No description available.

The determination of complexes formed in weakly acidic aqueous solutions containing pentavalent vanadium as well as hexavalent molybdenum has proved diffi cui t due to slow equilibria and 1 imi ted sol ubi 1 i ty of especially the vanadium species. The formation of several different polynuclear complexes with a very varied molybdenum/vanadium ratio also complicates the interpretation of Potentiometrie data. In order to clarify the picture of complexes formed and provide starting points for equilibrium calculations single-crystal X-ray studies were made on crystals obtained from âqueous solutions. In addition, these studies can provide information on bonding conditions and possibly formation mechanisms for molybdovanadate polyanions. Crystals were synthesized by slow evaporation of aqueous solutions. Solutions with varied molybdenum/vanadium ratios and also varied pH values were prepared and used in the synthesis experiments. The X-ray measurements were performed with Philips PAILRED, Syntex P21 and Syntex R3 automatic diffractometers. All data sets were corrected for absorption. Five of the structures were solved with heavy-atom methods and one by direct methods. The structures were refined by computer-performed least-squares methods. The following crystals were obtained and structurally determined: NaV03•1.89H2O, which contains chains of VO5 trigonal bipyramids. Na4V2O7 (H2O)18 , containing discrete V2O74- anions which are completely surrounded by sodium-coordinated water molecules. Discrete molybdovanadate polyanions were found in the structures of the compounds Na6Mo6\/2O26 (H2O)16 , K7Mo8V5O40 • 8H2O, K8Mo4,V8O36 - 12H20 and K6 (V2 , Mo10) VO40 • 13H20. The last substance belongs to a class of compounds named 'heteropoly blues', which contain metal atoms in mixed-valence states, and has one unpaired electron on the polyanion. This compound was also investigated with electron spin resonance spectroscopy. The bonding configurations of oxygen atoms coordinated to molybdenum or vanadium are described and discussed. As the Mo4V8O368-, Mo8V5O407- (which is an isomer of the Keggin anion but has a quite different structure) and Mo6V2O266- anions all contain remnants of mononuclear molybdate and vanadate anions, it seems likely that these polyanions are formed mainly through the condensation of mononuclear species.An electrostatic model for the simulation of bond distances in polyions, starting with perfectly regular idealized models, is presented. / <p>Härtill 6 delar.</p> / digitalisering@umu

Submitted by Natalia de Souza Gonçalves (natalia.goncalves@ufpe.br) on 2016-09-23T11:47:49Z No. of bitstreams: 2 license_rdf: 1232 bytes, checksum: 66e71c371cc565284e70f40736c94386 (MD5) TESE RLA_Número 128 do PROTEN (1).pdf: 33719595 bytes, checksum: b30f5b4c6bf01a2a0e411971586424f3 (MD5) / Made available in DSpace on 2016-09-23T11:47:50Z (GMT). No. of bitstreams: 2 license_rdf: 1232 bytes, checksum: 66e71c371cc565284e70f40736c94386 (MD5) TESE RLA_Número 128 do PROTEN (1).pdf: 33719595 bytes, checksum: b30f5b4c6bf01a2a0e411971586424f3 (MD5) Previous issue date: 2016-02-25 / CAPES / FACEPE / O sítio arqueológico Lagoa Uri de Cima é uma lagoa intermitente, hoje seca, localizada no município de Salgueiro, estado de Pernambuco, Brasil. Durante as escavações realizadas no local entre os anos de 2010 e 2013, ossadas de mamíferos de grande porte, atualmente extintos, conhecidos como animais da megafauna, típicos do período quaternário,foram encontradas nas camadas mais profundas da lagoa. Este trabalho apresenta os resultados das datações por espectroscopia por ressonância paramagnética eletrônica (RPE) realizadas em amostras de dentes, provenientes das ossadas da megafauna encontradas na Lagoa Uri de Cima: 1 dente da espécie Hippidion bonaerensis, 2 dentes da família Toxodontidae, e 2 dentes de espécie Haplomastodon waring. Sedimentos em diferentes níveis estratigráficos da lagoa também foram analisados e datados pela técnica de luminescência opticamente estimulada (LOE). As doses acumuladas nas amostras de dentes e sedimentos foram determinadas, respectivamente, através dos métodos de doses aditavas e doses regenerativas. A taxa de dose anual foi estimada através da determinação dos teores de urânio, tório e potássio presentes nas amostras de dentes analisadas, bem como nos sedimentos do local. Para as amostras de dentes, as taxas de dose anual e idades foram estimadas através dos programas ROSY e DATA, que levam em consideração fatores como umidade e forma como o urânio foi incorporado pelos tecidos dentários, através dos modelos de captação: precoce (CP), linear (CL) e combinado (CC). Para as amostras de sedimentos, foi utilizado o programa AGE. Em relação a datação dos dentes, valores semelhantes de taxas de dose anual e idades para cada amostra foram obtidos através dos dois programas. As maiores e menores idades estimadas foram, respectivamente, para a espécie Hippidion bonaerensis: 20 ± 0,90mil anos (CP), 22 ± 0,70mil anos (CL),20± 0,80 mil anos (CC); e Haplomastodon waring: 13 ± 0,70mil anos (CP), 15 ± 0,80mil anos (CL),13 ± 0,80 kanos (CC). Em relação à datação dos sedimentos, os resultados obtidos estão dentro das perspectivas dos arqueólogos que estudam a formação geológica do sítio Lagoa do Uri de Cima, tendo sido estimado para o nível mais superficial da lagoa a idade de 3,6 ± 0,60mil anos e para o nível mais profundo 152 ± 16mil anos. Levandose em consideração os níveis estratigráficos em que os dentes da megafauna foram coletados, as idades estimadas para os dentes mostram uma coerência com as idades estimadas para os sedimentos coletados nos diferentes níveis estratigráficos da lagoa através da técnica de datação por LOE, permitindo uma maior confiabilidade para a datação dos sedimentos. Além disso, este trabalho contribuiu para a implantação da técnica de datação de dentes por espectroscopia RPE no laboratório do Grupo de Metrologia Arqueológica e Patrimonial (MAP) da Universidade Federal de Pernambuco (UFPE), o que permitirá auxiliar outras pesquisas arqueológicas e geológicas realizadas em outros sítios, além das realizadas no sítio Lagoa Uri de Cima. / the municipality of Salgueiro, in Pernambuco state, Brazil. During the excavations at this site, between the years 2010 and 2013, fossils of large mammal, presently extinct, also known as megafauna animals, typical of the quaternary period, were found in the lower layers on bottom of this lake. This study presents the results of electron spin resonance (ESR) spectroscopy dating performed on samples of teeth from megafauna fossils found in "Lagoa Uri de Cima" site: a Hippidion bonaerensis tooth, two Toxodontidae teeth, and two Haplomastodon waring teeth. Sediments from different stratigraphic levels of the lake were also analyzed and dated by optically stimulated luminescence (OSL). Cumulative doses from the teeth and sediments samples were determined, respectively, by additive doses and regenerative doses methods. The annual dose rate was estimated by the determination of the levels of uranium, thorium and potassium present in the teeth samples as well in the surrounding sediments. For the teeth samples, annual dose rates and ages were estimated via ROSY and DATA softwares, which take into account factors such as humidity and how uranium was incorporated by dental tissues through the uptake models: early (EU), linear (LU) and combined (CU). For sediments, the AGE software was used. Concerning the teeth dating, similar values from annual dose rates and ages were obtained from both programs. The highest and lowest estimated ages were, respectively, for the species Hippidion bonaerensis: 20 ± 0,90 thousand years (EU), 22 ± 0,70 thousand years (LU), 20 ± 0,80 thousand years (CU); and Haplomastodon waring: 13 ± 0,70 thousand years (EU), 15 ± 0,80 thousand years (LU), 13 ± 0,80thousand years (CU).. Regarding the dating of the sediments, the results are within the perspectives of the archaeologists that study the geological formation of the “Lagoa Uri de Cima” site, having been estimated for the most superficial level of the lagoon an age of3,6 ± 0,60 thousand years and for the most deeper level an age of 152 ± 16 thousand years. Taking into account the stratigraphic levels in which the megafauna teeth were collected, the estimated ages for these teeth show a consistency with the estimated ages for the sediment collected at different stratigraphic levels of the lagoon, through the LOE dating method, allowing a greater reliability for the dating of the sediments. Furthermore, this work contributed to the implementation of the RPE dating for teeth by the group of “Metrologia Arqueológica e Patrimonial” (MAP) at the “Universidade Federal de Pernambuco” (UFPE), which will support other archaeological and geological researches, in other sites, beyond the researches performed at "Lagoa Uri de Cima" site.

No description available.

The epilepsies are a heterogenous group of symptom complexes, whose common features is the recurrence of seizures. There is no certain therapy for epilepsy. In order to promote new advances for the prevention of epilepsy the molecular mechanism of epileptic activities should be clarified. In the present study the goal is to obtain information for molecular mechanism of epilepsy. To achieve this, molecular alterations from pentylenetetrazol (PTZ)-induced epileptic activities on rat brain tissue and cell membranes were investigated by Fourier Transform Infrared (FTIR) spectroscopy, Fourier Transform Infrared Microscopy and Atomic Force Microscopy (AFM). Moreover, the therapeutic role of an antiepileptic agent vigabatrin (VGB) on epileptic rat brain membranes were examined at molecular level. For better understanding of the action mechanism of PTZ and an antiepileptic drug VGB in cell membranes we firstly studied at model level using multilamellar liposomes (MLVs). We investigated PTZ-DPPC MLVs interactions in terms of lipid phase behavior, order and dynamics and nature of hydrogen bonding around its polar part, using Fourier Transform Infrared (FTIR) spectroscopy, Differential Scanning Calorimetry (DSC), Electronspin Resonans Spectroscopy (ESR) and Steady State Fluorescence Spectroscopy. According to our data, PTZ has no ability to interact with membrane lipids. On the other hand, the results of VGB-DPPC interactions showed that VGB strongly interact with the head group and/or the region near the head of membrane phospholipids. The molecular investigation of PTZ-induced epileptic activities revealed that PTZ-induced seizures cause a decrease in the lipid and protein content, membrane fluidity and glycogen level. They stimulate alterations in membrane packing and the secondary structure of proteins as well as lipid peroxidation. In addition, our results show the transcription of early genes following high dose PTZ administration. All these molecular alterations variatins are only resulted from the consequences of epileptic activities not from convulsant agent PTZ itself. The important finding is that, VGB restored some of the alterations by PTZ-induced epileptic activities on brain cell membrane. For instance, it restored membrane fluidity, lipid peroxidation, phospholipid degradation and changes in membrane organization. However, it was found that VGB has no significant effects on the changes in protein secondary structure.

<p><strong>Apstrakt je obrađen tehnologijama za optičko prepoznavanje teksta (OCR).</strong></p><p>Ispitan je uticaj heksanskih, etanolnih i etil-acetanih ekstrakata zrna soje i punomasnih hraniva od zrna soje, ekstrudiranog sojinog griza i hidrotermički tretiranog zrna soje, na termičku i katalitičku oksidaciju metil-linoleata primenom ESR spektroskopije i &quot;spin- traping&quot; tehnike. Utvrđeno je da ispitivani ekstrakti inhibiraju termičku i katalitičku oksidaciju metil-linoleata različitim mehanizmima antioksidativnog delovanja. Ustanovljeni antioksidativni efekti dovedeni su u vezu sa vrstama i sadržajem liposolubilnih (a-tokoferol, P-karotin, ukupni ksantofili) i neliposolubilnih antioksidanata (izoflavoni i fitinska kiselina) soje, odnosno u vezu sa termičkim tretmanima primenjenim u proizvodnji ovih hraniva. Ispitani su i uticaji primene različitih rastvarača (etil-acetat, etanol, acetonitril) na antioksidativne efekte ekstrakata neliposolubilnih antioksidanata punomasnih hraniva od zrna soje tokom termičke i katalitičke oksidacije sojinog ulja primenom ESR.</p> / <p><strong>Abstract was processed by technology for Optical character recognition (OCR).</strong></p><p>The influence of hexane, ethanol and ethyl acetate extracts of soybean grain and full-fat feeds of soybean grain, fullfat extruded soybean grits and hydrothermal treated soybean grain on the thermal and catalytic oxidation of methyl linoleate has been studied by ESR spectroscopy and spin-trapping method. It has been found that the investigated extracts inhibit the thermal and catalytic oxidation of methyl linoleate through different mechanisms of antioxidation action. The antioxidative effects found were related to the kinds and contents of soybean liposolubile (a-tocopherol, P-carotene, total xanthophyls) and nonliposolibile antioxidants (isoflavones, phytic acid), that is, they were put in relation to thermal treatments used in production of these feeds. The effects of the application of different solvents on the antioxidative actions of the extracts of nonliposolubile antioxidants of full-fat soybean feeds during thermal and catalytic oxidation of soybean oil have been studied by ESR.</p>

Στην παρούσα διατριβή μελετήθηκε η μοριακή δομή και καταλυτική ενεργότητα καταλυτών V2O5/TiO2 και CrOx/TiO2 για την αντίδραση καταλυτικής αναγωγής των NO με χρήση NH3 (αντίδραση SCR) καθώς και καταλυτών V2O5-Cs2SO4/SiO2 (καταλύτες υγρής υποστηριγμένης φάσης) για την αντίδραση οξείδωσης του διοξειδίου του θείου. Η μελέτη της μοριακής δομής έγινε με χρήση in-situ φασματοσκοπία Raman υπό διάφορες αέριες συνθήκες (O2, NH3/N2, NH3/NO/N2, NH3/NO/O2/N2, 8% H2O/O2/N2, SO2/N2, SO2/O2/N2) και θερμοκρασίες. Γενικά σε χαμηλές φορτίσεις, σχηματίζονται αρχικά απομονωμένα τετραεδρικά βαναδικά (ή χρωμικά) είδη και αυξανόμενης της φόρτισης οδηγούμαστε στο σχηματισμό διμερών/ ολιμερών αλυσίδων. Η in-situ φασματοσκοπία ESR έδωσε συμπληρωματικές πληροφορίες για την μοριακή δομή των V4+, Cr5+ & Cr3+ ειδών, σε οξειδωτικές και αναγωγικές συνθήκες. Τέλος, η μελέτη της συμπεριφοράς της συχνότητας αναστροφής (TOF) στους καταλύτες βαναδίου έδειξε ότι η αντίδραση επιταχύνεται κατά την παρουσία γειτονικών κέντρων βαναδίου. Οι καταλύτες βαναδίου / καισίου είναι οι μοναδικοί στο είδος τους καταλύτες υποστηριγμένης υγρής φάσης, όπου σε συνθήκες αντίδρασης, η ενεργός φάση βρίσκεται υγρή ή διαλυμένη σε ένα μη πτητικό διάλυμα που “φιλοξενείται” στους πόρους του υποστρώματος. Η in-situ μελέτη Raman έδειξε ότι το ενεργό είδος για την καταλυτική οξείδωση του SO2 είναι τα βαναδικά οξοθειϊκά σύμπλοκα (VO)2O(SO4)44-. / In this ph.d. thesis, the molecular structure and catalytic reactivity of V2O5/TiO2 and CrOx/TiO2 catalysts was studied for the SCR reaction. Furthermore, the molecular structure of the unique SLP catalysts V2O5-Cs2SO4/SiO2 was studied for the reaction of the oxidation of SO2. This study was performed by the use of in-situ Raman spectroscopy in various “real” gas conditions (O2, NH3/N2, NH3/NO/N2, NH3/NO/O2/N2, 8% H2O/O2/N2, SO2/N2, SO2/O2/N2) and temperatures. In general, at low loadings isolated species are formed, and as the loading is increased, the formation of dimeric / oligomeric species is favoured. In situ ESR spectroscopy gave supplementary information about the structure of V4+, Cr5+ & Cr3+ species in oxidative / reductive environment. The behaviour of TOF numbers showed that the reaction is accelerated in the presence of neighbour vanadium centers (in case of vanadium catalysts). Finally, the vanadium / caesium catalysts are the unique in their kind molten salt catalysts, were in reaction conditions, the active phase is in liquid form or dissolved in a non-volatile solution which is “hosted” inside the pores of the support. Activation of these catalysts, following exposure to a SO2/O2/N2 mixture, results in uptake of SO3 and formation of a pyrosulfate molten salt which – as shown by in-situ Raman spectroscopy – vanadium occurs predominantly in the form if binuclear (VO)2O(SO4)44- which are considered to be the active species for the reaction.