Sample records for 2,4-pentanedione

  1. Infinite dilution partial molar volumes of platinum(II) 2,4-pentanedionate in supercritical carbon dioxide.


    Kong, Chang Yi; Siratori, Tomoya; Funazukuri, Toshitaka; Wang, Guosheng


    The effects of temperature and density on retention of platinum(II) 2,4-pentanedionate in supercritical fluid chromatography were investigated at temperatures of 308.15-343.15K and pressure range from 8 to 40MPa by the chromatographic impulse response method with curve fitting. The retention factors were utilized to derive the infinite dilution partial molar volumes of platinum(II) 2,4-pentanedionate in supercritical carbon dioxide. The determined partial molar volumes were small and positive at high pressures but exhibited very large and negative values in the highly compressible near critical region of carbon dioxide.

  2. SCC of Ti-6Al-4V foil by methanol - Effect of treatments with 2,4-pentanedione and its metal complexes.

    NASA Technical Reports Server (NTRS)

    Haney, E. G.; Fugassi, P.


    The susceptibility of Ti-6Al-4V foil to stress corrosion cracking (SCC) by methanol can be decreased by treatment of the foil with 2,4-pentanedione prior to its immersion in the corroding media. It is assumed that such treatments remove from the protective film formed on the foil by exposure to the atmosphere, certain metal ions whose oxides are more readily penetrated by the ions, Na + and Cl- or Fe(3+) and Cl-, present in the corroding media.

  3. Three-component reaction of tautomeric amidines with 3-ferrocenylmethylidene-2,4-pentanedione. Formation of polymeric coordination complexes of potassium ferrocenyl-(hexahydro)pyrimidoxides.


    Klimova, Elena I; Flores-Alamo, Marcos; Klimova, Tatiana; Maya, Sandra Cortez; Beletskaya, Irina P


    Acetamidine hydrochloride and p-aminobenzamidine dihydrochloride interact with 3-ferrocenylmethylidene-2,4-pentanedione at 80-82 °C in the presence of K2CO3 in the water-alcohol medium in two tautomeric forms (the amidoimine and enediamine ones) with formation of mixtures of pyrimidine and piperidone derivatives and polymeric coordination complexes of potassium ferrocenyl(hexahydro)pyrimidoxides. The structure of the resultant compounds is elucidated on the basis of IR, 1H- and 13C-NMR spectroscopy, mass spectrometry and elemental analysis data. The crystal structures of 6-ferrocenyl-4-hydroxy-4-methyl-2-piperidone, potassium 6-ferrocenyl-4-methyl-2-methylidene(hexahydro)pyrimidin-4-oxide and 2-(4-aminophenyl)-4-ferrocenyl-6-methyl-pyrimidine were determined by X-ray analysis of suitable single crystals. PMID:24362624

  4. Optimization of photoluminescence of Y2O3:Eu and Gd2O3:Eu phosphors synthesized by thermolysis of 2,4-pentanedione complexes

    NASA Astrophysics Data System (ADS)

    Antic, B.; Rogan, J.; Kremenovic, A.; Nikolic, A. S.; Vucinic-Vasic, M.; Bozanic, D. K.; Goya, G. F.; Colomban, Ph


    Spherical shaped nanoparticles of series Y2 - xEuxO3 (x = 0.06, 0.10, 0.20, and 2) and Gd2 - xEuxO3 (x = 0.06, 0.10) were prepared by thermolysis of 2,4-pentanedione complexes of Y, Gd, and Eu. The bixbyite phase of Gd2 - xEuxO3 samples was formed at 500 °C, whereas the thermal decomposition of Y and Eu complexes' mixtures occurred at higher temperatures. Linearity in the concentration dependence on lattice parameter confirmed the formation of solid solutions. The distribution of Eu3 + in Gd2 - xEuxO3 was changed with thermal annealing: in the as-prepared sample (x = 0.10) the distribution was preferential at C3i sites while in the annealed samples, Eu3 + were distributed at both C2 and C3i sites. Rietveld refinement of site occupancies as well as emission spectra showed a random distribution of cations in Y2 - xEuxO3. The photoluminescence (PL) measurements of the sample showed red emission with the main peak at 614 nm (5D0-7F2). The PL intensity increased with increasing concentration of Eu3 + in both series. Infrared excitation was required to obtain good Raman spectra. The linear dependence of the main Raman peak wavenumber offers a non-destructive method for monitoring the substitution level and its homogeneity at the micron scale.

  5. Induction of oxidative stress in Prototheca zopfii by indole-3-acetic acid/HRP or 2,4-pentanedione/HRP systems and their oxidation products.


    Cunha, L T; Pugine, S M P; Lins, P G; Brunetti, I L; De Melo, M P


    We investigated the toxic effects on Prototheca zopfii of indole-3-acetic acid (IAA) and 2,4-pentanedione (PD) combined with horseradish peroxidase (HRP) alongside the oxidation products of 3-methyl-2-oxindole (MOI) and indole-3-carbinol (I3C) from the IAA/HRP system and methylglyoxal (MGO) from the PD/HRP system. The microorganism was incubated in the absence (control) or presence of IAA, PD, IAA/HRP, PD/HRP, MOI, I3C and MGO and determined: (1) cytotoxicity by MTT (3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium) assay; (2) growth inhibitory concentration by resazurin assay and (3) antioxidant enzymes activities of: catalase (CAT), glutathione reductase (GR) and superoxide dismutase (SOD). P. zopfii was more susceptible to IAA at 40 mM than PD at the same concentration, which seems to indicate that IAA was more effective at initiating cell death. These data corroborate results from the resazurin assay. Concentrations of 40 mM of IAA, IAA/HRP and PD/HRP, 20 mM of PD/HRP, 10 mM of MOI, 2 mM of I3C and 8 mM of MGO inhibited the growth of P. zopfii. With sub-inhibitory concentrations of IAA and IAA/HRP at 30 mM, MOI at 8 mM and I3C at 1 mM, the activities of CAT and GR increased, whereas no statistical difference was observed for CAT activity with IAA/HRP. Thus, PD at 30 mM and MGO at 6 mM increased the activities of CAT and GR, whereas PD/HRP system at 15 mM decreased CAT activity and PD/HRP and MGO showed no statistical difference for SOD activity. In conclusion, IAA/HRP or PD/HRP systems and their oxidation products exert cytotoxic effects on P. zopffi; however, I3C and MGO appear to exert greater microbicidal effect on P. zopfii. PMID:25173924

  6. Structure and vibrational assignment of the enol form of 1,1,1-trifluoro-2,4-pentanedione.


    Zahedi-Tabrizi, Mansoureh; Tayyari, Fariba; Moosavi-Tekyeh, Zainab; Jalali, Alireza; Tayyari, Sayyed Faramarz


    Molecular structure of 1,1,1-trifluoro-pentane-2,4-dione, known as trifluoro-acetylacetone (TFAA), has been investigated by means of Density Functional Theory (DFT) calculations and the results were compared with those of acetylacetone (AA) and hexafluoro-acetylacetone (HFAA). The harmonic vibrational frequencies of both stable cis-enol forms were calculated at B3LYP level of theory using 6-31G** and 6-311++G** basis sets. We also calculated the anharmonic frequencies at B3LYP/6-31G** level of theory for both stable cis-enol isomers. The calculated frequencies, Raman and IR intensities, and depolarization ratios were compared with the experimental results. The energy difference between the two stable cis-enol forms, calculated at B3LYP/6-311++G**, is only 5.89 kJ/mol. The observed vibrational frequencies and Raman and IR intensities are in excellent agreement with the corresponding values calculated for the most stable conformation, 2TFAA. According to the theoretical calculations, the hydrogen bond strength for the most stable conformer is 57 kJ/mol, about 9.5kJ/mol less than that of AA and about 14.5 kJ/mol more than that of HFAA. These hydrogen bond strengths are consistent with the frequency shifts for OH/OD stretching and OH/OD out-of-plane bending modes upon substitution of CH(3) groups with CF(3) groups. By comparing the vibrational spectra of both theoretical and experimental data, it was concluded that 2TFAA is the dominant isomer. PMID:16500140

  7. Structure and vibrational assignment of the enol form of 1,1,1-trifluoro-2,4-pentanedione

    NASA Astrophysics Data System (ADS)

    Zahedi-Tabrizi, Mansoureh; Tayyari, Fariba; Moosavi-Tekyeh, Zainab; Jalali, Alireza; Tayyari, Sayyed Faramarz


    Molecular structure of 1,1,1-trifluoro-pentane-2,4-dione, known as trifluoro-acetylacetone (TFAA), has been investigated by means of Density Functional Theory (DFT) calculations and the results were compared with those of acetylacetone (AA) and hexafluoro-acetylacetone (HFAA). The harmonic vibrational frequencies of both stable cis-enol forms were calculated at B3LYP level of theory using 6-31G** and 6-311++G** basis sets. We also calculated the anharmonic frequencies at B3LYP/6-31G** level of theory for both stable cis-enol isomers. The calculated frequencies, Raman and IR intensities, and depolarization ratios were compared with the experimental results. The energy difference between the two stable cis-enol forms, calculated at B3LYP/6-311++G**, is only 5.89 kJ/mol. The observed vibrational frequencies and Raman and IR intensities are in excellent agreement with the corresponding values calculated for the most stable conformation, 2TFAA. According to the theoretical calculations, the hydrogen bond strength for the most stable conformer is 57 kJ/mol, about 9.5 kJ/mol less than that of AA and about 14.5 kJ/mol more than that of HFAA. These hydrogen bond strengths are consistent with the frequency shifts for OH/OD stretching and OH/OD out-of-plane bending modes upon substitution of CH 3 groups with CF 3 groups. By comparing the vibrational spectra of both theoretical and experimental data, it was concluded that 2TFAA is the dominant isomer.

  8. Substituent Effects on Keto-Enol Equilibria Using NMR Spectroscopy

    ERIC Educational Resources Information Center

    Manbeck, Kimberly A.; Boaz, Nicholas C.; Bair, Nathaniel C.; Sanders, Allix M. S.; Marsh, Anderson L.


    In this extension to a classic physical chemistry experiment, students record the proton nuclear magnetic resonance spectra of the [beta]-diketones 2,4-pentanedione, 3-methyl-2,4-pentanedione, and 3-chloro-2,4-pentanedione to investigate the effect of substituents on keto-enol tautomerization equilibria. From the integrated intensities of keto and…

  9. Spectroscopic investigation of the structure of complex compounds of Cu(II), Co(II), and Ni(II) with. cap alpha. - and. beta. -diketone

    SciTech Connect

    Krymova, N.M.; Ivanov, V.E.; Ostapkevich, N.A.


    In the reactions of Cu(II), Co(II), and Ni(II) chlorides with 2,3-butanedione and 2,4-pentanedione isonicotinoylhydrazones in neutral and weakly acid media complex compounds of the addition-product type are formed, but in an alkaline medium inner-complex compounds are formed. By methods of electronic and ESR spectroscopy it was shown that the Cu(II) complex compounds have a planar-square structure, the Ni(II) complexes are octrahedral, but the Co(II) complexes have a tetrahedral or distorted tetrahedral structure. In the spectrochemical series 2,3-butanedione and 2,4-pentanedione isonicotinoylhydrazones occupy positions between water and ammonia.

  10. Energy transfer and light yield properties of a new highly loaded indium(III) β-diketonate organic scintillator system

    NASA Astrophysics Data System (ADS)

    Buck, C.; Hartmann, F. X.; Motta, D.; Schoenert, S.


    We present combined experimental and model studies of the light yield and energy transfer properties of a newly developed high light yield scintillator based on indium(III)-tris(2,4-pentanedionate) in a 2-(4-biphenyl)-5-phenyloxazole (BPO), methoxybenzene organic liquid; of interest to the detection of solar electron neutrino oscillations. Optical measurements are made to understand the energy transfer properties and a model is advanced to treat the unusual conditions of high metal and fluor loadings. Such scintillator types are of interest to the exploration of novel luminescent materials and the development of large-scale detectors for studying fundamental properties of naturally occurring neutrinos.

  11. Ab Initio Molecular Dynamics Study of the Very Short O-H···O Hydrogen Bonds in the Condensed Phases.


    Durlak, Piotr; Latajka, Zdzisław


    In this paper are presented the results of theoretical studies of the structure and proton motion in very short O···O intramolecular hydrogen bonds in two molecular crystals. A comparison was conducted between 3-cyano-2,4-pentanedione (I) and 4-cyano-2,2,6,6-tetramethyl-3,5-heptanedione (II) in the solid state. The dynamics of proton motion in the O-H···O hydrogen bond were investigated in he NVT ensemble at 298 and 50 K, respectively, for crystals I and II using Car-Parrinello and path integral molecular dynamics. Very large delocalization of the bridging proton was noted especially in the path integral simulation where quantum effects are taken into account. The infrared spectrum was calculated, and a comparative vibrational analysis was performed. CPMD vibrational results appear to be in qualitative agreement with the experimental ones. PMID:26589010

  12. Walphos versus Biferrocene-Based Walphos Analogues in the Asymmetric Hydrogenation of Alkenes and Ketones

    PubMed Central


    Two representative Walphos analogues with an achiral 2,2″-biferrocenediyl backbone were synthesized. These diphosphine ligands were tested in the rhodium-catalyzed asymmetric hydrogenation of several alkenes and in the ruthenium-catalyzed hydrogenation of two ketones. The results were compared with those previously obtained on using biferrocene ligands with a C2-symmetric 2,2″-biferrocenediyl backbone as well as with those obtained with Walphos ligands. The application of one newly synthesized ligand in the hydrogenation of 2-methylcinnamic acid gave (R)-2-methyl-3-phenylpropanoic acid with full conversion and with 92% ee. The same ligand was used to transform 2,4-pentanedione quantitatively and diastereoselectively into (S,S)-2,4-pentanediol with 98% ee. PMID:24795493

  13. Asymmetric Synthesis of the Aminocyclitol Pactamycin, a Universal Translocation Inhibitor

    PubMed Central

    Sharpe, Robert J.; Malinowski, Justin T.; Johnson, Jeffrey S.


    An asymmetric total synthesis of the aminocyclopentitol pactamycin is described, which delivers the title compound in 15 steps from 2,4-pentanedione. Critical to this approach was the exploitation of a complex symmetry-breaking reduction strategy to assemble the C1, C2, and C7 relative stereochemistry within the first four steps of the synthesis. Multiple iterations of this reduction strategy are described, and a thorough analysis of stereochemical outcomes is detailed. In the final case, an asymmetric Mannich reaction was developed to install a protected amine directly at the C2 position. Symmetry-breaking reduction of this material gave way to a remarkable series of stereochemical outcomes leading to the title compound without recourse to non-strategic downstream manipulations. This synthesis is immediately accommodating to the facile preparation of structural analogs. PMID:24245656

  14. Preparation of Zeolite-like Pillared Metal(IV) Phosphate Materials

    NASA Astrophysics Data System (ADS)

    González, J. Santamaría.; Jiménez-López, A.; Lara, María. Martínez


    It is possible to obtain mixed aminopropyl sil-aluminum sesquioxanes by simultaneous hydrolysis of (3-aminopropyl)triethoxysilane and aluminum (III) diisopropoxide-2,4-pentanedionate with the stoichiometric amount of water in methanol. These oligomers are intercalated in a M(IV)-phosphate in which the number of POH groups are controlled substituting POH groups by phenyl phosphonates. The zeolite-like pillared materials obtained after thermal treatment at 600°C have high surface areas (up to 126 m 2 g -1) and high total acidity (up to 2.11 mmol of NH 3 desorbed between 100-500°C). XPS reveals that Al has tetrahedral coordination in these materials.

  15. Control of thin film processing behavior through precursor structural modifications

    SciTech Connect

    Schwartz, R.W.; Voigt, J.A.; Boyle, T.J.; Christenson, T.A.; Buchheit, C.D.


    In the sol-gel processing of ceramic thin films it has been frequently noted that the processing behavior, microstructure and properties of the films are dependent on the nature of the coating solution. In an attempt to understand such thin film processing-property relationships, the authors have systematically investigated the effects of varying the precursor nature on thin film densification and crystallization for ZrO{sub 2} and TiO{sub 2} films. Metal alkoxide starting compounds, e.g., zirconium n-butoxide{center_dot}n-butanol and titanium i-propoxide, were reacted with acetic acid and 2,4-pentanedione to prepare coating solutions for thin film deposition. The use of these chelating ligands resulted in solution oligomeric species of different nature. Studies of thin film processing indicated that film processing characteristics, i.e., consolidation, densification and crystallization, were strongly dependent on solution precursor nature. Ligand steric size, pyrolysis behavior, extent of chelation, and precursor reactivity were found to be key variables in controlling film processing characteristics.

  16. Use of a new hybrid sol-gel zirconia matrix in the removal of the herbicide MCPA: a sorption/degradation process.


    Aronne, Antonio; Sannino, Filomena; Bonavolontà, Serena R; Fanelli, Esther; Mingione, Alessio; Pernice, Pasquale; Spaccini, Riccardo; Pirozzi, Domenico


    A class II hybrid sol-gel material was prepared starting from zirconium(IV) propoxide and 2,4-pentanedione and its catalytic activity in the removal of the herbicide 4-chloro-2-methylphenoxyacetic acid (MCPA) was revealed. The thermal and structural characterization, performed by thermogravimetry, differential thermal analysis, and diffuse reflectance Fourier transform infrared spectroscopy, demonstrated the hybrid nature of the material. The structure of the material can be described as a polymeric network of zirconium oxo clusters, on the surface of which large part of Zr(4+) ions are involved in strong complexation equilibria with acetylacetonate (acac) ligands. The incubation of MCPA in the presence of this material yielded an herbicide removal fraction up to 98%. A two-step mechanism was proposed for the MCPA removal, in which a reversible first-order adsorption of the herbicide is followed by its catalytic degradation. The nature of the products of the MCPA catalytic degradation as well as the reaction conditions adopted do not support typical oxidation pathways involving radicals, suggesting the existence of a different mechanism in which the Zr(4+):acac enol-type complex can act as Lewis acid catalyst.

  17. Transport of metal sulfides in supercritical carbon dioxide

    SciTech Connect

    Propp, W.A.; Carleson, T.E.; Wai, C.M.; Huang, S.


    This report presents the results of studies of supercritical fluid extraction of selected organics and of transition metal sulfides using carbon dioxide with and without modifiers. For the metal sulfides, the modifiers water, aqueous EDTA, methanol, and methanolic 2,4-pentanedione (acetyl acetone) were added in amounts ranging from 1 to 10 wt% depending on the specific modifier used. Extraction efficiency was studied as a function of fluid composition and extraction temperature and pressure. The objective of the work was to investigate the scientific feasibility of using this type of extraction process for metallurgical or environmental applications. Theoretical modeling studies were performed in an attempt to develop predictive capabilities for both solubility calculations and extraction simulation. The experimental studies have established the scientific feasibility of extraction and transport of selected cations by these fluids. Depending on the metal and conditions, transport of up to 12% of the starting material has been observed; however, the observed extraction efficiencies for inorganics do not approach those typical for organics under similar conditions.

  18. Combinatorial and high-throughput screening of the effect of siloxane composition on the surface properties of crosslinked siloxane-polyurethane coatings.


    Ekin, Abdullah; Webster, Dean C


    Libraries of siloxane-polyurethane coatings were designed, formulated, and screened using high-throughput experimentation. Four independent variables that were analyzed were the molecular weight of poly(dimethylsiloxane) (PDMS), presence or absence of poly(epsilon-caprolactone) (PCL) blocks attached to the PDMS backbone, the length of the PCL blocks, and the siloxane polymer level in the coating formulations. In addition to the siloxane libraries (3-aminopropyl-terminated PDMS and poly(epsilon-caprolactone)-poly(dimethylsiloxane)-poly(epsilon-caprolactone) (PCL-PDMS-PCL) triblock copolymers), the coating formulation included a trifunctional isocyanate crosslinker, trifunctional poly(epsilon-caprolactone) polyol, 2,4-pentanedione (pot-life extender), dibutyltin diacetate (catalyst), and a blend of solvents. The resulting coatings were analyzed for their surface energy and pseudobarnacle adhesion both before and after aging the coatings for 30 days in water. The water and methylene iodide contact angle averages increase with increasing molecular weight of PDMS. Coatings prepared from PCL-PDMS-PCL triblock copolymers have lower surface energies than coatings prepared from 3-aminopropyl-terminated PDMS; however, lower pseudobarnacle adhesion results were obtained for the coatings prepared from 3-aminopropyl-terminated PDMS than coatings prepared from PCL-PDMS-PCL triblock copolymers. The siloxane polymer level in the coating formulations does not have a significant effect on the surface energy of the coatings, but it resulted in higher pseudobarnacle adhesion. PMID:17206846

  19. Synthesis and structural characterization of a new heterobimetallic coordination complex of barium and cobalt for use as a precursor for chemical vapor deposition.


    Tahir, Asif A; Molloy, Kieran C; Mazhar, Muhammad; Kociok-Köhn, Gabriele; Hamid, Mazhar; Dastgir, Sarim


    Ba(dmae)2 (dmaeH=N,N-dimethylaminoethanol, C4H11NO) reacts with Co(acac)2 (acac=2,4-pentanedionate) to produce the trinuclear coordination complex [Ba2Co(acac)4(dmae)3(dmaeH)] in an 85% yield. Spectroscopic and single-crystal X-ray diffraction experiments indicate that the complex possesses a structure in which two barium atoms and a cobalt atom are bridged by acac and dmae groups. The barium centers are eight and nine coordinate with BaO7N and BaO7N2 coordination spheres while the cobalt is a more regular CoO5N octahedron. This 2:1 heterobimetallic molecular complex was investigated as precursor for the deposition of thin film by AACVD. The film was characterized by SEM and XRD. TGA shows that the complex starts thermal decomposition upon heating in nitrogen atmosphere at 105 degrees C to produce barium cobalt oxide material of a Ba2CoO3 composition with an orthorhombic structure. The synthetic approach detailed here represents a unique route to the formation of a heterobimetallic barium cobalt coordination complex. PMID:16323901

  20. Photooxidation of water by NiTiO3 deposited from single source precursor [Ni2Ti2(OEt)2(micro-OEt)6(acac)4] by AACVD.


    Tahir, Asif Ali; Mazhar, Muhammad; Hamid, Mazhar; Wijayantha, K G Upul; Molloy, Kieran C


    A single-source heterobimetallic complex Ni2Ti2(OEt)2(mu-OEt)6(acac)4 (1) (acac=2,4-pentanedionate), having a low decomposition temperature and sufficient solubility in organic solvents, was synthesized by simple chemical techniques in high yield and analyzed by melting point, FTIR, single crystal X-ray analysis and thermal analysis. The TGA analysis proved that complex (1) underwent facile thermal decomposition at 500 degrees C to give NiTiO3 residue. In-house designed aerosol assisted chemical vapor deposition equipment was used to deposit high quality thin films of NiTiO3 on a SnO2 coated conducting glass substrate at 500 degrees C. An XRD analysis of the thin films proved the formation of crystalline NiTiO3 with average grain size 42 nm. Scanning electron microscopic studies (SEM) show that the thin films consist of flat, plate-like nanoparticles. The current-potential characteristics recorded under AM1.5 illumination indicate that NiTiO3 thin films are anodic and the photocurrent density at 1.23 V vs RHE (Reversible Hydrogen Electrode) is about 40 microA cm(-2). PMID:19417932

  1. Densification and crystallization of zirconia thin films prepared by sol-gel processing

    SciTech Connect

    Schwartz, R.W.; Voigt, J.A.; Buchheit, C.D.; Boyle, T.J.


    We have investigated the effects of precursor nature and heat treatment schedule on the densification and crystallization behavior of sol-gel derived zirconia thin films. Precursor solutions were prepared from n-propanol, zirconium (IV) n-propoxide, and either acetic acid, or 2,4-pentanedione (acac) and water additions. By controlling the ligand type and ligand-to-metal ratio, we were able to prepare films which displayed significant differences in densification behavior. We attribute the dissimilarity in densification to variations in the nature of the as-deposited films, as influenced by ligand type and concentration. While the acac- derived film was a physical gel, (i.e., a physical aggregation of the oligomeric species), the acetic acid-derived film, which exhibited less consolidation, was a chemical gel that could not be redissolved in the parent solvent. Films prepared with large acac/metal ratios and small water additions exhibited minimal crosslinking at 25{degree}C, displayed the greatest consolidation ({approximately}86% shrinkage) and the highest refractive index (n = 2.071) when heat treated. These results indicate the importance that M-O-M bonds (crosslinks) formed at low temperature can have on densification behavior. We also report on the effects of heat-treatment schedules and ramp rates on densification behavior. All of the films of the present study crystallized into the cubic phase, at temperatures ranging from {approximately}400{degree}C to greater than 700{degree}C, depending on the heating rate.

  2. Metal-assisted in situ formation of a tridentate acetylacetone ligand for complexation of fac-Re(CO)3+ for radiopharmaceutical applications.


    Benny, Paul D; Fugate, Glenn A; Barden, Adam O; Morley, Jennifer E; Silva-Lopez, Elsa; Twamley, Brendan


    Reaction of [NEt4]2[ReBr3(CO)3] with 2,4-pentanedione (acac) yields a complex of the type fac-Re(acac)(OH2)(CO)3 (1) under aqueous conditions. 1 was further reacted with a monodentate ligand (pyridine) to yield a fac-Re(acac)(pyridine)(CO)3 complex (2). Complex 1 was found to react with primary amines to generate a Schiff base (imine) in aqueous solutions. When a mixed-nitrogen donor bidentate ligand, 2-(2-aminoethyl)pyridine, that has different coordination affinities for fac-Re(acac)(OH2)(CO)3 was utilized, a unique tridentate ligand was formed in situ utilizing a metal-assisted Schiff base formation to yield a complex fac-Re(CO)3(3[(2-phenylethyl)imino]-2-pentanone) (3). Tridentate ligand formation was found to occur only with the Re-coordinated acac ligand. Reactions of acac with fac-Re(CO)3Br(2-(2-aminoethyl)pyridine) (4) or a mixture of [NEt4]2[ReBr3(CO)3], acac, and 2-(2-aminoethyl)pyridine did not yield the formation of complex 3 in water. PMID:18298058

  3. An iron(II) diketonate-diamine complex as precursor for thin film fabrication by atomic layer deposition

    NASA Astrophysics Data System (ADS)

    Bratvold, Jon E.; Carraro, Giorgio; Barreca, Davide; Nilsen, Ola


    A new divalent Fe precursor has been explored for deposition of iron-containing thin films by atomic layer deposition and molecular layer deposition (ALD/MLD). The Fe(II) β-diketonate-diamine complex, Fe(hfa)2TMEDA, (hfa = 1,1,1,5,5,5-hexafluoro-2,4-pentanedionate, TMEDA = N,N,N‧,N‧-tetramethylethylenediamine) can be handled in air, and sublimation at 60 °C ensures a satisfactory vaporization rate. The reactivity of the precursor does not allow for direct reaction with water as co-reactant. Nevertheless, it reacts with carboxylic acids, resulting in organic-inorganic hybrid materials, and with ozone, yielding α-Fe2O3. The divalent oxidation state of iron was maintained during deposition when oxalic acid was used as co-reactant, demonstrating the first preservation of Fe(II) from precursor to film during an MLD process. A self-saturating growth mode was proven by in situ quartz crystal microbalance (QCM) measurements, and the films were further characterized by grazing incidence X-ray diffraction (GIXRD), Fourier transform infrared spectroscopy (FTIR), and X-ray photoelectron spectroscopy (XPS).

  4. X-ray Emission Spectroscopy to Study Ligand Valence Orbitals in Mn Coordination Complexes

    SciTech Connect

    Smolentsev, Grigory; Soldatov, Alexander V; Messinger, Johannes; Merz, Kathrin; Weyhermuller, Thomas; Bergmann, Uwe; Pushkar, Yulia; Yano, Junko; Yachandra, Vittal K.; Glatzel, Pieter


    We discuss a spectroscopic method to determine the character of chemical bonding and for the identification of metal ligands in coordination and bioinorganic chemistry. It is based on the analysis of satellite lines in X-ray emission spectra that arise from transitions between valence orbitals and the metal ion 1s level (valence-to-core XES). The spectra, in connection with calculations based on density functional theory (DFT), provide information that is complementary to other spectroscopic techniques, in particular X-ray absorption (XANES and EXAFS). The spectral shape is sensitive to protonation of ligands and allows ligands, which differ only slightly in atomic number (e.g., C, N, O...), to be distinguished. A theoretical discussion of the main spectral features is presented in terms of molecular orbitals for a series of Mn model systems: [Mn(H2O)6]2+, [Mn(H2O)5OH]+, [Mn(H2O)5NH2]+, and [Mn(H2O)5NH3]2+. An application of the method, with comparison between theory and experiment, is presented for the solvated Mn2+ ion in water and three Mn coordination complexes, namely [LMn(acac)N3]BPh4, [LMn(B2O3Ph2)(ClO4)], and [LMn(acac)N]BPh4, where L represents 1,4,7-trimethyl-1,4,7-triazacyclononane, acac stands for the 2,4-pentanedionate anion, and B2O3Ph2 represents the 1,3-diphenyl-1,3-dibora-2-oxapropane-1,3-diolato dianion.

  5. An active-site lysine in avian liver phosphoenolpyruvate carboxykinase

    SciTech Connect

    Guidinger, P.F.; Nowak, T. )


    The participation of lysine in the catalysis by avian liver phosphoenolpyruvate carboxykinase was studied by chemical modification and by a characterization of the modified enzyme. The rate of inactivation by 2,4-pentanedione is pseudo-first-order and linearly dependent on reagent concentration with a second-order rate constant of 0.36 {plus minus} 0.025 M{sup {minus}1} min{sup {minus}1}. Inactivation by pyridoxal 5{prime}-phosphate of the reversible reaction catalyzed by phosphoenolpyruvate carboxykinase follows bimolecular kinetics with a second-order rate constant of 7,700 {plus minus} 860 m{sup {minus}1} min{sup {minus}1}. Treatment of the enzyme or one lysine residue modified concomitant with 100% loss in activity. A stoichiometry of 1:1 is observed when either the reversible or the irreversible reactions catalyzed by the enzyme are monitored. A study of k{sub obs} vs pH suggests this active-site lysine has a pK{sub a} of 8.1 and a pH-independent rate constant of inactivation of 47,700 m{sup {minus}1} min{sup {minus}1}. Proton relaxation rate measurements suggest that pyridoxal 5{prime}-phosphate modification alters binding of the phosphate-containing substrates. {sup 31}P NMR relaxation rate measurements show altered binding of the substrates in the ternary enzyme {center dot}Mn{sup 2+}{center dot}substrate complex. Circular dichroism studies show little change in secondary structure of pyridoxal 5{prime}-phosphate modified phosphoenolpyruvate carboxykinase. These results indicate that avian liver phosphoenolpyruvate carboxykinase has one reactive lysine at the active site and it is involved in the binding and activation of the phosphate-containing substrates.

  6. A new route for the synthesis of titanium silicalite-1

    SciTech Connect

    Vasile, Aurelia; Busuioc-Tomoiaga, Alina Maria


    Graphical abstract: Well-prepared TS-1 was synthesized by an innovative procedure using inexpensive reagents such as fumed silica and TPABr as structure-directing agent. This is the first time when highly crystalline TS-1 is obtained in basic medium, using sodium hydroxide as HO{sup -} ion source required for the crystallization process. Hydrolysis of titanium source has been prevented by titanium complexation with acetylacetone before structuring gel. Highlights: Black-Right-Pointing-Pointer TS-1 was obtained using cheap reagents as fumed silica and tetrapropylammonium bromide. Black-Right-Pointing-Pointer First time NaOH was used as source of OH{sup -} ions required for crystallization process. Black-Right-Pointing-Pointer The hydrolysis Ti alkoxides was controlled by Ti complexation with 2,4-pentanedione. -- Abstract: A new and efficient route using inexpensive reagents such as fumed silica and tetrapropylammonium bromide is proposed for the synthesis of titanium silicalite-1. High crystalline titanium silicalite-1 was obtained in alkaline medium, using sodium hydroxide as HO{sup -} ion source required for the crystallization process. Hydrolysis of titanium source with formation of insoluble oxide species was prevented by titanium complexation with before structuring gel. The final solids were fully characterized by powder X-ray diffraction, scanning electron microscopy, Fourier transform infrared, ultraviolet-visible diffuse reflectance, Raman and atomic absorption spectroscopies, as well as nitrogen sorption analysis. It was found that a molar ratio Ti:Si of about 0.04 in the initial reaction mixture is the upper limit to which well formed titanium silicalite-1 with channels free of crystalline or amorphous material can be obtained. Above this value, solids with MFI type structure containing both Ti isomorphously substituted in the network and extralattice anatase nanoparticles inside of channels is formed.

  7. Structure and NIR-luminescence of ytterbium(III) beta-diketonate complexes with 5-nitro-1,10-phenanthroline ancillary ligand: assessment of chain length and fluorination impact.


    Martín-Ramos, Pablo; Pereira da Silva, Pedro S; Lavín, Victor; Martín, Inocencio R; Lahoz, Fernando; Chamorro-Posada, Pedro; Silva, Manuela Ramos; Martín-Gil, Jesús


    Seven new tris(β-diketonear-nate)ytterbium(III) complexes with the general formula [Yb(β-diketonate)3(5NO2phen)] (where the β-diketone is either 4,4,4-trifluoro-1-(2-naphthyl)-1,3-butanedione, 4,4,4-trifluoro-1-(2-furyl)-1,3-butanedione, 1,1,1-trifluoro-2,4-pentanedione, 1,1,1-trifluoro-5,5-dimethyl-2,4-hexanedione, 1,1,1,5,5,6,6,7,7,7-decafluoro-2,4-heptanedione, 2,4-hexanedione or 2,6-dimethyl-3,5-heptanedione, and 5NO2phen = 5-nitro-1,10-phenanthroline) were synthesized and characterized by elemental analysis, attenuated total reflectance Fourier transform infrared spectroscopy and photoluminescence spectroscopy. Single crystal X-ray structures have been determined for three fluorinated complexes and ground state geometries of the other four complexes have been predicted using the Sparkle/PM6 model. These experimental structures and those designed by semi-empirical models reveal octacoordination around the Yb(3+) ion. Photoluminescence studies and lifetime measurements show that the increase in the fluorinated β-diketonate chain length is associated with a decrease in Yb(3+) luminescence intensity of the (2)F5/2→(2)F7/2 transition at around 980 nm and the (2)F5/2 excited state lifetime, while the ligand lifetime value remains almost unaffected. Finally, fluorination of the ligands is only advised when the complexes are to be used for co-doping with isostructural Er(3+) complexes for optical amplifiers, since it leads to a slight decrease in luminescence intensity for the same β-diketonate chain length.

  8. Harvard--MIT research program in short-lived radiopharmaceuticals

    SciTech Connect

    Not Available


    This report describes progress on five projects. The first project showed a 1000 fold concentration of the cationic complex {sup 99m}Tc (MIBI) in heart cell mitochondria vs heart cell cytoplasm, as determined by high resolution electron probe microanalysis. Additional technetium-99m based complexes are being developed and tested. The second project involves evaluating technetium acetylacteonates as potential indicators of cerebral blood flow. An intermediate in the synthesis of a technetium porphyrin complex has been synthesized; an oxotechnetium(V)-2,4-pentanedione complex has been prepared and is currently being characterized. The third project involves using radio labelled antibodies for diagnosis and treatment of cancer. An early discovery was that chloramine-T based iodination protocols resulted in a reversal of the charge on mouse lgGs. Immunoperoxidase-labelled monoclonal antibody MOv 18 was shown to bind specifically to the most frequent ovarian aderon carcinomas, and not to healthy tissue, making this antibody a good candidate for immunotherapy or immunodetection. Work on a specific immunotherapy protocol suffered a setback when one reagent, a {sup 125}I-biotin complex, proved to be unstable in vivo. The fourth project involves labelling antibodies with positron emitting radionuclides. Radiofluorination was accomplished through reductive alkylation of {sup 18}F-aldehyde, or pentafluorophenyl esters. Radioiodination was accomplished using alkyl-tin derivation exchange. The fifth project examined antibody modification for use in radioimmune imaging. Technetium-99m-labelled lgG was shown to be biologically equivalent to Indium-III-labelled lgG for imaging focal sites of inflamation. Also, Indium III labelling of small bioactive peptides was examined as a means of imaging important physiological processes. 44 refs., 2 figs.

  9. Synthesis of Ir(III) complexes with Tp(Me2) and acac ligands and their reactivity with electrophiles.


    Morales-Cerón, Judith P; Salazar-Pereda, Verónica; Mendoza-Espinosa, Daniel; Alvarado-Rodríguez, José G; Cruz-Borbolla, Julián; Andrade-López, Noemí; Vásquez-Pérez, José M


    The reaction of the bis(ethylene) complex [Tp(Me2)Ir(C2H4)2] () (Tp(Me2) = hydrotris(3,5-dimethylpyrazolyl)borate) with an excess of 2,4-pentanedione (acetylacetone, Hacac) at 70 °C produced a mixture of the Ir(iii) complex [Tp(Me2)Ir(acac)(C2H5)] () as a major product (67% yield) and two other side complexes [Tp(Me2)Ir(acac)(H)] () and [Tp(Me2)Ir(C9H14O2)] () in 20 and 13% yields, respectively. According to the proposed reaction mechanism and DFT calculations, complexes and are generated from an 18e(-) intermediate [Tp(Me2)Ir(C2H4)(acac)(C2H3)] () which undergoes either hydrogen insertion or β-hydride elimination followed by the subsequent loss of a molecule of ethylene. The lowest yielding complex which features a 2-iridafuran is presumably generated from an unusual thermal coupling between one vinylic and one acac moiety. The availability of the acidic α-proton of the acac ligand was tested by the treatment of complex with Br2 and Cu(NO3)2 rendering the substitution complexes [Tp(3-Br,Me2)Ir(3-Br-acac)Br] () and [Tp(Me2)Ir(3-NO2-acac)(C2H5)] () in good yields. The series of heteroleptic iridium(iii) compounds display air and moisture stability and have been characterized by NMR, IR, and elemental analyses, and, in the case of , and , by single-crystal X-ray diffraction analyses.

  10. Application of an Ir tracer to determine soot exposure to students commuting to school on Baltimore public buses

    NASA Astrophysics Data System (ADS)

    Wu, Charles C.; Suarez, Ana E.; Lin, Zhibo; Kidwell, Christopher B.; Borgoul, Polina V.; Caffrey, Peter F.; Ondov, John M.; Sattler, Barbara

    An important component of urban aerosol, diesel soot is a known respiratory irritant and contains mutagenic and carcinogenic organic compounds. To estimate student exposures to soot emitted from public diesel buses during commutes to city high schools, a portion of the Baltimore municipal fuel supply was tagged with an iridium tracer and exposure was monitored during commutes with personal aerosol monitors as a part of an Environmental Justice Project. A total of 68.2 g of Ir as iridium(III)-2,4-pentanedionate were used to induce a concentration of 48.5 μg Ir ℓ -1 of fuel. Twenty samples were collected over 10 days while four students commuted on regularly scheduled buses and a fifth student commuted by private car. Individual samples integrated from 1 to 4 round trips. Iridium analyses were performed instrumentally after neutron activation with a detection limit (DL) of about 500 fg. For students commuting by bus and following protocols, Ir tracer concentrations ranged from 53±38 to >1980±49 fg m -3. Concentrations up to 3530±220 fg m -3 were observed for student #5, who sampled only when boarding and disembarking. Exposure were greatest for students commuting through the heavily trafficked central business district. Corresponding estimates of exposures to soot emitted from municipal buses ranged from ⩽3 to 82 ng soot m -3 (⩽145 ng m -3 for student #5), i.e. well below the exposure level of 2-10 μg m -3 total C from all sources, including the more than 30,000 diesel trucks which pass through the city's major toll facilities each day. Ir was undetectable in samples collected by the student commuting by car when its windows were closed, but comparable to those of the other students when commutes were made with windows open. The Ir tracer DL corresponds to about 21 ng soot, about half of which is carbon. This is far below the 230 ng reported for analysis by a highly sensitive thermal-optical technique.

  11. Surface modified carbon nanoparticle papers and applications on polymer composites

    NASA Astrophysics Data System (ADS)

    Ouyang, Xilian

    a tensile strength of 360 MPa and an electrical conductivity of 4.45x104 S/m, much better than any similar materials reported in the literature. However, they didn't show good gas barrier properties. Since the GO paper presented zero gas permeability for both CO2 and H2, a hybrid paper fabrication approach was proposed to combine the advantages of individual GP and GO papers. This was done by filtering GP and GO layer by layer with GO sandwiched in between two layers of GP. The resulting hybrid papers showed high mechanical tensile strength and EMI shielding effectiveness that are close to GP nanopapers, and excellent gas barrier properties that comparable to GO nanopapers. The GP, GO and GP-Go-GP hybrid nanopapers have been successfully coated onto the thermoplastic surface by thermal lamination and injection molding. In the third part, the effect of PANI-CNF nanopapers and a chelating agent, 2, 4- Pentanedione (2, 4-P) on kinetics of an in-mold coating (IMC) resin was investigated. The results showed that the presence of amine functionalized carbon nanoparticles tended to retard the resin reaction, while 2, 4-P was capable of promoting the redox based free radical polymerization by forming a complex with the cobalt promoter in the initiation step. In order to understand the chemical and physical changes during the resin curing process, kinetics study on two major resin components, i.e. hexanediol diacrylate (HDDA) and styrene (St), were carried out using an integrated analysis design: differential scanning calorimetry (DSC) for overall reaction, Fourier transform infrared spectroscopy (FTIR) for individual component reactions, and rheometry for liquid-solid transition during the reaction. The gel point of this radical polymerization resin system was found to be <2% which implied that most curing was conducted in the solid phase. The results showed that the double bonds in acrylates and St followed an azeotropic polymerization pattern.

  12. The reactions of N-methylformamide and N,N-dimethylformamide with OH and their photo-oxidation under atmospheric conditions: experimental and theoretical studies.


    Bunkan, Arne Joakim C; Hetzler, Jens; Mikoviny, Tomáš; Wisthaler, Armin; Nielsen, Claus J; Olzmann, Matthias


    The reactions of OH radicals with CH3NHCHO (N-methylformamide, MF) and (CH3)2NCHO (N,N-dimethylformamide, DMF) have been studied by experimental and computational methods. Rate coefficients were determined as a function of temperature (T = 260-295 K) and pressure (P = 30-600 mbar) by the flash photolysis/laser-induced fluorescence technique. OH radicals were produced by laser flash photolysis of 2,4-pentanedione or tert-butyl hydroperoxide under pseudo-first order conditions in an excess of the corresponding amide. The rate coefficients obtained show negative temperature dependences that can be parameterized as follows: kOH+MF = (1.3 ± 0.4) × 10(-12) exp(3.7 kJ mol(-1)/(RT)) cm(3) s(-1) and kOH+DMF = (5.5 ± 1.7) × 10(-13) exp(6.6 kJ mol(-1)/(RT)) cm(3) s(-1). The rate coefficient kOH+MF shows very weak positive pressure dependence whereas kOH+DMF was found to be independent of pressure. The Arrhenius equations given, within their uncertainty, are valid for the entire pressure range of our experiments. Furthermore, MF and DMF smog-chamber photo-oxidation experiments were monitored by proton-transfer-reaction time-of-flight mass spectrometry. Atmospheric MF photo-oxidation results in 65% CH3NCO (methylisocyanate), 16% (CHO)2NH, and NOx-dependent amounts of CH2[double bond, length as m-dash]NH and CH3NHNO2 as primary products, while DMF photo-oxidation results in around 35% CH3N(CHO)2 as primary product and 65% meta-stable (CH3)2NC(O)OONO2 degrading to NOx-dependent amounts of CH3N[double bond, length as m-dash]CH2 (N-methylmethanimine), (CH3)2NNO (N-nitroso dimethylamine) and (CH3)2NNO2 (N-nitro dimethylamine). The potential for nitramine formation in MF photo-oxidation is comparable to that of methylamine whereas the potential to form nitrosamine and nitramine in DMF photo-oxidation is larger than for dimethylamine. Quantum chemistry supported atmospheric degradation mechanisms for MF and DMF are presented. Rate coefficients and initial branching ratios