior Control in the Synthesis of Zirconium Metal-Organic Frameworks.

    PubMed

    Gutov, Oleksii V; Molina, Sonia; Escudero-Adán, Eduardo C; Shafir, Alexandr

    2016-09-12

    The synthesis of zirconium metal-organic frameworks (Zr MOFs) modulated by various amino acids, including l-proline, glycine, and l-phenylalanine, is shown to be a straightforward approach toward functional-group incorporation and particle-size control. High yields in Zr-MOF synthesis are achieved by employing 5 equivalents of the modulator at 120 °C. At lower temperatures, the method provides a series of Zr MOFs with increased particle size, including many suitable for single-crystal X-ray diffraction studies. Furthermore, amino acid modulators can be incorporated at defect sites in Zr MOFs with an amino acid/ligand ratio of up to 1:1, depending on the ligand structure and reaction conditions. The MOFs obtained through amino acid modulation exhibit an improved CO2 -capture capacity relative to nonfunctionalized materials. PMID:27482849

  15. Porous Zirconium-Phytic Acid Hybrid: a Highly Efficient Catalyst for Meerwein-Ponndorf-Verley Reductions.

    PubMed

    Song, Jinliang; Zhou, Baowen; Zhou, Huacong; Wu, Lingqiao; Meng, Qinglei; Liu, Zhimin; Han, Buxing

    2015-08-01

    The utilization of compounds from natural sources to prepare functional materials is of great importance. Herein, we describe for the first time the preparation of organic-inorganic hybrid catalysts by using natural phytic acid as building block. Zirconium phosphonate (Zr-PhyA) was synthesized by reaction of phytic acid and ZrCl4 and was obtained as a mesoporous material with pore sizes centered around 8.5 nm. Zr-PhyA was used to catalyze the mild and selective Meerwein-Ponndorf-Verley (MPV) reduction of various carbonyl compounds, e.g., of levulinic acid and its esters into γ-valerolactone. Further studies indicated that both Zr and phosphate groups contribute significantly to the excellent performance of Zr-PhyA. PMID:26177726

  16. Zirconium-titanium phosphate acid catalysts synthesized by sol gel techniques

    SciTech Connect

    Jackson, N.B.; Thoma, S.G.; Kohler, S.; Nenoff, T.M.

    1998-03-01

    Recently a large effort has been put into identifying solid acid materials, particularly sulfated zirconia and other sulfated metal oxides, that can be used to replace environmentally hazardous liquid acids in industrial processes. The authors are studying a group of mixed metal phosphates, some of which have also been sulfated, for their catalytic and morphological characteristics. Zirconium and titanium are the metals used in this study and the catalysts are synthesized from alkoxide starting materials with H{sub 3}PO{sub 4}, H{sub 2}O, and sometimes H{sub 2}SO{sub 4} as gelling agents. The measurement of acidity was achieved by using the isomerization of 2-methyl-2-pentene as a model reaction. The phosphate stabilized the mixed metal sulfates, preventing them from calcining to oxides boosting their initial catalytic activity. The addition of sulfate prevented the formation of the catalytically inactive mixed metal pyrophosphates when calcined at high temperatures (> 773 K).

  17. How big is a Cp? Novel cycloheptatrienyl zirconium complexes with tri-, tetra- and pentasubstituted cyclopentadienyl ligands.

    PubMed

    Bauer, Heiko; Glöckner, Andreas; Tagne Kuate, Alain C; Schäfer, Sebastian; Sun, Yu; Freytag, Matthias; Tamm, Matthias; Walter, Marc D; Sitzmann, Helmut

    2014-11-14

    The new bulky cyclopentadienyl anions 1,2,4-tri(cyclopentyl)cyclopentadienide and 2,3-diisopropyl-1,4-dimethyl-5-trimethylsilyl-cyclopentadienide were prepared. These and the already known 1,2,4-tri(cyclohexyl)-, 1,2,4-tri(isopropyl)-, 2,3-diisopropyl-1,4-dimethyl-, 1,3,4-triisopropyl-2,5-dimethyl-, pentaphenyl-, and p-butylphenyl-tetraphenyl-cyclopentadienide as well as tert-butylindenide were coordinated to the cycloheptatrienylzirconium fragment [(CHT)ZrCl(tmeda)]. The nine zirconium complexes of the [(CHT)Zr(Cp)] type were characterized by elemental analysis and NMR spectroscopy. For five of the sandwich complexes X-ray crystal structure determination could be carried out; structures of the four others were obtained by DFT calculations. The data serve as a basis for cone angle measurements of cyclopentadienyl ligands to evaluate the steric demand of these ligands. PMID:25222005

  18. Evaluation of the acid properties of porous zirconium-doped and undoped silica materials

    NASA Astrophysics Data System (ADS)

    Fuentes-Perujo, D.; Santamaría-González, J.; Mérida-Robles, J.; Rodríguez-Castellón, E.; Jiménez-López, A.; Maireles-Torres, P.; Moreno-Tost, R.; Mariscal, R.

    2006-07-01

    A series of porous silica and Zr-doped silica molecular sieves, belonging to the MCM-41 and MSU families, were prepared and characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and N 2 adsorption at 77 K. Their acid properties have been evaluated by NH 3-TPD, adsorption of pyridine and deuterated acetonitrile coupled to FT-IR spectroscopy and the catalytic tests of isopropanol decomposition and isomerization of 1-butene. The acidity of purely siliceous solids were, in all cases, very low, while the incorporation of Zr(IV) into the siliceous framework produced an enhancement of the acidity. The adsorption of basic probe molecules and the catalytic behaviour revealed that Zr-doped MSU-type silica was more acidic than the analogous Zr-MCM-41 solid, with a similar Zr content. This high acidity observed in the case of Zr-doped silica samples is due to the presence of surface zirconium atoms with a low coordination, mainly creating Lewis acid sites.

  19. Ice Shaping Properties, Similar to That of Antifreeze Proteins, of a Zirconium Acetate Complex

    PubMed Central

    Deville, Sylvain; Viazzi, Céline; Leloup, Jérôme; Lasalle, Audrey; Guizard, Christian; Maire, Eric; Adrien, Jérôme; Gremillard, Laurent

    2011-01-01

    The control of the growth morphologies of ice crystals is a critical issue in fields as diverse as biomineralization, medicine, biology, civil or food engineering. Such control can be achieved through the ice-shaping properties of specific compounds. The development of synthetic ice-shaping compounds is inspired by the natural occurrence of such properties exhibited by antifreeze proteins. We reveal how a particular zirconium acetate complex is exhibiting ice-shaping properties very similar to that of antifreeze proteins, albeit being a radically different compound. We use these properties as a bioinspired approach to template unique faceted pores in cellular materials. These results suggest that ice-structuring properties are not exclusive to long organic molecules and should broaden the field of investigations and applications of such substances. PMID:22028886

  20. Synthetic and Mechanistic Studies of Strained Heterocycle Opening Reactions Mediated by Zirconium(IV) Imido Complexes

    PubMed Central

    Blum, Suzanne A.; Rivera, Vicki A.; Ruck, Rebecca T.; Michael, Forrest E.; Bergman, Robert G.

    2005-01-01

    The reactions of the bis(cyclopentadienyl)(tert-butylimido)zirconium complex (Cp2Zr=N-t-Bu)(THF) (1) with epoxides, aziridines, and episulfides were investigated. Heterocycles without accessible β-hydrogens undergo insertion/protonation of the C–X bond to produce 1,2-amino alcohols (X = O) and 1,2-diamines (X = NR), whereas heterocycles with accessible β-hydrogens undergo elimination/protonation to produce allylic alcohols (X = O) and allylic sulfides (X = S). Mechanistic investigations support a stepwise pathway with zwitterionic intermediates for the first reaction class and a concerted pathway for the second reaction class. Additionally, the feasibility of chirality transfer from the planar-chiral ebthi (ebthi = ethylenebis(tetrahydroindenyl)) ligand was demonstrated with a chiral analogue, (ebthi)-Zr=NAr(THF) (Ar = 2,6-dimethylphenyl), 2, through the diastereoselective ring opening of meso epoxides. PMID:16508693

  1. Zirconium-carbon hybrid sorbent for removal of fluoride from water: oxalic acid mediated Zr(IV) assembly and adsorption mechanism

    PubMed Central

    Halla, Velazquez-Jimenez Litza; Hurt Robert, H; Juan, Matos; Rene, Rangel-Mendez Jose

    2014-01-01

    When activated carbon (AC) is modified with zirconium(IV) by impregnation or precipitation, the fluoride adsorption capacity is typically improved. There is significant potential to improve these hybrid sorbent by controlling the impregnation conditions, which determine the assembly and dispersion of the Zr phases on carbon surfaces. Here, commercial activated carbon was modified with Zr(IV) together with oxalic acid (OA) used to maximize the zirconium dispersion and enhance fluoride adsorption. Adsorption experiments were carried out at pH 7 and 25 °C with a fluoride concentration of 40 mg L−1. The OA/Zr ratio was varied to determine the optimal conditions for subsequent fluoride adsorption. The data was analyzed using the Langmuir and Freundlich isotherm models. FTIR, XPS and the surface charge distribution were performed to elucidate the adsorption mechanism. Potentiometric titrations showed that the modified activated carbon (ZrOx-AC) possesses positive charge at pH lower than 7, and FTIR analysis demonstrated that zirconium ions interact mainly with carboxylic groups on the activated carbon surfaces. Moreover, XPS analysis demonstrated that Zr(IV) interacts with oxalate ions, and the fluoride adsorption mechanism is likely to involve –OH− exchange from zirconyl oxalate complexes. PMID:24359079

  2. Preparation and application of zirconium sulfate supported on SAPO-34 molecular sieve as solid acid catalyst for esterification

    SciTech Connect

    Xu, Dongyan Ma, Hong; Cheng, Fei

    2014-05-01

    Graphical abstract: - Highlights: • SAPO-34 supported zirconium sulfate solid acid catalyst was prepared. • Esterification of acetic acid with ethanol can be catalyzed by ZS/SAPO-34. • The hydration of ZS is vital to the acidic property and catalytic performance. • The ZS/SAPO-34 catalyst treated at 200 °C shows good reusability. - Abstract: Zirconium sulfate (ZS) was supported on SAPO-34 molecular sieve by using an incipient wetness impregnation method with zirconium sulfate as the precursor. The as-prepared catalysts were used as solid acid catalyst for esterification reaction of acetic acid with ethanol. The influence of calcination temperature on the acidic property, catalytic activity, and reusability of ZS/SAPO-34 catalysts were mainly investigated. FT-IR, SEM, EDS and TG analysis have been carried out to demonstrate the characteristics of ZS/SAPO-34 catalysts. It was found that the 30 wt%ZS/SAPO-34 catalysts display the property of superacid irrespective of calcination temperature. The ZS/SAPO-34 catalyst treated at 200 °C can enhance the interaction between the supported ZS and SAPO-34 and keep the catalyst remaining substantially active after several reaction cycles. However, further increasing calcination temperature will cause the transfer of ZS from hydrate to anhydrous phase, and thus the decrease of activity.

  3. η(6) -Arene-Zirconium-PNP-Pincer Complexes: Mechanism of Their Hydrogenolytic Formation and Their Reactivity as Zirconium(II) Synthons.

    PubMed

    Plundrich, Gudrun T; Wadepohl, Hubert; Clot, Eric; Gade, Lutz H

    2016-06-27

    The cyclometalated monobenzyl complexes [(Cbzdiphos(R) -CH)ZrBnX] 1 (iPr) Cl and 1 (Ph) I reacted with dihydrogen (10 bar) to yield the η(6) -toluene complexes [(Cbzdiphos(R) )Zr(η(6) -tol)X] 2 (iPr) Cl and 2 (Ph) I (cbzdiphos=1,8-bis(phosphino)-3,6-di-tert-butyl-9H-carbazole). The arene complexes were also found to be directly accessible from the triiodide [(Cbzdiphos(Ph) )ZrI3 ] through an in situ reaction with a dibenzylmagnesium reagent and subsequent hydrogenolysis, as exemplified for the η(6) -mesitylene complex [(Cbzdiphos(Ph) )Zr(η(6) -mes)I] (3 (Ph) I). The tolyl-ring in 2 (iPr) Cl adopts a puckered arrangement (fold angle 23.3°) indicating significant arene-1,4-diido character. Deuterium labeling experiments were consistent with an intramolecular reaction sequence after the initial hydrogenolysis of a Zr-C bond by a σ-bond metathesis. A DFT study of the reaction sequence indicates that hydrogenolysis by σ-bond metathesis first occurs at the cyclometalated ancillary ligand giving a hydrido-benzyl intermediate, which subsequently reductively eliminates toluene that then coordinates to the Zr atom as the reduced arene ligand. Complex 2 (Ph) I was reacted with 2,6-diisopropylphenyl isocyanide giving the deep blue, diamagnetic Zr(II) -diisocyanide complex [(Cbzdiphos(Ph) )Zr(CNDipp)2 I] (4 (Ph) I). DFT modeling of 4 (Ph) I demonstrated that the HOMO of the complex is primarily located as a "lone pair on zirconium", with some degree of back-bonding into the C≡N π* bond, and the complex is thus most appropriately described as a zirconium(II) species. Reaction of 2 (Ph) I with trimethylsilylazide (N3 TMS) and 2 (iPr) Cl with 1-azidoadamantane (N3 Ad) resulted in the formation of the imido complexes [(Cbzdiphos(R) )Zr=NR'(X)] 5 (iPr) Cl-NAd and 5 (Ph) I-NTMS, respectively. Reaction of 2 (iPr) Cl with azobenzene led to N-N bond scission giving 6 (iPr) Cl, in which one of the NPh-fragments is coupled with the carbazole

  4. IR-spectroscopic investigation of the acid properties of the surface of zirconium oxide modified by sulfate ions

    SciTech Connect

    Komarov, V.S.; Sinilo, M.F.

    1988-12-01

    The methods of IR spectroscopic and gravimetric measurements of the adsorption of pyridine and ammonia were used to study the acid properties of zirconium oxide, modified by sulfate ions. It was shown that the total acidity and the ratio of the numbers of Lewis and Broensted acid centers depend on the content of sulfate ions and the temperature of vacuum conditioning of the samples. It was established that the function of Broensted centers is performed by hydroxyl groups. It was shown that pyridine and ammonia molecules, chemisorbed on acid centers, are additionally coordinated by SO/sub 4//sup 2/minus// anions.

  5. Use of zirconium oxychloride to neutralize HF in the microwave-assisted acid dissolution of ceramic glazes for their chemical analysis by ICP-OES.

    PubMed

    Dondi, M; Fabbri, B; Mingazzini, C

    1998-04-01

    The use of a zirconium compound (ZrOCl(2)) to neutralize HF in the microwave-assisted acid dissolution of ceramic glazes for their chemical analysis was tested. Zr is a strong complexing agent for the fluorine ion and permits the determination of those elements which would form insoluble fluorides. The use of Zr implies strong spectral interferences and a high salt content; however, we found that at least 27 elements can be measured with low detection limits, and satisfactory precision and accuracy. In addition, the use of ZrOCl(2) would permit the complete analysis of a ceramic glaze with a single attack when acid-resistant mineral phases are not present. For potassium determinations in acid matrix, the addition of an ionization buffer was studied in order to increase sensitivity, avoiding ionization interferences and non-linear calibration curves. PMID:18967112

  6. SEPARATING HAFNIUM FROM ZIRCONIUM

    DOEpatents

    Lister, B.A.J.; Duncan, J.F.

    1956-08-21

    A dilute aqueous solution of zirconyl chloride which is 1N to 2N in HCl is passed through a column of a cation exchange resin in acid form thereby absorbing both zirconium and associated hafnium impurity in the mesin. The cation exchange material with the absorbate is then eluted with aqueous sulfuric acid of a O.8N to 1.2N strength. The first portion of the eluate contains the zirconium substantially free of hafnium.

  7. The results of HLW processing using zirconium salt of dibutyl phosphoric acid

    SciTech Connect

    Fedorov, Yury; Zilberman, Boris; Shmidt, Olga; Saprikin, Vladimir; Ryasantsev, Valery

    2007-07-01

    Available in abstract form only. Full text of publication follows: Zirconium salt of dibutyl-phosphoric acid (ZS HDBP) dissolved in a diluent, is a promising solvent for liquid HLW processing. The investigations carried out earlier showed that ZS HDBP can recover a series of radionuclides (TPE, RE, U, Pu, Np, Sr) and some other elements (Mo, Ca, Fe) from aqueous solutions. The possibility of TPE and RE effective recovery and separation into appropriate fractions with high purification from each other was demonstrated as well. The results of extraction tests in the mixer-settlers in the course of liquid HLW treatment in hot cells, using ZS HDBP (0.4 M HDBP and 0.044 M Zr) dissolved in 30% TBP are presented. 30 liters of the feed solution containing TPE, RE, Sr and Cs with the total specific activity of 520 MBq/L and acidity of 2 M HNO{sub 3} were processed using the two-cycle flowsheet. TPE and RE recovery with subsequent stripping was realized in the first cycle, while Sr was recovered and concentrated in the second cycle. Raffinate of the latter contained almost all Cs. The degree of TPE and RE recovery was 104, and that of Sr was {approx}10. Decontamination factor of TPE and RE from Cs and Sr was 104, and that of Sr from TPE and Cs was 103. So, ZS HDBP can be used for separation of long-lived radionuclides from HLW with respect to radio-toxic category of the process products. (authors)

  8. Zirconium(IV) tetramer/octamer hydrolysis equilibrium in aqueous hydrochloric acid solution

    SciTech Connect

    Singhal, A.; Toth, L.M.; Lin, J.S.; Affholter, K.

    1996-11-20

    Small-angle X-ray scattering measurements were performed on zirconium acidic aqueous solutions to investigate the structure and the size of polynuclear species larger than the previously identified tetrameric species. Solutions with [H{sup +}]{sub added} and [OH{sup -}]{sub added} ranging from 0.0 to 1.0 M and 0.0 to 0.02 M, respectively, were analyzed. This study demonstrates that an octameric species, Zr{sub 8}(OH){sub 20}(H{sub 2}O){sub 24}Cl{sub 12}, exists in equilibrium with the tetrameric species, Zr{sub 4}(OH){sub 8}(H{sub 2} O){sub 16}Cl{sub 6}{sup 2+}, such that, for 0.05 M Zr(IV) in highly acidic solutions ([H{sup +}]{sub added} = 0.6 M), the tetramer in the dominant species; and at conditions with [H{sup +}] added =0.05 M, the octameric species becomes predominant. The estimated value of the equilibrium quotient obtained for the tetramer/octamer equilibrium is 0.20 {+-} 0.05 M{sup 3}. The tetramer and octamer have radii of gyration of 3.8 and 5.1 {+-} 0.2 A and a hydrolysis ratio of 2.0 and 2.5, respectively. The octamer forms by stacking two tetramers on top of each other. At conditions where small amounts of NaOH are added, unidentified polymeric Zr(IV) species larger in size than the octameric species appear. 26 refs., 7 figs.

  9. Highly Amino Acid Selective Hydrolysis of Myoglobin at Aspartate Residues as Promoted by Zirconium(IV)-Substituted Polyoxometalates.

    PubMed

    Ly, Hong Giang T; Absillis, Gregory; Janssens, Rik; Proost, Paul; Parac-Vogt, Tatjana N

    2015-06-15

    SDS-PAGE/Edman degradation and HPLC MS/MS showed that zirconium(IV)-substituted Lindqvist-, Keggin-, and Wells-Dawson-type polyoxometalates (POMs) selectively hydrolyze the protein myoglobin at Asp-X peptide bonds under mildly acidic and neutral conditions. This transformation is the first example of highly sequence selective protein hydrolysis by POMs, a novel class of protein-hydrolyzing agents. The selectivity is directed by Asp residues located on the surface of the protein and is further assisted by electrostatic interactions between the negatively charged POMs and positively charged surface patches in the vicinity of the cleavage site. PMID:25950869

  10. Quercetin as colorimetric reagent for determination of zirconium

    USGS Publications Warehouse

    Grimaldi, F.S.; White, C.E.

    1953-01-01

    Methods described in the literature for the determination of zirconium are generally designed for relatively large amounts of this element. A good procedure using colorimetric reagent for the determination of trace amounts is desirable. Quercetin has been found to yield a sensitive color reaction with zirconium suitable for the determination of from 0.1 to 50?? of zirconium dioxide. The procedure developed involves the separation of zirconium from interfering elements by precipitation with p-dimethylaminoazophenylarsonic acid prior to its estimation with quercetin. The quercetin reaction is carried out in 0.5N hydrochloric acid solution. Under the operating conditions it is indicated that quercetin forms a 2 to 1 complex with zirconium; however, a 2 to 1 and a 1 to 1 complex can coexist under special conditions. Approximate values for the equilibrium constants of the complexes are K1 = 0.33 ?? 10-5 and K2 = 1.3 ?? 10-9. Seven Bureau of Standards samples of glass sands and refractories were analyzed with excellent results. The method described should find considerable application in the analysis of minerals and other materials for macro as well as micro amounts of zirconium.

  11. A simple spectrophotometric method for determination of zirconium or hafnium in selected molybdenum-base alloys

    NASA Technical Reports Server (NTRS)

    Dupraw, W. A.

    1972-01-01

    A simple analytical procedure is described for accurately and precisely determining the zirconium or hafnium content of molybdenum-base alloys. The procedure is based on the reaction of the reagent Arsenazo III with zirconium or hafnium in strong hydrochloric acid solution. The colored complexes of zirconium or hafnium are formed in the presence of molybdenum. Titanium or rhenium in the alloy have no adverse effect on the zirconium or hafnium complex at the following levels in the selected aliquot: Mo, 10 mg; Re, 10 mg; Ti, 1 mg. The spectrophotometric measurement of the zirconium or hafnium complex is accomplished without prior separation with a relative standard deviation of 1.3 to 2.7 percent.

  12. ZICOS - New project for neutrinoless double beta decay experiment using zirconium complex in liquid scintillator

    NASA Astrophysics Data System (ADS)

    Fukuda, Yoshiyuki

    2016-05-01

    A liquid scintillator containing a tetrakis (isopropyl acetoacetato) zirconium has been developed for new project of neutrinoless double beta decay experiment (ZICOS experiment). We have synthesized a tetrakis (isopropyl acetoacetato) zirconium, which have high solubility (over 31.2 wt.%) in anisole. We measured the performance of liquid scintillator containing 10 wt.% concentration of a tetrakis (isopropyl acetoacetato) zirconium, and obtained 48.7 ± 7.1% of the light yield of BC505 and the energy resolution of 4.1 ± 0.6% at 3.35 MeV assuming 40% photo coverage of the photomultiplier, respectively. We also estimated that ZICOS experiment should be sensitive to (mν) < 0.1 eV assuming gA = 1.25, gpp = 1.11 and QRPA model, if a radius of the inner detector is 1.5 m and the detector is filled with this liquid scintillator with an enriched 96Zr nucleus and we can reduce 208 Tl backgrounds to be one tenth order of magnitude of KamLAND-Zen using Cherenkov lights.

  13. Usage of Dibutyl Phosphoric Acid and Its Zirconium Salt for Extraction of Transplutonium Elements and Rare Earths with Their Partitioning

    SciTech Connect

    Zilberman, B.Ya.; Fedorov, Yu.S.; Shmidt, O.V.; Goletskiy, N.D.; Shishkin, D.N.; Esimantovskiy, V.M.; Rodionov, S.A.; Egorova, O.N.; Palenik, Yu.V.

    2007-07-01

    Dibutyl phosphoric acid (HDBP) formed by tributyl phosphate (TBP) destruction is soluble both in aqueous alkaline solutions and in organic solvents in acidic media. So, the solvent based on HDBP and its zirconium salt (ZS-HDBP) dissolved in polar diluent, e.g. in diluted TBP, is interesting for radwaste treatment, minimizing the amount of secondary organic wastes. Addition of Zr to 0.2 mol/L HDBP dissolved in 30% TBP results in successful extraction of lanthanides and actinides at the optimum ratio Zr:HDBP=1:(8-9) from 1.5 mol/L HNO{sub 3}, followed by their back-washing with 5 mol/L HNO{sub 3}. Partitioning of yttrium and cerium RE subgroups (the latter together with TPE) with the separation factor from 5 to 50 is also possible with purification from molybdenum. Strontium is extracted by 0.4 mol/L ZS HDBP from 0.3 mol/L HNO{sub 3} and stripped with 1.5 mol/L HNO{sub 3}. ZS-HDBP solution in 30% TBP is also capable of extraction of residual Np, Pu and corrosion-born iron. Stripping of these elements requires salt-free complexants. Solvents containing ZS-HDBP have high capacity, while TBP presence doubles it because of synergetic effect. The maximum solvent loading of 0.2 mol/L ZSHDBP in xylene was found as 8.0 g/L Eu and {approx}6 g/L Mo. The mixture of DTPA and formic acid is suitable for TPE/RE partitioning using ZS-HDBP as a solvent with separation factors for Ce/Am and Eu/Am of 67 and 9, respectively. Two variants of two-cycle flowsheet for TPE and RE partitioning after their joint recovery have been proposed, which differs by order of the cycles with acidic and buffer media at the partitioning. Both variants were successfully tested using simulate solutions on the centrifugal contactor rig with TPE/RE separation factor being {approx}60, the major impurity being Nd. Correction of the solvent composition because of HDBP loss due to its solubility in aqueous phase, especially at acidity less than 0.2 mol/L HNO{sub 3}, was also taken into consideration. Further

  14. Luminescence rigidochromism and redox chemistry of pyrazolate-bridged binuclear platinum(II) diimine complex intercalated into zirconium phosphate layers.

    PubMed

    Rivera, Eladio J; Barbosa, Cindy; Torres, Rafael; Rivera, Harry; Fachini, Estevao R; Green, Tyler W; Connick, William B; Colón, Jorge L

    2012-03-01

    The direct intercalation of a pyrazolate-bridged platinum(II) bipyridyl dimer ([{Pt(dmbpy)(μ-pz)}(2)](2+); dmbpy = 4,4'-dimethyl-2,2'-bipyridine, pz(-) = pyrazolate) within a zirconium phosphate (ZrP) framework has been accomplished. The physical and spectroscopic properties of [{Pt(dmbpy)(μ-pz)}(2)](2+) intercalated in ZrP were investigated by X-ray powder diffraction and X-ray photoelectron, infrared, absorption, and luminescence spectroscopies. Zirconium phosphate layers have a special microenvironment that is capable of supporting a variety of platinum oxidation states. Diffuse reflectance spectra from powders of the blue-gray intercalated materials show the formation of a low-energy band at 600 nm that is not present in the platinum dimer salt. The nonintercalated complex is nonemissive in room-temperature fluid solution, but gives rise to intense blue-green emission in a 4:1 ethanol/methanol 77 K frozen glassy solution. Powders and colloidal suspensions of [{Pt(dmbpy)(μ-pz)}(2)](2+)-exchanged ZrP materials exhibit intense emissions at room-temperature. PMID:22339702

  15. Boron and Zirconium from Crucible Refractories in a Complex Heat-Resistant Alloy

    NASA Technical Reports Server (NTRS)

    Decker, R F; Rowe, John P; Freeman, J W

    1958-01-01

    In a laboratory study of the factors involved in the influence of induction vacuum melting on 55ni-20cr-15co-4mo-3ti-3al heat resistant alloy, it was found that the major factor was the type of ceramic used as the crucible. The study concluded that trace amounts of boron or zirconium derived from reaction of the melt with the crucible refactories improved creep-rupture properties at 1,600 degrees F. Boron was most effective and, in addition, markedly improved hot-workability.

  16. Visible-light driven H₂ production utilizing iridium and rhodium complexes intercalated into a zirconium phosphate layered matrix.

    PubMed

    Mori, Kohsuke; Aoyama, Junya; Kawashima, Masayoshi; Yamashita, Hiromi

    2014-07-21

    Intercalation of photosensitizer cyclometalated iridium(III) ([Ir(ppy)2(bpy)]BF6) and proton reduction catalyst tris-2,2'-bipyridyl rhodium(III) ([Rh(bpy)3](BF6)3) complexes into a layered zirconium phosphate (ZrP) with an interlayer distance of 10.3 Å has been attained with the aim of developing a visible-light responsible photocatalyst for H2 production in aqueous media. Ir L(III)-edge and Rh K-edge X-ray absorption fine structure (XAFS) measurement indicates that both Ir and Rh complexes are intercalated into the layered interspace without structural change around metal environments. The photoluminescence emission of the exchanged Ir complex due to a triplet ligand-to-ligand charge transfer ((3)LLCT) and a metal-to-ligand charge-transfer ((3)MLCT) transition near 560 nm decreases with increasing the amount of adjacent Rh complexes, suggesting the occurrence of electron transfer from Ir complex to Rh complex. The Ir-Rh/ZrP catalyst exhibits both visible-light sensitization and H2 production from aqueous solution in the absence of an electron mediator. The photocatalytic activities are strongly dependent on the ratio of the components, and the maximum activity can be attained with a molar ratio of Ir : Rh = 10 : 1. PMID:24695787

  17. Zirconium alkoxide interfaces for adhesion enhancement and electrocatalysis

    NASA Astrophysics Data System (ADS)

    Vanderkam, Susan Killian

    Tetra(tert-butoxy)zirconium was chemisorbed onto the native oxide layers of aluminum, iron, copper, and porous silicon, forming surface bound di- or tri-alkoxy zirconium species. Poly(ethylene- co-acrylic acid) was subsequently reacted with the surface forming chemically bound copolymer through carboxyzirconium linkages. Copolymer bound through the zirconium complex adhered to the metal oxide surfaces better than without the zirconium alkoxide intermediate, as determined by FTIR spectroscopy. Copper substrates were subjected to a variety of stability tests, including exposure to ambient conditions, base washing, and chronocoulometry. The copper-zirconium-copolymer ensemble was shown to be very stable in all of these tests. Indium tin oxide (ITO) powder was titrated to determine surface hydroxyl content per unit area. ITO-coated glass slides were reacted with tetra( tert-butoxy)zirconium, and subsequently with both carboxylic acid and phenol derivatives. Ferrocene-carboxyzirconium-coated ITO was characterized electrochemically, and the surface loading of ferrocene was found to be approximately one monolayer. Phenoxyzirconium-coated ITO was also characterized electrochemically and tested for electrocatalytic properties for the oxidation of several compounds in solution. Phenoxyzirconium-coated ITO was found to improve the oxidation kinetics for ferrocene and tetramethylphenylenediamine in acetonitrile.

  18. Producing Zirconium Diboride Components with Complex, Near-Net Shape Geometries by Aqueous Room-Temperature Injection Molding

    NASA Technical Reports Server (NTRS)

    Wiesner, Valerie L.; Youngblood, Jeffrey; Trice, Rodney

    2014-01-01

    Room-temperature injection molding is proposed as a novel, low-cost and more energy efficient manufacturing process capable of forming complex-shaped zirconium diboride (ZrB2) parts. This innovative processing method utilized aqueous suspensions with high powder loading and a minimal amount (5 vol.) of water-soluble polyvinylpyrrolidone (PVP), which was used as a viscosity modifier. Rheological characterization was performed to evaluate the room-temperature flow properties of ZrB2-PVP suspensions. ZrB2 specimens were fabricated with high green body strength and were machinable prior to binder removal despite their low polymer content. After binder burnout and pressureless sintering, the bulk density and microstructure of specimens were characterized using Archimedes technique and scanning electron microscopy. X-Ray Diffraction was used to determine the phase compositions present in sintered specimens. Ultimate strength of sintered specimens will be determined using ASTM C1323-10 compressive C-ring test.

  19. SEPARATION PROCESS FOR ZIRCONIUM AND COMPOUNDS THEREOF

    DOEpatents

    Crandall, H.W.; Thomas, J.R.

    1959-06-30

    The separation of zirconium from columbium, rare earths, yttrium and the alkaline earth metals, such mixtures of elements occurring in zirconium ores or neutron irradiated uranium is described. According to the invention a suitable separation of zirconium from a one normal acidic aqueous solution containing salts, nitrates for example, of tetravalent zirconium, pentavalent columbium, yttrium, rare earths in the trivalent state and alkaline earths can be obtained by contacting the aqueous solution with a fluorinated beta diketonc alone or in an organic solvent solution, such as benzene, to form a zirconium chelate compound. When the organic solvent is present the zirconium chelate compound is directly extracted; otherwise it is separated by filtration. The zirconium may be recovered from contacting the organic solvent solution containing the chelated compound by back extraction with either an aqueous hydrofluoric acid or an oxalic acid solution.

  20. Preparation and photolithography of self-assembled monolayers of 10-mercaptodecanylphosphonic acid on glass mediated by zirconium for protein patterning.

    PubMed

    Han, Xuemingyue; Sun, Shuqing; He, Tao

    2013-08-01

    Self-assembled monolayers (SAMs) formed by adsorption of octadecylphosphonic acid (ODPA) on zirconium mediated glass substrates were prepared. In this sandwich structure, Zr(4+) was used as a bi-linker to bind phosphonic acid head group in ODPA to glass substrates. The contact angle of the as-prepared SAMs was measured to be around 104°. X-ray photoelectron spectroscopy (XPS) characterization indicated the modification of Zr(4+) on glass substrates was critical for the formation of reasonably dense, well-ordered SAMs similar in quality to those typically formed on other metal oxide surfaces. Bifunctional molecule, 10-mercaptodecanylphosphonic acid (MDPA), bearing thiol terminal groups for various chemical reactions, was synthesized and formed SAMs on glass using the same approach, which allowed us to control the surface chemistry and functionality through photooxidation of the thiol terminal group. Photopatterning of proteins was performed first by exposing the SAMs to UV light through a mask, followed by protein immobilization to the masked regions through a heterobifunctional linker, while the exposed areas prohibit nonspecific protein absorption. The present strategy, which combined the SAMs assembly and photolithography, offered a facile approach for the fabrication of biomolecule patterning and could be applied to construction of biochips and other applications. PMID:23524079

  1. Fulvene to cyclopentadienyl conversion with homoleptic complexes of zirconium and hafnium

    SciTech Connect

    Rogers, J.S.; Lachicotte, R.J.; Bazan, G.C.

    1999-09-27

    The reaction of 6,6-dimethylfulvene with M(CH{sub 2}Ph){sub 4} (M = Zr, Hf) in benzene gives [{eta}{sup 5}-C{sub 5}H{sub 4}(CMe{sub 2}CH{sub 2}Ph)]M(CH{sub 2}Ph){sub 3} (1, M = Zr; 2, M = Hf) without any observable byproducts. A similar reaction for M = Ti is not observed. The single-crystal X-ray study of 1 shows a three-legged piano-stool geometry with an {eta}{sup 2}-bound benzyl ligand. A second equivalent of 6,6-dimethylfulvene does not react with either 1 or 2. The bulkier 6,6-diphenyfulvene only reacts cleanly with the more Lewis acidic Hf(CH{sub 2}Ph){sub 4} to give [{eta}{sup 5}-C{sub 5}H{sub 4}(CPh{sub 2}CH{sub 2}Ph)]Hf(CH{sub 2}Ph){sub 3} (3). Using the tetraamido complexes M(NMe{sub 2}Ph){sub 4} and 6,6-dimethylfulvene, one obtains dimethylamine and [{eta}{sup 5}-C{sub 5}H{sub 4}(CMeCH{sub 2})]M(NMe{sub 2}){sub 3} (4 for M = Zr) in good yield. These products are formally derived from the deprotonation of a fulvene methyl group and subsequent coordination of the resulting 2-propenylcyclopentadienyl fragment. Reaction of 4 and 6,6-dimethylfulvene affords the bent metallocene [{eta}{sup 5}-C{sub 5}H{sub 4}(CMeCH{sub 2})]{sub 2}Zr(NMe{sub 2}){sub 2} (5). Excess 8,8-dimethylbenzofulvene and M(NMe{sub 2}){sub 4} provides exclusively the product with only one coordinated indene.

  2. SEPARATION OF HAFNIUM FROM ZIRCONIUM

    DOEpatents

    Overholser, L.B.; Barton, C.J. Sr.; Ramsey, J.W.

    1960-05-31

    The separation of hafnium impurities from zirconium can be accomplished by means of organic solvent extraction. The hafnium-containing zirconium feed material is dissolved in an aqueous chloride solution and the resulting solution is contacted with an organic hexone phase, with at least one of the phases containing thiocyanate. The hafnium is extracted into the organic phase while zirconium remains in the aqueous phase. Further recovery of zirconium is effected by stripping the onganic phase with a hydrochloric acid solution and commingling the resulting strip solution with the aqueous feed solution. Hexone is recovered and recycled by means of scrubbing the onganic phase with a sulfuric acid solution to remove the hafnium, and thiocyanate is recovered and recycled by means of neutralizing the effluent streams to obtain ammonium thiocyanate.

  3. Novel zirconium complexes with constrained cyclic β-enaminoketonato ligands: improved catalytic capability toward ethylene polymerization.

    PubMed

    Wang, Kai-Ti; Wang, Yong-Xia; Wang, Bin; Li, Yan-Guo; Li, Yue-Sheng

    2016-06-21

    Novel Zr(iv) and Hf(iv) complexes bearing two constrained bulky β-enaminoketonato ligands {[ArN[double bond, length as m-dash]CH-C8H3(CH2)n(R)O]2MBn2, M = Zr or Hf; n = 1, 2 or 3; R = H or C6H5; Ar = C6H5 or C6F5} were synthesized and clearly characterized. X-ray crystal structure analysis reveals that these complexes adopt a distorted octahedral geometry. Compared with non-constrained analogues, the Zr(iv) complexes with a cyclic skeleton exhibited high catalytic activities (up to 16.4 kgPE mmolZr(-1) h(-1)) toward ethylene polymerization at ambient pressure and elevated temperatures. Moreover, the catalytic properties of these complexes could be governed exquisitely by appropriate variation of the N-aryl substituents and the size of the benzocyclane. The Zr(iv) complexes bearing a non-fluorinated N-aryl group yielded oligomers, while the fluorinated analogues bearing a five-membered or six-membered cyclane group produced high molecular weight polyethylenes (33.4-306 kg mol(-1)) under similar conditions on account of the suppression effects on β-H elimination. The Zr(iv) complexes are more active toward ethylene polymerization than the Hf(iv) analogues, and the resulting polymers exhibited higher molecular weight and narrower molecular weight distribution. PMID:27241779

  4. Sulfuric acid functional zirconium (or aluminum) incorporated mesoporous MCM-48 solid acid catalysts for alkylation of phenol with tert-butyl alcohol

    NASA Astrophysics Data System (ADS)

    Jiang, Tingshun; Cheng, Jinlian; Liu, Wangping; Fu, Lie; Zhou, Xuping; Zhao, Qian; Yin, Hengbo

    2014-10-01

    Several zirconium (or aluminum) incorporated mesoporous MCM-48 solid acid catalysts (SO42-/Zr-MCM-48 and SO42-/Al-MCM-48) were prepared by the impregnation method and their physicochemical properties were characterized by means of XRD, FT-IR, TEM, NH3-TPD and N2 physical adsorption. Also, the catalytic activities of these solid acid catalysts were evaluated by the alkylation of phenol with tert-butyl alcohol. The effect of weight hour space velocity (WHSV), reaction time and reaction temperature on catalytic properties was also studied. The results show that the SO42-/Zr-MCM-48 and SO42-/Al-MCM-48 still have good mesoporous structure and long range ordering. Compared with the Zr (or Al)-MCM-48 samples, SO42-/Zr-MCM-48 and SO42-/Al-MCM-48 solid acid catalysts have strong acidity and exhibit high activities in alkylation reaction of phenol with tert-butyl alcohol. The SO42-/Zr-MCM-48-25 (molar ratio of Si/Zr=0.04) catalyst was found to be the most promising and gave the highest phenol conversion among all catalysts. A maximum phenol conversion of 91.6% with 4-tert-butyl phenol (4-TBP) selectivity of 81.8% was achieved when the molar ratio of tert-butyl alcohol:phenol is 2:1, reaction time is 2 h, the WHSV is 2 h-1 and the reaction temperature is 140 °C.

  5. Surface Complexation Modeling of Uranium(Vi) Sorbed Onto Zirconium Oxophosphate Versus Temperature: Thermodynamic And Structural Approaches

    SciTech Connect

    Almazan-Torres, M.G.; Drot, R.; Mercier-Bion, F.; Catalette, H.; Auwer, C.Den; Simoni, E.

    2009-05-11

    This work presents an investigation of the interaction mechanisms between uranyl ions and a solid phosphate, the zirconium oxophosphate: Zr{sub 2}O(PO{sub 4}){sub 2}. Both thermodynamic and structural points of view are developed. Indeed, prior to any simulation of the retention data, it is necessary to precisely characterize the system under study in order to gain information at a molecular scale. First, the intrinsic surface properties of this synthetic compound have been investigated for different temperatures ranging from 25 to 90 C. Mass and potentiometric titrations show that the surface site density remains constant between 25 and 90 C, while the experimental point of zero charge slightly decreases from 4.8 to 4.5 with an increasing temperature. The potentiometric titration data are simulated, for each temperature, using the constant capacitance model and taking into account two surface sites ({triple_bond}Zr{_}O and {triple_bond}P{_}O) with a total surface site density equal to 7.0 sites nm{sup -2}. For both reactive sites, the intrinsic protonation constants do not change with the temperature, while the deprotonation ones increase. These results led to the determination of the associated enthalpy and entropy changes according to the van't Hoff relation. Second, the speciation of U(VI) at the solid/solution interface has been studied using two complementary spectroscopic techniques probing the sorbed uranyl ions: time-resolved laser-induced fluorescence spectroscopy (TRLFS) and X-ray absorption spectroscopy (EXAFS). The substrate presents two different reactive surface sites against uranium retention, which are constituted by the oxygen atoms of the surface PO{sub 4} groups and the oxygen atoms linked to the zirconium atoms. Two inner-sphere complexes are thus present on the substrate, their relative proportion depending on the pH value of the suspension. The effects of the temperature (25-90 C) on the surrounding uranium were checked using the TRLFS

  6. Surface complexation modeling of uranium(VI) sorbed onto zirconium oxophosphate versus temperature: thermodynamic and structural approaches.

    PubMed

    Almazan-Torres, M G; Drot, R; Mercier-Bion, F; Catalette, H; Den Auwer, C; Simoni, E

    2008-07-01

    This work presents an investigation of the interaction mechanisms between uranyl ions and a solid phosphate, the zirconium oxophosphate: Zr2O(PO4)2. Both thermodynamic and structural points of view are developed. Indeed, prior to any simulation of the retention data, it is necessary to precisely characterize the system under study in order to gain information at a molecular scale. First, the intrinsic surface properties of this synthetic compound have been investigated for different temperatures ranging from 25 to 90 degrees C. Mass and potentiometric titrations show that the surface site density remains constant between 25 and 90 degrees C, while the experimental point of zero charge slightly decreases from 4.8 to 4.5 with an increasing temperature. The potentiometric titration data are simulated, for each temperature, using the constant capacitance model and taking into account two surface sites ([TRIPLE BOND]ZrO and [TRIPLE BOND]PO) with a total surface site density equal to 7.0 sites nm(-2). For both reactive sites, the intrinsic protonation constants do not change with the temperature, while the deprotonation ones increase. These results led to the determination of the associated enthalpy and entropy changes according to the van't Hoff relation. Second, the speciation of U(VI) at the solid/solution interface has been studied using two complementary spectroscopic techniques probing the sorbed uranyl ions: time-resolved laser-induced fluorescence spectroscopy (TRLFS) and X-ray absorption spectroscopy (EXAFS). The substrate presents two different reactive surface sites against uranium retention, which are constituted by the oxygen atoms of the surface PO4 groups and the oxygen atoms linked to the zirconium atoms. Two inner-sphere complexes are thus present on the substrate, their relative proportion depending on the pH value of the suspension. The effects of the temperature (25-90 degrees C) on the surrounding uranium were checked using the TRLFS technique. The

  7. Early-Late Heterometallic Complexes of Gold and Zirconium: Photoluminescence and Reactivity.

    PubMed

    Bestgen, Sebastian; Schoo, Christoph; Zovko, Christina; Köppe, Ralf; Kelly, Rory P; Lebedkin, Sergei; Kappes, Manfred M; Roesky, Peter W

    2016-05-17

    OH functionalized triarylphosphines were used to assemble zirconocene-based metalloligands with phosphine donor sites in varying positions. These complexes were subsequently treated with different gold precursors to obtain early-late heterometallic compounds in which the metal atoms exhibit different intermetallic distances. All compounds were fully investigated by spectroscopic techniques, photoluminescence measurements and single crystal X-ray diffraction. Quantum chemical calculations were also performed. Some compounds show bright emission even at room temperature with quantum yields of up to 19 % (excitation at 350 nm). Furthermore, the reactivity of dimethyl zirconocene derivatives towards gold complexes was investigated, revealing simultaneous ligand exchange and transmetallation reactions. PMID:27062296

  8. Synthesis of zirconium oxide nanoparticle by sol-gel technique

    SciTech Connect

    Lim, H. S.; Ahmad, A.; Hamzah, H.

    2013-11-27

    Zirconium oxide nanoparticle is synthesized using sol-gel technique. Various mole ratio of ammonia solution and nitric acid relative to zirconium propoxide is added in the reaction to study the effect on the crystallinity and particle size on zirconium oxide particle. Zirconium oxide synthesized with nitric acid have the smallest particle size under FESEM image and show the increasing formation of crystalline tetragonal phase under XRD diffractogram.

  9. Synthesis and structures of neutral and cationic rac-(ethylenebis(tetrahydroindenyl))zirconium(IV) benzyl complexes

    SciTech Connect

    Jordan, R.F.; LaPointe, R.E.; Baenziger, N.; Hinch, G.D. )

    1990-05-01

    Reaction of rac-(ethylenebis(tetrahydroindenyl))ZrCl{sub 2} (1) with 2 equiv of K(CH{sub 2}Ph) produces the dibenzyl complex (ethylenebis(tetrahydroindenyl))Zr(CH{sub 2}Ph){sub 2} (2). Reaction of 2 with ((C{sub 5}H{sub 4}Me){sub 2}Fe)(BPh{sub 4}) yields the cationic complex ((ethylenebis(tetrahydroindenyl))Zr(CH{sub 2}Ph)(THF))(BPh{sub 4}) (3). In CH{sub 3}CN solvent, 3 undergoes ligand substitution to yield ((ethylenebis(tetrahydroindenyl))Zr({eta}{sup 2}-CH{sub 2}Ph)(CH{sub 3}CN))(BPh{sub 4}) (4). The structures of 2 and 4 have been determined by X-ray diffraction. Complex 2 crystallizes in space group Pbcn with a = 10.008 (3) {angstrom}, b = 14.895 (4) {angstrom}, c = 17.532 (6) {angstrom}, V = 2,613.5 (2.4) {angstrom}{sup 3}, and Z = 4. Complex 4 crystallizes in space group P1 with a = 12.300 (2) {angstrom}, b = 12.493 (2) {angstrom}, c = 16.633 (3) {angstrom}, {alpha} = 84.61 (1){degree}, {beta} = 71.18 (1){degree}, {gamma} = 69.42 (1){degree}, V = 2,264.1 (9) {angstrom}{sup 3}, and Z = 2.

  10. Determination of zirconium in steels.

    PubMed

    Iyer, C S; Asari, T P

    1989-03-01

    The determination of zirconium in the range 0.01-0.20% is required for some special alloy steels. A method has been developed, based on initial removal of iron as its chloro-complex by extraction with methyl isobutyl ketone, followed by further extraction after addition of potassium thiocyanate, and determination of the zirconium left in the aqueous phase, with Arsenazo III. The absorbance is measured at 665 nm. PMID:18964725

  11. Process for producing zirconium based granules

    SciTech Connect

    Jade, S.S.

    1990-05-22

    This patent describes a process for the production f amorphous zirconium based granules. It comprises: adding about 2--15 wt % of a suitable phase stabilizer to an aqueous solutio, based upon the total weight of ZrO{sub 2} in solution, to produce an aqueous solution having a pH in the range of about 4 to 7 comprising a zirconium based complex and phase stabilizer and thereafter; drying the aqueous solution comprising the zirconium based complex and the phase stabilizer at a temperature below about 180{degrees} C. for a time sufficient to evaporate the aqueous solution thereby forming amorphous zirconium based granules containing the phase stabilizer.

  12. Processing fissile material mixtures containing zirconium and/or carbon

    DOEpatents

    Johnson, Michael Ernest; Maloney, Martin David

    2013-07-02

    A method of processing spent TRIZO-coated nuclear fuel may include adding fluoride to complex zirconium present in a dissolved TRIZO-coated fuel. Complexing the zirconium with fluoride may reduce or eliminate the potential for zirconium to interfere with the extraction of uranium and/or transuranics from fission materials in the spent nuclear fuel.

  13. DISSOLUTION OF ZIRCONIUM-CONTAINING FUEL ELEMENTS

    DOEpatents

    Horn, F.L.

    1961-12-12

    Uranium is recovered from spent uranium fuel elements containing or clad with zirconium. These fuel elements are placed in an anhydrous solution of hydrogen fluoride and nitrogen dioxide. Within this system uranium forms a soluble complex and zirconium forms an insoluble complex. The uranium can then be separated, treated, and removed from solution as uranium hexafluoride. (AEC)

  14. Functionalization of Complexed N2O in Bis(pentamethylcyclopentadienyl) Systems of Zirconium and Titanium

    PubMed Central

    2015-01-01

    Methyl triflate reacts with the metastable azoxymetallacyclopentene complex Cp*2Zr(N(O)NCPhCPh), generated in situ from nitrous oxide insertion into the Zr–C bond of Cp*2Zr(η2-PhCCPh) at −78 °C, to afford the salt [Cp*2Zr(N(O)N(Me)CPhCPh)][O3SCF3] (1) in 48% isolated yield. A single-crystal X-ray structure of 1 features a planar azoxymetallacycle with methyl alkylation taking place only at the β-nitrogen position of the former Zr(N(O)NCPhCPh) scaffold. In addition to 1, the methoxy-triflato complex Cp*2Zr(OMe)(O3SCF3) (2) was also isolated from the reaction mixture in 26% yield and fully characterized, including its independent synthesis from the alkylation of Cp*2Zr=O(NC5H5) with MeO3SCF3. Complex 2 could also be observed, spectroscopically, from the thermolysis of 1 (80 °C, 2 days). In contrast to Cp*2Zr(N(O)NPhCCPh), the more stable titanium N2O-inserted analogue, Cp*2Ti(N(O)NCPhCPh), reacts with MeO3SCF3 to afford a 1:1 mixture of regioisomeric salts, [Cp*2Ti(N(O)N(Me)CPhCPh)][O3SCF3] (3) and [Cp*2Ti(N(OMe)NCPhCPh)][O3SCF3] (4), in a combined 65% isolated yield. Single-crystal X-ray diffraction studies of a cocrystal of 3 and 4 show a 1:1 mixture of azoxymetallacyle salts resulting from methyl alkylation at both the β-nitrogen and the β-oxygen of the former Ti(N(O)NCPhCPh ring. As opposed to alkylation reactions, the one-electron reduction of Cp*2Ti(N(O)NCPhCPh) with KC8, followed by encapsulation with the cryptand 2,2,2-Kryptofix, resulted in the isolation of the discrete radical anion [K(2,2,2-Kryptofix)][Cp*2Ti(N(O)NCPhCPh)] (5) in 68% yield. Complex 5 was studied by single-crystal X-ray diffraction, and its solution X-band EPR spectrum suggested a nonbonding σ-type wedge hybrid orbital on titanium, d(z2)/d(x2–y2), houses the unpaired electron, without perturbing the azoxymetallacycle core in Cp*2Ti(N(O)NCPhCPh). Theoretical studies of Ti and the Zr analogue are also presented and discussed. PMID:24954968

  15. Cyclopentadienyl-bis(oxazoline) magnesium and zirconium complexes in aminoalkene hydroaminations

    DOE PAGESBeta

    Eedugurala, Naresh; Hovey, Megan; Ho, Hung -An; Jana, Barun; Lampland, Nicole L.; Ellern, Arkady; Sadow, Aaron D.

    2015-11-25

    Here, a new class of cyclopentadiene-bis(oxazoline) compounds and their piano-stool-type organometallic complexes have been prepared as catalysts for hydroamination of aminoalkenes. The two compounds MeC(OxMe2)2C5H5 (BoMCpH; OxMe2 = 4,4-dimethyl-2-oxazoline) and MeC(OxMe2)2C5Me4H (BoMCptetH) are synthesized from C5R4HI (R = H, Me) and MeC(OxMe2)2Li. These cyclopentadiene-bis(oxazolines) are converted into ligands that support a variety of metal centers in piano-stool-type geometries, and here we report the preparation of Mg, Tl, Ti, and Zr compounds. BoMCpH and BoMCptetH react with MgMe2(O2C4H8)2 to give the magnesium methyl complexes {BoMCp}MgMe and {BoMCptet}MgMe. BoMCpH and BoMCptetH are converted to BoMCpTl and BoMCptetTl by reaction with TlOEt. Themore » thallium derivatives react with TiCl3(THF)3 to provide [{BoMCp}TiCl(μ-Cl)]2 and [{BoMCptet}TiCl(μ-Cl)]2, the former of which is crystallographically characterized as a dimeric species. BoMCpH and Zr(NMe2)4 react to eliminate dimethylamine and afford {BoMCp}Zr(NMe2)3, which is crystallographically characterized as a monomeric four-legged piano-stool compound. {BoMCp}Zr(NMe2)3, {BoMCp}MgMe, and {BoMCptet}MgMe are efficient catalysts for the hydroamination/cyclization of aminoalkenes under mild conditions.« less

  16. Ship-in-bottle synthesis of the mixed-layered compounds of clay silicate/zirconium phosphate.

    PubMed

    Kawagoe, Hiroshi; Imo-oka, Naoya; Shinohara, Hiroyasu; Yamanaka, Shoji

    2014-07-21

    An attempt was made to synthesize artificial mixed-layered compounds between montmorillonite silicate and α-zirconium phosphate using a ship-in-bottle approach. The interlayer cations of montmorillonite were first exchanged with hydroxy-zirconium oligomeric cations, which were then subjected to a reaction with phosphoric acid or phenylphosphoric acid to develop α-zirconium phosphate layers (Zr(R-OPO3)2; R = H, C6H5) between the clay silicate layers. The attempt of the reaction with phosphoric acid failed; hydroxy-zirconium cations were removed out of the interlayer space, forming α-zirconium phosphate outside of montmorillonite. The phenylphosphate derivative, montmorillonite/Zr(C6H5OPO3)2, with a regular mixed-layered structure has been successfully obtained, showing a basal spacing corresponding to the sum of the thicknesses of the individual layers. When a polyvinyl alcohol (PVA) aqueous solution was used in the preparation of the hydroxy-zirconium exchanged montmorillonite, PVA was incorporated with hydroxy-zirconium complex cations between the silicate layers. The resulting compound can adsorb phosphate ions. Although this is not a mixed-layered compound in the context of this study, the selective and reversible phosphate ion exchange properties are worth noting for future study. PMID:24849848

  17. Cyclopentadienyl-bis(oxazoline) magnesium and zirconium complexes in aminoalkene hydroaminations

    SciTech Connect

    Eedugurala, Naresh; Hovey, Megan; Ho, Hung -An; Jana, Barun; Lampland, Nicole L.; Ellern, Arkady; Sadow, Aaron D.

    2015-11-25

    Here, a new class of cyclopentadiene-bis(oxazoline) compounds and their piano-stool-type organometallic complexes have been prepared as catalysts for hydroamination of aminoalkenes. The two compounds MeC(OxMe2)2C5H5 (BoMCpH; OxMe2 = 4,4-dimethyl-2-oxazoline) and MeC(OxMe2)2C5Me4H (BoMCptetH) are synthesized from C5R4HI (R = H, Me) and MeC(OxMe2)2Li. These cyclopentadiene-bis(oxazolines) are converted into ligands that support a variety of metal centers in piano-stool-type geometries, and here we report the preparation of Mg, Tl, Ti, and Zr compounds. BoMCpH and BoMCptetH react with MgMe2(O2C4H8)2 to give the magnesium methyl complexes {BoMCp}MgMe and {BoMCptet}MgMe. BoMCpH and BoMCptetH are converted to BoMCpTl and BoMCptetTl by reaction with TlOEt. The thallium derivatives react with TiCl3(THF)3 to provide [{BoMCp}TiCl(μ-Cl)]2 and [{BoMCptet}TiCl(μ-Cl)]2, the former of which is crystallographically characterized as a dimeric species. BoMCpH and Zr(NMe2)4 react to eliminate dimethylamine and afford {BoMCp}Zr(NMe2)3, which is crystallographically characterized as a monomeric four-legged piano-stool compound. {BoMCp}Zr(NMe2)3, {BoMCp}MgMe, and {BoMCptet}MgMe are efficient catalysts for the hydroamination/cyclization of aminoalkenes under mild conditions.

  18. SEPARATING HAFNIUM FROM ZIRCONIUM

    DOEpatents

    Lister, B.A.J.; Duncan, J.F.; Hutcheon, J.M.

    1956-08-21

    Substantially complete separation of zirconium from hafnium may be obtained by elution of ion exchange material, on which compounds of the elements are adsorbed, with an approximately normal solution of sulfuric acid. Preferably the acid concentration is between 0.8 N amd 1.2 N, amd should not exceed 1.5 N;. Increasing the concentration of sulfate ion in the eluting solution by addition of a soluble sulfate, such as sodium sulfate, has been found to be advantageous. The preferred ion exchange materials are sulfonated polystyrene resins such as Dowex 50,'' and are preferably arranged in a column through which the solutions are passed.

  19. Sulfuric acid functional zirconium (or aluminum) incorporated mesoporous MCM-48 solid acid catalysts for alkylation of phenol with tert-butyl alcohol

    SciTech Connect

    Jiang, Tingshun Cheng, Jinlian; Liu, Wangping; Fu, Lie; Zhou, Xuping; Zhao, Qian; Yin, Hengbo

    2014-10-15

    Several zirconium (or aluminum) incorporated mesoporous MCM-48 solid acid catalysts (SO{sub 4}{sup 2−}/Zr-MCM-48 and SO{sub 4}{sup 2−}/Al-MCM-48) were prepared by the impregnation method and their physicochemical properties were characterized by means of XRD, FT-IR, TEM, NH{sub 3}-TPD and N{sub 2} physical adsorption. Also, the catalytic activities of these solid acid catalysts were evaluated by the alkylation of phenol with tert-butyl alcohol. The effect of weight hour space velocity (WHSV), reaction time and reaction temperature on catalytic properties was also studied. The results show that the SO{sub 4}{sup 2−}/Zr-MCM-48 and SO{sub 4}{sup 2−}/Al-MCM-48 still have good mesoporous structure and long range ordering. Compared with the Zr (or Al)–MCM-48 samples, SO{sub 4}{sup 2−}/Zr-MCM-48 and SO{sub 4}{sup 2−}/Al-MCM-48 solid acid catalysts have strong acidity and exhibit high activities in alkylation reaction of phenol with tert-butyl alcohol. The SO{sub 4}{sup 2−}/Zr-MCM-48-25 (molar ratio of Si/Zr=0.04) catalyst was found to be the most promising and gave the highest phenol conversion among all catalysts. A maximum phenol conversion of 91.6% with 4-tert-butyl phenol (4-TBP) selectivity of 81.8% was achieved when the molar ratio of tert-butyl alcohol:phenol is 2:1, reaction time is 2 h, the WHSV is 2 h{sup −1} and the reaction temperature is 140 °C. - Highlights: • Sulfuric acid functional mesoporous solid acid catalysts were prepared via impregnation method. • The alkylation of phenol with tert-butyl alcohol was carried out over these solid acid catalysts. • The catalytic activity of SO{sub 4}{sup 2−}/Zr-MCM-48-25 catalyst is much higher than that of the others. • A maximum phenol conversion of 91.6% was achieved under optimum reaction conditions for SO{sub 4}{sup 2−}/Zr-MCM-48-25.

  20. New Type of Coordinatively Unsaturated Zirconium(IV) Complexes: (N,N,N'-Tris(trimethylsilyl)diamido -N''-(trimethylsilyl)-P-methylphosphonimidato)--trichlorozirconium(IV). Molecular Structure of the Product of Its Reaction with Tetrahydrofuran

    SciTech Connect

    Markovskii, L.N.; Chernege, A.N.; Romanenko, V.D.; Ruban, A.V.; Shul'gin, V.F.

    1986-01-01

    The authors use phosphenodiimidic amides for the preparation of coordinatively unsaturated complexes of transition metals. The synthesis of a stable complex of 5-coordinate zirconium stabilized with a phosphonimidic diamide ligand is described; up to now compounds such as these have been known only for some cyclopentadienyl derivatives.

  1. ZIRCONIUM PHOSPHATE ADSORPTION METHOD

    DOEpatents

    Russell, E.R.; Adamson, A.S.; Schubert, J.; Boyd, G.E.

    1958-11-01

    A method is presented for separating plutonium values from fission product values in aqueous acidic solution. This is accomplished by flowing the solutlon containing such values through a bed of zirconium orthophosphate. Any fission products adsorbed can subsequently be eluted by washing the column with a solution of 2N HNO/sub 3/ and O.lN H/sub 3/PO/sub 4/. Plutonium values may subsequently be desorbed by contacting the column with a solution of 7N HNO/sub 3/ .

  2. URANIUM DECONTAMINATION WITH RESPECT TO ZIRCONIUM

    DOEpatents

    Vogler, S.; Beederman, M.

    1961-05-01

    A process is given for separating uranium values from a nitric acid aqueous solution containing uranyl values, zirconium values and tetravalent plutonium values. The process comprises contacting said solution with a substantially water-immiscible liquid organic solvent containing alkyl phosphate, separating an organic extract phase containing the uranium, zirconium, and tetravalent plutonium values from an aqueous raffinate, contacting said organic extract phase with an aqueous solution 2M to 7M in nitric acid and also containing an oxalate ion-containing substance, and separating a uranium- containing organic raffinate from aqueous zirconium- and plutonium-containing extract phase.

  3. PROCESS OF DISSOLVING ZIRCONIUM ALLOYS

    DOEpatents

    Shor, R.S.; Vogler, S.

    1958-01-21

    A process is described for dissolving binary zirconium-uranium alloys where the uranium content is about 2%. In prior dissolution procedures for these alloys, an oxidizing agent was added to prevent the precipitation of uranium tetrafluoride. In the present method complete dissolution is accomplished without the use of the oxidizing agent by using only the stoichiometric amount or slight excess of HF required by the zirconium. The concentration of the acid may range from 2M to 10M and the dissolution is advatageously carried out at a temperature of 80 deg C.

  4. Complexation and molecular modeling studies of europium(III)-gallic acid-amino acid complexes.

    PubMed

    Taha, Mohamed; Khan, Imran; Coutinho, João A P

    2016-04-01

    With many metal-based drugs extensively used today in the treatment of cancer, attention has focused on the development of new coordination compounds with antitumor activity with europium(III) complexes recently introduced as novel anticancer drugs. The aim of this work is to design new Eu(III) complexes with gallic acid, an antioxida'nt phenolic compound. Gallic acid was chosen because it shows anticancer activity without harming health cells. As antioxidant, it helps to protect human cells against oxidative damage that implicated in DNA damage, cancer, and accelerated cell aging. In this work, the formation of binary and ternary complexes of Eu(III) with gallic acid, primary ligand, and amino acids alanine, leucine, isoleucine, and tryptophan was studied by glass electrode potentiometry in aqueous solution containing 0.1M NaNO3 at (298.2±0.1) K. Their overall stability constants were evaluated and the concentration distributions of the complex species in solution were calculated. The protonation constants of gallic acid and amino acids were also determined at our experimental conditions and compared with those predicted by using conductor-like screening model for realistic solvation (COSMO-RS) model. The geometries of Eu(III)-gallic acid complexes were characterized by the density functional theory (DFT). The spectroscopic UV-visible and photoluminescence measurements are carried out to confirm the formation of Eu(III)-gallic acid complexes in aqueous solutions. PMID:26827296

  5. Serum albumin complexation of acetylsalicylic acid metabolites.

    PubMed

    Jurkowski, Wiktor; Porebski, Grzegorz; Obtułowicz, Krystyna; Roterman, Irena

    2009-06-01

    One possible origin of the type I hypersensitivity reaction is reaction of drugs such as acetylsalicylic acid and its metabolites being complexed with human serum albumin. Albumin, being transporting molecule abundant in blood plasma is able to bind large array of ligands varying from small single carbon particles to long hydrophobic tailed lipidic acids (e.g. myristic acid). This non specificity is possible because of multi domain scaffold and large flexibility of inter-domain loops, which results in serious reorientation of domains. Hypothesis that acetylsalicylic acid metabolites may play indirect role in activation of allergic reaction has been tested. Binding of acetylsalicylic acid metabolites in intra-domain space causes significant increase of liability of domains IIIA and IIIB. One of metabolites, salicyluric acid, once is bound causes distortion and partial unfolding of helices in domains IA, IIB and IIIB. Changed are both directions and amplitude of relative motions as well as intra-domain distances. In result albumin is able to cross-link of adjacent IgE receptors which subsequently starts allergic reaction. PMID:19689242

  6. PROCESS OF RECOVERING ZIRCONIUM VALUES FROM HAFNIUM VALUES BY SOLVENT EXTRACTION WITH AN ALKYL PHOSPHATE

    DOEpatents

    Peppard, D.F.

    1960-02-01

    A process of separating hafnium nitrate from zirconium nitrate contained in a nitric acid solution by selectively. extracting the zirconium nitrate with a water-immiscible alkyl phosphate is reported.

  7. Thermodynamics and kinetics of the formation of the supramolecular complexes bisacetato(5,10,15,20-tetraphenylporphinate)zirconium(IV) with pyridine and imidazole

    NASA Astrophysics Data System (ADS)

    Tyulyaeva, E. Yu.; Lomova, T. N.

    2010-05-01

    The equilibria and rates of step reactions for the formation of the supramolecular complexes of bisacetato(5,10,15,20-tetraphenylporphinate)zirconium(IV) (AcO)2ZrTPP and bioactive bases pyridine (Py) and imidazole (Im) in toluene were studied using UV-Vis and IR spectroscopy. The step stoichiometric mechanism, including the reversible coordination of two Py molecules ( K 1 = 1.8 × 108 l2/mol2), the equilibrium of the displacement of two AcO- into the second coordination sphere by increasing the concentration of the solvent polar component ( K 2 = 2.4), and the coordination of the third and fourth Py molecules in a one step with the formation of [(Py)4ZrTPP]2+ · 2(AcO)- ( K 3 = 2.8 × 104 l2/mol2), was verified. It was established that the spectrophotometric titration is sensible for the two-stage π-π-complexation of [(Py)4ZrTPP]2+ · 2(AcO)- with Py molecules ( K 4 = 29 l/mol and K 5 = 1.8 l/mol). It was shown that the stronger base Im reacts irreversibly with (AcO)2ZrTPP. The thermodynamic and optical characteristics of (AcO)2ZrTPP required for using the complex in the detection of bioactive bases were studied.

  8. Sorption of palladium(II) from sulfate and perchlorate media on hydrated zirconium dioxide

    SciTech Connect

    Abovskaya, N.V.; Boichinova, E.S.; Simanova, S.A.

    1988-09-20

    Hydrated zirconium dioxide (HZD) is an amphoteric sorbent, acting as an anion-exchanger in acid solutions and a cation-exchanger in alkaline. The purpose of this work was to study the sorption activity of (HZD) with respect to palladium(II) in solutions of PdSO/sub 4/ x 3H/sub 2/O in sulfuric or perchloric acids. It was shown that HZD can extract cationic palladium(II) aqua complexes selectively and rapidly from weakly acidic solutions. The sorbed aqua complexes of Pd(II) undergo conversions with formation of hydroxo complexes in the sorbent phase.

  9. METHOD OF IMPROVING CORROSION RESISTANCE OF ZIRCONIUM

    DOEpatents

    Shannon, D.W.

    1961-03-28

    An improved intermediate rinse for zirconium counteracts an anomalous deposit that often results in crevices and outof-the-way places when ordinary water is used to rinse away a strong fluoride etching solution designed to promote passivation of the metal. The intermediate rinse, which is used after the etching solution and before the water, is characterized by a complexing agent for fluoride ions such as aluminum or zirconium nitrates or chlorides.

  10. Zirconium dioxide nanofilled poly(vinylidene fluoride-hexafluoropropylene) complexed with lithium trifluoromethanesulfonate as composite polymer electrolyte for electrochromic devices

    SciTech Connect

    Puguan, John Marc C.; Chinnappan, Amutha; Kostjuk, Sergei V.; Kim, Hern

    2015-09-15

    Highlights: • Successful synthesis of electrolyte by blending PVdF-HFP, ZrO{sub 2} and LiCF{sub 3}SO{sub 3}. • ZrO{sub 2} increased electrolyte conductivity by two orders of magnitude. • ZrO{sub 2} doubled bulk mechanical strength of electrolyte in terms of Young’s modulus. • Electrolytes gave a optimum optical transmittance of 52.6%. - Abstract: Poly(vinylidene fluoride-hexafluoropropylene) (PVdF-HFP) polymer electrolyte containing zirconium dioxide nanocrystals (ZrO{sub 2}-NC) and lithium trifluoromethanesulfonate (LiCF{sub 3}SO{sub 3}) has been synthesized using the conventional solution casting method. The addition of ZrO2-NC into the polymeric substrate gave remarkable properties in terms of the electrolyte’s ionic conductivity as well as its bulk mechanical strength. The enhanced amorphicity of the polymeric substrate due to ZrO{sub 2} and the nanofiller’s high dielectric constant make an excellent combination to increase the ionic conductivity (above 10{sup −4} S cm{sup −1}). Increasing the nanofiller content raises the ionic conductivity of the electrolyte by two orders of magnitude of which the optimum is 2.65 × 10{sup −4} S cm{sup −1} at 13.04 wt% ZrO{sub 2}-NC loading. Also, the Young’s modulus, an indicator of electrolyte’s mechanical stability, dramatically increased to 207 MPa upon loading 13.04 wt% ZrO{sub 2}-NC. Using UV–vis spectroscopy, the electrolytes with 13.04% ZrO{sub 2}-NC scanned from 200–800 nm wavelengths exhibited a maximum optical transmittance of 52.6% at 10 μm film thickness. The enhanced conductivity, high mechanical strength and reasonable optical transmittance shown by our composite polymer electrolyte make an excellent electrolyte for future energy saving smart windows such as electrochromic devices.

  11. PLUTONIUM-ZIRCONIUM ALLOYS

    DOEpatents

    Schonfeld, F.W.; Waber, J.T.

    1960-08-30

    A series of nuclear reactor fuel alloys consisting of from about 5 to about 50 at.% zirconium (or higher zirconium alloys such as Zircaloy), balance plutonium, and having the structural composition of a plutonium are described. Zirconium is a satisfactory diluent because it alloys readily with plutonium and has desirable nuclear properties. Additional advantages are corrosion resistance, excellent fabrication propenties, an isotropie structure, and initial softness.

  12. DNA binding studies of new valine derived chiral complexes of tin(IV) and zirconium(IV)

    NASA Astrophysics Data System (ADS)

    Arjmand, Farukh; Jamsheera, A.

    2011-01-01

    Valine derived chiral complexes of SnCl 4 ( 1) and ZrCl 4 ( 2) were designed as potent antitumor agents. These complexes were characterized by elemental analysis, IR, 1H NMR, 119Sn NMR and ESI mass spectroscopy. In vitro binding studies of complexes 1 and 2 under physiological conditions at room temperature with CT-DNA were carried out employing UV-vis absorption titration, fluorescence studies and viscosity measurements. The extent of binding was quantified by Kb values of complexes 1 and 2 which were found to be 1.97 × 10 4 and 1.17 × 10 3 M -1, respectively, suggesting that complex 1 has significantly greater DNA binding propensity in contrast to the complex 2. The mode of action at the molecular level was ascertained by the interaction of complex 1 with 5'GMP and 5'TMP which revealed that complex 1 binds via electrostatic mode with the oxygen of the negatively charged surface phosphate group of the DNA helix. The supercoiled pBR322 plasmid DNA cleavage activity of complex 1 was ascertained by gel electrophoresis assay.

  13. Methods to treat pyrophoric film on zirconium

    SciTech Connect

    Yau, T.L.

    1982-09-01

    Zirconium is a reactive but corrosion resistant metal. However, in a highly oxidizing or an oxygen deficient solution, corrosion of zirconium can be rapid and a pyrophoric film, which ignites easily, may be formed on the surface of zirconium. Although high corrosion rates only infrequently lead to the formation of pyrophoric films, great care should be exercised with testing coupons or equipment where rapid attack is suspected. Laboratory tests were conducted to find methods to treat pyrophoric films on zirconium. Burnable specimens were prepared by placing zirconium coupons in 77.5% sulfuric acid (H/sub 2/SO/sub 4/) with 200-ppm Fe/sup +3/ (as ferric sulfate) at 80/sup 0/C for 10 days withou stirring or agitation. Chemical, X-ray diffraction, and metallographic analyses indicate that the pyrophoric film is composed of ..gamma..-hydride, zirconium oxide, zirconium sulfate, and metallic particles. This pyrophoric film could not be removed easily using common pickling solutions, that is, nitric acid-hydrofluoric acid (HNO/sub 3/-HF) mixtures, or other aggressive media, for example, 80% H/sub 2/SO/sub 4/. It has been found that the pyrophoric film can be rendered nonpyrophoric by treating with hot air or steam. A 20 to 30 min treatment with 250/sup 0/C air or steam is sufficient to completely eliminate the pyrophoric tendency. Lower temperature air or steam can be used but require longer time: a few hours if the temperature is 200/sup 0/C, and a few days if the temperature is 100/sup 0/C. Use of this treatment in the field has proven effective.

  14. Studies in zirconium oxidation

    NASA Technical Reports Server (NTRS)

    Draley, J. E.; Drunen, C. J.; Levitan, J.

    1968-01-01

    Study provides insight into the oxidation mechanism of zirconium by combining electrical measurements with oxidation data. The measurement of electrical potential across growing scale on zirconium and the determination of conventional weight-change oxidation data were carried out at 550, 700, and 800 degrees C.

  15. Zirconium isotope separation

    SciTech Connect

    Siddall, M.B.

    1984-12-11

    A method of separating zirconium isotopes by converting the zirconium to its iodide salt prior to separation by usual isotope methods is disclosed. After separation the desired isotopes are converted from the salt to the metal by the van Arkel-de Boer iodide process.

  16. SEPARATION OF URANIUM FROM ZIRCONIUM AND NIOBIUM BY SOLVENT EXTRACTION

    DOEpatents

    Voiland, E.E.

    1958-05-01

    A process for separation of the uranium from zirconium and/or niobium values contained in 3 to 7M aqueous nitric acid solutions is described. This is accomplished by adding phosphoric acid anions to the nitric acid solution containing the uranium, zirconium, and/or niobium in an amount sufficient to make the solution 0.05 to 0.2M in phosphate ion and contacting the solution with an organic water-immiscible solvent such as MEK, whereby the uranyl values are taken up by the extract phase while the zirconium and niobium preferentially remain in the aqueous raffinate.

  17. Zirconium Hydride Complex Supported by a Tetradentate Carbon-Centered Tripodal Tris(aryloxide) Ligand: Synthesis, Structure, and Reactivity.

    PubMed

    Nakanishi, Yusuke; Ishida, Yutaka; Kawaguchi, Hiroyuki

    2016-04-18

    A dizirconium trihydride complex supported by a tetradentate carbon-centered tris(aryloxide) ligand [{Na(dme)}3{(O3C)Zr}2(μ-H)3] (2; [O3C] = [(3,5-(t)Bu2-2-O-C6H2)3C](4-)) was prepared by reacting [(O3C)Zr(thf)3] (1) with NaBHEt3 in toluene. Exposure of 2 in THF to CO2 (1 atm) resulted in facile insertion of CO2 into Zr-H bonds, yielding a formate complex [{Na(thf)2}3{(O3C)Zr}2(μ-O2CH)3] (3). Treatment of 2 with P4 in toluene led to formation of [Na(thf)5][{Na(thf)2}2{(O3C)Zr}2(μ-P3)] (4) and PH3, in which hydrogenation of P4 took place. Complex 2 reacted with Me3SiN3 to afford an azide-bridged cyclotrimer [{Na(thf)2}{(O3C)ZrN3(thf)}]3 (5) with concomitant liberation of Me3SiH. The molecular structures of these complexes 2-5 have been determined by X-ray diffraction analyses. PMID:27045559

  18. Zirconium(IV) and Hafnium(IV) Porphyrin and Phthalocyanine Complexes as New Dyes for Solar Cell Devices

    PubMed Central

    Radivojevic, Ivana; Bazzan, Giorgio; Burton-Pye, Benjamin P.; Ithisuphalap, Kemakorn; Saleh, Raihan; Durstock, Michael F.; Francesconi, Lynn C.; Drain, Charles Michael

    2012-01-01

    Metalloporphyrin and metallophthalocyanine dyes ligating Hf(IV) and Zr(IV) ions bind to semiconductor oxide surfaces such as TiO2 via the protruding group IV metal ions. The use of oxophylic metal ions with large ionic radii that protrude from the macrocycle is a unique mode of attaching chromophores to oxide surfaces in the design of dye-sensitized solar cells (DSSCs). Our previous report on the structure and physical properties of ternary complexes wherein the Hf(IV) and Zr(IV) ions are ligated to both a porphyrinoid and to a defect site on a polyoxometalate (POM) represents a model for this new way of binding dyes to oxide surfaces. The Zr(IV) and Hf(IV) complexes of 5,10,15,20-tetraphenylporphyrin (TPP) with two ligated acetates, (TPP)Hf(OAc)2 and (TPP)Zr(OAc)2, and the corresponding metallophthalocyanine (Pc) diacetate complexes, (Pc)Hf(OAc)2 and (Pc)Zr(OAc)2, were evaluated as novel dyes for the fabrication of dye-sensitized solar cells. Similarly to the ternary complexes with the POM, the oxide surface replaces the acetates to affect binding. In DSSCs the Zr(IV) phthalocyanine dye performs better than the Zr(IV) porphyrin dye, and reaches an overall efficiency of ~ 1.0%. The Hf(IV) dyes are less efficient. The photophysical properties of these complexes in solution suggested energetically favorable injection of electrons into the conduction band of TiO2 semiconductor nanoparticles, as well as a good band gap match with I3−/I− pair in liquid 1-butyl-3-methyl imidazolium iodide. The combination of blue absorbing TPP with the red absorbing Pc complexes can increase the absorbance of solar light in the device; however, the overall conversion efficiency of DSSCs using TiO2 nanoparticles treated with a mixture of both Zr(IV) complexes is comparable, but not greater than, the single (Pc)Zr. Thus, surface bound (TPP)Zr increases the absorbance in blue region of the spectra, but at the cost of diminished absorbance in the red in this DSSC architecture. PMID

  19. Yttrium oxide stabilized zirconium oxide

    SciTech Connect

    Ritsko, J.E.; Houck, D.L.; Acla, H.L.R.

    1987-09-22

    This patent describes a process comprising: (a) forming a solution by mixing yttrium hydroxide and a sufficient amount of an aqueous solution of acetic acid to dissolve the yttrium hydroxide. The solution has a concentration of yttrium ion of about 5% to about 20% by weight of the solution, (b) adding from about 80% to about 95% by weight of zirconium oxide having a particle size range from about 1 to about 5 microns to yield a Zr to Y weight ratio of from about 4:1 to about 19:1 and thereby forming a slurry, (c) spray drying the slurry to form spherical agglomerates consisting essentially of zirconium oxide and a relatively uniform distribution of yttrium acetate whereby the agglomerates have a size from about 20 to about 200 micrometers, (d) heating the agglomerates to about 600/sup 0/C to about 700/sup 0/C in a neutral or oxidizing atmosphere to convert yttrium acetate to yttrium oxide to thereby form zirconium oxide yttrium oxide agglomerates with about 5% to about 20% by weight of yttrium oxide.

  20. Phase Behavior of Complex Superprotonic Solid Acids

    NASA Astrophysics Data System (ADS)

    Panithipongwut, Chatr

    Superprotonic phase transitions and thermal behaviors of three complex solid acid systems are presented, namely Rb3H(SO4) 2-RbHSO4 system, Rb3H(SeO4)2-Cs 3H(SeO4)2 solid solution system, and Cs6 (H2SO4)3(H1.5PO4) 4. These material systems present a rich set of phase transition characteristics that set them apart from other, simpler solid acids. A.C. impedance spectroscopy, high-temperature X-ray powder diffraction, and thermal analysis, as well as other characterization techniques, were employed to investigate the phase behavior of these systems. Rb3H(SO4)2 is an atypical member of the M3H(XO4)2 class of compounds (M = alkali metal or NH4+ and X = S or Se) in that a transition to a high-conductivity state involves disproportionation into two phases rather than a simple polymorphic transition [1]. In the present work, investigations of the Rb3H(SO4)2-RbHSO4 system have revealed the disproportionation products to be Rb2SO 4 and the previously unknown compound Rb5H3(SO 4)4. The new compound becomes stable at a temperature between 25 and 140 °C and is isostructural to a recently reported trigonal phase with space group P3m of Cs5H 3(SO4)4 [2]. At 185 °C the compound undergoes an apparently polymorphic transformation with a heat of transition of 23.8 kJ/mol and a slight additional increase in conductivity. The compounds Rb3H(SeO4)2 and Cs 3H(SeO4)2, though not isomorphous at ambient temperatures, are quintessential examples of superprotonic materials. Both adopt monoclinic structures at ambient temperatures and ultimately transform to a trigonal (R3m) superprotonic structure at slightly elevated temperatures, 178 and 183 °C, respectively. The compounds are completely miscible above the superprotonic transition and show extensive solubility below it. Beyond a careful determination of the phase boundaries, we find a remarkable 40-fold increase in the superprotonic conductivity in intermediate compositions rich in Rb as compared to either end-member. The compound Cs6(H2

  1. Insertion and [beta]-hydride elimination reactions of ruthenium/zirconium complexes containing C[sub 2] bridges with bond orders of 1, 2, and 3

    SciTech Connect

    Lemke, F.R.; Bullock, R.M. )

    1992-12-01

    Carbon dioxide inserts into the Zr-C bond of Cp(PMe[sub 3])[sub 2]RuCH[double bond]CHZrClCp[sub 2], producing the carboxylate complex Cp(PMe[sub 3])[sub 2]RuCH[double bond]CHCO[sub 2]ZrClCp[sub 2]. An [eta][sup 2]-iminoacyl insertion product, Cp(PMe[sub 3])[sub 2]Ru-C[triple bond]C-C(N[sub t]Bu)ZrClCp[sub 2], results from insertion of [sup t]BuNC into the Zr-C bond of the dimetalloalkyne complex Cp(PMe[sub 3])[sub 2]Ru-C[triple bond]C-ZrClCp[sub 2]. The reaction of Cp(PMe[sub 3])[sub 2]RuCH[sub 2]CH[sub 2]ZrClCp[sub 2] with high concentrations of [sup t]BuNC also produces an [eta][sup 2]-iminoacyl insertion product, Cp(PMe[sub 3])[sub 2]RuCH[sub 2]CH[sub 2]C(N[sup t]Bu)ZrClCp[sub 2]. At low concentrations of [sup t]BuNC, a competing reaction is [beta]-hydride elimination from Cp(PMe[sub 3])[sub 2]RuCH[sub 2]CH[sub 2]ZrClCp[sub 2] to give Cp(PMe[sub 3])[sub 2]RuCH[double bond]CH[sub 2] and Cp[sub 2]Zr(H)Cl, which is trapped by [sup t]BuNC under these conditions to give Cp[sub 2]ZrCl([eta][sup 2]-[sup t]BuN[double bond]CH). The reaction of benzophenone with Cp(PMe[sub 3])[sub 2]RuCH[sub 2]CH[sub 2]ZrClCp[sub 2] gives the insertion product Cp(PMe[sub 3])[sub 2]RuCH[sub 2]CH[sub 2]CPh[sub 2]OZrClCp[sub 2]. [beta]-Hydride elimination is also observed from Cp(PMe[sub 3])[sub 2]RuCH[double bond]CHZrClCp[sub 2]; in the presence of excess [sup n]BuC[triple bond]CH, the products are Cp(PMe[sub 3])[sub 2]Ru-C[triple bond]C-H and the zirconium vinyl complex Cp[sub 2]Zr(Cl)CH[double bond]CH[sup n]Bu. 25 refs.

  2. Photoacoustic spectral studies on lanthanide amino acid complexes

    NASA Astrophysics Data System (ADS)

    Yang, Yue-tao; Zhao, Gui-wen; Zhang, Shu-yi

    2003-01-01

    Several kinds of lanthanide complexes with glycine, alanine, phenylalanine, and tryptophan were synthesized and their photoacoustic (PA) spectra were measured. For the complexes of weakly fluorescent lanthanide ions with amino acids, the PA spectra reflect the influences of the ligands on the energy levels of lanthanide ions, whereas for the complexes of fluorescent lanthanide ions with amino acids, the PA spectra can be used to study the energy transfer from aromatic amino acids to lanthanide ions. At last, separating the overlapping peaks of lanthanide complex with tryptophan using the PA phase resolved method is introduced.

  3. RECOVERY OF URANIUM FROM ZIRCONIUM-URANIUM NUCLEAR FUELS

    DOEpatents

    Gens, T.A.

    1962-07-10

    An improvement was made in a process of recovering uranium from a uranium-zirconium composition which was hydrochlorinated with gsseous hydrogen chloride at a temperature of from 350 to 800 deg C resulting in volatilization of the zirconium, as zirconium tetrachloride, and the formation of a uranium containing nitric acid insoluble residue. The improvement consists of reacting the nitric acid insoluble hydrochlorination residue with gaseous carbon tetrachloride at a temperature in the range 550 to 600 deg C, and thereafter recovering the resulting uranium chloride vapors. (AEC)

  4. Laser ablated zirconium plasma: A source of neutral zirconium

    SciTech Connect

    Yadav, Dheerendra; Thareja, Raj K.

    2010-10-15

    The authors report spectroscopic investigations of laser produced zirconium (Zr) plasma at moderate laser fluence. At low laser fluence the neutral zirconium species are observed to dominate over the higher species of zirconium. Laser induced fluorescence technique is used to study the velocity distribution of ground state neutral zirconium species. Two-dimensional time-resolved density distributions of ground state zirconium is mapped using planner laser induced fluorescence imaging and total ablated mass of neutral zirconium atoms is estimated. Temporal and spatial evolutions of electron density and temperature are discussed by measuring Stark broadened profile and ratio of intensity of emission lines, respectively.

  5. Zirconium fluoride glass - Surface crystals formed by reaction with water

    NASA Technical Reports Server (NTRS)

    Doremus, R. H.; Bansal, N. P.; Bradner, T.; Murphy, D.

    1984-01-01

    The hydrated surfaces of a zirconium barium fluoride glass, which has potential for application in optical fibers and other optical elements, were observed by scanning electron microscopy. Crystalline zirconium fluoride was identified by analysis of X-ray diffraction patterns of the surface crystals and found to be the main constituent of the surface material. It was also found that hydrated zirconium fluorides form only in highly acidic fluoride solutions. It is possible that the zirconium fluoride crystals form directly on the glass surface as a result of its depletion of other ions. The solubility of zirconium fluoride is suggested to be probably much lower than that of barium fluoride (0.16 g/100 cu cm at 18 C). Dissolution was determined to be the predominant process in the initial stages of the reaction of the glass with water. Penetration of water into the glass has little effect.

  6. Pentamethylcyclopentadienyl aminoborollide derivatives of zirconium and hafnium. A new class of amphoteric molecule having both Lewis acidic and Lewis basic sites

    SciTech Connect

    Quan, R.W.; Bazan, G.C.; Kiely, A.F.; Schaefer, W.P.; Bercaw, J.E. )

    1994-05-18

    Although dicarbollide complexes are similar to their bis(cyclopentadienyl) analogs in reactivity, the increase in overall negative charge generally reduces their electrophilicity. Moreover, crystal structure determinations for several dimeric dicarbollide complexes have revealed bridging interactions involving a B-H bond of the dicarbollide cage with the Lewis acidic metal that further reduce their reactivity. We have therefore examined the dianionic aminoborollide ligand, [C[sub 4]H[sub 4]BN(CHMe[sub 2])[sub 2

  7. Decomposition of peracetic acid catalyzed by vanadium complexes

    SciTech Connect

    Makarov, A.P.; Gekhman, A.E.; Moiseev, I.I.; Polotryuk, O.Y.

    1986-02-01

    This paper studies the decomposition of peracetic acid (AcOOH) in acetic acid (AcOH) catalyzed by vanadium complexes. It is shown that peractic acid in acetic acid solutions of ammonium anadate decomposes with the predominant formation of 0/sub 2/ and small amounts of CO/sub 2/, the yield of which increases with increasing temperature and peracetic acid concentration. Both reactions proceed without the formation of free radicals in amounts detectable by ESR spectroscopy. The rate of oxygen release under conditions in which the formation of CO/sub 2/ is insignificant obeys a kinetic equation indicating the intermediate formation of a complex between V/sup 5 +/ ions and peracetic acid and the slow conversion of this complex into the observed products.

  8. Titanium and zirconium complexes of the N,N'-bis(2,6-diisopropylphenyl)-1,4-diaza-butadiene ligand: syntheses, structures and uses in catalytic hydrosilylation reactions.

    PubMed

    Anga, Srinivas; Naktode, Kishor; Adimulam, Harinath; Panda, Tarun K

    2014-10-21

    We report here a number of dianionic 1,4-diaza-1,3-butadiene complexes of titanium and zirconium synthesised by a salt metathesis reaction. The reaction of either CpTiCl3 or Cp2TiCl2 with the dilithium salt of N,N'-bis(2,6-diisopropylphenyl)-1,4-diaza-1,3-butadiene [; abbreviated (Dipp)2DADLi2] afforded the mono-cyclopentadienyl titanium complex [η(5)-CpTi((Dipp)2DAD)Cl] () bearing a dianionic ene-diamide ligand, while the analogous reaction of zirconocene dichloride (Cp2ZrCl2) with the dilithium salt gave the bis-cyclopentadienyl zirconium complex [Cp2Zr{(Dipp)2DAD}] (). The metal dichloride complexes [Ti((Dipp)2DAD)Cl2] () and [{(Dipp)2DADZrCl(μ-Cl)}2(κ(3)-Cl)(Li)(OEt2)2] () were obtained by the reaction of and anhydrous metal tetrachloride in a 1 : 1 molar ratio in diethyl ether at room temperature. Meanwhile, the homoleptic titanium complex [Ti{((Dipp)2DAD)}2] () was isolated in good yield by the treatment of with TiCl4 in a 1 : 2 molar ratio in diethyl ether. The complexes and were further reacted with neosilyl lithium to afford mono- and bis-alkyl complexes of titanium [η(5)-CpTi{(Dipp)2DAD}(CH2SiMe3)] () and zirconium [Zr{(Dipp)2DAD}(CH2SiMe3)2] () respectively. Molecular structures of the complexes , , and in the solid states were confirmed by single crystal X-ray diffraction analysis. The solid state structures of all the complexes reveal that the metal ions are chelated through the amido-nitrogen atoms and the olefinic carbons of the [(Dipp)2DAD](2-) moiety, satisfying the σ(2),π coordination mode. Compound was used as a catalyst for the intermolecular hydrosilylation reaction of a number of olefins, and moderate activity of catalyst was observed. PMID:25177841

  9. Determination of boron in blood, urine and bone by electrothermal atomic absorption spectrometry using zirconium and citric acid as modifiers

    NASA Astrophysics Data System (ADS)

    Burguera, Marcela; Burguera, José Luis; Rondón, Carlos; Carrero, Pablo

    2001-10-01

    A comparative study of various potential chemical modifiers (Au, Ba, Be, Ca, Cr, Ir, La, Lu, Mg, Ni, Pd, Pt, Rh, Ru, Sr, V, W, and Zr), and different 'coating' treatments (Zr, W, and W+Rh) of the pyrolytic graphite platform of a longitudinally heated graphite tube atomizer for thermal stabilization and determination of boron was undertaken. The use of Au, Ba, Be, Cr, Ir, Pt, Rh, Ru, Sr and V as modifiers, and of W+Rh coating produced erratic, and noisy signals, while the addition of La, Ni and Pd as modifiers, and the W coating had positive effects, but with too high background absorption signals, rendering their use unsuitable for boron determination even in aqueous solutions. The atomic absorption signal for boron was increased and stabilized when the platform was coated with Zr, and by the addition of Ca, Mg, Lu, W or Zr as modifiers. Only the addition of 10 μg of Zr as a modifier onto Zr-treated platforms allowed the use of a higher pyrolysis temperature without analyte losses. The memory effect was minimized by incorporating a cleaning step with 10 μl of 50 g l -1 NH 4F HF after every three boron measurements. The addition of 10 μl of 15 g l -1 citric acid together with Zr onto Zr-treated platforms significantly improved the characteristic mass to m0=282 pg, which is adequate for biological samples such as urine and bone, although the sensitivity was still inadequate for the determination of boron in blood of subjects without supplementary diet. Under optimized conditions, the detection limit (3σ) was 60 μg l -1. The amount of boron found in whole blood, urine and femur head samples from patients with osteoporosis was in agreement with values previously reported in the literature.

  10. Starch-lipid complexes: Interesting material and applications from amylose-fatty acid salt inclusion complexes

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Aqueous slurries of high amylose starch can be steam jet cooked and blended with aqueous solutions of fatty acid salts to generate materials that contain inclusion complexes between amylose and the fatty acid salt. These complexes are simply prepared on large scale using commercially available steam...

  11. Intercalation chemistry of zirconium 4-sulfophenylphosphonate

    SciTech Connect

    Svoboda, Jan; Zima, Vítězslav; Melánová, Klára; Beneš, Ludvík; Trchová, Miroslava

    2013-12-15

    Zirconium 4-sulfophenylphosphonate is a layered material which can be employed as a host for the intercalation reactions with basic molecules. A wide range of organic compounds were chosen to represent intercalation ability of zirconium 4-sulfophenylphosphonate. These were a series of alkylamines from methylamine to dodecylamine, 1,4-phenylenediamine, p-toluidine, 1,8-diaminonaphthalene, 1-aminopyrene, imidazole, pyridine, 4,4′-bipyridine, poly(ethylene imine), and a series of amino acids from glycine to 6-aminocaproic acid. The prepared compounds were characterized by powder X-ray diffraction, thermogravimetry analysis and IR spectroscopy and probable arrangement of the guest molecules in the interlayer space of the host is proposed based on the interlayer distance of the prepared intercalates and amount of the intercalated guest molecules. - Graphical abstract: Nitrogen-containing organic compounds can be intercalated into the interlayer space of zirconium 4-sulfophenylphosphonate. - Highlights: • Zirconium 4-sulfophenylphosphonate was examined as a host material in intercalation chemistry. • A wide range of nitrogen-containing organic compounds were intercalated. • Possible arrangement of the intercalated species is described.

  12. Humic Acid Complexation of Th, Hf and Zr in Ligand Competition Experiments: Metal Loading and Ph Effects

    NASA Technical Reports Server (NTRS)

    Stern, Jennifer C.; Foustoukos, Dionysis I.; Sonke, Jeroen E.; Salters, Vincent J. M.

    2014-01-01

    The mobility of metals in soils and subsurface aquifers is strongly affected by sorption and complexation with dissolved organic matter, oxyhydroxides, clay minerals, and inorganic ligands. Humic substances (HS) are organic macromolecules with functional groups that have a strong affinity for binding metals, such as actinides. Thorium, often studied as an analog for tetravalent actinides, has also been shown to strongly associate with dissolved and colloidal HS in natural waters. The effects of HS on the mobilization dynamics of actinides are of particular interest in risk assessment of nuclear waste repositories. Here, we present conditional equilibrium binding constants (Kc, MHA) of thorium, hafnium, and zirconium-humic acid complexes from ligand competition experiments using capillary electrophoresis coupled with ICP-MS (CE- ICP-MS). Equilibrium dialysis ligand exchange (EDLE) experiments using size exclusion via a 1000 Damembrane were also performed to validate the CE-ICP-MS analysis. Experiments were performed at pH 3.5-7 with solutions containing one tetravalent metal (Th, Hf, or Zr), Elliot soil humic acid (EHA) or Pahokee peat humic acid (PHA), and EDTA. CE-ICP-MS and EDLE experiments yielded nearly identical binding constants for the metal- humic acid complexes, indicating that both methods are appropriate for examining metal speciation at conditions lower than neutral pH. We find that tetravalent metals form strong complexes with humic acids, with Kc, MHA several orders of magnitude above REE-humic complexes. Experiments were conducted at a range of dissolved HA concentrations to examine the effect of [HA]/[Th] molar ratio on Kc, MHA. At low metal loading conditions (i.e. elevated [HA]/[Th] ratios) the ThHA binding constant reached values that were not affected by the relative abundance of humic acid and thorium. The importance of [HA]/[Th] molar ratios on constraining the equilibrium of MHA complexation is apparent when our estimated Kc, MHA values

  13. ZIRCONIUM-CLADDING OF THORIUM

    DOEpatents

    Beaver, R.J.

    1961-11-21

    A method of cladding thorium with zirconium is described. The quality of the bond achieved between thorium and zirconium by hot-rolling is improved by inserting and melting a thorium-zirconium alloy foil between the two materials prior to rolling. (AEC)

  14. Zirconium carbide recrystallization

    SciTech Connect

    Lanin, A.G.; Erin, O.N.; Sul'Yanov, S.N.; Turchin, V.N.

    1986-02-01

    This paper studies the primary recrystallization process of the sintered polycrystalline zirconium carbide with a composition of ZrC /SUB 0.98/ . The properties of zirconium carbide samples deformed under compression are presented; the selected degree of deformation ensures a lower scatter of grain sizes at relative error of +/- 5% in the final deformation measurement. The established mechanisms of structural changes in zirconium carbide during plastic deformation and subsequent high temperature treatment indicate the possibility of using thermomechanical methods for the direct control of the structure of these mechanical methods for the direct control of the structure of these and obviously othe group IV and V carbides obtained by powder metallurgical methods.

  15. PHOTOLYSIS OF COPPER(II)-AMINO ACID COMPLEXES IN WATER

    EPA Science Inventory

    Kinetics of the photolysis of Cu2+-amino acid complexes were investigated under sunlight or monochromatic radiation. nder sunlight (latitude 40 degrees N) in the absence of dioxygen, the mean half-lives estimated for the photoreduction of the bis-Cu2+ complexes (CuL2) at pH 8.0 a...

  16. Polymeric complexes of isonicotinic acid hydrazide with antituberculosis effects.

    PubMed

    Slivkin, A I; Lapenko, V L; Bychuk, A I; Suslina, S N; Slivkin, D A; Kornienko, S V; Belenova, A S

    2013-10-01

    We studied the effects of an analogue of isonicotinic acid hydrazide on the treatment course of experimental tuberculosis. Complex analysis has demonstrated the efficiency of isonicotinic acid hydrazide immobilized on a carrier that consisted of water-soluble cation-active analogue of chitosan (N-chlorohydroxypropyl chitosan) in a complex with cobalt ions in the therapy of experimental tuberculosis. Immunostimulating activity of the polymeric metal complex was revealed. The obtained data can be used for the development of highly effective methods for tuberculosis treatment. PMID:24288761

  17. Zirconium Phosphate Supported MOF Nanoplatelets.

    PubMed

    Kan, Yuwei; Clearfield, Abraham

    2016-06-01

    We report a rare example of the preparation of HKUST-1 metal-organic framework nanoplatelets through a step-by-step seeding procedure. Sodium ion exchanged zirconium phosphate, NaZrP, nanoplatelets were judiciously selected as support for layer-by-layer (LBL) assembly of Cu(II) and benzene-1,3,5-tricarboxylic acid (H3BTC) linkers. The first layer of Cu(II) is attached to the surface of zirconium phosphate through covalent interaction. The successive LBL growth of HKUST-1 film is then realized by soaking the NaZrP nanoplatelets in ethanolic solutions of cupric acetate and H3BTC, respectively. The amount of assembled HKUST-1 can be readily controlled by varying the number of growth cycles, which was characterized by powder X-ray diffraction and gas adsorption analyses. The successful construction of HKUST-1 on NaZrP was also supported by its catalytic performance for the oxidation of cyclohexene. PMID:27175935

  18. Inorganic resist materials based on zirconium phosphonate for atomic force microscope lithography

    NASA Astrophysics Data System (ADS)

    Kang, Mankyu; Kim, Seonae; Jung, JinHyuck; Kim, Heebom; Shin, Inkyun; Jeon, Chanuk; Lee, Haiwon

    2014-03-01

    New inorganic resist materials based on metal complexes were investigated for atomic force microscope (AFM) lithography. Phosphoric acids are good for self-assembly because of their strong binding energy. In this work, zirconium phosphonate system are newly synthesized for spin-coatable materials in aqueous solutions and leads to negative tone pattern for improving line edge roughness. Low electron exposure by AFM lithography could generate a pattern by electrochemical reaction and cross-linking of metal-oxo complexes. It has been reported that the minimum pattern results are affected by lithographic speed, and the applied voltage between a tip and a substrate.

  19. Electroless deposition process for zirconium and zirconium alloys

    DOEpatents

    Donaghy, R. E.; Sherman, A. H.

    1981-08-18

    A method is disclosed for preventing stress corrosion cracking or metal embrittlement of a zirconium or zirconium alloy container that is to be coated on the inside surface with a layer of a metal such as copper, a copper alloy, nickel, or iron and used for holding nuclear fuel material as a nuclear fuel element. The zirconium material is etched in an etchant solution, desmutted mechanically or ultrasonically, oxidized to form an oxide coating on the zirconium, cleaned in an aqueous alkaline cleaning solution, activated for electroless deposition of a metal layer and contacted with an electroless metal plating solution. This method provides a boundary layer of zirconium oxide between the zirconium container and the metal layer. 1 fig.

  20. Electroless deposition process for zirconium and zirconium alloys

    DOEpatents

    Donaghy, Robert E.; Sherman, Anna H.

    1981-01-01

    A method is disclosed for preventing stress corrosion cracking or metal embrittlement of a zirconium or zirconium alloy container that is to be coated on the inside surface with a layer of a metal such as copper, a copper alloy, nickel, or iron and used for holding nuclear fuel material as a nuclear fuel element. The zirconium material is etched in an etchant solution, desmutted mechanically or ultrasonically, oxidized to form an oxide coating on the zirconium, cleaned in an aqueous alkaline cleaning solution, activated for electroless deposition of a metal layer and contacted with an electroless metal plating solution. This method provides a boundary layer of zirconium oxide between the zirconium container and the metal layer.

  1. Fluorometric determination of zirconium in minerals

    USGS Publications Warehouse

    Alford, W.C.; Shapiro, L.; White, C.E.

    1951-01-01

    The increasing use of zirconium in alloys and in the ceramics industry has created renewed interest in methods for its determination. It is a common constituent of many minerals, but is usually present in very small amounts. Published methods tend to be tedious, time-consuming, and uncertain as to accuracy. A new fluorometric procedure, which overcomes these objections to a large extent, is based on the blue fluorescence given by zirconium and flavonol in sulfuric acid solution. Hafnium is the only element that interferes. The sample is fused with borax glass and sodium carbonate and extracted with water. The residue is dissolved in sulfuric acid, made alkaline with sodium hydroxide to separate aluminum, and filtered. The precipitate is dissolved in sulfuric acid and electrolysed in a Melaven cell to remove iron. Flavonol is then added and the fluorescence intensity is measured with a photo-fluorometer. Analysis of seven standard mineral samples shows excellent results. The method is especially useful for minerals containing less than 0.25% zirconium oxide.

  2. Determination of vanadium in refractory metals, steel, cast iron, alloys and silicates by extraction of an NBPHA complex from a sulphuric-hydrofluoric acid medium.

    PubMed

    Donaldson, E M

    1970-07-01

    A method for determining up to 0.15% of vanadium in high-purity niobium and tantalum metals, cast iron, steel, non-ferrous alloys and silicates is described. The proposed method is based on the extraction of a red vanadium(V)-N-benzoyl-N-phenylhydroxylamine complex into chloroform from a sulphuric-hydrofluoric acid medium containing excess of ammonium persulphate as oxidant. The molar absorptivity of the complex is 428 l.mole(-1).mm(-5) at 475 nm, the wavelength of maximum absorption. Interference from chromium(VI) and cerium(IV) is eliminated by reduction with iron(II). Common ions, including large amounts of titanium, zirconium, molybdenum and tungsten, do not interfere. PMID:18960775

  3. Superstoichiometric hydride of zirconium

    SciTech Connect

    Kupryazhkin, A.Ya.; Shchepetkin, A.A.; Zabolotskaya, E.V.; Pletnev, R.N.; Alyamovskii, S.I.; Kitaev, G.A.

    1987-12-01

    Superstoichiometric hydrides of zirconium have been obtained all the way up to the composition ZrH/sub 2.4/ by additional hydrogenation of ZrH/sub 2/ as a result of redistribution of hydrogen atoms between t- and o-positions. In the preparation of the hydrides the authors used zirconium iodide with an impurity content no greater than 10/sup -2/ to 10/sup -2/ mole %; the hydrogen and helium used in this work had a minimum purity of 99.95%. The content of hydrogen in the specimens was determined by a volumetric method. The x-ray diffraction analysis was performed in a DRON-2.0 unit (CuK/sub ..cap alpha../ radiation). PMR spectra were recorded in a broad-line spectrometer in the temperature interval 150-450 K.

  4. The Exocyst Complex Regulates Free Fatty Acid Uptake by Adipocytes

    PubMed Central

    Inoue, Mayumi; Akama, Takeshi; Jiang, Yibin; Chun, Tae-Hwa

    2015-01-01

    The exocyst is an octameric molecular complex that drives vesicle trafficking in adipocytes, a rate-limiting step in insulin-dependent glucose uptake. This study assessed the role of the exocyst complex in regulating free fatty acid (FFA) uptake by adipocytes. Upon differentiating into adipocytes, 3T3-L1 cells acquire the ability to incorporate extracellular FFAs in an insulin-dependent manner. A kinetic assay using fluoresceinated FFA (C12 dodecanoic acid) uptake allows the real-time monitoring of FFA internalization by adipocytes. The insulin-dependent uptake of C12 dodecanoic acid by 3T3-L1 adipocytes is mediated by Akt and phosphatidylinositol 3 (PI3)-kinase. Gene silencing of the exocyst components Exo70 and Sec8 significantly reduced insulin-dependent FFA uptake by adipocytes. Consistent with the roles played by Exo70 and Sec8 in FFA uptake, mCherry-tagged Exo70 and HA-tagged Sec8 partially colocalize with lipid droplets within adipocytes, suggesting their active roles in the development of lipid droplets. Tubulin polymerization was also found to regulate FFA uptake in collaboration with the exocyst complex. This study demonstrates a novel role played by the exocyst complex in the regulation of FFA uptake by adipocytes. PMID:25768116

  5. Transition metal complexes of isonicotinic acid (2-hydroxybenzylidene)hydrazide.

    PubMed

    Abou-Melha, Khlood S

    2008-06-01

    A new series of transition metal complexes of Schiff base isonicotinic acid (2-hydroxybenzylidene)hydrazide, HL, have been synthesized. The Schiff base reacted with Cu(II), Ni(II), Co(II), Mn(II), Fe(III) and UO2(II) ions as monobasic tridentate ligand to yield mononuclear complexes of 1:2 (metal:ligand) except that of Cu(II) which form complex of 1:1 (metal:ligand). The ligand and its metal complexes were characterized by elemental analyses, IR, UV-vis, mass and 1H NMR spectra, as well as magnetic moment, conductance measurements, and thermal analyses. All complexes have octahedral configurations except Cu(II) complex which has an extra square planar geometry distorted towards tetrahedral. While, the UO2(II) complex has its favour hepta-coordination. The ligand and its metal complexes were tested against one strain Gram +ve bacteria (Staphylococcus aureus), Gram -ve bacteria (Escherichia coli), and Fungi (Candida albicans). The tested compounds exhibited higher antibacterial activities. PMID:17728178

  6. Transition metal complexes of isonicotinic acid (2-hydroxybenzylidene)hydrazide

    NASA Astrophysics Data System (ADS)

    Abou-Melha, Khlood S.

    2008-06-01

    A new series of transition metal complexes of Schiff base isonicotinic acid (2-hydroxybenzylidene)hydrazide, HL, have been synthesized. The Schiff base reacted with Cu(II), Ni(II), Co(II), Mn(II), Fe(III) and UO 2(II) ions as monobasic tridentate ligand to yield mononuclear complexes of 1:2 (metal:ligand) except that of Cu(II) which form complex of 1:1 (metal:ligand). The ligand and its metal complexes were characterized by elemental analyses, IR, UV-vis, mass and 1H NMR spectra, as well as magnetic moment, conductance measurements, and thermal analyses. All complexes have octahedral configurations except Cu(II) complex which has an extra square planar geometry distorted towards tetrahedral. While, the UO 2(II) complex has its favour hepta-coordination. The ligand and its metal complexes were tested against one strain Gram +ve bacteria ( Staphylococcus aureus), Gram -ve bacteria (Escherichia coli) , and Fungi ( Candida albicans). The tested compounds exhibited higher antibacterial activities.

  7. Pharmacology of bile acid receptors: Evolution of bile acids from simple detergents to complex signaling molecules.

    PubMed

    Copple, Bryan L; Li, Tiangang

    2016-02-01

    For many years, bile acids were thought to only function as detergents which solubilize fats and facilitate the uptake of fat-soluble vitamins in the intestine. Many early observations; however, demonstrated that bile acids regulate more complex processes, such as bile acids synthesis and immune cell function through activation of signal transduction pathways. These studies were the first to suggest that receptors may exist for bile acids. Ultimately, seminal studies by many investigators led to the discovery of several bile acid-activated receptors including the farnesoid X receptor, the vitamin D receptor, the pregnane X receptor, TGR5, α5 β1 integrin, and sphingosine-1-phosphate receptor 2. Several of these receptors are expressed outside of the gastrointestinal system, indicating that bile acids may have diverse functions throughout the body. Characterization of the functions of these receptors over the last two decades has identified many important roles for these receptors in regulation of bile acid synthesis, transport, and detoxification; regulation of glucose utilization; regulation of fatty acid synthesis and oxidation; regulation of immune cell function; regulation of energy expenditure; and regulation of neural processes such as gastric motility. Through these many functions, bile acids regulate many aspects of digestion ranging from uptake of essential vitamins to proper utilization of nutrients. Accordingly, within a short time period, bile acids moved beyond simple detergents and into the realm of complex signaling molecules. Because of the important processes that bile acids regulate through activation of receptors, drugs that target these receptors are under development for the treatment of several diseases, including cholestatic liver disease and metabolic syndrome. In this review, we will describe the various bile acid receptors, the signal transduction pathways activated by these receptors, and briefly discuss the physiological processes that

  8. Radiochemical separation of zirconium and hafnium from other radionuclides.

    PubMed

    Hahn, R B

    1972-11-01

    Radiozirconium and radiohafnium may be separated from all other radionuclides except scandium and protactinium by precipitation with mandelic acid from 5-10 M hydrochloric acid, using commercial zirconyl chloride as carrier. Scandium and protactinium are removed by dissolving the precipitate in sodium carbonate, then adding barium nitrate to precipitate barium carbonate which acts as a scavenger. Zirconium mandelate is finally reprecipitated and the sample weighed and counted in this form. The method was checked by analysing commercial zirconyl chloride and standard rock samples for zirconium and hafnium by neutron-activation analysis. PMID:18961201

  9. Nucleic Acid-Peptide Complex Phase Controlled by DNA Hybridization

    NASA Astrophysics Data System (ADS)

    Vieregg, Jeffrey; Lueckheide, Michael; Leon, Lorraine; Marciel, Amanda; Tirrell, Matthew

    When polyanions and polycations are mixed, counterion release drives formation of polymer-rich complexes that can either be solid (precipitates) or liquid (coacervates) depending on the properties of the polyelectrolytes. These complexes are important in many fields, from encapsulation of industrial polymers to membrane-free segregation of biomolecules such as nucleic acids and proteins. Condensation of long double-stranded DNA has been studied for several decades, but comparatively little attention has been paid to the polyelectrolyte behavior of oligonucleotides. We report here studies of DNA oligonucleotides (10 - 88 nt) complexed with polylysine (10 - 100 aa). Unexpectedly, we find that the phase of the resulting complexes is controlled by the hybridization state of the nucleic acid, with double-stranded DNA forming precipitates and single-stranded DNA forming coacervates. Stability increases with polyelectrolyte length and decreases with solution salt concentration, with complexes of the longer double-stranded polymers undergoing precipitate/coacervate/soluble transitions as ionic strength is increased. Mixing coacervates formed by complementary single-stranded oligonucleotides results in precipitate formation, raising the possibility of stimulus-responsive material design.

  10. Process for purifying zirconium sponge

    SciTech Connect

    Abodishish, H.A.M.; Kimball, L.S.

    1992-03-31

    This patent describes a Kroll reduction process wherein a zirconium sponge contaminated with unreacted magnesium and by-product magnesium chloride is produced as a regulus, a process for purifying the zirconium sponge. It comprises: distilling magnesium and magnesium chloride from: a regulus containing a zirconium sponge and magnesium and magnesium chloride at a temperature above about 800{degrees} C and at an absolute pressure less than about 10 mmHg in a distillation vessel to purify the zirconium sponge; condensing the magnesium and the magnesium chloride distilled from the zirconium sponge in a condenser; and then backfilling the vessel containing the zirconium sponge and the condenser containing the magnesium and the magnesium chloride with a gas; recirculating the gas between the vessel and the condenser to cool the zirconium sponge from above about 800{degrees} C to below about 300{degrees} C; and cooling the recirculating gas in the condenser containing the condensed magnesium and the condensed magnesium chloride as the gas cools the zirconium sponge to below about 300{degrees} C.

  11. Effect of inclusion complex on nitrous acid reaction with flavonoids

    NASA Astrophysics Data System (ADS)

    Khalafi, Lida; Rafiee, Mohammad; Sedaghat, Sajjad

    2011-10-01

    The kinetic of the nitrous acid reactions with quercetin and catechin has been studied using spectrophotometric method in aqueous solution. The results show that these antioxidants participate in oxidation reactions with nitrous acid which is derived from protonation of nitrite ion in mild acidic conditions. Corresponding o-quinones as relatively stable products were detected by spectrophotometric techniques. pH dependence of the reactions has been examined and the rate constants of reactions were obtained by non-linear fitting of kinetic profiles. The effect of β-cyclodextrin on the oxidation pathway was another object of this study. It is shown that β-cyclodextrin has an inhibitory effect on the oxidation reaction. The rate constants of oxidation reactions for complexed forms and their stability constants were obtained based on changes in the reaction rates as a function of β-cyclodextrin concentration.

  12. 21 CFR 700.16 - Use of aerosol cosmetic products containing zirconium.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... 21 Food and Drugs 7 2011-04-01 2010-04-01 true Use of aerosol cosmetic products containing... SERVICES (CONTINUED) COSMETICS GENERAL Requirements for Specific Cosmetic Products § 700.16 Use of aerosol cosmetic products containing zirconium. (a) Zirconium-containing complexes have been used as an...

  13. 21 CFR 700.16 - Use of aerosol cosmetic products containing zirconium.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... 21 Food and Drugs 7 2012-04-01 2012-04-01 false Use of aerosol cosmetic products containing... SERVICES (CONTINUED) COSMETICS GENERAL Requirements for Specific Cosmetic Products § 700.16 Use of aerosol cosmetic products containing zirconium. (a) Zirconium-containing complexes have been used as an...

  14. 21 CFR 700.16 - Use of aerosol cosmetic products containing zirconium.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... 21 Food and Drugs 7 2014-04-01 2014-04-01 false Use of aerosol cosmetic products containing... SERVICES (CONTINUED) COSMETICS GENERAL Requirements for Specific Cosmetic Products § 700.16 Use of aerosol cosmetic products containing zirconium. (a) Zirconium-containing complexes have been used as an...

  15. Estimating the acidity of transition metal hydride and dihydrogen complexes by adding ligand acidity constants.

    PubMed

    Morris, Robert H

    2014-02-01

    A simple equation (pKa(THF) = ∑AL + Ccharge + Cnd + Cd6) can be used to obtain an estimate of the pKa of diamagnetic transition metal hydride and dihydrogen complexes in tetrahydrofuran, and, by use of conversion equations, in other solvents. It involves adding acidity constants AL for each of the ligands in the 5-, 6-, 7-, or 8-coordinate conjugate base complex of the hydride or dihydrogen complex along with a correction for the charge (Ccharge = -15, 0 or 30 for x = +1, 0 or -1 charge, respectively) and the periodic row of the transition metal (Cnd = 0 for 3d or 4d metal, 2 for 5d metal) as well as a correction for d(6) octahedral acids (Cd6 = 6 for d(6) metal ion in the acid, 0 for others) that are not dihydrogen complexes. Constants AL are provided for 13 commonly occurring ligand types; of these, nine neutral ligands are correlated with Lever's electrochemical ligand parameters EL. This method gives good estimates of the over 170 literature pKa values that range from less than zero to 50 with a standard deviation of 3 pKa units for complexes of the metals chromium to nickel, molybdenum, ruthenium to palladium, and tungsten to platinum in the periodic table. This approach allows a quick assessment of the acidity of hydride complexes found in nature (e.g., hydrogenases) and in industry (e.g., catalysis and hydrogen energy applications). The pKa values calculated for acids that have bulky or large bite angle chelating ligands deviate the most from this correlation. The method also provides an estimate of the base strength of the deprotonated form of the complex. PMID:24410025

  16. Complexes of polyadenylic acid and the methyl esters of amino acids

    NASA Technical Reports Server (NTRS)

    Khaled, M. A.; Mulins, D. W., Jr.; Swindle, M.; Lacey, J. C., Jr.

    1983-01-01

    A study of amino acid methyl esters binding to polyadenylic acid supports the theory that the genetic code originated through weak but selective affinities between amino acids and nucleotides. NMR, insoluble complex analysis, and ultraviolet spectroscopy are used to illustrate a correlation between the hydrophybicities of A amino acids and their binding constants, which, beginning with the largest, are in the order of Phe (having nominally a hydrophobic AAA anticodon), Ile, Leu, Val and Gly (having a hydrophilic anticodon with no A). In general, the binding constants are twice the values by Reuben and Polk (1980) for monomeric AMP, which suggests that polymer amino acids are interacting with only one base. No real differences are found betwen poly A binding for free Phe, Phe methyl ester or Phe amide, except that the amide value is slightly lower.

  17. Polyacrylic acids-bovine serum albumin complexation: Structure and dynamics.

    PubMed

    Othman, Mohamed; Aschi, Adel; Gharbi, Abdelhafidh

    2016-01-01

    The study of the mixture of BSA with polyacrylic acids at different masses versus pH allowed highlighting the existence of two regimes of weak and strong complexation. These complexes were studied in diluted regime concentration, by turbidimetry, dynamic light scattering (DLS), zeta-potential measurements and nuclear magnetic resonance (NMR). We have followed the pH effect on the structure and properties of the complex. This allowed refining the interpretation of the phase diagram and understanding the observed phenomena. The NMR measurements allowed probing the dynamics of the constituents versus the pH. The computational method was used to precisely determine the electrostatic potential of BSA and how the polyelectrolyte binds to it at different pH. PMID:26478316

  18. Protic acid-fluorine interactions and reactions with acids of transition metal perfluoroalkyl and perfluoroolefin complexes

    SciTech Connect

    Barmore, R.M.; Richmond, T.G.

    1993-12-31

    The authors are interested in devising new methods of C-F and C-X bond activation which could be applied to destruction of environmentally significant molecules. Dihalocarbene complexes are thought to be intermediates in a variety of reactions of metal haloalkyl complexes which could be applied to this problem. This paper reports observations indicating initial interactions of protic acids and fluorocarbon complexes which can be applied toward the hydrolysis of C-F bonds. Reactions of long chain halocarbons and halolefins will also be discussed.

  19. Complexes of carborane acids linked by strong hydrogen bonds: acidity scales.

    PubMed

    Grabowski, Sławomir J

    2016-06-28

    Carborane acids, currently known as the strongest acis, are analyzed and compared with other species classified as superacids as well as with selected mineral acids and carbocations. Calculations (B3LYP/6-311++G(d,p) level) on these moieties as well as on their conjugate bases were performed to evaluate corresponding proton affinities. In addition, the complexes of these species with the CHB11F11(-) anion and the complexes of the conjugate bases with the trimethylammonium cation were analyzed. The scales, based on spectroscopic results, DFT energies and on the topological QTAIM (Quantum Theory of Atoms in Molecules) parameters, are introduced and discussed to order the acidity of the species analyzed here. The properties of the bond critical points corresponding to the intermolecular contacts are discussed. The majority of the results show that HCHB11F11 carborane acid is the strongest in agreement with the previous experimental studies of Reed and coworkers. Very often the abovementioned acidity scales show that carborane acids are able to protonate hydrocarbons. PMID:27253195

  20. Direct intercalation of cisplatin into zirconium phosphate nanoplatelets for potential cancer nanotherapy

    PubMed Central

    Díaz, Agustín; González, Millie L.; Pérez, Riviam J.; David, Amanda; Mukherjee, Atashi; Báez, Adriana; Clearfield, Abraham

    2014-01-01

    We report the use of zirconium phosphate nanoplatelets (ZrP) for the encapsulation of the anticancer drug cisplatin and its delivery to tumor cells. Cisplatin was intercalated into ZrP by direct-ion exchange and was tested in-vitro for cytotoxicity in the human breast cancer (MCF-7) cell line. The structural characterization of the intercalated cisplatin in ZrP suggests that during the intercalation process, the chloride ligands of the cisplatin complex were substituted by phosphate groups within the layers. Consequently, a new phosphate phase with the platinum complex directly bound to ZrP (cisPt@ZrP) is produced with an interlayer distance of 9.3 Å. The in-vitro release profile of the intercalated drug by pH stimulus shows that at low pH under lysosomal conditions the platinum complex is released with simultaneous hydrolysis of the zirconium phosphate material, while at higher pH the complex is not released. Experiments with the MCF-7 cell line show that cisPt@ZrP reduced the cell viability up to 40%. The cisPt@ZrP intercalation product is envisioned as a future nanotherapy agent for cancer. Taking advantage of the shape and sizes of the ZrP particles and controlled release of the drug at low pH, it is intended to exploit the enhanced permeability and retention effect of tumors, as well as their intrinsic acidity, for the destruction of malignant cells. PMID:24072038

  1. Synthesis and characterization of europium- trimesic acid luminescent complex nanorods

    NASA Astrophysics Data System (ADS)

    Ren, Huijuan; Liu, Guixia; Song, Xinyuan; Hong, Guangyan; Cui, Zhenfeng

    2006-01-01

    Eu(III)-trimesic acid (TMA) luminescent complex Nanorods were synthesized in the polyvinylpyrrolidone matrix. The obtained sample was characterized by elemental analysis, Inductively Coupled Plasma-atomic emission spectroscopy(ICP-AES), X-ray diffraction(XRD), Fourier-transform Infrared spectroscopy(FT-IR), transmission electron microscopy(TEM) and photoluminescence spectra (PL). The results demonstrated that its chemical constitution is PVP/Eu(MTA) • 2H IIO. The XRD patterns show that the complex was a new kind of crystal whose structure is totally different with the ligand. TEM image indicated that the complex is nanocrystal with rod shape in one dimension, the size of rod diameter is about 50~100 nm, and the length ranges from hundred nanometer to a few micrometers, in addition, the dispersity is better. Photoluminescence analysis indicated that the complex emits Eu 3+ characteristic luminescence under ultraviolet excitation. TG-DTA curves indicated that the complex is heat stable under the temperature of 454°C. Therefore an thermal decomposition mechanism is: Eu(MTA) • 2H IIO->Eu(MTA)-> Eu IIO 3.

  2. [PREPARATIONS OF PAMIDRONOVIC ACID IN COMPLEX TREATMENT ON OSTEOGENESIS IMPERFECTA].

    PubMed

    Zyma, A M; Guk, Yu M; Magomedov, O M; Gayko, O G; Kincha-Polishchuk, T A

    2015-07-01

    Modern view of drug therapy in the complex treatment of orthopedic manifestations of osteogenesis imperfecta (OI) was submitted. Developed and tested system of drug correction of structural and functional state of bone tissue (BT) using drugs pamidronovic acid, depending on osteoporosis severity and type of disease. Such therapy is appropriate to apply both independently and in conjunction with surgery to correct deformations of long bones of the lower extremities. Effectiveness and feasibility of the proposed methods of drug therapy was proved, most patients resume features walking and support. PMID:26591224

  3. Structure and function analysis of protein–nucleic acid complexes

    NASA Astrophysics Data System (ADS)

    Kuznetsova, S. A.; Oretskaya, T. S.

    2016-05-01

    The review summarizes published data on the results and achievements in the field of structure and function analysis of protein–nucleic acid complexes by means of main physical and biochemical methods, including X-ray diffraction, nuclear magnetic resonance spectroscopy, electron and atomic force microscopy, small-angle X-ray and neutron scattering, footprinting and cross-linking. Special attention is given to combined approaches. The advantages and limitations of each method are considered, and the prospects of their application for wide-scale structural studies in vivo are discussed. The bibliography includes 145 references.

  4. The biological activities of protein/oleic acid complexes reside in the fatty acid.

    PubMed

    Fontana, Angelo; Spolaore, Barbara; Polverino de Laureto, Patrizia

    2013-06-01

    A complex formed by human α-lactalbumin (α-LA) and oleic acid (OA), named HAMLET, has been shown to have an apoptotic activity leading to the selective death of tumor cells. In numerous publications it has been reported that in the complex α-LA is monomeric and adopts a partly folded or "molten globule" state, leading to the idea that partly folded proteins can have "beneficial effects". The protein/OA molar ratio initially has been reported to be 1:1, while recent data have indicated that the OA-complex is given by an oligomeric protein capable of binding numerous OA molecules per protein monomer. Proteolytic fragments of α-LA, as well as other proteins unrelated to α-LA, can form OA-complexes with biological activities similar to those of HAMLET, thus indicating that a generic protein can form a cytotoxic complex under suitable experimental conditions. Moreover, even the selective tumoricidal activity of HAMLET-like complexes has been questioned. There is recent evidence that the biological activity of long chain unsaturated fatty acids, including OA, can be ascribed to their effect of perturbing the structure of biological membranes and consequently the function of membrane-bound proteins. In general, it has been observed that the cytotoxic effects exerted by HAMLET-like complexes are similar to those reported for OA alone. Overall, these findings can be interpreted by considering that the protein moiety does not have a toxic effect on its own, but merely acts as a solubilising agent for the inherently toxic fatty acid. PMID:23499846

  5. METHOD FOR DISSOLVING ZIRCONIUM-URANIUM COMPOSITIONS

    DOEpatents

    Gens, T.A.

    1961-07-18

    A method is descrioed for treating a zirconium-- uranium composition to form a stable solution from which uranium and other values may be extracted by contacting the composition with at least a 4 molar aqueous solution of ammonium fluoride at a temperature of about 100 deg C, adding a peroxide, in incremental amounts, to the heated solution throughout the period of dissolution until all of the uranium is converted to soluble uranyl salt, adding nitric acid to the resultant solution to form a solvent extraction feed solution to convert the uranyl salt to a solvent extractable state, and thereafter recovering the uranium and other desired values from the feed solution by solvent extraction.

  6. The complexation behavior of neptunium and plutonium with nitrilotriacetic acid

    SciTech Connect

    Nitsche, H.; Becraft, K.

    1990-08-01

    The first stability constant of NpO{sub 2}{sup +} with nitrilotriacetic acid (NTA) was determined at four ionic strengths (0.5, 1.0, 2.0, 3.0 M) using spectrophotometry. Nonlinear least-squares data fitting identified the complex as NpO{sub 2}NTA{sup 2-}. The Specific Ion Interaction Theory (S.I.T) approximation method was used to determine the stability constants at infinite dilution. First results on Pu{sup 4+} and PuO{sub 2}{sup 2+} complexation with NTA are reported. The stability constant for the Pu(NTA){sup +} complex at I = 0.1 M strength is given. From results for PuO{sub 2}{sup 2+} complexation with NTA (I = 1 M) at pH < 3, the stability constant was derived for PuO{sub 2} NTA{sup {minus}}. At pH > 3, NTA partially reduced PuO{sub 2}{sup 2+} to PuO{sub 2}{sup +}. 3 refs., 5 figs., 4 tabs.

  7. Extraction chromatography of quadrivalent titanium and zirconium from succinate solution

    SciTech Connect

    Shete, S.D.; Shinde, V.M.

    1982-01-01

    Liquid ion exchangers such as tri-n-octyl amine (TOA), tri-iso-octylamine (TIOA) and Aliquat 336 have been used in this laboratory for analytical separation of vanadium(V) and niobium(V), indium(III), thalium(III), thorium(IV), cerium(IV) from succinate solutions. Extension of this study has revealed that benzene solutions of TOA, TIOA and Aliquat 336 could be used for anion exchange extraction of quadrivalent titanium and zirconium from succinate solution. The metal ions from the organic phase are stripped and determined spectrophotometrically. Solvent extraction methods for titanium(IV) and zirconium(IV) have been reviewed by De et al. and Korkisch in their monographs. Diethylamine, tri-ethylamine and tributylamine have been used for extraction of titanium from thiocyanate and citrate solution. Similarly high molecular weight amines such as TOA and TIOA have been used for the extraction of zirconium from mineral acids, but systematic solvent extraction separation of titanium(IV) and zirconium(IV) is lacking. In this communication we propose a new method for selective extraction and separation of titaium(IV) and zirconium(IV) from metal ions such as Mn, Cr, Mo, V, U, La, Ta, Th and Hf. The proposed method is comparatively free from drawbacks such as pre-equilibration of phases, multiple scrubbing, multiple extraction and coextraction of a large number of cations and anions.

  8. Process for electroless deposition of metals on zirconium materials

    DOEpatents

    Donaghy, Robert E.

    1978-01-01

    A process for the electroless deposition of a metal layer on an article comprised of zirconium or a zirconium alloy is disclosed. The article is activated in an aged aqueous solution comprising from about 10 to about 20 grams per liter ammonium bifluoride and from about 0.75 to about 2 grams per liter of sulfuric acid. The solution is aged by immersion of pickled zirconium in the solution for at least about 10 minutes. The loosely adhering film formed on the article in the activating step is removed and the article is contacted with an electroless plating solution containing the metal to be deposited on the article upon sufficient contact with the article.

  9. Process for electrolytic deposition of metals on zirconium materials

    DOEpatents

    Donaghy, Robert E.

    1979-01-30

    A process for the electrolytic deposition of a metal layer on an article comprised of zirconium or a zirconium alloy is disclosed. The article is activated in an aged aqueous solution comprising from about 10 to about 20 grams per liter ammonium bifluoride and from about 0.75 to about 2 grams per liter of sulfuric acid. The solution is aged by immersion of pickled zirconium in the solution for at least about 10 minutes. The loosely adhering film formed on the article in the activating step is removed and the article is contacted with an electrolytic plating solution containing the metal to be deposited on the article in the presence of an electrode receiving current.

  10. α-Lactalbumin:Oleic Acid Complex Spontaneously Delivers Oleic Acid to Artificial and Erythrocyte Membranes.

    PubMed

    Wen, Hanzhen; Strømland, Øyvind; Halskau, Øyvind

    2015-09-25

    Human α-lactalbumin made lethal to tumor cells (HAMLET) is a tumoricidal complex consisting of human α-lactalbumin and multiple oleic acids (OAs). OA has been shown to play a key role in the activity of HAMLET and its related complexes, generally known as protein-fatty acid (PFA) complexes. In contrast to what is known about the fate of the protein component of such complexes, information about what happens to OA during their action is still lacking. We monitored the membrane, OA and protein components of bovine α-lactalbumin complexed with OA (BLAOA; a HAMLET-like substance) and how they associate with each other. Using ultracentrifugation, we found that the OA and lipid components follow each other closely. We then firmly identify a transfer of OA from BLAOA to both artificial and erythrocyte membranes, indicating that natural cells respond similarly to BLAOA treatment as artificial membranes. Uncomplexed OA is unable to similarly affect membranes at the conditions tested, even at elevated concentrations. Thus, BLAOA can spontaneously transfer OA to a lipid membrane. After the interaction with the membrane, the protein is likely to have lost most or all of its OA. We suggest a mechanism for passive import of mainly uncomplexed protein into cells, using existing models for OA's effect on membranes. Our results are consistent with a membrane destabilization mediated predominantly by OA insertion being a significant contribution to PFA cytotoxicity. PMID:26297199

  11. Dual Fatty Acid Elongase Complex Interactions in Arabidopsis.

    PubMed

    Morineau, Céline; Gissot, Lionel; Bellec, Yannick; Hematy, Kian; Tellier, Frédérique; Renne, Charlotte; Haslam, Richard; Beaudoin, Frédéric; Napier, Johnathan; Faure, Jean-Denis

    2016-01-01

    Very long chain fatty acids (VLCFAs) are involved in plant development and particularly in several cellular processes such as membrane trafficking, cell division and cell differentiation. However, the precise role of VLCFAs in these different cellular processes is still poorly understood in plants. In order to identify new factors associated with the biosynthesis or function of VLCFAs, a yeast multicopy suppressor screen was carried out in a yeast mutant strain defective for fatty acid elongation. Loss of function of the elongase 3 hydroxyacyl-CoA dehydratase PHS1 in yeast and PASTICCINO2 in plants prevents growth and induces cytokinesis defects. PROTEIN TYROSIN PHOSPHATASE-LIKE (PTPLA) previously characterized as an inactive dehydratase was able to restore yeast phs1 growth and VLCFAs elongation but not the plant pas2-1 defects. PTPLA interacted with elongase subunits in the Endoplasmic Reticulum (ER) and its absence induced the accumulation of 3-hydroxyacyl-CoA as expected from a dehydratase involved in fatty acid (FA) elongation. However, loss of PTPLA function increased VLCFA levels, an effect that was dependent on the presence of PAS2 indicating that PTPLA activity repressed FA elongation. The two dehydratases have specific expression profiles in the root with PAS2, mostly restricted to the endodermis, while PTPLA was confined in the vascular tissue and pericycle cells. Comparative ectopic expression of PTPLA and PAS2 in their respective domains confirmed the existence of two independent elongase complexes based on PAS2 or PTPLA dehydratase that are functionally interacting. PMID:27583779

  12. [Adsorption Properties of Fluorine onto Fulvic Acid-Bentonite Complex].

    PubMed

    Fang, Dun; Tian, Hua-jing; Ye, Xin; He, Ci-li; Dan, You-meng; Wei, Shi-yong

    2016-03-15

    Fulvic Acid-Bentonite (FA-BENT) complex was prepared using coprecipitation method, and basic properties of the complex and sorption properties of fluorine at different environmental conditions were studied. XRD results showed that the d₀₀₁ spacing of FA- BENT complex had no obvious change compared with the raw bentonite, although the diffraction peak intensity of smectite in FA-BENT complex reduced, and indicated that FA mainly existed as a coating on the external surface of bentonite. Some functional groups (such as C==O, −OH, etc. ) of FA were observed in FA-BENT FTIR spectra, thus suggesting ligand exchange-surface complexation between FA and bentonite. Higher initial pH values of the reaction system were in favor of the adsorption of fluorine onto FA-BENT, while the equilibrium capacity decreased with the increase of pH at initial pH ≥ 4.50. The adsorption of fluorine onto FA-BENT was also affected by ionic strength, and the main reason might be the "polarity" effect. The adsorption of fluorine onto FA-BENT followed pseudo-second-order kinetic model and was controlled by chemical process ( R² = 0.999 2). Compared with the Freundlich model, Langmuir model was apparently of a higher goodness of fit (R² > 0.994 9) for absorption of fluorine onto FA-BENT. Thermodynamic parameters indicated that the adsorption process of fluorine was an spontaneously endothermic reaction, and was an entropy-driven process (ΔH 32.57 kJ · mol⁻¹, ΔS 112.31 J · (mol · K)⁻¹, ΔG −0.65- −1.76 kJ · mol⁻¹). PMID:27337896

  13. Ancestral genetic complexity of arachidonic acid metabolism in Metazoa.

    PubMed

    Yuan, Dongjuan; Zou, Qiuqiong; Yu, Ting; Song, Cuikai; Huang, Shengfeng; Chen, Shangwu; Ren, Zhenghua; Xu, Anlong

    2014-09-01

    Eicosanoids play an important role in inducing complex and crucial physiological processes in animals. Eicosanoid biosynthesis in animals is widely reported; however, eicosanoid production in invertebrate tissue is remarkably different to vertebrates and in certain respects remains elusive. We, for the first time, compared the orthologs involved in arachidonic acid (AA) metabolism in 14 species of invertebrates and 3 species of vertebrates. Based on parsimony, a complex AA-metabolic system may have existed in the common ancestor of the Metazoa, and then expanded and diversified through invertebrate lineages. A primary vertebrate-like AA-metabolic system via cyclooxygenase (COX), lipoxygenase (LOX), and cytochrome P450 (CYP) pathways was further identified in the basal chordate, amphioxus. The expression profiling of AA-metabolic enzymes and lipidomic analysis of eicosanoid production in the tissues of amphioxus supported our supposition. Thus, we proposed that the ancestral complexity of AA-metabolic network diversified with the different lineages of invertebrates, adapting with the diversity of body plans and ecological opportunity, and arriving at the vertebrate-like pattern in the basal chordate, amphioxus. PMID:24801744

  14. Paramagnetic titanium(III) and zirconium(III) metallocene complexes as precatalysts for the dehydrocoupling/dehydrogenation of amine-boranes.

    PubMed

    Helten, Holger; Dutta, Barnali; Vance, James R; Sloan, Matthew E; Haddow, Mairi F; Sproules, Stephen; Collison, David; Whittell, George R; Lloyd-Jones, Guy C; Manners, Ian

    2013-01-01

    Complexes of Group 4 metallocenes in the +3 oxidation state and amidoborane or phosphidoborane function as efficient precatalysts for the dehydrocoupling/dehydrogenation of amine-boranes, such as Me(2) NH⋅BH(3). Such Ti(III) -amidoborane complexes are generated in [Cp(2)Ti]-catalyzed amine-borane dehydrocoupling reactions, for which diamagnetic M(II) and M(IV) species have been previously postulated as precatalysts and intermediates. PMID:23197391

  15. Ternary Complexes of Iron, Amyloid-β and Nitrilotriacetic Acid

    PubMed Central

    Jiang, Dianlu; Li, Xiangjun; Williams, Renee; Patel, Sveti; Men, Lijie; Wang, Yinsheng; Zhou, Feimeng

    2009-01-01

    The interaction of amyloid-β (Aβ) and redox-active metals, two important biomarkers present in the senile plaques of AD brain, has been suggested to either enhance the Aβ aggregation or facilitate the generation of reactive oxygen species (ROS). The present study investigates the nature of the interaction between the metal-binding domain of Aβ, viz, Aβ(1-16), and the Fe(III) or Fe(II) complex with nitrilotriacetic acid (NTA). Using electrospray ionization mass spectrometry (ESI-MS), the formation of a ternary complex of Aβ(1-16), Fe(III), and NTA with a stoichiometry of 1:1:1 was identified. MS also revealed that the NTA moiety can be detached via collision-induced dissociation. The cumulative dissociation constants of both Aβ-Fe(III)-NTA and Aβ-Fe(II)-NTA were deduced to be 6.3 × 10-21 M2 and 5.0 × 10-12 M2, respectively, via measuring the fluorescence quenching of the sole tyrosine residue on Aβ upon the complex formation. The redox properties of these two complexes were investigated by cyclic voltammetry. The redox potential of the Aβ-Fe(III)-NTA complex was found to be 0.03 V vs. Ag/AgCl, which is negatively shifted by 0.54 V when compared to the redox potential of free Fe(III)/Fe(II). Despite such a large potential modulation, the redox potential of the Aβ-Fe(III)-NTA complex is still sufficiently high for occurrence of a range of redox reactions with cellular species. Aβ-Fe(II)-NTA electrogenerated from Aβ-Fe(III)-NTA was also found to catalyze the reduction of oxygen to produce H2O2. These findings provide significant insight into the role of iron and Aβ in the development of AD. The binding of iron by Aβ modulates the redox potential to a level where its redox cycling occurs. In the presence of a biological reductant (antioxidant), redox cycling of iron could disrupt the redox balance within the cellular milieu. As a consequence, not only ROS is continuously produced, but also oxygen and biological reductants can be depleted. A cascade of

  16. Effects of humic acid-metal complexes on hepatic carnitine palmitoyltransferase, carnitine acetyltransferase and catalase activities

    SciTech Connect

    Fungjou Lu; Youngshin Chen . Dept. of Biochemistry); Tienshang Huang . Dept. of Medicine)

    1994-03-01

    A significant increase in activities of hepatic carnitine palmitoyltransferase and carnitine acetyltransferase was observed in male Balb/c mice intraperitoneally injected for 40 d with 0.125 mg/0.1 ml/d humic acid-metal complexes. Among these complexes, the humic acid-As complex was relatively effective, whereas humic acid-25 metal complex was more effective, and humic acid-26 metal complex was most effective. However, humic acid or metal mixtures, or metal such as As alone, was not effective. Humic acid-metal complexes also significantly decreased hepatic catalase activity. A marked decrease of 60-kDa polypeptide in liver cytoplasm was also observed on SDS-polyacrylamide gel electrophoresis after the mice had been injected with the complexes. Morphological analysis of a histopathological biopsy of such treated mice revealed several changes in hepatocytes, including focal necrosis and cell infiltration, mild fatty changes, reactive nuclei, and hypertrophy. Humic acid-metal complexes affect activities of metabolic enzymes of fatty acids, and this results in accumulation of hydrogen peroxide and increase of the lipid peroxidation. The products of lipid peroxidation may be responsible for liver damage and possible carcinogenesis. Previous studies in this laboratory had shown that humic acid-metal complex altered the coagulation system and that humic acid, per se, caused vasculopathy. Therefore, humic acid-metal complexes may be main causal factors of not only so-called blackfoot disease, but also the liver cancer prevailing on the southwestern coast of Taiwan.

  17. Fine-grained zirconium-base material

    DOEpatents

    Van Houten, G.R.

    1974-01-01

    A method is described for making zirconium with inhibited grain growth characteristics, by the process of vacuum melting the zirconium, adding 0.3 to 0.5% carbon, stirring, homogenizing, and cooling. (Official Gazette)

  18. Fluorescent complexes of nucleic acids/8-hydroxyquinoline/lanthanum(III) and the fluorometry of nucleic acids

    SciTech Connect

    Cheng Zhi Huang; Ke An Li; Shen Yang Tong

    1996-07-01

    The ternary fluorescent complexes of nucleic acids/8-hydroxyquinoline/lanthanum (III) were studied. Nucleic acids in the study involve natured and thermally denatured calf thymus DNA, fish sperm DNA and yeast RNA. In the range of PH 8.0-8.4 (controlled by NH{sub 3}-NH{sub 4}Cl buffer) ternary fluorescent complexes are formed which emit at 485.0 nm for calf thymus DNA and at 480.0 nm for fish sperm DNA when excited at 265.0 nm. Based on the fluorescence reactions sensitive fluorometric methods for nucleic acids were proposed. Using optimal conditions, the calibration curves were linear in the range of 0.4 --3.6 {mu}g{sup .}ml{sup -1} for calf thymus DNA, 0.4 -- 4.0 {mu}g{sup .}ml{sup -1} for fish sperm DNA and 0.4 --4.0{mu}g{sup .}ml{sup -1} for yeast RNA, respectively. Five synthetic samples were determined with satisfaction.

  19. Single-site SBA-15 supported zirconium catalysts. Synthesis, characterization and toward cyanosilylation reaction

    NASA Astrophysics Data System (ADS)

    Xu, Wei; Yu, Bo; Zhang, Ying; Chen, Xi; Zhang, Guofang; Gao, Ziwei

    2015-01-01

    A successive anchoring of Zr(NMe2)4, cyclopentadiene and a O-donor ligand, 1-hydroxyethylbenzene (PEA), 1,1‧-bi-2-naphthol (Binol) or 2,3-dihydroxybutanedioic acid diethyl ester (Tartrate), on dehydroxylated SBA-15 pretreated at 500 °C for 16 h (SBA-15-500) was conducted by SOMC strategy in moderate conditions. The dehydoxylation of SBA-15 was monitored by in situ Fourier transform infrared spectroscopy (in situ FT-IR). The ligand-modified SBA-15-500 supported zirconium complexes were characterized by in situ FT-IR, 13C CP MAS-NMR, X-ray photoelectron spectroscopy (XPS), inductively coupled plasma mass spectrometry (ICP-MAS) and elemental analysis in detail, verifying that the surface zirconium species are single-sited. The catalytic activity of these complexes was evaluated by cyanosilylation of benzaldehyde. The results showed that the catalytic activity is dependent strongly on the structure of surface species and the configuration of the ligands.

  20. Polymer complexes. LX. Supramolecular coordination and structures of N(4-(acrylamido)-2-hydroxybenzoic acid) polymer complexes

    NASA Astrophysics Data System (ADS)

    Ghoneim, M. M.; El-Sonbati, A. Z.; El-Bindary, A. A.; Diab, M. A.; Serag, L. S.

    2015-04-01

    A number of novel polymer complexes of various anions of copper(II), cobalt(II), nickel(II) and uranyl(II) with N(4-(acrylamido)-2-hydroxy benzoic acid) (ABH) have been synthesized and characterized by elemental analysis, IR, 1H NMR, magnetic susceptibility measurements, electronic spin resonance, vibrational spectra and thermal analysis. The molecular structures of the ligand are optimized theoretically and the quantum chemical parameters are calculated. Tentative structures for the polymeric metal complexes due to their potential application are also suggested. The IR data exhibit the coordination of ONO2/OAc/SO4 with the metal ions in the polymeric metal complex. Vibrational spectra indicate coordination of carboxylate oxygen and phenolic OH of the ligand giving a MO4 square planar chromophore. Ligand field ESR spectra support square planar geometry around Cu(II). The thermal decomposition of the polymer complexes were discussed in relation to structure, and the thermodynamic parameters of the decomposition stages were evaluated applying Coast-Redfern and Horowitz-Metzger methods.

  1. Ablation Resistant Zirconium and Hafnium Ceramics

    NASA Technical Reports Server (NTRS)

    Bull, Jeffrey (Inventor); White, Michael J. (Inventor); Kaufman, Larry (Inventor)

    1998-01-01

    High temperature ablation resistant ceramic composites have been made. These ceramics are composites of zirconium diboride and zirconium carbide with silicon carbide, hafnium diboride and hafnium carbide with silicon carbide and ceramic composites which contain mixed diborides and/or carbides of zirconium and hafnium. along with silicon carbide.

  2. Zirconium and hafnium in meteorites

    NASA Technical Reports Server (NTRS)

    Ehmann, W. D.; Chyi, L. L.

    1974-01-01

    The abundances of zirconium and hafnium have been determined in nine stony meteorites by a new, precise neutron-activation technique. The Zr/Hf abundance ratios for the chondrites vary in a rather narrow range, consistent with previously published observations from our group. Replicate analyses of new, carefully selected clean interior samples of the Cl chondrite Orgueil yield mean zirconium and hafnium abundances of 5.2 and 0.10 ppm, respectively. These abundances are lower than we reported earlier for two Cl chondrite samples which we now suspect may have suffered contamination. The new Cl zirconium and hafnium abundances are in closer agreement with predictions based on theories of nucleosynthesis than the earlier data.

  3. Thermodynamic properties of zirconium disulfide

    SciTech Connect

    Volovik, L.S.; Kovalevskaya, E.I.; Litvinenko, V.F.

    1986-02-01

    This paper uses a method of comparative calculation -- double comparison -for the quantitative evaluation of the themodynamic characteristics of zirconium disulfide. The method enables one to apply known characteristics of compounds of the given or an adjacent group to analogous compounds of elements. The enthalpy of zirconium disulfide was determined by a formula and the calculation was carried out on the basis of data on the enthalpy of hafnium, niobium, and tantalum disulfides measured by the mixing method in the temperature range 500-1800 K.

  4. Proton exchange in acid-base complexes induced by reaction coordinates with heavy atom motions

    NASA Astrophysics Data System (ADS)

    Alavi, Saman; Taghikhani, Mahdi

    2012-06-01

    We extend previous work on nitric acid-ammonia and nitric acid-alkylamine complexes to illustrate that proton exchange reaction coordinates involve the rocking motion of the base moiety in many double hydrogen-bonded gas phase strong acid-strong base complexes. The complexes studied involve the biologically and atmospherically relevant glycine, formic, acetic, propionic, and sulfuric acids with ammonia/alkylamine bases. In these complexes, the magnitude of the imaginary frequencies associated with the proton exchange transition states are <400 cm-1. This contrasts with widely studied proton exchange reactions between symmetric carboxylic acid dimers or asymmetric DNA base pair and their analogs where the reaction coordinate is localized in proton motions and the magnitude of the imaginary frequencies for the transition states are >1100 cm-1. Calculations on complexes of these acids with water are performed for comparison. Variations of normal vibration modes along the reaction coordinate in the complexes are described.

  5. Complexation of NpO2+ with N-methyl-iminodiacetic Acid: in Comparison with Iminodiacetic and Dipicolinic Acids

    SciTech Connect

    Tian, Guoxin; Rao, Linfeng

    2010-10-01

    Complexation of Np(V) with N-methyl-iminodiacetic acid (MIDA) in 1 M NaClO{sub 4} solution was studied with multiple techniques including potentiometry, spectrophotometry, and microcalorimetry. The 1:2 complex, NpO{sub 2}(MIDA){sub 2}{sup 3-} was identified for the first time in aqueous solution. The correlation between its optical absorption properties and symmetry was discussed, in comparison with Np(V) complexes with two structurally related nitrilo-dicarboxylic acids, iminodiacetic acid (IDA) and dipicolinic acid (DPA). The order of the binding strength (DPA > MIDA > IDA) is explained by the difference in the structural and electronic properties of the ligands. In general, the nitrilo-dicarboxylates form stronger complexes with Np(V) than oxy-dicarboxylates due to a much more favorable enthalpy of complexation.

  6. Morphological characteristics, oxidative stability and enzymic hydrolysis of amylose-fatty acid complexes.

    PubMed

    Marinopoulou, Anna; Papastergiadis, Efthimios; Raphaelides, Stylianos N; Kontominas, Michael G

    2016-05-01

    Complexes of amylose with fatty acids varying in carbon chain length and degree of unsaturation were prepared at 30, 50 or 70°C by dissolving amylose in 0.1N KOH and mixing with fatty acid potassium soap solution. The complexes were obtained in solid form as precipitates after neutralization. SEM microscopy revealed that the morphology of the complexes was that of ordered lamellae separated from amorphous regions whereas confocal laser scanning microscopy showed images of the topography of the guest molecules in the complex matrix. FTIR spectroscopy revealed that the absorption peak attributed to carbonyl group of free fatty acid was shifted when the fatty acid was in the form of amylose complex. Thermo-gravimetry showed that the unsaturated fatty acids were effectively protected from oxidation when they were complexed with amylose whereas enzymic hydrolysis experiments showed that the guest molecules were quantitatively released from the amylose complexes. PMID:26877002

  7. Intramolecular deactivation processes in complexes of salicylic acid or glycolic acid with Eu(III)

    NASA Astrophysics Data System (ADS)

    Kuke, S.; Marmodée, B.; Eidner, S.; Schilde, U.; Kumke, M. U.

    2010-04-01

    The complexation of Eu(III) by 2-hydroxy benzoic acid (2HB) or glycolic acid (GL) was investigated using steady-state and time-resolved laser spectroscopy. Experiments were carried out in H 2O as well as in D 2O in the temperature range of 80Kcomplexes was determined. It is stressed that ligand-specific quenching processes (other than OH quenching induced by water molecules) need to be determined and considered in detail, in order to extract speciation-relevant information from luminescence data (e.g., estimation of the number of water molecules nO in the first coordination sphere of Eu(III)). In case of 2HB, conclusions drawn from the evaluation of the Eu(III) luminescence are compared with results of a X-ray structure analysis.

  8. Acid-catalyzed isomerization of rhenium alkyne complexes to rhenium allene complexes via 1-metallacyclopropene intermediates

    SciTech Connect

    Casey, C.P.; Brady, J.T.

    1998-10-12

    The alkyne complexes C{sub 5}Me{sub 5}(CO){sub 2}Re({eta}{sup 2}-MeC{triple_bond}CMe) (1) and C{sub 5}H{sub 5}(CO){sub 2}Re({eta}{sup 2}-MeC{triple_bond}CMe) (6) underwent acid-catalyzed isomerization by way of 1-metallacyclopropene intermediates to form the allene complexes C{sub 5}Me{sub 5}(CO){sub 2}Re({eta}{sup 2}-2,3-MeHC{double_bond}C{double_bond}CH{sub 2}) (5) and C{sub 5}H{sub 5}(CO){sub 2}Re({eta}{sup 2}-2,3-MeHC{double_bond}C{double_bond}CH{sub 2}) (7). Stoichiometric reaction of 1 with CF{sub 3}CO{sub 2}H initially produced the kinetic addition product C{sub 5}Me{sub 5}(CO){sub 2}Re[{eta}{sup 2}-(Z)-MeHC{double_bond}CMeO{sub 2}CCF{sub 3}] (8-Z), which slowly isomerized to the thermodynamically more stable E isomer 8-E. The reaction of 6 with CF{sub 3}CO{sub 2}H at {minus}73 C produced only C{sub 5}H{sub 5}(CO){sub 2}Re[{eta}{sup 2}-(E)-MeHC{double_bond}CMeO{sub 2}CCF{sub 3}] (9-E), which isomerized at -60 C to a 80:20 equilibrium mixture of 9-E and 9-Z. Treatment of 9-E and 9-Z with base led to formation of allene complex 7. The rate of this elimination was independent of base concentration. Labeling studies showed that the 1-metallacyclopropene intermediate C{sub 5}H{sub 5}(CO){sub 2}({eta}{sup 2}-CMeCHMe){sup +}CF{sub 3}CO{sub 2}{sup {minus}} (12-CF{sub 3}CO{sub 2}) undergoes a number of important reactions which include, in order of decreasing relative rates: (1) addition of trifluoroacetate to give enol trifluoroacetate complexes, (2) deprotonation to give complexed allenes, (3) degenerate 1,2-hydride migrations, (4) hydride migrations to give {eta}{sup 3}-allyl complexes, and (5) deprotonation to give complexed alkynes.

  9. Thermodynamics of the complexation of arabinogalactan with salicylic and p-aminobenzoic acids in aqueous solutions

    NASA Astrophysics Data System (ADS)

    Mudarisova, R. Kh.; Badykova, L. A.

    2016-03-01

    The thermodynamics of complexation of arabinogalactan with salicylic and p-aminobenzoic acids in aqueous solutions is studied by means spectroscopy. The standard thermodynamic characteristics (Δ H°; Δ G°; Δ S°) of complexation are calculated.

  10. The behavior and importance of lactic acid complexation in Talspeak extraction systems

    SciTech Connect

    Grimes, Travis S.; Nilsson, Mikael; Nash, Kenneth L.

    2008-07-01

    Advanced partitioning of spent nuclear fuel in the UREX +la process relies on the TALSPEAK process for separation of fission-product lanthanides from trivalent actinides. The classic TALSPEAK utilizes an aqueous medium of both lactic acid and diethylenetriaminepentaacetic acid and the extraction reagent di(2-ethylhexyl)phosphoric acid in an aromatic diluent. In this study, the specific role of lactic acid and the complexes involved in the extraction of the trivalent actinides and lanthanides have been investigated using {sup 14}C-labeled lactic acid. Our results show that lactic acid partitions between the phases in a complex fashion. (authors)

  11. Nanophase Nickel-Zirconium Alloys for Fuel Cells

    NASA Technical Reports Server (NTRS)

    Narayanan, Sekharipuram; Whitacre, jay; Valdez, Thomas

    2008-01-01

    Nanophase nickel-zirconium alloys have been investigated for use as electrically conductive coatings and catalyst supports in fuel cells. Heretofore, noble metals have been used because they resist corrosion in the harsh, acidic fuel cell interior environments. However, the high cost of noble metals has prompted a search for less-costly substitutes. Nickel-zirconium alloys belong to a class of base metal alloys formed from transition elements of widely different d-electron configurations. These alloys generally exhibit unique physical, chemical, and metallurgical properties that can include corrosion resistance. Inasmuch as corrosion is accelerated by free-energy differences between bulk material and grain boundaries, it was conjectured that amorphous (glassy) and nanophase forms of these alloys could offer the desired corrosion resistance. For experiments to test the conjecture, thin alloy films containing various proportions of nickel and zirconium were deposited by magnetron and radiofrequency co-sputtering of nickel and zirconium. The results of x-ray diffraction studies of the deposited films suggested that the films had a nanophase and nearly amorphous character.

  12. Phosphorus Recovery Using Zirconium-Loaded Saponified Orange Juice Residue

    NASA Astrophysics Data System (ADS)

    Harada, Hiroyuki; Kondo, Mitsunori; Biswas, Biplob K.; Ohura, Seichirou; Inoue, Katsutoshi; Ishikawa, Susumu; Kawakita, Hidetaka; Ohto, Keisuke

    Zirconium was immobilized to orange juice residue, to investigate the feasibility of using zirconium-loaded saponified orange juice residue (Zr-SOJR) for phosphorus recovery from secondary effluent and the extraction solution from incinerated sewage sludge ash by using H2SO4 and HCl. These had phosphorus concentrations of 68.2 mg/dm3 and 5.9 mg/dm3, respectively. The phosphorus removal rate secondary effluent increased with an increasing solid/liquid ratio in batch experiments. The adsorption capacity of Zr-SOJR was also compared with those obtained using a synthetic phosphorus solution and using zirconium-loaded ferrite. The prepared absorbent was effective for phosphorus removal and exhibited a reasonably high sorption capacity, twice that of zirconium ferrite. Secondary effluent was treated by packed column, and this reached break-through after 300 bed volumes. The results from phosphorous extraction from the ash indicate that can be treated with acid to efficiently recover phosphorous and thus can be absorbed by Zr-SOJR.

  13. Characterization of titanium and zirconium valerate sol-gel films

    SciTech Connect

    Severin, K.G.; Ledford, J.S.; Torgerson, B.A.; Berglund, K.A. )

    1994-07-01

    FTIR and XPS have been used to characterize titanium and zirconium valerate thin films prepared using sol-gel techniques. Films were prepared by hydrolysis of titanium(IV) isopropoxide or zirconium(IV) n-propoxide in excess valeric acid at room temperature. Film solution chemistry, from precursors to cast films, was followed with FTIR. The structure and chemical composition of films spin cast from fresh and day-old solutions were determined. Results of these studies suggest that all films consist of a metal-oxygen polymer backbone coordinated with bidentate valerate ligands. No evidence for the presence of alkoxide ligands has been found. A small amount of water is present in all cast films. While solution aging experiments indicate that the zirconium film structure does not change with solution reaction time, carboxylate ligand concentrations are higher in titanium films made from aged solutions. Titanium films made from aged solutions contain slightly less than 1.5 valerate ligands/titanium atom. Zirconium films are more highly carboxylated with almost two valerate groups per metal center. 57 refs., 6 figs., 1 tab.

  14. Surface characterization of anodized zirconium for biomedical applications

    NASA Astrophysics Data System (ADS)

    Sanchez, A. Gomez; Schreiner, W.; Duffó, G.; Ceré, S.

    2011-05-01

    Mechanical properties and corrosion resistance of zirconium make this material suitable for biomedical implants. Its good in vivo performance is mainly due to the presence of a protective oxide layer that minimizes corrosion rate, diminishes the amount of metallic ions released to the biological media and facilitates the osseointegration process. Since the implant surface is the region in contact with living tissues, the characteristics of the surface film are of great interest. Surface modification is a route to enhance both biocompatibility and corrosion resistance of permanent implant materials. Anodizing is presented as an interesting process to modify metal surfaces with good reproducibility and independence of the geometry. In this work the surface of zirconium before and after anodizing in 1 mol/L phosphoric acid solution at a fixed potential between 3 and 30 V, was characterized by means of several surface techniques. It was found that during anodization the surface oxide grows with an inhomogeneous coverage on zirconium surface, modifying the topography. The incorporation of P from the electrolyte to the surface oxide during the anodizing process changes the surface chemistry. After 30 days of immersion in Simulated Body Fluid (SBF) solution, Ca-P rich compounds were present on anodized zirconium.

  15. Amylose inclusion complexation of ferulic acid via lipophilization

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Ferulic acid is an interesting phytochemical that exhibits antioxidant, anti-inflammatory, antimicrobial, UV-absorber, and anticarcinogenic activities. These properties make it of interest in food formulations, cosmetics, polymer, and pharmaceutical applications. However, delivery of ferulic acid in...

  16. PROCESS OF PREPARING ZIRCONIUM OXYCHLORIDE

    DOEpatents

    Wilhelm, H.A.; Andrews, M.L.

    1960-06-28

    A process is given for preparing zirconyl chloride by mixing solid zirconyl chloride octahydrate and solid zirconium tetrachloride at room temperature whereby both chlorides are converted to zirconyl chloride trinydrate and hydrogen chloride is formed and volatilized by the reaction heat.

  17. 40 CFR 721.10297 - Tin, C16-18 and C18-unsatd. fatty acids castor-oil fatty acids complexes.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... acids castor-oil fatty acids complexes. 721.10297 Section 721.10297 Protection of Environment.... fatty acids castor-oil fatty acids complexes. (a) Chemical substances and significant new uses subject to reporting. (1) The chemical substance identified as tin, C16-18 and C18-unsatd. fatty acids...

  18. 40 CFR 721.10297 - Tin, C16-18 and C18-unsatd. fatty acids castor-oil fatty acids complexes.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... acids castor-oil fatty acids complexes. 721.10297 Section 721.10297 Protection of Environment.... fatty acids castor-oil fatty acids complexes. (a) Chemical substances and significant new uses subject to reporting. (1) The chemical substance identified as tin, C16-18 and C18-unsatd. fatty acids...

  19. 40 CFR 721.10297 - Tin, C16-18 and C18-unsatd. fatty acids castor-oil fatty acids complexes.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... acids castor-oil fatty acids complexes. 721.10297 Section 721.10297 Protection of Environment.... fatty acids castor-oil fatty acids complexes. (a) Chemical substances and significant new uses subject to reporting. (1) The chemical substance identified as tin, C16-18 and C18-unsatd. fatty acids...

  20. Stereoelectronic influence of the type of bifunctional ansa-monocyclopentadienyldimethylsilylamido ligand on the molecular structures displayed by zirconium dichloride and 1,4-diphenylbutadiene complexes.

    PubMed

    Braun, Leonie F; Dreier, Thorsten; Christy, Matthew; Petersen, Jeffrey L

    2004-06-28

    A series of organozirconium dichloride and 1,4-diphenylbutadiene complexes featuring a dianionic bifunctional ligand with a cyclopentadienyl-type functionality and an appended amido N donor have been prepared and structurally characterized. [(C(5)H(4))SiMe(2)(N-t-Bu)]ZrCl(2), 1, [(C(9)H(6))SiMe(2)(N-t-Bu)]ZrCl(2), 2, and [(C(5)Me(4))SiMe(2)(N-i-Pr)]ZrCl(2), 3, were prepared in two steps, with ligand chelation accomplished by an amine elimination reaction followed by treatment of the diamido Zr intermediate with an excess of SiMe(3)Cl. X-ray structural analyses reveal that in the solid state 2 is monomeric, whereas 1 and 3 are centrosymmetric dimers linked by a pair of bridging chlorides. The level of asymmetry displayed by the central Zr(2)(micro-Cl)(2) moiety is indicated by the variation in the pair of independent bridging Zr-Cl bond distances, which are 2.618(1) and 2.657(1) A in 1 and 2.542(1) and 2.745(1) A in 3, respectively. The metathetical reactions of [Mg(C(4)H(4)Ph(2))(THF)(3)](n)() with 1, 2, 3, and [(C(5)Me(4))SiMe(2)(N-t-Bu)]ZrCl(2) proceed to afford the corresponding 1,4-diphenylbutadiene derivatives 4, 5, 6, and 7, respectively. Solution NMR data show that 6 is obtained exclusively as the supine isomer, whereas compounds 4, 5, and 7 exist as >20:1, 6:1, and 2:1 mixtures of the supine and prone isomers at ambient temperature. The molecular structures of the supine forms of 4, 5, 6, and 7 are appreciably folded (70-80 degrees ) along the line of intersection between the plane containing the Zr and the two terminal butadiene carbons and the plane of the cis-butadiene fragment. An increase in the folding is accompanied by a decrease in the difference between the average Zr-C(terminal) and Zr-C(internal) bond distances and leads to a more pronounced long-short-long C-C bond sequence within the coordinated butadiene. PMID:15206879

  1. Aqueous sodium borohydride induced thermally stable porous zirconium oxide for quick removal of lead ions

    PubMed Central

    Nayak, Nadiya B.; Nayak, Bibhuti B.

    2016-01-01

    Aqueous sodium borohydride (NaBH4) is well known for its reducing property and well-established for the development of metal nanoparticles through reduction method. In contrary, this research paper discloses the importance of aqueous NaBH4 as a precipitating agent towards development of porous zirconium oxide. The boron species present in aqueous NaBH4 play an active role during gelation as well as phase separated out in the form of boron complex during precipitation, which helps to form boron free zirconium hydroxide [Zr(OH)4] in the as-synthesized condition. Evolved in-situ hydrogen (H2) gas-bubbles also play an important role to develop as-synthesized loose zirconium hydroxide and the presence of intra-particle voids in the loose zirconium hydroxide help to develop porous zirconium oxide during calcination process. Without any surface modification, this porous zirconium oxide quickly adsorbs almost hundred percentages of toxic lead ions from water solution within 15 minutes at normal pH condition. Adsorption kinetic models suggest that the adsorption process was surface reaction controlled chemisorption. Quick adsorption was governed by surface diffusion process and the adsorption kinetic was limited by pore diffusion. Five cycles of adsorption-desorption result suggests that the porous zirconium oxide can be reused efficiently for removal of Pb (II) ions from aqueous solution. PMID:26980545

  2. Aqueous sodium borohydride induced thermally stable porous zirconium oxide for quick removal of lead ions.

    PubMed

    Nayak, Nadiya B; Nayak, Bibhuti B

    2016-01-01

    Aqueous sodium borohydride (NaBH4) is well known for its reducing property and well-established for the development of metal nanoparticles through reduction method. In contrary, this research paper discloses the importance of aqueous NaBH4 as a precipitating agent towards development of porous zirconium oxide. The boron species present in aqueous NaBH4 play an active role during gelation as well as phase separated out in the form of boron complex during precipitation, which helps to form boron free zirconium hydroxide [Zr(OH)4] in the as-synthesized condition. Evolved in-situ hydrogen (H2) gas-bubbles also play an important role to develop as-synthesized loose zirconium hydroxide and the presence of intra-particle voids in the loose zirconium hydroxide help to develop porous zirconium oxide during calcination process. Without any surface modification, this porous zirconium oxide quickly adsorbs almost hundred percentages of toxic lead ions from water solution within 15 minutes at normal pH condition. Adsorption kinetic models suggest that the adsorption process was surface reaction controlled chemisorption. Quick adsorption was governed by surface diffusion process and the adsorption kinetic was limited by pore diffusion. Five cycles of adsorption-desorption result suggests that the porous zirconium oxide can be reused efficiently for removal of Pb (II) ions from aqueous solution. PMID:26980545

  3. Aqueous sodium borohydride induced thermally stable porous zirconium oxide for quick removal of lead ions

    NASA Astrophysics Data System (ADS)

    Nayak, Nadiya B.; Nayak, Bibhuti B.

    2016-03-01

    Aqueous sodium borohydride (NaBH4) is well known for its reducing property and well-established for the development of metal nanoparticles through reduction method. In contrary, this research paper discloses the importance of aqueous NaBH4 as a precipitating agent towards development of porous zirconium oxide. The boron species present in aqueous NaBH4 play an active role during gelation as well as phase separated out in the form of boron complex during precipitation, which helps to form boron free zirconium hydroxide [Zr(OH)4] in the as-synthesized condition. Evolved in-situ hydrogen (H2) gas-bubbles also play an important role to develop as-synthesized loose zirconium hydroxide and the presence of intra-particle voids in the loose zirconium hydroxide help to develop porous zirconium oxide during calcination process. Without any surface modification, this porous zirconium oxide quickly adsorbs almost hundred percentages of toxic lead ions from water solution within 15 minutes at normal pH condition. Adsorption kinetic models suggest that the adsorption process was surface reaction controlled chemisorption. Quick adsorption was governed by surface diffusion process and the adsorption kinetic was limited by pore diffusion. Five cycles of adsorption-desorption result suggests that the porous zirconium oxide can be reused efficiently for removal of Pb (II) ions from aqueous solution.

  4. Synthesis and thermal decomposition of a novel zirconium acetato-propionate cluster: [Zr12

    NASA Astrophysics Data System (ADS)

    Petit, Sarah; Morlens, Stéphanie; Yu, Zeming; Luneau, Dominique; Pilet, Guillaume; Soubeyroux, Jean-Louis; Odier, Philippe

    2011-03-01

    This work reports a novel Zirconium acetato-propionate complex herein called [Zr12] obtained by reaction of zirconium acetylacetonate Zr(acac) 4 with propionic acid. The molecular structure has been determined by X-ray diffraction on single crystals and proposed to be [Zr 12(μ 3-O) 16(CH 3CH 2CO 2) 12(CH 3CO 2) 8(μ 2-CH 3CH 2CO 2) 4]. This cluster involves oxo/hydroxo bonds in the direct surrounding of the metallic center. The decomposition of [Zr12] has been studied by thermal analysis and compared to Zr(acac) 4. Its temperature of decomposition is much lower than for acetylacetonate derivative. In consequence, the formation of ZrO 2 is easier from [Zr12] than from Zr(acac) 4. This phenomenon highlights the influence of the molecular structure on the process of decomposition. The local surrounding of Zr in [Zr12] and in ZrO 2 are very close, while it is markedly different in Zr(acac) 4.This difference of environment of the metallic ions is at the origin of the huge difference of thermal behavior of both compounds.

  5. Crystal structure of beta-cyclodextrin-benzoic acid inclusion complex.

    PubMed

    Aree, Thammarat; Chaichit, Narongsak

    2003-02-14

    The inclusion complex of beta-cyclodextrin (beta-CD) with benzoic acid (BA) has been characterized crystallographically. Two beta-CDs cocrystallize with two BAs, 0.7 ethanol and 20.65 water molecules [2(C(6)H(10)O(5))(7).2(C(7)H(6)O(2)).0.7(C(2)H(6)O).20.65H(2)O] in the triclinic space group P1 with unit cell constants: a=15.210(1), b=15.678(1), c=15.687(1) A, alpha=89.13(1), beta=74.64(1), gamma=76.40(1) degrees. The anisotropic refinement of 1840 atomic parameters against 16,201 X-ray diffraction data converged at R=0.078. In the crystal lattice, beta-CD forms dimers stabilized by direct O-2(m)_1/O-3(m)_1...O-2(n)_2/O-3(n)_2 hydrogen bonds (intradimer) and by indirect O-6(m)_1...,O-6(n)_2 hydrogen bonds with one or two bridging water molecules joined in between (interdimer). These dimers are stacked like coins in a roll constructing endless channels where the guest molecules are included. The BA molecules protrude with their COOH groups at the beta-CD O-6-sides and are maintained in positions by hydrogen bonding to the surrounding O-6-H groups and water molecules. Water molecules (20.65) are distributed over 30 positions in the interstices between beta-CD molecules, except the water sites W-1, W-2 that are located in the channel of the beta-CD dimer. Water site W-2 is hydrogen bonded to the disordered ethanol molecule (occupancy 0.7). PMID:12559746

  6. 78 FR 46265 - Complex Polymeric Polyhydroxy Acids; Exemption From the Requirement of a Tolerance

    Federal Register 2010, 2011, 2012, 2013, 2014

    2013-07-31

    ...This regulation establishes an exemption from the requirement of a tolerance for residues of Complex Polymeric Polyhydroxy Acids in or on all food commodities. This regulation eliminates the need to establish a maximum permissible level for residues of Complex Polymeric Polyhydroxy Acids (CPPA) under...

  7. Direct intercalation of cisplatin into zirconium phosphate nanoplatelets for potential cancer nanotherapy

    NASA Astrophysics Data System (ADS)

    Díaz, Agustín; González, Millie L.; Pérez, Riviam J.; David, Amanda; Mukherjee, Atashi; Báez, Adriana; Clearfield, Abraham; Colón, Jorge L.

    2013-11-01

    We report the use of zirconium phosphate (ZrP) nanoplatelets for the encapsulation of the anticancer drug cisplatin and its delivery to tumor cells. Cisplatin was intercalated into ZrP by direct ion exchange and was tested in vitro for cytotoxicity in the human breast cancer (MCF-7) cell line. The structural characterization of the intercalated cisplatin in ZrP suggests that during the intercalation process, the chloride ligands of the cisplatin complex were substituted by phosphate groups within the layers. Consequently, a new phosphate phase with the platinum complex directly bound to ZrP (cisPt@ZrP) is produced with an interlayer distance of 9.3 Å. The in vitro release profile of the intercalated drug upon a pH stimulus shows that at low pH under lysosomal conditions the platinum complex is released with simultaneous hydrolysis of the zirconium phosphate material, while at higher pH the complex is not released. Experiments with the MCF-7 cell line show that cisPt@ZrP reduced the cell viability up to 40%. The cisPt@ZrP intercalation product is envisioned as a future nanotherapy agent against cancer. Taking advantage of the shape and sizes of the ZrP particles and controlled release of the drug at low pH, it is intended to exploit the enhanced permeability and retention effect of tumors, as well as their intrinsic acidity, for the destruction of malignant cells.We report the use of zirconium phosphate (ZrP) nanoplatelets for the encapsulation of the anticancer drug cisplatin and its delivery to tumor cells. Cisplatin was intercalated into ZrP by direct ion exchange and was tested in vitro for cytotoxicity in the human breast cancer (MCF-7) cell line. The structural characterization of the intercalated cisplatin in ZrP suggests that during the intercalation process, the chloride ligands of the cisplatin complex were substituted by phosphate groups within the layers. Consequently, a new phosphate phase with the platinum complex directly bound to ZrP (cisPt@ZrP) is

  8. Phosphorus-bridged ansa-metallocene complexes of titanium, zirconium, and hafnium: The syntheses and structures of [PhP(C{sub 5}Me{sub 4}){sub 2}]MX{sub 2} and [Ph(E)P(C{sub 5}Me{sub 4}){sub 2}]MX{sub 2} (E = O, S, Se) derivatives

    SciTech Connect

    Shin, J.H.; Hascall, T.; Parkin, G.

    1999-01-04

    A series of phosphorus-bridged ansa-metallocene complexes of titanium, zirconium, and hafnium, [PhP(XC{sub 5}Me{sub 4}){sub 2}]MX{sub 2} and [Ph(E)P(C{sub 5}Me{sub 4}){sub 2}]MX{sub 2} (X = Cl, Me, CO, (Se{sub 3}){sub 0.5}; E = O, S, Se), has been synthesized. Structural characterization by X-ray diffraction indicates that, in comparison to their non-ansa counterparts (C{sub 5}Me{sub 5}){sub 2}MX{sub 2}, the cyclopentadienyl groups in phosphorus-bridged complexes are displaced from symmetric {eta}{sup 5}-coordination toward {eta}{sup 3}-coordination. Such {eta}{sup 3},{eta}{sup 3}-coordination creates more electrophilic metal centers than those in their permethylcyclopentadienyl counterparts, as judged by the {nu}(CO) stretching frequencies of the zirconium dicarbonyl complexes Cp{sup *}{sub 2}Zr(CO){sub 2} (1946 and 1853 cm{sup {minus}1}) and [PhP(C{sub 5}Me{sub 4}){sub 2}]Zr(CO){sub 2} (1959 and 1874 cm{sup {minus}1}).

  9. Effects of chemical and enzymatic modifications on starch-oleic acid complex formation.

    PubMed

    Arijaje, Emily Oluwaseun; Wang, Ya-Jane

    2015-04-29

    The solubility of starch-inclusion complexes affects the digestibility and bioavailability of the included molecules. Acetylation with two degrees of substitution, 0.041 (low) and 0.091 (high), combined without or with a β-amylase treatment was employed to improve the yield and solubility of the inclusion complex between debranched potato starch and oleic acid. Both soluble and insoluble complexes were recovered and analyzed for their degree of acetylation, complexation yields, molecular size distributions, X-ray diffraction patterns, and thermal properties. Acetylation significantly increased the amount of recovered soluble complexes as well as the complexed oleic acid in both soluble and insoluble complexes. High-acetylated debranched-only starch complexed the highest amount of oleic acid (38.0 mg/g) in the soluble complexes; low-acetylated starch with or without the β-amylase treatment resulted in the highest complexed oleic acid in the insoluble complexes (37.6-42.9 mg/g). All acetylated starches displayed the V-type X-ray pattern, and the melting temperature generally decreased with acetylation. The results indicate that starch acetylation with or without the β-amylase treatment can improve the formation and solubility of the starch-oleic acid complex. PMID:25877005

  10. Purifying transplutonium elements from iron, zirconium, and aluminum by extraction with D2EHPA from citrate solution

    SciTech Connect

    Kasimov, F.D.; Gordeev, Ya.N.; Kovanseva, S.N.; Kasimova, V.A.; Nikolaev, V.M.; Skobelev, N.F.; Filimonov, V.T.; Yadovin, A.A.

    1987-03-01

    A study has been made on the effects of various factors on the zirconium extraction kinetics in the system consisting of citric acid with di-(2-ethylhexyl) phosphoric acid. It has been found that zirconium, iron (III), and aluminum are extracted much more slowly than the transplutonium elements (TPE). The process can be operated under nonequilibrium conditions to increase the separation factors considerably, which has been employed to improve the purification of TPE.

  11. Immunogenicity of a purified and carrier-complexed streptococcal lipoteichoic acid.

    PubMed Central

    Fiedel, B A; Jackson, R W

    1976-01-01

    Solublie teichoic acid could not stimulate the formation of antibodies either as an aqueous solution or in an emulsion with Freund incomplete adjuvant. However, when given as precipitates with methylated bovine serum albumin, it stimulated strong anti-teichoic acid responses. High levels of anti-teichoic acid antibodies usually resulted in allergic symptoms upon secondary challenge either with immunogenic teichoic acid-methylated bovine albumin complexes or with non-immunogenic soluble teichoic acid. These symptoms suggested anaphylatic shock, but probably also included the formation of complement-consuming immune complexes. PMID:786876

  12. Zircon solubility and zirconium complexation in H2O+Na2O+SiO2±Al2O3 fluids at high pressure and temperature

    NASA Astrophysics Data System (ADS)

    Wilke, Max; Schmidt, Christian; Dubrail, Julien; Appel, Karen; Borchert, Manuela; Kvashnina, Kristina; Manning, Craig E.

    2012-10-01

    Zircon is an important host mineral for many high-field strength elements (HFSE), particularly Zr and Hf. Thus, its solubility in geologic fluids at high pressure and temperature plays an important role in terrestrial cycling of these elements during processes in the Earth's crust and mantle. We performed in-situ high-pressure, high-temperature measurements of zircon solubility in H2O-Na2Si3O7, H2O-Na2Si3O7+Al2O3, H2O-Na2Si2O5, H2O-NaAlSi3O8 fluids, as well as of baddeleyite solubility in H2O-NaOH fluids, by in-situ synchrotron radiation X-ray fluorescence analysis using hydrothermal diamond-anvil cells. Zirconium complexation in fluids in equilibrium with zircon was constrained by in-situ X-ray absorption near-edge structure (XANES) spectroscopy. Zircon solubility is strongly enhanced by addition of Na2Si3O7 to H2O. The degree of enhancement increases with Na2Si3O7 concentration. The Zr content of fluids containing 10 wt% Na2Si3O7 reached up to 86±2 ppm Zr at 550 °C and 400 MPa. At 30 wt% Na2Si3O7, the maximum Zr concentration was 997±6 ppm at 600 °C and 440 MPa. Zircon solubility in these fluids decreases considerably with pressure and increases slightly with temperature. Addition of Al2O3 decreases the zircon solubility. In H2O-NaAlSi3O8 fluids, the Zr concentrations are in the sub-ppm to ppm range. Zr concentrations in NaOH solutions in equilibrium with baddeleyite reached up to 390±2 ppm at 600 °C and 930 MPa and increase with pressure and temperature. In-situ XANES spectra collected on Zr in H2O-Na2Si3O7, H2O-Na2Si3O7+Al2O3, H2O-NaOH, and H2O-HCl fluids in equilibrium with zircon provide evidence for strong differences in the Zr complexation between these fluids. Comparison of XANES spectra to those of model compounds and ab-initio simulation of XANES spectra revealed [8]Zr for the HCl solution, [7]Zr for the NaOH solution, and [6]Zr for the Na-Al-silicate-bearing solutions. For the latter solutions, formation of alkali zircono-silicate complexes is

  13. Action of Natural Abscisic Acid Precursors and Catabolites on Abscisic Acid Receptor Complexes1[W

    PubMed Central

    Kepka, Michal; Benson, Chantel L.; Gonugunta, Vijay K.; Nelson, Ken M.; Christmann, Alexander; Grill, Erwin; Abrams, Suzanne R.

    2011-01-01

    The phytohormone abscisic acid (ABA) regulates stress responses and controls numerous aspects of plant growth and development. Biosynthetic precursors and catabolites of ABA have been shown to trigger ABA responses in physiological assays, but it is not clear whether these are intrinsically active or whether they are converted into ABA in planta. In this study, we analyzed the effect of ABA precursors, conjugates, and catabolites on hormone signaling in Arabidopsis (Arabidopsis thaliana). The compounds were also tested in vitro for their ability to regulate the phosphatase moiety of ABA receptor complexes consisting of the protein phosphatase 2C ABI2 and the coreceptors RCAR1/PYL9, RCAR3/PYL8, and RCAR11/PYR1. Using mutants defective in ABA biosynthesis, we show that the physiological activity associated with ABA precursors derives predominantly from their bioconversion to ABA. The ABA glucose ester conjugate, which is the most widespread storage form of ABA, showed weak ABA-like activity in germination assays and in triggering ABA signaling in protoplasts. The ABA conjugate and precursors showed negligible activity as a regulatory ligand of the ABI2/RCAR receptor complexes. The majority of ABA catabolites were inactive in our assays. To analyze the chemically unstable 8′- and 9′-hydroxylated ABA catabolites, we used stable tetralone derivatives of these compounds, which did trigger selective ABA responses. ABA synthetic analogs exhibited differential activity as regulatory ligands of different ABA receptor complexes in vitro. The data show that ABA precursors, catabolites, and conjugates have limited intrinsic bioactivity and that both natural and synthetic ABA-related compounds can be used to probe the structural requirements of ABA ligand-receptor interactions. PMID:21976481

  14. Zirconium tungstate hydroxide hydrate revisited: Crystallization dependence on halide and hydronium ions

    SciTech Connect

    Colin, Julie A. Camper, DeMarco V.; Gates, Stacy D.; Simon, Monty D. Witker, Karen L. Lind, Cora

    2007-12-15

    The formation of zirconium tungstate hydroxide hydrate, a precursor to the negative thermal expansion material cubic zirconium tungstate, shows a strong dependence on hydrothermal reaction conditions. It was found that not only the acid concentration, but also the acid counterion plays a significant role in the crystallization of ZrW{sub 2}O{sub 7}(OH){sub 2}.2H{sub 2}O. High temperatures, high acid concentrations, and the presence of chloride or bromide ions promote the formation of well-crystallized ZrW{sub 2}O{sub 7}(OH){sub 2}.2H{sub 2}O. For low acid concentrations, a new zirconium tungstate hydrate polymorph is observed, which transforms to tetragonal ZrW{sub 2}O{sub 7}(OH){sub 2}.2H{sub 2}O at longer reaction times. A study of crystallization kinetics in hydrochloric acid is presented. - Graphical abstract: The formation of ZrW{sub 2}O{sub 7}(OH){sub 2}.2H{sub 2}O shows a strong dependence on reaction conditions. Both acid concentration and acid counterion play a significant role in the crystallization. High temperatures, high acid concentrations, and the presence of chloride or bromide ions promote the formation of well-crystallized ZrW{sub 2}O{sub 7}(OH){sub 2}.2H{sub 2}O. For low acid concentrations, a new zirconium tungstate hydrate polymorph is observed.

  15. Matrix Isolation IR Spectroscopy of 1:1 Complexes of Acetic Acid and Trihaloacetic Acids with Water and Benzene

    NASA Astrophysics Data System (ADS)

    Banerjee, Pujarini; Chakraborty, Tapas

    2015-06-01

    A comparative study of infrared spectral effects for 1:1 complex formation of acetic acid (AA), trifluoroacetic acid (TFAA) and trichloroacetic acid (TFAA) with water and benzene has been carried out under a matrix isolation environment. Despite the large difference in aqueous phase acidities of the three acids, the measured νb{OH}stretching frequencies of the monomers of the three molecules are found to be almost same, and in agreement with gas phase electronic structure calculations. Intrinsic acidities are expressed only in the presence of the proton acceptors, water or benzene. Although electronic structure calculations predict distinct νb{OH} red-shifts for all three acids, the measured spectral features for TCAA and TFAA in this range do not allow unambiguous assignments for the 1:1 complex. On the other hand, the spectral changes in the νb{C=O} region are more systematic, and the observed changes are consistent with predictions of theory. Components of overall binding energy of each complex have been obtained from energy decomposition analysis, which allows determination of the relative contributions of various physical forces towards overall stability of the complexes, and the details will be discussed in the talk.

  16. Stability Constants of Mixed Ligand Complexes of Nickel(II) with Adenine and Some Amino Acids

    PubMed Central

    Türkel, Naciye

    2015-01-01

    Nickel is one of the essential trace elements found in biological systems. It is mostly found in nickel-based enzymes as an essential cofactor. It forms coordination complexes with amino acids within enzymes. Nickel is also present in nucleic acids, though its function in DNA or RNA is still not clearly understood. In this study, complex formation tendencies of Ni(II) with adenine and certain L-amino acids such as aspartic acid, glutamic acid, asparagine, leucine, phenylalanine, and tryptophan were investigated in an aqueous medium. Potentiometric equilibrium measurements showed that both binary and ternary complexes of Ni(II) form with adenine and the above-mentioned L-amino acids. Ternary complexes of Ni(II)-adenine-L-amino acids are formed by stepwise mechanisms. Relative stabilities of the ternary complexes are compared with those of the corresponding binary complexes in terms of Δlog10⁡K, log10⁡X, and % RS values. It was shown that the most stable ternary complex is Ni(II):Ade:L-Asn while the weakest one is Ni(II):Ade:L-Phe in aqueous solution used in this research. In addition, results of this research clearly show that various binary and ternary type Ni(II) complexes are formed in different concentrations as a function of pH in aqueous solution. PMID:26843852

  17. Recovery of nickel and cobalt from organic acid complexes: adsorption mechanisms of metal-organic complexes onto aminophosphonate chelating resin.

    PubMed

    Deepatana, A; Valix, M

    2006-09-21

    This study examined the recovery of nickel and cobalt from organic acid complexes using a chelating aminophosphonate Purolite S950 resin. These metal complexes are generated by bioleaching nickel laterite ores, a commercial nickel and cobalt mineral oxide, with heterotrophic organism and their metabolites or organic acid products. Equilibrium adsorption tests were conducted as a function of Ni and Co concentrations (15-2000 mg/L), solution pH (0.01 and 0.1 M acids) and three metabolic complexing agents (citrate, malate and lactate). It was shown that the adsorption of the various Ni- and Co-complexes on Purolite were quite low, 16-18 and 5.4-9 mg/g of resin, respectively, in comparison to the smaller nickel ions and nickel sulfate. This was attributed to the bulky organic ligands which promoted crowding effect or steric hindrance. The adsorption of these complexes was further hampered by the strong affinity of the resin to H+ ions under acidic conditions. Mechanisms of adsorption, as inferred from the fitted empirical Langmuir and Freundlich models, were correlated to the proposed steric hindrance and competitive adsorption effects. Nickel and cobalt elution from the resin were found be effective and were independent of the type of metal complexes and metal concentrations. This study demonstrated the relative challenges involved in recovering nickel and cobalt from bioleaching solutions. PMID:16698178

  18. Nickel(II) and copper(II) complexes with humic acid anions and their derivatives

    SciTech Connect

    Ryabova, I.N.

    2008-01-15

    Complexation of Ni(II) and Cu(II) in aqueous solutions with anions of humic acids, extracted from naturally oxidized coal, and with their hydroxymethyl derivatives is studied spectrophotometrically and potentiometrically. The complexation stoichiometry and the stability constants of the complexes are determined.

  19. Telomerization of amino acids with butadiene, catalyzed by palladium complexes

    SciTech Connect

    Dzhemilev, U.M.; Fakhretdinov, R.N.; Telin, A.G.

    1987-01-10

    The telomerization of ..cap alpha..-, ..beta..-, ..gamma..-, and epsilon-amino acids having various structures with butadiene under the influence of the three-component palladium catalyst Pd(acac)/sub 2/-PPh/sub 3/-AlEt/sub 3/ was investigated in DMSO-toluene solution. The ..cap alpha..- and epsilon-aliphatic and also the ..cap alpha..-, ..beta..-, and ..gamma..-aromatic amino acids react with butadiene, giving the products from octadienylation at the amino group exclusively. Under the conditions of telomerization aliphatic ..beta..-amino acids are cleaved with the formation of unsaturated tertiary amines. In the case of aliphatic ..gamma..-amino acids it is possible to obtain telomers alkylated at the carbonyl group.

  20. 21 CFR 172.315 - Nicotinamide-ascorbic acid complex.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... (CONTINUED) FOOD FOR HUMAN CONSUMPTION (CONTINUED) FOOD ADDITIVES PERMITTED FOR DIRECT ADDITION TO FOOD FOR...: (a) The additive is the product of the controlled reaction between ascorbic acid and...

  1. 21 CFR 172.315 - Nicotinamide-ascorbic acid complex.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... (CONTINUED) FOOD ADDITIVES PERMITTED FOR DIRECT ADDITION TO FOOD FOR HUMAN CONSUMPTION Special Dietary and... the controlled reaction between ascorbic acid and nicotinamide, melting in the range 141 °C to 145...

  2. 21 CFR 172.315 - Nicotinamide-ascorbic acid complex.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... (CONTINUED) FOOD FOR HUMAN CONSUMPTION (CONTINUED) FOOD ADDITIVES PERMITTED FOR DIRECT ADDITION TO FOOD FOR...: (a) The additive is the product of the controlled reaction between ascorbic acid and...

  3. 21 CFR 172.315 - Nicotinamide-ascorbic acid complex.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... (CONTINUED) FOOD FOR HUMAN CONSUMPTION (CONTINUED) FOOD ADDITIVES PERMITTED FOR DIRECT ADDITION TO FOOD FOR...: (a) The additive is the product of the controlled reaction between ascorbic acid and...

  4. 21 CFR 172.315 - Nicotinamide-ascorbic acid complex.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... (CONTINUED) FOOD FOR HUMAN CONSUMPTION (CONTINUED) FOOD ADDITIVES PERMITTED FOR DIRECT ADDITION TO FOOD FOR...: (a) The additive is the product of the controlled reaction between ascorbic acid and...

  5. Complexing of amino acids to DNA by chromate in intact cells.

    PubMed Central

    Voitkun, V; Zhitkovich, A; Costa, M

    1994-01-01

    Using o-pthaldialdehyde (OPT) fluorescence, the amino acids associated with DNA were studied following exposure of intact Chinese hamster ovary cells to chromate. Rigorous extraction with EDTA, acid, or base was required to release the amino acids cross-linked to the DNA isolated from control or chromate-treated cells by standard procedures (i.e., proteinase K, phenol, etc.). Amino acids resisting extraction from DNA were not studied since analysis was limited to those that could be released by these procedures. There was a chromate dose-dependent increase in amino acids complexed with the DNA that could be released by EDTA, acid, and base, and these amino acids were separated by HPLC and identified. Substantial increases in cysteine, glutamine, glutamic acid, histidine, threonine, and tyrosine were found as a function of increasing concentrations of chromate. There was also a time-dependent increase in complexing of these amino acids to the DNA by chromate. The amino acids found complexed to DNA in intact cells by chromate were thought to originate from reactions of free amino acids or small peptides with the DNA rather than being proteolytic products derived from larger proteins that were cross-linked to the DNA. This was supported by a number of experiments: a) free amino acids or bovine serum albumin (BSA) were cross-linked by chromium to DNA in vitro and the DNA was isolated by standard procedures.(ABSTRACT TRUNCATED AT 250 WORDS) PMID:7843108

  6. An Experiment on Isomerism in Metal-Amino Acid Complexes.

    ERIC Educational Resources Information Center

    Harrison, R. Graeme; Nolan, Kevin B.

    1982-01-01

    Background information, laboratory procedures, and discussion of results are provided for syntheses of cobalt (III) complexes, I-III, illustrating three possible bonding modes of glycine to a metal ion (the complex cations II and III being linkage/geometric isomers). Includes spectrophotometric and potentiometric methods to distinguish among the…

  7. Design of stereoelectronically promoted super lewis acids and unprecedented chemistry of their complexes.

    PubMed

    Foroutan-Nejad, Cina; Vicha, Jan; Marek, Radek

    2014-09-01

    A new family of stereoelectronically promoted aluminum and scandium super Lewis acids is introduced on the basis of state-of-the-art computations. Structures of these molecules are designed to minimize resonance electron donation to central metal atoms in the Lewis acids. Acidity of these species is evaluated on the basis of their fluoride-ion affinities relative to the antimony pentafluoride reference system. It is demonstrated that introduced changes in the stereochemistry of the designed ligands increase acidity considerably relative to Al and Sc complexes with analogous monodentate ligands. The high stability of fluoride complexes of these species makes them ideal candidates to be used as weakly coordinating anions in combination with highly reactive cations instead of conventional Lewis acid-fluoride complexes. Further, the interaction of all designed molecules with methane is investigated. All studied acids form stable pentavalent-carbon complexes with methane. In addition, interactions of the strongest acid of this family with very weak bases, namely, H2, N2, carbon oxides, and noble gases were investigated; it is demonstrated that this compound can form considerably stable complexes with the aforementioned molecules. To the best of our knowledge, carbonyl and nitrogen complexes of this species are the first hypothetical four-coordinated carbonyl and nitrogen complexes of aluminum. The nature of bonding in these systems is studied in detail by various bonding analysis approaches. PMID:25055748

  8. Complexation of U(VI) with 1-Hydroxyethane-1,1-diphosphonicAcid (HEDPA) in Acidic to Basic Solutions

    SciTech Connect

    Reed, W A; Rao, L; Zanonato, P; Garnov, A; Powell, B A; Nash, K L

    2007-01-24

    Complexation of U(VI) with 1-hydroxyethane-1,1-diphosphonic acid (HEDPA) in acidic to basic solutions has been studied with multiple techniques. A number of 1:1 (UO{sub 2}H{sub 3}L), 1:2 (UO{sub 2}H{sub j}L{sub 2} where j = 4, 3, 2, 1, 0 and -1) and 2:2 ((UO{sub 2}){sub 2}H{sub j}L{sub 2} where j = 1, 0 and -1) complexes form, but the 1:2 complexes are the major species in a wide pH range. Thermodynamic parameters (formation constants, enthalpy and entropy of complexation) were determined by potentiometry and calorimetry. Data indicate that the complexation of U(VI) with HEDPA is exothermic, favored by the enthalpy of complexation. This is in contrast to the complexation of U(VI) with dicarboxylic acids in which the enthalpy term usually is unfavorable. Results from electrospray ionization mass spectrometry (ESI-MS) and {sup 31}P NMR have confirmed the presence of 1:1, 1:2 and 2:2 U(VI)-HEDPA complexes.

  9. Determination of fluoride in water - A modified zirconium-alizarin method

    USGS Publications Warehouse

    Lamar, W.L.

    1945-01-01

    A convenient, rapid colorimetric procedure using the zirconium-alizarin indicator acidified with sulfuric acid for the determination of fluoride in water is described. Since this acid indicator is stable indefinitely, it is more useful than other zirconium-alizarin reagents previously reported. The use of sulfuric acid alone in acidifying the zirconium-alizarin reagent makes possible the maximum suppression of the interference of sulfate. Control of the pH of the samples eliminates errors due to the alkalinity of the samples. The fluoride content of waters containing less than 500 parts per million of sulfate and less than 1000 p.p.m. of chloride may be determined within a limit of 0.1 p.p.m. when a 100-ml. sample is used.

  10. Stability constants of europium complexes with a nitrogen heterocycle substituted methane-1,1-diphosphonic acid

    SciTech Connect

    Jensen, M.P.; Rickert, P.G.; Schmidt, M.A.; Nash, K.L.

    1996-06-01

    Even in moderately acidic solutions ([H{sup +}] > 0.01 M), N-piperidinomethane-1,1-diphosphonic acid (H{sub 4}PMDPA) is a strong complexant of trivalent lanthanide ions that shows enhanced complex solubility over previously studied 1,1-diphosphonic acids. The protonation constants of PMDPA in 2.0 M H/NaClO{sub 4} were determined by potentiometric and NMR titrations, and the stability constants for formation of complexes with Eu{sup 3+} were determined by solvent extraction. Difference in protonation equilibria induced by addition of the nitrogen heterocycle results in an increase in the complexation strength of PMDPA. In solutions containing 0.1 M H{sup +} and ligand concentrations greater than 0.02 M, PMDPA is the most effective 1,1-diphosphonic acid for europium complexation studied thus far.

  11. Spectral and thermal study of the ternary complexes of nickel with sulfasalazine and some amino acids

    NASA Astrophysics Data System (ADS)

    Soliman, Ahmed A.

    2006-12-01

    The ternary complexes of Ni(II) with sulfasalazine (H 3SS) as a primary ligand and alanine (ala), aspartic acid (asp), histidene (hist), methionine (meth) and serine (ser) amino acids as secondary ligands have been synthesized. Characterization of the complexes was based on elemental analyses, IR, UV-vis, mass spectra, magnetic moment and thermal analysis (TG). The isolated complexes were found to have the general formula [M(HSS)(AA)]4H 2O (AA = ala, asp, hist, meth, or ser amino acid) where nickel is tetra-coordinated. The thermal stability of the complexes was studied and the weight losses for the decomposition of the complexes were calculated and correlated with the mass fragmentation pattern. In most cases, the amino acid moiety is removed along with the Schiff base moiety leaving NiO as a metallic residue. The metallic residue was confirmed by powder XRD measurements.

  12. Trifluoroacetic acid as excipient destabilizes melittin causing the selective aggregation of melittin within the centrin-melittin-trifluoroacetic acid complex.

    PubMed

    Pastrana-Rios, Belinda; Del Valle Sosa, Liliana; Santiago, Jorge

    2015-07-01

    Trifluoroacetic acid (TFA) may be the cause of the bottleneck in high resolution structure determination for protein-peptide complexes. Fragment based drug design often involves the use of synthetic peptides which contain TFA (excipient). Our goal was to explore the effects of this excipient on a model complex: centrin-melittin-TFA. We performed Fourier transform infrared, two-dimensional infrared correlation spectroscopies and spectral simulations to analyze the amide I'/I'* band for the components and the ternary complex. Melittin (MLT) was observed to have increased helicity upon its interaction with centrin, followed by the thermally induced aggregation of MLT within the ternary complex in the TFA presence. PMID:26798810

  13. Influence of fulvic acid on bacteriophage adsorption and complexation in soil.

    PubMed Central

    Bixby, R L; O'Brien, D J

    1979-01-01

    The effect of fulvic acid, the major fraction of natural soluble organic matter, on the adsorption of MS2 bacteriophage to soil was investigated in controlled laboratory experiments. Batch experiments together with scanning electron microscopy-energy-dispersive X-ray analysis showed that fulvic acid complexed phage, which prevented its adsorption to soil. Phage strongly adsorbed to soil in the absence of fulvic acid. Phage which was complexed with fulvic acid was not irreversibly inactivated and could become viable under proper conditions, illustrating the importance of assay and elution procedures in the recovery of virus from aqueous solutions. PMID:396884

  14. Polymers with complexing properties. Simple poly(amino acids)

    NASA Technical Reports Server (NTRS)

    Roque, J. M.

    1978-01-01

    The free amino (0.3 equiv/residue) and carboxyl (0.5 equiv/residue) groups of thermal polylysine increased dramatically on treatment with distilled water. The total hydrolysis of such a polymer was abnormal in that only about 50% of the expected amino acids were recovered. Poly (lysine-co-alanine-co-glycine) under usual conditions hydrolyzed completely in 8 hours; whereas, when it was pretreated with diazomethane, a normal period of 24 hours was required to give (nearly) the same amounts of each free amino acid as compared with those obtained from the untreated polymer. The amino groups of the basic thermal poly(amino acids) were sterically hindered. The existence of nitrogen atoms linking two or three chains and reactive groups (anhydride, imine) were proposed.

  15. Method for preparing hydrous zirconium oxide gels and spherules

    DOEpatents

    Collins, Jack L.

    2003-08-05

    Methods for preparing hydrous zirconium oxide spherules, hydrous zirconium oxide gels such as gel slabs, films, capillary and electrophoresis gels, zirconium monohydrogen phosphate spherules, hydrous zirconium oxide spherules having suspendable particles homogeneously embedded within to form a composite sorbent, zirconium monohydrogen phosphate spherules having suspendable particles of at least one different sorbent homogeneously embedded within to form a composite sorbent having a desired crystallinity, zirconium oxide spherules having suspendable particles homogeneously embedded within to form a composite, hydrous zirconium oxide fiber materials, zirconium oxide fiber materials, hydrous zirconium oxide fiber materials having suspendable particles homogeneously embedded within to form a composite, zirconium oxide fiber materials having suspendable particles homogeneously embedded within to form a composite and spherules of barium zirconate. The hydrous zirconium oxide spherules and gel forms prepared by the gel-sphere, internal gelation process are useful as inorganic ion exchangers, catalysts, getters and ceramics.

  16. Metal ion adsorption to complexes of humic acid and metal oxides: Deviations from the additivity rule

    SciTech Connect

    Vermeer, A.W.P.; McCulloch, J.K.; Van Riemsdijk, W.H.; Koopal, L.K.

    1999-11-01

    The adsorption of cadmium ions to a mixture of Aldrich humic acid and hematite is investigated. The actual adsorption to the humic acid-hematite complex is compared with the sum of the cadmium ion adsorptivities to each of the isolated components. It is shown that the sum of the cadmium ion adsorptivities is not equal to the adsorption to the complex. In general, the adsorption of a specific metal ion to the complex can be understood and qualitatively predicted using the adsorptivities to each of the pure components and taking into account the effect of the pH on the interaction between humic acid and iron oxide on the metal ion adsorption. Due to the interaction between the negatively charged humic acid and the positively charged iron oxide, the adsorption of metal ions on the mineral oxide in the complex will increase as compared to that on the isolated oxide, whereas the adsorption to the humic acid will decrease as compared to that on the isolated humic acid. As a result, the overall adsorption of a specific metal ion to the complex will be smaller than predicted by the additivity rule when this metal ion has a more pronounced affinity for the humic acid than for the mineral oxide, whereas it will be larger than predicted by the additivity rule when the metal ion has a higher affinity for the oxide than for the humic acid.

  17. The complex amino acid diet of Francisella in infected macrophages

    PubMed Central

    Barel, Monique; Ramond, Elodie; Gesbert, Gael; Charbit, Alain

    2015-01-01

    Francisella tularensis, the agent of the zoonotic disease tularemia, is a highly infectious bacterium for a large number of animal species and can be transmitted to humans by various means. The bacterium is able to infect a variety of cell types but replicates in mammalian hosts mainly in the cytosol of infected macrophages. In order to resist the stressful and nutrient-restricted intracellular environments, it encounters during its systemic dissemination, Francisella has developed dedicated stress resistance mechanisms and adapted its metabolic and nutritional needs. Recent data form our laboratory and from several other groups have shown that Francisella simultaneously relies on multiple host amino acid sources during its intracellular life cycle. This review will summarize how intracellular Francisella use different amino acid sources, and their role in phagosomal escape and/or cytosolic multiplication and systemic dissemination. We will first summarize the data that we have obtained on two amino acid transporters involved in Francisella phagosomal escape and cytosolic multiplication i.e., the glutamate transporter GadC and the asparagine transporter AnsP, respectively. The specific contribution of glutamate and asparagine to the physiology of the bacterium will be evoked. Then, we will discuss how Francisella has adapted to obtain and utilize host amino acid resources, and notably the contribution of host transporters and autophagy process in the establishment of a nutrient-replete intracellular niche. PMID:25705612

  18. Transition Metal Complexes of Phosphinous Acids Featuring a Quasichelating Unit: Synthesis, Characterization, and Hetero-bimetallic Complexes.

    PubMed

    Allefeld, Nadine; Bader, Julia; Neumann, Beate; Stammler, Hans-Georg; Ignat'ev, Nikolai; Hoge, Berthold

    2015-08-17

    Diorganophosphane oxides were employed as preligands for the synthesis of catalytically active transition metal complexes of the phosphinous acids (CF3)2POH and (C2F5)2POH. Their reactions with solid PtCl2 and PdCl2 led to the formation of mononuclear phosphinous acid complexes [Cl2M{P(R(f))2OH}2] (M = Pd, Pt; R(f) = C2F5, CF3), which can be crystallized, for example, as its pyridinium salts, 2[HPy](+)[Cl2Pd{P(CF3)2O}2](2-). In vacuo HCl is liberated from the neutral palladium complexes affording mixtures of di- and polynuclear complexes. Moreover, (C2F5)2POH was reacted with several β-diketonato complexes of palladium, platinum, and nickel yielding air- and moisture-stable complexes [(acac)M{[P(R(f))2O]2H}], featuring a quasichelating phosphinous acid phosphinito unit {P(R(f))2O···H···O(R(f))2P}(-). Treatment of [Ni(Cp)2] (Cp = cyclopentadienyl) and [(cod)RhCl]2 (cod = 1,5-cyclooctadiene) with (C2F5)2POH leads to the substitution of one Cp or chloro ligand by a quasichelating unit. The novel coordination compounds were characterized by NMR and IR spectroscopies, mass spectrometry, and X-ray diffraction analysis. The platinum complex [(acac)Pt{[P(C2F5)2O]2H}] (acac = acetylacetonato) was used for the construction of hetero-bimetallic complexes by the treatment with [(cod)RhCl]2 and [Ni(Cp)2]. The trinuclear bimetallic complex [{(acac)Pt[P(C2F5)2O]2}2Ni] is the first structurally characterized hetero-bimetallic species containing a bis(perfluoroalkyl)phosphinito bridge. PMID:26242286

  19. Supramolecular adducts based on weak interactions between the trimeric Lewis acid complex (perfluoro-ortho-phenylene)mercury and polypnictogen complexes.

    PubMed

    Fleischmann, Martin; Jones, James S; Balázs, Gábor; Gabbaï, François P; Scheer, Manfred

    2016-09-21

    Reactions of the trinuclear Lewis acid perfluoro-ortho-phenylene)mercury [(o-HgC6F4)3] (1) with the polypnictogen complex [CpMo(CO)2(η(3)-P3)] (2) containing a cyclo-P3 ligand and the series of E2 complexes [{CpMo(CO)2}2(μ,η(2):η(2)-E2)] (E = P(3a), As(3b), Sb(3c), Bi(3d)) are reported. In all cases, the reaction products show very weak interactions between the En ligand complexes and the Lewis acid 1, as evidenced by their highly dynamic behaviour in solution and the formation of adducts in the solid state showing HgE contacts below the respective sum of the van der Waals radii. The complexes 2 (P3), 3a (P2) and 3b (As2) show interactions of only one pnictogen atom with all three Hg atoms of 1. The complex 3c (Sb2) forms two adducts with 1 showing either a side-on coordination of the Sb2 dumbbell towards Hg or an end-on coordination of both Sb atoms towards two independent molecules of 1. The Bi2 complex 3d shows an almost parallel alignment of the Bi2 dumbbell situated above the center of the planar Lewis acid 1. The arrangements of the E2 complex series towards 1 are rationalized with the help of electrostatic potential maps obtained by DFT calculations. Finally the structural characterizations of a new modification of the free Sb2 complex 3c, the Bi2 complex 3d, the starting material of its preparation [Bi{CpMo(CO)3}3] (4) and an unprecedented 'Cr4As5' cluster 5 are presented. PMID:27461890

  20. Evaluation of structural and functional properties of chitosan-chlorogenic acid complexes.

    PubMed

    Wei, Zihao; Gao, Yanxiang

    2016-05-01

    The objectives of the present study were to first synthesize chitosan-chlorogenic acid (CA) covalent complex and then compare structural and functional properties between chitosan-CA covalent complex and physical complex. First, chitosan-CA covalent complex was synthesized and its total phenolic content was as high as 276.5 ± 6.2 mg/g. Then structural and functional properties of chitosan-CA covalent and physical complexes were analyzed. The covalent reaction induced formation of both amide and ester bonds in chitosan. Data of X-ray diffraction (XRD) and scanning electron microscopy (SEM) indicated that the complexations of CA changed crystallinity and morphology of chitosan, and covalent complexation induced a larger change of physical structure than physical complexation. In terms of functional properties, chitosan-CA covalent complex exhibited better thermal stability than physical complex in terms of antioxidant activity, and the viscosity of chitosan was significantly increased by covalent modification. PMID:26820353

  1. Superiority of zinc complex of acetylsalicylic acid to acetylsalicylic acid in preventing postischemic myocardial dysfunction.

    PubMed

    Korkmaz, Sevil; Atmanli, Ayhan; Li, Shiliang; Radovits, Tamás; Hegedűs, Peter; Barnucz, Enikő; Hirschberg, Kristóf; Loganathan, Sivakkanan; Yoshikawa, Yutaka; Yasui, Hiroyuki; Karck, Matthias; Szabó, Gábor

    2015-09-01

    The pathophysiology of ischemic myocardial injury involves cellular events, reactive oxygen species, and an inflammatory reaction cascade. The zinc complex of acetylsalicylic acid (Zn(ASA)2) has been found to possess higher anti-inflammatory and lower ulcerogenic activities than acetylsalicylic acid (ASA). Herein, we studied the effects of both ASA and Zn(ASA)2 against acute myocardial ischemia. Rats were pretreated with ASA (75 mg/kg) or Zn(ASA)2 (100 mg/kg) orally for five consecutive days. Isoproterenol (85 mg/kg, subcutaneously [s.c.]) was applied to produce myocardial infarction. After 17-22 h, animals were anesthetized with sodium pentobarbital (60 mg/kg, intraperitoneally [i.p.]) and both electrical and mechanical parameters of cardiac function were evaluated in vivo. Myocardial histological and gene expression analyses were performed. In isoproterenol-treated rats, Zn(ASA)2 treatment normalized significantly impaired left-ventricular contractility index (Emax 2.6 ± 0.7 mmHg/µL vs. 4.6 ± 0.5 mmHg/µL, P < 0.05), increased stroke volume (30 ± 3 µL vs. 50 ± 6 µL, P < 0.05), decreased systemic vascular resistance (7.2 ± 0.7 mmHg/min/mL vs. 4.2 ± 0.5 mmHg/min/mL, P < 0.05) and reduced inflammatory infiltrate into the myocardial tissues. ECG revealed a restoration of elevated ST-segment (0.21 ± 0.03 mV vs. 0.09 ± 0.02 mV, P < 0.05) and prolonged QT-interval (79.2 ± 3.2 ms vs. 69.5 ± 2.5 ms, P < 0.05) by Zn(ASA)2. ASA treatment did not result in an improvement of these parameters. Additionally, Zn(ASA)2 significantly increased the mRNA-expression of superoxide dismutase 1 (+73 ± 15%), glutathione peroxidase 4 (+44 ± 12%), and transforming growth factor (TGF)-β1 (+102 ± 22%). In conclusion, our data demonstrate that oral administration of zinc and ASA in the form of bis(aspirinato)zinc(II) complex is superior to ASA in preventing electrical

  2. Metal ion complexation properties of fulvic acids extracted from composted sewage sludge as compared to a soil fulvic acid.

    PubMed

    Esteves da Silva, Joaquim C G; Oliveira, César J S

    2002-07-01

    Complexation properties of an anthropogenic fulvic acid (FA) extracted from a composted sewage sludge (csFA) for Cu(II), Pb(II) and Cd(II) were studied at pH=6 and at a concentration of 25 mg L(-1). For the case of Cu(II), a particular analysis of the complexation phenomena was done at pH values of 3, 4, 5 and 6 and at aqueous FA concentrations of 25, 50 and 100 mg L(-1) by synchronous excitation molecular fluorescence spectroscopy (SyF). Potentiometric titrimetry with Cu(II), Pb(II), Cd(II) and H+ ion-selective electrodes and acid-base conductimetric titrations were used to obtain experimental information about the acid properties and complexation phenomena. A comparison of the results obtained for csFA with a natural soil FA (sFA) was made. Differences have been detected in the structural composition of the two samples and in the structure of the binding sites. In the csFA, binding site structures containing nitrogen probably play an important role in the complexation, besides oxygen containing structures. Complexation by sFA is mainly due to carboxylic and phenolic structures. Nevertheless, this work shows that csFA have macroscopic complexation properties (magnitude of the conditional stability constant and binding sites concentration) somewhat similar to the natural sFA samples. PMID:12188141

  3. The properties of solid Zn(II)-amino acid complexes in the form of suspensions.

    PubMed

    Dolińska, B

    2001-10-01

    An investigation was made into the experimental conditions for the formation of poorly soluble complexes of the divalent Zinc(II) combined with the following selected amino acids: tyrosine, tryptophan, cysteine, histidine, and alanine, in the form of suspensions for parenteral administration. The number of Zn(II)-binding sites in the amino acid (n) as well as the amino acid affinity to Zn(II) (Ka), were determined. Cysteine was found to have the highest number of Zn(II)-binding sites--3, whereas alanine the lowest--1. In the conditions described herein, Zn(II) amino acid complexes of diverse stability (durability) were obtained. The analysis of the kinetics of the binding revealed that the most stable complexes were those formed by Zn(II) in combination with tryptophan (Ka = 405.78 microM(-1) +/- 12.17), and with tyrosine (Ka = 343.88 microM +/- 22.35); whereas the least stable complexes were those formed by Zn(II) in combination with histidine (Ka = 29.90 microM +/- 4.78), and with alanine (Ka = 13.0 microM(-1) +/- 1.04). Cysteine formed complexes of intermediate stability (Ka = 168.53 microM(-1) +/- 12.36). The stability ofthe Zn(II) amino acid complexes obtained was conditioned by both the molecular weight (P = 0.033) of the amino acid and its isoelectric point (P < 0.001). PMID:11718265

  4. [Study of the circular dichroism for tribasic complex of amine derivative of beta-cyclodextrindien-Cu2+ -benzoic acid].

    PubMed

    Hu, J; Zhang, H; Shen, B

    1998-02-01

    The circular dichroism spectra of beta-cyclodextrindien, beta-cyclodextrindien-Cu2+ complex, beta-cyclodextrindien-benzoic acid complex, tribasic complex of beta-cyclodextrindien-Cu2+ -benzoic acid were determined by using JASCO J-20C automatic recording spectropolarimeter. The attribution of the bands obtained were made according to the order of orbit energy of Cu2+ complex and benzoic acid, and the coordination structure of tribasic complex of amine derivative of beta-cyclodextrindien-Cu2+ -benzoic acid were decided acording to the structure character of Cu2+ complex and KAJART sector rule of inclusion complex of beta-cyclodextrindien with aromatic compounds. PMID:15810322

  5. Metal complexes of salicylhydroxamic acid (H2Sha), anthranilic hydroxamic acid and benzohydroxamic acid. Crystal and molecular structure of [Cu(phen)2(Cl)]Cl x H2Sha, a model for a peroxidase-inhibitor complex.

    PubMed

    O'Brien, E C; Farkas, E; Gil, M J; Fitzgerald, D; Castineras, A; Nolan, K B

    2000-04-01

    Stability constants of iron(III), copper(II), nickel(II) and zinc(II) complexes of salicylhydroxamic acid (H2Sha), anthranilic hydroxamic acid (HAha) and benzohydroxamic acid (HBha) have been determined at 25.0 degrees C, I=0.2 mol dm(-3) KCl in aqueous solution. The complex stability order, iron(III) > copper(II) > nickel(II) approximately = zinc(II) was observed whilst complexes of H2Sha were found to be more stable than those of the other two ligands. In the preparation of ternary metal ion complexes of these ligands and 1,10-phenanthroline (phen) the crystalline complex [Cu(phen)2(Cl)]Cl x H2Sha was obtained and its crystal structure determined. This complex is a model for hydroxamate-peroxidase inhibitor interactions. PMID:10830846

  6. Method of making crack-free zirconium hydride

    DOEpatents

    Sullivan, Richard W.

    1980-01-01

    Crack-free hydrides of zirconium and zirconium-uranium alloys are produced by alloying the zirconium or zirconium-uranium alloy with beryllium, or nickel, or beryllium and scandium, or nickel and scandium, or beryllium and nickel, or beryllium, nickel and scandium and thereafter hydriding.

  7. SEPARATION OF POLONIUM, PROTACTINIUM OR MIXTURES THEREOF IN AQUEOUS SOLUTION FROM BISMUTH, LEAD, ZIRCONIUM AND/OR COLUMBIUM VALUES

    DOEpatents

    Van Winkle, Q.; Kraus, K.A.

    1959-10-27

    A process is presented for separating polonium, protactinium, or mixtures thereof in aqueous solution from bismuth, zirconium, lead, and niobium values contained in the solution. The method comprises providing hydrochloric acid in the solution in a concentration of at least 5N. contacting the aqueous solution with a substantially waterimmiscible organic solvent such as diisopropyl ketone, and separating the aqueous phase containing the bismuth, zirconium, lead, and niobium from the organic extract phase containing the polonium, protactinium, or mixture thereof.

  8. Complexation of di-amides of dipicolinic acid with neodymium

    SciTech Connect

    Lapka, J.L.; Paulenova, A.

    2013-07-01

    Di-amides have undergone significant studies as possible ligands for use in the partitioning of trivalent minor actinides and lanthanides. The binding affinities of three isomeric ligands with neodymium in acetonitrile solution have been investigated. The stability constants of the metal-ligand complexes formed between different isomers of N,N'-diethyl-N,N'- ditolyl-di-picolinamide (EtTDPA) and trivalent neodymium in acetonitrile have been determined by spectrophotometric and calorimetric methods. Each isomer of EtTDPA has been found to be capable of forming three complexes with trivalent neodymium, Nd(EtTDPA), Nd(EtTDPA){sub 2}, and Nd(EtTDPA){sub 3}. Values from spectrophotometric and calorimetric titrations are within reasonable agreement with each other. The order of stability constants for each metal:ligand complex decreases in the order Et(m)TDPA > Et(p)TDPA > Et(o)TDPA. The obtained values are comparable to other di-amidic ligands obtained under similar system conditions and mirror previously obtained solvent extraction data for EtTDPA at low ionic strengths. (authors.

  9. Analysis of Complexation Equilibria of Polyacrylic Acid by a Donnan-Based Concept

    PubMed

    Miyajima; Mori; Ishiguro

    1997-03-01

    Complexation equilibria of uni- and divalent metal ions (Ag+, Ca2+, Cu2+, and Pb2+) with polyacrylic acid (PAA) have been studied at various degrees of dissociation (alpha) of PAA under different sodium salt concentration levels at 25°C. Both pH and pM(MZ+ = Ag+, Ca2+, Cu2+, and Pb2+) of equilibrium mixture solutions of MZ+/PAA/Na+ (excess) have been determined concurrently by a potentiometric titration method. The electrostatic effect inherent in the polyion-metal ion binding equilibria has been evaluated by a Donnan-based concept and is corrected for by the use of a nonideality term of acid dissociation equilibria of the polyacid as a probe. For Ag+-PAA and Ca2+-PAA bindings, only monodentate ligand complexes, (MA)(Z-1), have proven to be formed, whereas for Cu2+ and Pb2+ ion bindings, formation of both monodentate and bidentate ligand complexes have been observed. For both Cu2+-PAA and Pb2+-PAA systems, bidentate carboxylate complex formation is predominant at alpha > ca. 0.3, whereas at alpha < ca. 0.3, formation of monodentate carboxylate complexes becomes appreciable as alpha decreases. Stability constants of these complexes together with the intra-molecular complexation equilibrium constants expressed by the ratio of the concentrations of bidentate complexes to monodentate complexes have successfully been evaluated and are compared with each other in order to discuss the multidentate complexation properties of the polycarboxylic acid. PMID:9245334

  10. Preparation of solid drug/cyclodextrin complexes of acidic and basic drugs.

    PubMed

    Loftsson, T; Sigurdsson, H H; Másson, M; Schipper, N

    2004-01-01

    One of the main obstacles in pharmaceutical applications of cyclodextrins is their increase of the formulation bulk. Even at maximum incorporation 500 mg of a solid drug/cyclodextrin complex will only contain between 50 and 125 mg of the drug, assuming a low molecular weight drug (MW 200 to 400 Dalton) and an average molecular weight cyclodextrin (MW about 1500 Dalton). In general, the complexation efficiency is low and consequently the complex powder contains a significant amount of empty cyclodextrin molecules. In the present study the complexation efficiency is increased by ionization of the drug molecule through addition of volatile acid (i.e. acetic acid) or base (i.e. ammonia) to the aqueous complexation media of basic or acidic drugs, respectively. The volatile acid or base was then removed during lyophilization and heating in a vacuum oven resulting in formation of solid cyclodextrin complexes of the unionized drug. Thus, the complexation efficiency was temporary increased by the ionization but then again decreased leading to formation of the thermodynamically unstable solid drug/cyclodextrin complexes. When dissolved the energy of the system was lowered by expelling the drug molecules from the cyclodextrin cavities resulting in formation of supersaturated drug solutions and ultimately precipitation of the drug. PMID:14964417

  11. Luminescent and triboluminescent properties of europium(III) complex with cinnamic acid

    NASA Astrophysics Data System (ADS)

    Kalinovskaya, I. V.; Mirochnik, A. G.; Nagornyi, I. G.

    2014-10-01

    An intensely emitting crystalline europium(III) complex with cinnamic acid [Eu(Cin)3] n and exhibiting triboluminescent properties is synthesized. It is established that the measured photo- and triboluminescence spectra are identical for the above polymeric non-centrosymmetric complex and are determined by the characteristic f-f luminescence of the europium(III) ion.

  12. Synthesis of zirconium tungstate-zirconia core-shell composite particles

    SciTech Connect

    Khazeni, Nasser; Mavis, Bora; Guenduez, Guengoer; Colak, Uner

    2011-11-15

    Highlights: {yields} ZrW{sub 2}O{sub 8}-ZrO{sub 2} core-shell particles to offer solutions for sintering problems. {yields} Core synthesis by a precursor based on tungstic acid and zirconium acetate. {yields} Shell phase by urea hydrolysis in the presence of zirconium ions. {yields} [Urea]/[ZrOCl{sub 2}] ratio controls the rate of shell precursor precipitation. -- Abstract: In this work, ZrW{sub 2}O{sub 8}-ZrO{sub 2} core-shell composite particles were synthesized. ZrW{sub 2}O{sub 8} that was used in the core is a material with negative coefficient of thermal expansion, and it was synthesized from a high-pH precursor based on use of tungstic acid and zirconium acetate. Shell layer was composed of ZrO{sub 2} nanocrystallites and precipitated from an aqueous solution by urea hydrolysis. While volume of the shell was effectively controlled by the initial zirconium ion concentration in the solutions, the rate of precipitation was a function of the ratio of initial concentrations of urea to zirconium ions. It is hypothesized that isolation of the ZrW{sub 2}O{sub 8} within a layer of ZrO{sub 2}, will be a key element in solving problems associated with reactivity of ZrW{sub 2}O{sub 8} towards other components in sintering of ceramic-ceramic composites with tuned or zero thermal expansion coefficient.

  13. Thermodynamics of lanthanide and uranyl complexes with tetrahydrofuran-2,3,4,5-tetracarboxylic acid (THFTCA).

    SciTech Connect

    Morss, L. R.; Nash, K. L.; Tennessee Technological Univ.

    2000-01-01

    We present the results of an investigation of the thermochemistry of the complexation of La{sup 3+} Nd{sup 3+}, Eu{sup 3+}, Dy{sup 3+}, Tm{sup 3+}, and UO{sub 2}{sup 2+} by tetrahydrofuran-2,3,4,5-tetracarboxylic acid (THFTCA). This predisposed structural analog to oxydiacetic acid (ODA) has been previously shown both to exhibit greater sensitivity to lanthanide cation radius than complexes with the unconstrained ODA and to form anomalously weak complexes with UO{sub 2}{sup 2+}. Our purpose is to interpret these observations in terms of the balance between enthalpy and entropy contributions to the overall complexation thermodynamics. Enthalpies have been calculated from titration calorimetry experiments both for the protonation of the free ligand and for the formation of selected 1:1 and 1:2 complexes in pH 2-3 acidic media (I = 0.1 M). The complexation entropies for the lanthanide complexes have been calculated using the previously reported stability constants for the MH{sub 2}L{sup +}, MHL, and M(H{sub 2}L){sup 2-}. The stability constants for the uranyl complexes have been determined by potentiometric titration and these values used to calculate the thermodynamic parameters. Complexation enthalpies for the 1:1 lanthanide-THFTCA complexes (MH{sub 2}L{sup +} species) are nearly identical to those of the lanthanide ODA complexes. Therefore, the size-selectivity observed in the lanthanide-THFTCA complexes arises from the complexation entropy. The comparative weakness of the uranyl complexes with THFTCA also is accounted for thermodynamically in the entropy term. Calculations based on an electrostatic model for complexation entropy and molecular mechanics modeling are used to help interpret the experimental results.

  14. Method of etching zirconium diboride

    SciTech Connect

    Heath, L.S.; Kwiatkowski, B.

    1988-03-31

    The invention described herein may be manufactured, used, and licensed by or for the Government for governmental purposes without the payment to us of any royalty thereon. This invention relates in general to a method of etching, zirconium diboride(ZrB/sub 2/) and, in particular, to a method of dry etching a thin film of ZrB/sub 2/ that has been deposited onto a substrate and patterned using photolithography. U.S. patent application S.N. 156, 124, filed 16 February, 1988, of Linda S. Heath for Method of Etching Titanium Diboride and assigned to a common assignee and with which this application is copending describes and claims a method of etching titanium diboride with a dry etch. Zirconium diboride, like titanium diboride, TiB/sub 2/, has become of interest in laboratory research because of its resistance to change or degradation at high temperatures. By adjusting the process parameters, one is able to attain etch rates of 67 to 140 A/min for ZrB/sub 2/. This is useful for patterning ZrB/sub 2/ as a diffusion barrier or a Schottky contact to semiconductors. The ZrB/sub 2/ film may be on a GaAs substrate.

  15. Spectra, energy levels, and energy transition of lanthanide complexes with cinnamic acid and its derivatives.

    PubMed

    Zhou, Kaining; Feng, Zhongshan; Shen, Jun; Wu, Bing; Luo, Xiaobing; Jiang, Sha; Li, Li; Zhou, Xianju

    2016-04-01

    High resolution spectra and luminescent lifetimes of 6 europium(III)-cinnamic acid complex {[Eu2L6(DMF)(H2O)]·nDMF·H2O}m (L=cinnamic acid I, 4-methyl-cinnamic acid II, 4-chloro-cinnamic acid III, 4-methoxy-cinnamic acid IV, 4-hydroxy-cinnamic acid V, 4-nitro-cinnamic acid VI; DMF=N, N-dimethylformamide, C3H7NO) were recorded from 8 K to room temperature. The energy levels of Eu(3+) in these 6 complexes are obtained from the spectra analysis. It is found that the energy levels of the central Eu(3+) ions are influenced by the nephelauxetic effect, while the triplet state of ligand is lowered by the p-π conjugation effect of the para-substituted functional groups. The best energy matching between the ligand triplet state and the central ion excited state is found in complex I. While the other complexes show poorer matching because the gap of (5)D0 and triplet state contracts. PMID:26802538

  16. Spectra, energy levels, and energy transition of lanthanide complexes with cinnamic acid and its derivatives

    NASA Astrophysics Data System (ADS)

    Zhou, Kaining; Feng, Zhongshan; Shen, Jun; Wu, Bing; Luo, Xiaobing; Jiang, Sha; Li, Li; Zhou, Xianju

    2016-04-01

    High resolution spectra and luminescent lifetimes of 6 europium(III)-cinnamic acid complex {[Eu2L6(DMF)(H2O)]·nDMF·H2O}m (L = cinnamic acid I, 4-methyl-cinnamic acid II, 4-chloro-cinnamic acid III, 4-methoxy-cinnamic acid IV, 4-hydroxy-cinnamic acid V, 4-nitro-cinnamic acid VI; DMF = N, N-dimethylformamide, C3H7NO) were recorded from 8 K to room temperature. The energy levels of Eu3 + in these 6 complexes are obtained from the spectra analysis. It is found that the energy levels of the central Eu3 + ions are influenced by the nephelauxetic effect, while the triplet state of ligand is lowered by the p-π conjugation effect of the para-substituted functional groups. The best energy matching between the ligand triplet state and the central ion excited state is found in complex I. While the other complexes show poorer matching because the gap of 5D0 and triplet state contracts.

  17. [Preparation and spectra of the complexes of the first series transition metals with diphenic acid].

    PubMed

    Wu, Ai-zhi; Wang, Jian-jun; Ren, Yan-wei; Chen, Jing; Li, Jun; Zhang, Feng-xing

    2004-04-01

    The ligand diphenic acid has been synthesized and the corresponding complexes of transition metal Co, Ni and Mn with diphenic acid have been prepared and characterized by the elementary analysis, IR spectra and ultraviolet-visible spectra. The results of IR show that the vas and vs of -CO2- in the complexes are lower than those of ligand diphenic acid, which can be explained by the coordinating between metal and ligand. In addition, compared with the complex IR spectra, the IR spectra of ligand became complicated due to the ligand polymerization through hydrogen bond. The UV-Vis spectra show that the ligand has three absorption peaks at 288, 273 and 270 nm, respectively, and these are slightly shifted in the complexes. Because the metal d-d absorption is weak, only in Co(C14H8O4) x 2H2O there is a d-d absorption at 537 nm. PMID:15766146

  18. Crystallization of bFGF-DNA Aptamer Complexes Using a Sparse Matrix Designed for Protein-Nucleic Acid Complexes

    NASA Technical Reports Server (NTRS)

    Cannone, Jaime J.; Barnes, Cindy L.; Achari, Aniruddha; Kundrot, Craig E.; Whitaker, Ann F. (Technical Monitor)

    2001-01-01

    The Sparse Matrix approach for obtaining lead crystallization conditions has proven to be very fruitful for the crystallization of proteins and nucleic acids. Here we report a Sparse Matrix developed specifically for the crystallization of protein-DNA complexes. This method is rapid and economical, typically requiring 2.5 mg of complex to test 48 conditions. The method was originally developed to crystallize basic fibroblast growth factor (bFGF) complexed with DNA sequences identified through in vitro selection, or SELEX, methods. Two DNA aptamers that bind with approximately nanomolar affinity and inhibit the angiogenic properties of bFGF were selected for co-crystallization. The Sparse Matrix produced lead crystallization conditions for both bFGF-DNA complexes.

  19. Synthesis, spectral studies and biological evaluation of 2-aminonicotinic acid metal complexes.

    PubMed

    Nawaz, Muhammad; Abbasi, Muhammad Waseem; Hisaindee, Soleiman; Zaki, Muhammad Javed; Abbas, Hira Fatima; Mengting, Hu; Ahmed, M Arif

    2016-05-15

    We synthesized 2-aminonicotinic acid (2-ANA) complexes with metals such as Co(II), Fe(III), Ni(II), Mn(II), Zn(II), Ag(I),Cr(III), Cd(II) and Cu(II) in aqueous media. The complexes were characterized and elucidated using FT-IR, UV-Vis, a fluorescence spectrophotometer and thermo gravimetric analysis (TGA). TGA data showed that the stoichiometry of complexes was 1:2 metal/ligand except for Ag(I) and Mn(II) where the ratio was 1:1. The metal complexes showed varied antibacterial, fungicidal and nematicidal activities. The silver and zinc complexes showed highest activity against Bacillus subtilis and Bacillus licheniformis respectively. Fusarium oxysporum was highly susceptible to nickel and copper complexes whereas Macrophomina phaseolina was completely inert to the complexes. The silver and cadmium complexes were effective against the root-knot nematode Meloidogyne javanica. PMID:26945123

  20. Synthesis, spectral studies and biological evaluation of 2-aminonicotinic acid metal complexes

    NASA Astrophysics Data System (ADS)

    Nawaz, Muhammad; Abbasi, Muhammad Waseem; Hisaindee, Soleiman; Zaki, Muhammad Javed; Abbas, Hira Fatima; Mengting, Hu; Ahmed, M. Arif

    2016-05-01

    We synthesized 2-aminonicotinic acid (2-ANA) complexes with metals such as Co(II), Fe(III), Ni(II), Mn(II), Zn(II), Ag(I),Cr(III), Cd(II) and Cu(II) in aqueous media. The complexes were characterized and elucidated using FT-IR, UV-Vis, a fluorescence spectrophotometer and thermo gravimetric analysis (TGA). TGA data showed that the stoichiometry of complexes was 1:2 metal/ligand except for Ag(I) and Mn(II) where the ratio was 1:1. The metal complexes showed varied antibacterial, fungicidal and nematicidal activities. The silver and zinc complexes showed highest activity against Bacillus subtilis and Bacillus licheniformis respectively. Fusarium oxysporum was highly susceptible to nickel and copper complexes whereas Macrophomina phaseolina was completely inert to the complexes. The silver and cadmium complexes were effective against the root-knot nematode Meloidogyne javanica.

  1. Accurate ab initio prediction of NMR chemical shifts of nucleic acids and nucleic acids/protein complexes

    PubMed Central

    Victora, Andrea; Möller, Heiko M.; Exner, Thomas E.

    2014-01-01

    NMR chemical shift predictions based on empirical methods are nowadays indispensable tools during resonance assignment and 3D structure calculation of proteins. However, owing to the very limited statistical data basis, such methods are still in their infancy in the field of nucleic acids, especially when non-canonical structures and nucleic acid complexes are considered. Here, we present an ab initio approach for predicting proton chemical shifts of arbitrary nucleic acid structures based on state-of-the-art fragment-based quantum chemical calculations. We tested our prediction method on a diverse set of nucleic acid structures including double-stranded DNA, hairpins, DNA/protein complexes and chemically-modified DNA. Overall, our quantum chemical calculations yield highly/very accurate predictions with mean absolute deviations of 0.3–0.6 ppm and correlation coefficients (r2) usually above 0.9. This will allow for identifying misassignments and validating 3D structures. Furthermore, our calculations reveal that chemical shifts of protons involved in hydrogen bonding are predicted significantly less accurately. This is in part caused by insufficient inclusion of solvation effects. However, it also points toward shortcomings of current force fields used for structure determination of nucleic acids. Our quantum chemical calculations could therefore provide input for force field optimization. PMID:25404135

  2. Accurate ab initio prediction of NMR chemical shifts of nucleic acids and nucleic acids/protein complexes.

    PubMed

    Victora, Andrea; Möller, Heiko M; Exner, Thomas E

    2014-12-16

    NMR chemical shift predictions based on empirical methods are nowadays indispensable tools during resonance assignment and 3D structure calculation of proteins. However, owing to the very limited statistical data basis, such methods are still in their infancy in the field of nucleic acids, especially when non-canonical structures and nucleic acid complexes are considered. Here, we present an ab initio approach for predicting proton chemical shifts of arbitrary nucleic acid structures based on state-of-the-art fragment-based quantum chemical calculations. We tested our prediction method on a diverse set of nucleic acid structures including double-stranded DNA, hairpins, DNA/protein complexes and chemically-modified DNA. Overall, our quantum chemical calculations yield highly/very accurate predictions with mean absolute deviations of 0.3-0.6 ppm and correlation coefficients (r(2)) usually above 0.9. This will allow for identifying misassignments and validating 3D structures. Furthermore, our calculations reveal that chemical shifts of protons involved in hydrogen bonding are predicted significantly less accurately. This is in part caused by insufficient inclusion of solvation effects. However, it also points toward shortcomings of current force fields used for structure determination of nucleic acids. Our quantum chemical calculations could therefore provide input for force field optimization. PMID:25404135

  3. Ternary complexation of carvedilol, beta-cyclodextrin and citric acid for mouth-dissolving tablet formulation.

    PubMed

    Pokharkar, Varsha; Khanna, Abhishek; Venkatpurwar, Vinod; Dhar, Sheetal; Mandpe, Leenata

    2009-06-01

    The purpose of this study was to improve the solubility and dissolution rate of carvedilol by forming a ternary complex with beta-cyclodextrin and citric acid and to formulate its mouth-dissolving tablets. The rationale for preparing mouth-dissolving tablet of carvedilol was to make the drug available in a soluble form in the mouth, which would facilitate its absorption from the buccal cavity. This would help to overcome its first-pass metabolism and thereby improve bioavailability. Phase solubility studies revealed the ability of beta-cyclodextrin and citric acid to complex with carvedilol and significantly increase its solubility. Ternary complexation of carvedilol was carried out with beta-cyclodextrin and citric acid by physical mixing, kneading and spray drying methods and the prepared complexes were characterized by Fourier transform infra red spectroscopy, differential scanning calorimetry, powder X-ray diffractometry, scanning electron microscopy and complexation efficiency. The complex obtained by the spray drying method resulted in highest complexation efficiency and a 110-fold increase in the solubility of carvedilol. The mouth-dissolving tablets formulated using the spray dried complex with suitable excipients showed 100 % dissolution within five minutes. Accelerated stability studies of mouth-dissolving tablets carried out as per ICH guidelines revealed that the tablets were stable. PMID:19564138

  4. A complex of equine lysozyme and oleic acid with bactericidal activity against Streptococcus pneumoniae.

    PubMed

    Clementi, Emily A; Wilhelm, Kristina R; Schleucher, Jürgen; Morozova-Roche, Ludmilla A; Hakansson, Anders P

    2013-01-01

    HAMLET and ELOA are complexes consisting of oleic acid and two homologous, yet functionally different, proteins with cytotoxic activities against mammalian cells, with HAMLET showing higher tumor cells specificity, possibly due to the difference in propensity for oleic acid binding, as HAMLET binds 5-8 oleic acid molecules per protein molecule and ELOA binds 11-48 oleic acids. HAMLET has been shown to possess bactericidal activity against a number of bacterial species, particularly those with a respiratory tropism, with Streptococcus pneumoniae displaying the greatest degree of sensitivity. We show here that ELOA also displays bactericidal activity against pneumococci, which at lower concentrations shows mechanistic similarities to HAMLET's bactericidal activity. ELOA binds to S. pneumoniae and causes perturbations of the plasma membrane, including depolarization and subsequent rupture, and activates an influx of calcium into the cells. Selective inhibition of calcium channels and sodium/calcium exchange activity significantly diminished ELOA's bactericidal activity, similar to what we have observed with HAMLET. Finally, ELOA-induced death was also accompanied by DNA fragmentation into high molecular weight fragments - an apoptosis-like morphological phenotype that is seen during HAMLET-induced death. Thus, in contrast to different mechanisms of eukaryote cell death induced by ELOA and HAMLET, these complexes are characterized by rather similar activities towards bacteria. Although the majority of these events could be mimicked using oleic acid alone, the concentrations of oleic acid required were significantly higher than those present in the ELOA complex, and for some assays, the results were not identical between oleic acid alone and the ELOA complex. This indicates that the lipid, as a common denominator in both complexes, is an important component for the complexes' bactericidal activities, while the proteins are required both to solubilize and/or present the

  5. Membrane protein complexes catalyze both 4- and 3-hydroxylation of cinnamic acid derivatives in monolignol biosynthesis.

    PubMed

    Chen, Hsi-Chuan; Li, Quanzi; Shuford, Christopher M; Liu, Jie; Muddiman, David C; Sederoff, Ronald R; Chiang, Vincent L

    2011-12-27

    The hydroxylation of 4- and 3-ring carbons of cinnamic acid derivatives during monolignol biosynthesis are key steps that determine the structure and properties of lignin. Individual enzymes have been thought to catalyze these reactions. In stem differentiating xylem (SDX) of Populus trichocarpa, two cinnamic acid 4-hydroxylases (PtrC4H1 and PtrC4H2) and a p-coumaroyl ester 3-hydroxylase (PtrC3H3) are the enzymes involved in these reactions. Here we present evidence that these hydroxylases interact, forming heterodimeric (PtrC4H1/C4H2, PtrC4H1/C3H3, and PtrC4H2/C3H3) and heterotrimeric (PtrC4H1/C4H2/C3H3) membrane protein complexes. Enzyme kinetics using yeast recombinant proteins demonstrated that the enzymatic efficiency (V(max)/k(m)) for any of the complexes is 70-6,500 times greater than that of the individual proteins. The highest increase in efficiency was found for the PtrC4H1/C4H2/C3H3-mediated p-coumaroyl ester 3-hydroxylation. Affinity purification-quantitative mass spectrometry, bimolecular fluorescence complementation, chemical cross-linking, and reciprocal coimmunoprecipitation provide further evidence for these multiprotein complexes. The activities of the recombinant and SDX plant proteins demonstrate two protein-complex-mediated 3-hydroxylation paths in monolignol biosynthesis in P. trichocarpa SDX; one converts p-coumaric acid to caffeic acid and the other converts p-coumaroyl shikimic acid to caffeoyl shikimic acid. Cinnamic acid 4-hydroxylation is also mediated by the same protein complexes. These results provide direct evidence for functional involvement of membrane protein complexes in monolignol biosynthesis. PMID:22160716

  6. Rapid complexing of oxoacylglycerols with amino acids, peptides and aminophospholipids.

    PubMed

    Kurvinen, J P; Kuksis, A; Ravandi, A; Sjövall, O; Kallio, H

    1999-03-01

    We prepared model Schiff bases from 2-[9-oxo]nonanoyl glycerol (2-MAG-ALD) and various amino compounds. 2-MAG-ALD was obtained by pancreatic lipase hydrolysis of trioleoyl glycerol and reductive ozonolysis of the resulting 2-monooleoyl glycerol. The reaction products were purified by thin-layer chromatography. Schiff bases were synthesized in greater than 50% yield by reacting 2-MAG-ALD with twofold molar excess of valine, Nalpha-acetyl-L-lysine methyl ester and the tripeptides glycyl-glycyl-glycine, glycyl-glycyl-histidine, and glycyl-histidyl-lysine in aqueous methanol and with 1-palmitoyl-2-stearoyl glycerophosphoethanolamine (PE) in chloroform/methanol for 16 h at room temperature. Prior to analysis the bases were reduced with sodium cyanoborohydride in methanol for 30 min at 4 degrees C. Reaction products were analyzed by high-performance liquid chromatography/electrospray ionization/mass spectrometry (HPLC/ESI/MS). Reduced Schiff bases of 2-MAG-ALD with PE and amino acids were analyzed by normal-phase HPLC/ESI/MS and those with peptides by reversed-phase HPLC/ESI/MS. Single adducts were obtained in all cases and both the alpha-amino group of valine and the epsilon-amino group of Nalpha-acetyl-L-lysine methyl ester were reactive. Molecular ions of reaction products were the only detected ions in the negative ionization mode, whereas in the positive ion mode sodiated molecular ions were also detected. The present study suggests that 2-MAG-ALD may form Schiff base adducts with amino compounds in other aqueous media, such as the intestinal lumen and in the hydrophobic environment of cell membranes. PMID:10230725

  7. Complex formation with nucleic acids and aptamers alters the antigenic properties of platelet factor 4

    PubMed Central

    Jaax, Miriam E.; Krauel, Krystin; Marschall, Thomas; Brandt, Sven; Gansler, Julia; Fürll, Birgitt; Appel, Bettina; Fischer, Silvia; Block, Stephan; Helm, Christiane A.; Müller, Sabine; Preissner, Klaus T.

    2013-01-01

    The tight electrostatic binding of the chemokine platelet factor 4 (PF4) to polyanions induces heparin-induced thrombocytopenia, a prothrombotic adverse drug reaction caused by immunoglobulin G directed against PF4/polyanion complexes. This study demonstrates that nucleic acids, including aptamers, also bind to PF4 and enhance PF4 binding to platelets. Systematic assessment of RNA and DNA constructs, as well as 4 aptamers of different lengths and secondary structures, revealed that increasing length and double-stranded segments of nucleic acids augment complex formation with PF4, while single nucleotides or single-stranded polyA or polyC constructs do not. Aptamers were shown by circular dichroism spectroscopy to induce structural changes in PF4 that resemble those induced by heparin. Moreover, heparin-induced anti-human–PF4/heparin antibodies cross-reacted with human PF4/nucleic acid and PF4/aptamer complexes, as shown by an enzyme immunoassay and a functional platelet activation assay. Finally, administration of PF4/44mer–DNA protein C aptamer complexes in mice induced anti–PF4/aptamer antibodies, which cross-reacted with murine PF4/heparin complexes. These data indicate that the formation of anti-PF4/heparin antibodies in postoperative patients may be augmented by PF4/nucleic acid complexes. Moreover, administration of therapeutic aptamers has the potential to induce anti-PF4/polyanion antibodies and a prothrombotic diathesis. PMID:23673861

  8. Incorporation of Deoxyribonucleic Acid Precursors by T4 Deoxyribonucleic Acid-Protein Complexes Retained on Glass Fiber Filters

    PubMed Central

    Miller, Robert C.; Kozinski, Andrzej W.

    1970-01-01

    Bacteriophage T4 deoxyribonucleic acid (DNA)-protein complexes were retained preferentially on glass fiber filters. DNA polymerase activity in the complex was detected through the incorporation of 3H-labeled DNA precursors. The primer-product DNA hybridized with both phage and Escherichia coli DNA. Density labeling experiments showed that about 30% of incorporated 3H-deoxyadenosine triphosphate was found in DNA which hybridized with phage DNA; this DNA was found to be covalently attached to the primer DNA. PMID:5497903

  9. Non-covalent complexes of folic acid and oleic acid conjugated polyethylenimine: An efficient vehicle for antisense oligonucleotide delivery

    PubMed Central

    Yang, Shuang; Yang, Xuewei; Liu, Yan; Zheng, Bin; Meng, Lingjun; Lee, Robert J.; Xie, Jing; Teng, Lesheng

    2016-01-01

    Polyethylenimine (PEI) was conjugated to oleic acid (PEI-OA) and evaluated as a delivery agent for LOR-2501, an antisense oligonucleotide against ribonucleotide reductase R1 subunit. PEI-OA/LOR-2501 complexes were further coated with folic acid (FA/PEI-OA/LOR-2501) and evaluated in tumor cells. The level of cellular uptake of FA/PEI-OA/LOR-2501 was more than double that of PEI/LOR-2501 complexes, and was not affected by the expression level of folate receptor (FR) on the cell surface. Efficient delivery was seen in several cell lines. Furthermore, pathway specific cellular internalization inhibitors and markers were used to reveal the principal mechanism of cellular uptake. FA/PEI-OA/LOR-2501 significantly induced the downregulation of R1 mRNA and R1 protein. This novel formulation of FA/PEI-OA provides a reliable and highly efficient method for delivery of oligonucleotide and warrants further investigation. PMID:26263216

  10. Preparation and spectral investigation of inclusion complex of caffeic acid with hydroxypropyl-β-cyclodextrin

    NASA Astrophysics Data System (ADS)

    Zhang, Min; Li, Jinxia; Zhang, Liwei; Chao, Jianbin

    2009-01-01

    The inclusion complexation behavior of caffeic acid (CA) with hydroxypropyl-β-cyclodextrin (HP-β-CD) was studied by UV-vis, fluorescence spectroscopy and nuclear magnetic resonance spectroscopy (NMR). Experimental conditions including the concentration of HP-β-CD and media acidity were investigated in detail. The result suggested HP-β-CD was more suitable for including CA in acidity solution. The binding contants ( K) of the inclusion complexes were determined by linear regression analysis and the inclusion ratio was found to be 1:1. The water solubility of CA was increased by inclusion with HP-β-CD according to the phase-solubility diagram. The spatial configuration of complex has been proposed based on 1H NMR and two-dimensional (2D) NMR, the result suggested that CA was entrapped inside the hydrophobic core of HP-β-CD with the lipophilic aromatic ring and the portion of ethylene.

  11. Kinetics of acid hydrolysis and reactivity of some antibacterial hydrophilic iron(II) imino-complexes

    NASA Astrophysics Data System (ADS)

    Shaker, Ali Mohamed; Nassr, Lobna Abdel-Mohsen Ebaid; Adam, Mohamed Shaker Saied; Mohamed, Ibrahim Mohamed Abdelhalim

    2015-05-01

    Kinetic study of acid hydrolysis of some hydrophilic Fe(II) Schiff base amino acid complexes with antibacterial properties was performed using spectrophotometry. The Schiff base ligands were derived from sodium 2-hydroxybenzaldehyde-5-sulfonate and glycine, L-alanine, L-leucine, L-isoleucine, DL-methionine, DL-serine, or L-phenylalanine. The reaction was studied in aqueous media under conditions of pseudo-first order kinetics. Moreover, the acid hydrolysis was studied at different temperatures and the activation parameters were calculated. The general rate equation was suggested as follows: rate = k obs [Complex], where k obs = k 2 [H+]. The evaluated rate constants and activation parameters are consistent with the hydrophilicity of the investigated complexes.

  12. Communication: Physical origins of ionization potential shifts in mixed carboxylic acids and water complexes

    NASA Astrophysics Data System (ADS)

    Gu, Quanli; Tang, Zhen; Su, Peifeng; Wu, Wei; Yang, Zhijun; Trindle, Carl O.; Knee, Joseph L.

    2016-08-01

    The ionization potential (IP) of the aromatic alpha hydroxy carboxylic acid, 9-hydroxy-9-fluorene carboxylic acid (9HFCA), is shifted by complexation with hydrogen bonding ligands such as water and formic acid. Generalized Kohn-Sham energy decomposition analysis decomposes the intermolecular binding energies into a frozen energy term, polarization, correlation, and/or dispersion energy terms, as well as terms of geometric relaxation and zero point energy. We observe that in each dimer the attractive polarization always increases upon ionization, enhancing binding in the cation and shifting the IP toward the red. For 9HFCA—H2O, a substantial decrease of the repulsive frozen energy in cation further shifts the IP toward red. For 9HFCA—HCOOH, the increase of the frozen energy actually occurs in the cation and shifts the IP toward blue. Consistent with the experimental measurements, our analysis provides new, non-intuitive perspectives on multiple hydrogen bonds interactions in carboxylic acids and water complexes.

  13. Oxidation of formic acid on platinum surfaces decorated with cobalt(III) macrocyclic complexes

    NASA Astrophysics Data System (ADS)

    Stevanović, S.; Babić-Samardžija, K.; Sovilj, S. P.; Tripković, A.; Jovanović, V. M.

    2009-09-01

    Platinum electrode decorated with three different mixed-ligand cobalt(III) complexes of the general formula [Co(Rdtc)cyclam](ClO4)2 [cyclam = 1,4,8,11-tetraazacyclotetradecane, Rdtc- = morpholine-(Morphdtc), piperidine-(Pipdtc), and 4-methylpiperidine-(4-Mepipdtc) dithiocarbamates, respectively] was used to study oxidation of formic acid in acidic solution. The complexes were adsorbed on differently prepared Pt surfaces, at open circuit potential. The preliminary results show increased catalytic activity of Pt for formic acid oxidation with complex ion adsorbed on the polycrystalline surfaces. The increase in catalytic activity depends on the structure of the complex applied and follows the order of metal-coordinated bidentate ligand as Morphdtc > Pipdtc > 4-Mepipdtc. Based on IR and NMR data, the main characteristics of the Rdtc ligands do not vary dramatically, but high symmetry of the corresponding complexes decreases in the same order. Accordingly, the complexes are distinctively more mobile, causing chemical interactions to occur on the surface with appreciable speed and enhanced selectivity. The effect of the complexes on catalytic activity presumably depends on structural changes on Pt surfaces caused by their adsorption.

  14. DISSOLUTION OF ZIRCONIUM AND ALLOYS THEREFOR

    DOEpatents

    Swanson, J.L.

    1961-07-11

    The dissolution of zirconium cladding in a water solution of ammonium fluoride and ammonium nitrate is described. The method finds particular utility in processing spent fuel elements for nuclear reactors. The zirconium cladding is first dissolved in a water solution of ammonium fluoride and ammonium nitrate; insoluble uranium and plutonium fiuorides formed by attack of the solvent on the fuel materiai of the fuel element are then separated from the solution, and the fuel materiai is dissolved in another solution.

  15. Hydrogen spillover on platinum-zirconium alloys and feasibility of its use in electrocatalysis

    SciTech Connect

    Petrii, O.A.; Vasina, S.Ya.; Seropegin, Yu.D.

    1995-12-01

    The effect of hydrogen spillover on electrodes prepared from Pt-Zr (from 0.4 to 4 wt% Zr) alloys, which were subjected to heat-treatment in the atmosphere of air or in vacuum at temperatures ranging from 600 to 800{degrees}C, is discovered and investigated. The superequivalent (with respect to the oxygen being adsorbed and copper adatoms) quantity of reversibly adsorbed hydrogen is shown to depend on the concentration of zirconium in the alloy as well as on the temperature and annealing time of the sample. A conclusion is made that a disperse oxide-zirconium phase may form at the surface of the alloys, to which hydrogen spills from the platinum centers. The zirconium additives are found to lower the electrocatalytic activity of platinum in the methanol oxidation reaction. The presence of the spillover effect leads to an increase in the reduction currents of maleic acid.

  16. Vapor transport of zirconium and silicon during heat-treatment of Zircaloy in silica

    SciTech Connect

    Knittel, D.R.; Cubicciotti, D.

    1980-01-01

    When pieces of Zircaloy are heated above 600/sup 0/C in sealed silica capsules, silicon is deposited on the Zircaloy surface as zirconium silicides and zirconium is deposited on the silica in two forms: as an oxide layer in the high temperature region and as a metallic mirror on lower temperature surfaces. Samples of Zircaloy were heated in silica capsules under various conditions and analyzed by scanning electron microscopy. The results indicate that the deposits resulted from vapor transport processes involving volatile zirconium and silicon fluorides. Residual fluoride on Zircaloy surfaces, remaining from acid pickling treatments, was observed by Auger electron spectroscopy and mass spectroscopy in amounts sufficient to cause the transport. The thermodynamics of the vapor transport reactions are in accord with the fluoride mechanism. 4 figures.

  17. APPLICATION OF FORMOHYDROXAMIC ACID IN NUCLEAR PROCESSING: SYNTHESIS AND COMPLEXATION WITH TECHNETIUM-99

    SciTech Connect

    Amber Wright; Edward Mausolf; Keri Campbell; Frederic Poineau; P. Paviet-Hartmann

    2010-05-01

    Acetohydroxamic acid (AHA) is an organic ligand planned for use in the Uranium Extraction (UREX) process. It reduces neptunium and plutonium, and the resultant hydrophilic complexes are separated from uranium by extraction with tributyl phosphate (TBP) in a hydrocarbon diluent. AHA undergoes hydrolysis to acetic acid which will impede the recycling of nitric acid. During recent discussions of the UREX process, it has been proposed to replace AHA by formohydroxamic acid (FHA). FHA will undergo hydrolysis to formic acid which is volatile, thus allowing the recycling of nitric acid. The reported reduction potentials of AHA and pertechnetate (TcO{sub 4}{sup -}) indicated that it may be possible for AHA to reduce technetium, altering its fate in the fuel cycle. At UNLV, it has been demonstrated that TcO{sub 4}{sup -} undergoes reductive nitrosylation by AHA under a variety of conditions. The resulting divalent technetium is complexed by AHA to form the pseudo-octahedral trans-aquonitrosyl (diacetohydroxamic)-technetium(II) complex ([Tc{sup II}(NO)(AHA){sub 2}H{sub 2}O]{sup +}). In this paper, we are reporting the synthesis of FHA and its complex formation with technetium along with the characterization of FHA crystals achieved by NMR and IR spectroscopy. Two experiments were conducted to investigate the complexation of FHA with Tc and the results were compared with previous data on AHA. The first experiment involved the elution of Tc from a Reillex HP anion exchange resin, and the second one monitored the complexation of technetium with FHA by UV-visible spectrophotometry.

  18. Asymmetric epoxidation of allylic alcohols catalyzed by vanadium-binaphthylbishydroxamic Acid complex.

    PubMed

    Noji, Masahiro; Kobayashi, Toshihiro; Uechi, Yuria; Kikuchi, Asami; Kondo, Hisako; Sugiyama, Shigeo; Ishii, Keitaro

    2015-03-20

    A vanadium-binaphthylbishydroxamic acid (BBHA) complex-catalyzed asymmetric epoxidation of allylic alcohols is described. The optically active binaphthyl-based ligands BBHA 2a and 2b were synthesized from (S)-1,1'-binaphthyl-2,2'-dicarboxylic acid and N-substituted-O-trimethylsilyl (TMS)-protected hydroxylamines via a one-pot, three-step procedure. The epoxidations of 2,3,3-trisubstituted allylic alcohols using the vanadium complex of 2a were easily performed in toluene with a TBHP water solution to afford (2R)-epoxy alcohols in good to excellent enantioselectivities. PMID:25714329

  19. Bioreduction of Uranium(VI) Complexed with Citric Acid by Clostridia Affects its Structure and Mobility

    SciTech Connect

    Francis, A.; Dodge, C

    2008-01-01

    Uranium contamination of the environment from mining and milling operations, nuclear-waste disposal, and ammunition use is a widespread global problem. Natural attenuation processes such as bacterial reductive precipitation and immobilization of soluble uranium is gaining much attention. However, the presence of naturally occurring organic ligands can affect the precipitation of uranium. Here, we report that the anaerobic spore-forming bacteria Clostridia, ubiquitous in soils, sediments, and wastes, capable of reduction of Fe(III) to Fe(II), Mn(IV) to Mn(II), U(VI) to U(IV), Pu(IV) to Pu(III), and Tc(VI) to Tc(IV); reduced U(VI) associated with citric acid in a dinuclear 2:2 U(VI):citric acid complex to a biligand mononuclear 1:2 U(IV):citric acid complex, which remained in solution, in contrast to reduction and precipitation of uranium. Our findings show that U(VI) complexed with citric acid is readily accessible as an electron acceptor despite the inability of the bacterium to metabolize the complexed organic ligand. Furthermore, it suggests that the presence of organic ligands at uranium-contaminated sites can affect the mobility of the actinide under both oxic and anoxic conditions by forming such soluble complexes.

  20. Bioreduction of uranium(VI) complexed with citric acid by Clostridia affects its structure and solubility.

    PubMed

    Francis, A J; Dodge, C J

    2008-11-15

    Uranium contamination of the environment from mining and milling operations, nuclear-waste disposal, and ammunition use is a widespread global problem. Natural attenuation processes such as bacterial reductive precipitation and immobilization of soluble uranium is gaining much attention. However, the presence of naturally occurring organic ligands can affect the precipitation of uranium. Here, we report that the anaerobic spore-forming bacteria Clostridia, ubiquitous in soils, sediments, and wastes, capable of reduction of Fe(III) to Fe(II), Mn(IV) to Mn(II), U(VI) to U(IV), Pu(IV) to Pu(III), and Tc(VI) to Tc(IV); reduced U(VI) associated with citric acid in a dinuclear 2:2 U(VI): citric acid complex to a biligand mononuclear 1:2 U(IV):citric acid complex,which remained in solution, in contrast to reduction and precipitation of uranium. Our findings show that U(VI) complexed with citric acid is readily accessible as an electron acceptor despite the inability of the bacterium to metabolize the complexed organic ligand. Furthermore, it suggests that the presence of organic ligands at uranium-contaminated sites can affect the mobility of the actinide under both oxic and anoxic conditions by forming such soluble complexes. PMID:19068806

  1. Mononuclear metal complexes of organic carboxylic acid derivatives: Synthesis, spectroscopic characterization, thermal investigation and antimicrobial activity

    NASA Astrophysics Data System (ADS)

    Abd El-Wahab, Zeinab H.

    2007-05-01

    Two Schiff base ligands bearing organic acid moiety, vis., N-(2-thienylmethylidene)-2-amino-4-chlorobenzoic acid (HL 1) and N-(2-hydroxybenzylidene)-2-amino-4-chlorobenzoic acid (H 2L 2) have been synthesized by the interaction of 2-thiophenecarboxaldehyde and 2-hydroxybenzaldehyde with 2-amino-4-chlorobenzoic acid. Co(II), Ni(II), Cu(II) and Zn(II) complexes of these ligands have been prepared. They are characterized on the basis of analytical data, molar conductance, IR, 1H NMR, UV-vis, mass spectra, magnetic measurements, thermal analysis and X-ray powder diffraction technique. The molar conductance data reveal that these complexes are non-electrolytes. The ligands are coordinated to the metal ions in a terdentate manner with ONO/ONS donor sites of the carbonyl oxygen, azomethine nitrogen and phenolic oxygen or thiophenic sulphur. An octahedral structure is proposed for the prepared metal complexes and some ligand field parameters ( Dq, B and β) in addition to CFSE were calculated. The thermal stability of the metal complexes is evaluated. The Schiff base ligands and their metal complexes have been tested against four species of bacteria as well as four species of fungi and the results have been compared with some known antibiotics.

  2. The chitosan-gelatin (bio)polyelectrolyte complexes formation in an acidic medium.

    PubMed

    Voron'ko, Nicolay G; Derkach, Svetlana R; Kuchina, Yuliya A; Sokolan, Nina I

    2016-03-15

    The interaction of cationic polysaccharide chitosan and gelatin accompanied by the stoichiometric (bio)polyelectrolyte complexes formation has been studied by the methods of capillary viscometry, UV and FTIR spectroscopy and dispersion of light scattering. Complexes were formed in the aqueous phase, with pH being less than the isoelectric point of gelatin (pIgel). The particle size of the disperse phase increases along with the growth of the relative viscosity in comparison with sols of the individual components-polysaccharide and gelatin. Possible models and mechanism of (bio)polyelectrolyte complexes formation have been discussed. It was shown that the complex formation takes place not only due to the hydrogen bonds, but also due to the electrostatic interactions between the positively charged amino-groups of chitosan and negatively charged amino acid residues (glutamic Glu and aspartic Asp acids) of gelatin. PMID:26794762

  3. Complexation Constants of Ubiquinone,0 and Ubiquinone,10 with Nucleosides and Nucleic Acid Bases

    NASA Astrophysics Data System (ADS)

    Rahawi, Kassim Y.; Shanshal, Muthana

    2008-02-01

    UV spectrophotometric measurements were done on mixtures of the ubiquinones Ub,0 and Ub,10 in their monomeric form (c < 10-5 mol/l) with the nucleosides; adenosine, cytidine, 2'-desoxyadenosine, 2'-desoxy-quanosine, guanosine and thymidine, as well as the nucleic acid bases; adenine, cytosine, hypoxanthine, thymine and uracil. Applying the Liptay method, it was found that both ubiquinones form 1 : 1 interaction complexes with the nucleic acid components. The complexation constants were found in the order of 105 mol-1. The calculated ΔG values were negative (˜-7.0 kcal/mol), suggesting a favoured hydrogen bridge formation. This is confirmed by the positive change of the entropy ΔS. The complexation enthalpies ΔH for all complexes are negative, suggesting exothermal interactions.

  4. Experimental and theoretical investigation of the complexation of methacrylic acid and diisopropyl urea.

    PubMed

    Pogány, Peter; Razali, Mayamin; Szekely, Gyorgy

    2017-01-01

    The present paper explores the complexation ability of methacrylic acid which is one of the most abundant functional monomer for the preparation of molecularly imprinted polymers. Host-guest interactions and the mechanism of complex formation between methacrylic acid and potentially genotoxic 1,3-diisopropylurea were investigated in the pre-polymerization solution featuring both experimental (NMR, IR) and in silico density functional theory (DFT) tools. The continuous variation method revealed the presence of higher-order complexes and the appearance of self-association which were both taken into account during the determination of the association constants. The quantum chemical calculations - performed at B3LYP 6-311++G(d,p) level with basis set superposition error (BSSE) corrections - are in agreement with the experimental observations, reaffirming the association constants and justifying the validity of computational investigation of such systems. Furthermore, natural bond orbital analysis was carried out to appraise the binding properties of the complexes. PMID:27419640

  5. Competition of hydrogen bonds and halogen bonds in complexes of hypohalous acids with nitrogenated bases.

    PubMed

    Alkorta, Ibon; Blanco, Fernando; Solimannejad, Mohammad; Elguero, Jose

    2008-10-30

    A theoretical study of the complexes formed by hypohalous acids (HOX, X = F, Cl, Br, I, and At) with three nitrogenated bases (NH 3, N 2, and NCH) has been carried out by means of ab initio methods, up to MP2/aug-cc-pVTZ computational method. In general, two minima complexes are found, one with an OH...N hydrogen bond and the other one with a X...N halogen bond. While the first one is more stable for the smallest halogen derivatives, the two complexes present similar stabilities for the iodine case and the halogen-bonded structure is the most stable one for the hypoastatous acid complexes. PMID:18837495

  6. Synthesis and spectroscopic studies of iron (III) complex with a quinolone family member (pipemidic acid)

    NASA Astrophysics Data System (ADS)

    Skrzypek, D.; Szymanska, B.; Kovala-Demertzi, Dimitra; Wiecek, Joanna; Talik, E.; Demertzis, Mavroudis A.

    2006-12-01

    The interaction of iron (III) with pipemidic acid, Hpipem, afforded the complex [Fe (pipem) (HO)2 (H2O)]2. The new complex has been characterised by elemental analyses, infra-red, EPR and XPS spectroscopies. The monoanion, pipem, exhibits O, O ligation through the carbonyl and carboxylato oxygen atoms. Six coordinate dimer distorted octahedral configuration has been proposed for [Fe (pipem) (HO)2 (H2O)]2.

  7. Hydrolysis of oxaliplatin-evaluation of the acid dissociation constant for the oxalato monodentate complex.

    PubMed

    Jerremalm, Elin; Eksborg, Staffan; Ehrsson, Hans

    2003-02-01

    Alkaline hydrolysis of the platinum anticancer drug oxaliplatin gives the oxalato monodentate complex and the dihydrated oxaliplatin complex in two consecutive steps. The acid dissociation constant for the oxalato monodentate intermediate was determined by a kinetic approach. The pK(a) value was estimated as 7.23. The monodentate intermediate is assumed to rapidly react with endogenous compounds, resulting in a continuous conversion of oxaliplatin via the monodentate form. PMID:12532393

  8. Arsenic speciation and identification of monomethylarsonous acid and monomethylthioarsonic acid in a complex matrix.

    PubMed

    Yathavakilla, Santha Ketavarapu V; Fricke, Michael; Creed, Patricia A; Heitkemper, Douglas T; Shockey, Nohora V; Schwegel, Carol; Caruso, Joseph A; Creed, John T

    2008-02-01

    Anion-exchange chromatography was utilized for speciation of arsenite (As(III)), arsenate (As(V)), dimethylarsinic acid (DMA(V)), monomethylarsonic acid (MMA(V)), monomethylarsonous acid (MMA(III)), and the new As species monomethylthioarsonic acid (MMTA), using inductively coupled plasma mass spectrometric (ICPMS) detection. MMA(III) and MMTA were identified for the first time in freeze-dried carrot samples that were collected over 25 years ago as part of a joint U.S. EPA, U.S. FDA, and USDA study on trace elements in agricultural crops. The discovery of MMA(III) and MMTA in terrestrial foods necessitated the analytical characterization of synthetic standards of both species, which were used for standard addition in carrot extracts. The negative ion mode, high-resolution electrospray mass spectrometry (HR-ESI-MS) data produced molecular ions of m/z 122.9418 and 154.9152 for MMA(III) and MMTA, respectively. However, ESI-MS was not sensitive enough to directly identify MMA(III) and MMTA in the carrot extracts. Therefore, to further substantiate the identification of MMA(III) and MMTA, two additional separations using an Ion-120 column were developed using the more sensitive ICPMS detection. The first separation used 20 mM tetramethylammonium hydroxide at pH 12.2 with MMA(III) eluting in less than 7 min. In the second separation, MMTA eluted at 11.2 min by utilizing 40 mM ammonium carbonate at pH 9.0. Oxidation of MMA(III) and MMTA to MMA(V) with hydrogen peroxide was observed for standards and carrot extracts alike. Several samples of carrots collected from local markets in 2006 were also analyzed and found to contain low levels of inorganic arsenic species. PMID:18181583

  9. Determination of complex formation constants by phase sensitive alternating current polarography: Cadmium-polymethacrylic acid and cadmium-polygalacturonic acid.

    PubMed

    Garrigosa, Anna Maria; Gusmão, Rui; Ariño, Cristina; Díaz-Cruz, José Manuel; Esteban, Miquel

    2007-10-15

    The use of phase sensitive alternating current polarography (ACP) for the evaluation of complex formation constants of systems where electrodic adsorption is present has been proposed. The applicability of the technique implies the previous selection of the phase angle where contribution of capacitive current is minimized. This is made using Multivariate Curve Resolution by Alternating Least Squares (MCR-ALS) in the analysis of ACP measurements at different phase angles. The method is checked by the study of the complexation of Cd by polymethacrylic (PMA) and polygalacturonic (PGA) acids, and the optimal phase angles have been ca. -10 degrees for Cd-PMA and ca. -15 degrees for Cd-PGA systems. The goodness of phase sensitive ACP has been demonstrated comparing the determined complex formation constants with those obtained by reverse pulse polarography, a technique that minimizes the electrode adsorption effects on the measured currents. PMID:19073101

  10. Chitosan-poly(acrylic) acid polyionic complex: in vivo study to demonstrate prolonged gastric retention.

    PubMed

    Torrado, Susana; Prada, Pablo; de la Torre, Paloma M; Torrado, Santiago

    2004-02-01

    The aim of this study was to develop a chitosan-poly(acrylic) acid based controlled drug release system for gastric antibiotic delivery. Different mixtures of amoxicillin (A), chitosan (CS), and poly(acrylic) acid (PAA) were employed to obtain these polyionic complexes. A non-invasive method was employed for determining the gastric residence time of the formulations. It was studied the swelling behavior and drug release from these complexes. Gastric emptying rate study was performed by means of the [13C]octanoic acid breath test. The gastric emptying rates of two different formulations (conventional and gastric retentive system) were studied. Swelling studies indicated that the extent of swelling was greater in the polyionic complexes than in the single chitosan formulations. The amoxicillin diffusion from the hydrogels was controlled by the polymer/drug interaction. The property of these complexes to control the solute diffusion depends on the network mesh size, which is a significant factor in the overall behavior of the hydrogels. The gastric half-emptying time of the polyionic complex was significantly delayed compared to the reference formulation, showing mean values of 164.32+/-26.72 and 65.06+/-11.50min, respectively (P<0.01). The results of this study suggest that, these polyionic complexes are good systems for specific gastric drug delivery. PMID:14609680

  11. A convenient method for the preparation of barbituric and thiobarbituric acid transition metal complexes.

    PubMed

    Refat, Moamen S; El-Korashy, Sabry A; Ahmed, Ahmed S

    2008-12-01

    A convenient method for the preparation of barbiturate transition metal complexes: (i) Cr(3+), Mn(2+), Fe(3+), Zn(2+) and Cd(2+) ions with barbituric acid (H(2)L) and (ii) Cr(3+) and Mo(5+) with 2-thiobarbituric acid (H(2)L') was reported and this has enabled seven complexes to be formulated as: [Cr(HL)(2)(OH)(H(2)O)].H(2)O, [Mn(HL)(2)(H(2)O)(2)], [Fe(2)(L)(OH)(3)(H(2)O)(4)].2H(2)O, [Zn(HL)(2)], [Cd(HL)(2)], [Cr(HL')(OH)(2)(H(2)O)].H(2)O and [Mo(HL')(2)]Cl. These new barbiturate complexes were synthesized and characterized by elemental analysis, molar conductivity, magnetic measurements, spectral methods (mid infrared, (1)H NMR, mass, X-ray powder diffraction and UV/vis spectra) and simultaneous thermal analysis (TG and DTG) techniques. The molar conductance measurements proved that, all complexes of barbituric and 2-thiobarbituric acids are non-electrolytes except for [Mo(HL')(2)]Cl. The electronic spectra and magnetic susceptibility measurements were used to infer the structures. The IR spectra of the ligands and their complexes are used to identify the mode of coordination. Kinetic and thermodynamic parameters such as: E, DeltaH, DeltaS and DeltaG are estimated according to the DTG curves. The two ligands and their complexes have been studied for their possible biological antifungal activity. PMID:18420451

  12. Metallurgical and Biological Activity of Peroxo Complexes of Molybdenum (VI) Containing Organic Acid and Amine Bases

    NASA Astrophysics Data System (ADS)

    Nasrin, Jahanara; Saidul Islam, M.

    This study describes with the preparation, characterization and bioactivity of peroxo complexes [A: MoO(O2)(gly)(Q); B: MoO(O2)(ala)(2-pic)]of Mo(VI)] containing organic acid and amine bases. Both the complexes A and B were characterized by a variety of physicochemical techniques, viz., elemental analyses, molar conductivity, IR, NMR and electronic spectral studies. The analytical data were in good agreement with the proposed emperical formulae of both the complexes. The molar conductance values indicated both the complexes are non-electrolytes in DMF revealing that the anions are covalently bonded in all the cases. The magnetic moment values indicated that both the complexes were dimagnetic in nature suggesting that there were no changes in the oxidation states of the metal ions upon complexation. The electronic spectral data of the complexes A and B showed bands at 315-355 nm region due to the charge transfers band only. The antimicrobial properties of the peroxo complexes of Mo(VI) indicated that both the complexes were stronger antibacterial and antifungal agents. However, the highest antifungal activity was shown in the complex B against A. niger (16 mm) while the complex A of Mo(VI) showed lowest activity (10 mm). The MIC experiment showed that the complex B of Mo(VI) were more potent against all the bacteria tested than the complex A. Results showed that the complex A of Mo(VI) exhibits more toxic to brine shrimp compared to complex B of Mo(VI) indicating the lower values of LC50 for both the exposure 16 and 36 h.

  13. Thermodynamic Features of Benzene-1,2-Diphosphonic Acid Complexes with Several Metal Ions

    SciTech Connect

    Syouhei Nishihama; Ryan P. Witty; Leigh R Martin; Kenneth L. Nash

    2013-08-01

    Among his many contributions to the advancement of f-element chemistry and separation science, Professor Gregory R. Choppin’s research group completed numerous investigations featuring the application of distribution techniques to the determination of metal complexation equilibrium quotients. Most of these studies focused on the chemistry of lanthanide and actinide complexes. In keeping with that tradition, this report discusses the complex formation equilibrium constants for complexes of trivalent europium (Eu3+) with benzene-1,2-diphosphonic acid (H4BzDP) determined using solvent extraction distribution experiments in 0.2 M (Na,H)ClO4 media in the temperature range of 5 – 45 degrees C. Protonation constants for HnBzDP4-n and stoichiometry and stability of BzDP4- complexes with Zn2+, Ni2+, and Cu2+ have also been determined using potentiometric titration (at I = 0.1 M) and 31P NMR spectroscopy. Heats of protonation of HnBzDPn-4 species have been determined by titration calorimetry. From the temperature dependence of the complex Eu3+-HnBzDPn-4 equilibrium constant, a composite enthalpy (?H = -15.1 (+/-1.0) kJ mol-1) of complexation has been computed. Comparing these thermodynamic parameters with literature reports on other diphosphonic acids and structurally similar carboxylic acids indicates that exothermic heats of complexation are unique to the Eu-BzDP system. Comparisons with thermodynamic data from the literature indicate that the fixed geometry imposed by the benzene ring enhances complex stability.

  14. Characterization of folic acid/native cyclodextrins host-guest complexes in solution

    NASA Astrophysics Data System (ADS)

    Ceborska, Magdalena; Zimnicka, Magdalena; Wszelaka-Rylik, Małgorzata; Troć, Anna

    2016-04-01

    The complexation of folic acid (FA) with native cyclodextrins was studied and this process was used for the comparison of 1H NMR, ITC and ESIMS for the evaluation of association constants. The stability increases in the series: α-cyclodextrin/FA < γ-cyclodextrin/FA < β-cyclodextrin/FA. 1H NMR and ITC gave comparable results in regard to association constant values, while results obtained for MS were considerably higher due to different interactions (electrostatic instead of hydrophobic) responsible for the stabilization of the complexes. The dimerization of FA in water was also studied, as well as its impact on the process of complexation with native cyclodextrins.

  15. Structural organization of films based on polyaniline/polysulfonic acid complexes depending on the synthesis method

    SciTech Connect

    Simagina, L. V. Gaynutdinov, R. V.; Stepina, N. D.; Sorokina, K. L.; Morozova, O. V.; Shumakovich, G. P.; Yaropolov, A. I.; Tolstikhina, A. L.

    2010-07-15

    The optical properties and morphology of complexes based on polyaniline (PANI) and poly(2-acrylamido-2-methyl-1-propanesulfonic acid) (PAMPS), depending on their synthesis conditions, have been characterized by UV-visible spectroscopy and atomic force microscopy. The dependence of the electron absorption spectra of PANI/PAMPS complexes and the surface topography of their films on the initiation way of PANI formation (chemical and enzymatic) and the use of promoters of aniline polymerization has been investigated. The aniline polymerization kinetics with and without polymerization promoters has been studied. All PANI/PAMPS complexes are found to have a nanocomposite time-stable structure.

  16. [The favorable effect of humic acid based complex micro-element preparations in cadmium exposure].

    PubMed

    Hudák, A; Náray, M; Nagy, I; Molnár, M; Gömöry, I; Ungváry, G

    1997-06-01

    The authors have studied the effect of consumption of a humic acid based complex microelement preparation (potassium, magnesium, iron, zinc, manganese, copper, vanadium, cobalt, molibden, selenium bound to humic acids) for six weeks (10 ml daily) on the biological exposure indices (blood and urine cadmium levels) and clinical laboratory parameters (liver and kidney tests, blood picture) of men (n = 18; 39.7 +/- 10.4 years of age;) working in cadmium exposure for 8.3 +/- 5.0 years. The initial mean blood and urine cadmium levels of the non-smoking subjects was twice higher than that of the non-smoking male controls living in the same urban area (n = 35), and significantly correlated with the length of exposure. Their mean serum alanin-aminotransferase, gamma-glutamyl-transferase, creatinine, uric acid and urinary N-acetyl-beta-D-glucosaminidase levels were significantly higher than that of the controls. After the six-week treatment blood cadmium level, activity of serum alanin-aminotransferase, serum uric acid and urinary protein concentrations decreased significantly, the abnormal serum iron levels normalized. According to this results, the absorption of cadmium decreased on the effect of the complex microelement supplementation and the adverse laboratory changes attributable partly to cadmium exposure improved. Therefore humic acid based complex microelement supplementation is recommended as an effective tool for prevention and health protection in occupational cadmium exposure as well as for smokers known to be considerably burdened by cadmium. PMID:9254361

  17. PHOTODEGRADATION OF A TERNARY IRON(III)-URANIUM(VI)-CITRIC ACID COMPLEX

    EPA Science Inventory

    The mechanisms of photodegradation of binary iron- and uranium-citrate and ternary iron-uranium-citrate complexes were elucidated. Citric acid degradation products were identified by HPLC and GC, and the metal precipitates were identified by XRD and EXAFS. Photodegradation of a b...

  18. Hydrolysis of phosphodiesters by diiron complexes: design of nonequivalent iron sites in purple acid phosphatase models.

    PubMed

    Verge, François; Lebrun, Colette; Fontecave, Marc; Ménage, Stéphane

    2003-01-27

    New mu-oxo-diferric complexes have been designed for hydrolysis of phosphodiesters. To mimic the diiron active site of purple acid phosphatase, a combinatorial method has been used to select complexes containing two distinct iron coordination spheres. The introduction of a bidentate ligand, a substituted phenanthroline (L) into complex 1, [Fe2O(bipy)4(OH2)2](NO3)4, generates in solution the complex [Fe2O(bipy)3(L)(OH2)2](NO3)4 as shown by ESI/MS and 1H NMR studies. The latter complex was found to be 20-fold more active than complex 1. On the basis of kinetic studies, we demonstrated that the complex [Fe2O(bipy)3(L)(OH)(OH2)](NO3)3 was the active species and the reaction proceeded through the formation of a ternary complex in which one iron binds a hydroxide and the second, the substrate. At nonsaturating concentrations of the substrate, the increased activity with increased methyl substituents in L was due to an increased affinity of the complex for the substrate. The activity of [Fe2O(bipy)3(33'44'Me2-Phen)(OH2)2](NO3)4 [33'44'Me2Phen = 3,3',4,4'-dimethyl-1,10-phenanthroline] was found to be comparable to that reported for Co(III) or Ce(IV) complexes. PMID:12693232

  19. ZIRCONIUM OXIDE NANOSTRUCTURES PREPARED BY ANODIC OXIDATION

    SciTech Connect

    Dang, Y. Y.; Bhuiyan, M.S.; Paranthaman, M. P.

    2008-01-01

    Zirconium oxide is an advanced ceramic material highly useful for structural and electrical applications because of its high strength, fracture toughness, chemical and thermal stability, and biocompatibility. If highly-ordered porous zirconium oxide membranes can be successfully formed, this will expand its real-world applications, such as further enhancing solid-oxide fuel cell technology. Recent studies have achieved various morphologies of porous zirconium oxide via anodization, but they have yet to create a porous layer where nanoholes are formed in a highly ordered array. In this study, electrochemical methods were used for zirconium oxide synthesis due to its advantages over other coating techniques, and because the thickness and morphology of the ceramic fi lms can be easily tuned by the electrochemical parameters, such as electrolyte solutions and processing conditions, such as pH, voltage, and duration. The effects of additional steps such as pre-annealing and post-annealing were also examined. Results demonstrate the formation of anodic porous zirconium oxide with diverse morphologies, such as sponge-like layers, porous arrays with nanoholes ranging from 40 to 75 nm, and nanotube layers. X-ray powder diffraction analysis indicates a cubic crystallographic structure in the zirconium oxide. It was noted that increased voltage improved the ability of the membrane to stay adhered to the zirconium substrate, whereas lower voltages caused a propensity for the oxide fi lm to fl ake off. Further studies are needed to defi ne the parameters windows that create these morphologies and to investigate other important characteristics such as ionic conductivity.

  20. Zirconium Oxide Nanostructures Prepared by Anodic Oxidation

    SciTech Connect

    Dang, Ying Yi; Bhuiyan, Md S; Paranthaman, Mariappan Parans

    2008-01-01

    Zirconium oxide is an advanced ceramic material highly useful for structural and electrical applications because of its high strength, fracture toughness, chemical and thermal stability, and biocompatibility. If highly-ordered porous zirconium oxide membranes can be successfully formed, this will expand its real-world applications, such as further enhancing solid-oxide fuel cell technology. Recent studies have achieved various morphologies of porous zirconium oxide via anodization, but they have yet to create a porous layer where nanoholes are formed in a highly ordered array. In this study, electrochemical methods were used for zirconium oxide synthesis due to its advantages over other coating techniques, and because the thickness and morphology of the ceramic films can be easily tuned by the electrochemical parameters, such as electrolyte solutions and processing conditions, such as pH, voltage, and duration. The effects of additional steps such as pre-annealing and post-annealing were also examined. Results demonstrate the formation of anodic porous zirconium oxide with diverse morphologies, such as sponge-like layers, porous arrays with nanoholes ranging from 40 to 75 nm, and nanotube layers. X-ray powder diffraction analysis indicates a cubic crystallographic structure in the zirconium oxide. It was noted that increased voltage improved the ability of the membrane to stay adhered to the zirconium substrate, whereas lower voltages caused a propensity for the oxide film to flake off. Further studies are needed to define the parameters windows that create these morphologies and to investigate other important characteristics such as ionic conductivity.

  1. Extraction of pyridines into fluorous solvents based on hydrogen bond complex formation with carboxylic acid receptors.

    PubMed

    O'Neal, Kristi L; Geib, Steven; Weber, Stephen G

    2007-04-15

    A molecular receptor embedded in a 'poor-solvent' receiving phase, such as a fluorous phase, should offer the ideal medium for selective extraction and sensing. The limited solubility of most solutes in fluorous phases enhances selectivity by reducing the extraction of unwanted matrix components. Thus, receptor-doped fluorous phases may be ideal extraction media. Unfortunately, sufficient data do not exist to judge the capability of this approach. The solubilities of very few nonfluorous solutes are known. As far as we are aware, such important quantities as the strength of a hydrogen bond in a fluorous environment are not known. Thus, it is currently impossible to predict whether a particular receptor/solute complex based on a particular set of noncovalent interactions will provide enough thermodynamic stabilization to extract the solute into the fluorous phase. In this work, fluorous carboxylic acids (a carboxylic acid-terminated perfluoropolypropylene oxide called Krytox and perfluorodecanoic acid (PFDA)) were used as receptors and substituted pyridines as solutes to show that the fluorous receptor dramatically enhances the liquid-liquid extraction of the polar substrates from chloroform into perfluorohexanes. The method of continuous variations was used to determine the receptor-pyridine complex stoichiometry of 3:1. The free energies of formation of the 3:1 complexes from one pyridine and 3/2 H-bonded cyclic dimers of the fluorous carboxylic acid are -30.4 (Krytox) and -37.3 kJ mol-1 (PFDA). The free energy required to dissociate the dimer in perfluorohexanes is +16.5 kJ mol-1 (Krytox). The crystal structure of the complex showed a 1:1 stoichiometry with a mixed strong-weak hydrogen-bonded motif. Based on the stoichiometry, crystal structure, and UV and IR spectroscopic shifts, we propose that the 3:1 complex has four hydrogen bonds and the carboxylic acid transfers a proton to pyridine. The resulting pyridinium carboxylate N+H-O- hydrogen bond is accompanied

  2. Methods of staining target chromosomal DNA employing high complexity nucleic acid probes

    DOEpatents

    Gray, Joe W.; Pinkel, Daniel; Kallioniemi, Ol'li-Pekka; Kallioniemi, Anne; Sakamoto, Masaru

    2006-10-03

    Methods and compositions for staining based upon nucleic acid sequence that employ nucleic acid probes are provided. Said methods produce staining patterns that can be tailored for specific cytogenetic analyses. Said probes are appropriate for in situ hybridization and stain both interphase and metaphase chromosomal material with reliable signals. The nucleic acid probes are typically of a complexity greater than 50 kb, the complexity depending upon the cytogenetic application. Methods and reagents are provided for the detection of genetic rearrangements. Probes and test kits are provided for use in detecting genetic rearrangements, particularly for use in tumor cytogenetics, in the detection of disease related loci, specifically cancer, such as chronic myelogenous leukemia (CML), retinoblastoma, ovarian and uterine cancers, and for biological dosimetry. Methods and reagents are described for cytogenetic research, for the differentiation of cytogenetically similar but genetically different diseases, and for many prognostic and diagnostic applications.

  3. Cytoxicity and Apoptotic Mechanism of Ruthenium(II) Amino Acid Complexes in Sarcoma-180 Tumor Cells

    PubMed Central

    Lima, Aliny Pereira; Pereira, Flávia Castro; Almeida, Marcio Aurelio Pinheiro; Mello, Francyelli Mariana Santos; Pires, Wanessa Carvalho; Pinto, Thallita Monteiro; Delella, Flávia Karina; Felisbino, Sérgio Luis; Moreno, Virtudes; Batista, Alzir Azevedo; de Paula Silveira-Lacerda, Elisângela

    2014-01-01

    Over the past several decades, much attention has been focused on ruthenium complexes in antitumor therapy. Ruthenium is a transition metal that possesses several advantages for rational antitumor drug design and biological applications. In the present study, five ruthenium complexes containing amino acids were studied in vitro to determine their biological activity against sarcoma-180 tumor cells. The cytotoxicity of the complexes was evaluated by an MTT assay, and their mechanism of action was investigated. The results demonstrated that the five complexes inhibited the growth of the S180 tumor cell line, with IC50 values ranging from 22.53 µM to 50.18 µM, and showed low cytotoxicity against normal L929 fibroblast cells. Flow cytometric analysis revealed that the [Ru(gly)(bipy)(dppb)]PF6 complex (2) inhibited the growth of the tumor cells by inducing apoptosis, as evidenced by an increased number of Annexin V-positive cells and G0/G1 phase cell cycle arrest. Further investigation showed that complex 2 caused a loss of mitochondrial membrane potential; activated caspases 3, caspase-8, and caspase-9 and caused a change in the mRNA expression levels of caspase 3, caspase-9 as well as the bax genes. The levels of the pro-apoptotic Bcl-2 family protein Bak were increased. Thus, we demonstrated that ruthenium amino acid complexes are promising drugs against S180 tumor cells, and we recommend further investigations of their role as chemotherapeutic agents for sarcomas. PMID:25329644

  4. Synthesis, Crystal Structure, and Thermal Decomposition of the Cobalt(II) Complex with 2-Picolinic Acid

    PubMed Central

    Li, Di

    2014-01-01

    The cobalt(II) complex of 2-picolinic acid (Hpic), namely, [Co(pic)2(H2O)2] · 2H2O, was synthesized with the reaction of cobalt acetate and 2-picolinic acid as the reactants by solid-solid reaction at room temperature. The composition and structure of the complex were characterized by elemental analysis, infrared spectroscopy, single crystal X-ray diffraction, and thermogravimetry-differential scanning calorimetry (TG-DSC). The crystal structure of the complex belongs to monoclinic system and space group P2(1)/n, with cell parameters of a = 9.8468(7) Å, b = 5.2013(4) Å, c = 14.6041(15) Å, β = 111.745(6)°, V = 747.96(11) Å3, Z = 2, Dc = 1.666 g cm−3, R1 = 0.0297, and wR2 = 0.0831. In the title complex, the Co(II) ion is six-coordinated by two pyridine N atoms and two carboxyl O atoms from two 2-picolinic acid anions, and two O atoms from two H2O molecules, and forming a slightly distorted octahedral geometry. The thermal decomposition processes of the complex under nitrogen include dehydration and pyrolysis of the ligand, and the final residue is cobalt oxalate at about 450°C. PMID:24578654

  5. A comparative study of the complexation of uranium(VI) withoxydiacetic acid and its amide derivatives

    SciTech Connect

    Rao, Linfeng; Tian, Guoxin

    2005-05-01

    There has been significant interest in recent years in the studies of alkyl-substituted amides as extractants for actinide separation because the products of radiolytic and hydrolytic degradation of amides are less detrimental to separation processes than those of organophosphorus compounds traditionally used in actinide separations. Stripping of actinides from the amide-containing organic solvents is relatively easy. In addition, the amide ligands are completely incinerable so that the amount of secondary wastes generated in nuclear waste treatment could be significantly reduced. One group of alkyl-substituted oxa-diamides have been shown to be promising in the separation of actinides from nuclear wastes. For example, tetraoctyl-3-oxa-glutaramide and tetraisobutyl-oxa-glutaramide form actinide complexes that can be effectively extracted from nitric acid solutions. To understand the thermodynamic principles governing the complexation of actinides with oxa-diamides, we have studied the complexation of U(VI) with dimethyl-3-oxa-glutaramic acid (DMOGA) and tetramethyl-3-oxa-glutaramide (TMOGA) in aqueous solutions, in comparison with oxydiacetic acid (ODA) (Figure 1). Previous studies have indicated that the complexation of U(VI) with ODA is strong and entropy-driven. Comparing the results for DMOGA and TMOGA with those for ODA could provide insight into the energetics of amide complexation with U(VI) and the relationship between the thermodynamic properties and the ligand structure.

  6. Probing inclusion complexes of cyclodextrins with amino acids by physicochemical approach.

    PubMed

    Roy, Mahendra Nath; Roy, Aditi; Saha, Subhadeep

    2016-10-20

    Formations of host-guest inclusion complexes of two natural amino acids, viz., l-Leucine and l-Isoleucine as guests with α and β-cyclodextrins have been investigated which include diverse applications in modern science such as controlled delivery in the field of pharmaceuticals, food processing etc. Surface tension and conductivity studies establish the formation of inclusion complexes with 1:1 stoichiometry. The interactions of cyclodextrins with amino acids have been supported by density, viscosity, refractive index, hydration and solvation number measurements indicating higher degree of inclusion in case of α-cyclodextrin. l-Leucine interacts more with the hydrophobic cavity of cyclodextrin than its isomer. With the help of stability constant by NMR titration, hydrophobic effect, H-bonds and structural effects the formations of inclusion complexes have been explained. PMID:27474589

  7. Separation of glycols from dilute aqueous solutions via complexation with boronic acids

    SciTech Connect

    Randel, L.A.; King, C.J.

    1991-07-01

    This work examines methods of separating low molecular weight glycols from dilute aqueous solution. Extraction into conventional solvents is generally not economical, since, in the literature reviewed, distribution ratios for the two- to four-carbon glycols are all less than one. Distribution ratios can be increased, however, by incorporating into the organic phase an extracting agent that will complex with the solute of interest. The extracting agent investigated in this work is 3-nitrophenylboronic acid (NPBA). NPBA, a boric acid derivative, reversibly complexes with many glycols. The literature on complexation of borate and related compounds with glycols, including mechanistic data, measurement techniques, and applications to separation processes, provides information valuable for designing experiments with NPBA and is reviewed herein. 88 refs., 15 figs., 24 tabs.

  8. Intermolecular hydrogen bond complexes by in situ charge transfer complexation of o-tolidine with picric and chloranilic acids

    NASA Astrophysics Data System (ADS)

    Refat, Moamen S.; Saad, Hosam A.; Adam, Abdel Majid A.

    2011-08-01

    A two new charge transfer complexes formed from the interactions between o-tolidine (o-TOL) and picric (PA) or chloranilic (CA) acids, with the compositions, [(o-TOL)(PA) 2] and [(o-TOL)(CA) 2] have been prepared. The 13C NMR, 1H NMR, 1H-Cosy, and IR show that the charge-transfer chelation occurs via the formation of chain structures O-H⋯N intermolecular hydrogen bond between 2NH 2 groups of o-TOL molecule and OH group in each PA or CA units. Photometric titration measurements concerning the two reactions in methanol were performed and the measurements show that the donor-acceptor molar ratio was found to be 1:2 using the modified Benesi-Hildebrand equation. The spectroscopic data were discussed in terms of formation constant, molar extinction coefficient, oscillator strength, dipole moment, standard free energy, and ionization potential. Thermal behavior of both charge transfer complexes showed that the complexes were more stable than their parents. The thermodynamic parameters were estimated from the differential thermogravimetric curves. The results indicated that the formation of molecular charge transfer complexes is spontaneous and endothermic.

  9. Peat humic acids and their complex forming properties as influenced by peat humification

    NASA Astrophysics Data System (ADS)

    Dudare, D.; Klavins, M.

    2012-04-01

    To study paleoenvironmental changes of importance is understanding of processes of organic matter diagenesis, especially changes of refractory part of natural organic substances - humic substances. Studies of the living organic matter humification process are also essential for understanding of the carbon biogeochemical cycle. The aim of this study was to analyze peat organic matter diagenesis: changes of properties of humic acids, relations between the humification process, properties of peat, peat humic acids, their ability to interact with metal ions, as well ability to accumulate metals. The analysis were carried out on samples of humic substances preparatively extracted from three ombrotrophic bog peat profiles to identify the links between peat age, decomposition and humification degree, botanical composition and properties of peat humic acids elemental (C, H, N, O), functional (-COOH, -OH) composition, structural characteristics - UV, fluorescence, FTIR. The found variability of peat properties is less significant than differences in the properties of peat-forming living matter, thus revealing the dominant impact of humification process on the properties of peat. Correspondingly, composition of peat humic acids is little affected by differences in the properties of precursor living organic material, and such indicators as decomposition degree, humification degree, humic acid elemental ratio and concentrations of acidic functional groups are the best descriptors of changes in organic matter during the process of organic matter diagenesis and humification. Peat ability to accumulate major and trace elements depends on the character of element supply, potency of metal ions to bind functionalities in the peat, with an emphasis on the structure of peat humic acid, pH reaction, oxygen presence, presence of complexing compounds, inorganic ions and many other factors. Major and trace element presence in peat is of importance as an indicator of peat genesis and

  10. Olfactory discrimination of complex mixtures of amino acids by the black bullhead Ameiurus melas.

    PubMed

    Valentincic, T; Miklavc, P; Kralj, S; Zgonik, V

    2011-07-01

    On the basis of previous findings of behavioural discrimination of amino acids and on the knowledge of electrophysiology of the catfish (genera Ictalurus and Ameiurus) olfactory organs, behavioural experiments that investigated olfactory discrimination of amino acid mixtures were carried out on the black bullhead Ameiurus melas. Repeated presentations of food-rewarded mixtures released increased swimming activity measured by counting the number of turns >90° within 90 s of stimulus addition. Non-rewarded amino acids and their mixtures released little swimming activity, indicating that A. melas discriminated between the conditioned and the non-conditioned stimuli. Two questions of mixture discrimination were addressed: (1) Are A. melas able to detect components within simple and complex amino acid mixtures? (2) What are the smallest differences between two complex mixtures that A. melas can detect? Three and 13 component mixtures tested were composed primarily of equipotent amino acids [determined by equal electroolfactogram (EOG) amplitude] that contained L-Cys at ×100 the equipotent concentration. Ameiurus melas initially perceived the ternary amino acid mixture as its more stimulatory component alone [i.e. cysteine (Cys)], whereas the conditioned 13 component mixture containing the more stimulatory L-Cys was perceived immediately as different from L-Cys alone. The results indicate that components of ternary mixtures are detectable by A. melas but not those of more complex mixtures. To test for the smallest detectable differences in composition between similar multimixtures, all mixture components were equipotent. Initially, A. melas were unable to discriminate the mixtures of six amino acids from the conditioned mixtures of seven amino acids, whereas they discriminated immediately the mixtures of four and five amino acids from the conditioned mixture. Experience with dissimilar mixtures enabled the A. melas to start discriminating the seven

  11. Zirconium: biomedical and nephrological applications.

    PubMed

    Lee, David B N; Roberts, Martin; Bluchel, Christian G; Odell, Ross A

    2010-01-01

    Recent years have witnessed a rapid increase in the use of zirconium (Zr)-containing compounds in artificial internal organs. Examples include dental implants and other restorative practices, total knee and hip replacement, and middle-ear ossicular chain reconstruction. In nephrological practice, Zr-containing sorbents have been used in hemofiltration, hemodialysis, peritoneal dialysis, and in the design and construction of wearable artificial kidneys. Zr compounds continue to be widely and extensively used in deodorant and antiperspirant preparations. In the public health arena, Zr compounds have been studied or used in controlling phosphorus pollution and in the reclamation of poison and bacteria-contaminated water. Experimental and clinical studies support the general consensus that Zr compounds are biocompatible and exhibit low toxicity. Reports on possible Zr-associated adverse reactions are rare and, in general, have not rigorously established a cause-and-effect relationship. Although publications on the use of Zr compounds have continued to increase in recent years, reports on Zr toxicity have virtually disappeared from the medical literature. Nevertheless, familiarity with, and continued vigilant monitoring of, the use of these compounds are warranted. This article provides an updated review on the biomedical use of Zr compounds. PMID:21245802

  12. Effect of environmental factors on the complexation of iron and humic acid.

    PubMed

    Fang, Kai; Yuan, Dongxing; Zhang, Lei; Feng, Lifeng; Chen, Yaojin; Wang, Yuzhou

    2015-01-01

    A method of size exclusion chromatography coupled with ultraviolet spectrophotometry and off-line graphite furnace atomic absorption spectrometry was developed to assess the complexation properties of iron (Fe) and humic acid (HA) in a water environment. The factors affecting the complexation of Fe and HA, such as ionic strength, pH, temperature and UV radiation, were investigated. The Fe-HA complex residence time was also studied. Experimental results showed that pH could influence the deprotonation of HA and hydrolysis of Fe, and thus affected the complexation of Fe and HA. The complexation was greatly disrupted by the presence of NaCl. Temperature had some influence on the complexation. The yield of Fe-HA complexes showed a small decrease at high levels of UV radiation, but the effect of UV radiation on Fe-HA complex formation at natural levels could be neglected. It took about 10 hr for the complexation to reach equilibrium, and the Fe-HA complex residence time was about 20 hr. Complexation of Fe and HA reached a maximum level under the conditions of pH 6, very low ionic strength, in the dark and at a water temperature of about 25°C, for 10 hr. It was suggested that the Fe-HA complex could form mainly in freshwater bodies and reach high levels in the warm season with mild sunlight radiation. With changing environmental parameters, such as at lower temperature in winter or higher pH and ionic strength in an estuary, the concentration of the Fe-HA complex would decrease. PMID:25597677

  13. Group 11 complexes with amino acid derivatives: Synthesis and antitumoral studies.

    PubMed

    Ortego, Lourdes; Meireles, Margarida; Kasper, Cornelia; Laguna, Antonio; Villacampa, M Dolores; Gimeno, M Concepción

    2016-03-01

    Gold(I), gold(III), silver(I) and copper(I) complexes with modified amino acid esters and phosphine ligands have been prepared in order to test their cytotoxic activity. Two different phosphine fragments, PPh3 and PPh2py (py=pyridine), have been used. The amino acid esters have been modified by introducing an aromatic amine as pyridine that coordinates metal fragments through the nitrogen atom, giving complexes of the type [M(L)(PR3)](+) or [AuCl3(L)] (L=l-valine-N-(4-pyridylcarbonyl) methyl ester (L1), l-alanine-N-(4-pyridylcarbonyl) methyl ester (L2), l-phenylalanine-N-(4-pyridylcarbonyl) methyl-ester) (L3); M=Au(I), Ag(I), Cu(I), PR3=PPh3, PPh2py). The in vitro cytotoxic activity of metal complexes was tested against four tumor human cell lines and one tumor mouse cell line. A metabolic activity test (3-(4,5-dimethyl-thiazol-2-yl)-2,5-diphenyl tetrazolium bromide, MTT) was used and IC50 values were compared with those obtained for cisplatin. Several complexes displayed significant cytotoxic activities. In order to determine whether antiproliferation and cell death are associated with apoptosis, NIH-3T3 cells were exposed to five selected complexes (Annexin V+ FITC, PI) and analyzed by flow cytometry. These experiments showed that the mechanism by which the complexes inhibit cell proliferation inducing cell death in NIH-3T3 cells is mainly apoptotic. PMID:26780577

  14. 40 CFR 721.9973 - Zirconium dichlorides (generic).

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Zirconium dichlorides (generic). 721... Substances § 721.9973 Zirconium dichlorides (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substances identified generically as zirconium dichlorides (PMNs...

  15. 40 CFR 721.9973 - Zirconium dichlorides (generic).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Zirconium dichlorides (generic). 721... Substances § 721.9973 Zirconium dichlorides (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substances identified generically as zirconium dichlorides (PMNs...

  16. 40 CFR 721.9973 - Zirconium dichlorides (generic).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Zirconium dichlorides (generic). 721... Substances § 721.9973 Zirconium dichlorides (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substances identified generically as zirconium dichlorides (PMNs...

  17. 40 CFR 721.9973 - Zirconium dichlorides (generic).

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Zirconium dichlorides (generic). 721... Substances § 721.9973 Zirconium dichlorides (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substances identified generically as zirconium dichlorides (PMNs...

  18. 40 CFR 721.9973 - Zirconium dichlorides (generic).

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Zirconium dichlorides (generic). 721... Substances § 721.9973 Zirconium dichlorides (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substances identified generically as zirconium dichlorides (PMNs...

  19. 40 CFR 721.10708 - Zirconium substituted heteropolycyclic (generic).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Zirconium substituted heteropolycyclic... Specific Chemical Substances § 721.10708 Zirconium substituted heteropolycyclic (generic). (a) Chemical... as zirconium substituted heteropolycyclic (PMN P-13-152) is subject to reporting under this...

  20. 40 CFR 721.10601 - Lanthanum lead titanium zirconium oxide.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Lanthanum lead titanium zirconium... Specific Chemical Substances § 721.10601 Lanthanum lead titanium zirconium oxide. (a) Chemical substance... titanium zirconium oxide (PMN P-11-273; CAS No. 1227908-26-0) is subject to reporting under this...

  1. 40 CFR 721.10598 - Lead strontium titanium zirconium oxide.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Lead strontium titanium zirconium... Specific Chemical Substances § 721.10598 Lead strontium titanium zirconium oxide. (a) Chemical substance... titanium zirconium oxide (PMN P-11-270; CAS No. 61461-40-3) is subject to reporting under this section...

  2. Effect of Four Methods of Surface Treatment on Shear Bond Strength of Orthodontic Brackets to Zirconium

    PubMed Central

    Yassaei, Soghra; Aghili, Hossein Agha; Davari, Abdolrahim

    2015-01-01

    Objectives: Providing reliable attachment between bracket base and zirconia surface is a prerequisite for exertion of orthodontic force. The purpose of the present study was to evaluate the effect of four zirconium surface treatment methods on shear bond strength (SBS) of orthodontic brackets. Materials and Methods: One block of zirconium was trimmed into four zirconium surfaces, which served as our four study groups and each had 18 metal brackets bonded to them. Once the glazed layer was removed, the first group was etched with 9.6% hydrofluoric acid (HF), and the remaining three groups were prepared by means of sandblasting and 1W, and 2W Er: YAG laser, respectively. After application of silane, central incisor brackets were bonded to the zirconium surfaces. The SBS values were measured by a Dartec testing machine with a crosshead speed of 1 mm/min. Data were analyzed using one-way ANOVA and Tukey’s HSD for multiple comparisons. Results: The highest SBS was achieved in the sandblasted group (7.81±1.02 MPa) followed in a descending order by 2W laser group (6.95±0.87 MPa), 1W laser group (6.87±0.92 MPa) and HF acid etched group (5.84±0.78 MPa). The differences between the study groups were statistically significant except between the laser groups (P<0.05). Conclusion: In terms of higher bond strength and safety, sandblasting and Er: YAG laser irradiation with power output of 1W and 2W can be considered more appropriate alternatives to HF acid etching for zirconium surface treatment prior to bracket bonding. PMID:26622283

  3. [Molluscacide activity of a mixture of 6-n-alkyl salicylic acids (anacardic acid) and 2 of its complexes with copper (II) and lead (II)].

    PubMed

    Mendes, N M; de Oliveira, A B; Guimarães, J E; Pereira, J P; Katz, N

    1990-01-01

    The molluscicide activity of hexanic extract from Anacardium occidentale L. (cashew) nut shell, of copper (II) complex, of lead (II) complex and anacardic acid has been compared in the laboratory in an attempt to obtain better stability than anacardic acid. This was obtained from the hexanic extract of the cashew nut shell by precipitation with lead (II) hydroxide or cupric sulfate plus sodium hydroxide or (II) cupric hydroxide followed by treatment of lead (II) complex with a diluted solution of sulfuric acid. Ten products of the mixture obtained were tested on adults snails of Biomphalaria glabrata at 1 to 10 ppm. The most active products were copper (II) complex, obtained by cupric sulfate plus sodium hydroxide, and anacardic acid (sodium hydroxide) which presented activity at 4 ppm. The anacardic acid's lead content was above the limits accepted by the United States standards. PMID:2133588

  4. Sunlight-initiated Chemistry of Aqueous Pyruvic Acid: Building Complexity in the Origin of Life

    NASA Astrophysics Data System (ADS)

    Griffith, Elizabeth C.; Shoemaker, Richard K.; Vaida, Veronica

    2013-10-01

    Coupling chemical reactions to an energy source is a necessary step in the origin of life. Here, we utilize UV photons provided by a simulated sun to activate aqueous pyruvic acid and subsequently prompt chemical reactions mimicking some of the functions of modern metabolism. Pyruvic acid is interesting in a prebiotic context due to its prevalence in modern metabolism and its abiotic availability on early Earth. Here, pyruvic acid (CH3COCOOH, a C3 molecule) photochemically reacts to produce more complex molecules containing four or more carbon atoms. Acetoin (CH3CHOHCOCH3), a C4 molecule and a modern bacterial metabolite, is produced in this chemistry as well as lactic acid (CH3CHOHCOOH), a molecule which, when coupled with other abiotic chemical reaction pathways, can provide a regeneration pathway for pyruvic acid. This chemistry is discussed in the context of plausible environments on early Earth such as near the ocean surface and atmospheric aerosol particles. These environments allow for combination and exchange of reactants and products of other reaction environments (such as shallow hydrothermal vents). The result could be a contribution to the steady increase in chemical complexity requisite in the origin of life.

  5. Investigating the inclusion properties of aromatic amino acids complexing beta-cyclodextrins in model peptides.

    PubMed

    Caso, Jolanda Valentina; Russo, Luigi; Palmieri, Maddalena; Malgieri, Gaetano; Galdiero, Stefania; Falanga, Annarita; Isernia, Carla; Iacovino, Rosa

    2015-10-01

    Cyclodextrins are commonly used as complexing agents in biological, pharmaceutical, and industrial applications since they have an effect on protein thermal and proteolytic stability, refolding yields, solubility, and taste masking. β-cyclodextrins (β-CD), because of their cavity size are a perfectly suited complexing agent for many common guest moieties. In the case of peptide-cyclodextrin and protein-cyclodextrin host-guest complexes the aromatic amino acids are reported to be the principal responsible of the interaction. For these reasons, we have investigated the inclusion properties of nine designed tripeptides, obtained permuting the position of two L-alanines (Ala, A) with that of one L-tryptophan (Trp, W), L-phenylalanine (Phe, F), or L-tyrosine (Tyr, Y), respectively. Interestingly, the position of the aromatic side-chain in the sequence appears to modulate the β-CD:peptide binding constants, determined via UV-Vis and NMR spectroscopy, which in turn assumes values higher than those reported for the single amino acid. The tripeptides containing a tyrosine showed the highest binding constants, with the central position in the Ac-AYA-NH2 peptide becoming the most favorite for the interaction. A combined NMR and Molecular Docking approach permitted to build detailed complex models, highlighting the stabilizing interactions of the neighboring amino acids backbone atoms with the upper rim of the β-CD. PMID:25985927

  6. Complexations of polyoligothiophenes films with transition metals, and their use for electrocatalysis of ascorbic acid

    NASA Astrophysics Data System (ADS)

    Maouche, N.; Chelli, S.; Nessark, B.; Aeiyach, S.

    2009-11-01

    Chemically modified electrodes prepared by electropolymerization of oligothiophenes such as: 2,2'-bithiophene (BT), 2,2'-bithiophene-5-carboxylic acid (BTCA) and terthiophene aldehyde (TTCHO) on platinum (Pt) electrodes, in acetonitrile solution containing 0.1 M tetrabutylammonium perchlorate (TBAP) and 0.01 M of monomer, are characterized by cyclic volammetry (CV), and X-ray photoelectron spectroscopy (XPS) measurements. By immersing the prepared modified electrodes in transition metals (Cu2+, Co2+ and Ag+) solutions, the metal ions were complexed with films. The electrochemical response shows clearly, the presence of oxidation and reduction peaks corresponding to metallic couple redox. XPS technique reveal that the films complexed with metal ions and determine the mode of the connection with film's atoms. The obtained polyoligothiophenes-metal modified electrodes exhibited good electrocatalytic properties towards ascorbic acid (AA) oxidation after their complexation with metallic ions. The electrocatalytic response was evaluated by cyclic voltammetry with regard to the film nature, the metallic ion nature, immersion time, ascorbic acid concentration, and other variables. The results reveal that the catalytic activity of Ag+ complexed with BTCA thin-film is the best toward AA oxidation and it can be detected a very low concentration (∼1 μM), of AA in a solution which can be utilized as an efficient electrochemical sensor.

  7. Spectrophotometric study of the charge transfer complex between 2-amino-4-picoline with chloranilic acid

    NASA Astrophysics Data System (ADS)

    Alghanmi, Reem M.; Al-Attas, Amirah S.; Habeeb, Moustafa M.

    2013-02-01

    Charge transfer complex formation between 2-amino-4-picoline (2A4P) as the electron donor with chloranilic acid (CLA) as the electron acceptor has been studied spectrophotometrically in different polar solvents included acetone (AcN), ethanol (EtOH) and acetonitrile (AN). The molecular composition of the formed complex was recognized utilizing Job's, photometric and conductometric titration methods to be 1:1. The formation constants and molecular extinction coefficients were estimated using Benesi-Hildebrand equation; they recorded high values confirming high stability of the formed complex. Moreover, the results showed that the complex is more stable in acetone with lower electric permittivity compared with ethanol or acetonitrile of higher ones. The values of some spectroscopic physical parameters like oscillator strength f, transition dipole moment μ, resonance energy RN, charge transfer energy ECT, dissociation energy W, ionization potential IP and standard free energy ΔGo were determined and evaluated. The solid complex was isolated and its molecular composition was determined by elemental analysis to be 1:1. Furthermore, the solid complex was characterized using FTIR and 1H NMR measurements. They confirmed the presence of proton transfer beside charge transfer in the obtained complex. Molecular orbital calculations utilizing GAMESS computations were carried out to predict infrared spectra. They also confirmed the presence of proton transfer beside charge transfer in the formed complex.

  8. Calculations of oxidation rates of zirconium

    SciTech Connect

    Condon, J.B.

    1981-12-01

    The rates of oxidation for zirconium metal in oxygen are calculated using perfusive-precipitation modeling with the boundary conditions that: there is no moving boundary and metal matrix saturation is reached for oxygen solubility. The perfusive-precipitation model is a diffusion model with a chemical reaction. It uses Fick's Second Law of Diffusion with an added sink term. The sink term is an overall second order reaction, first order with respect to each the dissolved oxygen and the metal. The stationary boundary condition is valid for the ductile zirconium as long as the expansion due to the reaction product formation does not cause metal failure or spalling. The metal matrix saturated condition implies an upper limit to the metastable solubility of oxygen in the zirconium metal and is approximated from the phase diagram. The calculated rates are compared to the rates listed in the literature. These calculated rates, using no variable parameters, are in good agreement with experimental data.

  9. Protic Acid Hydrogen Bonding in Chlorofluoroethylenes: the Hydrogen Fluoride-Vinyl Chloride Complex

    NASA Astrophysics Data System (ADS)

    Leung, Helen O.; Marshall, Mark D.

    2012-06-01

    Our studies of intermolecular complexes formed in the gas phase between protic acids (HX) and chlorofluoroethylene complexes to date have demonstrated a preference for HX binding to a F atom over hydrogen bond formation with the Cl atom. Ab initio calculations suggest that this may not be true for species with an increased degree of halogen substitution on the ethylene. To characterize the nature of hydrogen bond formation with the less electronegative, but more polarizable Cl atom, we have obtained the microwave spectrum of HF-vinyl chloride complex. Analysis of the spectra for the 35Cl and 37Cl isotopologues demonstrate that the complex is planar and provides structural parameters for this species. This allows comparisons to be made between the HX hydrogen bond to Cl and that to F.

  10. Efficient in vivo gene transfection by stable DNA/PEI complexes coated by hyaluronic acid.

    PubMed

    Ito, Tomoko; Iida-Tanaka, Naoko; Koyama, Yoshiyuki

    2008-05-01

    Plasmid DNA was mixed with polyethyleneimine (PEI) and hyaluronic acid (HA) to afford ternary complexes with negative surface charge regardless of the mixing order. They showed reduced non-specific interactions with blood components. When DNA and PEI were mixed at a high concentration such as that used in in vivo experiments, they soon aggregated, and large particles were formed. On the other hand, pre-addition of HA to DNA prior to PEI effectively diminished the aggregation, and 10% (in volume) of the complexes remained as small particles with a diameter below 80 nm. Those negatively charged small ternary complexes induced a much stronger extra-gene expression in tumor than binary DNA/PEI complex after intratumoral or intravenous injection into the mice bearing B16 cells. PMID:18446606

  11. Ruthenium(II) multi carboxylic acid complexes: chemistry and application in dye sensitized solar cells.

    PubMed

    Shahroosvand, Hashem; Nasouti, Fahimeh; Sousaraei, Ahmad

    2014-04-01

    Novel ruthenium multi carboxylic complexes (RMCCs) have been synthesized by using ruthenium nitrosyl nitrate, 1,2,4,5-benzenetetracarboxylic acid (H4btec) and 4,7-diphenyl-1,10-phenanthroline (BPhen) as photosensitizers for titanium dioxide semiconductor solar cells. The complexes were characterized by (1)H-NMR, FT-IR, UV-Vis, ICP and CHN analyses. The reaction details and features were then described. SEM analysis revealed that the penetration of dyes into the pores of the nanocrystalline TiO2 surface was improved by increasing the number of btec units. The solar energy to electricity conversion efficiency of complexes shows that the number of attached carboxylates on a dye has an influence on the photoelectrochemical properties of the dye-sensitized electrode. An incident photon-to-current conversion efficiency (IPCE) of 13% at 510 nm was obtained for ruthenium complexes with three btec units. PMID:24500312

  12. Hyaluronic acid-siRNA conjugate/reducible polyethylenimine complexes for targeted siRNA delivery.

    PubMed

    Jang, Yeon Lim; Ku, Sook Hee; Jin, So; Park, Jae Hyung; Kim, Won Jong; Kwon, Ick Chan; Kim, Sun Hwa; Jeong, Ji Hoon

    2014-10-01

    The clinical applications of therapeutic siRNA remain as a challenge due to the lack of efficient delivery system. In the present study, hyaluronic acid-siRNA conjugate (HA-SS-siRNA)/reducible polyethylenimine (BPEI1.2k-SS) complexes were developed to efficiently deliver the siRNA to HA receptor abundant region with the improved siRNA stability. HA and siRNA were conjugated with disulfide bonds, which are cleavable in cytoplasm. The synthesized HA-SS-siRNA was further complexed with BPEI1.2k-SS, resulting in the formation of spherical nanostructures with approximately 190 nm of size and neutral surface charge. HA-SS-siRNA/BPEI1.2k-SS complexes exhibited the improved stability against serum proteins or polyanions. These complexes were successfully translocated into intracellular region via HA receptor-mediated endocytosis, and silenced target gene expression. PMID:25942799

  13. Fractionation of SWNT/nucleic acid complexes by agarose gel electrophoresis

    NASA Astrophysics Data System (ADS)

    Vetcher, Alexandre A.; Srinivasan, Srimeenakshi; Vetcher, Ivan A.; Abramov, Semen M.; Kozlov, Mikhail; Baughman, Ray H.; Levene, Stephen D.

    2006-08-01

    We show that aqueous dispersions of single-walled carbon nanotubes (SWNTs), prepared with the aid of nucleic acids (NAs) such as RNA or DNA, can be separated into fractions using agarose gel electrophoresis. In a DC electric field, SWNT/NA complexes migrate in the gel in the direction of positive potential to form well-defined bands. Raman spectroscopy as a function of band position shows that nanotubes having different spectroscopic properties possess different electrophoretic mobilities. The migration patterns for SWNT/RNA and SWNT/DNA complexes differ. Parallel elution of the SWNT/NA complexes from the gel during electrophoresis and subsequent characterization by AFM reveals differences in nanotube diameter, length and curvature. The results suggest that fractionation of nanotubes can be achieved by this procedure. We discuss factors affecting the mobility of the nanotube complexes and propose analytical applications of this technique.

  14. Radiation effects on corrosion of zirconium alloys

    SciTech Connect

    Johnson, A.B. Jr.

    1989-06-01

    From the wide use of zirconium alloys as components in nuclear reactors, has come clear evidence that reactor radiation is a major corrosion parameter. The evidence emerges from comparisons of zirconium alloy corrosion behavior in different reactor types, for example, BWRs versus PWRs and in corresponding reactor loop chemistries; also, oxidation rates differ with location along components such as fuel rods and reactor pressure tubes. In most respects, oxidation effects on power reactor components are paralleled by oxidation behavior on specimens exposed to radiation in reactor loops.

  15. Process for separation of zirconium-88, rubidium-83 and yttrium-88

    DOEpatents

    Heaton, Richard C.; Jamriska, Sr., David J.; Taylor, Wayne A.

    1994-01-01

    A process for selective separation of strontium-82 and strontium-85 from proton irradiated molybdenum targets is provided and includes dissolving the molybdenum target in a hydrogen peroxide solution to form a first ion-containing solution, passing the first ion-containing solution through a first cationic resin whereby ions selected from the group consisting of molybdenum, niobium, technetium, selenium, vanadium, arsenic, germanium, zirconium and rubidium remain in the first ion-containing solution while ions selected from the group consisting of rubidium, zinc, beryllium, cobalt, iron, manganese, chromium, strontium, yttrium and zirconium are selectively adsorbed by the first resin, contacting the first resin with an acid solution capable of stripping adsorbed ions from the first cationic exchange resin whereby the adsorbed ions are removed from the first resin to form a second ion-containing solution, evaporating the second ion-containing solution for time sufficient to remove substantially all of the acid and water from the second ion-containing solution whereby a residue remains, dissolving the residue from the evaporated second-ion containing solution in a dilute acid to form a third ion-containing solution, said third ion-containing solution having an acid molarity adapted to permit said ions to be adsorbed by a cationic exchange resin, passing the third ion-containing solution through a second cationic resin whereby the ions are adsorbed by the second resin, contacting the second resin with a dilute sulfuric acid solution whereby the adsorbed ions selected from the group consisting of rubidium, zinc, beryllium, cobalt, iron, manganese, chromium, and zirconium are selectively removed from the second resin, and contacting the second resin with a dilute acid solution whereby the adsorbed strontium ions are selectively removed. Zirconium, rubidium, and yttrium radioisotopes can also be recovered with additional steps.

  16. Branched-chain amino acids complex inhibits melanogenesis in B16F0 melanoma cells.

    PubMed

    Cha, Jae-Young; Yang, Hyun-Ju; Moon, Hyung-In; Cho, Young-Su

    2012-04-01

    Present study was investigated the effect of each or complex of three branched-chain amino acids (BCAAs; isoleucine, leucine, and valine) on melanin production in B16F0 melanoma cells treated with various concentrations (1-16 mM) for 72 h. Among the 20 amino acids, lysine and glycine showed the highest activities of DPPH radical scavenging and mushroom tyrosinase inhibition, respectively. Each and combination of BCAAs reduced melanogenesis in a concentration-dependent manner without any morphological changes and cell viability in melanoma cells. Present study was also investigated the inhibitory effects of each or complex of BCAAs at each 10 mM concentration on the 100 μM IBMX-mediated stimulation of melanogenesis in melanoma cells for 72 h and found that IBMX treatment was stimulated to enhance melanin synthesis and that the complex of BCAAs was the most effectively inhibited in the melanin amounts of cellular and extracellular and the whitening the cell pellet. When the inhibitory effect of BCAAs on tyrosinase was examined by intracellular tyrosinase assay, both isoleucine and valine exhibit slightly inhibition, but leucine and combination of BCAAs did not inhibit the cell-derived tyrosinase activity. Present study demonstrated that complex of BCAAs inhibited melanin production without changes intercellular tyrosinase activity. Thus, the complex of BCAAs may be used in development of safe potentially depigmenting agents. PMID:21854182

  17. Molecular mechanism of the assembly of an acid-sensing receptor ion channel complex.

    PubMed

    Yu, Yong; Ulbrich, Maximilian H; Li, Ming-Hui; Dobbins, Scott; Zhang, Wei K; Tong, Liang; Isacoff, Ehud Y; Yang, Jian

    2012-01-01

    Polycystic kidney disease (PKD) family proteins associate with transient receptor potential (TRP) channel family proteins to form functionally important complexes. PKD proteins differ from known ion channel-forming proteins and are generally thought to act as membrane receptors. Here we find that PKD1L3, a PKD protein, functions as a channel-forming subunit in an acid-sensing heteromeric complex formed by PKD1L3 and TRPP3, a TRP channel protein. Single amino-acid mutations in the putative pore region of both proteins alter the channel's ion selectivity. The PKD1L3/TRPP3 complex in the plasma membrane of live cells contains one PKD1L3 and three TRPP3. A TRPP3 C-terminal coiled-coil domain forms a trimer in solution and in crystal, and has a crucial role in the assembly and surface expression of the PKD1L3/TRPP3 complex. These results demonstrate that PKD subunits constitute a new class of channel-forming proteins, enriching our understanding of the function of PKD proteins and PKD/TRPP complexes. PMID:23212381

  18. Inhibition of acid, alkaline, and tyrosine (PTP1B) phosphatases by novel vanadium complexes.

    PubMed

    McLauchlan, Craig C; Hooker, Jaqueline D; Jones, Marjorie A; Dymon, Zaneta; Backhus, Emily A; Greiner, Bradley A; Dorner, Nicole A; Youkhana, Mary A; Manus, Lisa M

    2010-03-01

    In the course of our investigations of vanadium-containing complexes for use as insulin-enhancing agents, we have generated a series of novel vanadium coordination complexes with bidentate ligands. Specifically we have focused on two ligands: anthranilate (anc(-)), a natural metabolite of tryptophan, and imidizole-4-carboxylate (imc(-)), meant to mimic naturally occurring N-donor ligands. For each ligand, we have generated a series of complexes containing the V(III), V(IV), and V(V) oxidation states. Each complex was investigated using phosphatase inhibition studies of three different phosphatases (acid, alkaline, and tyrosine (PTP1B) phosphatase) as prima facia evidence for potential use as an insulin-enhancing agent. Using p-nitrophenyl phosphate as an artificial phosphatase substrate, the levels of inhibition were determined by measuring the absorbance of the product at 405nm using UV/vis spectroscopy. Under our experimental conditions, for instance, V(imc)(3) appears to be as potent an inhibitor of alkaline phosphatase as sodium orthovanadate when comparing the K(cat)/K(m) term. VO(anc)(2) is as potent an inhibitor of acid phosphatase and tyrosine phosphatase as the Na(3)VO(4). Thus, use of these complexes can increase our mechanistic understanding of the effects of vanadium in vivo. PMID:20071031

  19. First fluorescence spectroscopic investigation of Am(III) complexation with an organic carboxylic ligand, pyromellitic acid.

    PubMed

    Barkleit, Astrid; Geipel, Gerhard; Acker, Margret; Taut, Steffen; Bernhard, Gert

    2011-01-01

    For the first time Am(III) complexation with a small organic ligand could be identified and characterized with time-resolved laser-induced fluorescence spectroscopy (TRLFS) at room temperature and trace metal concentration. With pyromellitic acid (1,2,4,5-benzene-tetracarboxylic acid, BTC) as ligand spectroscopic characteristics for the Am-BTC complex system were determined at pH 5.0, an ionic strength of 0.1 M (NaClO4) and room temperature. The fluorescence lifetimes were determined to be 23.2±2.2 ns for Am3+(aq) and 27.2±1.2 ns for the Am-BTC 1:1 complex; the emission maximum for the 5D1-(7)F1 transition is 691 nm for both species. The complex stability constant for the Am-BTC 1:1 complex was calculated to be logβ110=5.42±0.16. PMID:20943431

  20. Stability of rare-earth complexes with acetylacetone and methaccrylic acid in aqueous solution

    SciTech Connect

    Panyushkin, V.T.; Akhrimenko, N.V.

    1995-09-01

    The stability constants for lanthanide (Ln) complexes with methacrylic acid (HL) (log{beta}{sub LnL}{sup Ln}), acetylacetone (HAA) (log{beta}{sub Ln(AA){sub 3}}{sup Ln}), and mixed-ligand complexes (log{beta}{sub LnL(AA){sub 2}}{sup Ln}), [Ln(III)=La, Pr, Nd, Sm, Eu, Gd, Tb, Ho, Er, Yb, Lu] in aqueous solution are determined by potentiometric titration at 25{degrees}C and {mu}=0.1 (KCl). A nonmonotonous change in the stability constants with an increase in the atomic number number of the rare-earth metal is found to occur.

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

    SciTech Connect

    Kiefer, P.

    1980-07-01

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

  2. Quantum-chemical studies of dimethylformamide 1 : 1 complexes with phosphoric acid

    NASA Astrophysics Data System (ADS)

    Krest'yaninov, M. A.; Kiselev, M. G.; Safonova, L. P.

    2012-12-01

    The structures of two phosphoric acid conformations, dimethylformamide (DMFA), four protonated DMFA forms, and nine DMFA-H3PO4 complexes in which the proton acceptor is a oxygen or nitrogen atom of the DMFA molecule are optimized by DFT/B3LYP using the 6-31++G( d, p) basis set. The structural changes in DMFA that occur upon its protonation are discussed. The stabilization energy and transferred charge values upon the formation of a hydrogen bond are calculated for all of the studied complexes by means of NBO analysis. The potential energy surface is scanned to study the possibility of proton transfer.

  3. Modification of Different Zirconium Propoxide Precursors by Diethanolamine. Is There a Shelf Stability Issue for Sol-Gel Applications?

    PubMed Central

    Spijksma, Gerald I.; Blank, Dave H. A.; Bouwmeester, Henny J. M.; Kessler, Vadim G.

    2009-01-01

    Modification of different zirconium propoxide precursors with H2dea was investigated by characterization of the isolated modified species. Upon modification of zirconium n-propoxide and [Zr(OnPr)(OiPr)3(iPrOH)]2 with ½ a mol equivalent of H2dea the complexes [Zr2(OnPr)6(OCH2CH2)2NH]2 (1) and [Zr2(OnPr)2(OiPr)4(OCH2CH2)2NH]2 (2) were obtained. However, 1H-NMR studies of these tetranuclear compounds showed that these are not time-stable either in solution or solid form. The effect of this time instability on material properties is demonstrated by light scattering and TEM experiments. Modification of zirconium isopropoxide with either ½ or 1 equivalent mol of H2dea results in formation of the trinuclear complex, Zr{η3μ2-NH(C2H4O)2}3[Zr(OiPr)3]2(iPrOH)2 (3) countering a unique nona-coordinated central zirconium atom. This complex 3 is one of the first modified zirconium propoxide precursors shown to be stable in solution for long periods of time. The particle size and morphology of the products of sol-gel synthesis are strongly dependent on the time factor and eventual heat treatment of the precursor solution. Reproducible sol-gel synthesis requires the use of solution stable precursors. PMID:20087472

  4. Metal ion-humic acid nanoparticle interactions: role of both complexation and condensation mechanisms.

    PubMed

    Town, Raewyn M; van Leeuwen, Herman P

    2016-07-21

    Purely Donnan type models for electrostatic binding by humic acid (HA) nanoparticles are shown to be physically incomplete. To describe the extent of ion binding by HA, such models need to invoke parameters that are not consistent with experimental observations. These disparate parameters include anomalously high Donnan potentials, as well as intrinsic affinity constants for electrostatically associating ions such as Ca(2+). In contrast, the recently introduced counterion condensation - Donnan model (CCD) provides a physicochemically realistic description of the electrostatic contribution to metal ion binding by humic acid nanoparticles. The extent of Ca(2+)-HA association can be adequately described solely in terms of electrostatics only, including counterion condensation in the intraparticulate double layer in addition to Donnan partitioning in the remainder of the particle body. The binding of Cd(ii), Pb, (ii) and Cu(ii) by HA also involves inner-sphere complex formation leading to intraparticulate metal species distributions with major proportions of condensed and complexed ions. PMID:27327433

  5. Local Solvent Acidities in β-Cyclodextrin Complexes with PRODAN Derivatives

    PubMed Central

    Naughton, Hannah R.; Abelt, Christopher J.

    2013-01-01

    The local solvent acidities (SA scale) of six 6-carbonyl-2-aminonaphthalene derivatives as β-cyclodextrin complexes in water are determined through fluorescence quenching. The local polarities (ETN scale) are determined through the shift of the emission center-of-mass. The apparent SA values reflect the solvent structure surrounding the guest’s carbonyl group, whereas the apparent ETN values reveal the net polarity of the entire guest molecule. Comparison of these values affords greater insight into the structures of the host-guest complexes. Derivatives 1 and 5 show unusually large acidities indicative of highly exposed carbonyl groups. The remaining compounds give emission intensities pointing to shielded carbonyl groups. In this study PRODAN and its derivatives are functioning as dual channel sensors of their local environment. PMID:23473052

  6. Production of complex nucleic acid libraries using highly parallel in situ oligonucleotide synthesis.

    PubMed

    Cleary, Michele A; Kilian, Kristopher; Wang, Yanqun; Bradshaw, Jeff; Cavet, Guy; Ge, Wei; Kulkarni, Amit; Paddison, Patrick J; Chang, Kenneth; Sheth, Nihar; Leproust, Eric; Coffey, Ernest M; Burchard, Julja; McCombie, W Richard; Linsley, Peter; Hannon, Gregory J

    2004-12-01

    Generation of complex libraries of defined nucleic acid sequences can greatly aid the functional analysis of protein and gene function. Previously, such studies relied either on individually synthesized oligonucleotides or on cellular nucleic acids as the starting material. As each method has disadvantages, we have developed a rapid and cost-effective alternative for construction of small-fragment DNA libraries of defined sequences. This approach uses in situ microarray DNA synthesis for generation of complex oligonucleotide populations. These populations can be recovered and either used directly or immortalized by cloning. From a single microarray, a library containing thousands of unique sequences can be generated. As an example of the potential applications of this technology, we have tested the approach for the production of plasmids encoding short hairpin RNAs (shRNAs) targeting numerous human and mouse genes. We achieved high-fidelity clone retrieval with a uniform representation of intended library sequences. PMID:15782200

  7. DNA/polyethyleneimine/hyaluronic acid small complex particles and tumor suppression in mice.

    PubMed

    Ito, Tomoko; Yoshihara, Chieko; Hamada, Katsuyuki; Koyama, Yoshiyuki

    2010-04-01

    The highest barriers for non-viral vectors to an efficient in vivo gene transfection would be (1) non-specific interaction with biological molecules, and (2) large size of the DNA complex particles. Protective coating of the DNA/polyethyleneimine (PEI) complexes by hyaluronic acid (HA) effectively diminished the adverse interactions with biological molecules. Here we found HA also protected the DNA/PEI complexes against aggregation and inactivation through lyophilization-and-rehydration procedures. It allows us to prepare the concentrated very small DNA complex particles (<70 nm) suspension by preparing the complexes at highly diluted conditions, followed by lyophilized-and-rehydrated to a small volume. In vivo gene expression efficiency of the small complex was examined with mice subcutaneously inoculated with B16 melanoma cells. These formulations showed high reporter-gene expression level in tumor after intravenous injection into tumor-bearing mice. Small complex was then made of the plasmid encoding GM-CSF gene, and injected into the mice bearing subcutaneous solid B16 tumor. After intravenous injection, it induced apparent tumor growth suppression in 50% of the mice. Notably, significant therapeutic effect was detected in the mice that received intratumoral injection, and 75% of the mice were completely cured with disappearance of tumor. PMID:20047759

  8. Studying Arsenite-Humic Acid Complexation Using Size Exclusion Chromatography-Inductively Coupled Plasma Mass Spectrometry

    PubMed Central

    Liu, Guangliang; Cai, Yong

    2012-01-01

    Arsenic (As) can form complexes with dissolved organic matter (DOM), which affects the fate of arsenic in waste sites and natural environments. It remains a challenge to analyze DOM-bound As, in particular by using a direct chromatographic separation method. Size exclusion chromatography (SEC) hyphenated with UV spectrophotometer and inductively coupled plasma mass spectrometry (ICP-MS) was developed to characterize the complexation of arsenite (AsIII) with DOM. This SEC-UV-ICP-MS method is able to differentiate AsIII-DOM complexes from free As species and has the advantage of direct determination of both free and DOM-bound AsIII through mild separation. The suitability of this method for studying AsIII-DOM complexation was demonstrated by its application, in combination with the Scatchard plot and nonlinear regression of ligand binding model, for characterizing AsIII complexation with humic acid (HA) in the absence or presence of natural sand. The results suggest that, consistent with polyelectrolytic nature of HA, the AsIII-HA complexation should be accounted for by multiple classes of binding sites. By loosely classifying the binding sites into strong (S1) and weak (S2) sites, the apparent stability constants (Ks) of the resulting As-DOM complexes were calculated as log Ks1 = 6.5–7.1 while log Ks2 = 4.7–5.0. PMID:22664255

  9. Hydration effect on proton transfer in melamine-cyanuric acid complex.

    PubMed

    Yan, Shihai; Kang, Baotao; Lee, Jin Yong; Sun, Lixiang

    2016-07-01

    Self-assembly of melamine-cyanuric acid (MC) leads to urinary tract calculi and renal failure. The hydration effects on molecular geometry, the IR spectra, the frontier molecular orbital, the energy barrier of proton transfer (PT), as well as the stability of MC were explored by density functional theory (DFT) calculations. The intramolecular PT breaks the big π-conjugated ring of melamine or converts the p-π conjugation (:N-C'=O) to π-π conjugation (O=C-N=C') of cyanuric acid. The intermolecular PT varies the coupling between melamine and cyanuric acid from pure hydrogen bonds (Na…HNd and NH…O) to the cooperation of cation…anion electrostatic interaction (NaH(+)…Nd (-)) and two NH…O hydrogen bonds. Distinct IR spectra shifts occur for Na…HNd stretching mode upon PT, i.e., blue-shift upon intramolecular PT and red-shift upon intermolecular PT. It is expected that the PT would inhibit the generation of rosette-like structure or one-dimensional tape conformer for the MC complexes. Hydration obviously effects the local geometric structure around the water binding site, as well as the IR spectra of NH…O and N…HN hydrogen bonds. Hydration decreases the intramolecular PT barrier from ~45 kcal mol(-1) in anhydrous complex to ~11.5 kcal mol(-1) in trihydrated clusters. While, the hydration effects on intermolecular PT barrier is slight. The relative stability of MC varies slightly by hydration due to the strong hydrogen bond interaction between melamine and cyanuric acid fragments. Graphical Abstract Hydration effect on proton transfer in melamine-cyanuric acid complex. PMID:27351422

  10. Interconversion of CO2 and formic acid by bio-inspired Ir complexes with pendent bases.

    PubMed

    Fujita, Etsuko; Muckerman, James T; Himeda, Yuichiro

    2013-01-01

    Recent investigations of the interconversion of CO2 and formic acid using Ru, Ir and Fe complexes are summarized in this review. During the past several years, both the reaction rates and catalyst stabilities have been significantly improved. Remarkably, the interconversion (i.e., reversibility) has also been achieved under mild conditions in environmentally benign water solvent by slightly changing the pH of the aqueous solution. Only a few catalysts seem to reflect a bio-inspired design such as the use of proton responsive ligands, ligands with pendent bases or acids for a second-coordination-sphere interaction, electroresponsive ligands, and/or ligands having a hydrogen bonding function with a solvent molecule or an added reagent. The most successful of these is an iridium dinuclear complex catalyst that at least has the first three of these characteristics associated with its bridging ligand. By utilizing an acid/base equilibrium for proton removal, the ligand becomes a strong electron donor, resulting in Ir(I) character with a vacant coordination site at each metal center in slightly basic solution. Complemented by DFT calculations, kinetic studies of the rates of formate production using a related family of Ir complexes with and without such functions on the ligand reveal that the rate-determining step for the CO2 hydrogenation is likely to be H2 addition through heterolytic cleavage involving a "proton relay" through the pendent base. The dehydrogenation of formic acid, owing to the proton responsive ligands changing character under slightly acidic pH conditions, is likely to occur by a mechanism with a different rate-determining step. This article is part of a Special Issue entitled: Metals in Bioenergetics and Biomimetics Systems. PMID:23174332

  11. Design and evaluation of Lumefantrine – Oleic acid self nanoemulsifying ionic complex for enhanced dissolution

    PubMed Central

    2013-01-01

    Background Lumefantrine, an antimalarial molecule has very low and variable bioavailability owing to its extremely poor solubility in water. It is recommended to be taken with milk to enhance its solubility and bioavailability. The aim of present study was to develop a Self Nanoemulsifying Delivery system (SNEDs) of lumefantrine (LF) to achieve rapid and complete dissolution independent of food-fat and surfactant in dissolution media. Methods Solubility of LF in oil, co-solvent/co-surfactant and surfactant solution and emulsification efficiency of surfactant were analyzed to optimize the LF loaded self nanoemulsifying preconcentrate. Effect of LF-oleic acid complexation on emulsification, droplet size, zeta potential and dissolution were investigated. Effect of milk concentration and fat content on saturation solubility and dissolution of LF was investigated. Dissolution of marketed formulation and LF-SNEDs was carried out in pH 1.2 and pH 6.8 phosphate buffer. Results LF exhibited very high solubility in oleic acid owing to complexation between tertiary amine of LF and carboxyl group of oleic acid (OA). Cremophore EL and medium chain monoglyceride were selected surfactant and co-surfactant, respectively. Significantly smaller droplet size (37 nm), shift in zeta potential from negative to positive value, very high drug loading in lipid based system (> 10%), no precipitation after dissolution are the major distinguish characteristics contributed by LF-OA complex in the SNED system. Saturation solubility and dissolution study in milk containing media pointed the significant increment in solubility of LF in the presence of milk-food fat. LF-SNEDs showed > 90% LF release within 30 min in pH 1.2 while marketed tablet showed almost 0% drug release. Conclusion Self nanoemulsification promoting ionic complexation between basic drug and oleic acid hold great promise in enhancing solubility of hydrophobic drugs. PMID:23531442

  12. Phosphine and thiophene cyclopalladated complexes: hydrolysis reactions in strong acidic media.

    PubMed

    García, Begoña; Hoyuelos, Francisco J; Ibeas, Saturnino; Muñoz, María S; Navarro, Ana M; Peñacoba, Indalecio A; Leal, José M

    2010-12-01

    The mechanisms for the hydrolysis of organopalladium complexes [Pd(CNN)R]BF(4) (R=P(OPh)(3), PPh(3), and SC(4)H(8)) were investigated at 25 °C by using UV/Vis absorbance measurements in 10 % v/v ethanol/water mixtures containing different sulphuric acid concentrations in the 1.3-11.7 M range. In all cases, a biphasic behavior was observed with rate constants k(1obs), which corresponds to the initial step of the hydrolysis reaction, and k(2obs), where k(1obs)>k(2obs). The plots of k(1obs) and k(2obs) versus sulfuric acid concentration suggest a change in the reaction mechanism. The change with respect to the k(1obs) value corresponds to 35 %, 2 %, and 99 % of the protonated complexes for R=PPh(3), P(OPh)(3), and SC(4)H(8), respectively. Regarding k(2obs), the change occurred in all cases at about 6.5 M H(2)SO(4) and matched up with the results reported for the hydrolysis of the 2-acetylpyridinephenylhydrazone (CNN) ligand. By using the excess acidity method, the mechanisms were elucidated by carefully looking at the variation of k(i),(obs) (i=1,2) versus cH+. The rate-determining constants, k(0,A-1), k(0,A-2), and k(0,A-SE2) were evaluated in all cases. The R=P(OPh)(3) complex was most reactive due to its π-acid character, which favors the rupture of the trans nitrogen-palladium bond in the A-2 mechanism and also that of the pyridine nitrogen-palladium bond in the A-1 mechanism. The organometallic bond exerts no effect on the relative basicity of the complexes, which are strongly reliant on the substituent. PMID:21125574

  13. Tandem Catalytic Depolymerization of Lignin by Water-Tolerant Lewis Acids and Rhodium Complexes.

    PubMed

    Jastrzebski, Robin; Constant, Sandra; Lancefield, Christopher S; Westwood, Nicholas J; Weckhuysen, Bert M; Bruijnincx, Pieter C A

    2016-08-23

    Lignin is an attractive renewable feedstock for aromatic bulk and fine chemicals production, provided that suitable depolymerization procedures are developed. Here, we describe a tandem catalysis strategy for ether linkage cleavage within lignin, involving ether hydrolysis by water-tolerant Lewis acids followed by aldehyde decarbonylation by a Rh complex. In situ decarbonylation of the reactive aldehydes limits loss of monomers by recondensation, a major issue in acid-catalyzed lignin depolymerization. Rate of hydrolysis and decarbonylation were matched using lignin model compounds, allowing the method to be successfully applied to softwood, hardwood, and herbaceous dioxasolv lignins, as well as poplar sawdust, to give the anticipated decarbonylation products and, rather surprisingly, 4-(1-propenyl)phenols. Promisingly, product selectivity can be tuned by variation of the Lewis-acid strength and lignin source. PMID:27440544

  14. Preparation of Monodisperse Iron Oxide Nanoparticles via the Synthesis and Decomposition of Iron Fatty Acid Complexes

    PubMed Central

    2009-01-01

    Iron fatty acid complexes (IFACs) are prepared via the dissolution of porous hematite powder in hot unsaturated fatty acid. The IFACs are then decomposed in five different organic solvents under reflux conditions in the presence of the respective fatty acid. The XRD analysis results indicate that the resulting NPs comprise a mixture of wustite, magnetite, and maghemite phases. The solvents with a higher boiling point prompt the formation of larger NPs containing wustite as the major component, while those with a lower boiling point produce smaller NPs with maghemite as the major component. In addition, it is shown that unstable NPs with a mixed wustite–magnetite composition can be oxidized to pure maghemite by extending the reaction time or using an oxidizing agent. PMID:20628451

  15. Metallo-hydrazone complexes immobilized in zeolite Y: Synthesis, identification and acid violet-1 degradation

    NASA Astrophysics Data System (ADS)

    Ahmed, Ayman H.; Thabet, M. S.

    2011-12-01

    Copper(II), cobalt(II) and nickel(II) complexes of hydrazone ligand (SAPH) derived from salicylaldehyde and phenylhydrazine have been encapsulated in zeolite-Y super cages via ship-in-a-bottle synthesis. Detailed characterization of the intrazeolitic complexes were performed by elemental analysis, spectral (FT-IR, UV-Vis.) studies, magnetic measurements and X-ray diffraction. Furthers, surface texture and thermal analysis (TG, DTG, DTA) have provided further evidence for successful immobilization of the metal complexes inside zeolite Y. Investigation of the stereochemistry of these incorporated chelates pointed out that, SAPH ligand is capable to coordinate with the central metal through the (C dbnd N), phenolic (OH) and (NH) groups forming polynuclear structures. The involvement of zeolite oxygen in coordination was postulated in the hybrid materials. The intrazeolitic copper, cobalt and nickel-SAPH complexes have distorted tetrahedral, octahedral and square-pyramidal configurations, respectively. The zeolite encapsulated complexes are thermally stable up to 800 °C except Cu(II) sample which is thermally stable up to midpoint 428 °C. The assessment of the catalytic activity was performed by the use of the photo-degradation of acid violet-1 dye as a probe reaction in presence of H 2O 2 as an oxidant. Decolorization of acid violet-1 dye was examined under the same conditions whereas the unpromoted zeolite and Cu II, Co II, Ni II-hydrazone complexes supported on zeolite showed 13% and 76%, 53%, 43% color removal, respectively. The results revealed that, the zeolite encapsulated Cu(II) complex generally exhibited better catalytic efficiency (76%) compared with other investigated zeolite encapsulated metal-hydrazone samples.

  16. Signs of antimetastatic activity of palladium complexes of methylenediphosphonic acid in IR spectra

    NASA Astrophysics Data System (ADS)

    Tolstorozhev, G. B.; Skornyakov, I. V.; Pekhnio, V. I.; Kozachkova, A. N.; Sharykina, N. I.

    2012-07-01

    We have used Fourier transform IR spectroscopy methods to study normal mouse lung tissue and also after subcutaneous transplantation of a B-16 melanoma tumor in the tissue. We also studied tissues with B-16 melanoma after they were treated with coordination compounds based on palladium complexes of methylenediphosphonic acid. The IR spectra of the lung tissues with metastases in the region of the C = O stretching vibrations are different from the IR spectra of normal tissue. We identified spectroscopic signs of the presence of metastases in the lung. We show that when a cancerous tumor is treated with a preparation of palladium complexes of methylenediphosphonic acid, the spectroscopic signs of the presence of metastases in the lung are missing. After treatment with the optimal dose of this drug, the IR spectrum of the lung tissue in which multiple metastases were present before treatment corresponds to the spectrum of normal tissue. We have determined the efficacy of the antitumor activity of coordination compounds based on palladium complexes of methylenediphosphonic acid.

  17. Luminescence behavior of terbium sulphosalicylic acid complexes in sol-gel derived host materials

    SciTech Connect

    Fan, X.; Wang, M.; Wang, Z.; Hong, Z.

    1997-08-01

    The formation and luminescence behavior of terbium sulphosalicylic acid (TbSSA) complexes in sol-gel derived host materials have been investigated. The 5-sulphosalicylic acid (H{sub 3}SSA) was dissolved in ethanol in advance, and then the TbCl{sub 3} and ethanol containing H{sub 3}SSA were introduced into the initial precursor sol, respectively. The resulting sol exhibits intramolecular energy transfer from the coordinated sulphosalicylic acid to the terbium ion. The TbSSA complex has formed in the TbCl{sub 3} and H{sub 3}SSA codoped sol. The complexes were found to have notably higher fluorescence intensities than TbCl{sub 3} in both the sol and the gel. In the sol, the concentration quenching was a diffusion-controlled process due to aggregation and effective collision between molecules and the fluorescence was decreased with increase of H{sub 3}SSA concentration. On the other hand, the molecules in the gel were isolated in the pores of the silica network. The fluorescence intensities of TbSSA in the gel were increased with the increase of concentration ratio of H{sub 3}SSA/TbCl{sub 3}. Maximum fluorescence intensity was obtained at H{sub 3}SSA/TbCl{sub 3} = 2.

  18. Cationic liposome–nucleic acid complexes for gene delivery and gene silencing

    PubMed Central

    Ewert, Kai K.; Majzoub, Ramsey N.; Leal, Cecília

    2014-01-01

    Cationic liposomes (CLs) are studied worldwide as carriers of DNA and short interfering RNA (siRNA) for gene delivery and gene silencing, and related clinical trials are ongoing. Optimization of transfection efficiency and silencing efficiency by cationic liposome carriers requires a comprehensive understanding of the structures of CL–nucleic acid complexes and the nature of their interactions with cell membranes as well as events leading to release of active nucleic acids within the cytoplasm. Synchrotron x-ray scattering has revealed that CL–nucleic acid complexes spontaneously assemble into distinct liquid crystalline phases including the lamellar, inverse hexagonal, hexagonal, and gyroid cubic phases, and fluorescence microscopy has revealed CL–DNA pathways and interactions with cells. The combining of custom synthesis with characterization techniques and gene expression and silencing assays has begun to unveil structure–function relations in vitro. As a recent example, this review will briefly describe experiments with surface-functionalized PEGylated CL–DNA nanoparticles. The functionalization, which is achieved through custom synthesis, is intended to address and overcome cell targeting and endosomal escape barriers to nucleic acid delivery faced by PEGylated nanoparticles designed for in vivo applications. PMID:25587216

  19. Communication: Physical origins of ionization potential shifts in mixed carboxylic acids and water complexes.

    PubMed

    Gu, Quanli; Tang, Zhen; Su, Peifeng; Wu, Wei; Yang, Zhijun; Trindle, Carl O; Knee, Joseph L

    2016-08-01

    The ionization potential (IP) of the aromatic alpha hydroxy carboxylic acid, 9-hydroxy-9-fluorene carboxylic acid (9HFCA), is shifted by complexation with hydrogen bonding ligands such as water and formic acid. Generalized Kohn-Sham energy decomposition analysis decomposes the intermolecular binding energies into a frozen energy term, polarization, correlation, and/or dispersion energy terms, as well as terms of geometric relaxation and zero point energy. We observe that in each dimer the attractive polarization always increases upon ionization, enhancing binding in the cation and shifting the IP toward the red. For 9HFCA-H2O, a substantial decrease of the repulsive frozen energy in cation further shifts the IP toward red. For 9HFCA-HCOOH, the increase of the frozen energy actually occurs in the cation and shifts the IP toward blue. Consistent with the experimental measurements, our analysis provides new, non-intuitive perspectives on multiple hydrogen bonds interactions in carboxylic acids and water complexes. PMID:27497532

  20. Hydrogen pickup mechanism of zirconium alloys

    NASA Astrophysics Data System (ADS)

    Couet, Adrien

    Although the optimization of zirconium based alloys has led to significant improvements in hydrogen pickup and corrosion resistance, the mechanisms by which such alloy improvements occur are still not well understood. In an effort to understand such mechanisms, a systematic study of the alloy effect on hydrogen pickup is conducted, using advanced characterization techniques to rationalize precise measurements of hydrogen pickup. The hydrogen pick-up fraction is accurately measured for a specially designed set of commercial and model alloys to investigate the effects of alloying elements, microstructure and corrosion kinetics on hydrogen uptake. Two different techniques to measure hydrogen concentrations were used: a destructive technique, Vacuum Hot Extraction, and a non-destructive one, Cold Neutron Prompt Gamma Activation Analysis. The results indicate that hydrogen pickup varies not only from alloy to alloy but also during the corrosion process for a given alloy. For instance Zircaloy type alloys show high hydrogen pickup fraction and sub-parabolic oxidation kinetics whereas ZrNb alloys show lower hydrogen pickup fraction and close to parabolic oxidation kinetics. Hypothesis is made that hydrogen pickup result from the need to balance charge during the corrosion reaction, such that the pickup of hydrogen is directly related to (and indivisible of) the corrosion mechanism and decreases when the rate of electron transport or oxide electronic conductivity sigmao xe through the protective oxide increases. According to this hypothesis, alloying elements (either in solid solution or in precipitates) embedded in the oxide as well as space charge variations in the oxide would impact the hydrogen pick-up fraction by modifying sigmaox e, which drives oxidation and hydriding kinetics. Dedicated experiments and modelling were performed to assess and validate these hypotheses. In-situ electrochemical impedance spectroscopy (EIS) experiments were performed on Zircaloy-4 tubes

  1. Oleic Acid Stimulates Complete Oxidation of Fatty Acids through Protein Kinase A-dependent Activation of SIRT1-PGC1α Complex*

    PubMed Central

    Lim, Ji-Hong; Gerhart-Hines, Zachary; Dominy, John E.; Lee, Yoonjin; Kim, Sungjin; Tabata, Mitsuhisa; Xiang, Yang K.; Puigserver, Pere

    2013-01-01

    Fatty acids are essential components of the dynamic lipid metabolism in cells. Fatty acids can also signal to intracellular pathways to trigger a broad range of cellular responses. Oleic acid is an abundant monounsaturated omega-9 fatty acid that impinges on different biological processes, but the mechanisms of action are not completely understood. Here, we report that oleic acid stimulates the cAMP/protein kinase A pathway and activates the SIRT1-PGC1α transcriptional complex to modulate rates of fatty acid oxidation. In skeletal muscle cells, oleic acid treatment increased intracellular levels of cyclic adenosine monophosphate (cAMP) that turned on protein kinase A activity. This resulted in SIRT1 phosphorylation at Ser-434 and elevation of its catalytic deacetylase activity. A direct SIRT1 substrate is the transcriptional coactivator peroxisome proliferator-activated receptor γ coactivator 1-α (PGC1α), which became deacetylated and hyperactive after oleic acid treatment. Importantly, oleic acid, but not other long chain fatty acids such as palmitate, increased the expression of genes linked to fatty acid oxidation pathway in a SIRT1-PGC1α-dependent mechanism. As a result, oleic acid potently accelerated rates of complete fatty acid oxidation in skeletal muscle cells. These results illustrate how a single long chain fatty acid specifically controls lipid oxidation through a signaling/transcriptional pathway. Pharmacological manipulation of this lipid signaling pathway might provide therapeutic possibilities to treat metabolic diseases associated with lipid dysregulation. PMID:23329830

  2. Crystal structures of complexes of vitamin D receptor ligand-binding domain with lithocholic acid derivatives

    PubMed Central

    Masuno, Hiroyuki; Ikura, Teikichi; Morizono, Daisuke; Orita, Isamu; Yamada, Sachiko; Shimizu, Masato; Ito, Nobutoshi

    2013-01-01

    The secondary bile acid lithocholic acid (LCA) and its derivatives act as selective modulators of the vitamin D receptor (VDR), although their structures fundamentally differ from that of the natural hormone 1α,25-dihydroxyvitamin D3 [1,25(OH)2D3)]. Here, we have determined the crystal structures of the ligand-binding domain of rat VDR (VDR-LBD) in ternary complexes with a synthetic partial peptide of the coactivator MED1 (mediator of RNA polymerase II transcription subunit 1) and four ligands, LCA, 3-keto LCA, LCA acetate, and LCA propionate, with the goal of elucidating their agonistic mechanism. LCA and its derivatives bind to the same ligand-binding pocket (LBP) of VDR-LBD that 1,25(OH)2D3 binds to, but in the opposite orientation; their A-ring is positioned at the top of the LBP, whereas their acyclic tail is located at the bottom of the LBP. However, most of the hydrophobic and hydrophilic interactions observed in the complex with 1,25(OH)2D3 are reproduced in the complexes with LCA and its derivatives. Additional interactions between VDR-LBD and the C-3 substituents of the A-ring are also observed in the complexes with LCA and its derivatives. These may result in the observed difference in the potency among the LCA-type ligands. PMID:23723390

  3. A study of the metal binding capacity of saccharinic acids formed during the alkali catalysed decomposition of cellulosic materials: nickel complexation by glucoisosaccharinic acids and xyloisosaccharinic acids.

    PubMed

    Almond, Michael; Belton, Daniel; Humphreys, Paul N; Laws, Andrew P

    2016-06-01

    The stoichiometry of the metal complexes formed between nickel and the ligand β-glucoisosaccharinic acid (β-GISA) and a racemic mixture of enantiomers of xyloisosaccharinic acid (XISA) has been determined at both neutral and alkaline pHs. Bjerrum plots, Job's plots and conductance measurements indicated that for each of the systems one to one Ni(ligand) complexes were formed at near neutral pHs (<7.5). At intermediate alkaline pHs (7.5-13) there is evidence to support the formation and precipitation of Ni2(ligand)(OH)3 complexes, finally, at high pH (>13) sparingly soluble Ni2(ligand)(OH)4 complexes were formed. The stability constants for the Ni(β-GISA), Ni(α-GISA) and Ni(XISA) complexes formed at neutral pH were determined under identical conditions using polarographic studies. The measured stability constants for Ni(β-GISA) (log10 β = 1.94 ± 0.15) and for Ni(α-GISA)(log10 β = 2.07 ± 0.13) are very similar; the value measured for the Ni(XISA) complex (log10 β = 0.83) was an order of magnitude smaller. The stability constants for the Ni2(Ligand)(OH)4 complexes formed at highly alkaline pHs were determined using the Schubert method. The measured stability constant for Ni2(β-GISA)(OH)4 (log10 β = 30.6 ± 0.5) was an order of magnitude bigger than the value for Ni2(α-GISA)(OH)4 (log10 β = 29.0 ± 0.5) measured under identical conditions. Attempts to measure the stability constant for Ni2(XISA)(OH)4 were unsuccessful; Ni2(XISA)(OH)4 complexes were not present in significant amounts at high pH to allow the log10β value to be determined by the Schubert method. PMID:27107221

  4. Characterization and dynamic properties for the solid inclusion complexes of β-cyclodextrin and perfluorooctanoic acid.

    PubMed

    Karoyo, Abdalla H; Sidhu, Paul; Wilson, Lee D; Hazendonk, Paul

    2013-07-11

    The structural characterization and dynamic properties of solid-state inclusion complexes (ICs) formed between β-cyclodextrin (β-CD; host) and perfluorooctanoic acid (PFOA; guest) were investigated using (13)C NMR spectroscopy. The 1:1 and 2:1 host/guest solid-state complexes were prepared using a modified dissolution method to obtain complexes with high phase purity. These complexes were further characterized using differential scanning calorimetry (DSC), FT-IR spectroscopy, powder X-ray diffraction (PXRD), (19)F directpolarization (DP), and (13)C cross-polarization (CP) with magic-angle spinning (MAS) NMR spectroscopy. The (19)F → (13)C CP results provided unequivocal support for the formation of well-defined inclusion compounds. The phase purity of the complexes formed between β-CD and PFOA were assessed using the (19)F DP NMR technique at variable temperature (VT) and MAS at 20 kHz. The complexes were found to be of high phase purity when prepared in accordance with the modified dissolution method. The motional dynamics of the guest in the solid complexes were assessed using T1/T2/T1ρ relaxation NMR methods at ambient and VT conditions. The relaxation data revealed reliable and variable guest dynamics for the 1:1 versus 2:1 complexes at the VTs investigated. The motional dynamics of the guest molecules involve an ensemble of axial motions of the whole chain and 120° rotational jumps of the methyl (CF3) group at the termini of the perfluorocarbon chain. The axial and rotational dynamics of the guest in the 1:1 and 2:1 complexes differ in distribution and magnitude in accordance with the binding geometry of the guest within the host. PMID:23713518

  5. Amino-Functionalized Layered Crystalline Zirconium Phosphonates: Synthesis, Crystal Structure, and Spectroscopic Characterization.

    PubMed

    Taddei, Marco; Sassi, Paola; Costantino, Ferdinando; Vivani, Riccardo

    2016-06-20

    Two new layered zirconium phosphonates functionalized with amino groups were synthesized starting from aminomethylphosphonic acid in the presence of different mineralizers, and their structures were solved from powder X-ray diffraction data. Their topologies are unprecedented in zirconium phosphonate chemistry: the first, of formula ZrH[F3(O3PCH2NH2)], prepared in the presence of hydrofluoric acid, features uncommon ZrO2F4 units and a remarkable thermal stability; the second, of formula Zr2H2[(C2O4)3(O3PCH2NH2)2]·2H2O, prepared in the presence of oxalic acid, is based on ZrO7 units with oxalate anions coordinated to the metal atom, which were never observed before in any zirconium phosphonate. In addition, the structure of another compound based on (2-aminoethyl)phosphonic acid is reported, which was the object of a previously published study. This compound has layered α-type structure with -NH3(+) groups located in the interlayer space. All of the reported compounds were further characterized by means of vibrational spectroscopy, which provided important information on fine structural details that cannot be deduced from the powder X-ray diffraction data. PMID:27254781

  6. Dehydration of fructose to 5-hydroxymethylfurfural in sub-critical water over heterogeneous zirconium phosphate catalysts.

    PubMed

    Asghari, Feridoun Salak; Yoshida, Hiroyuki

    2006-10-16

    Dehydration of fructose to 5-hydroxymethylfurfural in a batch-type process with sub-critical water (sub-CW) was performed in the presence of different laboratory-made zirconium phosphate solid acids at 240 degrees C. A direct relation was found between increasing the crystallinity and decreasing the surface area of solid acids. However, irrespective of the different surface areas, similar catalytic behaviors were observed. Meanwhile, calcination of the samples showed no improvement in the activity of the solid acids. In the presence of the amorphous form of zirconium phosphate, about 80% of fructose was decomposed in sub-critical water at 240 degrees C after 120 s, and the selectivity of the dehydration reaction of fructose to 5-hydroxymethylfurfural rose to 61%. No rehydration products were identified. Soluble polymers and furaldehyde were the only major and minor side products found, respectively. Finally it was found that zirconium phosphate solid acids were stable under sub-CW conditions, and they can easily be recovered without changing their catalytic properties. PMID:16870164

  7. Superconductivity in zirconium-rhodium alloys

    NASA Technical Reports Server (NTRS)

    Zegler, S. T.

    1969-01-01

    Metallographic studies and transition temperature measurements were made with isothermally annealed and water-quenched zirconium-rhodium alloys. The results clarify both the solid-state phase relations at the Zr-rich end of the Zr-Rh alloy system and the influence upon the superconducting transition temperature of structure and composition.

  8. METHOD AND ALLOY FOR BONDING TO ZIRCONIUM

    DOEpatents

    McCuaig, F.D.; Misch, R.D.

    1960-04-19

    A brazing alloy can be used for bonding zirconium and its alloys to other metals, ceramics, and cermets, and consists of 6 to 9 wt.% Ni, 6 to 9 wn~.% Cr, Mo, or W, 0 to 7.5 wt.% Fe, and the balance Zr.

  9. Zirconium modified nickel-copper alloy

    NASA Technical Reports Server (NTRS)

    Whittenberger, J. D. (Inventor)

    1977-01-01

    An improved material for use in a catalytic reactor which reduces nitrogen oxide from internal combustion engines is in the form of a zirconium-modified, precipitation-strengthened nickel-copper alloy. This material has a nominal composition of Ni-30 Cu-0.2 Zr and is characterized by improved high temperature mechanical properties.

  10. Electron transfer reactions of osmium(II) complexes with phenols and phenolic acids

    NASA Astrophysics Data System (ADS)

    Rajeswari, Angusamy; Ramdass, Arumugam; Muthu Mareeswaran, Paulpandian; Velayudham, Murugesan; Rajagopal, Seenivasan

    2016-07-01

    Three [Os(NN)3]2+ complexes (NN = polypyridine) with ligands of varying hydrophobicity were synthesized and characterized by NMR spectral techniques. The geometry of the molecules are optimized by DFT calculations. The interaction between [Os(NN)3]2+ complexes and phenolate ion in ground state is confirmed by absorption spectral study and the binding constant values are in the range of 3-740 M-1. The photoinduced electron transfer reaction of these [Os(NN)3]2+ complexes with phenols and phenolic acids at pH 12.5 leads to the formation of phenoxyl radical confirmed through transient absorption spectral study. Binding constants and electron transfer rate constants within the [Os(NN)3]2+-phenolate ion adduct account for the change for the overall quenching constant with the change of structure of reactants.

  11. Influence of Humic Acid Complexation with Metal Ions on Extracellular Electron Transfer Activity.

    PubMed

    Zhou, Shungui; Chen, Shanshan; Yuan, Yong; Lu, Qin

    2015-01-01

    Humic acids (HAs) can act as electron shuttles and mediate biogeochemical cycles, thereby influencing the transformation of nutrients and environmental pollutants. HAs commonly complex with metals in the environment, but few studies have focused on how these metals affect the roles of HAs in extracellular electron transfer (EET). In this study, HA-metal (HA-M) complexes (HA-Fe, HA-Cu, and HA-Al) were prepared and characterized. The electron shuttle capacities of HA-M complexes were experimentally evaluated through microbial Fe(III) reduction, biocurrent generation, and microbial azoreduction. The results show that the electron shuttle capacities of HAs were enhanced after complexation with Fe but were weakened when using Cu or Al. Density functional theory calculations were performed to explore the structural geometry of the HA-M complexes and revealed the best binding sites of the HAs to metals and the varied charge transfer rate constants (k). The EET activity of the HA-M complexes were in the order HA-Fe > HA-Cu > HA-Al. These findings have important implications for biogeochemical redox processes given the ubiquitous nature of both HAs and various metals in the environment. PMID:26593782

  12. Influence of Humic Acid Complexation with Metal Ions on Extracellular Electron Transfer Activity

    PubMed Central

    Zhou, Shungui; Chen, Shanshan; Yuan, Yong; Lu, Qin

    2015-01-01

    Humic acids (HAs) can act as electron shuttles and mediate biogeochemical cycles, thereby influencing the transformation of nutrients and environmental pollutants. HAs commonly complex with metals in the environment, but few studies have focused on how these metals affect the roles of HAs in extracellular electron transfer (EET). In this study, HA-metal (HA-M) complexes (HA-Fe, HA-Cu, and HA-Al) were prepared and characterized. The electron shuttle capacities of HA-M complexes were experimentally evaluated through microbial Fe(III) reduction, biocurrent generation, and microbial azoreduction. The results show that the electron shuttle capacities of HAs were enhanced after complexation with Fe but were weakened when using Cu or Al. Density functional theory calculations were performed to explore the structural geometry of the HA-M complexes and revealed the best binding sites of the HAs to metals and the varied charge transfer rate constants (k). The EET activity of the HA-M complexes were in the order HA-Fe > HA-Cu > HA-Al. These findings have important implications for biogeochemical redox processes given the ubiquitous nature of both HAs and various metals in the environment. PMID:26593782

  13. DNA binding mode of novel tetradentate amino acid based 2-hydroxybenzylidene-4-aminoantipyrine complexes

    NASA Astrophysics Data System (ADS)

    Raman, N.; Sobha, S.; Selvaganapathy, M.; Mahalakshmi, R.

    2012-10-01

    Few transition metal complexes of tetradentate N2O2 donor Schiff base ligands containing 2-hydroxybenzylidene-4-aminoantipyrine and amino acids (alanine/valine) abbreviated to KHL1/KHL2 have been synthesized. All the metal complexes have been fully characterized with the help of elemental analyses, molecular weights, molar conductance values, magnetic moments and spectroscopic data. The Schiff bases KHL1/KHL2 are found to act as tetradentate ligands using N2O2 donor set of atoms leading to a square-planar geometry for the complexes around the metal ions. The binding behaviors of the complexes to calf thymus DNA have been investigated by absorption spectra, viscosity measurements and cyclic voltammetry. The DNA binding constants reveal that all these complexes interact with DNA through minor groove binding mode. The studies on mechanism of photocleavage reveal that singlet oxygen (1O2) and superoxide anion radical (O2rad -) may play an important role in the photocleavage. The Schiff bases and their metal complexes have been screened for their in vitro antibacterial activities against Staphylococcus aureus, Pseudomonas aeruginosa, Escherichia coli, Staphylococcus epidermidis, Klebsiella pneumoniae and antifungal activities against Aspergillus niger, Fusarium solani, Culvularia lunata, Rhizoctonia bataicola and Candida albicans by MIC method.

  14. Influence of Humic Acid Complexation with Metal Ions on Extracellular Electron Transfer Activity

    NASA Astrophysics Data System (ADS)

    Zhou, Shungui; Chen, Shanshan; Yuan, Yong; Lu, Qin

    2015-11-01

    Humic acids (HAs) can act as electron shuttles and mediate biogeochemical cycles, thereby influencing the transformation of nutrients and environmental pollutants. HAs commonly complex with metals in the environment, but few studies have focused on how these metals affect the roles of HAs in extracellular electron transfer (EET). In this study, HA-metal (HA-M) complexes (HA-Fe, HA-Cu, and HA-Al) were prepared and characterized. The electron shuttle capacities of HA-M complexes were experimentally evaluated through microbial Fe(III) reduction, biocurrent generation, and microbial azoreduction. The results show that the electron shuttle capacities of HAs were enhanced after complexation with Fe but were weakened when using Cu or Al. Density functional theory calculations were performed to explore the structural geometry of the HA-M complexes and revealed the best binding sites of the HAs to metals and the varied charge transfer rate constants (k). The EET activity of the HA-M complexes were in the order HA-Fe > HA-Cu > HA-Al. These findings have important implications for biogeochemical redox processes given the ubiquitous nature of both HAs and various metals in the environment.

  15. Binary and ternary complexes of some inner transition metal ions with amino acids and acetyl acetone

    NASA Astrophysics Data System (ADS)

    Abu-Eittah, R. H.; Abdou, M. M.; Salem, M. B.

    1998-05-01

    The stability constants of the 1:1 and 1:2 (whenever possible) complexes formed between La3+, Ce3+, Th4+ and the amino acid anions L-alaninate, L-phenylalaninate and L-histidinate were determined by potentiometric titration in aqueous solution (25± 1 ^circC, I = 0.1 M KCl) and compared together with the constants previously determined. The various formation degree of the resulting M(L) and M(L)2 were determined. In order to relate the formation degree of M(L) and M(L)2 with the basicity of the amino acid anion (L^-), the acidity constants of the protonated amino acids, H2L^+, were also measured. The main results of this work prove that Th4+ ion forms the strongest complex with the studied amino acids. It is the only ion which forms a 1:2 complex. The heterocyclic ring of histidine plays a significant role in complexing with the studied metal ions as is clearly seen from the distribution of the degree of formation of the different complexes. The stability constants of the 1:1:1, 1:2:1 and 1:1:2 complexes formed between La3+, Ce3+, Th4+ and the anions L-alaninate, L-phenylalaninate and L-histidinate together with the acetyl acetonate ion were also determined following the same experimental set up used in the study of the simple complexes. The mixed-ligand complexes turned out to be very much stronger than the simple ligand complexes. Formation of a mixed ligand complex can be considered as a type of senergism. Les constantes de stabilité des complexes 1:1 et 2:2 (lorsque cela est possible) formés entre La3+, Ce3+, Th4+ et les anions aminoacides L-alaninate, L-phénylalaninate et L-histidinate ont été déterminées par dosage potentiométrique en solution aqueuse (25± 1 ^circC, I = 0,1 M KCl), et comparées à celles de la littérature. Les différents degrés de formation de M(L) et M(L)2 ont été quantifiés. Pour mettre en évidence la relation entre le degré de formation de M(L) et M(L)2 et la basicité des anions aminoacides (L^-), les constantes d

  16. DNA interaction with octahedral and square planar Ni(II) complexes of aspartic-acid Schiff-bases

    NASA Astrophysics Data System (ADS)

    Sallam, S. A.; Orabi, A. S.; Abbas, A. M.

    2011-12-01

    Ni(II) complexes of (S,E)-2-(2-OHbenzilydene)aspartic acid; (S,E)-2-(2,3-diOHbenzilydene)aspartic acid-; (S,E)-2-(2,4-diOH-benzilydene)aspartic acid; (S,E)-2-(2,5-diOHbenzilydene)aspartic acid and (S,E)-2-((2-OHnaphthalene-1-yl)methylene)aspartic acid Schiff-bases have been synthesized by template method in ethanol or ammonia media. They were characterized by elemental analyses, conductivity measurements, magnetic moment, UV, IR and 1H nmr spectra as well as thermal analysis (TG, DTG, DTA). The Schiff-bases are dibasic tridentate or tetradentate donors and the complexes have square planar and octahedral structures. The complexes decompose in two or three steps where kinetic and thermodynamic parameters of the decomposition steps were computed. The interactions of the formed complexes with FM-DNA were monitored by UV and fluorescence spectroscopy.

  17. Mixed-ligand complex compounds of rare-earth elements (REE) with acetylacetone and fumaric or maleic acid

    SciTech Connect

    Panyushkin, V.T.; Akhrimenko, N.V.

    1994-10-01

    Previously the authors investigated the possibility of synthesis of the f-block element mixed complexes with {beta}-diketones and organic unsaturated acids. The mixed-ligand complexes of lanthanides [Ln = Nd(III), Sm(III), Eu(III), Tb(III), Dy(III), Ho(III), and Yb(III)] with acetylacetone (acac) and fumaric or maleic acid (AcidH{sub 2}) were synthesized. The mixed-ligand complexes were prepared by the interaction of REE tris(acetylacetonates) [Ln(acac){sub 3}{center_dot} 3H{sub 2}O] with half as much excess of the organic acid in a solution of diethyl ether. According to the data of elemental analysis and thermogravimetric and spectroscopic investigations, the mixed complexes studied are of composition Ln(acac){sub 2}(AcidH){center_dot}H{sub 2}O.

  18. Preferable removal of phosphate from water using hydrous zirconium oxide-based nanocomposite of high stability.

    PubMed

    Chen, Liang; Zhao, Xin; Pan, Bingcai; Zhang, Weixian; Hua, Ming; Lv, Lu; Zhang, Weiming

    2015-03-01

    In this study, we employed a new nanocomposite adsorbent HZO-201, which featured high stability under varying solution chemistry, for preferable removal of phosphate from synthetic solution and a real effluent. An anion exchange resin (D-201) was employed as the host of HZO-201, where nano-hydrous zirconium oxide (HZO) was encapsulated as the active species. D-201 binds phosphate through nonspecific electrostatic affinity, whereas the loaded HZO nanoparticles capture phosphate through formation of the inner-sphere complexes. Quantitative contribution of both species to phosphate adsorption was predicted based on the double-Langmuir model. Preferable removal of phosphate by HZO-201 was observed in the presence of the competing anions at higher levels (Cl(-), NO3(-), SO4(2-), HCO3(-)). Fixed-bed adsorption indicated that the effective volume capacity of a synthetic water (2.0 mg P-PO4(3-)/L) by using HZO-201 was ∼1600 BV in the first run (<0.5mg P-PO4(3-)/L), comparable to Fe(III)-based nanocomposite HFO-201 (∼1500 BV) and much larger than D-201 (<250 BV). The exhausted HZO-201 can be in situ regenerated by using a binary NaOH-NaCl solution for cyclic runs, whether fed with the synthetic solution or real effluent. In general, HZO-201 is a promising alternative to Fe(III)-based adsorbents for trace phosphate removal from effluent particularly at acidic pH. PMID:25463215

  19. International strategic minerals inventory summary report; zirconium

    USGS Publications Warehouse

    Towner, R.R.

    1992-01-01

    Zircon, a zirconium silicate, is currently the most important commercial zirconium-bearing mineral. Baddeleyite, a natural form of zirconia, is less important but has some specific end uses. Both zircon and baddeleyite occur in hard-rock and placer deposits, but at present all zircon production is from placer deposits. Most baddeleyite production is from hard-rock deposits, principally as a byproduct of copper and phosphate-rock mining. World zirconium resources in identified, economically exploitable deposits are about 46 times current production rates. Of these resources, some 71 percent are in South Africa, Australia, and the United States. The principal end uses of zirconium minerals are in ceramic applications and as refractories, abrasives, and mold linings in foundries. A minor amount, mainly of zircon, is used for the production of hafnium-free zirconium metal, which is used principally for sheathing fuel elements in nuclear reactors and in the chemical-processing industry, aerospace engineering, and electronics. Australia and South Africa are the largest zircon producers and account for more than 70 percent of world output; the United States and the Soviet Union account for another 20 percent. South Africa accounts for almost all the world's production of baddeleyite, which is about 2 percent of world production of contained zirconia. Australia and South Africa are the largest exporters of zircon. Unless major new deposits are developed in countries that have not traditionally produced zircon, the pattern of world production is unlikely to change by 2020. The proportions, however, of production that come from existing producing countries may change somewhat.

  20. Zirconium oxidation on the atomic scale.

    PubMed

    Hudson, Daniel; Cerezo, Alfred; Smith, George D W

    2009-04-01

    Zirconium alloys are used in the nuclear industry as fuel rod cladding. They are chosen for this role because of their good mechanical properties and low thermal neutron absorption. Oxidation of these alloys by coolant is one of the chief limiting factors of the fuel burn-up efficiency. The aim of the present study is to understand these oxidation mechanisms. As a first step, a fundamental study of the oxidation of commercially pure zirconium has been conducted using the 3D atom probe (3DAP). The current generation of 3DAPs allows both voltage and laser pulsing, providing data sets of many millions of ions. According to the literature the only stable oxide of zirconium is ZrO(2). However, the 3DAP shows that an initial layer a few nanometres thick forms with a composition of ZrO(1-)(x) when subjected to light oxidation. This result confirms and extends the work of Wadman et al. [Colloque de Physique 50 (1989) C8 303; Journal de Physique, 11 (1988) C6 49] and Wadman and Andrén [in: C.M. Euchen, A.M. Garde (Eds.), Zirconium in the Nuclear Industry: Ninth Symposium, ASTM STP 1132, ASTM, USA, 1991, p. 461], who used 1DAP techniques, obtaining reduced data sets. Segregation of hydrogen to the metal-oxide interface and a distinct ZrH phase were observed in this study. A novel kinetics study of the room temperature oxidation of zirconium showed the ZrO layer to be non-protective over the time period investigated (up to 1h). PMID:19101084

  1. Zirconium(IV)-Benzene Phosphonate Coordination Polymers: Lanthanide and Actinide Extraction and Thermal Properties.

    PubMed

    Luca, Vittorio; Tejada, Juan J; Vega, Daniel; Arrachart, Guilhem; Rey, Cyrielle

    2016-08-15

    Coordination polymers with different P/(Zr + P) molar ratios were prepared by combining aqueous solutions of Zr(IV) and benzenephosphonate derivatives. 1,3,5-Benzenetrisphosphonic acid (BTP) as well as phosphonocarboxylate derivatives in which carboxylate substitutes one or two of the phosphonate groups were chosen as the building blocks. The precipitates obtained on combining the two solutions were not X-ray amorphous but rather were indicative of poorly ordered materials. Hydrothermal treatment did not alter the structure of the materials produced but did result in improved crystalline order. The use of HF as a mineralizing agent during hydrothermal synthesis resulted in the crystallization of at least three relatively crystalline phases whose structure could not be determined owing to the complexity of the diffraction patterns. Gauging from the similarity of the diffraction patterns of all the phases, the poorly ordered precipitates and crystalline materials appeared to have similar underlying structures. The BTP-based zirconium phosphonates all showed a higher selectivity for lanthanides and thorium compared with cations such as Cs(+), Sr(2+), and Co(2+). Substitution of phosphonate groups by carboxylate groups did little to alter the pattern of selectivity implying that selectivity in the system was entirely determined by the -POH group with little influence from the -COOH groups. Samples with the highest phosphorus content showed the highest extraction efficiencies for lanthanide elements, especially the heavy lanthanides such as Dy(3+) and Ho(3+) with separation factors of around four with respect to La(3+). In highly acid solutions (4 M HNO3) there was a pronounced variation in extraction efficiency across the lanthanide series. In situ, nonambient diffraction was performed on ZrBTP-0.8 loaded with Th, Ce, and a complex mixture of lanthanides. In all cases the crystalline Zr2P2O7 pyrophosphate phase was formed at ∼800 °C demonstrating the versatility of

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

    NASA Astrophysics Data System (ADS)

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

    2013-05-01

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

  3. ESR study of irradiated single crystals of the cocrystalline complex of cytidine: Salicylic acid

    SciTech Connect

    Close, D.M.; Sagstuen, E.

    1983-12-01

    Irradiation at 77 K of single crystals of the 1:1 complex of cytidine and salicylic acid produces a phenoxyl radical formed by oxidation of the salicylic acid. Anisotropic hyperfine coupling tensors have been determined for this radical which are associated with the para and ortho hydrogens. No cytidine oxidation products (alkoxy or hydroxyalkyl radicals) were observed at 77 K. Following the decay of the phenoxyl radical at room temperature, four radicals were detected. These include the cytosine 5--yl and 6--yl radicals, formed by H addition to the cytosine ring, and an anisotropic doublet. By UV irradiation at room temperature, it is possible to convert a significant fraction of 6-yl radicals into 5-yl radicals. Hyperfine coupling and g tensors determined for the anisotropic doublet indicate that this radical is formed in the C/sub 1'/-C/sub 2'/ region of the sugar moiety. These results indicate a shift in radiation damage away from the salicylic acid upon warming, and show that the radiation chemistry of the cocrystalline complex is different from that of the isolated bases.

  4. Intestinal peptidases form functional complexes with the neutral amino acid transporter B0AT1

    PubMed Central

    Fairweather, Stephen J.; Bröer, Angelika; O'Mara, Megan L.; Bröer, Stefan

    2012-01-01

    The brush-border membrane of the small intestine and kidney proximal tubule are the major sites for the absorption and re-absorption of nutrients in the body respectively. Transport of amino acids is mediated through the action of numerous secondary active transporters. In the mouse, neutral amino acids are transported by B0AT1 [broad neutral (0) amino acid transporter 1; SLC6A19 (solute carrier family 6 member 19)] in the intestine and by B0AT1 and B0AT3 (SLC6A18) in the kidney. Immunoprecipitation and Blue native electrophoresis of intestinal brush-border membrane proteins revealed that B0AT1 forms complexes with two peptidases, APN (aminopeptidase N/CD13) and ACE2 (angiotensin-converting enzyme 2). Physiological characterization of B0AT1 expressed together with these peptidases in Xenopus laevis oocytes revealed that APN increased the substrate affinity of the transporter up to 2.5-fold and also increased its surface expression (Vmax). Peptide competition experiments, in silico modelling and site-directed mutagenesis of APN suggest that the catalytic site of the peptidase is involved in the observed changes of B0AT1 apparent substrate affinity, possibly by increasing the local substrate concentration. These results provide evidence for the existence of B0AT1-containing digestive complexes in the brush-border membrane, interacting differentially with various peptidases, and responding to the dynamic needs of nutrient absorption in the intestine and kidney. PMID:22677001

  5. Synthesis, crystal structures, and properties of three metal complexes with N-phenylanthranilic acid

    NASA Astrophysics Data System (ADS)

    Tan, Yu-Hui; Xiong, Jian-Bo; Gao, Ji-Xing; Xu, Qing; Fu, Chao-Wu; Tang, Yun-Zhi; Yang, Shao-Ping; Wen, He-Rui

    2015-04-01

    The hydrothermal reactions between N-phenylanthranilic acid (NPA), transition metal hydroxide salts and ex-bidentate N-donor ligands in CH3CH2OH/H2O solutions afforded three new complexes, [Cd1.5(NPA)3(2,2‧-bipy)] (1), [Zn(NPA)2(2,2‧-bipy)] (2,2‧-bipy = 2,2‧-bipyridine) (2) and [Mn(NPA)2(Phen)2] (Phen = 1,10-phenanthroline) (3). X-ray structural determination indicates that all of the title complexes crystallize in the same triclinic crystal system with space group p 1 bar . Complex 1 displays a symmetrical trinuclear aggregate, while complexs 2 and 3 display mononuclear structures. All the NPA ligands adopt total different coordination modes in complexes 1, 2 and 3. The comparison of solid-state fluorescence spectra among 1, 2 and free NPA shows that 1 and 2 exist a large red-shifted emission compared to free NPA ligand.

  6. Trimethylglycine complexes with carboxylic acids and HF: solvation by a polar aprotic solvent.

    PubMed

    Guo, Jing; Koeppe, Benjamin; Tolstoy, Peter M

    2011-02-14

    A series of strong H-bonded complexes of trimethylglycine, also known as betaine, with acetic, chloroacetic, dichloroacetic, trifluoroacetic and hydrofluoric acids as well as the homo-conjugated cation of betaine with trifluoroacetate as the counteranion were investigated by low-temperature (120-160 K) liquid-state NMR spectroscopy using CDF(3)/CDF(2)Cl mixture as the solvent. The temperature dependencies of (1)H NMR chemical shifts are analyzed in terms of the solvent-solute interactions. The experimental data are explained assuming the combined action of two main effects. Firstly, the solvent ordering around the negatively charged OHX region of the complex (X = O, F) at low temperatures, which leads to a contraction and symmetrisation of the H-bond; this effect dominates for the homo-conjugated cation of betaine. Secondly, at low temperatures structures with a larger dipole moment are preferentially stabilized, an effect which dominates for the neutral betaine-acid complexes. The way this second contribution affects the H-bond geometry seems to depend on the proton position. For the Be(+)COO(-)···HOOCCH(3) complex (Be = (CH(3))(3)NCH(2)-) the proton displaces towards the hydrogen bond center (H-bond symmetrisation, O···O contraction). In contrast, for the Be(+)COOH···(-)OOCCF(3) complex the proton shifts further away from the center, closer to the betaine moiety (H-bond asymmetrisation, O···O elongation). Hydrogen bond geometries and their changes upon lowering the temperature were estimated using previously published H-bond correlations. PMID:21132169

  7. Molecular structure of hydrated complex of trigonelline with L(+)-tartaric acid

    NASA Astrophysics Data System (ADS)

    Dega-Szafran, Z.; Dutkiewicz, G.; Kosturkiewicz, Z.; Szafran, M.; Barczyński, P.

    2011-04-01

    Crystal structure of the 1:1:1 complex of trigonelline with L(+)-tartaric acid and water has been determined by X-ray diffraction. The crystals are monoclinic, space group P2 1. Trigonelline is protonated and it is linked with the semi-tartrate anion by the COOH⋯OOC hydrogen bond of 2.475(2) Å. The semi-tartrate anions form infinite chains through the COOH⋯OOC hydrogen bonds of 2.599(2) Å. Water molecules play a role of double donors and double acceptors of hydrogen bonds with the semi-tartrate anions and link them into a three-dimensional net. In the optimized structure of the title complex at the B3LYP/6-31G(d,p) level of theory trigonelline is linked with L(+)-tartaric acid by the COO⋯HOOC hydrogen bond of 2.473 Å. The solid-state FTIR spectrum is consistent with the X-ray results. The 1H and 13C NMR spectra elucidate the structure of the complex investigated in aqueous solutions. The value of p Ka of trigonelline has been determined by the potentiometric titration of its hydrochloride.

  8. Bioavailability of an R-α-Lipoic Acid/γ-Cyclodextrin Complex in Healthy Volunteers

    PubMed Central

    Ikuta, Naoko; Okamoto, Hinako; Furune, Takahiro; Uekaji, Yukiko; Terao, Keiji; Uchida, Ryota; Iwamoto, Kosuke; Miyajima, Atsushi; Hirota, Takashi; Sakamoto, Norihiro

    2016-01-01

    R-α-lipoic acid (R-LA) is a cofactor of mitochondrial enzymes and a very strong antioxidant. R-LA is available as a functional food ingredient but is unstable against heat or acid. Stabilized R-LA was prepared through complexation with γ-cyclodextrin (CD), yielding R-LA/CD. R-LA/CD was orally administered to six healthy volunteers and showed higher plasma levels with an area under the plasma concentration-time curve that was 2.5 times higher than that after oral administration of non-complexed R-LA, although the time to reach the maximum plasma concentration and half-life did not differ. Furthermore, the plasma glucose level after a single oral administration of R-LA/CD or R-LA was not affected and no side effects were observed. These results indicate that R-LA/CD could be easily absorbed in the intestine. In conclusion, γ-CD complexation is a promising technology for delivering functional but unstable ingredients like R-LA. PMID:27314343

  9. Luminescent properties of europium(III) and terbium(III) complexes with para- and ortho-ethoxybenzoic acids

    NASA Astrophysics Data System (ADS)

    Panyushkin, V. T.; Mutuzova, M. Kh.; Shamsutdinova, M. Kh.

    2016-02-01

    The luminescent properties of europium(III) and terbium(III) complexes with para- and ortho-ethoxybenzoic acids are studied. The excitation energies of the triplet states of ligands are determined, a hypothesis is made about the efficient luminescence of europium(III) and terbium(III) complexes, the geometry of the coordination polyhedron of a europium complex is established, and the luminescence quantum yields of the complexes in solution are determined.

  10. Formation of host-guest complexes of β-cyclodextrin and perfluorooctanoic acid.

    PubMed

    Karoyo, Abdalla H; Borisov, Alex S; Wilson, Lee D; Hazendonk, Paul

    2011-08-11

    Structural characterization and dynamic properties of solid-state inclusion complexes of β-cyclodextrin (β-CD) with perfluorooctanoic acid (PFOA) were investigated by (19)F/(13)C solid-state and (19)F/(1)H solution NMR spectroscopy. The complexes in the solid state were prepared using dissolution and slow cool methods, where thermal analyses (DSC and TGA), PXRD, and FT-IR results provided complementary support that inclusion complexes were formed between β-CD and PFOA with variable stoichiometry and inclusion geometry. (19)F DP (direct polarization) and (13)C CP (cross-polarization) with magic-angle spinning (MAS) solids NMR, along with (19)F/(1)H solution NMR were used to characterize the complexes in the solid and solution phases, respectively. The dynamics of the guest molecules in the inclusion complexes (ICs) were studied using variable temperature (VT) (19)F DP/MAS NMR experiments in the solid state. The guest molecules were observed to be in several different molecular environments, providing strong evidence of variable host-guest stoichiometry and inclusion geometry, in accordance with the preparation method of the complex and the conformational preference of PFOA. It was concluded from PXRD that β-CD and PFOA form inclusion complexes with "channel-type" structures. Variable spin rate (VSR) (19)F DP/MAS NMR was used to assess the phase purity of the complexes, and it was revealed that slow cooling resulted in relatively pure phases. In the solution state, (1)H and (19)F NMR complexation-induced chemical shifts (CISs) of β-CD and PFOA, respectively, provided strong support for the formation of 1:1 and 2:1 β-CD/PFOA inclusion complexes. The dynamics of the guest molecule in the β-CD/PFOA complexes in D(2)O solutions were probed using VT (19)F NMR and revealed some guest conformational and exchange dynamics as a function of temperature and the relative concentrations of the host and guest. PMID:21688796

  11. Differential inhibitory effects of methylmalonic acid on respiratory chain complex activities in rat tissues.

    PubMed

    Pettenuzzo, Leticia F; Ferreira, Gustavo da C; Schmidt, Anna Laura; Dutra-Filho, Carlos S; Wyse, Angela T S; Wajner, Moacir

    2006-02-01

    Methylmalonic acidemia is an inherited metabolic disorder biochemically characterized by tissue accumulation of methylmalonic acid (MMA) and clinically by progressive neurological deterioration and kidney failure, whose pathophysiology is so far poorly established. Previous studies have shown that MMA inhibits complex II of the respiratory chain in rat cerebral cortex, although no inhibition of complexes I-V was found in bovine heart. Therefore, in the present study we investigated the in vitro effect of 2.5mM MMA on the activity of complexes I-III, II, II-III and IV in striatum, hippocampus, heart, liver and kidney homogenates from young rats. We observed that MMA caused a significant inhibition of complex II activity in striatum and hippocampus (15-20%) at low concentrations of succinate in the medium, but not in the peripheral tissues. We also verified that the inhibitory property of MMA only occurred after exposing brain homogenates for at least 10 min with the acid, suggesting that this inhibition was mediated by indirect mechanisms. Simultaneous preincubation with the nitric oxide synthase inhibitor Nomega-nitro-L-arginine methyl ester (L-NAME) and catalase (CAT) plus superoxide dismutase (SOD) did not prevent MMA-induced inhibition of complex II, suggesting that common reactive oxygen (superoxide, hydrogen peroxide and hydroxyl radical) and nitric (nitric oxide) species were not involved in this effect. In addition, complex II-III (20-35%) was also inhibited by MMA in all tissues tested, and complex I-III only in the kidney (53%) and liver (38%). In contrast, complex IV activity was not changed by MMA in all tissues studied. These results indicate that MMA differentially affects the activity of the respiratory chain pending on the tissues studied, being striatum and hippocampus more vulnerable to its effect. In case our in vitro data are confirmed in vivo in tissues from methylmalonic acidemic patients, it is feasible that that the present findings may be

  12. Water oxidation catalysis with nonheme iron complexes under acidic and basic conditions: homogeneous or heterogeneous?

    PubMed

    Hong, Dachao; Mandal, Sukanta; Yamada, Yusuke; Lee, Yong-Min; Nam, Wonwoo; Llobet, Antoni; Fukuzumi, Shunichi

    2013-08-19

    Thermal water oxidation by cerium(IV) ammonium nitrate (CAN) was catalyzed by nonheme iron complexes, such as Fe(BQEN)(OTf)2 (1) and Fe(BQCN)(OTf)2 (2) (BQEN = N,N'-dimethyl-N,N'-bis(8-quinolyl)ethane-1,2-diamine, BQCN = N,N'-dimethyl-N,N'-bis(8-quinolyl)cyclohexanediamine, OTf = CF3SO3(-)) in a nonbuffered aqueous solution; turnover numbers of 80 ± 10 and 20 ± 5 were obtained in the O2 evolution reaction by 1 and 2, respectively. The ligand dissociation of the iron complexes was observed under acidic conditions, and the dissociated ligands were oxidized by CAN to yield CO2. We also observed that 1 was converted to an iron(IV)-oxo complex during the water oxidation in competition with the ligand oxidation. In addition, oxygen exchange between the iron(IV)-oxo complex and H2(18)O was found to occur at a much faster rate than the oxygen evolution. These results indicate that the iron complexes act as the true homogeneous catalyst for water oxidation by CAN at low pHs. In contrast, light-driven water oxidation using [Ru(bpy)3](2+) (bpy = 2,2'-bipyridine) as a photosensitizer and S2O8(2-) as a sacrificial electron acceptor was catalyzed by iron hydroxide nanoparticles derived from the iron complexes under basic conditions as the result of the ligand dissociation. In a buffer solution (initial pH 9.0) formation of the iron hydroxide nanoparticles with a size of around 100 nm at the end of the reaction was monitored by dynamic light scattering (DLS) in situ and characterized by X-ray photoelectron spectra (XPS) and transmission electron microscope (TEM) measurements. We thus conclude that the water oxidation by CAN was catalyzed by short-lived homogeneous iron complexes under acidic conditions, whereas iron hydroxide nanoparticles derived from iron complexes act as a heterogeneous catalyst in the light-driven water oxidation reaction under basic conditions. PMID:23895380

  13. Formation constants of ternary complexes of some heavy metal ions with N-(2-acetamido)iminodiacetic acid and aliphatic or aromatic acids

    SciTech Connect

    Hamed, M.M.A.; Mahmoud, M.R. . Dept. of Chemistry); Saleh, M.B.; Ahmed, I.T. . Dept. of Chemistry)

    1994-07-01

    N-(2-Acetamido)iminodiacetic acid (H[sub 2]ADA) is considered as one of the biologically important ligands. It is used as a complexing agent in the field of metal ion buffers working at the physiological pH range. Furthermore, it is widely used as an analytical chelating agent for the spectrophotometric determination of metal ions. Solution equilibria of the ternary systems involving La(III), Y(III), Ce(III), and UO[sub 2][sup 2+], N-(2-acetamido)iminodiacetic acid, and some aliphatic or aromatic acids have been investigated potentiometrically. The formation of 1:1:1 mixed ligand complexes is inferred from the potentiometric titration curves. Formation constants of the different binary and ternary complexes formed in such systems were determined at 25 [+-] 0.1 C and [mu] = 0.1 mol dm[sup [minus]3] (KNO[sub 3]). It is deduced that the mixed ligand complexes are more stable than the corresponding binary complexes containing the aliphatic or aromatic acidate moiety. The order of stability of the binary and ternary complexes is investigated and discussed in terms of the nature of both the metal ion and the secondary ligand (aliphatic or aromatic acid).

  14. Inclusion complex of ellagic acid with β-cyclodextrin: Characterization and in vitro anti-inflammatory evaluation

    NASA Astrophysics Data System (ADS)

    Bulani, Vipin D.; Kothavade, Pankaj S.; Kundaikar, Harish S.; Gawali, Nitin B.; Chowdhury, Amrita A.; Degani, Mariam S.; Juvekar, Archana R.

    2016-02-01

    Freeze-dried inclusion complex of ellagic acid/β-cyclodextrin (EACD) was investigated both in solution and solid state by means of aqueous solubility, in vitro dissolution, absorption, fluorescence, Fourier transform infrared spectroscopy (FTIR), powder X-ray diffractometry (XRD), scanning electron microscopy (SEM), nuclear magnetic resonance (NMR) and molecular modeling methods. The phase solubility study showed that ellagic acid formed 1:2 stoichiometric inclusion complex with β-cyclodextrin (β-CD). The FTIR study indicates that carbonyl group of ellagic acid interact with β-CD. The NMR results demonstrate that ellagic acid was partly included into the β-CD from the wider side of the cavity. Molecular modeling studies revealed that hydrogen bonding interactions played an important role in the inclusion process and higher negative values for the complexation energies imply that 1:2 complex was more stable than 1:1 complex. The solubility and in vitro dissolution of ellagic acid was significantly enhanced by complexation with β-CD as compared to the free ellagic acid. Additionally, the complexation of EACD positively influences it's in vitro anti-inflammatory activity by protecting from protein denaturation and lysis of erythrocyte membrane.

  15. Chlorogenic acid ameliorates intestinal mitochondrial injury by increasing antioxidant effects and activity of respiratory complexes.

    PubMed

    Zhou, Yan; Zhou, Lili; Ruan, Zheng; Mi, Shumei; Jiang, Min; Li, Xiaolan; Wu, Xin; Deng, Zeyuan; Yin, Yulong

    2016-05-01

    Dietary polyphenols are thought to be beneficial for human health by acting as antioxidants. Chlorogenic acid (CGA) is abundant in plant-based foods as an ester of caffeic acid and quinic acid. In this study, we investigated the effects of CGA on mitochondrial protection. Our results demonstrated that pretreatment with CGA ameliorated the intestinal mitochondrial injury induced by H2O2; membrane potential was increased, mitochondrial swelling, levels of reactive oxygen species, contents of 8-hydroxy-2-deoxyguanosine, and cytochrome c released were decreased. The beneficial effects of CGA were accompanied by an increase in antioxidant and respiratory-chain complex I, IV, and V activities. In trinitrobenzene-sulfonic acid-induced colitic rats indicated that CGA supplementation improved mitochondria ultrastructure and decreased mitochondrial injury. Our results suggest a promising role for CGA as a mitochondria-targeted antioxidant in combating intestinal oxidative injury. Daily intake of diets containing CGA, such as coffee and honeysuckle, may be useful for prevention of intestinal diseases. PMID:26824685

  16. Self-assembled ternary complexes stabilized with hyaluronic acid-green tea catechin conjugates for targeted gene delivery.

    PubMed

    Liang, Kun; Bae, Ki Hyun; Lee, Fan; Xu, Keming; Chung, Joo Eun; Gao, Shu Jun; Kurisawa, Motoichi

    2016-03-28

    Nanosized polyelectrolyte complexes are attractive delivery vehicles for the transfer of therapeutic genes to diseased cells. Here we report the application of self-assembled ternary complexes constructed with plasmid DNA, branched polyethylenimine and hyaluronic acid-green tea catechin conjugates for targeted gene delivery. These conjugates not only stabilize plasmid DNA/polyethylenimine complexes via the strong DNA-binding affinity of green tea catechin, but also facilitate their transport into CD44-overexpressing cells via receptor-mediated endocytosis. The hydrodynamic size, surface charge and physical stability of the complexes are characterized. We demonstrate that the stabilized ternary complexes display enhanced resistance to nuclease attack and polyanion-induced dissociation. Moreover, the ternary complexes can efficiently transfect the difficult-to-transfect HCT-116 colon cancer cell line even in serum-supplemented media due to their enhanced stability and CD44-targeting ability. Confocal microscopic analysis demonstrates that the stabilized ternary complexes are able to promote the nuclear transport of plasmid DNA more effectively than binary complexes and hyaluronic acid-coated ternary complexes. The present study suggests that the ternary complexes stabilized with hyaluronic acid-green tea catechin conjugates can be widely utilized for CD44-targeted delivery of nucleic acid-based therapeutics. PMID:26855049

  17. One-Step Assembly of Phytic Acid Metal Complexes for Superhydrophilic Coatings.

    PubMed

    Li, Longbiao; Zhang, Guangyu; Su, Zhaohui

    2016-07-25

    While of immense scientific interest, superhydrophilic surfaces are usually difficult to prepare, and preparation methods are typically substrate specific. Herein, a one-step coating method is described that can endow superhydrophilicity to a variety of substrates, both inorganic and organic, using the coordination complexes of natural phytic acid and Fe(III) ions. Coating deposition occurs in minutes, and coatings are ultrathin, colorless, and transparent. Superhydrophilicity is attributed, in part, to the high density of phosphonic acid groups. The ease, rapidness, and mildness of the assembly process, which is also cost-effective and environmental-friendly, points towards potential applications, such as self-cleaning, oil/water separation, antifogging. PMID:27377349

  18. Modeling of fermentation with continuous lactic acid removal by extraction utilizing reversible chemical complexation

    SciTech Connect

    Dai, Y.; King, C.J.

    1995-07-01

    Extractive fermentation is a technique that can be used to reduce end-product inhibition by removing fermentation products in situ or in an external recycle loop. A model is presented for fermentation with continuous lactic acid removal by extraction utilizing chemical complexation. The model is formulated considering the kinetics of cell growth and the equilibrium distribution of lactic acid between aqueous and organic phases. Simulations have been carried out for different sets of operating conditions. The choice of pH balances faster kinetics at higher pH against lower product concentrations in the solvent and more difficult regeneration. A key need is for liquid extractants or solid sorbents combining stronger uptake ability with economical regeneration and satisfactory biocompatibility.

  19. Determination of trace iron in zirconium by isotope dilution-thermal ionization mass spectrometry

    NASA Astrophysics Data System (ADS)

    Elliot, N. L.; Campbell, M. A.; Green, L. W.

    1995-08-01

    An isotope dilution-thermal ionization mass spectrometry method for the determination of parts-per-million levels of iron in zirconium is required for precise, accurate analyses in studies of the effects of iron on the irradiation deformation of nuclear alloys. A two-stage purification procedure was developed to avoid the signal suppression and interference caused by the zirconium matrix. After sample dissolution and spiking with 54Fe, the bulk of the zirconium is removed by ion exchange chromatography, and the eluted Fe(III) is further purified by micro-solvent extraction into tributyl phosphate-impregnated resin beads. The iron is back-extracted, submicrogram amounts are loaded onto previously outgassed zone-refined Re filaments, and 54/56 ratios are measured at 1170°C. A silica gel/boric acid ionization enhancer is used to obtain stable Fe+ currents as strong as 2 × 10-14. A from nanogram loadings of pure iron. The procedural blank of 20 ± 6 ng is sufficiently low to allow determination of ppm levels of iron in 0.1 g zirconium samples. The analyses of solution standards showed agreement within 2% between measured and expected values, and a good fit, r2 = 0.99997, to a linear regression. The analyses of metal standards exhibited a similar good fit to a linear regression of measured against expected values, and showed good agreement with other methods. The method meets the requirements for zirconium metallurgical studies, and may be extended to other applications.

  20. Anion-π interactions in complexes of proteins and halogen-containing amino acids.

    PubMed

    Borozan, Sunčica Z; Zlatović, Mario V; Stojanović, Srđan Đ

    2016-06-01

    We analyzed the potential influence of anion-π interactions on the stability of complexes of proteins and halogen-containing non-natural amino acids. Anion-π interactions are distance and orientation dependent and our ab initio calculations showed that their energy can be lower than -8 kcal mol(-1), while most of their interaction energies lie in the range from -1 to -4 kcal mol(-1). About 20 % of these interactions were found to be repulsive. We have observed that Tyr has the highest occurrence among the aromatic residues involved in anion-π interactions, while His made the least contribution. Furthermore, our study showed that 67 % of total interactions in the dataset are multiple anion-π interactions. Most of the amino acid residues involved in anion-π interactions tend to be buried in the solvent-excluded environment. The majority of the anion-π interacting residues are located in regions with helical secondary structure. Analysis of stabilization centers for these complexes showed that all of the six residues capable of anion-π interactions are important in locating one or more of such centers. We found that anion-π interacting residues are sometimes involved in simultaneous interactions with halogens as well. With all that in mind, we can conclude that the anion-π interactions can show significant influence on molecular organization and on the structural stability of the complexes of proteins and halogen-containing non-natural amino acids. Their influence should not be neglected in supramolecular chemistry and crystal engineering fields as well. PMID:26910415

  1. Encapsulation of gallic acid/cyclodextrin inclusion complex in electrospun polylactic acid nanofibers: Release behavior and antioxidant activity of gallic acid.

    PubMed

    Aytac, Zeynep; Kusku, Semran Ipek; Durgun, Engin; Uyar, Tamer

    2016-06-01

    Cyclodextrin-inclusion complexes (CD-ICs) possess great prominence in food and pharmaceutical industries due to their enhanced ability for stabilization of active compounds during processing, storage and usage. Here, CD-IC of gallic acid (GA) with hydroxypropyl-beta-cyclodextrin (GA/HPβCD-IC) was prepared and then incorporated into polylactic acid (PLA) nanofibers (PLA/GA/HPβCD-IC-NF) using electrospinning technique to observe the effect of CD-ICs in the release behavior of GA into three different mediums (water, 10% ethanol and 95% ethanol). The GA incorporated PLA nanofibers (PLA/GA-NFs) were served as control. Phase solubility studies showed an enhanced solubility of GA with increasing amount of HPβCD. The detailed characterization techniques (XRD, TGA and (1)H-NMR) confirmed the formation of inclusion complex between GA and HPβCD. Computational modeling studies indicated that the GA made an efficient complex with HPβCD at 1:1 either in vacuum or aqueous system. SEM images revealed the bead-free and uniform morphology of PLA/GA/HPβCD-IC-NF. The release studies of GA from PLA/GA/HPβCD-IC-NF and PLA/GA-NF were carried out in water, 10% ethanol and 95% ethanol, and the findings revealed that PLA/GA/HPβCD-IC-NF has released much more amount of GA in water and 10% ethanol system when compared to PLA/GA-NF. In addition, GA was released slowly from PLA/GA/HPβCD-IC-NF into 95% ethanol when compared to PLA/GA-NF. It was also observed that electrospinning process had no negative effect on the antioxidant activity of GA when GA was incorporated in PLA nanofibers. PMID:27040215

  2. Acridine-based complex as amino acid anion fluorescent sensor in aqueous solution

    NASA Astrophysics Data System (ADS)

    Dai, Yanpeng; Xu, Kuoxi; Li, Qian; Wang, Chaoyu; Liu, Xiaoyan; Wang, Peng

    2016-03-01

    Novel acridine-based fluorescence sensors containing alaninol ligands, L1 and D1, were designed and synthesized. The structure of the compound was characterized by IR, 1H NMR, 13C NMR, MS spectra. L1 and D1 possess efficient Cu2 + cation ON-OFF selective signaling behavior based on ligand-to-metal binding mechanism at physiological pH condition. Additionally, the L1-Cu(II) and D1-Cu(II) complexes could further serve as reversible OFF-ON signaling sensing ensemble to allow ratiometric response to amino acid anion in aqueous solution.

  3. Formic acid dehydrogenation catalysed by ruthenium complexes bearing the tripodal ligands triphos and NP3.

    PubMed

    Mellone, Irene; Peruzzini, Maurizio; Rosi, Luca; Mellmann, Dörthe; Junge, Henrik; Beller, Matthias; Gonsalvi, Luca

    2013-02-21

    The selective formic acid dehydrogenation to a mixture of CO(2) and H(2) was achieved with moderate to good productivities in the presence of homogeneous Ru catalysts bearing the polydentate tripodal ligands 1,1,1-tris-(diphenylphosphinomethyl)ethane (triphos) and tris-[2-(diphenylphosphino)ethyl]amine (NP(3)), either made in situ from suitable Ru(III) precursors or as molecular complexes. Preliminary mechanistic studies highlighting subtle differences due to ligand effects in the corresponding systems under study are also presented. PMID:23212285

  4. Fatty acid ethanolamide levels are altered in borderline personality and complex posttraumatic stress disorders.

    PubMed

    Schaefer, Carola; Enning, Frank; Mueller, Juliane K; Bumb, J Malte; Rohleder, Cathrin; Odorfer, Thorsten M; Klosterkötter, Joachim; Hellmich, Martin; Koethe, Dagmar; Schmahl, Christian; Bohus, Martin; Leweke, F Markus

    2014-08-01

    Borderline personality (BPD) and complex posttraumatic stress disorders (PTSD) are both powerfully associated with the experience of interpersonal violence during childhood and adolescence. The disorders frequently co-occur and often result in pervasive problems in, e.g., emotion regulation and altered pain perception, where the endocannabinoid system is deeply involved. We hypothesize an endocannabinoid role in both disorders. We investigated serum levels of the endocannabinoids anandamide and 2-arachidonoylglycerol and related fatty acid ethanolamides (FAEs) in BPD, PTSD, and controls. Significant alterations were found for both endocannabinoids in BPD and for the FAE oleoylethanolamide in PTSD suggesting a respective link to both disorders. PMID:24253425

  5. Synthesis, structural characterization and antimicrobial activities of diorganotin(IV) complexes with azo-imino carboxylic acid ligand: Crystal structure and topological study of a doubly phenoxide-bridged dimeric dimethyltin(IV) complex appended with free carboxylic acid groups

    NASA Astrophysics Data System (ADS)

    Roy, Manojit; Roy, Subhadip; Devi, N. Manglembi; Singh, Ch. Brajakishor; Singh, Keisham Surjit

    2016-09-01

    Diorganotin(IV) complexes appended with free carboxylic acids were synthesized by reacting diorganotin(IV) dichlorides [R2SnCl2; R = Me (1), Bu (2) and Ph (3)] with an azo-imino carboxylic acid ligand i.e. 2-{4-hydroxy-3-[(2-hydroxyphenylimino)methyl]phenylazo}benzoic acid in presence of triethylamine. The complexes were characterized by elemental analysis, IR and multinuclear NMR (1H, 13C and 119Sn) spectroscopy. The structure of 1 in solid state has been determined by X-ray crystallography. Crystal structure of 1 reveals that the compound crystallizes in monoclinic space group P21/c and is a dimeric dimethyltin(IV) complex appended with free carboxylic acid groups. In the structure of 1, the Sn(IV) atoms are hexacoordinated and have a distorted octahedral coordination geometry in which two phenoxy oxygen atoms and the azomethine nitrogen atom of the ligand coordinate to each tin atom. One of the phenoxy oxygen atom bridges the two tin centers resulting in a planar Sn2O2 core. Topological analysis is used for the description of molecular packing in 1. Tin NMR spectroscopy study indicates that the complexes have five coordinate geometry around tin atom in solution state. Since the complexes have free carboxylic acids, these compounds could be further used as potential metallo-ligands for the synthesis of other complexes. The synthesized diorganotin(IV) complexes were also screened for their antimicrobial activities and compound 2 showed effective antimicrobial activities.

  6. Structure and spectroscopic studies of homo-and heterometallic complexes of adipic acid dihydrazide.

    PubMed

    Jeragh, Bakir; El-Asmy, Ahmed A

    2014-05-01

    A single crystal of adipic acid dihydrazide, ADH, has been analyzed. Its reaction with Co(2+), Ni(2+), Cu(2+), Zn(2+), Cd(2+), Hg(2+), Ag(+), Pd(2+) and/or Pt(2+) gave homometallic and heterometallic complexes which are characterized by partial elemental analysis, spectra (MS, ESR, (1)H NMR, electronic; IR), thermal analysis and magnetic measurements. Some complexes: Zn(0.73)Cu(ADH)Cl4·H2O; Zn(0.71)Hg(0.36)(ADH)Cl4·H2O; Zn(0.65)Cd(0.46)(ADH)Cl4·½H2O; Zn(0.75)Co(0.41)(ADH-2H)Cl2·3H2O; Cd0.85Co0.43(ADH)Cl4·½EtOH were isolated having nonstiochiometric metal ratios. The ligand behaves as a neutral (bidentate or tetradentate) and/or binegative tetradentate. A square-pyramid, square-planar and tetrahedral structures were proposed for the homo Co(II), Cu(II) and Ni(II) complexes, respectively. A similar and different stereochemistry around each metal ion (tetrahedral+tetrahedral; tetrahedral+square-planar; tetrahedral+tetrahedral and/or tetrahedral+octahedral) was suggested for the heterometallic complexes. Some complexes were found highly stable with stability point >240 °C; the most stable is [HgNi(ADH-2H)Cl2]. The presence of diamagnetic atom (Zn, Cd or Hg) reduces the magnetic moments and gave anomalous moments. The degradation steps and the hydrated complexes are confirmed through the TGA study. The order of covalency of [Zn(0.73)Cu(ADH)Cl4]·H2O, [CdCu(ADH)Cl4]·H2O and [HgCu(ADH-2H)Cl2] matches with the size of the second metal (Zn complex>Cd complex>Hg complex). Some heterometallic complexes were found nonstoichiometric through the analysis of their metal content and supported by TGA. PMID:24530707

  7. Structure and spectroscopic studies of homo-and heterometallic complexes of adipic acid dihydrazide

    NASA Astrophysics Data System (ADS)

    Jeragh, Bakir; El-Asmy, Ahmed A.

    A single crystal of adipic acid dihydrazide, ADH, has been analyzed. Its reaction with Co2+, Ni2+, Cu2+, Zn2+, Cd2+, Hg2+, Ag+, Pd2+ and/or Pt2+ gave homometallic and heterometallic complexes which are characterized by partial elemental analysis, spectra (MS, ESR, 1H NMR, electronic; IR), thermal analysis and magnetic measurements. Some complexes: Zn0.73Cu(ADH)Cl4·H2O; Zn0.71Hg0.36(ADH)Cl4·H2O; Zn0.65Cd0.46(ADH)Cl4·½H2O; Zn0.75Co0.41(ADH-2H)Cl2·3H2O; Cd0.85Co0.43(ADH)Cl4·½EtOH were isolated having nonstiochiometric metal ratios. The ligand behaves as a neutral (bidentate or tetradentate) and/or binegative tetradentate. A square-pyramid, square-planar and tetrahedral structures were proposed for the homo Co(II), Cu(II) and Ni(II) complexes, respectively. A similar and different stereochemistry around each metal ion (tetrahedral + tetrahedral; tetrahedral + square-planar; tetrahedral + tetrahedral and/or tetrahedral + octahedral) was suggested for the heterometallic complexes. Some complexes were found highly stable with stability point >240 °C; the most stable is [HgNi(ADH-2H)Cl2]. The presence of diamagnetic atom (Zn, Cd or Hg) reduces the magnetic moments and gave anomalous moments. The degradation steps and the hydrated complexes are confirmed through the TGA study. The order of covalency of [Zn0.73Cu(ADH)Cl4]·H2O, [CdCu(ADH)Cl4]·H2O and [HgCu(ADH-2H)Cl2] matches with the size of the second metal (Zn complex > Cd complex > Hg complex). Some heterometallic complexes were found nonstoichiometric through the analysis of their metal content and supported by TGA.

  8. Plutonium (IV) complexation by nitrate in acid solutions of ionic strengths from 2 to 19 molal

    SciTech Connect

    Berg, J.M.; Veirs, D.K.; Vaughn, R.B.; Cisneros, M.A.; Smith, C.A.

    1997-09-01

    Titrations of Pu(IV) with HNO{sub 3} in a series of aqueous HClO{sub 4} solutions ranging in ionic strength from 2 to 19 molal were followed using absorption spectrophotometry. The Pu 5f-5f spectra in the visible and near IR range change with complex formation. At each ionic strength, a series of spectra were obtained by varying nitrate concentration. Each series was deconvoluted into spectra f Pu{sup 4+}(aq), Pu(NO{sub 3}){sup 3+} and Pu(NO{sub 3}){sub 2}{sup 2+} complexes, and simultaneously their formation constants were determined. When corrected for the incomplete dissociation of nitric acid, the ionic strength dependence of each formation constant can be described by two parameters, {beta}{sup 0} and {Delta}{var_epsilon} using the formulae of specific ion interaction theory. The difficulties with extending this analysis to higher nitrate coordination numbers are discussed.

  9. Survey on the complexation character of p-sulfonatocalix[n]arenes and Caffeic acid

    NASA Astrophysics Data System (ADS)

    Chao, Jianbin; Liu, Yuhong; Zhang, Yan; Wang, Yu; Zhao, Wei; Zhang, Bingtai

    2014-11-01

    In this work the inclusion complex formation of Caffeic acid (CA) with p-sulfonatocalix[n]arenes (SCXn, n = 4, 6, 8) is reported aiming to improve the antioxidant activity, thermal stability and photostability properties of CA. Evidence for the formation was obtained using fluorescence spectroscopy, nuclear magnetic resonance spectroscopy (NMR), pulsed field gradient NMR (PFG-NMR), Fourier transform infrared spectroscopy (FT-IR), differential scanning calorimetry (DSC) and scanning electron microphotographs (SEM). Experimental conditions including concentrations of SCXn and pH were investigated for the inclusion formation in detail. The results showed that CA was able to form inclusion complexes with SCXn in a molar ratio of 1:1, and the formation constants were varied with the pH conditions. NMR spectroscopy indicated that both the aromatic ring and the vinyl group of CA were partially covered by SCXn.

  10. Arachidonic acid stimulates formation of a novel complex containing nucleolin and RhoA.

    PubMed

    Garcia, Melissa C; Williams, Jason; Johnson, Katina; Olden, Kenneth; Roberts, John D

    2011-02-18

    Arachidonic acid (AA) stimulates cell adhesion through a p38 mitogen activated protein kinase-mediated RhoA signaling pathway. Here we report that a proteomic screen following AA-treatment identified nucleolin, a multifunctional nucleolar protein, in a complex with the GTPase, RhoA, that also included the Rho kinase, ROCK. AA-stimulated cell adhesion was inhibited by expression of nucleolin-targeted shRNA and formation of the multiprotein complex was blocked by expression of dominant-negative RhoA. AA-treatment also induced ROCK-dependent serine phosphorylation of nucleolin and translocation of nucleolin from the nucleus to the cytoplasm, where it appeared to co-localize with RhoA. These data suggest the existence of a new signaling pathway through which the location and post-translational state of nucleolin are modulated. PMID:21281639

  11. Complexes of fulvic acid on the surface of hematite, goethite, and akaganeite: FTIR observation.

    PubMed

    Fu, Hongbo; Quan, Xie

    2006-04-01

    The present work extended our knowledge on the binding and complexation of a fulvic acid (FA) derived from leonardite and the iron oxides (hematite, goethite and akaganeite) by Fourier transform infrared spectroscopy (FTIR). As a prerequisite, the iron oxides were firstly prepared and characterized by transmission electron micrograph (TEM). All iron phases were single and well-described crystalloid. The FTIR data obtained by two different sampling preparation methods gave the consisting evidences that under our experimental conditions the interaction mechanism was to the ligand-exchange involving carboxylic functional groups of the FA and the surfaces sites of both hematite and goethite, while no complexation can be evidenced in the case of akaganeite, only surface adsorption. In general, the binding affinities of the iron oxides with the FA was in the order of hematite>goethite>akaganeite. The present method, although associated with some uncertainties, provided an opportunity to increase the knowledge in the field of the humic chemistry. PMID:16293289

  12. Toxicity to embryo and adult zebrafish of copper complexes with two malonic acids as models for dissolved organic matter

    SciTech Connect

    Palmer, F.B.; Evans, C.W.; Butler, C.A.; Timperley, M.H.

    1998-08-01

    The toxicity to embryo and adult zebrafish (Danio rerio) of Cu complexes with two substituted malonic acids, benzyl- and n-hexadecyl-, chosen as models for low-molecular-weight natural dissolved organic matter, were investigated. Toxicity test solutions at pH 6.5 {+-} 0.1 with the required Cu ion-specific electrode. In the absence of malonic acids, concentrations of Cu{sup 2+} up to 1.13 {mu}mol/L increased the embryo hatching time from approx. 2 d in control solutions (no Cu or malonic acid) and solutions containing malonic acids without Cu to approx. 8 d. The Cu-benzylmalonic acid complex in the presence of inorganic Cu species did not delay hatching beyond that attributable to Cu{sup 2+}. In contrast, 0.60 {mu}mol/L Cu-n-hexadecylmalonic complexes delayed hatching by 5.5 d in excess of that attributable to 1.13 {mu}mol/L Cu{sup 2+}, assuming that the hatching delays caused by the different Cu species were additive, possibly because of Cu entry into the embryo as the lipophilic Cu-n-hexadecylmalonic complex. None of the Cu-malonic acid complexes was acutely toxic to adult zebrafish at concentrations up to 1.4 {mu}mol/L, possibly because Cu was removed from the Cu-malonic acid complexes by stronger chelating groups at the gill surface. Substituted malonic acids with similar proton and Cu association constants can be readily prepared with a variety of simple substituents, radiolabeled if required. Their results show that these acids could be useful ligands for investigating intracellular transport and metabolism of metal-organic complexes.

  13. Modeling precipitate evolution in zirconium alloys during irradiation

    NASA Astrophysics Data System (ADS)

    Robson, J. D.

    2016-08-01

    The second phase precipitates (SPPs) in zirconium alloys are critical in controlling their performance. During service, SPPs are subject to both thermal and irradiation effects that influence volume fraction, number, and size. In this paper, a model has been developed to capture the combined effect of thermal and irradiation exposure on the Zr(Fe,Cr)2 precipitates in Zircaloy. The model includes irradiation induced precipitate destabilization integrated into a classical size class model for nucleation, growth and coarsening. The model has been applied to predict the effect of temperature and irradiation on SPP evolution. Increasing irradiation displacement rate is predicted to strongly enhance the loss of particles that arises from coarsening alone. The effect of temperature is complex due to competition between coarsening and irradiation damage. As temperature increases, coarsening is predicted to become increasingly important compared to irradiation induced dissolution and may increase resistance to irradiation induced dissolution by increasing particle size.

  14. Raman spectra of zirconium oxychloride crystalline hydrate and solutions

    SciTech Connect

    Kozhevnikova, G.V.; Myund, L.A.; Burkov, K.A.

    1988-08-01

    Raman spectra of zirconium oxychloride crystalline hydrate and its deuteroanalogs in the 50-4000 cm/sup -1/ region have been obtained and examined. They have been compared with the spectra of solutions. In the region of nu/sub Zr-O/ vibrations the Raman spectrum of the solution has been resolved into its components with the aid of a computer. Spectral properties of the nu/sub Zr-OH/ and nu/sub Zr-O(H)/sub 2/) bands of the (Zr/sub 4/(OH)/sub 8/(H/sub 2/O)/sub 16/)/sup 8 +/ complexes in the crystalline hydrate and in solution have been obtained.

  15. Synthesis and characterization of tin(II) complexes of fluorinated Schiff bases derived from amino acids

    NASA Astrophysics Data System (ADS)

    Singh, Har Lal

    2010-07-01

    New tin(II) complexes of general formula Sn(L) 2 (L = monoanion of 3-methyl-4-fluoro-acetophenone phenylalanine L 1H, 3-methyl-4-fluoro-acetophenone alanine L 2H, 3-methyl-4-fluoro acetophenone tryptophan L 3H, 3-methyl-4-fluoro-acetophenone valine L 4H, 3-methyl-4-fluoro-acetophenone isoleucine L 5H and 3-methyl-4-fluoro-acetophenone glycine L 6H) have been prepared. It is characterized by elemental analyses, molar conductance measurements and molecular weight determinations. Bonding of these complexes is discussed in terms of their UV-visible, infrared, and nuclear magnetic resonance ( 1H, 13C, 19F and 119Sn NMR) spectral studies. The ligands act as bidentate towards metal ions, via the azomethine nitrogen and deprotonated oxygen of the respective amino acid. Elemental analyses and NMR spectral data of the ligands with their tin(II) complexes agree with their proposed square pyramidal structures. A few representative ligands and their tin complexes have been screened for their antibacterial activities and found to be quite active in this respect.

  16. Asymmetrical Macromolecular Complex Formation of Lysophosphatidic Acid Receptor 2 (LPA2) Mediates Gradient Sensing in Fibroblasts*

    PubMed Central

    Ren, Aixia; Moon, Changsuk; Zhang, Weiqiang; Sinha, Chandrima; Yarlagadda, Sunitha; Arora, Kavisha; Wang, Xusheng; Yue, Junming; Parthasarathi, Kaushik; Heil-Chapdelaine, Rick; Tigyi, Gabor; Naren, Anjaparavanda P.

    2014-01-01

    Chemotactic migration of fibroblasts toward growth factors relies on their capacity to sense minute extracellular gradients and respond to spatially confined receptor-mediated signals. Currently, mechanisms underlying the gradient sensing of fibroblasts remain poorly understood. Using single-particle tracking methodology, we determined that a lysophosphatidic acid (LPA) gradient induces a spatiotemporally restricted decrease in the mobility of LPA receptor 2 (LPA2) on chemotactic fibroblasts. The onset of decreased LPA2 mobility correlates to the spatial recruitment and coupling to LPA2-interacting proteins that anchor the complex to the cytoskeleton. These localized PDZ motif-mediated macromolecular complexes of LPA2 trigger a Ca2+ puff gradient that governs gradient sensing and directional migration in response to LPA. Disruption of the PDZ motif-mediated assembly of the macromolecular complex of LPA2 disorganizes the gradient of Ca2+ puffs, disrupts gradient sensing, and reduces the directional migration of fibroblasts toward LPA. Our findings illustrate that the asymmetric macromolecular complex formation of chemoattractant receptors mediates gradient sensing and provides a new mechanistic basis for models to describe gradient sensing of fibroblasts. PMID:25542932

  17. Structure and Stability of Carbohydrate-Lipid Interactions. Methylmannose Polysaccharide-Fatty Acid Complexes.

    PubMed

    Liu, Lan; Siuda, Iwona; Richards, Michele R; Renaud, Justin; Kitova, Elena N; Mayer, Paul M; Tieleman, D Peter; Lowary, Todd L; Klassen, John S

    2016-08-17

    We report a detailed study of the structure and stability of carbohydrate-lipid interactions. Complexes of a methylmannose polysaccharide (MMP) derivative and fatty acids (FAs) served as model systems. The dependence of solution affinities and gas-phase dissociation activation energies (Ea ) on FA length indicates a dominant role of carbohydrate-lipid interactions in stabilizing (MMP+FA) complexes. Solution (1) H NMR results reveal weak interactions between MMP methyl groups and FA acyl chain; MD simulations suggest the complexes are disordered. The contribution of FA methylene groups to the Ea is similar to that of heats of transfer of n-alkanes from the gas phase to polar solvents, thus suggesting that MMP binds lipids through dipole-induced dipole interactions. The MD results point to hydrophobic interactions and H-bonds with the FA carboxyl group. Comparison of collision cross sections of deprotonated (MMP+FA) ions with MD structures suggests that the gaseous complexes are disordered. PMID:27253157

  18. Preparation and characterization of aqueous dispersions of high amylose starch and conjugated linoleic acid complex.

    PubMed

    Seo, Tae-Rang; Kim, Hee-Young; Lim, Seung-Taik

    2016-11-15

    Crystalline starch-CLA complexes were prepared by blending an alcoholic solution of conjugated linoleic acid (CLA) in an aqueous high-amylose maize starch dispersion. Recovery yield of CLA in the precipitates obtained by centrifuging the dispersion was dependent on reaction conditions such as temperature, time and pH. The CLA recovery reached a maximum when the reaction was performed at 90°C for 6h at neutral pH, with 67.7% of the initial CLA being co-precipitated with starch. The precipitates contained amylose-CLA complex exhibiting a V6I-type crystalline structure under X-ray diffraction analysis and a type II polymorph under DSC analysis. Ultrasonic treatment for the re-dispersed starch-CLA complex in water resulted in the reduction of hydrodynamic diameter of the complex particles to 201.5nm. The dispersion exhibited a zeta potential of -27.0mV and remained stable in an ambient storage without forming precipitates for more than 4weeks. PMID:27283663

  19. Asymmetrical macromolecular complex formation of lysophosphatidic acid receptor 2 (LPA2) mediates gradient sensing in fibroblasts.

    PubMed

    Ren, Aixia; Moon, Changsuk; Zhang, Weiqiang; Sinha, Chandrima; Yarlagadda, Sunitha; Arora, Kavisha; Wang, Xusheng; Yue, Junming; Parthasarathi, Kaushik; Heil-Chapdelaine, Rick; Tigyi, Gabor; Naren, Anjaparavanda P

    2014-12-26

    Chemotactic migration of fibroblasts toward growth factors relies on their capacity to sense minute extracellular gradients and respond to spatially confined receptor-mediated signals. Currently, mechanisms underlying the gradient sensing of fibroblasts remain poorly understood. Using single-particle tracking methodology, we determined that a lysophosphatidic acid (LPA) gradient induces a spatiotemporally restricted decrease in the mobility of LPA receptor 2 (LPA2) on chemotactic fibroblasts. The onset of decreased LPA2 mobility correlates to the spatial recruitment and coupling to LPA2-interacting proteins that anchor the complex to the cytoskeleton. These localized PDZ motif-mediated macromolecular complexes of LPA2 trigger a Ca(2+) puff gradient that governs gradient sensing and directional migration in response to LPA. Disruption of the PDZ motif-mediated assembly of the macromolecular complex of LPA2 disorganizes the gradient of Ca(2+) puffs, disrupts gradient sensing, and reduces the directional migration of fibroblasts toward LPA. Our findings illustrate that the asymmetric macromolecular complex formation of chemoattractant receptors mediates gradient sensing and provides a new mechanistic basis for models to describe gradient sensing of fibroblasts. PMID:25542932

  20. Regulation of hepatic branched-chain alpha-keto acid dehydrogenase complex in rats fed a high-fat diet

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Objective: Branched-chain alpha-keto acid dehydrogenase complex (BCKDC) regulates branched-chain amino acid (BCAA) metabolism at the level of branched chain alpha-ketoacid (BCKA) catabolism. It has been demonstrated that the activity of hepatic BCKDC is markedly decreased in type 2 diabetic animal...

  1. Comparison of microwave processing and excess steam jet cooking for spherulite production from amylose-fatty acid inclusion complexes

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Helical inclusion complexes of amylose with fatty acids can form spherulites of various morphological types. Previous studies have described the spherulites obtained by cooling dispersions of steam jet cooked corn starch either by itself or supplemented with various fatty acids. In light of potent...

  2. Tuning the reactivity of mononuclear nonheme manganese(iv)-oxo complexes by triflic acid

    SciTech Connect

    Chen, Junying; Yoon, Heejung; Lee, Yong -Min; Seo, Mi Sook; Sarangi, Ritimukta; Fukuzumi, Shunichi; Nam, Wonwoo

    2015-04-14

    Triflic acid (HOTf)-bound nonheme Mn(IV)-oxo complexes, [(L)MnIV(O)]2+–(HOTf)2 (L = N4Py and Bn-TPEN; N4Py = N,N-bis(2-pyridylmethyl)-N-bis(2-pyridyl)methylamine and Bn-TPEN = N-benzyl-N,N',N'-tris(2-pyridylmethyl)ethane-1,2-diamine), were synthesized by adding HOTf to the solutions of the [(L)MnIV(O)]2+ complexes and were characterized by various spectroscopies. The one-electron reduction potentials of the MnIV(O) complexes exhibited a significant positive shift upon binding of HOTf. The driving force dependences of electron transfer (ET) from electron donors to the MnIV(O) and MnIV(O)–(HOTf)2 complexes were examined and evaluated in light of the Marcus theory of ET to determine the reorganization energies of ET. The smaller reorganization energies and much more positive reduction potentials of the [(L)MnIV(O)]2+–(HOTf)2 complexes resulted in greatly enhanced oxidation capacity towards one-electron reductants and para-X-substituted-thioanisoles. The reactivities of the Mn(IV)-oxo complexes were markedly enhanced by binding of HOTf, such as a 6.4 × 105-fold increase in the oxygen atom transfer (OAT) reaction (i.e., sulfoxidation). Such a remarkable acceleration in the OAT reaction results from the enhancement of ET from para-X-substituted-thioanisoles to the MnIV(O) complexes as revealed by the unified ET driving force dependence of the rate constants of OAT and ET reactions of [(L)MnIV(O)]2+–(HOTf)2. In contrast, deceleration was observed in the rate of H-atom transfer (HAT) reaction of [(L)MnIV(O)]2+–(HOTf)2 complexes with 1,4-cyclohexadiene as compared with those of the [(L)MnIV(O)]2+ complexes. Thus, the binding of two HOTf molecules to the MnIV(O) moiety resulted in remarkable acceleration of the ET

  3. Tuning the reactivity of mononuclear nonheme manganese(iv)-oxo complexes by triflic acid

    DOE PAGESBeta

    Chen, Junying; Yoon, Heejung; Lee, Yong -Min; Seo, Mi Sook; Sarangi, Ritimukta; Fukuzumi, Shunichi; Nam, Wonwoo

    2015-04-14

    Triflic acid (HOTf)-bound nonheme Mn(IV)-oxo complexes, [(L)MnIV(O)]2+–(HOTf)2 (L = N4Py and Bn-TPEN; N4Py = N,N-bis(2-pyridylmethyl)-N-bis(2-pyridyl)methylamine and Bn-TPEN = N-benzyl-N,N',N'-tris(2-pyridylmethyl)ethane-1,2-diamine), were synthesized by adding HOTf to the solutions of the [(L)MnIV(O)]2+ complexes and were characterized by various spectroscopies. The one-electron reduction potentials of the MnIV(O) complexes exhibited a significant positive shift upon binding of HOTf. The driving force dependences of electron transfer (ET) from electron donors to the MnIV(O) and MnIV(O)–(HOTf)2 complexes were examined and evaluated in light of the Marcus theory of ET to determine the reorganization energies of ET. The smaller reorganization energies and much more positive reduction potentialsmore » of the [(L)MnIV(O)]2+–(HOTf)2 complexes resulted in greatly enhanced oxidation capacity towards one-electron reductants and para-X-substituted-thioanisoles. The reactivities of the Mn(IV)-oxo complexes were markedly enhanced by binding of HOTf, such as a 6.4 × 105-fold increase in the oxygen atom transfer (OAT) reaction (i.e., sulfoxidation). Such a remarkable acceleration in the OAT reaction results from the enhancement of ET from para-X-substituted-thioanisoles to the MnIV(O) complexes as revealed by the unified ET driving force dependence of the rate constants of OAT and ET reactions of [(L)MnIV(O)]2+–(HOTf)2. In contrast, deceleration was observed in the rate of H-atom transfer (HAT) reaction of [(L)MnIV(O)]2+–(HOTf)2 complexes with 1,4-cyclohexadiene as compared with those of the [(L)MnIV(O)]2+ complexes. Thus, the binding of two HOTf molecules to the MnIV(O) moiety resulted in remarkable acceleration of the ET rate when the ET is thermodynamically feasible. When the ET reaction is highly endergonic, the rate of the HAT reaction is decelerated due to the steric effect of the counter anion of HOTf.« less

  4. METHOD OF MAKING DELTA ZIRCONIUM HYDRIDE MONOLITHIC MODERATOR PIECES

    DOEpatents

    Vetrano, J.B.

    1962-01-23

    A method is given for preparing large, sound bodies of delta zirconium hydride. The method includes the steps of heating a zirconium body to a temperature of not less than l000 deg C, providing a hydrogen atmosphere for the zirconium body at a pressure not greater than one atmosphere, reducing the temperature slowly to 800 deg C at such a rate that cracks do not form while maintaining the hydrogen pressure substantially constant, and cooling in an atmosphere of hydrogen. (AEC)

  5. ELECTROLYTIC CLADDING OF ZIRCONIUM ON URANIUM

    DOEpatents

    Wick, J.J.

    1959-09-22

    A method is presented for coating uranium with zircoalum by rendering the uranium surface smooth and oxidefree, immersing it in a molten electrolytic bath in NaCI, K/sub 2/ZrF/sub 6/, KF, and ZrO/sub 2/, and before the article reaches temperature equilibrium with the bath, applying an electrolyzing current of 60 amperes per square dectmeter at approximately 3 volts to form a layer of zirconium metal on the uranium.

  6. Thermal sprayed zirconium coatings for corrosion resistance

    SciTech Connect

    Bamola, R.K.

    1992-01-01

    Vacuum Plasma Spraying (VPS) is conducted in inert reduced pressures. This results in higher particle velocities than in atmospheric plasma spraying. Reverse arc sputter cleaning and pre-heating of the workpiece lead to elevated substrate temperatures during deposition, allowing sintering of the coating and, thus, enhanced densities and bond strengths. Inert Environment Electric Arc Spraying (IEAS) is performed in inert gas chambers, utilizing wire as the feedstock. This leads to lower gas content in the coating, since the initial gas content in wire is lower than that of the powder feedstock used in VPS. Controlled atmosphere sprayed zirconium coatings had inferior mechanical and corrosion properties when compared with bulk zirconium. The VPS coatings displayed higher bond strengths and better cavitation erosion resistance than did the IEAS coatings. The IEAS coatings had lower gas content and showed better electrochemical and corrosion behavior. The lower gas content for IEAS was due to a lower initial gas level in the wire feedstock used in this process. Also, scanning electron microscopy revealed that larger particles result in the IEAS process. Thus, a smaller surface-area-to-volume ratio is available for gas-metal reactions to occur. Improvements in mechanical and corrosion properties for the IEAS coatings were due to elevated substrate temperatures during deposition. Compressive surface stresses induced by post-spray shot-peening enhanced corrosion and cavitation resistance of IEAS coatings. Coating porosity caused failure during immersion testing. Therefore, it was concluded that controlled environment thermal spraying of zirconium is not suitable for forming corrosion resistant coatings on steel. ZrN coatings were formed by electric arc spraying using a nitrogen shroud and post-spray nitriding. Two phases; ZrN and zirconium solid solution, exist in the as-sprayed coating. Nitriding increases the proportion of ZrN.

  7. Use of the ion exchange method for the determination of stability constants of trivalent metal complexes with humic and fulvic acids--part I: Eu3+ and Am3+ complexes in weakly acidic conditions.

    PubMed

    Wenming, Dong; Hongxia, Zhang; Meide, Huang; Zuyi, Tao

    2002-06-01

    The conditional stability constants for tracer concentrations of Eu(III) and Am(III) with a red earth humic acid (REHA), a red earth fulvic acid (REFA) and a fulvic acid from weathered coal (WFA) were determined at pH 5.2-6.4 (such values are similar to those in non-calcareous soils) in the presence of HAc/NaAc or NaNO3 by using the cation exchange method. It was found that 1:1 complexes were predominately formed in weakly acidic conditions. The total exchangeable proton capacities and the degrees of dissociation of these humic substances were determined by using a potentiometric titration method. The key parameters necessary for the experimental determination of the conditional stability constants of metal ions with humic substances in weakly acidic conditions by using the cation exchange method were discussed. The conditional stability constants of 1:1 complexes obtained in this paper were compared with the literature data of Am(III) determined by using the ion exchange method and the solvent extraction method and with the stability constants of 1:1 complexes of UO2(2+) and Th4+ with the same soil humic substances. These results indicate the great stability of bivalent UO2(2+), trivalent Eu3+, Am3+ and tetravalent Th4+ complexes with humic and fulvic acids in weakly acidic conditions. PMID:12102358

  8. Chemical cross-linking/mass spectrometry targeting acidic residues in proteins and protein complexes.

    PubMed

    Leitner, Alexander; Joachimiak, Lukasz A; Unverdorben, Pia; Walzthoeni, Thomas; Frydman, Judith; Förster, Friedrich; Aebersold, Ruedi

    2014-07-01

    The study of proteins and protein complexes using chemical cross-linking followed by the MS identification of the cross-linked peptides has found increasingly widespread use in recent years. Thus far, such analyses have used almost exclusively homobifunctional, amine-reactive cross-linking reagents. Here we report the development and application of an orthogonal cross-linking chemistry specific for carboxyl groups. Chemical cross-linking of acidic residues is achieved using homobifunctional dihydrazides as cross-linking reagents and a coupling chemistry at neutral pH that is compatible with the structural integrity of most protein complexes. In addition to cross-links formed through insertion of the dihydrazides with different spacer lengths, zero-length cross-link products are also obtained, thereby providing additional structural information. We demonstrate the application of the reaction and the MS identification of the resulting cross-linked peptides for the chaperonin TRiC/CCT and the 26S proteasome. The results indicate that the targeting of acidic residues for cross-linking provides distance restraints that are complementary and orthogonal to those obtained from lysine cross-linking, thereby expanding the yield of structural information that can be obtained from cross-linking studies and used in hybrid modeling approaches. PMID:24938783

  9. Chemical cross-linking/mass spectrometry targeting acidic residues in proteins and protein complexes

    PubMed Central

    Leitner, Alexander; Joachimiak, Lukasz A.; Unverdorben, Pia; Walzthoeni, Thomas; Frydman, Judith; Förster, Friedrich; Aebersold, Ruedi

    2014-01-01

    The study of proteins and protein complexes using chemical cross-linking followed by the MS identification of the cross-linked peptides has found increasingly widespread use in recent years. Thus far, such analyses have used almost exclusively homobifunctional, amine-reactive cross-linking reagents. Here we report the development and application of an orthogonal cross-linking chemistry specific for carboxyl groups. Chemical cross-linking of acidic residues is achieved using homobifunctional dihydrazides as cross-linking reagents and a coupling chemistry at neutral pH that is compatible with the structural integrity of most protein complexes. In addition to cross-links formed through insertion of the dihydrazides with different spacer lengths, zero-length cross-link products are also obtained, thereby providing additional structural information. We demonstrate the application of the reaction and the MS identification of the resulting cross-linked peptides for the chaperonin TRiC/CCT and the 26S proteasome. The results indicate that the targeting of acidic residues for cross-linking provides distance restraints that are complementary and orthogonal to those obtained from lysine cross-linking, thereby expanding the yield of structural information that can be obtained from cross-linking studies and used in hybrid modeling approaches. PMID:24938783

  10. Detection of nucleic acid-nuclear hormone receptor complexes with mass spectrometry.

    PubMed

    Bich, Claudia; Bovet, Cédric; Rochel, Natacha; Peluso-Iltis, Carole; Panagiotidis, Andreas; Nazabal, Alexis; Moras, Dino; Zenobi, Renato

    2010-04-01

    Nuclear receptors, such as the retinoic acid receptor (RAR) or the 9-cis retinoic acid receptor (RXR), interact not only with their ligands but also with other types of receptors and with DNA. Here, two complementary mass spectrometry (MS) methods were used to study the interactions between retinoic receptors (RXR/RAR) and DNA: non-denaturing nano-electrospray (nanoESI MS), and high-mass matrix-assisted laser desorption ionization (MALDI MS) combined with chemical cross-linking. The RAR x RXR heterodimer was studied in the presence of a specific DNA sequence (DR5), and a specific RAR x RXR x DNA complex was detected with both MS techniques. RAR by itself showed no significant homodimerization. A complex between RAR and the double stranded DR5 was detected with nanoESI. After cross-linking, high-mass MALDI mass spectra showed that the RAR binds the single stranded DR5, and the RAR dimer binds both single and double stranded DR5. Moreover, the MALDI mass spectrum shows a larger RAR dimer signal in the presence of DNA. These results suggest that a gene-regulatory site on DNA can induce quaternary structural changes in a transcription factor such as RAR. PMID:20097575

  11. Associations between free fatty acids, cumulus oocyte complex morphology and ovarian function during in vitro fertilization

    PubMed Central

    Jungheim, Emily S.; Macones, George A.; Odem, Randall R.; Patterson, Bruce W.; Lanzendorf, Susan E.; Ratts, Valerie S.; Moley, Kelle H.

    2011-01-01

    Objective To determine if follicular free fatty acid (FFA) levels are associated with cumulus oocyte complex morphology Design Prospective cohort study Setting University in vitro fertilization (IVF) practice Patients 102 women undergoing IVF Interventions Measurement of FFAs in serum and ovarian follicular fluid Main Outcome Measures Total and specific follicular and serum FFA levels, correlations between follicular and serum FFAs, and associations between follicular FFA levels and markers of oocyte quality including cumulus oocyte complex (COC) morphology Results Predominant follicular fluid and serum FFAs were oleic, palmitic, linoleic and stearic acids. Correlations between follicular and serum FFA concentrations were weak (r=0.252, 0.288, 0.236, 0.309 respectively for specific FFAs; r=0.212 for total FFAs). A receiver operator characteristic curve determined total follicular FFAs ≥ 0.232 µmol/ml distinguished women with lower versus higher percentage COCs with favorable morphology. Women with elevated follicular FFAs (n=31) were more likely to have COCs with poor morphology than others (n=71) (OR 3.3, 95% CI:1.2–9.2). This relationship held after adjusting for potential confounders including age, BMI, endometriosis and amount of gonadotropin administered (β=1.2; OR 3.4, 95% CI:1.1–10.4). Conclusions Elevated follicular FFA levels are associated with poor COC morphology. Further work is needed to determine what factors influence follicular FFA levels and if these factors impact fertility. PMID:21353671

  12. Manufacturing process to reduce large grain growth in zirconium alloys

    DOEpatents

    Rosecrans, P.M.

    1984-08-01

    It is an object of the present invention to provide a procedure for desensitizing zirconium-based alloys to large grain growth (LGG) during thermal treatment above the recrystallization temperature of the alloy. It is a further object of the present invention to provide a method for treating zirconium-based alloys which have been cold-worked in the range of 2 to 8% strain to reduce large grain growth. It is another object of the present invention to provide a method for fabricating a zirconium alloy clad nuclear fuel element wherein the zirconium clad is resistant to large grain growth.

  13. Effects of titanium and zirconium on iron aluminide weldments

    SciTech Connect

    Mulac, B.L.; Edwards, G.R.; Burt, R.P.; David, S.A.

    1997-12-01

    When gas-tungsten arc welded, iron aluminides form a coarse fusion zone microstructure which is susceptible to hydrogen embrittlement. Titanium inoculation effectively refined the fusion zone microstructure in iron aluminide weldments, but the inoculated weldments had a reduced fracture strength despite the presence of a finer microstructure. The weldments fractured by transgranular cleavage which nucleated at cracked second phase particles. With titanium inoculation, second phase particles in the fusion zone changed shape and also became more concentrated at the grain boundaries, which increased the particle spacing in the fusion zone. The observed decrease in fracture strength with titanium inoculation was attributed to increased spacing of second phase particles in the fusion zone. Current research has focused on the weldability of zirconium- and carbon-alloyed iron aluminides. Preliminary work performed at Oak Ridge National Laboratory has shown that zirconium and carbon additions affect the weldability of the alloy as well as the mechanical properties and fracture behavior of the weldments. A sigmajig hot cracking test apparatus has been constructed and tested at Colorado School of Mines. Preliminary characterization of hot cracking of three zirconium- and carbon-alloyed iron aluminides, each containing a different total concentration of zirconium at a constant zirconium/carbon ratio of ten, is in progress. Future testing will include low zirconium alloys at zirconium/carbon ratios of five and one, as well as high zirconium alloys (1.5 to 2.0 atomic percent) at zirconium/carbon ratios of ten to forty.

  14. Sm(II)-Mediated Electron Transfer to Carboxylic Acid Derivatives: Development of Complexity-Generating Cascades.

    PubMed

    Just-Baringo, Xavier; Procter, David J

    2015-05-19

    exploited productively in efficient new processes. First, we have used internal directing groups in substrates to "switch on" productive ET to esters and amides and have exploited such an approach in tag-removal cyclization processes that deliver molecular scaffolds of significance in biology and materials science. Second, we have exploited external ligands to facilitate ET to carboxylic acid derivatives and have applied the strategy in telescoped reaction sequences. Finally, we have employed follow-up cyclizations with alkenes, alkynes, and allenes to intercept radical anion intermediates formed along the reaction path and have employed this strategy in complexity-generating cascade approaches to biologically significant molecular architectures. From our studies, it is now clear that Sm(II)-mediated ET to carboxylic acid derivatives constitutes a general strategy for inverting the polarity of the carbonyl, allowing nucleophilic carbon-centered radicals to be formed and exploited in novel chemical processes. PMID:25871998

  15. High temperature behavior of zirconium germanates

    SciTech Connect

    Utkin, A.V.; Baklanova, N.I.; Vasilyeva, I.G.

    2013-05-01

    The high temperature behavior of zirconium germanates ZrGeO₄ and Zr₃GeO₈ up to 2300 °C has been studied using the original photoemission thermal analysis technique with the comprehensive physicochemical study of solid and gaseous intermediate and final products. The two-stage process of incongruent sublimation of GeO₂ was established and the phase boundary of the homogeneity range for ZrGeO₄ and Zr₃GeO₈ were deduced from the thermal analysis, X-ray diffraction and Raman spectroscopy studies. A high tendency to sintering of the final ZrO₂ product is discussed. - Graphical abstract: The decomposition of zirconium germanates leads to the formation of gaseous GeO₂ and solid sintered ZrO₂ and occurs via two stages with the formation of intermediate ZrO₂-rich solid solution. Highlights: •Thermal behavior of ZrGeO₄ and Zr₃GeO₈ was studied using the original thermal analysis technique in wide temperature range. •The decomposition occurs via two stages with the formation of intermediate ZrO₂-rich solid solution. •The decomposition of zirconium germanates leads to the formation of gaseous GeO₂ and solid sintered ZrO₂. •The temperature of decomposition is strongly depended on the total gas pressure.

  16. From Zirconium Nanograins to Zirconia Nanoneedles.

    PubMed

    Zalnezhad, E; Hamouda, A M S; Jaworski, J; Do Kim, Young

    2016-01-01

    Combinations of three simple techniques were utilized to gradually form zirconia nanoneedles from zirconium nanograins. First, a physical vapor deposition magnetron sputtering technique was used to deposit pure zirconium nanograins on top of a substrate. Second, an anodic oxidation was applied to fabricate zirconia nanotubular arrays. Finally, heat treatment was used at different annealing temperatures in order to change the structure and morphology from nanotubes to nanowires and subsequently to nanoneedles in the presence of argon gas. The size of the pure zirconium nanograins was estimated to be approximately 200-300 nm. ZrO2 nanotubular arrays with diameters of 70-120 nm were obtained. Both tetragonal and monoclinic ZrO2 were observed after annealing at 450 °C and 650 °C. Only a few tetragonal peaks appeared at 850 °C, while monoclinic ZrO2 was obtained at 900 °C and 950 °C. In assessing the biocompatibility of the ZrO2 surface, the human cell line MDA-MB-231 was found to attach and proliferate well on surfaces annealed at 850 °C and 450 °C; however, the amorphous ZrO2 surface, which was not heat treated, did not permit extensive cell growth, presumably due to remaining fluoride. PMID:27623486

  17. Self-assembly and cytotoxicity study of waterwheel-like dinuclear metal complexes: the first metal complexes appended with multiple free hydroxamic acid groups.

    PubMed

    Wang, Wen-Hua; Liu, Wei-Sheng; Wang, Ya-Wen; Li, Yang; Zheng, Li-Fang; Wang, Da-Qi

    2007-02-01

    Two waterwheel-like dinuclear complexes [M(2)(PHA)(4)(H(2)O)(2)] (M = Cu(II) (1), Zn(II) (2); HPHA = phthal-hydroxamic acid) appended with four free hydroxamic acid groups, namely, free hydroxamic acid metal complexes (FHAMCs) have been synthesized and characterized. The crystal structure of complex 1 was determined by single crystal X-ray diffraction, which adopts the paddlewheel motif with four bidentate carboxylate ligands joining two Cu(II) ions. The relative cytotoxicities of compounds 1 and 2 against SMMC-7721 and HO-8910 cell lines are similar and more predominant than HPHA (IC(50): Cu(II)>Zn(II)>HPHA). The synergic effect of the bound water molecules, multiple free hydroxamic acid groups and dimetal active sites with bridging carboxylate may have significant impacts on their pharmacological activity. As the prototype for a new class of hydroxamic acid derivatives, the self-assembly of FHAMCs presents a promising new strategy in designing multiple hydroxamic acids with remarkable bioactivities. PMID:17125839

  18. Depolarization-induced release of amino acids from the vestibular nuclear complex.

    PubMed

    Godfrey, Donald A; Sun, Yizhe; Frisch, Christopher; Godfrey, Matthew A; Rubin, Allan M

    2012-04-01

    There is evidence from immunohistochemistry, quantitative microchemistry, and pharmacology for several amino acids as neurotransmitters in the vestibular nuclear complex (VNC), including glutamate, γ-aminobutyrate (GABA), and glycine. However, evidence from measurements of release has been limited. The purpose of this study was to measure depolarization-stimulated calcium-dependent release of amino acids from the VNC in brain slices. Coronal slices containing predominantly the VNC were prepared from rats and perfused with artificial cerebrospinal fluid (ACSF) in an interface chamber. Fluid was collected from the chamber just downstream from the VNC using a microsiphon. Depolarization was induced by 50 mM potassium in either control calcium and magnesium concentrations or reduced calcium and elevated magnesium. Amino acid concentrations in effluent fluid were measured by high performance liquid chromatography. Glutamate release increased fivefold during depolarization in control calcium concentration and twofold in low calcium/high magnesium. These same ratios were 6 and 1.5 for GABA, 2 and 1.3 for glycine, and 2 and 1.5 for aspartate. Differences between release in control and low calcium/high magnesium ACSF were statistically significant for glutamate, GABA, and glycine. Glutamine release decreased during and after depolarization, and taurine release slowly increased. No evidence for calcium-dependent release was found for serine, glutamine, alanine, threonine, arginine, taurine, or tyrosine. Our results support glutamate and GABA as major neurotransmitters in the VNC. They also support glycine as a neurotransmitter and some function for taurine. PMID:22147284

  19. Amino acid-dependent NPRL2 interaction with Raptor determines mTOR Complex 1 activation.

    PubMed

    Kwak, Sang Su; Kang, Kyung Hwa; Kim, Seyun; Lee, Seoeun; Lee, Jeung-Hoon; Kim, Jin Woo; Byun, Boohyeong; Meadows, Gary G; Joe, Cheol O

    2016-02-01

    We assign a new function to a tumor suppressor NPRL2 that activates the mTOR complex 1 (mTORC1) activity. The positive regulation of mTORC1 activity by NPRL2 is mediated through NPRL2 interaction with Raptor. While NPRL2 interacts with Rag GTPases, RagD in particular, to interfere with mTORC1 activity in amino acid scarcity, NPRL2 interacts with Raptor in amino acid sufficiency to activate mTORC1. A reciprocal relationship exists between NPRL2 binding to Rag GTPases and Raptor. NPRL2 majorly locates in the lysosomal membranes and has a higher binding affinity to the dominant negative mutant heterodimer of RagA(GDP)/RagD(GTP) that inactivates mTORC1. However, the binding affinity of NPRL2 with Raptor is much less pronounced in cells expressing the dominant negative mutant heterodimer of RagA(GDP)/RagD(GTP) than in cells expressing the dominant positive mutant heterodimer, RagA(GTP)/RagD(GDP). The positive effect of NPRL2 on TORC1 pathway was also evidenced in Drosophila animal model. Here, we propose a 'seesaw' model in which the interactive behavior of NPRL2 with Raptor determines mTORC1 activation by amino acid signaling in animal cells. PMID:26582740

  20. Complex formation equilibria of binary and ternary complexes involving 3,3-bis(1-methylimidazol-2yl)propionic acid and bio-relevant ligands as 1-aminocyclopropane carboxylic acid with reference to plant hormone

    NASA Astrophysics Data System (ADS)

    Shoukry, Mohamed M.; Hassan, Safaa S.

    2014-01-01

    The formation equilibria for the binary complexes of Cu(II) with 1-aminocyclopropane carboxylic acid (ACC) and 3,3-bis(1-methylimidazol-2-yl)propionic acid (BIMP) were investigated. ACC and BIMP form the complexes 1 1 0, 1 2 0 and 1 1 -1. The ternary complexes of Cu(II) with BIMP and biorelevant ligands as some selected amino acids, peptides and DNA constituents are formed in a stepwise mechanism. The stability constants of the complexes formed were determined and their distribution diagrams were evaluated. The kinetics of hydrolysis of glycine methyl ester in presence of [Cu(BIMP)]+ was investigated by pH-stat technique and the mechanism was discussed.

  1. Interaction of antitumor alpha-lactalbumin-oleic acid complexes with artificial and natural membranes.

    PubMed

    Zherelova, Olga M; Kataev, Anatoly A; Grishchenko, Valery M; Knyazeva, Ekaterina L; Permyakov, Sergei E; Permyakov, Eugene A

    2009-06-01

    The specific complexes of human alpha-lactalbumin (alpha-LA) with oleic acid (OA), HAMLET and LA-OA-17 (OA-complexes), possess cytotoxic activity against tumor cells but the mechanism of their cell penetration remains unclear. To explore the molecular mechanisms underlying interaction of the OA-complexes with the cell membrane, their interactions with small unilamellar dipalmitoylphosphatidylcholine (DPPC) vesicles and electroexcitable plasma membrane of internodal native and perfused cells of the green alga Chara corallina have been studied. The fractionation (Sephadex G-200) of mixtures of the OA-complexes with the vesicles shows that OA-binding increases the affinity of alpha-LA to DPPC vesicles. Calcium association decreases protein affinity to the vesicles; the effect being less pronounced for LA-OA-17. The voltage clamp technique studies show that LA-OA-17, HAMLET, and their constituents produce different modifying effects on the plasmalemmal ionic channels of the Chara corallina cells. The irreversible binding of OA-complexes to the plasmalemma is accompanied by changes in the activation-inactivation kinetics of developing integral transmembrane currents, suppression of the Ca(2+) current and Ca(2+)-activated Cl(-) current, and by increase in the nonspecific K(+) leakage currents. The latter reflects development of nonselective permeability of the plasma membrane. The HAMLET-induced effects on the plasmalemmal currents are less pronounced and potentiated by LA-OA-17. The control experiments with OA and intact alpha-LA show their qualitatively different and much less pronounced effects on the transmembrane ionic currents. Thus, the modification of alpha-LA by OA results in an increase in the protein association with the model lipid bilayer and in drastic irreversible changes in permeability of several types of the plasmalemmal ionic channels. PMID:19588235

  2. Evidence for Physical Association of Mitochondrial Fatty Acid Oxidation and Oxidative Phosphorylation Complexes

    PubMed Central

    Wang, Yudong; Mohsen, Al-Walid; Mihalik, Stephanie J.; Goetzman, Eric S.; Vockley, Jerry

    2010-01-01

    Fatty acid β-oxidation (FAO) and oxidative phosphorylation (OXPHOS) are key pathways involved in cellular energetics. Reducing equivalents from FAO enter OXPHOS at the level of complexes I and III. Genetic disorders of FAO and OXPHOS are among the most frequent inborn errors of metabolism. Patients with deficiencies of either FAO or OXPHOS often show clinical and/or biochemical findings indicative of a disorder of the other pathway. In this study, the physical and functional interactions between these pathways were examined. Extracts of isolated rat liver mitochondria were subjected to blue native polyacrylamide gel electrophoresis (BNGE) to separate OXPHOS complexes and supercomplexes followed by Western blotting using antisera to various FAO enzymes. Extracts were also subjected to sucrose density centrifugation and fractions analyzed by BNGE or enzymatic assays. Several FAO enzymes co-migrated with OXPHOS supercomplexes in different patterns in the gels. When palmitoyl-CoA was added to the sucrose gradient fractions containing OXPHOS supercomplexes in the presence of potassium cyanide, cytochrome c was reduced. Cytochrome c reduction was completely blocked by myxothiazol (a complex III inhibitor) and 3-mercaptopropionate (an inhibitor of the first step of FAO), but was only partially inhibited by rotenone (a complex I inhibitor). Although palmitoyl-CoA and octanoyl-CoA provided reducing equivalents to OXPHOS-containing supercomplex fractions, no accumulation of their intermediates was detected. In contrast, short branched acyl-CoA substrates were not metabolized by OXPHOS-containing supercomplex fractions. These data provide evidence of a multifunctional FAO complex within mitochondria that is physically associated with OXPHOS supercomplexes and promotes metabolic channeling. PMID:20663895

  3. Spectroscopic studies of R(+)-α-lipoic acid--cyclodextrin complexes.

    PubMed

    Ikuta, Naoko; Tanaka, Akira; Otsubo, Ayako; Ogawa, Noriko; Yamamoto, Hiromitsu; Mizukami, Tomoyuki; Arai, Shoji; Okuno, Masayuki; Terao, Keiji; Matsugo, Seiichi

    2014-01-01

    α-Lipoic acid (ALA) has a chiral center at the C6 position, and exists as two enantiomers, R(+)-ALA (RALA) and S(-)-ALA (SALA). RALA is naturally occurring, and is a cofactor for mitochondrial enzymes, therefore playing a major role in energy metabolism. However, RALA cannot be used for pharmaceuticals or nutraceuticals because it readily polymerizes via a 1,2-dithiolane ring-opening when exposed to light or heat. So, it is highly desired to find out the method to stabilize RALA. The purpose of this study is to provide the spectroscopic information of stabilized RALA and SALA through complexation with cyclodextrins (CDs), α-CD, β-CD and γ-CD and to examine the physical characteristics of the resultant complexes in the solid state. The RALA-CD structures were elucidated based on the micro fourier transform infrared (FT-IR) and Raman analyses. The FT-IR results showed that the C=O stretching vibration of RALA appeared at 1717 cm⁻¹ and then shifted on formation of the RALA-CD complexes. The Raman spectra showed that the S-S and C-S stretching vibrations for RALA at 511 cm⁻¹ (S-S), 631 cm⁻¹ (C-S) and 675 cm⁻¹ (C-S) drastically weakened and almost disappeared upon complexation with CDs. Several peaks indicative of O-H vibrations also shifted or changed in intensity. These results indicate that RALA and CDs form host-guest complexes by interacting with one another. PMID:25387076

  4. Deciphering the binding patterns and conformation changes upon the bovine serum albumin-rosmarinic acid complex.

    PubMed

    Peng, Xin; Wang, Xiangchao; Qi, Wei; Huang, Renliang; Su, Rongxin; He, Zhimin

    2015-08-01

    Rosmarinic acid (RA) is an importantly and naturally occurring polyphenol from plants of the mint family with potent biological activities. Here, the in vitro interaction of RA with bovine serum albumin (BSA) has been investigated using various biophysical approaches as well as molecular modeling methods, to ascertain its binding mechanism and conformational changes. The fluorescence results demonstrated that the fluorescence quenching of BSA by RA was mainly the result of the formation of a ground state BSA-RA complex, and BSA had one high affinity RA binding site with a binding constant of 4.18 × 10(4) mol L(-1) at 298 K. Analysis of thermodynamic parameters revealed that hydrophobic and hydrogen bond interactions were the dominant intermolecular force in the complex formation. The primary binding site of RA in BSA (site I) had been identified by site marker competitive experiments. The distance between RA and the tryptophan residue of BSA was evaluated at 3.12 nm based on Förster's theory of non-radiation energy transfer. The UV-vis absorption, synchronous fluorescence, three-dimensional fluorescence, 8-anilino-1-naphthalenesulfonic acid (ANS) fluorescence, circular dichroism (CD), and Fourier transform infrared (FT-IR) spectra confirmed that the conformation and structure of BSA were altered in the presence of RA. Moreover, the nuclear magnetic spectroscopy showed that the aromatic groups of RA took part in the binding reaction during the BSA-RA complexation. In addition, the molecular picture of the interaction mechanism between BSA and RA at the atomic level was well examined by molecular docking and dynamics studies. In brief, RA can bind to BSA with noncovalent bonds in a relatively stable way, and these findings will be beneficial to the functional food research of RA. PMID:26146359

  5. Cytotoxicity of bovine α-lactalbumin: oleic acid complexes correlates with the disruption of lipid membranes.

    PubMed

    Wen, Hanzhen; Glomm, Wilhelm R; Halskau, Oyvind

    2013-11-01

    HAMLET/BAMLET (Human/Bovine α-Lactalbumin Made Lethal to Tumors) is a tumoricidal substance composed of partially unfolded human/bovine α-lactalbumin (HLA/BLA) and several oleic acid (OA) molecules. The HAMLET mechanism of interaction involves an insufficiently understood effect on the membrane or its embedded components. We examined the effect of BLAOA (bovine α-lactalbumin complexed with oleic acid, a HAMLET-like substance) and its individual components on cells and artificial lipid membranes using viability staining and metabolic dyes, fluorescence spectroscopy, leakage integrity assays and microscopy. Our results show a dose-dependency of OA used to prepare BLAOA on its ability to induce tumor cell death, and a correlation between leakage and cell death. BLAOA incorporates into the membrane, tightens the lipid packing and lowers their solvent accessibility. Fluorescence imaging reveals that giant unilamellar vesicles (GUVs) develop blebs and eventually collapse upon exposure to BLAOA, indicating that the lipid packing reorganization can translate into observable morphological effects. These effects are observed to be local in GUVs, and a tightly packed and solvent-shielded lipid environment is associated with leakage and GUV disruption. Furthermore, the effects of BLAOA on membrane are pH dependent, with an optimum of activity on artificial membranes near neutral pHs. While BLA alone is effective at membrane disruption at acidic pHs, OA is ineffective in a pH range of 4.5 to 9.1. Taken together, this supports a model where the lipid, fatty acid and protein components enhance each other's ability to affect the overall integrity of the membrane. PMID:23916586

  6. Inhibition of the fungal fatty acid synthase type I multienzyme complex

    PubMed Central

    Johansson, Patrik; Wiltschi, Birgit; Kumari, Preeti; Kessler, Brigitte; Vonrhein, Clemens; Vonck, Janet; Oesterhelt, Dieter; Grininger, Martin

    2008-01-01

    Fatty acids are among the major building blocks of living cells, making lipid biosynthesis a potent target for compounds with antibiotic or antineoplastic properties. We present the crystal structure of the 2.6-MDa Saccharomyces cerevisiae fatty acid synthase (FAS) multienzyme in complex with the antibiotic cerulenin, representing, to our knowledge, the first structure of an inhibited fatty acid megasynthase. Cerulenin attacks the FAS ketoacyl synthase (KS) domain, forming a covalent bond to the active site cysteine C1305. The inhibitor binding causes two significant conformational changes of the enzyme. First, phenylalanine F1646, shielding the active site, flips and allows access to the nucleophilic cysteine. Second, methionine M1251, placed in the center of the acyl-binding tunnel, rotates and unlocks the inner part of the fatty acid binding cavity. The importance of the rotational movement of the gatekeeping M1251 side chain is reflected by the cerulenin resistance and the changed product spectrum reported for S. cerevisiae strains mutated in the adjacent glycine G1250. Platensimycin and thiolactomycin are two other potent inhibitors of KSs. However, in contrast to cerulenin, they show selectivity toward the prokaryotic FAS system. Because the flipped F1646 characterizes the catalytic state accessible for platensimycin and thiolactomycin binding, we superimposed structures of inhibited bacterial enzymes onto the S. cerevisiae FAS model. Although almost all side chains involved in inhibitor binding are conserved in the FAS multienzyme, a different conformation of the loop K1413–K1423 of the KS domain might explain the observed low antifungal properties of platensimycin and thiolactomycin. PMID:18725634

  7. Lactic acid bacteria contribution to gut microbiota complexity: lights and shadows

    PubMed Central

    Pessione, Enrica

    2012-01-01

    Lactic Acid Bacteria (LAB) are ancient organisms that cannot biosynthesize functional cytochromes, and cannot get ATP from respiration. Besides sugar fermentation, they evolved electrogenic decarboxylations and ATP-forming deiminations. The right balance between sugar fermentation and decarboxylation/deimination ensures buffered environments thus enabling LAB to survive in human gastric trait and colonize gut. A complex molecular cross-talk between LAB and host exists. LAB moonlight proteins are made in response to gut stimuli and promote bacterial adhesion to mucosa and stimulate immune cells. Similarly, when LAB are present, human enterocytes activate specific gene expression of specific genes only. Furthermore, LAB antagonistic relationships with other microorganisms constitute the basis for their anti-infective role. Histamine and tyramine are LAB bioactive catabolites that act on the CNS, causing hypertension and allergies. Nevertheless, some LAB biosynthesize both gamma-amino-butyrate (GABA), that has relaxing effect on gut smooth muscles, and beta-phenylethylamine, that controls satiety and mood. Since LAB have reduced amino acid biosynthetic abilities, they developed a sophisticated proteolytic system, that is also involved in antihypertensive and opiod peptide generation from milk proteins. Short-chain fatty acids are glycolytic and phosphoketolase end-products, regulating epithelial cell proliferation and differentiation. Nevertheless, they constitute a supplementary energy source for the host, causing weight gain. Human metabolism can also be affected by anabolic LAB products such as conjugated linoleic acids (CLA). Some CLA isomers reduce cancer cell viability and ameliorate insulin resistance, while others lower the HDL/LDL ratio and modify eicosanoid production, with detrimental health effects. A further appreciated LAB feature is the ability to fix selenium into seleno-cysteine. Thus, opening interesting perspectives for their utilization as

  8. Covalent grafting of copper amino acid complexes onto chloropropylated silica gel—an FT-IR study

    NASA Astrophysics Data System (ADS)

    Jakab, N. I.; Hernadi, K.; Kiss, J. T.; Pálinkó, I.

    2005-06-01

    Cu(amino acid) complexes were immobilised on silica gel by covalent anchoring. The amino acids were L-histidine and L-tyrosine and their BOC—( tert-butoxycarbonyl) or methyl ester protected derivatives. To gain control over the synthesis the appropriately protected amino acid was reacted with chloropropylated silica gel first. This modified material as is, or after deprotecting the anchored amino acids, was used in further steps of building the immobilised Cu(II) complex. The covalently grafted complexes were studied by FT-IR spectroscopy and computer modelling. Materials containing protected histidine ligands showed catalase activity (decomposition of H 2O 2), those containing protected or unprotected tyrosine ligands displayed tyrosinase activity (the decomposed H 2O 2 oxidised the tyrosine skeleton to a quinoidal structure).

  9. Synthesis of amorphous supermicroporous zirconium phosphate materials by nonionic surfactant templating

    SciTech Connect

    Zhao, G.L.; Yuan, Z.Y. . E-mail: zyyuan@mail.nankai.edu.cn; Chen, T.H.

    2005-11-03

    Supermicroporous zirconium phosphate materials possessing wormhole-like pores in the size range 1.3-1.8 nm were synthesized by using nonionic poly(ethylene oxide) surfactant (e.g., C{sub 16}H{sub 33}(EO){sub 10}, C{sub 18}H{sub 35}(EO){sub 10}) as a structure directing agent. The textural and structural properties were characterized by powder X-ray diffraction, N{sub 2} adsorption analysis, differential thermal analysis, scanning and transmission electron microscopy, {sup 31}P MAS NMR and infrared spectroscopy. The synthesized materials are amorphous, exhibiting high surface areas, narrow pore size distributions, excellent thermal stabilities (over 800 deg. C) and acidic properties. The supermicropore size of the synthesized zirconium phosphate may be tunable by the variation of alkyl chain length of the surfactant.

  10. Health hazard evaluation report HETA 93-0501-2580, Western Zirconium, Ogden, Utah

    SciTech Connect

    Husberg, B.; Berardinelli, S.

    1996-05-01

    In response to an employee request, an investigation was begun into possible hazardous working conditions at Western Zirconium, Ogden, Utah. The requestor expressed concern over work related asthma and respiratory problems reported among employees at the facility. The company employed 430 workers at the site in the production of zirconium metal parts for use in nuclear power reactors. Records indicated occupational overexposure to hydrogen-chloride and chlorine gas and the sporadic release of hydrofluoric-acid. Spirometry data indicated that five current workers at the site had significant cross sectional changes in their spirometry. Five current workers had longitudinal changes in their spirometry and four had both cross sectional and longitudinal changes. The authors conclude that there was a potential for occupational exposure to respiratory irritants.

  11. Wet Etching of Heat Treated Atomic Layer Chemical Vapor Deposited Zirconium Oxide in HF Based Solutions

    NASA Astrophysics Data System (ADS)

    Balasubramanian, Sriram; Raghavan, Srini

    2008-06-01

    Alternative materials are being considered to replace silicon dioxide as gate dielectric material. Of these, the oxides of hafnium and zirconium show the most promise. However, integrating these new high-k materials into the existing complementary metal-oxide-semiconductor (CMOS) process remains a challenge. One particular area of concern is the wet etching of heat treated high-k dielectrics. In this paper, work done on the wet etching of heat treated atomic layer chemical vapor deposited (ALCVD) zirconium oxide in HF based solutions is presented. It was found that heat treated material, while refractory to wet etching at room temperature, is more amenable to etching at higher temperatures when methane sulfonic acid is added to dilute HF solutions. Selectivity over SiO2 is still a concern.

  12. Synthesis, structural characterization and biological studies of some nalidixic acid-metal complexes: Metalloantibiotic complexes of some divalent and trivalent metal ions

    NASA Astrophysics Data System (ADS)

    Al-Khodir, Fatima A. I.; Refat, Moamen S.

    2015-08-01

    This article describes the synthesis, characterization, computational and biological assessments of some divalent and trivalent metal (Ca(II), Fe(III), Pd(II) and Au(III)) complexes of nalidixic acid (nixH). The structures of these complexes were assigned using elemental analyses and spectral measurements e.g., IR, Raman, 1H NMR, 13C NMR and electronic techniques. These results indicated that, nalidixic acid reacts as a bidentate ligand bound to the metal ion through the oxygen atoms of carbonyl and carboxylate groups. The molar conductance measurements of the complexes in DMSO correspond to be non-electrolyte nature. Thus, these complexes may be formulated as [Ca(nix)(Cl)(H2O)3]. H2O, [Fe(nix)(Cl)2(H2O)2]·3H2O, [Pd(nix)(Cl)(H2O)] and [Au(nix)(Cl)2]. Base on the Coats-Redfern and Horowitz-Metzeger methods, the kinetic thermodynamic parameters (E∗, ΔS∗, ΔH∗ and ΔG∗) of the thermal decomposition reactions have been calculated from thermogravimetric curves of TG and DTG. The nano-scale range of the nalidixic acid complexes have been discussed using X-ray powder diffraction (XRD), scanning electron microscope (SEM) and transmission electron microscopy (TEM) analyzer. The computational studies for the synthesized complexes have been estimated.

  13. New copper(II) complexes with dopamine hydrochloride and vanillymandelic acid: Spectroscopic and thermal characterization

    NASA Astrophysics Data System (ADS)

    Mohamed, Gehad G.; Nour El-Dien, F. A.; El-Nahas, R. G.

    2011-10-01

    The dopamine derivatives participate in the regulation of wide variety of physiological functions in the human body and in medication life. Increase and/or decrease in the concentration of dopamine in human body reflect an indication for diseases such as Schizophrenia and/or Parkinson diseases. The Cu(II) chelates with coupled products of dopamine hydrochloride (DO.HCl) and vanillymandelic acid (VMA) with 4-aminoantipyrine (4-AAP) are prepared and characterized. Different physico-chemical techniques namely IR, magnetic and UV-vis spectra are used to investigate the structure of these chelates. Cu(II) forms 1:1 (Cu:DO) and 1:2 (Cu:VMA) chelates. DO behave as a uninegative tridentate ligand in binding to the Cu(II) ion while VMA behaves as a uninegative bidentate ligand. IR spectra show that the DO is coordinated to the Cu(II) ion in a tridentate manner with ONO donor sites of the phenolic- OH, -NH and carbonyl- O, while VMA is coordinated with OO donor sites of the phenolic- OH and -NH. Magnetic moment measurements reveal the presence of Cu(II) chelates in octahedral and square planar geometries with DO and VMA, respectively. The thermal decomposition of Cu(II) complexes is studied using thermogravimetric (TG) and differential thermal analysis (DTA) techniques. The activation thermodynamic parameters, such as, energy of activation, enthalpy, entropy and free energy change of the complexes are evaluated and the relative thermal stability of the complexes are discussed.

  14. Enantioselective Hydrolysis of Amino Acid Esters Promoted by Bis(β-cyclodextrin) Copper Complexes

    NASA Astrophysics Data System (ADS)

    Xue, Shan-Shan; Zhao, Meng; Ke, Zhuo-Feng; Cheng, Bei-Chen; Su, Hua; Cao, Qian; Cao, Zhen-Kun; Wang, Jun; Ji, Liang-Nian; Mao, Zong-Wan

    2016-02-01

    It is challenging to create artificial catalysts that approach enzymes with regard to catalytic efficiency and selectivity. The enantioselective catalysis ranks the privileged characteristic of enzymatic transformations. Here, we report two pyridine-linked bis(β-cyclodextrin) (bisCD) copper(II) complexes that enantioselectively hydrolyse chiral esters. Hydrolytic kinetic resolution of three pairs of amino acid ester enantiomers (S1-S3) at neutral pH indicated that the “back-to-back” bisCD complex CuL1 favoured higher catalytic efficiency and more pronounced enantioselectivity than the “face-to-face” complex CuL2. The best enantioselectivity was observed for N-Boc-phenylalanine 4-nitrophenyl ester (S2) enantiomers promoted by CuL1, which exhibited an enantiomer selectivity of 15.7. We observed preferential hydrolysis of L-S2 by CuL1, even in racemic S2, through chiral high-performance liquid chromatography (HPLC). We demonstrated that the enantioselective hydrolysis was related to the cooperative roles of the intramolecular flanking chiral CD cavities with the coordinated copper ion, according to the results of electrospray ionization mass spectrometry (ESI-MS), inhibition experiments, rotating-frame nuclear Overhauser effect spectroscopy (ROESY), and theoretical calculations. Although the catalytic parameters lag behind the level of enzymatic transformation, this study confirms the cooperative effect of the first and second coordination spheres of artificial catalysts in enantioselectivity and provides hints that may guide future explorations of enzyme mimics.

  15. Bis(allyl)-ruthenium(iv) complexes with phosphinous acid ligands as catalysts for nitrile hydration reactions.

    PubMed

    Tomás-Mendivil, Eder; Francos, Javier; González-Fernández, Rebeca; González-Liste, Pedro J; Borge, Javier; Cadierno, Victorio

    2016-09-14

    Several mononuclear ruthenium(iv) complexes with phosphinous acid ligands [RuCl2(η(3):η(3)-C10H16)(PR2OH)] have been synthesized (78-86% yield) by treatment of the dimeric precursor [{RuCl(μ-Cl)(η(3):η(3)-C10H16)}2] (C10H16 = 2,7-dimethylocta-2,6-diene-1,8-diyl) with 2 equivalents of different aromatic, heteroaromatic and aliphatic secondary phosphine oxides R2P([double bond, length as m-dash]O)H. The compounds [RuCl2(η(3):η(3)-C10H16)(PR2OH)] could also be prepared, in similar yields, by hydrolysis of the P-Cl bond in the corresponding chlorophosphine-Ru(iv) derivatives [RuCl2(η(3):η(3)-C10H16)(PR2Cl)]. In addition to NMR and IR data, the X-ray crystal structures of representative examples are discussed. Moreover, the catalytic behaviour of complexes [RuCl2(η(3):η(3)-C10H16)(PR2OH)] has been investigated for the selective hydration of organonitriles in water. The best results were achieved with the complex [RuCl2(η(3):η(3)-C10H16)(PMe2OH)], which proved to be active under mild conditions (60 °C), with low metal loadings (1 mol%), and showing good functional group tolerance. PMID:27510460

  16. Pickering Emulsion Gels Prepared by Hydrogen-Bonded Zein/Tannic Acid Complex Colloidal Particles.

    PubMed

    Zou, Yuan; Guo, Jian; Yin, Shou-Wei; Wang, Jin-Mei; Yang, Xiao-Quan

    2015-08-26

    Food-grade colloidal particles and complexes, which are formed via modulation of the noncovalent interactions between macromolecules and natural small molecules, can be developed as novel functional ingredients in a safe and sustainable way. For this study was prepared a novel zein/tannic acid (TA) complex colloidal particle (ZTP) based on the hydrogen-bonding interaction between zein and TA in aqueous ethanol solution by using a simple antisolvent approach. Pickering emulsion gels with high oil volume fraction (φ(oil) > 50%) were successfully fabricated via one-step homogenization. Circular dichroism (CD) and small-angle X-ray scattering (SAXS) measurements, which were used to characterize the structure of zein/TA complexes in ethanol solution, clearly showed that TA binding generated a conformational change of zein without altering their supramolecular structure at pH 5.0 and intermediate TA concentrations. Consequently, the resultant ZTP had tuned near neutral wettability (θ(ow) ∼ 86°) and enhanced interfacial reactivity, but without significantly decreased surface charge. These allowed the ZTP to stabilize the oil droplets and further triggered cross-linking to form a continuous network among and around the oil droplets and protein particles, leading to the formation of stable Pickering emulsion gels. Layer-by-layer (LbL) interfacial architecture on the oil-water surface of the droplets was observed, which implied a possibility to fabricate hierarchical interface microstructure via modulation of the noncovalent interaction between hydrophobic protein and natural polyphenol. PMID:26226053

  17. Complexes between ovalbumin nanoparticles and linoleic acid: Stoichiometric, kinetic and thermodynamic aspects.

    PubMed

    Sponton, Osvaldo E; Perez, Adrián A; Carrara, Carlos R; Santiago, Liliana G

    2016-11-15

    Stoichiometric, kinetic and thermodynamic aspects of complex formation between heat-induced aggregates of ovalbumin (ovalbumin nanoparticles, OVAn) and linoleic acid (LA) were evaluated. Extrinsic fluorescence data were fitted to modified Scatchard model yielding the following results: n: 49±2 LA molecules bound per OVA monomer unit and Ka: 9.80±2.53×10(5)M. Kinetic and thermodynamic properties were analyzed by turbidity measurements at different LA/OVA monomer molar ratios (21.5-172) and temperatures (20-40°C). An adsorption approach was used and a pseudo-second-order kinetics was found for LA-OVAn complex formation. This adsorption process took place within 1h. Thermodynamic parameters indicated that LA adsorption on OVAn was a spontaneous, endothermic and entropically-driven process, highlighting the hydrophobic nature of the LA and OVAn interaction. Finally, Atomic Force Microscopy imaging revealed that both OVAn and LA-OVAn complexes have a roughly rounded form with size lower than 100nm. PMID:27283701

  18. Enantioselective Hydrolysis of Amino Acid Esters Promoted by Bis(β-cyclodextrin) Copper Complexes.

    PubMed

    Xue, Shan-Shan; Zhao, Meng; Ke, Zhuo-Feng; Cheng, Bei-Chen; Su, Hua; Cao, Qian; Cao, Zhen-Kun; Wang, Jun; Ji, Liang-Nian; Mao, Zong-Wan

    2016-01-01

    It is challenging to create artificial catalysts that approach enzymes with regard to catalytic efficiency and selectivity. The enantioselective catalysis ranks the privileged characteristic of enzymatic transformations. Here, we report two pyridine-linked bis(β-cyclodextrin) (bisCD) copper(II) complexes that enantioselectively hydrolyse chiral esters. Hydrolytic kinetic resolution of three pairs of amino acid ester enantiomers (S1-S3) at neutral pH indicated that the "back-to-back" bisCD complex CuL(1) favoured higher catalytic efficiency and more pronounced enantioselectivity than the "face-to-face" complex CuL(2). The best enantioselectivity was observed for N-Boc-phenylalanine 4-nitrophenyl ester (S2) enantiomers promoted by CuL(1), which exhibited an enantiomer selectivity of 15.7. We observed preferential hydrolysis of L-S2 by CuL(1), even in racemic S2, through chiral high-performance liquid chromatography (HPLC). We demonstrated that the enantioselective hydrolysis was related to the cooperative roles of the intramolecular flanking chiral CD cavities with the coordinated copper ion, according to the results of electrospray ionization mass spectrometry (ESI-MS), inhibition experiments, rotating-frame nuclear Overhauser effect spectroscopy (ROESY), and theoretical calculations. Although the catalytic parameters lag behind the level of enzymatic transformation, this study confirms the cooperative effect of the first and second coordination spheres of artificial catalysts in enantioselectivity and provides hints that may guide future explorations of enzyme mimics. PMID:26916830

  19. Structural basis of intramitochondrial phosphatidic acid transport mediated by Ups1-Mdm35 complex

    PubMed Central

    Yu, Fang; He, Fangyuan; Yao, Hongyan; Wang, Chengyuan; Wang, Jianchuan; Li, Jianxu; Qi, Xiaofeng; Xue, Hongwei; Ding, Jianping; Zhang, Peng

    2015-01-01

    Ups1 forms a complex with Mdm35 and is critical for the transport of phosphatidic acid (PA) from the mitochondrial outer membrane to the inner membrane. We report the crystal structure of the Ups1-Mdm35-PA complex and the functional characterization of Ups1-Mdm35 in PA binding and transfer. Ups1 features a barrel-like structure consisting of an antiparallel β-sheet and three α-helices. Mdm35 adopts a three-helical clamp-like structure to wrap around Ups1 to form a stable complex. The β-sheet and α-helices of Ups1 form a long tunnel-like pocket to accommodate the substrate PA, and a short helix α2 acts as a lid to cover the pocket. The hydrophobic residues lining the pocket and helix α2 are critical for PA binding and transfer. In addition, a hydrophilic patch on the surface of Ups1 near the PA phosphate-binding site also plays an important role in the function of Ups1-Mdm35. Our study reveals the molecular basis of the function of Ups1-Mdm35 and sheds new light on the mechanism of intramitochondrial phospholipid transport by the MSF1/PRELI family proteins. PMID:26071601

  20. Zirconium hydride containing explosive composition

    DOEpatents

    Walker, Franklin E.; Wasley, Richard J.

    1981-01-01

    An improved explosive composition is disclosed and comprises a major portion of an explosive having a detonation velocity between about 1500 and 10,000 meters per second and a minor amount of a donor additive comprising a non-explosive compound or mixture of non-explosive compounds which when subjected to an energy fluence of 1000 calories/cm.sup.2 or less is capable of releasing free radicals each having a molecular weight between 1 and 120. Exemplary donor additives are dibasic acids, polyamines and metal hydrides.

  1. Complexation of Hg (II) ions with humic acids of tundra soils

    NASA Astrophysics Data System (ADS)

    Vasilevich, Roman

    2013-04-01

    Humic acids (HA) play an important role in processes of heavy metals migration, controlling their geochemical streams in environment. Accumulative and detoxification abilities of HA to heavy metals are realized by means of formation of steady complexes salycylate and pyrocatechin types. Modern researches show that HA of the Arctic and Subarctic areas are poorly enriched by aromatic frames, so and metalbinding centres. The work purpose is to study interaction mechanisms of Hg (II) ions with HA and to define tread possibilities of a tundra soils humic acids. It is established that binding ability of Hg (II) ions depends on concentration of an element, on quantity of functional groups in peripheral and nuclear parts of HA molecule as well as on a solution pH. coomplexation proceeds at pH 2.5-3.5 efficiently. On the basis of kinetic models it is shown that HA interaction with Hg (II) ions, at microconcentration of a pollutant (0.025-5.0 mkmol/dm3), has a zero order of reaction. Rate of a reaction does not depend on initial components concentration and is defined by process of Hg (II) ions diffusion to organic ligands. High correlation of a HA sorption capacity to Hg (II) ions is observed: with the nitrogen content and maintenance of amino groups (according to a 13C-NMR, element composition) and negative correlation - with degree of HA aromaticity. It testifies to primary binding of Hg (II) ions by amino-acid fragments of a HA molecule peripheral part. When concentration of Hg (II) ions increases, binding proceeds on carboxylic and phenolic groups of a molecule nuclear part. Higher order of kinetic models reaction and FTIR spectroscopy data testify to it. Comparison of FTIR spectra of HA preparations and mercury humates, shows that Hg (II) ions binding in humate complexes is carried out mainly by -COOH. Reduction of a spectral line intensity not ionized -COOH at 1700-1720 sm-1 and intensity increases of dissymetric valency vibration at 1610-1650 sm-1 diagnose increase

  2. Stereoselective analysis of D and L dansyl amino acids as the mixed chelate copper(II) complexes by HPLC.

    PubMed

    Lam, S

    1984-09-01

    This paper reviews the mixed chelation approach to resolution of the optical isomers of D and L dansyl amino acids by high performance liquid chromatography. The use of eluants containing Cu(II) complexes of L-proline, L-arginine, L-histidine, and L-histidine methyl ester effected the separation of many D and L amino acids, including those with aliphatic, polar, and aromatic substituents. The mechanism of separation, which is based on the preferential ternary complex formation of the analyte amino acid and the chiral chelate with Cu(II) in the mobile phase, is discussed. The stereoselectivity depends mainly on the different steric interactions between the alkyl side chains of the amino acid analytes and the chiral ligands coordinating around Cu(II), although such parameters as pH, temperature, organic modifier, and concentration of the chiral additive also affect the chromatographic separation. Among the chiral ligands studied, L-histidine methyl ester is unique in that it possesses both achiral selectivity for the dansyl amino acids and chiral selectivity for the respective D and L enantiomers. With a mobile phase gradient of acetonitrile in a buffer containing Cu(II) L-histidine methyl ester complex, a stereoselective procedure was devised for the analysis of D and L amino acid enantiomers, achieving the separation that the current amino acid analyzer could not perform. Finally, the use of the mixed chelation approach in two biomedical studies is described. In the first application, the histidine methyl ester gradient was adapted for analyzing amino acids in cerebrospinal fluid; in the second, an L-aspartame Cu(II) complex eluant was developed for measuring the urine concentration of D and L pipecolic acid (piperidine-2-carboxylic acid), a metabolite of lysine. PMID:6490790

  3. Novel one-dimensional lanthanide acrylic acid complexes: an alternative chain constructed by hydrogen bonding

    SciTech Connect

    Li Hui . E-mail: lihui@bit.edu.cn; Hu Changwen

    2004-12-01

    Novel one-dimensional (1D) chains of three lanthanide complexes La(L{sup 1}){sub 3}(CH{sub 3}OH)].CH{sub 3}OH (L{sup 1}=(E)-3-(2-hydroxyl-phenyl)-acrylic acid) 1, La(L{sup 2}){sub 3}(H{sub 2}O){sub 2}].2.75H{sub 2}O (L{sup 2}=(E)-3-(3-hydroxyl-phenyl)-acrylic acid) 2, and La(L{sup 3}){sub 3}(CH{sub 3}OH){sub 2}(H{sub 2}O)].CH{sub 3}OH (L{sup 3}=(E)-3-(4-hydroxyl-phenyl)-acrylic acid) 3 are reported. The crystal structure data are as follows for 1: C{sub 29}H{sub 29}LaO{sub 11}, monoclinic, P2{sub 1}/n, a=15.4289(12)A, b=7.9585(6)A, c=23.041(2)A, {beta}=99.657(2){sup o}, Z=4, R{sub 1}=0.0637, wR{sub 2}=0.0919; for 2: C{sub 27}H{sub 30.50}LaO{sub 13.75}, triclinic, P-1, a=8.4719(17)A, b=13.719(3)A, c=14.570(3)A, {alpha}=62.19(3){sup o}, {beta}=99.657(2){sup o}, {gamma}=78.22(3){sup o}, Z=2, R{sub 1}=0.0384, wR{sub 2}=0.0820; and for 3: C{sub 30}H{sub 35}LaO{sub 13}, monoclinic, P2(1)/c, a=9.5667(6)A, b=24.3911(15)A, c=14.0448(9)A, {beta}=109.245(2){sup o}, Z=4, R{sub 1}=0.0374, wR{sub 2}=0.0630. All the three structure data were collected using graphite monochromated molybdenum K{alpha} radiation and refined using full-matrix least-squares techniques on F{sup 2}. These structures show that four kinds of the carboxylato bridge modes are included in these chains to link the La(III) ions. It is the first time that it has been found that the intra-chain hydrogen bonding can construct an alternative chain even, when the coordination bridge mode is the same along the chain (complex 2). There are 2D and 3D hydrogen bonding in the crystal lattices of complexes 1-3.

  4. Characterization of the Mycobacterial Acyl-CoA Carboxylase Holo Complexes Reveals Their Functional Expansion into Amino Acid Catabolism

    PubMed Central

    Ehebauer, Matthias T.; Zimmermann, Michael; Jakobi, Arjen J.; Noens, Elke E.; Laubitz, Daniel; Cichocki, Bogdan; Marrakchi, Hedia; Lanéelle, Marie-Antoinette; Daffé, Mamadou; Sachse, Carsten; Dziembowski, Andrzej; Sauer, Uwe; Wilmanns, Matthias

    2015-01-01

    Biotin-mediated carboxylation of short-chain fatty acid coenzyme A esters is a key step in lipid biosynthesis that is carried out by multienzyme complexes to extend fatty acids by one methylene group. Pathogenic mycobacteria have an unusually high redundancy of carboxyltransferase genes and biotin carboxylase genes, creating multiple combinations of protein/protein complexes of unknown overall composition and functional readout. By combining pull-down assays with mass spectrometry, we identified nine binary protein/protein interactions and four validated holo acyl-coenzyme A carboxylase complexes. We investigated one of these - the AccD1-AccA1 complex from Mycobacterium tuberculosis with hitherto unknown physiological function. Using genetics, metabolomics and biochemistry we found that this complex is involved in branched amino-acid catabolism with methylcrotonyl coenzyme A as the substrate. We then determined its overall architecture by electron microscopy and found it to be a four-layered dodecameric arrangement that matches the overall dimensions of a distantly related methylcrotonyl coenzyme A holo complex. Our data argue in favor of distinct structural requirements for biotin-mediated γ-carboxylation of α−β unsaturated acid esters and will advance the categorization of acyl-coenzyme A carboxylase complexes. Knowledge about the underlying structural/functional relationships will be crucial to make the target category amenable for future biomedical applications. PMID:25695631

  5. Topical polyriboinosinic-polyribocytidylic acid complex in the treatment of recurrent genital herpes.

    PubMed Central

    Crane, L R; Levy, H B; Lerner, A M

    1982-01-01

    Polyriboinosinic-polyribocytidylic acid complexed with poly-l-lysine and carboxymethylcellulose [poly(ICLC)] is a potent interferon inducer when given parenterally to humans. Topical application in animal models has shown beneficial antiviral and clinical effects. In a randomized, double-blinded, placebo-controlled trial of topical poly(ICLC) in recurrent genital herpes simplex virus infection, five clinical and two virological parameters were followed. Fifty-seven men and women, with 78 recurrences of genital herpes, were stratified by sex. No clinical or antiviral differences between poly(ICLC) and placebo groups in either stratum were found. Further analysis of male subgroups by age and size of lesions showed no changes in the rapidity of healing or viral shedding. PMID:7049075

  6. Filler modification for papermaking with starch/oleic acid complexes with the aid of calcium ions.

    PubMed

    Huang, Xiujie; Shen, Jing; Qian, Xueren

    2013-10-15

    To mitigate the negative effect of filler addition on paper strength and improve filler retention, filler modification with hydrogen bonding polymers (e.g., starch) or their composites is an interesting research topic. Differing from previous reports, the concept related to the deposition of starch/oleic acid complexes on precipitated calcium carbonate (PCC) with the aid of calcium ions was demonstrated. The introduction of calcium ions resulted in effective starch deposition. As a result of filler modification, filler retention and the tensile strength of the filled paper were simultaneously improved essentially due to the aggregation of PCC particles in filler modification process as well as improved filler bondability. The concept demonstrated in this brief study may provide an alternative approach to filler bondability enhancement for improved papermaking performances. PMID:23987430

  7. Effect of iron poly (sorbitolgluconic acid) complex on urinary cellular excretion.

    PubMed

    Elliott, H L; Lawrence, J R; Campbell, B C; Goldberg, A; Smart, L E

    1981-01-01

    The intramuscular injection of 250 mg iron poly (sorbitol-gluconic acid) complex caused no increase in urinary cellular or bacterial excretion in 8 patients with chronic pyelonephritis, 4 patients with non-infective renal disease, and 4 controls. However, in 4 patients with chronic infective disease of the renal tract given 500 g there was a significant increase in cellular excretion. This response was not seen in 2 control patients, nor in 2 patients with non-infective renal disease. Using a differential staining technique, this increase in urinary cellular excretion was found to be due, not to leucocytes, but to renal tubular cells. The precise significance of this is unclear, but there would be concern that the high concentration of excreted iron was providing a 'toxic' insult to susceptible, infection-damaged cells. PMID:7226874

  8. A pharmacokinetic and clinical evaluation of iron poly (sorbitol-gluconic acid) complex.

    PubMed

    Campbell, B C; Lawrence, J R; Sumner, D J; Kelman, A; Smith, A; Elliott, H L; Goldberg, A

    1980-01-01

    The pharmacokinetics of iron poly (sorbitol-gluconic acid) complex (IPSG) were studied following a single intramuscular injection of 59Fe-labelled IPSG to 4 iron deficient-patients. The results showed a more rapid uptake of iron from the site of injection than that reported with iron dextran while there was a lower urinary excretion than found with iron sorbitol citrate. A clinical study was carried out in 11 patients with iron deficiency anaemia. Patients were allocated at random to receive IPSG as either 250 mg or 500 mg elemental iron per week for 8 weeks. A satisfactory response to therapy was obtained with each regimen whether measured by an increase in haemoglobin concentration or in serum ferritin concentration. Few side-effects were encountered but discomfort and staining at the injection site was found on the higher dose schedule. PMID:7208542

  9. Extraction of lycopene from tomato paste by ursodeoxycholic acid using the selective inclusion complex method.

    PubMed

    Seifi, Mahmoud; Seifi, Parisa; Hadizadeh, Farzin; Mohajeri, Seyed Ahmad

    2013-11-01

    Lycopene, a precursor of β-carotene with well-known antioxidant activity and powerful health properties, can be found in many natural products such as tomato (Lycopersicon esculentum), watermelon, red pepper, and papaya. Many separation methods have been reported for extracting lycopene from its sources. The inclusion complex is an effective method for extraction and purification of organic chemicals. This procedure has 2 main components: host and guest molecules. In this study, lycopene (guest) was extracted from tomato paste by ursodeoxycholic acid, the inclusive agent (host). The molecular structure of the extracted lycopene was then confirmed by (1) HNMR and its purity was evaluated using high-performance liquid chromatography and UV-Vis spectrophotometry methods, in comparison with a standard product. The results indicated that the proposed separation method was very promising and could be used for the extraction and purification of lycopene from tomato paste. PMID:24111697

  10. The guanidine and maleic acid (1:1) complex. The additional theoretical and experimental studies

    NASA Astrophysics Data System (ADS)

    Drozd, Marek; Dudzic, Damian

    2012-04-01

    On the basis of experimental literature data the theoretical studies for guanidinium and maleic acid complex with using DFT method are performed. In these studies the experimental X-ray data for two different forms of investigated crystal were used. During the geometry optimization process one equilibrium structure was found, only. According to this result the infrared spectrum for one theoretical molecule was calculated. On the basis of potential energy distribution (PED) analysis the clear-cut assignments of observed bands were performed. For the calculated molecule with energy minimum the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) were obtained and graphically illustrated. The energy difference (GAP) between HOMO and LUMO was analyzed. Additionally, the nonlinear properties of this molecule were calculated. The α and β (first and second order) hyperpolarizability values are obtained. On the basis of these results the title crystal was classified as new second order NLO generator.

  11. Inelastic neutron scattering study of tetramethylpyrazine in the complex with chloranilic acid

    NASA Astrophysics Data System (ADS)

    Prager, M.; Pawlukojc, A.; Sobczyk, L.; Grech, E.; Grimm, H.

    2005-09-01

    The tunnel splitting of the methyl librational ground states in the hydrogen bonded tetramethylpyrazine-chloranilic acid (TMP-CLA) complex are determined for temperatures T<=28 K by high resolution neutron spectroscopy. Three tunnel modes are resolved at T = 2.4 K. Their relative intensities show that the crystal structure must be different from the proposed space group. Tunnelling and methyl librational modes from the measured density of states are combined into rotational potentials. There are discrepancies of activation energies calculated for these potentials and those obtained from quasielastic scattering of neutrons at T>=50 K due to structural differences in the two respective temperature regimes. Rotational potentials in TMP-CLA are significantly weaker as in pure TMP.

  12. Capillary HPLC/QTOF-MS for characterizing complex naphthenic acid mixtures and their microbial transformation.

    PubMed

    Bataineh, M; Scott, A C; Fedorak, P M; Martin, J W

    2006-12-15

    A rapidly expanding oil sands industry in Canada produces and indefinitely stores large volumes of toxic aqueous tailings containing high concentrations of naphthenic acids (NAs), a complex mixture of naturally occurring aliphatic or alicyclic carboxylic acids. Although there is an acknowledged need to reduce the environmental risks posed by NAs, little is understood about their environmental fate due to a lack of appropriate analytical methods. A dilute-and-shoot reversed-phase capillary HPLC/QTOF-MS method was developed that combines high specificity and sensitivity, quantitative capabilities, the ability to detect novel transformation products, and new structural information within each NA isomer class. HPLC separated NAs, based on carbon number, degree of cyclization, and the extent of alkyl branching, and in so doing increased analytical sensitivity up to 350-fold while providing additional specificity compared to infusion techniques. For tailings water, an interlaboratory study revealed many differences in isomer class profiles compared to an established GC/MS method, much of which was attributed to the misclassification of oxidized NAs (i.e., NA + O) by low-resolution GC/MS. HPLC/QTOF-MS enabled the detection of oxidized products in the same chromatographic run, and Van Krevelen diagrams were adapted to visualize the complex data. A marked decrease of retention times was evident in Syncrude tailings water compared to a commercial mixture, suggesting that tailings water is dominated by highly persistent alkyl-substituted isomers. A biodegradation study revealed that tailings water microorganisms preferentially deplete the least alkyl-substituted fraction and may be responsible for the NA profile in aged tailings water. PMID:17165827

  13. Standard specification for zirconium and zirconium alloy sheet, strip, and plate for nuclear application. ASTM standard

    SciTech Connect

    1998-04-01

    This specification is under the jurisdiction of ASTM Committee B-10 on Reactive and Refractory Metals and Alloys and is the direct responsibility of Subcommittee B10.02 on Zirconium and Hafnium. Current edition approved Oct. 10, 1997. Published April 1998. Originally published as B 352-60T. Last previous edition B 352-92.

  14. Standard specification for zirconium and zirconium alloy strip, sheet, and plate. ASTM standard

    SciTech Connect

    1998-05-01

    This specification is under the jurisdiction of ASTM Committee B-10 on Reactive and Refractory Metals and is the direct responsibility of Subcommittee B10.02 on Zirconium and Hafnium. Current edition approved Apr. 10, 1997. Published May 1998. Originally published as B 551-71. Last previous edition B 551-92.

  15. PROCESS FOR DISSOLVING BINARY URANIUM-ZIRCONIUM OR ZIRCONIUM-BASE ALLOYS

    DOEpatents

    Jonke, A.A.; Barghusen, J.J.; Levitz, N.M.

    1962-08-14

    A process of dissolving uranium-- zirconium and zircaloy alloys, e.g. jackets of fuel elements, with an anhydrous hydrogen fluoride containing from 10 to 32% by weight of hydrogen chloride at between 400 and 450 deg C., preferably while in contact with a fluidized inert powder, such as calcium fluoride is described. (AEC)

  16. NEUTRON REACTOR FUEL ELEMENT UTILIZING ZIRCONIUM-BASE ALLOYS

    DOEpatents

    Saller, H.A.; Keeler, J.R.; Szumachowski, E.R.

    1957-11-12

    This patent relates to clad fuel elements for use in neutronic reactors and is drawn to such a fuel element which consists of a core of fissionable material, comprised of an alloy of zirconium and U/sup 235/ enriched uranium, encased in a jacket of a binary zirconium-tin alloy in which the tin content ranges between 1 and 15% by weight.

  17. [The clinical application of zirconium-dioxide-ceramics. Case report].

    PubMed

    Somfai, Dóra; Zsigmond, Ágnes; Károlyházy, Katalin; Kispély, Barbara; Hermann, Péter

    2015-12-01

    Due to its outstanding physical, mechanical and esthetic properties, zirconium-dioxide is one of the most popular non-metal denture, capable of surpassing PFM in most cases. The recent advances of CAD/CAM technology makes it a good alternitve. Here we show the usefulness of zirconium-dioxide in everyday dental practice through three case reports. PMID:26863816

  18. Process of precipitating zirconium or hafnium from spent pickling solutions

    SciTech Connect

    Aguilar, C.L.; Walker, R.G.

    1991-12-31

    This patent describes a process for regenerating a spent, fluoride-containing pickle solution used in the pickling of zirconium or hafnium metal or their alloys. It comprises adding to the spent pickle solution a sufficient amount of sodium sulfate to precipitate sodium zirconium or hafnium fluoride.

  19. 40 CFR 721.10602 - Lead niobium titanium zirconium oxide.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Lead niobium titanium zirconium oxide... Specific Chemical Substances § 721.10602 Lead niobium titanium zirconium oxide. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as lead niobium...

  20. 40 CFR 721.10602 - Lead niobium titanium zirconium oxide.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Lead niobium titanium zirconium oxide... Specific Chemical Substances § 721.10602 Lead niobium titanium zirconium oxide. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as lead niobium...

  1. Neodymium(III) Complexes of Dialkylphosphoric and Dialkylphosphonic Acids Relevant to Liquid-Liquid Extraction Systems.

    PubMed

    Lumetta, Gregg J; Sinkov, Sergey I; Krause, Jeanette A; Sweet, Lucas E

    2016-02-15

    The complexes formed during the extraction of neodymium(III) into hydrophobic solvents containing acidic organophosphorus extractants were probed by single-crystal X-ray diffractometry, visible spectrophotometry, and Fourier-transform infrared spectroscopy. The crystal structure of the compound Nd(DMP)3 (1, DMP = dimethyl phosphate) revealed a polymeric arrangement in which each Nd(III) center is surrounded by six DMP oxygen atoms in a pseudo-octahedral environment. Adjacent Nd(III) ions are bridged by (MeO)2POO(-) anions, forming the polymeric network. The diffuse reflectance visible spectrum of 1 is nearly identical to that of the solid that is formed when an n-dodecane solution of di(2-ethylhexyl)phosphoric acid (HA) is saturated with Nd(III), indicating a similar coordination environment around the Nd center in the NdA3 solid. The visible spectrum of the HA solution fully loaded with Nd(III) is very similar to that of the NdA3 material, both displaying hypersensitive bands characteristic of an pseudo-octahedral coordination environment around Nd. These spectral characteristics persisted across a wide range of organic Nd concentrations, suggesting that the pseudo-octahedral coordination environment is maintained from dilute to saturated conditions. PMID:26815878

  2. Fatty acid nitroalkenes induce resistance to ischemic cardiac injury by modulating mitochondrial respiration at complex II

    PubMed Central

    Koenitzer, Jeffrey R.; Bonacci, Gustavo; Woodcock, Steven R.; Chen, Chen-Shan; Cantu-Medellin, Nadiezhda; Kelley, Eric E.; Schopfer, Francisco J.

    2015-01-01

    Nitro-fatty acids (NO2-FA) are metabolic and inflammatory-derived electrophiles that mediate pleiotropic signaling actions. It was hypothesized that NO2-FA would impact mitochondrial redox reactions to induce tissue-protective metabolic shifts in cells. Nitro-oleic acid (OA-NO2) reversibly inhibited complex II-linked respiration in isolated rat heart mitochondria in a pH-dependent manner and suppressed superoxide formation. Nitroalkylation of Fp subunit was determined by BME capture and the site of modification by OA-NO2 defined by mass spectrometric analysis. These effects translated into reduced basal and maximal respiration and favored glycolytic metabolism in H9C2 cardiomyoblasts as assessed by extracellular H+ and O2 flux analysis. The perfusion of NO2-FA induced acute cardioprotection in an isolated perfused heart ischemia/reperfusion (IR) model as evidenced by significantly higher rate-pressure products. Together these findings indicate that NO2-FA can promote cardioprotection by inducing a shift from respiration to glycolysis and suppressing reactive species formation in the post-ischemic interval. PMID:26722838

  3. Fatty acid nitroalkenes induce resistance to ischemic cardiac injury by modulating mitochondrial respiration at complex II.

    PubMed

    Koenitzer, Jeffrey R; Bonacci, Gustavo; Woodcock, Steven R; Chen, Chen-Shan; Cantu-Medellin, Nadiezhda; Kelley, Eric E; Schopfer, Francisco J

    2016-08-01

    Nitro-fatty acids (NO2-FA) are metabolic and inflammatory-derived electrophiles that mediate pleiotropic signaling actions. It was hypothesized that NO2-FA would impact mitochondrial redox reactions to induce tissue-protective metabolic shifts in cells. Nitro-oleic acid (OA-NO2) reversibly inhibited complex II-linked respiration in isolated rat heart mitochondria in a pH-dependent manner and suppressed superoxide formation. Nitroalkylation of Fp subunit was determined by BME capture and the site of modification by OA-NO2 defined by mass spectrometric analysis. These effects translated into reduced basal and maximal respiration and favored glycolytic metabolism in H9C2 cardiomyoblasts as assessed by extracellular H(+) and O2 flux analysis. The perfusion of NO2-FA induced acute cardioprotection in an isolated perfused heart ischemia/reperfusion (IR) model as evidenced by significantly higher rate-pressure products. Together these findings indicate that NO2-FA can promote cardioprotection by inducing a shift from respiration to glycolysis and suppressing reactive species formation in the post-ischemic interval. PMID:26722838

  4. nC60 deposition kinetics: the complex contribution of humic acid, ion concentration, and valence.

    PubMed

    McNew, Coy P; LeBoeuf, Eugene J

    2016-07-01

    The demonstrated toxicity coupled with inevitable environmental release of nC60 raise serious concerns about its environmental fate and transport, therefore it is crucial to understand how nC60 will interact with subsurface materials including attached phase soil and sediment organic matter (AP-SOM). This study investigated the attachment of nC60 onto a Harpeth humic acid (HHA) coated silica surface under various solution conditions using a quartz crystal microbalance with dissipation monitoring. The HHA coating greatly enhanced nC60 attachment at low ion concentrations while hindering attachment at high ion concentrations in the presence of both mono and divalent cations. At low ion concentrations, the HHA greatly reduced the surface potential of the silica, enhancing nC60 deposition through reduction in the electrostatic repulsion. At high ion concentrations however, the reduced surface potential became less important due to the near zero energy barrier to deposition and therefore non-DLVO forces dominated, induced by compaction of the HHA layer, and leading to hindered attachment. In this manner, observed contributions from the HHA layer were more complex than previously reported and by monitoring surface charge and calculated DLVO interaction energy alongside attachment experiments, this study advances the mechanistic understanding of the variable attachment contributions from the humic acid layer. PMID:27061365

  5. Arginase-boronic acid complex highlights a physiological role in erectile function.

    PubMed

    Cox, J D; Kim, N N; Traish, A M; Christianson, D W

    1999-11-01

    The crystal structure of the complex between the binuclear manganese metalloenzyme arginase and the boronic acid analog of L-arginine, 2(S)-amino-6-boronohexanoic acid (ABH), has been determined at 1.7 A resolution from a crystal perfectly twinned by hemihedry. ABH binds as the tetrahedral boronate anion, with one hydroxyl oxygen symmetrically bridging the binuclear manganese cluster and a second hydroxyl oxygen coordinating to Mn2+A. This binding mode mimics the transition state of a metal-activated hydroxide mechanism. This transition state structure differs from that occurring in NO biosynthesis, thereby explaining why ABH does not inhibit NO synthase. We also show that arginase activity is present in the penis. Accordingly, the tight binding and specificity of ABH allows us to probe the physiological role of arginase in modulating the NO-dependent smooth muscle relaxation required for erection. Strikingly, ABH causes significant enhancement of nonadrenergic, noncholinergic nerve-mediated relaxation of penile corpus cavernosum smooth muscle, suggesting that arginase inhibition sustains L-arginine concentrations for NO synthase activity. Therefore, human penile arginase is a potential target for therapeutic intervention in the treatment of erectile dysfunction. PMID:10542097

  6. Solar-thermal complex sample processing for nucleic acid based diagnostics in limited resource settings

    PubMed Central

    Gumus, Abdurrahman; Ahsan, Syed; Dogan, Belgin; Jiang, Li; Snodgrass, Ryan; Gardner, Andrea; Lu, Zhengda; Simpson, Kenneth; Erickson, David

    2016-01-01

    The use of point-of-care (POC) devices in limited resource settings where access to commonly used infrastructure, such as water and electricity, can be restricted represents simultaneously one of the best application fits for POC systems as well as one of the most challenging places to deploy them. Of the many challenges involved in these systems, the preparation and processing of complex samples like stool, vomit, and biopsies are particularly difficult due to the high number and varied nature of mechanical and chemical interferents present in the sample. Previously we have demonstrated the ability to use solar-thermal energy to perform PCR based nucleic acid amplifications. In this work demonstrate how the technique, using similar infrastructure, can also be used to perform solar-thermal based sample processing system for extracting and isolating Vibrio Cholerae nucleic acids from fecal samples. The use of opto-thermal energy enables the use of sunlight to drive thermal lysing reactions in large volumes without the need for external electrical power. Using the system demonstrate the ability to reach a 95°C threshold in less than 5 minutes and maintain a stable sample temperature of +/− 2°C following the ramp up. The system is demonstrated to provide linear results between 104 and 108 CFU/mL when the released nucleic acids were quantified via traditional means. Additionally, we couple the sample processing unit with our previously demonstrated solar-thermal PCR and tablet based detection system to demonstrate very low power sample-in-answer-out detection. PMID:27231636

  7. Solar-thermal complex sample processing for nucleic acid based diagnostics in limited resource settings.

    PubMed

    Gumus, Abdurrahman; Ahsan, Syed; Dogan, Belgin; Jiang, Li; Snodgrass, Ryan; Gardner, Andrea; Lu, Zhengda; Simpson, Kenneth; Erickson, David

    2016-05-01

    The use of point-of-care (POC) devices in limited resource settings where access to commonly used infrastructure, such as water and electricity, can be restricted represents simultaneously one of the best application fits for POC systems as well as one of the most challenging places to deploy them. Of the many challenges involved in these systems, the preparation and processing of complex samples like stool, vomit, and biopsies are particularly difficult due to the high number and varied nature of mechanical and chemical interferents present in the sample. Previously we have demonstrated the ability to use solar-thermal energy to perform PCR based nucleic acid amplifications. In this work demonstrate how the technique, using similar infrastructure, can also be used to perform solar-thermal based sample processing system for extracting and isolating Vibrio Cholerae nucleic acids from fecal samples. The use of opto-thermal energy enables the use of sunlight to drive thermal lysing reactions in large volumes without the need for external electrical power. Using the system demonstrate the ability to reach a 95°C threshold in less than 5 minutes and maintain a stable sample temperature of +/- 2°C following the ramp up. The system is demonstrated to provide linear results between 10(4) and 10(8) CFU/mL when the released nucleic acids were quantified via traditional means. Additionally, we couple the sample processing unit with our previously demonstrated solar-thermal PCR and tablet based detection system to demonstrate very low power sample-in-answer-out detection. PMID:27231636

  8. Ternary copper complexes and manganese (III) tetrakis(4-benzoic acid) porphyrin catalyze peroxynitrite-dependent nitration of aromatics.

    PubMed

    Ferrer-Sueta, G; Ruiz-Ramírez, L; Radi, R

    1997-12-01

    Peroxynitrite is a powerful oxidant formed in biological systems from the reaction of nitrogen monoxide and superoxide and is capable of nitrating phenols at neutral pH and ambient temperature. This peroxynitrite-mediated nitration is catalyzed by a number of Lewis acids, including CO2 and transition-metal ion complexes. Here we studied the effect of ternary copper-(II) complexes constituted by a 1,10-phenanthroline and an amino acid as ligands. All the complexes studied accelerate both the decomposition of peroxynitrite and its nitration of 4-hydroxyphenylacetic acid at pH > 7. The rate of these reactions depends on the copper complex concentration in a hyperbolic plus linear manner. The yield of nitrated products increases up to 2.6-fold with respect to proton-catalyzed nitration and has a dependency on the concentration of copper complexes which follows the same function as observed for the rate constants. The manganese porphyrin complex, Mn(III)tetrakis(4-benzoic acid)porphyrin [Mn(tbap)], also promoted peroxynitrite-mediated nitration with an even higher yield (4-fold increase) than the ternary copper complexes. At pH = 7.5 +/- 0.2 the catalytic behavior of the copper complexes can be linearly correlated with the pKa of the phenanthroline present as a ligand, implying that a peroxynitrite anion is coordinated to the copper ion prior to the nitration reaction. These observations may prove valuable to understand the biological effects of these transition-metal complexes (i.e., copper and manganese) that can mimic superoxide dismutase activity and, in the case of the ternary copper complexes, show antineoplastic activity. PMID:9437523

  9. Effects of pH and fulvic acids concentration on the stability of fulvic acids--cerium (IV) oxide nanoparticle complexes.

    PubMed

    Oriekhova, Olena; Stoll, Serge

    2016-02-01

    The behavior of cerium (IV) oxide nanoparticles has been first investigated at different pH conditions. The point of zero charge was determined as well as the stability domains using dynamic light scattering, nanoparticle tracking analysis and scanning electron microscopy. A baseline hydrodynamic diameter of 180 nm was obtained indicating that individual CeO2 nanoparticles are forming small aggregates. Then we analyzed the particle behavior at variable concentrations of fulvic acids for three different pH-electrostatic scenarios corresponding to positive, neutral and negative CeO2 surface charges. The presence of fulvic acids was found to play a key role on the CeO2 stability via the formation of electrostatic complexes. It was shown that a small amount of fulvic acids (2 mg L(-1)), representative of environmental fresh water concentrations, is sufficient to stabilize CeO2 nanoparticles (50 mg L(-1)). When electrostatic complexes are formed between negatively charged FAs and positively charged CeO2 NPs the stability of such complexes is obtained with time (up to 7 weeks) as well as in pH changing conditions. Based on zeta potential variations we also found that the fulvic acids are changing the CeO2 acid-base surface properties. Obtained results presented here constitute an important outcome in the domain of risk assessment, transformation and removal of engineered nanomaterials released into the environment. PMID:26347935

  10. Uranium-preextraction in zirconium/hafnium separations processs

    SciTech Connect

    Feuling, R.J.

    1990-04-03

    This patent describes an improvement in a process for recovering zirconium values from uranium containing zircon ore. The process comprising a fluidized bed carbochlorination of the zircon ore at 800{degrees}--1250{degrees} C., producing a relatively impure, hafnium-containing zirconium tetrachloride stream and by-product silicon tetrachloride, which silicon tetrachloride by-product is separated by differential condensation, and wherein uranium chloride is volatilized at the ore chlorinator temperature and follows as an impurity in the zirconium-hafnium tetrachloride stream, mixing the zirconium-hafnium tetrachloride with water to produce a zirconium-hafnium oxychloride solution, and removing iron impurities by liquid--liquid iron extraction with a methyl isobutyl ketone extractant.

  11. Complexation of mercury(II) ions with humic acids in tundra soils

    NASA Astrophysics Data System (ADS)

    Vasilevich, R. S.; Beznosikov, V. A.; Lodygin, E. D.; Kondratenok, B. M.

    2014-03-01

    The interaction mechanisms of mercury(II) ions with preparations of humic acids (HAs) isolated from organic horizons of surface-gleyed soils (Haplic Stagnosol (Gelic, Siltic)) of shrub tundra and hydromorphic peat gley soils (Histic Cryosol (Reductaquic, Siltic)) of moss-lichen tundra have been studied. The particular features of the interactions between the mercury(II) ions and the HAs are related to the molecular structure of the HAs, the mercury concentration range, and the environmental parameters. The fixation of mercury(II) ions into stable coordination compounds is most efficient in the pH range of 2.5-3.5. At the element concentrations below 0.50 μmol/dm3, the main complexing sites of HAs are their peripheral aminoacid functional groups. Pyrocatechol, salicylate, and phenolic groups from the nuclear moiety of molecules interact in the concentration range of 0.0005-0.50 mmol/dm3; the physical sorption of mercury hydroxo complexes by the surface of HAs is the main process occurring in the system.

  12. Determination of uranium(IV) by derivative spectrophotometry of its complexes with hydroethylidenediphosphomic acid

    SciTech Connect

    Perfil'ev, V.A.; Mishchenko, V.T.; Poluektov, N.S.

    1985-05-20

    This paper reports on a study of the spectral characteristics of complex compounds of uranium-(IV) with a ligand containing the phosphonic groups - hydroxyethyllidenediphosphonic acid (HEDPA) - and its possible use for analysis. The method of derivative spectrophotometry has been used since absorption bands corresponding to a mixture of compounds can thus be resolved into absorption bands of the individual components, and their fine structure can be studied. The method ensures accuracy and reproducibility of the analysis of the mixture of compounds. It was found that, depending on the ratio of the components in the solution, compounds with composition of U(IV) . HEDPA . and U(IV) . 2 HEDPA are formed. It is shown that the complexes studied can be used for the determination of uraniun(IV) in pure salts (C /SUB min/ = 0.05 ..mu..g/ml) and also in the presence of iron (II) ions. In this latter case, the second derivatives of the absorption spectra were used.

  13. Hybrid polymeric hydrogels via peptide nucleic acid (PNA)/DNA complexation.

    PubMed

    Chu, Te-Wei; Feng, Jiayue; Yang, Jiyuan; Kopeček, Jindřich

    2015-12-28

    This work presents a new concept in hybrid hydrogel design. Synthetic water-soluble N-(2-hydroxypropyl)methacrylamide (HPMA) polymers grafted with multiple peptide nucleic acids (PNAs) are crosslinked upon addition of the linker DNA. The self-assembly is mediated by the PNA-DNA complexation, which results in the formation of hydrophilic polymer networks. We show that the hydrogels can be produced through two different types of complexations. Type I hydrogel is formed via the PNA/DNA double-helix hybridization. Type II hydrogel utilizes a unique "P-form" oligonucleotide triple-helix that comprises two PNA sequences and one DNA. Microrheology studies confirm the respective gelation processes and disclose a higher critical gelation concentration for the type I gel when compared to the type II design. Scanning electron microscopy reveals the interconnected microporous structure of both types of hydrogels. Type I double-helix hydrogel exhibits larger pore sizes than type II triple-helix gel. The latter apparently contains denser structure and displays greater elasticity as well. The designed hybrid hydrogels have potential as novel biomaterials for pharmaceutical and biomedical applications. PMID:26394062

  14. Acid-base and catalytic properties of the products of oxidative thermolysis of double complex compounds

    NASA Astrophysics Data System (ADS)

    Pechenyuk, S. I.; Semushina, Yu. P.; Kuz'mich, L. F.; Ivanov, Yu. V.

    2016-01-01

    Acid-base properties of the products of thermal decomposition of [M(A)6] x; [M1(L)6] y (where M is Co, Cr, Cu, Ni; M1 is Fe, Cr, Co; A is NH3, 1/2 en, 1/2 pn, CO(NH2)2; and L is CN, 1/2C2O4) binary complexes in air and their catalytic properties in the oxidation reaction of ethanol with atmospheric oxygen are studied. It is found that these thermolysis products are mixed oxides of the central atoms of complexes characterized by pH values of the zero charge point in the region of 4-9, OH-group sorption limits from 1 × 10-4 to 4.5 × 10-4 g-eq/g, OH-group surface concentrations of 10-50 nm-2 in 0.1 M NaCl solutions, and S sp from 3 to 95 m2/g. Their catalytic activity is estimated from the apparent rate constant of the conversion of ethanol in CO2. The values of constants are (1-6.5) × 10-5 s-1, depending on the gas flow rate and the S sp value.

  15. EXAFS determinations of uranium structures: The uranyl ion complexed with tartaric, citric, and malic acids

    SciTech Connect

    Allen, P.G.; Shuh, D.K.; Bucher, J.J.

    1996-01-31

    Studies of the coordination chemistry of uranium in aqueous solutions are increasingly important for understanding the behavior of uranium in the environment. Actinide speciation information is essential for assessing and developing long-term strategies addressing problems such as migration in nuclear waste repositories or improvements in the processing of nuclear waste and materials. Relative to the latter, one method for removing uranium contamination from soils involves extraction using a chelating agent such as Tiron, or citrate. These types of extractants are quite efficient at binding the uranyl ion and thus are suitable for removing uranium contamination when it is in the hexavalent uranyl ion form. Martell et al. and Markovits et al. have published a series of articles detailing the complexation of the uranyl ion with tartaric, malic, and citric acids as a function of pH. Using the functional dependencies of potentiometric titration results, they showed that, in the pH range 2-4, the uranyl ion forms a 2:2 dimeric species, (UO{sub 2}){sub 2-} (L){sub 2}, where L = tartrate, malate, or citrate ligands. The authors have reinvestigated the solution structures of the uranyl complexes formed in these systems with the structural technique extended X-ray absorption fine-structure (EXAFS) spectroscopy.

  16. Electrocatalytic Oxidation of Formate with Nickel Diphosphane Dipeptide Complexes. Effect of Ligands Modified with Amino Acids

    SciTech Connect

    Galan, Brandon R.; Reback, Matthew L.; Jain, Avijita; Appel, Aaron M.; Shaw, Wendy J.

    2013-09-03

    A series of nickel bis-diphosphine complexes with dipeptides appended to the ligands were investigated for the catalytic oxidation of formate. Typical rates of ~7 s-1 were found, similar to the parent complex (~8 s-1), with amino acid size and positioning contributing very little to rate or operating potential. Hydroxyl functionalities did result in lower rates, which were recovered by protecting the hydroxyl group. The results suggest that the overall dielectric introduced by the dipeptides does not play an important role in catalysis, but free hydroxyl groups do influence activity suggesting contributions from intra- or intermolecular interactions. These observations are important in developing a fundamental understanding of the affect that an enzyme-like outer coordination sphere can have upon molecular catalysts. This work was funded by the US DOE Basic Energy Sciences, Chemical Sciences, Geoscience and Biosciences Division (BRG, AJ, AMA, WJS), the US DOE Basic Energy Sciences, Physical Bioscience program (MLR). Pacific Northwest National Laboratory is operated by Battelle for the U.S. Department of Energy.

  17. Synthesis of titanium, zirconium, and hafnium complexes that contain diamido donor ligands of the type [(t-BuN-o-C{sub 6}H{sub 4}){sub 2}O]{sup 2{minus}} and an evaluation of activated versions for the polymerization of 1-hexene

    SciTech Connect

    Schrock, R.R.; Baumann, R.; Reid, S.M.; Goodman, J.T.; Stumpf, R.; Davis, W.M.

    1999-08-30

    Titanium, zirconium, and hafnium dialkyl complexes that contain the [(t-Bu-d{sub 6}-N-o-C{sub 6}H{sub 4}){sub 2}O]{sup 2{minus}} ([t-BuNON]{sup 2{minus}}) ligand have been prepared. Only [T-BuNON]TiMe{sub 2} could be isolated, but [t-BuNON]ZrR{sub 2} and [t-BuNON]HfR{sub 2} complexes could be isolated in which (for example) R = Me, Et, or i-Bu. X-ray studies showed [t-BuNON]MMe{sub 2} structures (M = Tk or Zr) to be of the twisted fac variety in which two amido nitrogens occupy equatorial positions in a distorted trigonal bypyramid. However, in solution all such species show equivalent alkyl groups on the NMR time scale as a consequence of formation of an intermediate mer structure that contains a planar oxygen donor. In analogous complexes that contain the {l_brace}[Me(CD{sub 3}){sub 2}CNC{sub 6}H{sub 4}][Me(CD{sub 3}){sub 2}CN-2,4-Me{sub 2}C{sub 6}H{sub 2}]O{r_brace}{sup 2{minus}} or {l_brace}[Me(CD{sub 3}){sub 2}CNC{sub 6}H{sub 4}][Me(CD{sub 3}){sub 2}-N-2-EtC{sub 6}H{sub 3}]O{r_brace}{sup 2{minus}} ligand the two metal alkyl groups are inequivalent on the NMR time scale. Addition of trimethylphosphine to [t-BuNON]Zr(CH{sub 2}CH{sub 3}){sub 2} yields structurally characterized pseudooctahedral [t-BuNON]Zr({eta}{sup 2}-C{sub 2}H{sub 4})(PMe{sub 3}){sub 2}. Addition of B(C{sub 6}F{sub 5}){sub 3} to [t-BuNON]ZrMe{sub 2} yields structurally characterized {l_brace}[t-BuNON]ZrMe{r_brace}[MeB(C{sub 6}F{sub 5}){sub 3}], while addition of [PhNMe{sub 2}H]-[B(C{sub 6}F{sub 4}){sub 4}] to [t-BuNON]ZrMe{sub 2} in bromobenzene-d{sub 5} generates {l_brace}[t-BuNON]ZrMe(PhNMe{sub 2}){r_brace}-[B(C{sub 6}F{sub 5}){sub 4}], which is an active catalyst for the polymerization of up to 500 equiv of 1-hexene in a living manner at 0 C. The analogous hafnium systems are not as well behaved, since the dimethylaniline is insufficiently labile. No polymerization activity is observed for activated titanium dialkyl complexes. Polymerization activity is quenched upon addition of THF or

  18. Cytotoxicity of copper(II)-complexes with some S-alkyl derivatives of thiosalicylic acid. Crystal structure of the binuclear copper(II)-complex with S-ethyl derivative of thiosalicylic acid

    NASA Astrophysics Data System (ADS)

    Nikolić, Miloš V.; Mijajlović, Marina Ž.; Jevtić, Verica V.; Ratković, Zoran R.; Novaković, Slađana B.; Bogdanović, Goran A.; Milovanović, Jelena; Arsenijević, Aleksandar; Stojanović, Bojana; Trifunović, Srećko R.; Radić, Gordana P.

    2016-07-01

    The spectroscopically predicted structure of the obtained copper(II)-complex with S-ethyl derivative of thiosalicylic acid was confirmed by X-ray structural study and compared to previously reported crystal structure of the Cu complex with S-methyl derivative. Single crystals suitable for X-ray measurements were obtained by slow crystallization from a water solution. Cytotoxic effects of S-alkyl (R = benzyl (L1), methyl (L2), ethyl (L3), propyl (L4) and butyl (L5)) derivatives of thiosalicylic acid and the corresponding binuclear copper(II)-complexes on murine colon carcinoma cell lines, CT26 and CT26.CL25 and human colon carcinoma cell line HCT-116 were reported here. The analysis of cancer cell viability showed that all the tested complexes had low cytotoxic effect on murine colon carcinoma cell lines, but several times higher cytotoxicity on normal human colon carcinoma cells.

  19. ROCKY MOUNTAIN ACID DEPOSITION MODEL ASSESSMENT: EVALUATION OF MESOSCALE ACID DEPOSITION MODELS FOR USE IN COMPLEX TERRAIN

    EPA Science Inventory

    The report includes an evaluation of candidate meteorological models and acid deposition models. The hybrid acid deposition/air quality modeling system for the Rocky Mountains makes use of a mesoscale meteorological model, which includes a new diagnostic wind model, as a driver f...

  20. Electro-olfactogram and multiunit olfactory receptor responses to complex mixtures of amino acids in the channel catfish, Ictalurus punctatus.

    PubMed

    Kang, J S; Caprio, J

    1991-10-01

    In vivo electrophysiological recordings from populations of olfactory receptor neurons in the channel catfish, Ictalurus punctatus, clearly showed that both electro-olfactogram and integrated neural responses of olfactory receptor cells to complex mixtures consisting of up to 10 different amino acids were predictable with knowledge of (a) the responses to the individual components in the mixture and (b) the relative independence of the respective receptor sites for the component stimuli. All amino acid stimuli used to form the various mixtures were initially adjusted in concentration to provide approximately equal response magnitudes. Olfactory receptor responses to both multimixtures and binary mixtures were recorded. Multimixtures were formed by mixing equal aliquots of 3-10 different amino acids. Binary mixtures were formed by mixing equal aliquots of two equally stimulatory solutions. Solution 1 contained either one to nine different neutral amino acids with long side-chains (LCNs) or one to five different neutral amino acids with short side-chains (SCNs). Solution 2, comprising the binary mixture, consisted of only a single stimulus, either a LCN, SCN, basic, or acidic amino acid. The increasing magnitude of the olfactory receptor responses to mixtures consisting of an increasing number of neutral amino acids indicated that multiple receptor site types with highly overlapping specificities exist to these compounds. For both binary mixtures and multimixtures composed of neutral and basic or neutral and acidic amino acids, the receptor responses were significantly enhanced compared with those mixtures consisting of an equal number of only neutral amino acids. These results demonstrate that receptor sites for the basic and acidic amino acids, respectively, are highly independent of those for the neutral amino acids, and suggest that a mechanism for synergism is the simultaneous activation of relatively independent receptor sites by the components in the mixture

  1. Preparation, characterization, and bioavailability of ursodeoxycholic acid-phospholipid complex in vivo.

    PubMed

    Yue, Peng-Fei; Yuan, Hai-Long; Xie, Huan; Xiao, Xiao-He; Yang, Ming; Liao, Mei-Xiang; Zhu, Wei-Feng; Cai, Pei-Lie

    2008-07-01

    The aim of this study was to prepare ursodeoxycholic acid-phospholipid complex (UDCA-PLC) to enhance oral bioavailability of UDCA, and the physicochemical properties of the complex were studied. Compared with those of UDCA tablet after oral administration in rats, the main pharmacokinetic characteristics and bioavailability of UDCA-PLC orally administered were evaluated. Tetrahydrofuran was used as a reaction medium, UDCA and phospholipids were resolved into the medium, and UDCA-PLC was formed after the organic solvent was evaporated off under vacuum condition. The physicochemical properties of the complex were evaluated using scanning electron microscopy (SEM), transmission electron microscopy (TEM), differential scanning calorimetry (DSC), X-ray diffraction, particle size distribution analysis, and n-octanol/water partition coefficient (P) study. The blood concentrations of UDCA-PLC and UDCA tablet at different time points after oral administration in rats were assayed by high-performance liquid chromatography (HPLC) after derivatization. The pharmacokinetic parameters were computed by software program 3p87. The X-ray diffraction and DSC studies showed that UDCA and phospholipids in the UDCA-PLC were combined by noncovalent bond, not forming a new compound, and n-octanol/water partition coefficient (P) of UDCA-PLC was effectively enhanced. The mean serum concentration-time curves of UDCA after oral administration of UDCA-PLC and UDCA tablet in rats were both in accordance with open two-compartment model. Pharmacokinetic parameters of UDCA tablet and the PLC in rats were T(max) 1.9144 and 1.5610 h, C(max) 0.0576 and 0.1346 microg/mL, and AUC(0-infinity) 4.736 and 11.437 microg h/mL, respectively. The bioavailability of UDCA in rats was significantly different (p < .05) compared with those of UDCA tablet after administration. The UDCA-PLC would be more prospective formulation in future. PMID:18612911

  2. Effects of soluble ferri-hydroxide complexes on microbial neutralization of acid mine drainage.

    PubMed

    Bilgin, A Azra; Silverstein, JoAnn; Hernandez, Mark

    2005-10-15

    Heterotrophic respiration of ferric iron by Acidiphilium cryptum was investigated in anoxic microcosms with initial media pH values from 1.5 to 3.5. No organic carbon consumption or iron reduction was observed with an initial pH of 1.5, indicating that A. cryptum may not be capable of iron respiration at this pH. Significant iron reduction was observed at pH 2.5 and 3.5, with different effects. When the initial pH was 3.5, pH increased to 4.7-5.5 over 60 days of incubation with simultaneous production of 0.4 g L(-1) Fe2+. However, at an initial pH of 2.5, no significant change in pH was observed during iron respiration, although the accumulation of soluble ferrous iron was significantly higher, averaging 1.1 g L(-1) Fe2+. The speciation of the ferric iron electron acceptor may explain these results. At pH values of 3.5 and higher, precipitated ferric hydroxide Fe- (OH)3 would have been the primary source of ferric iron, with reduction resulting in net production of OH- ions and the significant increases in media pH observed. However at pH 2.5, soluble complexes, FeOH2+ and Fe(OH)2+, may have been the more prevalent electron acceptors, and the alkalinity generated by reduction of complexed iron was low. The existence of charged ferri-hydroxide complexes at pH 2.5 was verified by voltammetry. Results suggest that initiation of bacterial iron reduction may result in neutralization of acid mine drainage. However, this effect is extremely sensitive to iron speciation within a relatively small and critical pH range. PMID:16295843

  3. Enantioselective Hydrolysis of Amino Acid Esters Promoted by Bis(β-cyclodextrin) Copper Complexes

    PubMed Central

    Xue, Shan-Shan; Zhao, Meng; Ke, Zhuo-Feng; Cheng, Bei-Chen; Su, Hua; Cao, Qian; Cao, Zhen-Kun; Wang, Jun; Ji, Liang-Nian; Mao, Zong-Wan

    2016-01-01

    It is challenging to create artificial catalysts that approach enzymes with regard to catalytic efficiency and selectivity. The enantioselective catalysis ranks the privileged characteristic of enzymatic transformations. Here, we report two pyridine-linked bis(β-cyclodextrin) (bisCD) copper(II) complexes that enantioselectively hydrolyse chiral esters. Hydrolytic kinetic resolution of three pairs of amino acid ester enantiomers (S1–S3) at neutral pH indicated that the “back-to-back” bisCD complex CuL1 favoured higher catalytic efficiency and more pronounced enantioselectivity than the “face-to-face” complex CuL2. The best enantioselectivity was observed for N-Boc-phenylalanine 4-nitrophenyl ester (S2) enantiomers promoted by CuL1, which exhibited an enantiomer selectivity of 15.7. We observed preferential hydrolysis of L-S2 by CuL1, even in racemic S2, through chiral high-performance liquid chromatography (HPLC). We demonstrated that the enantioselective hydrolysis was related to the cooperative roles of the intramolecular flanking chiral CD cavities with the coordinated copper ion, according to the results of electrospray ionization mass spectrometry (ESI-MS), inhibition experiments, rotating-frame nuclear Overhauser effect spectroscopy (ROESY), and theoretical calculations. Although the catalytic parameters lag behind the level of enzymatic transformation, this study confirms the cooperative effect of the first and second coordination spheres of artificial catalysts in enantioselectivity and provides hints that may guide future explorations of enzyme mimics. PMID:26916830

  4. Bovine lactoferrin binds oleic acid to form an anti-tumor complex similar to HAMLET.

    PubMed

    Fang, Bing; Zhang, Ming; Tian, Mai; Jiang, Lu; Guo, Hui Yuan; Ren, Fa Zheng

    2014-04-01

    α-Lactalbumin (α-LA) can bind oleic acid (OA) to form HAMLET-like complexes, which exhibited highly selective anti-tumor activity in vitro and in vivo. Considering the structural similarity to α-LA, we conjectured that lactoferrin (LF) could also bind OA to obtain a complex with anti-tumor activity. In this study, LF-OA was prepared and its activity and structural changes were compared with α-LA-OA. The anti-tumor activity was evaluated by methylene blue assay, while the apoptosis mechanism was analyzed using flow cytometry and Western blot. Structural changes of LF-OA were measured by fluorescence spectroscopy and circular dichroism. The interactions of OA with LF and α-LA were evaluated by isothermal titration calorimetry (ITC). LF-OA was obtained by heat-treatment at pH8.0 with LD50 of 4.88, 4.95 and 4.62μM for HepG2, HT29, and MCF-7 cells, respectively, all of which were 10 times higher than those of α-LA-OA. Similar to HAMLET, LF-OA induced apoptosis in tumor cells through both death receptor- and mitochondrial-mediated pathways. Exposure of tryptophan residues and the hydrophobic regions as well as the loss of tertiary structure were observed in LF-OA. Besides these similarities, LF showed different secondary structure changes when compared with α-LA, with a decrease of α-helix and β-turn and an increase of β-sheet and random coil. ITC results showed that there was a higher binding number of OA to LF than to α-LA, while both of the proteins interacted with OA through van der Waals forces and hydrogen bonds. This study provides a theoretical basis for further exploration of protein-OA complexes. PMID:24368211

  5. Cherenkov and Scintillation Properties of Cubic Zirconium

    NASA Technical Reports Server (NTRS)

    Christl, M.J.; Adams, J.H.; Parnell, T.A.; Kuznetsov, E.N.

    2008-01-01

    Cubic zirconium (CZ) is a high index of refraction (n =2.17) material that we have investigated for Cherenkov counter applications. Laboratory and proton accelerator tests of an 18cc sample of CZ show that the expected fast Cherenkov response is accompanied by a longer scintillation component that can be separated by pulse shaping. This presents the possibility of novel particle spectrometers which exploits both properties of CZ. Other high index materials being examined for Cherenkov applications will be discussed. Results from laboratory tests and an accelerator exposure will be presented and a potential application in solar energetic particle instruments will be discussed

  6. Short-time oxidation of zirconium.

    NASA Technical Reports Server (NTRS)

    Srivastava, L. P.; Archbold, T. F.

    1972-01-01

    Study of zirconium oxidation kinetics for maximum exposure times of 3 min and in the temperature range 440 to 850 C. 'Discontinuous' oxidation runs were employed whereby a specimen was inserted into the gas stream for a predetermined time, removed and weighed, and reinserted into the oxidation atmosphere. It is considered that the increase in the observed activation energy for the early stage parabolic oxidation is a manifestation of a change from an n-type oxide to a predominantly p-type oxide, in agreement with the authors' earlier conclusion (1971) based on pressure effects.

  7. Diffusion of hydrogen in zirconium foil

    SciTech Connect

    Schur, D.V.; Pishuk, V.K.; Adejev, V.M.; Zaginaichenko, S.Y.

    1998-12-31

    The authors of present research have used in experiments the atomic hydrogen and metallic foil 25--30 {micro}m thick. It has been supposed that these technical operations will permit excluding the influence of surface and diffusional processes on the rate of Me-H interaction. The series of experiments have been carried out and they confirm this assumption. It has been shown that hydrogenation reaction of zirconium foil in atomic hydrogen conforms to the topochemical model of volume segregation of interaction product, and the rate of its flow is independent of the surface processes and hydrogen diffusion in volume.

  8. In situ hydrogen loading on zirconium powder

    PubMed Central

    Maimaitiyili, Tuerdi; Blomqvist, Jakob; Steuwer, Axel; Bjerkén, Christina; Zanellato, Olivier; Blackmur, Matthew S.; Andrieux, Jérôme; Ribeiro, Fabienne

    2015-01-01

    For the first time, various hydride phases in a zirconium–hydrogen system have been prepared in a high-energy synchrotron X-ray radiation beamline and their transformation behaviour has been studied in situ. First, the formation and dissolution of hydrides in commercially pure zirconium powder were monitored in real time during hydrogenation and dehydrogenation, then whole pattern crystal structure analysis such as Rietveld and Pawley refinements were performed. All commonly reported low-pressure phases presented in the Zr–H phase diagram are obtained from a single experimental arrangement. PMID:26134803

  9. ZIRCONIUM-TITANIUM-BERYLLIUM BRAZING ALLOY

    DOEpatents

    Gilliland, R.G.; Patriarca, P.; Slaughter, G.M.; Williams, L.C.

    1962-06-12

    A new and improved ternary alloy is described which is of particular utility in braze-bonding parts made of a refractory metal selected from Group IV, V, and VI of the periodic table and alloys containing said metal as a predominating alloying ingredient. The brazing alloy contains, by weight, 40 to 50 per cent zirconium, 40 to 50 per cent titanium, and the balance beryllium in amounts ranging from 1 to 20 per cent, said alloy having a melting point in the range 950 to 1400 deg C. (AEC)

  10. Shell model description of zirconium isotopes

    SciTech Connect

    Sieja, K.; Nowacki, F.; Langanke, K.; Martinez-Pinedo, G.

    2009-06-15

    We calculate the low-lying spectra and several high-spin states of zirconium isotopes (Z=40) with neutron numbers from N=50 to N=58 using a large valence space with the {sup 78}Ni inert core, which a priori allows one to study the interplay between spherical and deformed configurations, necessary for the description of nuclides in this part of the nuclear chart. The effective interaction is derived by monopole corrections of the realistic G matrix. We reproduce essential nuclear properties, such as subshell closures in {sup 96}Zr and {sup 98}Zr. The spherical-to-deformed shape transition in {sup 100}Zr is addressed as well.

  11. Two coordination modes around the Cu(II) cations in complexes with benzo[b]furancarboxylic acids

    NASA Astrophysics Data System (ADS)

    Drzewiecka, Aleksandra; Koziol, Anna E.; Klepka, Marcin T.; Wolska, Anna; Jimenez-Pulido, Sonia B.; Lis, Tadeusz; Ostrowska, Kinga; Struga, Marta

    2013-02-01

    Three Cu(II) complexes with derivatives of the benzo[b]furancarboxylic acid have been synthesized and characterized by the elemental and thermal analyses, and IR spectroscopy. The geometry of metal-ligand interaction for all compounds has been described using X-ray absorption spectroscopy and for one of them by X-ray crystallography. Two mononuclear Cu(II) complexes, with 7-acetyl-5-bromo-6-hydroxy-3-methylbenzo[b]furan-2-carboxylic and 6-acetyl-5-hydroxy-2-methylbenzo[b]furan-3-carboxylic acids, exhibit a tetra-fold coordination, CuO4. The Cu(II) cation in crystals with 7-acetyl-6-methoxy-3-methyl-benzo[b]furan-2-carboxylic acid is penta-coordinated; the bridging COO- groups and ethanol molecule stabilize the dinuclear center Cu2O10. The powdered form of this complex is based on the Cu2O8 units, indicating the absence of the ethanol molecules.

  12. Synthesis, physicochemical studies, embryos toxicity and DNA interaction of some new Iron(II) Schiff base amino acid complexes

    NASA Astrophysics Data System (ADS)

    Abdel-Rahman, Laila H.; El-Khatib, Rafat M.; Nassr, Lobna A. E.; Abu-Dief, Ahmed M.

    2013-05-01

    New Fe(II) Schiff base amino acid complexes derived from the condensation of o-hydroxynaphthaldehyde with L-alanine, L-phenylalanine, L-aspartic acid, L-histidine and L-arginine were synthesized and characterized by elemental analysis, IR, electronic spectra, and conductance measurements. The stoichiometry and the stability constants of the complexes were determined spectrophotometrically. The investigated Schiff bases exhibited tridentate coordination mode with the general formulae [Fe(HL)2]·nH2O for all amino acids except L-histidine. But in case of L-histidine, the ligand acts as tetradentate ([FeL(H2O)2]·2H2O), where HL = mono anion and L = dianion of the ligand. The structure of the prepared complexes is suggested to be octahedral. The prepared complexes were tested for their toxicity on chick embryos and found to be safe until a concentration of 100 μg/egg with full embryos formation. The interaction between CT-DNA and the investigated complexes were followed by spectrophotometry and viscosity measurements. It was found that, the prepared complexes bind to DNA via classical intercalative mode and showed a different DNA cleavage activity with the sequence: nhi > nari > nali > nasi > nphali. The thermodynamic Profile of the binding of nphali complex and CT-DNA was constructed by analyzing the experimental data of absorption titration and UV melting studies with the McGhee equation, van't Hoff's equation, and the Gibbs-Helmholtz equation.

  13. Purification and properties of the fatty acids synthetase complex from Neurospora crassa, and the nature of the fas-mutation.

    PubMed Central

    Elovson, J

    1975-01-01

    A procedure is described for the purification of the fatty acid synthetase complex (FAS) from Neurospora crassa. The enzyme complex has a molecular weight of 2.3 times 10(6), contains 6 mol of 4'-phosphopantetheine per mol, and on polyacrylamide gel electrophoresis in the presence of sodium dodecyl sulfate gives a single band, or a closely spaced doublet, which comigrates with standard myosin (molecular weight, 2 times 10(5)). Since the slightly retarded component in the doublet accounts for all protein-bound 4'-phosphopantetheine, the complex appears to be made up of 11 to 12 equally sized subunits, 6 of which carry the acyl carrier protein function. In this unusual arrangement, notably the lack of the low-molecular-weight acyl carrier protein component seen in other FAS systems, as well as in its enzymatic properties, the Neurospora FAS complex is quite similar to the yeast enzyme. The FAS complex of a saturated fatty acid-requiring mutant, previously disignated cel-, contains less than 2% of the 4'-phosphopantetheine prosthetic groups found in the wild-type complex. The leaky phenotype of this mutant, here designated fas-, is accounted for by a residual fatty acid synthesizing activity in its FAS complex, which is several-fold higher than expected from its residual content of 4'-phosphopanthetheine. Images PMID:126228

  14. Prevention of Acid Mine Drainage Through Complexation of Ferric Iron by Soluble Microbial Growth Products

    NASA Astrophysics Data System (ADS)

    Pandey, S.; Yacob, T. W.; Silverstein, J.; Rajaram, H.; Minchow, K.; Basta, J.

    2011-12-01

    Acid mine drainage (AMD) is a widespread environmental problem with deleterious impacts on water quality in streams and watersheds. AMD is generated largely by the oxidation of metal sulfides (i.e. pyrite) by ferric iron. This abiotic reaction is catalyzed by conversion of ferrous to ferric iron by iron and sulfur oxidizing microorganisms. Biostimulation is currently being investigated as an attempt to inhibit the oxidation of pyrite and growth of iron oxidizing bacteria through addition of organic carbon. This may stimulate growth of indigenous communities of acidophilic heterotrophic bacteria to compete for oxygen. The goal of this research is to investigate a secondary mechanism associated with carbon addition: complexation of free Fe(III) by soluble microbial growth products (SMPs) produced by microorganisms growing in waste rock. Exploratory research at the laboratory scale examined the effect of soluble microbial products (SMPs) on the kinetics of oxidation of pure pyrite during shaker flask experiments. The results confirmed a decrease in the rate of pyrite oxidation that was dependent upon the concentration of SMPs in solution. We are using these data to verify results from a pyrite oxidation model that accounts for SMPs. This reactor model involves differential-algebraic equations incorporating total component mass balances and mass action laws for equilibrium reactions. Species concentrations determined in each time step are applied to abiotic pyrite oxidation rate expressions from the literature to determine the evolution of total component concentrations. The model was embedded in a parameter estimation algorithm to determine the reactive surface area of pyrite in an abiotic control experiment, yielding an optimized value of 0.0037 m2. The optimized model exhibited similar behavior to the experiment for this case; the root mean squared of residuals for Fe(III) was calculated to be 7.58 x 10-4 M, which is several orders of magnitude less than the actual

  15. Effects of RAMEA-complexed polyunsaturated fatty acids on the response of human dendritic cells to inflammatory signals

    PubMed Central

    Rajnavölgyi, Éva; Laczik, Renáta; Kun, Viktor; Szente, Lajos

    2014-01-01

    Summary The n−3 fatty acids are not produced by mammals, although they are essential for hormone synthesis and maintenance of cell membrane structure and integrity. They have recently been shown to inhibit inflammatory reactions and also emerged as potential treatment options for inflammatory diseases, such as rheumatoid arthritis, asthma and inflammatory bowel diseases. Dendritic cells (DC) play a central role in the regulation of both innate and adaptive immunity and upon inflammatory signals they produce various soluble factors among them cytokines and chemokines that act as inflammatory or regulatory mediators. In this study we monitored the effects of α-linoleic acid, eicosapentaenoic acid and docosahexaenoic acid solubilized in a dimethyl sulfoxide (DMSO)/ethanol 1:1 mixture or as complexed by randomly methylated α-cyclodextrin (RAMEA) on the inflammatory response of human monocyte-derived dendritic cells (moDC). The use of RAMEA for enhancing aqueous solubility of n−3 fatty acids has the unambiguous advantage over applying RAMEB (the β-cyclodextrin analog), since there is no interaction with cell membrane cholesterol. In vitro differentiated moDC were left untreated or were stimulated by bacterial lipopolysaccharide and polyinosinic:polycytidylic acid, mimicking bacterial and viral infections, respectively. The response of unstimulated and activated moDC to n−3 fatty acid treatment was tested by measuring the cell surface expression of CD1a used as a phenotypic and CD83 as an activation marker of inflammatory moDC differentiation and activation by using flow cytometry. Monocyte-derived DC activation was also monitored by the secretion level of the pro- and anti-inflammatory cytokines IL-1β, TNF-α, IL-6, IL-10 and IL-12, respectively. We found that RAMEA-complexed n−3 fatty acids reduced the expression of CD1a protein in both LPS and Poly(I:C) stimulated moDC significantly, but most efficiently by eicosapentaenic acid, while no significant change

  16. Synthesis, characterization, theoretical study and biological activities of oxovanadium (IV) complexes with 2-thiophene carboxylic acid hydrazide.

    PubMed

    Jabeen, Mudassir; Ali, Saqib; Shahzadi, Saira; Sharma, Saroj K; Qanungo, Kushal

    2014-07-01

    Oxovanadium (IV) complexes (1)-(3) have been synthesized by treating 2-thiophene carboxylic acid hydrazide with VOSO4⋅xH2O and VCl3(THF)3 in different M/L ratios. These complexes have been characterized by elemental analysis, UV-vis, FT-IR and mass spectrometry. The FT-IR data predicts the bidentate nature of the ligand which is also confirmed by semi-empirical study. Mass spectrometric data shows that molecular ion peak is only observed for 2-thiophene carboxylic acid hydrazide. The ESP map and thermodynamic parameters shows the presence of partial charge on atoms and stability of synthesized oxovanadium complexes, respectively. DNA binding study of complexes (1)-(3) was carried out by UV-vis and cyclic voltammetric methods which suggests the intercalative binding mode of the complexes with DNA. Cytotoxicity was checked by brine shrimp lethality assay and complex (1) showed greater cytotoxicity towards Artemia salina as compared to free ligand. Immuno-modulatory activity data shows that hydrazide ligand was more active as compared to oxovanadium complexes and standard drug. Complex (2) shows significant urease inhibition activity. The ligand and synthesized complexes were found inactive against all tested bacterial and fungal strains. PMID:24844618

  17. Investigation of the aggregation of then neodymium complexes of dialkylphosphoric,--oxothiophosphinic, and --dithiophosphinic acids in toluene.

    SciTech Connect

    Jensen, M. P.; Chiarizia, R.; Urban, V.; Chemistry

    2001-01-01

    Small angle neutron scattering and visible absorption spectroscopy were used to study the neodymium complexes of a series of acidic organophosphorus extractants in deuterated toluene at high ({>=}33% theoretical capacity) metal loading. Organic phases containing 0.10 M bis(2-ethylhexyl)phosphoric acid (HDEHP), bis(2,4,4-trimethylpentyl)oxothiophosphinic acid (HC302), or bis(2,4,4-trimethylpentyl)dithiophosphinic acid (HC301) were used. Under these conditions, the neutron scattering experiments show that HDEHP and HC302 exist as dimeric species in the absence of Nd. Extraction of Nd disrupts the dimeric structure of the extractants to form dinuclear complexes with the formula Nd{sub 2}(DEHP){sub 6} or Nd{sub 2}(C302){sub 6}. In contrast, 0.10 M HC301 is not dimeric in deuterated toluene. At 86% of the theoretical Nd capacity, the extracted complex is also dinuclear with the average formula Nd{sub 2}(C301){sub 6}, but at 46% of the theoretical Nd capacity only the mononuclear complex, Nd(C301){sub 3}, is formed. The Nd hypersensitive transitions in the visible region of the spectrum provide further support for this interpretation of the neutron scattering data and the equivalence of the Nd coordination in highly loaded HDEHP and bis(2,4,4-trimethylpentyl)phosphinic acid.

  18. Modification of different zirconium propoxide precursors by diethanolamine. Is there a shelf stability issue for sol-gel applications?

    PubMed

    Spijksma, Gerald I; Blank, Dave H A; Bouwmeester, Henny J M; Kessler, Vadim G

    2009-11-01

    Modification of different zirconium propoxide precursors with H(2)dea was investigated by characterization of the isolated modified species. Upon modification of zirconium n-propoxide and [Zr(O(n)Pr)(O(i)Pr)(3)((i)PrOH)](2) with (1/2) a mol equivalent of H(2)dea the complexes [Zr(2)(O(n)Pr)(6)(OCH(2)CH(2))(2)NH](2) (1) and [Zr(2)(O(n)Pr)(2)(O(i)Pr)(4)(OCH(2)CH(2))(2)NH](2) (2) were obtained. However, (1)H-NMR studies of these tetranuclear compounds showed that these are not time-stable either in solution or solid form. The effect of this time instability on material properties is demonstrated by light scattering and TEM experiments. Modification of zirconium isopropoxide with either (1/2) or 1 equivalent mol of H(2)dea results in formation of the trinuclear complex, Zr{eta(3)mu(2)-NH(C(2)H(4)O)(2)}(3)[Zr(O(i)Pr)(3)](2)(iPrOH)(2) (3) countering a unique nona-coordinated central zirconium atom. This complex 3 is one of the first modified zirconium propoxide precursors shown to be stable in solution for long periods of time. The particle size and morphology of the products of sol-gel synthesis are strongly dependent on the time factor and eventual heat treatment of the precursor solution. Reproducible sol-gel synthesis requires the use of solution stable precursors. PMID:20087472

  19. Acidity and complex formation studies of 3-(adenine-9-yl)-propionic and 3-(thymine-1-yl)-propionic acids in ethanol-water media

    NASA Astrophysics Data System (ADS)

    Hammud, Hassan H.; El Shazly, Shawky; Sonji, Ghassan; Sonji, Nada; Bouhadir, Kamal H.

    2015-05-01

    The ligands 3-(adenine-9-yl)propionic acid (AA) and 3-(thymine-1-yl)propionic acid (TA) were prepared by N9-alkylation of adenine and N1-alkylation of thymine with ethylacrylate in presence of a base catalyst, followed by acid hydrolysis of the formed ethyl esters to give the corresponding propionic acid derivatives. The products were characterized by spectral methods (FTIR, 1H NMR and 13C NMR), which confirm their structures. The dissociation constants of ligands, were potentiometrically determined in 0.3 M KCl at 20-50 °C temperature range. The work was extended to study complexation behavior of AA and TA with various biologically important divalent metal ions (Co2+, Ni2+, Cu2+, Zn2+, Cd2+, Mn2+ and Pb2+) in 50% v/v water-ethanol medium at four different temperatures, keeping ionic strength constant (0.3 M KCl). The order of the stability constants of the formed complexes decreases in the sequence Cu2+ > Pb2+ > Zn2+ > Ni2+ > Co2+ > Mn2+ > Cd2+ for both ligands. The effect of temperature was also studied and the corresponding thermodynamic functions (ΔG, ΔH, ΔS) were derived and discussed. The formation of metal complexes has been found to be spontaneous, and the stability constants were dependant markedly on the basicity of the ligands.

  20. Retrospective Reactor Dosimetry with Zirconium Alloy Samples

    SciTech Connect

    Greenwood, Lawrence R.; Foster, John P.

    2009-11-01

    Retrospective measurements are routinely performed with stainless steel samples. Recent experiments have been successfully conducted using zirconium alloy samples, involving somewhat different neuron activation reactions than are normally encountered with stainless steel samples. The alloy composition consisted of nominally 1% (by weight) niobium, 1% tin, and 0.1% iron, with the balance zirconium. The activation products observed in the samples by gamma spectroscopy included Zr-95, Nb-95, Sn-113, Sb-125, Mn-54, Co-60, Nb-94, and Ta-182. The niobium was then chemically separated following ASTM procedure E1297 and the Nb-93m activities were measured by x-ray spectroscopy. The thermal neutron fluences, as determined independently by the neutron capture gamma reactions to Zr-95, Sn-113, Nb-94, and Sn/Sb-125, were in excellent agreement. The fast neutron fluences, as determined separately by the Fe-54(n,p)Mn-54 and Nb-93(n,n’)Nb-93m reactions, were also in good agreement, thus demonstrating the versatility of the retrospective dosimetry technique.