Fe-Mn/ZrO2 catalysts: Sulfate-based-advanced oxidation process for the degradation of olive oil industry model pollutants

Fe, Mn and a bimetallic Fe[sbnd]Mn catalysts supported on ZrO2 were synthesized and tested for the activation of persulfate (PS) and peroxymonosulfate (PMS) in the degradation reaction of three different organic compounds: cinnamic acid (CA), benzoic acid (BA), and catechol (C). The catalysts were prepared and tested in order to evaluate the effect of the metal and the metal combination on the generation of reactive oxygen species (ROS). The characterization of the catalysts was carried out by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and atomic absorption spectroscopy (AAS). The best degradation results were obtained when PMS was activated with the bimetallic Fe-Mn/ZrO2 catalyst in the CA degradation. Moreover, the Fe-Mn/ZrO2 catalyst reusability was tested for up to three consecutive cycles of reaction, with mineralization levels >90%. A synergistic effect between the Fe and Mn metal species, which increases the catalyst activity if compared to the monometallic catalysts, is postulated. Both sulfate and hydroxyl radicals were generated in the PMS activation process. The activation mechanisms of the oxidants were proposed.Fil: Loffredo, Camila Macarena. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Instituto de Química del Sur. Universidad Nacional del Sur. Departamento de Química. Instituto de Química del Sur; ArgentinaFil: Dennehy, Mariana. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Instituto de Química del Sur. Universidad Nacional del Sur. Departamento de Química. Instituto de Química del Sur; ArgentinaFil: Alvarez, Mariana. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Instituto de Química del Sur. Universidad Nacional del Sur. Departamento de Química. Instituto de Química del Sur; Argentin

A triclinic polymorph of cyclo-tetra - Thio-saccharinato- 8 S:S-tetra-kis[(triphenyl-phosphane-P)silver(I)]

The triclinic structure of the title compound, cyclo-tetra-kis-(-1,1-dioxo- 1 6,2-benzothia-zole-3-thiol-ato- 2 S:S)tetra-kis- [(triphenyl-phosphane-P)silver(I)], [Ag4(C7H4NO2S2)4(C18H15P)4], is a polymorph of the previously reported monoclinic structure [Dennehy, Mandolesi, Quinzani & Jennings (2007). Z. Anorg. Allg. Chem. 633, 2746-2752]. In both polymorphs, the complex lies on a crystallographic inversion centre and the bond distances are closely comparable. Some differences can be found in the inter-atomic angles and torsion angles involving the inner Ag4S4 skeleton. The polymorphs contain essentially identical two-dimensional layers, but with different layer stacking arrangements. In the triclinic form, all layers are related by lattice translation, while in the monoclinic form they are arranged around glide planes so that adjacent layers are mirrored with respect to each other.Fil: Dennehy, Mariana. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Universidad Nacional del Sur; ArgentinaFil: Freire Espeleta, Eleonora. Comisión Nacional de Energía Atómica. Gerencia del Área de Energía Nuclear. Unidad de Actividad de Materiales (CAC); Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; ArgentinaFil: Baggio, Ricardo Fortunato. Comisión Nacional de Energía Atómica. Gerencia del Área de Energía Nuclear. Unidad de Actividad de Materiales (CAC); Argentin

The conformations of two copper(I) complexes of 1H-benzimidazole- 2(3H)-thione and thiosaccharinate

(Acetonitrile-1N)[-1H-benzimidazole-2(3H)-thione-1:2 2 S:S][1H-benzimidazole-2(3H)-thione-2S]bis-(-1,1-dioxo-1 6,2-benzothia- zole-3-thiol-ato)-1:2 2 S 3:N;1:2 2 S 3:S 3-dicopper(I)(Cu - Cu), [Cu2(C7H4NO2S2)2(C7H6N2S) 2(CH3CN)] or [Cu2(tsac)2(Sbim)2(CH3CN)] [tsac is thio-saccharinate and Sbim is 1H-benzimidazole-2(3H)-thione], (I), is a new copper(I) compound that consists of a triply bridged dinuclear Cu - Cu unit. In the complex mol-ecule, two tsac anions and one neutral Sbim ligand bind the metals. One anion bridges via the endocyclic N and exocyclic S atoms (-S:N). The other anion and one of the mercaptobenzimidazole mol-ecules bridge the metals through their exocyclic S atoms (-S:S). The second Sbim ligand coordinates in a monodentate fashion (S) to one Cu atom, while an acetonitrile mol-ecule coordinates to the other Cu atom. The Cu I - Cu I distance [2.6286 (6) Å] can be considered a strong cuprophilic inter-action. In the case of [-1H-benzimidazole-2(3H)-thione-1:2 2 S:S]bis-[1H-benzimidazole-2(3H)- thione]-1S;2S-bis-(-1,1-dioxo-1 6,2-benzo-thia-zole-3-thiol-ato)-1: 2 2 S 3:N;1:2 2 S 3:S 3-dicopper(I)(Cu - Cu), [Cu2(C7H4NO2S2)2(C7H6N2S)3] or [Cu2(tsac)2(Sbim)3], (II), the acetonitrile mol-ecule is substituted by an additional Sbim ligand, which binds one Cu atom via the exocylic S atom. In this case, the Cu I - Cu I distance is 2.6068 (11) Å.Fil: Dennehy, Mariana. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Instituto de Química del Sur. Universidad Nacional del Sur. Departamento de Química. Instituto de Química del Sur; ArgentinaFil: Quinzani, Oscar Valentín. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Instituto de Química del Sur. Universidad Nacional del Sur. Departamento de Química. Instituto de Química del Sur; ArgentinaFil: Faccio, Ricardo. Universidad de la República; UruguayFil: Freire Espeleta, Eleonora. Comisión Nacional de Energía Atómica. Centro Atómico Constituyentes; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; ArgentinaFil: Mombru, Alvaro W.. Universidad de la República; Urugua

Structure and electrical properties of a one-dimensional polymeric silver thiosaccharinate complex with argentophilic interactions

Among the potential applications of coordination polymers, electrical con­ductivity ranks high in technological inter­est. We report the synthesis, crystal structure and spectroscopic analysis of an AgI–thio­saccharinate one-dimensional coordination polymer {systematic name: catena-poly[[[aqua­tetra­kis­(μ3-1,1-dioxo-1,2-benziso­thia­zole-3-thiol­ato-κ3N:S3:S3)tetra­silver(I)]-μ2-4,4′-(propane-1,3-di­yl)di­pyridine-κ2N:N′] dimethyl sulfoxide hemisolvate]}, {[Ag4(C7H4NO2S2)4(C13H14N2)(H2O)]·0.5C2H6OS}n, with the 4,4′-(propane-1,3-di­yl)di­pyridine ligand acting as a spacer. A relevant feature of the structure is the presence of an unusually short Ag...Ag distance of 2.8306 (9) Å, well within the range of argentophilic inter­actions, confirmed experimentally as such by a Raman study on the low-frequency spectrum, and corroborated theoretically by an Atoms in Mol­ecules (AIM) analysis of the calculated electron density. Electrical conductivity measurements show that this complex can act as a semiconductor with moderate conductivity.Fil: Dennehy, Mariana. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Instituto de Química del Sur. Universidad Nacional del Sur. Departamento de Química. Instituto de Química del Sur; ArgentinaFil: Amo Ochoa, Pilar. Universidad Autónoma de Madrid; EspañaFil: Freire Espeleta, Eleonora. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Universidad Nacional de San Martín. Escuela de Ciencia y Tecnología; Argentina. Comisión Nacional de Energía Atómica. Centro Atómico Constituyentes; ArgentinaFil: Suarez, Sebastian. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; Argentina. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Departamento de Química Inorgánica, Analítica y Química Física; ArgentinaFil: Halac, Emilia. Comisión Nacional de Energía Atómica. Centro Atómico Constituyentes; Argentina. Universidad Nacional de San Martín. Escuela de Ciencia y Tecnología; ArgentinaFil: Baggio, Ricardo. Comisión Nacional de Energía Atómica. Centro Atómico Constituyentes; Argentin

Zn thiosacharinates: From ionic to polymeric structures. Synthesis, characterization and cell proliferation inhibition studies

A series of Zn thiosacharinates complexes with nitrogen donor co-ligands were synthesized: [Zn(tsac)2(o-phen)], [Zn(tsac)2(TMDP)]n, [(4,4′-bipy)H2][Zn(tsac)4] [Zn(tsac)2(2,2′-bipy)], [Zn(tsac)2(2,2′-bquin)], (tsac, thiosaccharinate anion: 1,1-dioxo-1,2-benzisothiazole-3-thiolato, C7H4NO2S2−, o-phen: 1,10′-phenantroline, TMDP: trimethylenedipyridine, 2,2′-bipy: 2,2′-bipyridine, 4,4′-bipy: 4,4′-bipyridine, 2,2′-bquin: 2,2′-biquinoline). They were fully characterized by means of FTIR, 13C and 1H NMR, elemental analysis and conductivity measurements. Three of them, [Zn(tsac)2(o-phen)], [(4,4′-bipy)H2][Zn(tsac)4], [Zn(tsac)2(TMDP)]n were also characterized by X-ray single crystal diffractometry and their crystal structures are described herein. DFT geometry optimization for the [Zn(tsac)2(o-phen)] complex was performed and its vibrational spectra was predicted. Moreover, we studied the effects of the five complexes on cell proliferation, thus providing preliminary evidence for their therapeutic potential as anti-cancer drugs.Fil: Delgado, Fermin. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Instituto de Química del Sur. Universidad Nacional del Sur. Departamento de Química. Instituto de Química del Sur; ArgentinaFil: Freire Espeleta, Eleonora. Universidad Nacional de San Martín. Escuela de Ciencia y Tecnología; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Comisión Nacional de Energía Atómica. Centro Atómico Constituyentes; ArgentinaFil: Baggio, Ricardo. Comisión Nacional de Energía Atómica. Centro Atómico Constituyentes; ArgentinaFil: González Pardo, María Verónica. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Instituto de Ciencias Biológicas y Biomédicas del Sur. Universidad Nacional del Sur. Departamento de Biología, Bioquímica y Farmacia. Instituto de Ciencias Biológicas y Biomédicas del Sur; ArgentinaFil: Dorn, Viviana. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Instituto de Química del Sur. Universidad Nacional del Sur. Departamento de Química. Instituto de Química del Sur; ArgentinaFil: Dennehy, Mariana. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Instituto de Química del Sur. Universidad Nacional del Sur. Departamento de Química. Instituto de Química del Sur; Argentin

Therapeutic properties, SOD and catecholase mimetic activities of novel ternary copper(II) complexes of the anti-inflammatory drug Fenoprofen with imidazole and caffeine

The copper(II) ternary complexes of the non-steroidal anti-inflammatory drug Fenoprofen (Hfen) and the biologically relevant molecules imidazole (im) and caffeine (caf) as auxiliary ligands were investigated as novel anti-inflammatory agents. The new copper(II) complexes with formula [Cu(fen) 2(im) 2] (1) and Cu 2(fen) 4(caf) 2 (2) were synthesized from the dinuclear complex [Cu 2(fen) 4(dmf) 2] and characterized by IR, UV-Vis, EPR spectral and elemental analysis. The molecular structure of complex 1 was determined by X-ray crystallography. Both complexes 1 and 2 present enhanced and prolongued anti-inflammatory properties against the parent drug calcium Fenoprofenate, Ca(fen) 2·2H 2O, with a better performance for complex 1. Ternary complexes are potential models for several mono and poly-nuclear metal enzymes. The measured superoxide dismutase (SOD) mimetic activities of the complexes indicated a higher SOD mimic activity for complex 2 (IC 50 of 0.24 μM) than complex 1 (IC 50 of 0.70 μM), and also than the native enzyme evaluated by the same method (IC 50 of 0.480 μM). The catecholase activity of the complexes toward the aerobic oxidation of 3,5-di-tert-butylcatechol (dtbc) onto 3,5-di-tert-butylquinone (dtbq) showed that both complexes have moderate catalytic oxidase activity.Fil: Agotegaray, Mariela Alejandra. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Instituto de Química del Sur. Universidad Nacional del Sur. Departamento de Química. Instituto de Química del Sur; ArgentinaFil: Dennehy, Mariana. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Instituto de Química del Sur. Universidad Nacional del Sur. Departamento de Química. Instituto de Química del Sur; ArgentinaFil: Boeris, Mónica Alejandra. Universidad Nacional de La Pampa. Facultad de Ciencias Veterinarias; ArgentinaFil: Grela, Maria Alejandra. Universidad Nacional de Mar del Plata. Facultad de Ciencias Exactas y Naturales. Departamento de Química; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Mar del Plata; ArgentinaFil: Burrow, Robert A.. Universidade Federal de Santa Maria; BrasilFil: Quinzani, Oscar Valentín. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Instituto de Química del Sur. Universidad Nacional del Sur. Departamento de Química. Instituto de Química del Sur; Argentin

Ni-thiosaccharinate complexes: Synthesis, characterization and DFT studies. Biological properties as superoxide dismutase mimetics and as anti-carcinogenic agents

This report describes the synthesis and characterization of two nickel thiosaccharinate complexes, [Ni(tsac)2(PPh3)2] (1) and [Ni(tsac)2(dppe)]·CH3CN (2), where tsac = thiosaccharinate anion, PPh3 = triphenylphosphane and dppe = bis(diphenylphosphanyl)ethane. Elemental analysis, FTIR, 1H, 13C and 31P NMR spectra and single crystal X ray diffraction studies of the complexes are presented. DFT optimizations of the two new compounds were performed in order to verify the FTIR vibrational assignations. The two nickel(II) thiosaccharinate complexes consist of mononuclear units in which the Ni atoms are the centre of square-planar coordination spheres, surrounded by two sulfur thiosaccharinate atoms and two phosphorous atoms from the phosphane ligands. In both complexes, the anions are mono-coordinated to the metal. In the [Ni(tsac)2(PPh3)2] structure, the phosphane moieties are located in trans position. In the [Ni(tsac)2(dppe)] structure, the dppe ligand chelates to the metal centre, as expected. Additionally, the superoxide dismutase (SOD) mimetic activity of the complexes was measured and it is reported herein. The effects of the complexes on cell proliferation were also studied and are described.Fil: Delgado, Fermin. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Instituto de Química del Sur. Universidad Nacional del Sur. Departamento de Química. Instituto de Química del Sur; ArgentinaFil: Nicova, Eva. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Instituto de Química del Sur. Universidad Nacional del Sur. Departamento de Química. Instituto de Química del Sur; ArgentinaFil: Agotegaray, Mariela Alejandra. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Instituto de Química del Sur. Universidad Nacional del Sur. Departamento de Química. Instituto de Química del Sur; ArgentinaFil: González Pardo, María Verónica. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Instituto de Ciencias Biológicas y Biomédicas del Sur. Universidad Nacional del Sur. Departamento de Biología, Bioquímica y Farmacia. Instituto de Ciencias Biológicas y Biomédicas del Sur; ArgentinaFil: Dorn, Viviana. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Instituto de Química del Sur. Universidad Nacional del Sur. Departamento de Química. Instituto de Química del Sur; ArgentinaFil: Burrow, Robert A.. Universidade Federal de Santa Maria; BrasilFil: Dennehy, Mariana. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Instituto de Química del Sur. Universidad Nacional del Sur. Departamento de Química. Instituto de Química del Sur; Argentin

Synthesis and Spectroscopic Characterization of Two New Thiosaccharinate Salts : Molecular Structure of Bis(triphenylphosphine)iminium thiosaccharinate, PNP(tsac)

We report the synthesis, FTIR, Raman and NMR spectroscopic features of bis(triphenylphosphine)iminium and tetrabutylammonium thiosaccharinates, PNP(tsac) and NBu₄(tsac) (tsac: thiosaccharinate anion, PNP: bis(triphenylphosphine)iminium). The molecular structure of the former compound was determined by X-ray diffraction methods. The salt crystallizes in the monoclinic P2₁/n space group with a = 9.6481(9), b = 29.258(3), c = 13.177(2) Å, β = 97.53(1)°, and Z = 4 molecules per unit cell. Slight but significant changes in the bonding structure of the thiosaccharinate anion as compared with those reported for the neutral molecule are observed.Centro de Química InorgánicaInstituto de Física La Plat

Activation of Peroxymonosulfate and Persulfate by Metal Loaded Mesoporous Catalysts for Orange G Dye Degradation

The main objective of this research was to study the catalytic activation of two different oxidants (potassium persulfate, PS and peroxymonosulfate, PMS) employing sulfate-based Advanced Oxidation Processes (AOPs). For this purpose, heterogeneous copper and cobalt catalysts were synthesized supported on MCM-41 mesoporous material. These catalysts were characterized by means of Atomic Absorption Spectroscopy (AA), X-ray diffraction (XRD), and Transmission Electron Microscopy (TEM). The metal charge of the catalysts ranged from 5% to 18%. The mesoporous arrangement was held after the metal loading and calcination, as shown by XRD patterns and TEM micrographs. The catalytic degradation of Orange G azo dye (Orange G: OG, disodium 7-hydroxy-8-[(E)-phenyldiazenyl]-1,3-naphthalenedisulfonate) was analysed, and the catalyst activities were determined in a batch reactor. The combination of PMS and higher metal-content Co-supported catalyst attained the best efficiency. In these conditions, the complete decolourization (100%) of the dye was achieved in the first minutes of reaction, while its mineralization reached after 4 h was 49%. Additionally, the catalytic activity of the Co/PMS system (a measure of the catalyst’s reusability) remained constant after three cycles of usage.Fil: Schlichter, Sofia. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Instituto de Química del Sur. Universidad Nacional del Sur. Departamento de Química. Instituto de Química del Sur; ArgentinaFil: Dennehy, Mariana. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Instituto de Química del Sur. Universidad Nacional del Sur. Departamento de Química. Instituto de Química del Sur; ArgentinaFil: Alvarez, Mariana. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Instituto de Química del Sur. Universidad Nacional del Sur. Departamento de Química. Instituto de Química del Sur; Argentin

Stable and efficient metal-biochar supported catalyst: degradation of model pollutants through sulfate radical-based advanced oxidation processes

This study focuses on the synthesis of metal-based biochar catalysts and their catalytic activation of peroxymonosulfate (PMS, HSO5−) for the degradation of three diferent wastewater model pollutants employing advanced oxidation processes (AOP). Iron, copper, and two diferent cobalt-based catalysts were prepared and evaluated. The catalysts were supported on a biochar obtained from the pyrolysis of woody pruning wastes. They were characterized by C, H, and N elemental analysis,X-Ray difraction (XRD), Fourier-transform infrared spectroscopy (FTIR), and scanning electron microscope (SEM). The metal content in each catalyst was determined by means of atomic absorption spectroscopy (AAS). The degradation reactions of benzoic acid (BA), catechol (C), and cinnamic acid (CA) were carried out in a lab scale batch glass reactor and were followed by UV -Visible spectroscopy (UV-Vis). A colorimetric technique was employed to verify the presence of oxidant during the reaction progress. The catalyst/oxidant optimal ratio was determined for the cobalt catalysts. The mineralization degree of the pollutants after the degradations was verifed by means of total organic carbon (TOC) content in the residual liquids. After 4 h of reaction, the maximum mineralization was reached when C was treated with a cobalt-based catalyst (> 80%), and its stability was evaluated through successive cycles of useFil: Delgado, Fermin. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Instituto de Química del Sur. Universidad Nacional del Sur. Departamento de Química. Instituto de Química del Sur; ArgentinaFil: Gutierrez, Victoria Soledad. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Planta Piloto de Ingeniería Química. Universidad Nacional del Sur. Planta Piloto de Ingeniería Química; ArgentinaFil: Dennehy, Mariana. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Instituto de Química del Sur. Universidad Nacional del Sur. Departamento de Química. Instituto de Química del Sur; ArgentinaFil: Alvarez, Mariana. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Instituto de Química del Sur. Universidad Nacional del Sur. Departamento de Química. Instituto de Química del Sur; Argentin