Synthesis, characterization and thermal behaviour of solid-state compounds of 2-methoxybenzoate with some bivalent transition metal ions

Solid-state M-2-MeO-Bz compounds, where M stands for bivalent Mn, Co, Ni, Cu and Zn and 2-MeO-Bz is 2-methoxybenzoate, have been synthesized. Simultaneous thermogravimetry-differential thermal analysis (TG-DTA), thermogravimetry, derivative thermogravimetry (TG/DTG), differential scanning calorimetry (DSC), X-ray powder diffractometry, infrared spectroscopy and complexometry were used to characterize and to study the thermal behaviour of these compounds. The results led to have information about the composition, dehydration, thermal stability and thermal decomposition of the isolated compounds.

Influence of the synthesis conditions on the characteristics and metal adsorption properties of the 3-(1,4-phenylenediamine)propylsilica xerogel

The hybrid 3-(1,4-phenylenediamine)propylsilica xerogel was obtained starting from two different organic precursor quantity (5 and 8 mmol) to 22 mmol of TEOS, in the synthesis. The xerogel samples were characterized by using CHN elemental analysis, N2 adsorption-desorption isotherms, infrared thermal analysis. The xerogel was used as metal sorbent for Cu2+, Cd2+ and Pb2+ in aqueous solution with concentration range of 10-3 to 10-5 mmol l-1. The quantity of organic precursor added in the synthesis influences the characteristics of the xerogel as morphology and thermal stability, as well as the metal adsorption capacity.

Thermal degradation behaviour of some polydithiooxamide metal complexes

The thermal decomposition behavior of the Fe(II), Co(II), Ni(II) and Zn(II) complexes of polydithiooxamide has been investigated by thermogravimetric analysis (TGA) at a heating rate of 20°C min-1 under nitrogen. The Coats-Redfern integral method is used to evaluate the kinetic parameters for the successive steps in the decomposition sequence observed in the TGA curves. The processes of thermal decomposition taking place in the four complexes are studied comparatively as the TGA curves indicate the difference in the thermal decomposition behavior of these complexes. The thermal stabilities of these complexes are discussed in terms of repulsion among electron pairs in the valence shell of the central ion and electronegativity effects.

Biheterocyclic ligands: synthesis, characterization and coordinating properties of bis(4-amino-5-mercapto-1,2,4-triazol-3-yl) alkanes with transition metal ions and their thermokinetic and biological studies

The Co(II), Ni(II) and Cu(II) metal ions complexes of Bis(4-amino-5-mercapto-1,2,4-triazol-3-yl) alkanes (BATs) have been prepared and characterized by elemental analysis, conductivity measurements infrared, magnetic susceptibility, the electronic spectral data and thermal studies. Based on spectral and magnetic results, the ligands are tetradentate coordinating through the N and S-atoms of BATs; six-coordinated octahedral or distorted octahedral and some times four-coordinated square planar were proposed for these complexes. Activation energies computed for the thermal decomposition steps were compared. The ligands and their metal complexes were tested in vitro for their biological effects. Their activities against two gram-positive, two gram-negative bacteria and two fungal species were found to vary from moderate to very strong.

Synthesis, characterization and thermal behaviour on solid pyruvates of some bivalent metal ions

Solid state M-L compounds, were M stands for bivalent Mn, Fe, Co, Ni, Cu, Zn and L is pyruvate, have been synthesized. Thermogravimetry and derivative thermogravimetry (TG/DTG), differential scanning calorimetry (DSC), X-Ray powder diffractometry, infrared spectroscopy, elemental analysis, and complexometry were used to characterize and to study the thermal behaviour of these compounds. The results led to information about the composition, dehydration, ligand denticity, and thermal decomposition of the isolated compounds.

Comparison of the dehydration kinetics of solid state compounds of 2-methoxybenzylidenepyruvate with some divalent metal ions

Divalent metal complexes of ligand 2-methoxybenzylidenepyruvate with Fe, Co, Ni, Cu and Zn as well as sodium salt were synthesized and investigated in the solid state. TG curves of these compounds were obtained with masses sample of 1 and 5mg under nitrogen atmosphere. Different heating rates were used to characterize and study these compounds from the kinetic point of view. The activation energy and pre-exponential factor were obtained applying the Wall-Flynn-Ozawa method to the TG curves. The obtained data were evaluated and the values of activation energy (Ea / kJ mol-1) was plotted in function of the conversion degree (α). The results show that due to mass sample, different activation energies were obtained. The results are discussed mainly taking into account the linear dependence between the activation energy and the pre exponential factor, where was verified the effect of kinetic compensation (KCE) and possible linear relations between the dehydrations steps of these compounds.

Synthesis, characterization and thermal behaviour of solid 2-methoxycinnamylidenepyruvate of some bivalent metal ions in CO2 and N2 atmospheres

Solid State M-2-MeO-CP compounds, where M stands for bivalent metals (Mn, Fe, Co, Ni, Cu and Zn) and 2-MeO-CP is 2-methoxycinnamylidenepyruvate, were synthesized. Simultaneous thermogravimetry and differential thermal analysis (TG-DTA), differential scanning calorimetry (DSC), elemental analysis and complexometry were used to establish the stoichiometry and to study the thermal behaviour of these compounds in CO2 and N2 atmospheres. The results were consistent with the general formula: M(L)2∙H2O. In both atmospheres (CO2, N2) the thermal decomposition occurs in consecutive steps which are characteristic of each compound. For CO2 atmosphere the final residues were: Mn3O4, Fe3O4, Co3O4, NiO, Cu2O and ZnO, while under N2 atmosphere the thermal decomposition is still observed at 1000 º C.

Thermal behaviour of succinic acid, sodium succinate and its compounds with some bivalent transitions metal ions in dynamic N2 and CO2 atmospheres

Thermal stability and thermal decomposition of succinic acid, sodium succinate and its compounds with Mn(II), Fe(II), Co(II), Ni(II), Cu(II) and Zn(II) were investigated employing simultaneous thermogravimetry and differential thermal analysis (TG-DTA) in nitrogen and carbon dioxide atmospheres and TG-FTIR in nitrogen atmosphere. On heating, in both atmospheres the succinic acid melt and evaporate, while for the sodium succinate the thermal decomposition occurs with the formation of sodium carbonate. For the transition metal succinates the final residue up to 1180 ºC in N2 atmosphere was a mixture of metal and metal oxide in no simple stoichiometric relation, except for Zn compound, where the residue was a small quantity of carbonaceous residue. For the CO2 atmosphere the final residue up to 980 ºC was: MnO, Fe3O4, CoO, ZnO and mixtures of Ni, NiO and Cu, Cu2O.

Faster for the master! : exploring issues of religious expression and alternative Christian identity within the Finnish Christian metal music scene

Populärkulturen har i dagens läge kommit att utgöra en allt mer viktig och central inspirationskälla för allt fler människors konstruktion av den egna religiösa identiteten även inom traditionella och institutionella kristna sammanhang. Denna avhandling belyser denna utveckling i ljuset av den finländska kristna metallmusik-kulturen - en sällsynt stark sammanblanding av protestantisk kristendom och en utpräglad och kontroversiell populärmusikform och dess kultur. Fokus riktas framför allt på hur den kristna metallmusik-kulturen blir meningsfull för sina medlemmar genom de sätt på vilka den konstrueras diskursivt, dvs. genom de sätt på vilka den representeras och talas om bland sina egna anhängare. Den diskursiva konstruktionen av den kristna metallmusik-kulturen utforskas på ett såväl bredare transnationellt som ett finländskt nationellt plan. Studien redogör även för den kristna metalmusikens och -kulturens huvudsakliga verbala, visuella och estetiska kännetecken. Uppbyggnaden och spridningen av dagens transnationella kristna metallmusik-kultur undersöks även i ljuset av det teoretiska konceptet scene. Avhandlingens centrala argument är att den kristna metallmusikscenen erbjuder sina medlemmar en mängd resurser för skapandet av ett alternativt och komplementärt religiöst uttrycksätt, religiös praxis och en alternativ kristen identitet.

Mening genom (kristen) metal

Kirja-arvio

The Structural Basis for inorganic Pyrophosphatase Catalysis and Regulation

Inorganic pyrophosphatases (PPases) are essential enzymes for every living cell. PPases provide the necessary thermodynamic pull for many biosynthetic reactions by hydrolyzing pyrophosphate. There are two types of PPases: integral membrane-bound and soluble enzymes. The latter type is divided into two non-homologous protein families, I and II. Family I PPases are present in all kingdoms of life, whereas family II PPases are only found in prokaryotes, including archae. Family I PPases, particularly that from Saccharomyces cerevisiae, are among the most extensively characterized phosphoryl transfer enzymes. In the present study, we have solved the structures of wild-type and seven active site variants of S. cerevisiae PPase bound to its natural metal cofactor, magnesium ion. These structures have facilitated derivation of the complete enzyme reaction scheme for PPase, fulfilling structures of all the reaction intermediates. The main focus in this study was on a novel subfamily of family II PPases (CBSPPase) containing a large insert formed by two CBS domains and a DRTGG domain within the catalytic domain. The CBS domain (named after cystathionine beta-synthase in which it was initially identified) usually occurs as tandem pairs with two or four copies in many proteins in all kingdoms of life. The structure formed by a pair of CBS domains is also known as a Bateman domain. CBS domains function as regulatory units, with adenylate ligands as the main effectors. The DRTGG domain (designated based on its most conserved residues) occurs less frequently and only in prokaryotes. Often, the domain co-exists with CBS domains, but its function remains unknown. The key objective of the current study was to explore the structural rearrangements in the CBS domains induced by regulatory adenylate ligands and their functional consequences. Two CBS-PPases were investigated, one from Clostridium perfringens (cpCBS-PPase) containing both CBS and DRTGG domains in its regulatory region and the other from Moorella thermoacetica (mt CBS-PPase) lacking the DRTGG domain. We additionally constructed a separate regulatory region of cpCBS-PPase (cpCBS). Both full-length enzymes and cpCBS formed homodimers. Two structures of the regulatory region of cpCBS-PPase complexed with the inhibitor, AMP, and activator, diadenosine tetraphosphate, were solved. The structures were significantly different, providing information on the structural pathway from bound adenylates to the interface between the regulatory and catalytic parts. To our knowledge, these are the first reported structures of a regulated CBS enzyme, which reveal large conformational changes upon regulator binding. The activator-bound structure was more open, consistent with the different thermostabilities of the activator- and inhibitor-bound forms of cpCBS-PPase. The results of the functional studies on wild-type and variant CBS-PPases provide support for inferences made on the basis of structural analyses. Moreover, these findings indicate that CBS-PPase activity is highly sensitive to adenine nucleotide distribution between AMP, ADP and ATP, and hence to the energy level of the cell. CBS-PPase activity is markedly inhibited at low energy levels, allowing PPi energy to be used for cell survival instead of being converted into heat.

Atomic level phenomena on transition metal surfaces

In this study we discuss the atomic level phenomena on transition metal surfaces. Transition metals are widely used as catalysts in industry. Therefore, reactions occuring on transition metal surfaces have large industrial intrest. This study addresses problems in very small size and time scales, which is an important part in the overall understanding of these phenomena. The publications of this study can be roughly divided into two categories: The adsorption of an O2 molecule to a surface, and surface structures of preadsorbed atoms. These two categories complement each other, because in the realistic case there are always some preadsorbed atoms at the catalytically active surfaces. However, all transition metals have an active d-band, and this study is also a study of the in uence of the active d-band on other atoms. At the rst part of this study we discuss the adsorption and dissociation of an O2 molecule on a clean stepped palladium surface and a smooth palladium surface precovered with sulphur and oxygen atoms. We show how the reactivity of the surface against the oxygen molecule varies due to the geometry of the surface and preadsorbed atoms. We also show how the molecular orbitals of the oxygen molecule evolve when it approaches the di erent sites on the surface. In the second part we discuss the surface structures of transition metal surfaces. We study the structures that are intresting on account of the Rashba e ect and charge density waves. We also study the adsorption of suphur on a gold surface, and surface structures of it. In this study we use ab-initio based density functional theory methods to simulate the results. We also compare the results of our methods to the results obtained with the Low-Energy-Electron-Difraction method.

Modelos de transferência de metal pesado na cana-de-açúcar adubada com composto de lixo urbano

A pesquisa aborda a reciclagem do composto de lixo urbano (CLU) como fertilizante alternativo na cana-de-açúcar e como solução social e ambiental ao acúmulo de resíduos sólidos nos centros urbanos. Utilizou-se da modelagem matemática para conhecer a dinâmica dos metais pesados, visando ao estabelecimento de critérios e procedimentos para o uso seguro do CLU, limitado pela quantidade desses elementos. Foram construídos modelos compartimentais a partir de dados de experimentos em condições controladas e parcialmente validados com dados de campo. Esse modelo descreveu a transferência de metais pesados no sistema solo-raiz-parte aérea para a cana-de-açúcar. Pôde-se concluir, pelas condições desta pesquisa, que o metal mais preocupante foi o níquel, pois demora, aproximadamente, três anos para ser atenuado no solo e chega em maior quantidade na parte aérea. Quanto aos fatores argila, óxidos e pH do solo, notou-se que, nos solos de maior poder tampão, a passagem da maioria dos metais foi mais lenta. Esse modelo pode tornar-se importante aliado na definição de leis de utilização do CLU, visando à não-contaminação ambiental, redução no acúmulo de lixo e de custos de produção.

Democracy begins at home : parenting, empathy, and adolescents' support for democratic values

Bakgrund Demokratiska samhällen är sårbara och historiskt sett sällsynta. Förutsättningarna för en fungerande demokrati innefattar mer än formella institutioner eller enbart frånvaron av diktatorer och extremgrupper. För att en regim skall fungera enligt demokratiska principer behövs medborgare som stöder demokratiska värden. Därför är det av vikt att förstå de processer som får individer att känna tilltro till demokratiska värden. Trots att man kan anta att stöd för sådana värderingar utvecklas som ett resultat av social inlärning är de konkreta omständigheterna som leder till ett dylikt lärande mindre uppenbara. Den klassiska litteraturen beträffande politisk socialisation lyfte fram föräldrarna som avgörande för de ungas medborgerliga fostran, men i moderna samhällen har föräldrarna sällan som en uttalad målsättning att försöka påverka sina barns nuvarande eller framtida politiska preferenser. Den föreliggande studiens mål var att fördjupa diskursen kring politisk socialisation gen om att analysera föräldraskapets betydelse för demokratiska värderingar hos ungdomar. Metod Den föreliggande studien utgick från två slumpmässiga urval. Det ena omfattade 1341 studerande, 17 år gamla, inom andra stadiets utbildning i tre regioner i Finland (södra, syd-västra och västra) och det andra 678 studerande, 16 år gamla vid studiens inledande, från den flamländska delen av Belgien. Studien innefattade frågeformulär som besvarades under skoltid. Resultat De centrala resultaten från studien kan sammanfattas i fyra punkter. För det första kunde empatiskt tänkande konstateras vara en god förklarande variabel för ungdomars demokratiska värderingar (Artikel 1). För det andra gav studien stöd för antagandet att stödjande föräldraskap är av betydelse för utvecklingen av empati under ungdomsåren (Artikel 2). För det tredje utvärderades empati, i relation till andra betydelsefulla variabler, som förklarande variabel för demokratiska värderingar (Artikel 3). För det fjärde gav den föreliggande studien bevis för att demokratiskt föräldraskap, både direkt och indirekt, är relaterat till demokratiska värderingar hos ungdomar. Sammanfattning Sammanfattningsvis visade den föreliggande studien hur föräldraskap både direkt och indirekt kan påverka demokratiska värderingar hos ungdomar och hur dessa resultat kunde användas för demokratisk samhällsfostran.

A decision support system for cost determination in grain storage facility operations

Many research works have being carried out on analyzing grain storage facility costs; however a few of them had taken into account the analysis of factors associated to all pre-processing and storage steps. The objective of this work was to develop a decision support system for determining the grain storage facility costs and utilization fees in grain storage facilities. The data of a CONAB storage facility located in Ponta Grossa - PR, Brazil, was used as input of the system developed to analyze its specific characteristics, such as amount of product received and stored throughout the year, hourly capacity of drying, cleaning, and receiving, and dispatch. By applying the decision support system, it was observed that the reception and expedition costs were exponentially reduced as the turnover rate of the storage increased. The cleaning and drying costs increased linearly with grain initial moisture. The storage cost increased exponentially as the occupancy rate of the storage facility decreased.