Englische Reichs- und Rechtsgeschichte : seit der Ankunft der Normannen im Jahre 1066 nach Christi Geburt /

"Tractatus de legibus et consuetudinibus regni Angliæ, tempore regis Henrici Secundi compositus, justicie gubernacula tenente illustri viro Ranulpho de Glanvilla": v. 2, p. [335]-473.

Synthetic, spectroscopic and X-ray crystallographic structural study of the monomeric [Cu(pysme)(sac)(MeOH)] and dimeric [Cu(6mptsc)(sac)](2) complexes [pysme = anion of the pyridine-2-carboxaldehyde Schiff base of S-methyldithiocarbazate, 6mptsc=the anio

New mixed-ligand copper(II) complexes of empirical formulas [Cu(pysme)(sac) (CH3OH)] and [Cu(6mptsc)(sac)](2) have been synthesized and characterized by conductance, magnetic, IR and electronic spectroscopic techniques. X-ray crystallographic structure analyses of these complexes indicate that in both complexes the copper(II) ions adopt a five-coordinate distorted square-pyramidal geometry with an N3SO donor environment. The Schiff bases are coordinated to the copper(II) ions as tridentate NNS chelates via the pyridine nitrogen atom, the azomethine nitrogen atom and the thiolate sulfur atom. In the monomeric [Cu(pysme)(sac)(MeOH)] complex, the saccharinate anion acts as a monodentate ligand coordinating the copper(II) ion via the imino nitrogen atom whereas in the dimeric [Cu(6mptsc)(sac)](2) complex, the sac anion behaves as a bridging bidentate ligand providing the imino nitrogen donor atom to one of the copper(II) ions and the carbonyl oxygen as a weakly coordinated axial ligand atom to the other Cu(II) ion. In both complexes, the copper(II) ions have distorted square-pyramidal environments. The distortion from an ideal square-pyramidal geometry is attributed to the restricted bite angles of the planar tridentate ligand. (C) 2004 Elsevier Ltd. All rights reserved.

Stereocontrol in complexes of cyclam-like macrocycles - influences of chirality

Enforcement of chirality upon a macrocyclic tetramine ligand structure by the introduction of an asymmetric pendent arm which does not significantly modify the macrocycle conformation has no significant effect upon the geometry of the coordination sphere of a bound metal. Where substitution engendering chirality does cause a change in the ligand conformation, in particular for a ligand of restricted stereochemistry, these effects can be much greater. Thus, conversion of 3,7-diazacycloheptane to a macrocycle via attachment of chiral sidearms and ring closure through a template reaction leads to cyclam derivatives with unusual coordination properties. (C) 2004 Elsevier Ltd. All rights reserved.

Filmes de nanopartículas de TiO2 e óxido de grafeno para fotocatálise

Dissertação (mestrado)—Universidade de Brasília, Instituto de Química, Programa de Pós-Graduação em Química, 2016.

Remoção de ibuprofeno de águas por oxidação catalítica

A ocorrência e destino de fármacos no ambiente aquático tem vindo a ser reconhecido como um problema emergente em química ambiental. Alguns compostos são resistentes à degradação nas estações de tratamento de águas residuais, ETARs, enquanto que outros, ainda que sofram degradação parcial, continuam a ser lançados nos meios aquáticos em quantidades apreciáveis. O Ibuprofeno, IB, um dos anti­ inflamatórios mais consumidos por todo o mundo, é um dos fármacos mais detectados no meio hídrico. Apesar dos sistemas de tratamento convencionais utilizados nas ETARs removerem até 90% do IB das águas residuais, é frequente o efluente descarregado conter ainda quantidades significativas deste poluente. A presença destes compostos no ambiente deve ser avaliada dado que possuem actividade biológica, mesmo a baixas concentrações. Os processos avançados de oxidação com peróxido de hidrogénio, na presença de catalisadores heterogéneos, permitem melhorar significativamente a remoção deste tipo de compostos em águas. Assim, foi objectivo deste trabalho o estudo da utilização de peróxido de hidrogénio como agente oxidante na remoção de IB em soluções aquosas, na presença de complexo de acetilacetonato de Ni (II) disperso em PDMS ou encapsulado em zeólitos NaY. Para o doseamento do fármaco em solução foi necessário desenvolver um método analítico consistindo de separação cromatográfica por HPLC e detecção e quantificação por UV-Vis. Não houve necessidade de recorrer a um passo de pré­ concentração de amostras por extracção em fase sólida (SPE) devido ao facto das concentrações de IB medidas ao longo do trabalho se terem sempre encontrado acima do LOQ (811 g L-1) do método analítico por injecção directa. Deste estudo pode concluir-se que o catalisador que apresentou melhor actividade catalítica e consequentemente maior remoção do IB em solução, foi o complexo de acetilacetonato de Ni (II), disperso em PDMS. Foi avaliada a influência, na conversão do IB, de diferentes parâmetros como a concentração inicial de peróxido de hidrogénio adicionada, quantidade de catalisador utilizada na mistura reaccional e temperatura. Os resultados permitiram concluir que os aumentos destes parâmetros conduzem a um aumento da actividade catalítica da reacção. A estabilidade catalítica do acetilacetonato de Ni (II)/PDMS, foi avaliada em ensaios consecutivos com a mesma amostra e nas mesmas condições, tendo-se observado que, após 8 utilizações, o catalisador perde ligeiramente a actividade (cerca de 11% do seu valor inicial). ABSTRACT: The presence and fate of pharmaceuticals in the aquatic environment is an emergent issue in environmental chemistry. Some compounds are poorly removed in wastewater treatment plants (WWTPs) while others, in spite of being partially removed, are still present in the WWTPs effluents and discharged in the receiving water bodies. Ibuprofen, IB, a non-steroid anti-inflammatory drug, is one of the most used and also one of the most frequently detected pharmaceutical contaminants in aquifers worldwide. Its removal by conventional wastewater treatment processes used in most WWTPs is usually high (up to 90% of incoming IB may be removed), but duet the high loads present in the influents, still significant amounts of IB usually leave the WWTPs in the treated effluents. The presence of these compounds in the environment must be evaluated considering that they may have some biological activity even at low concentrations. Advanced oxidation processes using hydrogen peroxide, in the presence of heterogeneous catalysts, provide a significantly improved removal of this type of substances from waters. Therefore, it was the aim of this work to study the use of hydrogen peroxide as an oxidizing agent in the removal of IB from aqueous solutions, in the presence of the catalyst nickel (II) acetylacetonate dispersed in PDMS or encapsulated in the NaY zeolite. For the quantification of the pharmaceutical in aqueous solution it was necessary to develop an analytical methodology based in chromatographic separation by HPLC and with UV-Vis detection and quantification. There was no need for a pre­concentration step of the samples by solid phase extraction (SPE) as the IB concentrations measured were always above the limit of quantification (811 bL1 of) the analytical method. The results from this study have shown that the catalyst which presented the best catalytic activity and the highest IB removal in solution was nickel (II) acetylacetonate dispersed in PDMS.

Sinthesys of heteroleptic zinc complexes for imaging in living cells

This thesis arose from an interest in luminescence heteroleptic bis(dipyrrinato) Zn (II) complexes and their application in cell imaging, due to their attractive and fascinating characteristics. Among imaging technologies, near-infrared fluorescence imaging has been dedicated immense attention owing to its low absorption and autofluorescence from surrounding organism and tissues in this specific spectral region, which minimize background interference and improve tissue depth penetration. An ideal near-infrared probe should be equipped with excellence chemical and photophysical properties. The target of this work is the synthesis of new heteroleptic bis(dipyrrinato) Zn (II) complexes having two main features: the emission in the near-infrared region and water-solubility. In order to purse these intentions, the low-energy emission was achieved by expansion of π-conjugation of simple dipyrrins using Knoevenagel condensation106 and tri(ethylene)glycol chain was introduced to increase the water solubility of the final complex. Photophysical and luminescent properties of the new complexes were investigated. Finally, with a view to a potential biological use of these new complexes in biological environments, their biocompatibility was tested using a cell viability assay: (3-(4,5-dimethylthiazol-2-yl)-2’-5’-diphenyltetrazolium bromide (MTT) assay.

cis-Bis[1,1-dibenzyl-3-(furan-2-ylcarbonyl)thioureato-kappa(2)O,S]copper(II)

In the title compound, [Cu(C(20)H(17)N(2)O(2)S)(2)], the Cu(II) atom is coordinated by the S and O atoms of two 1,1-dibenzyl-3-(furan-2-ylcarbonyl)thioureate ligands in a distorted square-planar geometry. The two O and two S atoms are mutually cis to each other. The Cu-S and Cu-O bond lengths lie within the ranges of those found in related structures. The dihedral angle between the planes of the two chelating rings is 26.15 (6)degrees.

The Ni-II, Hg-II and Cu-II complexes of 12-membered-ring mixed-donor macrocycles

The structures of diaqua(1,7-dioxa-4-thia-10-azacyclododecane)nickel dinitrate, [Ni(C8H17NO2S)(H2O)(2)](NO3)(2), (I), bis(nitrato-O,O')(1,4,7-trioxa-10-azacyclododecane)mercury, [Hg(NO3)(2)(C8H17NO3)], (II), and aqua(nitrato-O)(1-oxa-4,7,10-triazacyclododecane)copper nitrate, [Cu(NO3)(C8H19N3O)(H2O)]NO3, (III), reveal each macrocycle binding in a tetradentate manner. The conformations of the ligands in (I) and (III) are the same and distinct from that identified for (II). These differences are in agreement with molecular-mechanics predictions of ligand conformation as a function of metal-ion size.

On the structure, electrochemistry, and spectroscopy of the (N,N'-bis(2'-(dimethylamino)ethyl)-N,N'-dimethylpropane-1,3-diamine)copper(II) ion

The synthesis, spectroscopy, and electrochemistry of the acyclic tertiary tetraamine copper(II) complex [CuL(1)](ClO4)(2) (L(1) = N,N-bis(2'-(dimethylamino)ethyl)-N,N'-dimethylpropane-1,3-diamine) is reported. The X-ray crystal structure of [CuL(1)(OClO3)(2)] reveals a tetragonally elongated CuN4O2 coordination sphere, exhibiting relatively long Cu-N bond lengths for a Cu-II tetraamine, and a small tetrahedral distortion of the CuN4 plane. The [CuL(1)](2+) ion displays a single, reversible, one-electron reduction at -0.06 V vs Ag/AgCl. The results presented herein illustrate the inherent difficulties associated with the separation and characterization of Cu-II complexes of tertiary tetraamines, and some previously incorrect assertions and unexplained observations of other workers are discussed.

Macrocycle formation through carbon acid-formaldehyde condensation reactions of bis(propane-1,2-diamine)- and bis (2-methylpropane-1,2-diamine)-copper(II) ions

The reaction of the bis(1,2-diamine) copper(II) complexes of racemic propane-1,2-diamine (pn) and 2-methylpropane-1,2-diamine (dmen) with formaldehyde and nitroethane in methanol under basic conditions yields minor macrocyclic condensation products in addition to the major acyclic products. Where C-pendant methyl groups on the pair of coordinated diamines are in cis dispositions, the first -NH-CH2-C(CH3)(NO2)-CH2-NH- ring formation occurs at amine pairs distant from these C-methyl substituents, and further reaction to yield a macrocycle is not observed. However, where the C-methyl substituents are in trans dispositions, the chemistry proceeds to yield the macrocycle. Commencing with pn, trans-(6,13-diammonio-2,6,9,13-tetramethyl-1,4,7,10-tetraazacyclotetradecane)copper(II) perchlorate formed and crystallized in the space group P2(1)/n, with a 9.782(2), b 9.2794(6), c 17.017(4) Angstrom, beta 103.24(1)degrees. The copper ion is found in a square-planar environment, with the two methyl groups of the pn residues and the pairs of introduced pendant groups all in trans arrangements.

Coordination Chemistry of the (eta(6)-p-Cymene)ruthenium(II) Fragment with Bis-, Tris-, andTetrakis(pyrazol-1-yl)borate Ligands: Synthesis, Structural, Electrochemical, and CatalyticDiastereoselective Nitroaldol Reaction Studies

Novel [Ru(eta(6)-p-cymene)(kappa(2)-L)X] and [Ru(eta(6)-p-cymene)(kappa(3)-L)]X center dot nH(2)O complexes (L = bis-, tris-, or tetrakis-pyrazolylborate; X = Cl, N-3, PF6, or CF3SO3) are prepared by treatment of [Ru(eta(6)-p-cymene)Cl-2](2) with poly-(pyrazolyl)borate derivatives [M(L)] (L in general; in detail L = Ph(2)Bp = diphenylbis-(pyrazol-1-yl)borate; L = Tp = hydrotris(pyrazol-1-yl)borate; L = pzTp = tetrakis(pyrazol-1-yl)borate; L = Tp(4Bo) = hydrotris(indazol-1-yl)borate, L = T-p4Bo,T-5Me = (5-methylindazol-1-yl)borate; L = Tp(Bn,4Ph) = hydrotris(3-benzyl-4-phenylpyrazol-1-yl)borate; M = Na, K, or TI) and characterized by analytical and spectral data (IR, ESIMS, H-1 and C-13 NMR). The structures of [Ru(eta(6)-p-cymene)(Ph(2)Bp)Cl] (1) and [Ru(eta(6)-p-cymene)(Tp)Cl] (3) have been established by single-crystal X-ray diffraction analysis. Electrochemical studies allowed comparing the electron-donor characters of Tp and related ligands and estimating the corresponding values of the Lever E-L ligand parameter. The complexes [Ru(eta(6)-p-cymene)-(kappa(2)-L)X] and [Ru(eta(6)-p-cymene)(kappa(3)-L)]X center dot nH(2)O act as catalyst precursors for the diastereoselective nitroaldol reaction of benzaldehyde and nitroethane to the corresponding beta-nitroalkanol (up to 82% yield, at room temperature) with diastereoselectivity toward the formation of the threo isomer.

Copper(II) aza-bis(oxazoline) complex immobilized onto ITQ-2 and MCM-22 based materials as heterogeneous catalysts for the cyclopropanation of styrene

A copper(II) chiral aza-bis(oxazoline) homogeneous catalyst (CuazaBox) was anchored onto the external surface of MCM-22 and ITQ-2 structures, as well as encapsulated into hierarchical MCM-22. The transition metal complex loading onto the porous solids was determined by ICP-AES and the materials were also characterized by elemental analysis (C, N, H, S), FTIR, XPS, TG and low temperature N-2 adsorption isotherms. The materials were tested as heterogeneous catalysts in the benchmark reaction of cyclopropanation of styrene to check the effect of the immobilization procedure on the catalytic parameters, as well as on their reutilization in several catalytic cycles. Catalyst CuazaBox anchored onto the external surface of MCM-22 and ITQ-2 materials were more active and enantioselective in the cyclopropanation of styrene than the corresponding homogeneous phase reaction run under similar experimental conditions. This is due to the propylation of the acidic aza-Box nitrogen. HMCM-22 was nevertheless the best heterogeneous catalyst. Encapsulation of CuazaBox on post-synthesis modified MCM-22 materials led to low activities and enantioselectivities. But reversal on the stereochemical course of the reaction was observed, probably due to confinement effect. (C) 2013 Elsevier Inc. All rights reserved.

Mu-Chlorido-Bridged Dimanganese(II) complexes of the schiff base derived from [2+2] condensation of 2,6-diformyl-4-methylphenol and 1,3-bis(3-aminopropyl)tetramethyldisloxane: structure, magnetismo, electrochemical behaviour, and catalytic oxidation of secondary alcohols

The reaction of 2,6-diformyl-4-methylphenol with 1,3-bis(3-aminopropyl)tetramethyldisiloxane in the presence of MnCl2 in a 1:1:2 molar ratio in methanol afforded a dinuclear -chlorido-bridged manganese(II) complex of the macrocyclic [2+2] condensation product (H2L), namely, [Mn2Cl2(H2L)(HL)]Cl center dot 3H(2)O (1). The latter afforded a new compound, namely, [Mn2Cl2(H2L)(2)][MnCl4]center dot 4CH(3)CN center dot 0.5CHCl(3 center dot)0.4H(2)O (2), after recrystallisation from 1:1 CHCl3/CH3CN. The co-existence of the free and complexed azomethine groups, phenolato donors, mu-chlorido bridges, and the disiloxane unit were well evidenced by ESI mass spectrometry and FTIR spectroscopy and confirmed by X-ray crystallography. The magnetic measurements revealed an antiferromagnetic interaction between the two high-spin (S = 5/2, g = 2) manganese(II) ions through the mu-chlorido bridging ligands. The electrochemical behaviour of 1 and 2 has been studied, and details of their redox properties are reported. Both compounds act as catalysts or catalyst precursors in the solvent-free low-power microwave-assisted oxidation of selected secondary alcohols, for example, 1-phenylethanol, cyclohexanol, 2- and 3-octanol, to the corresponding ketones in the absence of solvent. The highest yield of 72% was achieved for 1-phenylethanol by using a maximum of 1% molar ratio of catalyst relative to substrate.

µ-Chlorido-bridged dimanganese(II) complexes of the schiff base derived from [2+2] condensation of 2,6-diformyl-4-methylphenol and 1,3-bis(3-aminopropyl)tetramethyldisiloxane: structure, magnetismo, electrochemical behaviour, and catalytic oxidation of secondary alcohols

The reaction of 2,6-diformyl-4-methylphenol with 1,3-bis(3-aminopropyl)tetramethyldisiloxane in the presence of MnCl2 in a 1:1:2 molar ratio in methanol afforded a dinuclear -chlorido-bridged manganese(II) complex of the macrocyclic [2+2] condensation product (H2L), namely, [Mn2Cl2(H2L)(HL)]Cl center dot 3H(2)O (1). The latter afforded a new compound, namely, [Mn2Cl2(H2L)(2)][MnCl4]center dot 4CH(3)CN center dot 0.5CHCl(3 center dot)0.4H(2)O (2), after recrystallisation from 1:1 CHCl3/CH3CN. The co-existence of the free and complexed azomethine groups, phenolato donors, mu-chlorido bridges, and the disiloxane unit were well evidenced by ESI mass spectrometry and FTIR spectroscopy and confirmed by X-ray crystallography. The magnetic measurements revealed an antiferromagnetic interaction between the two high-spin (S = 5/2, g = 2) manganese(II) ions through the mu-chlorido bridging ligands. The electrochemical behaviour of 1 and 2 has been studied, and details of their redox properties are reported. Both compounds act as catalysts or catalyst precursors in the solvent-free low-power microwave-assisted oxidation of selected secondary alcohols, for example, 1-phenylethanol, cyclohexanol, 2- and 3-octanol, to the corresponding ketones in the absence of solvent. The highest yield of 72% was achieved for 1-phenylethanol by using a maximum of 1% molar ratio of catalyst relative to substrate.

Fate of nickel ion in (II-III) hydroxysulphate green rust synthesized by precipitation and coprecipitation

In order to investigate the efficiency of sulfate green rust (GR2) to remove Ni from solution, GR2 samples were synthesized under controlled laboratory conditions. Some GR2 samples were synthesized from Fe(II) and Fe(III) sulfate salts by precipitation. Other samples were prepared by coprecipitation, of Ni(II), Fe(II) and Fe(III) sulfate salts, i.e., in the presence of Ni. In another sample, Ni(II) sulfate salt was added to pre-formed GR2. After an initial X-ray diffraction (XRD) characterization all samples were exposed to ambient air in order to understand the role of Ni in the transformation of the GR2 samples. XRD was repeated after 45 days. The results showed that Nious GR2 prepared by coprecipitation is isomorphous to Ni-free GR2, i.e. Ni is incorporated into the crystalline structure. Fe(II) was not replaced by Ni(II) in the crystalline structure of GR2 formed prior to exposure to solution-phase Ni. This suggests Ni was adsorbed to the GR2 surface. Sulfate green rust is more efficient in removing Ni from the environment by coprecipitation.