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Sample records for demetallization

  1. Microdroplet fusion mass spectrometry: accelerated kinetics of acid-induced chlorophyll demetallation.

    Science.gov (United States)

    Lee, Jae Kyoo; Nam, Hong Gil; Zare, Richard N

    2017-01-01

    Kinetics of acid-induced chlorophyll demetallation was recorded in microdroplets by fusing a stream of microdroplets containing 40 µM chlorophyll a or b dissolved in methanol with a stream of aqueous microdroplets containing 35 mM hydrochloric acid (pH = 1·46). The kinetics of the demetallation of chlorophyll in the fused microdroplets (14 ± 6 µm diameter; 84 ± 18 m s-1 velocity) was recorded by controlling the traveling distance of the fused microdroplets between the fusion region and the inlet of a mass spectrometer. The rate of acid-induced chlorophyll demetallation was about 960 ± 120 times faster in the charged microdroplets compared with that reported in bulk solution. If no voltage was applied to the sprayed microdroplets, then the acceleration factor was about 580 ± 90, suggesting that the applied voltage is not a major factor determining the acceleration. Chlorophyll a was more rapidly demetallated than chlorophyll b by a factor of ~26 in bulk solution and ~5 in charged microdroplets. The demetallation kinetics was second order in the H+ concentration, but the acceleration factor of microdroplets compared with bulk solution appeared to be unchanged in going from pH = 1·3 to 7·0. The water:methanol ratio of the fused microdroplets was varied from 7:3 to 3:7 causing an increase in the reaction rate of chlorophyll a demetallation by 20%. This observation demonstrates that the solvent composition, which has different evaporation rates, does not significantly affect the acceleration. We believe that a major portion of the acceleration can be attributed to confinement effects involving surface reactions rather than either to evaporation of solvents or to the introduction of charges to the microdroplets.

  2. Crystal structure of Bfr A from Mycobacterium tuberculosis: incorporation of selenomethionine results in cleavage and demetallation of haem.

    Directory of Open Access Journals (Sweden)

    Vibha Gupta

    Full Text Available Emergence of tuberculosis as a global health threat has necessitated an urgent search for new antitubercular drugs entailing determination of 3-dimensional structures of a large number of mycobacterial proteins for structure-based drug design. The essential requirement of ferritins/bacterioferritins (proteins involved in iron storage and homeostasis for the survival of several prokaryotic pathogens makes these proteins very attractive targets for structure determination and inhibitor design. Bacterioferritins (Bfrs differ from ferritins in that they have additional noncovalently bound haem groups. The physiological role of haem in Bfrs is not very clear but studies indicate that the haem group is involved in mediating release of iron from Bfr by facilitating reduction of the iron core. To further enhance our understanding, we have determined the crystal structure of the selenomethionyl analog of bacterioferritin A (SeMet-BfrA from Mycobacterium tuberculosis (Mtb. Unexpectedly, electron density observed in the crystals of SeMet-BfrA analogous to haem location in bacterioferritins, shows a demetallated and degraded product of haem. This unanticipated observation is a consequence of the altered spatial electronic environment around the axial ligands of haem (in lieu of Met52 modification to SeMet52. Furthermore, the structure of Mtb SeMet-BfrA displays a possible lost protein interaction with haem propionates due to formation of a salt bridge between Arg53-Glu57, which appears to be unique to Mtb BfrA, resulting in slight modulation of haem binding pocket in this organism. The crystal structure of Mtb SeMet-BfrA provides novel leads to physiological function of haem in Bfrs. If validated as a drug target, it may also serve as a scaffold for designing specific inhibitors. In addition, this study provides evidence against the general belief that a selenium derivative of a protein represents its true physiological native structure.

  3. Demetalation of Fe, Mn, and Cu chelates and complexes: application to the NMR analysis of micronutrient fertilizers.

    Science.gov (United States)

    López-Rayo, Sandra; Lucena, Juan J; Laghi, Luca; Cremonini, Mauro A

    2011-12-28

    The application of nuclear magnetic resonance (NMR) for the quality control of fertilizers based on Fe(3+), Mn(2+), and Cu(2+) chelates and complexes is precluded by the strong paramagnetism of metals. Recently, a method based on the use of ferrocyanide has been described to remove iron from commercial iron chelates based on the o,o-EDDHA [ethylenediamine-N,N'bis(2-hydroxyphenylacetic)acid] chelating agent for their analysis and quantification by NMR. The present work extended that procedure to other paramagnetic ions, manganese and copper, and other chelating, EDTA (ethylenediaminetetraacetic acid), IDHA [N-(1,2-dicarboxyethyl)-d,l-aspartic acid], and complexing agents, gluconate and heptagluconate. Results showed that the removal of the paramagnetic ions was complete, allowing us to obtain (1)H NMR spectra characterized by narrow peaks. The quantification of the ligands by NMR and high-performance liquid chromatography showed that their complete recovery was granted. The NMR analysis enabled detection and quantification of unknown impurities without the need of pure compounds as internal standards.

  4. Process for the desulfurization and demetallization of high boiling crude oil hydrocarbons. Verfahren zum Entschwefeln und Feinentmetallisieren hochsiedender Erdoel-Kohlenwasserstoff-Rohstoffe

    Energy Technology Data Exchange (ETDEWEB)

    Schuetter, H.; Doehler, E.; Franke, H.; Bierwagen, H.; Limmer, H.; Hergeth, H.; Becker, K.; John, H.; Berrouschot, H.D.

    1981-04-30

    Co/Mo catalysts on an aluminium oxide carrier are used for the hydrating catalytic desulphurisation and demetallisation of crude oil. The catalytic bed has two components, where the pore radia on one are 2.25 - 3.75 nm and of the other 4.25 - 6.25 nm. Less than 5% of the two catalysts have larger pore radii. The two different catalysts can be in separate layers or in a mixed bed in the reactor. In order to protect the two component catalytic bed, a layer of catalyst bodies of larger dimensions can be mounted in front of it.

  5. Reactions of copper macrocycles with antioxidants and HOCl: potential for biological redox sensing.

    Science.gov (United States)

    Sowden, Rebecca J; Trotter, Katherine D; Dunbar, Lynsey; Craig, Gemma; Erdemli, Omer; Spickett, Corinne M; Reglinski, John

    2013-02-01

    A series of simple copper N(2)S(2) macrocycles were examined for their potential as biological redox sensors, following previous characterization of their redox potentials and crystal structures. The divalent species were reduced by glutathione or ascorbate at a biologically relevant pH in aqueous buffer. A less efficient reduction was also achieved by vitamin E in DMSO. Oxidation of the corresponding univalent copper species by sodium hypochlorite resulted in only partial (~65 %) recovery of the divalent form. This was concluded to be due to competition between metal oxidation and ligand oxidation, which is believed to contribute to macrocycle demetallation. Electrospray mass spectrometry confirmed that ligand oxidation had occurred. Moreover, the macrocyclic complexes could be demetallated by incubation with EDTA and bovine serum albumin, demonstrating that they would be inappropriate for use in biological systems. The susceptibility to oxidation and demetallation was hypothesized to be due to oxidation of the secondary amines. Consequently these were modified to incorporate additional oxygen donor atoms. This modification led to greater resistance to demetallation and ligand oxidation, providing a better platform for further development of copper macrocycles as redox sensors for use in biological systems.

  6. Resolution of limonene 1,2-epoxide diastereomers by mercury(II) ions

    NARCIS (Netherlands)

    Werf, M. van der; Jongejan, H.; Franssen, M.C.R.

    2001-01-01

    When HgCl2 was added to a diastereomeric mixture of cis- and trans-(4S)-limonene 1,2-epoxide, the Hg(II) ions stereoselectively complexed to the cis epoxide, enabling ring opening by water. The resulting mercuric salt could be demetalated by treatment with NaBH4, giving a mixture of diastereomeric

  7. Process for hydroprocessing heavy oils utilizing sepiolite-based catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Auden, C.A.; Yan, T.-Y.

    1986-04-15

    A process is described for demetallizing and desulfurizing a hydrocarbon oil comprising contacting the hydrocarbon oil in the presence of hydrogen and a sepiolite-based catalyst composition under conditions of pressure and temperature sufficient to effect demetallization and desulfurization. The sepiolite-based catalyst composition has been prepared by first contacting the sepiolite with an aqueous solution of a first metal salt, then contacting the resultant metal ion-exchanged sepiolite with an aqueous solution of a compound of a second metal selected from the group consisting of molybdenum, tungsten and vanadium, and finally contacting the resultant metal-exchanged sepiolite product with an aqueous solution of a magnesium compound, thereby effecting a magnesium ion-exchange with the metal-exchanged sepiolite product and neutralizing acid sites on the sepiolite product.

  8. Experimental and Computational Study of an Unexpected Iron-Catalyzed Carboetherification by Cooperative Metal and Ligand Substrate Interaction and Proton Shuttling

    KAUST Repository

    El-Sepelgy, Osama; Brzozowska, Aleksandra; Azofra, Luis Miguel; Jang, Yoon Kyung; Cavallo, Luigi; Rueping, Magnus

    2017-01-01

    An iron-catalyzed cycloisomerization of allenols to deoxygenated pyranose glycals has been developed. Combined experimental and computational studies show that the iron complex exhibits a dual catalytic role in that the non-innocent cyclopentadienone ligand acts as proton shuttle by initial hydrogen abstraction from the alcohol and by facilitating protonation and deprotonation events in the isomerization and demetalation steps. Molecular orbital analysis provides insight into the unexpected and selective formation of the 3,4-dihydro-2H-pyran.

  9. Experimental and Computational Study of an Unexpected Iron-Catalyzed Carboetherification by Cooperative Metal and Ligand Substrate Interaction and Proton Shuttling

    KAUST Repository

    El-Sepelgy, Osama

    2017-09-26

    An iron-catalyzed cycloisomerization of allenols to deoxygenated pyranose glycals has been developed. Combined experimental and computational studies show that the iron complex exhibits a dual catalytic role in that the non-innocent cyclopentadienone ligand acts as proton shuttle by initial hydrogen abstraction from the alcohol and by facilitating protonation and deprotonation events in the isomerization and demetalation steps. Molecular orbital analysis provides insight into the unexpected and selective formation of the 3,4-dihydro-2H-pyran.

  10. Solvent extraction

    Energy Technology Data Exchange (ETDEWEB)

    Coombs, D.M.; Latimer, E.G.

    1988-01-05

    It is an object of this invention to provide for the demetallization and general upgrading of heavy oil via a solvent extracton process, and to improve the efficiency of solvent extraction operations. The yield and demetallization of product oil form heavy high-metal content oil is maximized by solvent extractions which employ either or all of the following techniques: premixing of a minor amount of the solvent with feed and using countercurrent flow for the remaining solvent; use of certain solvent/free ratios; use of segmental baffle tray extraction column internals and the proper extraction column residence time. The solvent premix/countercurrent flow feature of the invention substantially improves extractions where temperatures and pressures above the critical point of the solvent are used. By using this technique, a greater yield of extract oil can be obtained at the same metals content or a lower metals-containing extract oil product can be obtained at the same yield. Furthermore, the premixing of part of the solvent with the feed before countercurrent extraction gives high extract oil yields and high quality demetallization. The solvent/feed ratio features of the invention substanially lower the captial and operating costs for such processes while not suffering a loss in selectivity for metals rejection. The column internals and rsidence time features of the invention further improve the extractor metals rejection at a constant yield or allow for an increase in extract oil yield at a constant extract oil metals content. 13 figs., 3 tabs.

  11. Prediction of the FCC feedstocks crackability

    International Nuclear Information System (INIS)

    Martinez Cruz, Francy L; Navas Guzman, Gustavo; Osorio Suarez, Juan Pablo

    2009-01-01

    This paper presents a statistical model for prediction of feed stock's crackability (potential to generate valuable products on catalytic cracking process), based on experimental reactivity data by micro activity test (MAT - Microscale Fixed Bed Reactor) and detailed physicochemical characterization. A minimum amount of experimental tests corresponding to feed properties (typically available at refinery) is used to build a more complete description of feedstocks including chemical composition and hydrocarbon distribution. Both measured and calculated physicochemical properties are used to predict the yields of main products at several MAT reaction severities. Different well known functions correlating yields and conversion (previously tested with experimental data MAT) allows the evaluation of maximum point of gasoline yield. This point is used like a crackability index and qualitative point comparison of feed stock's potential. Extensive feedstocks data base from Instituto Colombiano del Petroleo (ICP) with a wide range of composition were used to build the model, including the following feeds: 1. Light feedstocks - Ga soils of refinery and laboratory cuts from different types of Colombian crude oils and 2. Heavy feedstocks - Residues or feedstocks combined (blending of ga soil [GO], atmospheric tower bottom [ATB], demetallized oil [DMO] and demetallized oil hydrotreated [DMOH] in several proportions) from the four fluid catalytic cracking units (FCCU) at Ecopetrol S.A. refinery in Barrancabermeja - Colombia. The results of model show the prediction of valuable products such as gasoline for different refinery feedstocks within acceptable accuracy, thus obtaining a reliable ranking of crackability.

  12. Thermal Adsorption Processing Of Hydrocarbon Residues

    Directory of Open Access Journals (Sweden)

    Sudad H. Al.

    2017-04-01

    Full Text Available The raw materials of secondary catalytic processes must be pre-refined. Among these refining processes are the deasphalting and demetallization including their thermo adsorption or thermo-contact adsorption variety. In oil processing four main processes of thermo-adsorption refining of hydrocarbon residues are used ART Asphalt Residual Treating - residues deasphaltizing 3D Discriminatory Destructive Distillation developed in the US ACT Adsorption-Contact Treatment and ETCC Express Thermo-Contact Cracking developed in Russia. ART and ACT are processes with absorbers of lift type reactor while 3D and ETCC processes are with an adsorbing reactor having ultra-short contact time of the raw material with the adsorbent. In all these processes refining of hydrocarbon residues is achieved by partial Thermo-destructive transformations of hydrocarbons and hetero-atomic compounds with simultaneous adsorption of the formed on the surface of the adsorbents resins asphaltene and carboids as well as metal- sulphur - and nitro-organic compounds. Demetallized and deasphalted light and heavy gas oils or their mixtures are a quality raw material for secondary deepening refining processes catalytic and hydrogenation cracking etc. since they are characterized by low coking ability and low content of organometallic compounds that lead to irreversible deactivation of the catalysts of these deepening processes.

  13. Differential effect of plant lectins on mast cells of different origins

    Directory of Open Access Journals (Sweden)

    F.C. Lopes

    2005-06-01

    Full Text Available Histamine release induced by plant lectins was studied with emphasis on the carbohydrate specificity, external calcium requirement, metal binding sites, and mast cell heterogeneity and on the importance of antibodies bound to the mast cell membrane to the lectin effect. Peritoneal mast cells were obtained by direct lavage of the rat peritoneal cavity and guinea pig intestine and hamster cheek pouch mast cells were obtained by dispersion with collagenase type IA. Histamine release was induced with concanavalin A (Con A, lectins from Canavalia brasiliensis, mannose-specific Cymbosema roseum, Maackia amurensis, Parkia platycephala, Triticum vulgaris (WGA, and demetallized Con A and C. brasiliensis, using 1-300 µg/ml lectin concentrations applied to Wistar rat peritoneal mast cells, peaking on 26.9, 21.0, 29.1, 24.9, 17.2, 10.7, 19.9, and 41.5%, respectively. This effect was inhibited in the absence of extracellular calcium. The lectins were also active on hamster cheek pouch mast cells (except demetallized Con A and on Rowett nude rat (animal free of immunoglobulins peritoneal mast cells (except for mannose-specific C. roseum, P. platycephala and WGA. No effect was observed in guinea pig intestine mast cells. Glucose-saturated Con A and C. brasiliensis also released histamine from Wistar rat peritoneal mast cells. These results suggest that histamine release induced by lectins is influenced by the heterogeneity of mast cells and depends on extracellular calcium. The results also suggest that this histamine release might occur by alternative mechanisms, because the usual mechanism of lectins is related to their binding properties to metals from which depend the binding to sugars, which would be their sites to bind to immunoglobulins. In the present study, we show that the histamine release by lectins was also induced by demetallized lectins and by sugar-saturated lectins (which would avoid their binding to other sugars. Additionally, the lectins

  14. Voltammetric, in-situ spectroelectrochemical and in-situ electrocolorimetric characterization of phthalocyanines

    Energy Technology Data Exchange (ETDEWEB)

    Koca, Atif [Department of Chemical Engineering, Faculty of Engineering, Marmara University, Goeztepe, 34722 Istanbul (Turkey)], E-mail: akoca@eng.marmara.edu.tr; Bayar, Serife; Dincer, Hatice A. [Department of Chemistry, Technical University of Istanbul, Maslak, 34469 Istanbul (Turkey); Gonca, Erguen [Department of Chemistry, Fatih University, TR34500 B.Cekmece, Istanbul (Turkey)

    2009-04-01

    In this work, electrochemical, and in-situ spectroelectrochemical characterization of the metallophthalocyanines bearing tetra-(1,1-(dicarbethoxy)-2-(2-methylbenzyl))-ethyl 3,10,17,24-tetra chloro groups were performed. Voltammetric and in-situ spectroelectrochemical measurements show that while cobalt phthalocyanine complex gives both metal-based and ring-based redox processes, zinc and copper phthalocyanines show only ring-based reduction and oxidation processes. The redox processes are generally diffusion-controlled, reversible and one-electron transfer processes. Differently lead phthalocyanine demetallized during second oxidation reaction while it was stable during reduction processes. An in-situ electrocolorimetric method, based on the 1931 CIE (Commission Internationale de l'Eclairage) system of colorimetry, has been applied to investigate the color of the electro-generated anionic and cationic forms of the complexes for the first time in this study.

  15. Current knowledge and potential applications of cavitation technologies for the petroleum industry.

    Science.gov (United States)

    Avvaru, Balasubrahmanyam; Venkateswaran, Natarajan; Uppara, Parasuveera; Iyengar, Suresh B; Katti, Sanjeev S

    2018-04-01

    Technologies based on cavitation, produced by either ultrasound or hydrodynamic means, are part of growing literature for individual refinery unit processes. In this review, we have explained the mechanism through which these cavitation technologies intensify individual unit processes such as enhanced oil recovery, demulsification of water in oil emulsions during desalting stage, crude oil viscosity reduction, oxidative desulphurisation/demetallization, and crude oil upgrading. Apart from these refinery processes, applications of this technology are also mentioned for other potential crude oil sources such as oil shale and oil sand extraction. The relative advantages and current situation of each application/process at commercial scale is explained. Copyright © 2017 Elsevier B.V. All rights reserved.

  16. Synthesis and reactions of imines of α,β-ethylenic silicon-containing aldehydes with complex metal hydrides

    International Nuclear Information System (INIS)

    Surnin, V.A.; Stadnichuk, M.D.

    1986-01-01

    Imines of 3-trimethylsilyl-2-propenal or its hydrocarbon analog are reduced chemoselectively at the C=N double bond by sodium borohydride. The direction of lithium aluminum hydride reduction of these imines is not influenced by the nature of the element attached to the C=C bond silicon versus carbon, but rather is determined by the nature of the radical group attached to the nitrogen atom; N-arylimines undergo addition with lithium aluminum hydride at the C=N bond exclusively, whereas for N-alkylimines the addition reactions occur either partially or in full in the 1,4-position, depending on the reaction conditions, to give imines of saturated aldehydes after demetallation

  17. Self-assembly of natural light-harvesting bacteriochlorophylls of green sulfur photosynthetic bacteria in silicate capsules as stable models of chlorosomes.

    Science.gov (United States)

    Saga, Yoshitaka; Akai, Sho; Miyatake, Tomohiro; Tamiaki, Hitoshi

    2006-01-01

    Naturally occurring bacteriochlorophyll(BChl)s-c, -d, and -e from green sulfur photosynthetic bacteria were self-assembled in an aqueous solution in the presence of octadecyltriethoxysilane and tetraethoxysilane, followed by polycondensation of the alkoxysilanes by incubation for 50 h at 25 degrees C. The resulting BChl self-assemblies in silicate capsules exhibited visible absorption and circular dichroism spectra similar to the corresponding natural light-harvesting systems (chlorosomes) of green sulfur bacteria. Dynamic light scattering measurements indicated that the silicate capsules had an average hydrodynamic diameter of several hundred nanometers. BChl self-aggregates in silicate capsules were significantly stable to a nonionic surfactant Triton X-100, which was apt to decompose the BChl aggregates to their monomeric form, compared with conventional micelle systems. BChls in silicate capsules were more tolerant to demetalation of the central magnesium under acidic conditions than the natural systems.

  18. Features of proteolytic properties of tetraphenylporphyrin complex with lanthanide group metals

    Science.gov (United States)

    Tobolkina, Elena A.; Skripnikova, Tatiana A.; Starikova, Anna A.; Shumilova, Galina I.; Pendin, Andrey A.

    2018-01-01

    Demetallation of metalloporphyrin molecules is one of the essential degradation reactions in photosynthesis. The effect of metalloporphyrin nature on removal of central metals from tetraphenylporphyrin complexes based on lanthanide group metals (Dy, Er, Lu, Ho) has been studied. pH values, at which the metal ions leave the metalloporphyrin complex were established using two-phase spectrophotometric titration with potentiometric pH-control. The pH values decrease with the increase of atomic numbers of lanthanide groups, as well as with increase of 4f-electrons. The reaction of an extra ligand exchange for the hydroxide ion was studied. For Dy-, Er- and Ho-tetraphenylporphyrin complexes one particle of extra ligand coordinates with one porphyrin complex. A complex with dimeric particles can be formed for the system of Lu-tetraphenylporphyrin. Constants of the ion exchange reactions were calculated.

  19. Capped Mesoporous Silica Nanoparticles for the Selective and Sensitive Detection of Cyanide.

    Science.gov (United States)

    Sayed, Sameh El; Licchelli, Maurizio; Martínez-Máñez, Ramón; Sancenón, Félix

    2017-10-18

    The development of easy and affordable methods for the detection of cyanide is of great significance due to the high toxicity of this anion and the potential risks associated with its pollution. Herein, optical detection of cyanide in water has been achieved by using a hybrid organic-inorganic nanomaterial. Mesoporous silica nanoparticles were loaded with [Ru(bipy) 3 ] 2+ , functionalized with macrocyclic nickel(II) complex subunits, and capped with a sterically hindering anion (hexametaphosphate). Cyanide selectively induces demetallation of nickel(II) complexes and the removal of capping anions from the silica surface, allowing the release of the dye and the consequent increase in fluorescence intensity. The response of the capped nanoparticles in aqueous solution is highly selective and sensitive towards cyanide with a limit of detection of 2 μm. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. Developments in hydroconversion processes for residues

    Energy Technology Data Exchange (ETDEWEB)

    Douwes, C T [Shell Res. B.V.; Wijffels, J B; Van Klinken, J; Van Zijll Langhout, W C

    1979-01-01

    A review of recent developments in hydrotreating processes for demetallization, desulfurization, and conversion to distillate products of residues covers catalyst developments for suppression of coke formation, maximum metals tolerance, and conversion selectivity; the effects of hydrogen pressure and temperature on catalyst deactivation and conversion; basic operating characteristics of conventional fixed-bed trickle-flow reactors, and of onstream catalyst replacement reactors, including the expanded-bed and the moving-bed reactor; a comparison of catalyst bed activity level, dirt tolerance, reactor effectiveness, temperature control, and thermal stability of the expanded-bed and moving-bed reactors; residue upgrading in slurry-bed reactors of dispersed vanadium sulfide catalyst in the oil; design and control features for safety and reliability; and a cost comparison between the indirect hydrotreating route, in which the asphalt fraction is separated prior to hydrotreating, and the as yet incompletely developed direct route.

  1. Studies on lectins. XXXII. Application of affinity electrophoresis to the study of the interaction of lectins and their derivatives with sugars.

    Science.gov (United States)

    Horejsí, V; Tichá, M; Kocourek, J

    1977-09-29

    Affinity electrophoresis was used to study the sugar binding heterogeneity of lectins or their derivatives. Commercial and demetallized preparations of concanavalin A could be resolved by affinity electrophoresis into three components with different affinity to immobilized sugar. Similarly the Vicia cracca lectin obtained by affinity chromatography behaved on affinity gels as a mixture of active and inactive molecular species. Affinity electrophoresis has shown that the nonhemagglutinating acetylated lentil lectin and photo-oxidized or sulfenylated pea lectin retain their sugar binding properties; dissociation constants of saccharide complexes of these derivatives are similar to those of native lectins. The presence of specific immobilized sugar in the affinity gel improved the resolution of isolectins from Dolichos biflorus and Ricinus communis seeds.

  2. Electrochemical removal of metals from crude oil samples

    Energy Technology Data Exchange (ETDEWEB)

    Welter, K.; Salazar, E.; Balladores, Y.; Marquez, O.P.; Marquez, J.; Martinez, Y. (Laboratorio de Electroquimica, Facultad de Ciencias, Universidad de Los Andes, Merida 5101-Venezuela)

    2009-02-15

    Removal of vanadium from vanadyl (IV) meso-tetra-phenylporphyrin (VO-MTPP) and vanadyl (IV) octa-ethylporphyrin (VO-OEP) and metals removal from Ayacucho Venezuelan crude oil samples were performed using electrochemical techniques. According to cyclic voltammograms, a potential of - 2.3 V vs. Ag/AgNO{sub 3} (0.1 M), LiClO{sub 4} (0.1 M) in acetonitrile, was chosen for running electrolysis at platinum (Pt), graphite (G) and glassy carbon (GC) electrodes. Qualitative analysis was done by cyclic voltammetry (CV) and atomic absorption spectroscopy (AAS) while quantification was performed by AAS and inductively coupled plasma/atomic emission spectrometry (ICP/AES). Three stages (best results) of the study are reported: (a) when using commercial porphyrins; the best conditions for electrolysis were: tetrahydrofuran (THF)/20% methanol (MeOH)/1% perchloric acid (HClO{sub 4}) on GC, producing 84% hydro-demetalation (HDM) for VO-MTPP, and 78% HDM for VO-OEP; (b) when using extracts of crude oil; demetalation percentages, after 90 min of electrolysis, on graphite, and after 120 min of electrolysis on platinum, were 66.44% and 64.10% HDM respectively, no discrimination of metals under these conditions (c) from electrolysis in whole crude oil, quantitative analysis gave: vanadium (V) 31.2 mg/kg, iron (Fe) 65, 0 mg/kg and nickel (Ni) 6, 3 mg/kg, with charge efficiencies of V (7.5%), Fe (79.6%) and Ni (8.2%). (author)

  3. The cobalt-mediated [2+2+2]cycloaddition of thiophenes and benzofurans to alkynes

    Energy Technology Data Exchange (ETDEWEB)

    Malaska, M.J.

    1991-01-01

    The cobalt-mediated [2+2+2]cycloaddition of thiophenes and benzofurans to alkynes was investigated. The cocyclization of 2-propynyloxymethylthiophenes provided two types of cyclohexadiene complexes. It was found that one of these complexes could be converted to the other by a thermal rearrangement. This novel transformation was investigated by deuterium-labelling and kinetic studies, and a mechanism was proposed. The complexes could be oxidatively demetallated to provide the liberated organic framework. Further reorganization of these dienes were observed during the decomplexation process and in the presence of CpCo(C[sub 2]H[sub 4])[sub 2]. In this manner several new heterocyclic ring systems could be constructed from 2-substituted thiophenes. Following the success of the thiophene cyclizations, the cocyclization of the benzofuran nucleus was examined. Reagents and conditions were developed that provide an efficient synthesis of alkynols from carboxylic acids; other functional group interconversions of the alkynols were briefly studied. The synthesis and cyclization of 1-[7-methoxy-4-benzofuranyl]-3-butyn-2-ol produced a cobalt complex containing the A,B,C, and D rings of the morphine skeleton. A synthetic advantage of this methodology would be the ease of substitution at pharmaco-logically relevant C-6 and C-7 positions of the morphine framework. Synthetic routes using a cobalt cyclization strategy were proposed.

  4. The Role of Metal Binding in the Amyotrophic Lateral Sclerosis-Related Aggregation of Copper-Zinc Superoxide Dismutase

    Directory of Open Access Journals (Sweden)

    Ivana Sirangelo

    2017-08-01

    Full Text Available Protein misfolding and conformational changes are common hallmarks in many neurodegenerative diseases involving formation and deposition of toxic protein aggregates. Although many players are involved in the in vivo protein aggregation, physiological factors such as labile metal ions within the cellular environment are likely to play a key role. In this review, we elucidate the role of metal binding in the aggregation process of copper-zinc superoxide dismutase (SOD1 associated to amyotrophic lateral sclerosis (ALS. SOD1 is an extremely stable Cu-Zn metalloprotein in which metal binding is crucial for folding, enzymatic activity and maintenance of the native conformation. Indeed, demetalation in SOD1 is known to induce misfolding and aggregation in physiological conditions in vitro suggesting that metal binding could play a key role in the pathological aggregation of SOD1. In addition, this study includes recent advances on the role of aberrant metal coordination in promoting SOD1 aggregation, highlighting the influence of metal ion homeostasis in pathologic aggregation processes.

  5. Catalytic hydroprocessing of heavy oil feedstocks

    International Nuclear Information System (INIS)

    Okunev, A G; Parkhomchuk, E V; Lysikov, A I; Parunin, P D; Semeikina, V S; Parmon, V N

    2015-01-01

    A grave problem of modern oil refining industry is continuous deterioration of the produced oil quality, on the one hand, and increase in the demand for motor fuels, on the other hand. This necessitates processing of heavy oil feedstock with high contents of sulfur, nitrogen and metals and the atmospheric residue. This feedstock is converted to light oil products via hydrogenation processes catalyzed by transition metal compounds, first of all, cobalt- or nickel-promoted molybdenum and tungsten compounds. The processing involves desulfurization, denitrogenation and demetallization reactions as well as reactions converting heavy hydrocarbons to lighter fuel components. The review discusses the mechanisms of reactions involved in the heavy feedstock hydroprocessing, the presumed structure and state of the catalytically active components and methods for the formation of supports with the desired texture. Practically used and prospective approaches to catalytic upgrading of heavy oil feedstock as well as examples of industrial processing of bitumen and vacuum residues in the presence of catalysts are briefly discussed. The bibliography includes 140 references

  6. Catalytic hydrotreatment of refinery waste

    Energy Technology Data Exchange (ETDEWEB)

    1989-01-01

    The object of the project is to produce liquid hydrocarbons by the catalytic hydroprocessing of solid refinery wastes (hard pitches) in order to improve the profitability of deep conversion processes and reduce the excess production of heavy fuels. The project was mostly carried out on the ASVAHL demonstration platform site, at Solaize, and hard pitches were produced primarily by deasphalting of atmospheric or vacuum distillation residues. The project includes two experimental phases and an economic evaluation study phase. In phase 1, two granular catalysts were used to transform pitch into standard low sulphur fuel oil: a continuously moving bed, with demetallation and conversion catalyst; a fixed bed, with hydrorefining catalyst. In phase 2 of the project, it was proven that a hydrotreatment process using a finely dispersed catalyst in the feedstock, can, under realistic operating conditions, transform with goods yields hard pitch into distillates that can be refined through standard methods. In phase 3 of the project, it was shown that the economics of such processes are tightly linked to the price differential between white and black oil products, which is expected to increase in the future. Furthermore, the evolution of environmental constraints will impel the use of such methods, thus avoiding the coproduction of polluting solid residues.

  7. Catalytic hydrotreatment of refinery waste: Demonstration project

    Energy Technology Data Exchange (ETDEWEB)

    1989-01-01

    The object of this project and report is to produce liquid hydrocarbons by the catalytic hydroprocessing of solid refinery wastes (hard pitches) in order to improve the profitability of deep conversion processes and reduce the excess production of heavy fuels. The project was mostly carried out on the ASVAHL demonstration platform site, at Solaize, and hard pitches were produced primarily by deasphalting of atmospheric or vacuum distillation residues. The project includes two experimental phases and an economic evaluation study phase. In Phase 1, two granular catalysts were used to transform pitch into standard low sulfur fuel oil: a continuously moving bed, with demetallation and conversion catalyst; a fixed bed, with hydrorefining catalyst. In Phase 2 of the project, it was proven that a hydrotreatment process using a finely dispersed catalyst in the feedstock, can, under realistic operating conditions, transform with good yields hard pitch into distillates that can be refined through standard methods. In Phase 3 of the project, it was shown that the economics of such processes are tightly linked to the price differential between white'' and black'' oil products, which is expected to increase in the future. Furthermore, the evolution of environmental constraints will impel the use of such methods, thus avoiding the coproduction of polluting solid residues. 11 figs., 1 tab.

  8. Catalytic hydroprocessing of heavy oil feedstocks

    Science.gov (United States)

    Okunev, A. G.; Parkhomchuk, E. V.; Lysikov, A. I.; Parunin, P. D.; Semeikina, V. S.; Parmon, V. N.

    2015-09-01

    A grave problem of modern oil refining industry is continuous deterioration of the produced oil quality, on the one hand, and increase in the demand for motor fuels, on the other hand. This necessitates processing of heavy oil feedstock with high contents of sulfur, nitrogen and metals and the atmospheric residue. This feedstock is converted to light oil products via hydrogenation processes catalyzed by transition metal compounds, first of all, cobalt- or nickel-promoted molybdenum and tungsten compounds. The processing involves desulfurization, denitrogenation and demetallization reactions as well as reactions converting heavy hydrocarbons to lighter fuel components. The review discusses the mechanisms of reactions involved in the heavy feedstock hydroprocessing, the presumed structure and state of the catalytically active components and methods for the formation of supports with the desired texture. Practically used and prospective approaches to catalytic upgrading of heavy oil feedstock as well as examples of industrial processing of bitumen and vacuum residues in the presence of catalysts are briefly discussed. The bibliography includes 140 references.

  9. Hydrodesulfurization and hydrodemetalation reactions of residue oils over CoMo/aluminum borate catalysts in a trickle bed reactor

    International Nuclear Information System (INIS)

    Tsai, M.C.; Chen, Y.W.; Kang, B.C.; Wu, J.C.; Leu, L.J.

    1991-01-01

    In this paper, a series of aluminum borates (AB) with various Al/B mole ratios is prepared by the precipitation method. The results indicated that the exhibited properties are dependent on the Al/B ratio of the material. The monodisperse pore size distributions of these samples simply that it is a true microcomposite structure rather than a mixture of the individual materials. Hydrodesulfurization (HDS) and hydrodemetalation (HDM) of heavy Kuwait atmospheric residuum over CoMo/AB catalysts were carried out in a bench-scale trickle bed reactor at 663 K and 7582 kPa. The weight hourly space velocity of residue oils was 1.5, and the hydrogen flow rate was kept constant at 300 mL/min (STP). The results showed that these catalysts are much more active than the conventional CoMo/Al 2 O 3 catalyst in HDS and HDM reactions. The results of desulfurization activity are mainly interpreted on the basis of difference in dispersion and the interaction of Mo species with the support. The demetalation activity was strongly influenced by the intraparticle diffusion of metal porphyrins

  10. Upgrading during difficult times

    International Nuclear Information System (INIS)

    Tiefenbach, K.

    1993-01-01

    The Co-op Upgrader is part of an integrated refinery and upgrader complex in Regina, Saskatchewan. The upgrader processes 50,000 bbl/d heavy sour crude oil, mostly Fosterton and dilute Lloydminster crude, via hydrogen addition and carbon rejection, desulfurization, demetallization, and denitrification to yield a synthetic crude blend. The synthetic crude is refined to produce gasoline and diesel fuel. Byproducts from the integrated operation include 100,000 tonnes/y of petroleum coke, 65,000 tonnes/y of sulfur, propane, butane, fuel oil, and metals (Ni and V) in the form of spent catalysts. Recent operational and economic challenges faced by the upgrader are reviewed. Technical challenges include operating the upgrader's high-temperature high-pressure heavy oil hydrotreating unit and distillate hydrogenation unit, removal and replacement of the desulfurization catalyst, waste management, and producing coke of sufficient quality. Economic challenges include the shrinking differential between light and heavy oil, higher prices for natural gas (the main raw material for hydrogen production for upgrading), seasonal changes in product specifications, and lower prices for sulfur and metal byproducts. The upgrader is also affected by interest rates since borrowing costs are the single largest expenditure after crude oil purchases. 4 figs

  11. Vanadium in organic fossils as determined by nuclear-physical methods of analysis

    International Nuclear Information System (INIS)

    Nadirov, N.N.; Solodukhin, V.P.

    1998-01-01

    Results are presented of several year investigation to study possibilities of the NPMA for the determination of vanadium in organic fossils and applications of these methods to scientific and practical tasks. For these purposes, various versions of activation analysis (AA), X-ray fluorescence analysis (XRFA), electron spin resonance (ESR) spectroscopy and atomic emission with inductively coupled plasma spectroscopy (AES-ICP). Advantages and pitfalls of individual methods are discussed. The techniques developed can be used for estimation and calculation of stocks of vanadium in organic fossils at the territories of Kazakstan, Tatarstan and along the Volga-river. Analysis results helped in discovering new, industrially important deposits of this valuable metal. Quantitative determination of vanadium was carried out at different stages of technological processes of its extraction from high-viscous oils and oil-bitumen rocks. Results of analyses allowed to reveal the most effective versions of technologies of demetallization of these fossils. Content of vanadium was also studied in different locations of high-viscous oil deposits being explored by the method of inside-stratum burning. Results of analyses showed that the concentration of vanadium in oil decreases considerably with increasing temperature, that is, a considerable part of vanadium (up to 60 percent) may be lost irretrievably. Thus, for the exploration of these deposits a method of vapor-thermal influence onto the stratum was recommended, by using of which the loss of vanadium is insignificant

  12. Super oil cracking update

    International Nuclear Information System (INIS)

    Mulraney, D.

    1997-01-01

    The conversion of residual fuel oil to usable middle distillates was discussed. The residue conversion processing paths are usually based on separation, carbon rejection, or hydrogen addition principles. Super Oil Cracking (SOC) uses a slurry catalyst system in a new, tubular reactor to achieve high levels of hydrothermal conversion. SOC can upgrade a variety of heavy, high metals residue feedstocks with high yields of middle distillates. The SOC products can also be further treated into feedstocks for FCC or hydrocracking. The SOC process can be incorporated easily into a refinery to obtain incremental residue conversion directly. It can also be integrated with other residue processes, acting as a demetallization and decarbonization step which results in enhanced overall conversion. The relative rate of coke formation and its handling are distinguishing characteristics between residue upgrading technologies. The SOC process operates at higher temperatures that other residue hydrocracking processes resulting in higher rates of thermal decomposition, thus preventing coke formation. SOC process can operate as a stand-alone upgrader or can be integrated with other bottoms processing steps to extend the refiner's range of options for increasing bottoms conversion.3 tabs., 14 figs

  13. Synthesis, characterization, MCD spectroscopy, and TD-DFT calculations of copper-metalated nonperipherally substituted octaoctyl derivatives of tetrabenzotriazaporphyrin, cis- and trans-tetrabenzodiazaporphyrin, tetrabenzomonoazaporphyrin, and tetrabenzoporphyrin.

    Science.gov (United States)

    Mack, John; Sosa-Vargas, Lydia; Coles, Simon J; Tizzard, Graham J; Chambrier, Isabelle; Cammidge, Andrew N; Cook, Michael J; Kobayashi, Nagao

    2012-12-03

    Synthesis of the title compounds has been achieved through refinement of a recently reported synthetic protocol whereby varying equivalents of MeMgBr are reacted with 1,4-dioctylphthalonitrile to produce mixtures favoring specific hybrid structures. The initially formed magnesium-metalated compounds are obtained as pure materials and include, for the first time, both isomers (cis and trans) of tetrabenzodiazaporphyrin. The compounds were demetalated to the metal-free analogues, which were then converted into the copper-metalated derivatives. The X-ray structure of the copper tetrabenzotriazaporphyrin derivative is reported. The metal-free and copper-metalated macrocycles exhibit columnar mesophase behavior, and it is found that the mesophase stability is unexpectedly reduced in the diazaporphyrin derivatives compared to the rest of the series. The results of time-dependent density functional theory calculations for the copper complexes are compared to the observed optical properties. Michl's perimeter model was used as a conceptual framework for analyzing the magnetic circular dichroism spectral data, which predicted and accounted for trends in the observed experimental spectra.

  14. Bio-desulfurization technology in Japan; Wagakuni ni okeru baio datsuryu gijutsu

    Energy Technology Data Exchange (ETDEWEB)

    Maruhashi, K. [Petroleum Energy Center, Tokyo (Japan)

    2000-05-01

    A bio-reaction of microbes (catalytic reaction by an enzyme) is characterized in that the reaction is carried out at a normal temperature and under a normal pressure and has particularly high specificity with respect to substrate (reactant). It is considered that a low loading process of environment harmony type can be constructed by applying the bio-reaction in petroleum refinery process. CO{sub 2} exhaust and energy consumption in the bio-desulfurization (BDS) is estimated to be 70 to 80% lower than those in hydrodesulfurization (HDS). The bio-technologies that can be applied to the petroleum refinery process include, for example, desulfurization, demetallation, dewaxing, denitration, cracking and so on. In this paper, the present state of bio-desulphurization technology is introduced. Particularly, as the research results in Japan, acquirement of mesophile R.erythropolis KA2-5-1 strain, thermophile Paenibacillus sp. A11-2 strain whose optimum temperature is 50 degrees C, BT degradation fungus Rhodococcus sp. T09 and the like are introduced. (NEDO)

  15. N-(m-[125I]iodophenyl)maleimide: an agent for high yield radiolabeling of antibodies

    International Nuclear Information System (INIS)

    Khawli, L.A.; Van den Abbeele, A.D.; Kassis, A.I.

    1992-01-01

    In an effort to radiolabel antibodies, N-(m-[ 125 I]iodophenyl)maleimide (m-[ 125 I]IPM) was prepared by the demetallation of an N-[m-tri-(n-butyl)stannylphenyl]maleimide intermediate. The unlabeled intermediate was synthesized in ≥ 75% yield using a palladium catalyzed reaction of hexabutylditin with m-bromoaniline, followed by reaction with maleic anhydride and ring annulation. All products were confirmed by NMR and elemental analysis. Labeling with 125 I was carried out in a biphasic mixture containing chloramine-T (radiochemical yield ≥ 70%). Rabbit IgG modified with the heterobifunctional crosslinking agent N-succinimidyl-3-(2-pyridyldithio)propionate (SPDP) and bovine serum albumin were conjugated with m-[ 125 I]IPM (yield: 40 and 80%, respectively). In addition, m-[ 125 I]IPM was conjugated to rabbit IgG subunits (HL) in 70% yield. The in vitro stability of the radiolabeled proteins in serum showed < 1% deiodination over 24h. (author)

  16. Novel non-symmetrical bifunctionally-substituted phthalonitriles and corresponding d-metal phthalocyaninates

    Science.gov (United States)

    Vashurin, Artur; Maizlish, Vladimir; Tikhomirova, Tatiyana; Nemtseva, Marina; Znoyko, Serafima; Aleksandriiskii, Viktor

    2018-05-01

    The work reports synthesis of 4-(2-tert-butyl-4,5-dicyanophenylsulfonyl)benzene and its analogue containing carboxyl group in phenyl fragment by nucleophilic substitution of nitro-group of 4-tert-butyl-5-nitrophthalonitrile. Unique structure of the obtained compounds is explained by presence of bulky tert-butyl substituent in combination with carboxyl group, which being part of phthalocyanine molecule impart it higher solubility within different solvents (organic and water mediums) and act as anchoring groups. Based on obtained nitriles phthalocyanine complexes of copper, nickel, cobalt and magnesium are synthesized with good yields. Demetallization of initial magnesium phthalocyanine by hydrochloric acid was performed in order to obtain ligand of phthalocyanine. Synthetic and purification techniques are described in detail. Obtained substances are of specific structure making them to be applied in sensorics for smart materials production, as sensitizers or part of molecular magnets. The structure, NMR and IR spectra are modeled using special software. Resulting experimental and theoretical data are compared. The results show sufficient correlation that confirms correctness of chosen methods and its applicability for theoretical studying compounds related to investigated ones.

  17. Effect of Selected Alternative Fuels and Raw Materials on the Cement Clinker Quality

    Directory of Open Access Journals (Sweden)

    Strigáč Július

    2015-11-01

    Full Text Available The article deals with the study of the effects of alternative fuels and raw materials on the cement clinker quality. The clinker quality was expressed by the content of two principal minerals alite C3S and belite C2S. The additions of alternative fuels ashes and raw materials, in principle, always increased the belite content and conversely reduced the amount of alite. The alternative fuels with high ash content were used such as the meat-bone meal, sewage sludge from sewage treatment plants and paper sludge and the used alternative raw materials were metallurgical slags - granulated blastfurnace slag, air cooled blastfurnace slag and demetallized steel slag, fluidized bed combustion fly ash and waste glass. Meat-bone meal, sewage sludge from sewage treatment plants and paper sludge were evaluated as moderately suitable alternative fuels which can be added in the amounts of 2.8 wt. % addition of meat-bone meals ash, 3.64 wt. % addition of sewage sludge ash and 3.8 wt. % addition of paper sludge ash to the cement raw mixture. Demetallised steel slag is suitable for production of special sulphate resistant cement clinker for CEM I –SR cement with addition up to 5 wt. %. Granulated blastfurnace slag is a suitable alternative raw material with addition 4 wt. %. Air cooled blastfurnace slag is a suitable alternative raw material with addition 4.2 wt. %. Waste glass is not very appropriate alternative raw material with addition only 1.16 wt. %. Fluidized bed combustion fly ash appears not to be equally appropriate alternative raw material for cement clinker burning with less potential utilization in the cement industry and with addition 3.41 wt. %, which forms undesired anhydrite CaSO4 in the cement clinker.

  18. Temperature shift effect on the Chlorobaculum tepidum chlorosomes.

    Science.gov (United States)

    Tang, Joseph Kuo-Hsiang; Xu, Ying; Muhlmann, Guillermo M; Zare, Farrokh; Khin, Yadana; Tam, Sun W

    2013-05-01

    Chlorobaculum [Cba.] tepidum is known to grow optimally at 48-52 °C and can also be cultured at ambient temperatures. In this paper, we prepared constant temperature, temperature shift, and temperature shift followed by backshift cultures and investigated the intrinsic properties and spectral features of chlorosomes from those cultures using various approaches, including temperature-dependent measurements on circular dichroism (CD), UV-visible, and dynamic light scattering. Our studies indicate that (1) chlorosomes from constant temperature cultures at 50 and 30 °C exhibited more resistance to heat relative to temperature shift cultures; (2) as temperature increases bacteriochlorophyll c (BChl c) in chlorosomes is prone to demetalation, which forms bacteriopheophytin c, and degradation under aerobic conditions. Some BChl c aggregates inside reduced chlorosomes prepared in low-oxygen environments can reform after heat treatments; (3) temperature shift cultures synthesize and incorporate more BChl c homologs with a smaller substituent at C-8 on the chlorin ring and less BChl c homologs with a larger long-chain alcohol at C-17(3) versus constant-temperature cultures. We hypothesize that the long-chain alcohol at C-17(3) (and perhaps together with the substituent at C-8) may account for thermal stability of chlorosomes and the substituent at C-8 may assist self-assembling BChls; and (4) while almost identical absorption spectra are detected, chlorosomes from different growth conditions exhibited differences in the rotational length of the CD signal, and aerobic and reduced chlorosomes also display different Qy CD intensities. Further, chlorosomes exhibited changes of CD features in response to temperature increases. Additionally, we compare temperature-dependent studies for the Cba. tepidum chlorosomes and previous studies for the Chloroflexus aurantiacus chlorosomes. Together, our work provides useful and novel insights on the properties and organization of

  19. Disulfide scrambling in superoxide dismutase 1 reduces its cytotoxic effect in cultured cells and promotes protein aggregation.

    Directory of Open Access Journals (Sweden)

    Lina Leinartaitė

    Full Text Available Mutations in the gene coding for superoxide dismutase 1 (SOD1 are associated with familiar forms of the neurodegenerative disease amyotrophic lateral sclerosis (ALS. These mutations are believed to result in a "gain of toxic function", leading to neuronal degeneration. The exact mechanism is still unknown, but misfolding/aggregation events are generally acknowledged as important pathological events in this process. Recently, we observed that demetallated apoSOD1, with cysteine 6 and 111 substituted for alanine, is toxic to cultured neuroblastoma cells. This toxicity depended on an intact, high affinity Zn(2+ site. It was therefor contradictory to discover that wild-type apoSOD1 was not toxic, despite of its high affinity for Zn(2+. This inconsistency was hypothesized to originate from erroneous disulfide formation involving C6 and C111. Using high resolution non-reducing SDS-PAGE, we have in this study demonstrated that the inability of wild-type apoSOD1 to cause cell death stems from formation of non-native intra-molecular disulfides. Moreover, monomeric apoSOD1 variants capable of such disulfide scrambling aggregated into ThT positive oligomers under physiological conditions without agitation. The oligomers were stabilized by inter-molecular disulfides and morphologically resembled what has in other neurodegenerative diseases been termed protofibrils. Disulfide scrambling thus appears to be an important event for misfolding and aggregation of SOD1, but may also be significant for protein function involving cysteines, e.g. mitochondrial import and copper loading.

  20. Synthesis, Characterization, Antimicrobial Studies and Corrosion Inhibition Potential of 1,8-dimethyl-1,3,6,8,10,13-hexaazacyclotetradecane: Experimental and Quantum Chemical Studies

    Directory of Open Access Journals (Sweden)

    Henry U. Nwankwo

    2016-02-01

    Full Text Available The macrocylic ligand, 1,8-dimethyl-1,3,6,8,10,13-hexaazacyclotetradecane (MHACD was synthesized by the demetallation of its freshly synthesized Ni(II complex (NiMHACD. Successful synthesis of NiMHACD and the free ligand (MHACD was confirmed by various characterization techniques, including Fourier transform infra-red (FT-IR, proton nuclear magnetic resonance (1H-NMR, carbon-13 nuclear magnetic resonance (13C-NMR, ultraviolet-visible (UV-vis, and energy dispersive x-ray (EDX spectroscopic techniques. The anti-bacteria activities of MHACD were investigated against Staphylococcus aureus and Enterococcus species and the results showed that MHACD possesses a spectrum of activity against the two bacteria. The electrochemical cyclic voltammetry study on MHACD revealed that it is a redox active compound with promising catalytic properties in electrochemical applications. The inhibition potential of MHACD for mild steel corrosion in 1 M HCl was investigated using potentiodynamic polarization method. The results showed that MHACD inhibits steel corrosion as a mixed-type inhibitor, and the inhibition efficiency increases with increasing concentration of MHACD. The adsorption of MHACD obeys the Langmuir adsorption isotherm; it is spontaneous and involves competitive physisorption and chemisorption mechanisms. Quantum chemical calculations revealed that the energy of the highest occupied molecular orbital (HOMO of MHACD is high enough to favor forward donation of charges to the metal during adsorption and corrosion inhibition. Natural bond orbital (NBO analysis revealed the presence of various orbitals in the MHACD that are capable of donating or accepting electrons under favorable conditions.

  1. On the lability and functional significance of the type 1 copper pool in ceruloplasmin.

    Science.gov (United States)

    Musci, G; Fraterrigo, T Z; Calabrese, L; McMillin, D R

    1999-08-01

    The possibility that ceruloplasmin (CP) functions as a copper transferase has fueled a continuing interest in studies of the copper release process. The principal goal of the current investigation has been to identify the most labile copper centers in sheep protein. In fact, subjecting the enzyme to a slow flux of cyanide at pH 5.2 under nitrogen in the presence of ascorbate and a phenanthroline ligand produces partially demetalated forms of the protein. By standard chromatographic techniques it is possible to isolate protein with a Cu/CP ratio of approximately 4 or approximately 5 as opposed to the native protein which has Cu/CP = 5.8. In contrast to other blue oxidases, analysis suggests that CP preferentially loses its type 1 coppers under these conditions. Thus, the spectroscopic signals from the type 1 centers exhibit a loss of intensity while the EPR signal of the type 2 copper becomes stronger. Furthermore, the Cu/CP approximately 4 and Cu/ CP approximately 5 components retain about 50% of the activity of the native protein, consistent with an intact type 2/type 3 cluster. All three type 1 copper sites appear to suffer copper loss. Reconstitution with a copper(I) reagent restores the spectroscopic properties of the native protein and 90% of the original activity. The results suggest a possible functional significance for the presence of three type 1 coppers in CP. By employing a pool of redox-active but relatively labile type 1 copper centers, the enzyme can serve as a copper donor, if necessary, without completely sacrificing its oxidase activity.

  2. Evaluación de indicadores subjetivos durante el diseño optimo con objetivos múltiples de herramientas para la conformación de metales // Evaluating subjective character indicators in the process of multiple objective metal conforming die design

    Directory of Open Access Journals (Sweden)

    J. Arzola Ruiz

    2001-01-01

    Full Text Available En este trabajo se exponen de forma breve la aplicación de un Enfoque Integrador para el Análisis y la Síntesis de Sistemas deIngeniería para la Preparación y Toma de Decisiones bajo Criterios Múltiplesa la generación de tecnologías de conformación demetales en el ejemplo de dos sistemas desarrollados por el Centro de Estudios CAD/CAM en colaboración con la Unidad DocenteMetalúrgica del ISPJAE en los que se utiliza el dibujo paramétrico tridimensional. Se trata del sistema TROQUEL, el que permite eldiseño de troqueles de corte y punzonado simples y progresivos y del sistema DiesFor, el que permite el diseño de estampas de Forja,determinando y diseñando las herramientas para las etapas intermedias necesarias, en el proceso. Con el fin de una correcta evaluaciónde las opciones de solución ofertadas ambos sistemas brindan como resultado dibujos paramétricos de cada uno de los elementos, asícomo, los planos de conjunto y despiece correspondientes.Palabras claves: Optimización multiobjetivo, deformación plástica, cad/cam, troqueles, forja._____________________________________________________________________________Abstract:In this work are exposed, in a brief way, the application of an integrative approach for the analysis and synthesisengineering systems for preparation and making decisions under multiple criterions for metal conforming technologies with the example of two concrete systems developed by CAD/CAM's Studies Center of HolguinUniversity in collaboration with the Department of Metallurgy of José Antonio Echeverría Polytechnical Institutein which three-dimensional parametric drawing are used. The examples are: system DIE, which allows the designand progressive cutting dies and the system DiesFor, the one that allows the design of Forge Die, determiningand designing the tools for the necessary intermediate stages in the process. With the purpose of a correctevaluation of the offered solution options, both systems

  3. Synthesis of chlorophyll-c derivatives by modifying natural chlorophyll-a.

    Science.gov (United States)

    Xu, Meiyun; Kinoshita, Yusuke; Matsubara, Shogo; Tamiaki, Hitoshi

    2016-03-01

    Chlorophyll-a (Chl-a) was extracted from cyanobacterial cells and modified to methyl pyropheophorbide-a. The 3-vinyl-chlorin was transformed to zinc complex of the corresponding 3-acetyl-porphyrin. The zinc porphyrin was oxidized to give cis-7,8- and 17,18-dihydroxy-chlorins as well cis-7,8-cis-17,18-tetrahydroxybacteriochlorin. After zinc-demetallation, the isolated cis-7,8- and 17,18-diols were reduced at the 3-acetyl group and triply dehydrated under acidic conditions to afford two regioisomeric 3-vinyl-porphyrins, methyl divinyl-pyroprotopheophorbide-a possessing the 8-vinyl group and 17-propionate residue (one of the divinyl-protoChl-a derivatives) and methyl pyropheophorbide-c 1 possessing the 8-ethyl group and 17-acrylate residue (one of the Chl-c 1 derivatives), respectively. The resulting 7,8,17,18-tetrol was reduced and then acidically treated, giving five-fold dehydrated free base porphyrin, methyl pyropheophorbide-c 2 possessing the 3,8-divinyl groups and 17-acrylate residue (one of the Chl-c 2 derivatives). The visible absorption and fluorescence emission spectra of the three semi-synthetic 3-vinyl-porphyrins in dichloromethane were compared with those of the corresponding 8-ethyl-porphyrin bearing the 17-propionate residue, methyl pyroprotopheophorbide-a (one of the protoChl-a derivatives). The Soret and Qy absorption maxima were shifted to longer wavelengths with an increase of π-conjugation in a molecule: protoChl-a (8-CH2CH3/17-CH2CH2COOCH3) < divinyl-protoChl-a (8-CH=CH2/17-CH2CH2COOCH3) < Chl-c 1 (8-CH2CH3/17-CH=CHCOOCH3) < Chl-c 2 derivatives (8-CH=CH2/17-CH=CHCOOCH3). The 17(1),17(2)-dehydrogenation broadened the absorption bands. The emission maxima were bathochromically shifted in the same order. The reaction mechanism of the present dehydration indicates that the biosynthetic pathway of Chls-c would include the hydroxylation of the 17-propionate reside at the 17(1)-position and successive dehydration to the 17-acrylate residue.

  4. Synthesis of Symmetrical Tetrameric Conjugates of the Radiolanthanide Chelator DOTPI for Application in Endoradiotherapy by Means of Click Chemistry

    Directory of Open Access Journals (Sweden)

    Alexander Wurzer

    2018-04-01

    Full Text Available Due to its 4 carbonic acid groups being available for bioconjugation, the cyclen tetraphosphinate chelator DOTPI, 1,4,7,10-tetraazacyclododecane-1,4,7, 10-tetrakis[methylene(2-carboxyethylphosphinic acid], represents an ideal scaffold for synthesis of tetrameric bioconjugates for labeling with radiolanthanides, to be applied as endoradiotherapeuticals. We optimized a protocol for bio-orthogonal DOTPI conjugation via Cu(I-catalyzed Huisgen-cycloaddition of terminal azides and alkynes (CuAAC, based on the building block DOTPI(azide4. A detailed investigation of kinetic properties of Cu(II-DOTPI complexes aimed at optimization of removal of DOTPI-bound copper by transchelation. Protonation and equilibrium properties of Ca(II-, Zn(II, and Cu(II-complexes of DOTPI and its tetra-cyclohexylamide DOTPI(Chx4 (a model for DOTPI conjugates as well as kinetic inertness (transchelation challenge in the presence of 20 to 40-fold excess of EDTA were investigated by pH-potentiometry and spectrophotometry. Similar stability constants of CaII-, ZnII, and CuII-complexes of DOTPI (logK(CaL = 8.65, logK(ZnL = 15.40, logK(CuL = 20.30 and DOTPI(Chx4 (logK(CaL = 8.99, logK(ZnL = 15.13, logK(CuL = 20.42 were found. Transchelation of Cu(II-complexes occurs via proton-assisted dissociation, whereafter released Cu(II is scavenged by EDTA. The corresponding dissociation rates [kd = 25 × 10−7 and 5 × 10−7 s−1 for Cu(DOTPI and Cu(DOTPI(Chx4, respectively, at pH 4 and 298 K] indicate that conjugation increases the kinetic inertness by a factor of 5. However, demetallation is completed within 4.5 and 7.2 h at pH 2 and 25°C, respectively, indicating that Cu(II removal after formation of CuAAC can be achieved in an uncomplicated manner by addition of excess H4EDTA. For proof-of-principle, tetrameric DOTPI conjugates of the prostate-specific membrane antigen (PSMA targeting motif Lys-urea-Glu (KuE were synthesized via CuAAC as well as dibenzo-azacyclooctine (DBCO based

  5. Synthesis of Symmetrical Tetrameric Conjugates of the Radiolanthanide Chelator DOTPI for Application in Endoradiotherapy by Means of Click Chemistry

    Science.gov (United States)

    Wurzer, Alexander; Vágner, Adrienn; Horváth, Dávid; Fellegi, Flóra; Wester, Hans-Jürgen; Kálmán, Ferenc K.; Notni, Johannes

    2018-01-01

    Due to its 4 carbonic acid groups being available for bioconjugation, the cyclen tetraphosphinate chelator DOTPI, 1,4,7,10-tetraazacyclododecane-1,4,7, 10-tetrakis[methylene(2-carboxyethylphosphinic acid)], represents an ideal scaffold for synthesis of tetrameric bioconjugates for labeling with radiolanthanides, to be applied as endoradiotherapeuticals. We optimized a protocol for bio-orthogonal DOTPI conjugation via Cu(I)-catalyzed Huisgen-cycloaddition of terminal azides and alkynes (CuAAC), based on the building block DOTPI(azide)4. A detailed investigation of kinetic properties of Cu(II)-DOTPI complexes aimed at optimization of removal of DOTPI-bound copper by transchelation. Protonation and equilibrium properties of Ca(II)-, Zn(II), and Cu(II)-complexes of DOTPI and its tetra-cyclohexylamide DOTPI(Chx)4 (a model for DOTPI conjugates) as well as kinetic inertness (transchelation challenge in the presence of 20 to 40-fold excess of EDTA) were investigated by pH-potentiometry and spectrophotometry. Similar stability constants of CaII-, ZnII, and CuII-complexes of DOTPI (logK(CaL) = 8.65, logK(ZnL = 15.40, logK(CuL) = 20.30) and DOTPI(Chx)4 (logK(CaL) = 8.99, logK(ZnL) = 15.13, logK(CuL) = 20.42) were found. Transchelation of Cu(II)-complexes occurs via proton-assisted dissociation, whereafter released Cu(II) is scavenged by EDTA. The corresponding dissociation rates [kd = 25 × 10−7 and 5 × 10−7 s−1 for Cu(DOTPI) and Cu(DOTPI(Chx)4), respectively, at pH 4 and 298 K] indicate that conjugation increases the kinetic inertness by a factor of 5. However, demetallation is completed within 4.5 and 7.2 h at pH 2 and 25°C, respectively, indicating that Cu(II) removal after formation of CuAAC can be achieved in an uncomplicated manner by addition of excess H4EDTA. For proof-of-principle, tetrameric DOTPI conjugates of the prostate-specific membrane antigen (PSMA) targeting motif Lys-urea-Glu (KuE) were synthesized via CuAAC as well as dibenzo-azacyclooctine (DBCO

  6. A shortcut to high-affinity Ga-68 and Cu-64 radiopharmaceuticals: one-pot click chemistry trimerisation on the TRAP platform.

    Science.gov (United States)

    Baranyai, Zsolt; Reich, Dominik; Vágner, Adrienn; Weineisen, Martina; Tóth, Imre; Wester, Hans-Jürgen; Notni, Johannes

    2015-06-28

    Due to its 3 carbonic acid groups being available for bioconjugation, the TRAP chelator (1,4,7-triazacyclononane-1,4,7-tris(methylene(2-carboxyethylphosphinic acid))) is chosen for the synthesis of trimeric bioconjugates for radiolabelling. We optimized a protocol for bio-orthogonal TRAP conjugation via Cu(I)-catalyzed Huisgen-cycloaddition of terminal azides and alkynes (CuAAC), including a detailed investigation of kinetic properties of Cu(II)-TRAP complexes. TRAP building blocks for CuAAC, TRAP(alkyne)3 and TRAP(azide)3 were obtained by amide coupling of propargylamine/3-azidopropyl-1-amine, respectively. For Cu(II) complexes of neat and triply amide-functionalized TRAP, the equilibrium properties as well as pseudo-first-order Cu(II)-transchelation, using 10 to 30 eq. of NOTA and EDTA, were studied by UV-spectrophotometry. Dissociation of any Cu(II)-TRAP species was found to be independent on the nature or excess of a competing chelator, confirming a proton-driven two-step mechanism. The respective thermodynamic stability constants (log K(ML): 19.1 and 17.6) and dissociation rates (k: 38 × 10(-6) and 7 × 10(-6) s(-1), 298 K, pH 4) show that the Cu(II) complex of the TRAP-conjugate possesses lower thermodynamic stability but higher kinetic inertness. At pH 2-3, its demetallation with NOTA was complete within several hours/days at room temperature, respectively, enabling facile Cu(II) removal after click coupling by direct addition of NOTA trihydrochloride to the CuAAC reaction mixture. Notwithstanding this, an extrapolated dissociation half life of >100 h at 37 °C and pH 7 confirms the suitability of TRAP-bioconjugates for application in Cu-64 PET (cf. t(1/2)(Cu-64) = 12.7 h). To showcase advantages of the method, TRAP(DUPA-Pep)3, a trimer of the PSMA inhibitor DUPA-Pep, was synthesized using 1 eq. TRAP(alkyne)3, 3.3 eq. DUPA-Pep-azide, 10 eq. Na ascorbate, and 1.2 eq. Cu(II)-acetate. Its PSMA affinity (IC50), determined by the competition assay on LNCa

  7. Synthesis of symmetrical tetrameric conjugates of the radiolanthanide chelator DOTPI for application in endoradiotherapy by means of click chemistry

    Science.gov (United States)

    Wurzer, Alexander; Vágner, Adrienn; Horváth, Dávid; Fellegi, Flóra; Wester, Hans-Jürgen; Kálmán, Ferenc K.; Notni, Johannes

    2018-04-01

    Due to its 4 carbonic acid groups being available for bioconjugation, the cyclen tetraphosphinate chelator DOTPI, 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetrakis[methylene(2-carboxyethylphosphinic acid)], represents an ideal scaffold for synthesis of tetrameric bioconjugates for labeling with radiolanthanides, to be applied as endoradiotherapeuticals. We optimized a protocol for bio-orthogonal DOTPI conjugation via Cu(I)-catalyzed Huisgen-cycloaddition of terminal azides and alkynes (CuAAC), based on the building block DOTPI(azide)4. A detailed investigation of kinetic properties of Cu(II)-DOTPI complexes aimed at optimization of removal of DOTPI-bound copper by transchelation. Protonation and equilibrium properties of Ca(II)-, Zn(II) and Cu(II)-complexes of DOTPI and its tetra-cyclohexylamide DOTPI(Chx)4 (a model for DOTPI conjugates) as well as kinetic inertness (transchelation challenge in the presence of 20 to 40-fold excess of EDTA) were investigated by pH-potentiometry and spectrophotometry. Similar stability constants of CaII-, ZnII and CuII-complexes of DOTPI (logK(CaL)=8.65, logK(ZnL=15.40, logK(CuL)=20.30) and DOTPI(Chx)4 (logK(CaL)=8.99, logK(ZnL)=15.13, logK(CuL)=20.42) were found. Transchelation of CuII-complexes occurs via proton-assisted dissociation, whereafter released Cu(II) is scavenged by EDTA. The corresponding dissociation rates (kd=25×10‑7 and 5×10‑7 s‑1 for Cu(DOTPI) and Cu(DOTPI(Chx)4), respectively, at pH 4 and 298 K) indicate that conjugation increases the kinetic inertness by a factor of 5. However demetallation is completed within 4.5 and 7.2 hours at pH 2 and 25 °C, respectively, indicating that CuII removal after formation of CuAAC can be achieved in an uncomplicated manner by addition of excess H4EDTA. For proof-of-principle, tetrameric DOTPI conjugates of the prostate-specific membrane antigen (PSMA) targeting motif Lys-urea-Glu (KuE) were synthesized via CuAAC as well as dibenzo-cyclooctine (DBCO) based, strain

  8. Simulation de la désactivation d'un catalyseur d'hydrodémétallisation à géométrie ouverte Simulation of the Deactivation of a Hydrodemetallization Catalyst with an Open Geometry

    Directory of Open Access Journals (Sweden)

    Tanoubi I.

    2006-11-01

    éveloppement rationnel de nouveaux catalyseurs industriels. A predictive simulation method is proposed for the deactivation of a hydrodemetallization catalyst in time. It is based on a model of the geometry of the catalyst associated with a diffusion law of the reactants, with consideration being given to the textural evolution of the catalyst during the reaction. Textural evolution is due to the solid deposition of reaction products in the catalytic pores. The deposit also catalyzes the reaction, but much less effectively than the catalyst fresh. Deactivation is linked to the decrease in the specific surface area and to the progressive plugging up of the pores. The geometry taken into consideration reflects the original socalled chestnut-burrtexture characterizing new catalysts developed by Institut Français du Pétrole (IFP for the hydrotreatment of residues. Simulation shows that this specific geometry brings about better catalyst stability in relation to deactivation factors. The model first considers a simple kinetics involving solely the demetallization reaction. Likewise, it is capable of introducing a competitive reaction to justify experimental observations in an environment contaminated by asphaltenes, i. e. the occurrence of maximum concentrations of a solid deposit inside the catalyst grains and not on their immediate periphery. The simulation predicts the evolution in time of the profiles along the grain, the specific surface area, the void fraction, the reactant concentration in the pores and the mass of metals deposited. It also determines at all times the reactant flux on the surface of the grain as well as the Tamm factor and the metal capture rate. The model gives a satisfactory account of the leading experimental observations and also provides a very useful qualitative tool for the rational development of new industrial catalysts.

  9. Cellular uptake, nuclear localization and cytotoxicity of 125I-labelled DNA minor groove binding ligands in K562, human erythroleukaemia cells

    International Nuclear Information System (INIS)

    Karagiannis, T.C.; Lobachevsky, P.N.; Martin, R.F.

    2000-01-01

    Full text: Iodine-125 decays by orbital electron capture and internal conversion resulting in the emission of numerous Auger electrons which produce a highly localised radiochemical damage in the immediate vicinity of the site of decay. Given the requirement to deliver 125 I to the nuclear DNA, a minor groove binding bibenzimidazole, 125 I-iodoHoechst 33258 was investigated. It has been noted that this analogue may be prone to de-iodination in vitro and in vivo, given the presence of an orthoiodophenol moiety which is analogous to that in thyroxins. Therefore, an 125 I -iodoHoechst analogue without the hydroxyl group was also studied. The 125 I -iodoHoechst 33258 analogue was prepared by direct iodination of Hoechst 33258 and 125 I iodoHoechst was prepared by demetallation of a trimethylstannyl precursor. DNA binding studies indicated that both iodo-analogues bind to calf thymus DNA, K D = 89 ± 30nM, n = 0.018 bp - 1 for iodoHoechst 33258 and K D = 121 ± 31nM, n = 0.024 bp -1 for iodoHoechst. Similarly, nuclear localization following incubation with 5μM of either ligand at 37 deg C was observed in K562 cells by fluorescence microscopy. Flow cytometry was used to investigate the kinetics of drug uptake and efflux in K562 cells. The results indicated that when 10 6 cells were incubated with 5μM ligand at 37 deg C, the uptake reached a plateau at approximately 43 minutes for iodoHoechst 33258 and approximately 52 minutes for iodoHoechst. Ligand efflux results indicated two-phase kinetics. The initial phase which involves 50-60% of drug was characterised by a half-life time (t 1/2 ) of 55.4 minutes for efflux of iodoHoechst 33258 and a t 1/2 of 10.3 minutes for efflux of iodoHoechst, at 37 deg C. Furthermore, the results suggested that the DNA binding sites in a 10 6 cell/ml suspension were saturated by incubation with 3μM iodoHoechst 33258 and 5μM iodoHoechst. In the initial cytotoxicity experiments using 125 I-iodoHoechst 33258, K562 cells were incubated for 1