Dissertations / Theses on the topic 'ARSIWA'

Pit crater and pit crater chains associated to the volcano Arsia Mons on Mars have been mapped to analyse their spatial pattern and to conclude about their formation. For the mapping, high resolution satellite data gathered during the Mars Express mission were used. The spatial distribution of the pit craters was then compared with typical patterns of magmatic sheet intrusions within volcanoes as they are known from Earth. The results show that the pattern of the mapped pit craters and pit crater chains are in good agreement with these sheet intrusions and are therefore likely related to Martian sheet intrusions.
Kollapskratrar och kraterkedjor relaterade till vulkanen Arsia Mons på Mars har karterats för att analysera deras spatiala mönster och för att komma till slutsatser för deras tillblivelse. Högupplösta satellitbilder tagna av Mars Express-sonden har använts för karteringen. Fördelningen av de karterade kraterkedjorna jämfördes med typiska fördelningar av magmatiska gångbergarter från vulkaner på jorden. Resultaten visar att fördelningen av kollapskratrar och kraterkedjor överensstämmer enligt förväntningarna och påvisar en relation mellan kollapskratrar och magmatiska gångbergarter på Mars.

Accidental exposure to arsine (AsH₃) is possible in the semiconductor industry, metal mining, painting and herbicide preparation. First symptoms include intravascular hemolysis and dark red urine (hematuria), followed by abdominal pain, jaundice, and anemia. Exposure to AsH₃ is fatal in up to 25% of the reported human cases, usually caused by acute oliguric renal failure. The mechanism of AsH₃ toxicity in the kidney is unknown and was studied in vitro using established cell lines, primary cells, and isolated kidney. The hypothesis was that AsH₃ cause renal toxicity by its conversion to arsenite (AsIII). Renal cells were more susceptible to As(III) cytotoxic effects on ion homeostasis and cell integrity, but AsH₃ showed oxidative stress-like toxicity. Red blood cells were only susceptible to direct AsH₃ cytotoxicity. Hepatocytes, chosen because liver is also affected by AsH₃, were susceptible to both arsenicals. It was established that AsH₃ produce tissue specific toxicity. The toxicity of the AsH₃-produced hemolysate was also investigated. The complete hemolysate was toxic and this toxicity was associated with the soluble hemolytic products. AsH₃-induced nephrotoxicity was also studied in the isolated rat kidney. Unmetabolized AsH₃ was more toxic than hemolytic products in this system. Damage was found in the glomeruli, tubular epithelial cells, and vascular peritubular capillaries. Finally, the total amount of arsenicals produced by AsH₃ oxidation in the rat kidney and liver homogenates was determined. As(III) was formed four times as much compared to As(V) in the kidney. By comparison, the liver metabolized less than half of the arsenite formed by the kidney. In summary, in vitro systems were used to model tissue selectivity for AsH₃ toxicity and to investigate AsH₃ renal cytotoxicity. Red blood cells and hepatocytes were susceptible to unmetabolized AsH₃. AsH₃ was required to form As(III) to produce renal toxicity. The soluble hemolytic products produced by AsH₃ also contributed to the in vitro renal toxicity. Renal dysfunction produced by AsH₃ exposure (the cause for mortality), is caused by a combination of AsH₃-produced oxidative-stress toxicity and by cell integrity damage produced by As(III) formed from AsH₃ oxidation, and delivered to the kidney as soluble toxicants in the hemolysate.

This thesis reports a study of metal complexes of trimethyl-phosphine and trimethylarsine oxides. X-ray crystal structure determinations and other physical studies, notably infrared and nmr, were used to assess the factors that influence the stereo-chemistries of these complexes. It was observed that the compounds, (Mg(Me₃AsO)₅)(ClO₄)₂, (Ni(Me₃AsO)₅)(ClO₄)₂ and (Mg(Me₃PO)₅)(ClO₄)₂, readily adopt the square-pyramidal geometry. Two unusual features have been found in these complexes. The axial metal-oxygen bonds are consistently shorter than the corresponding basal metal-oxygen bonds, and the penultimate atoms (phosphorus and arsenic) of the basal ligands are coplanar with the square-base of the pyramid. This latter feature produces a large space in the region of the vacant sixth coordination site. The shorter axial metal-oxygen bond is discussed in terms of a stronger π interaction in the axial direction while the stability of the square-pyramidal geometry is explained in terms of electrostatic interactions between adjacent basal oxygen and arsenic atoms. Further evidence of this type of interaction was obtained from coulombic calculations. The crystal structures of (Mg(Me₃PO)₅)(ClO₄)₂ and (Mg(Me₃PO)₅H₂O)(ClO₄)₂ enable the influence of a sixth ligand on the coordination geometry to be assessed. The significance of the formation of the five-coordinate square-pyramidal geometry and the stereochemical effects of the binding of a sixth ligand are discussed in relation to the possible importance of these geometrical features in the biological function of calcium and magnesium ions. Comparisons between the donor powers of the phosphine oxide and arsine oxide are made. While arsine oxide has a greater σ donor strength, phosphine oxide is capable of a stronger π interaction. An interesting dinuclear structure was determined for a calcium arsine oxide complex. This complex, (Ca₂(Me₃AsO)₉)(ClO₄)₄, was found to be bridged by arsine oxide ligands. The different donor capacities of the terminal and bridging ligands are discussed in relation to X-ray and nmr results.

A series of complexes of general formula [OsX₃L₃] and [OsCl₃L₂L'] where X is a chloride or bromide and L and L' are different tertiary phosphines or arsines have been synthesised. The X-ray diffraction crystal structures of the complexes, mer-[OsCl₃(PMe₂Ph)₃], mer-[OsCl₃(PEt₂Ph)₃], mer-[OsBr₃(PPrⁿ₃)₃], mer-[OsCl₃(AsME₂Ph)₃], mer-[OsCl₃(PPrⁿ₂)₂(AsPrⁿ₃)], mer-[OsCl₃(PPrⁿ₂)₂(PEtPh₂)] and mer-[OsCl₃(P(OMe)₂Ph)₂(AsPrⁿ₃)] show them to have slightly distorted octahedral metal environments with the trans influence of the Group 15 ligands evident. The mer complexes have been studied electrochemically and all show two one-electron processes; an oxidation and a reduction process. Both couples involve the osmium metal centre. The one electron reduction step is rapidly followed by a chemical reaction resulting in the formation of an electroactive daughter product of general formula [OsCl₂L₃Y] where Y is a neutral coordinating ligand. The chemical reaction has been studied by kinetic and spectrochemical methods. The redox potentials of the mer species gives a good linear correlation with Tolmans electronic parameter for the tertiary phosphine. The electronic spectra of the compounds have been recorded and the peaks assigned to specific electronic transitions via the use of Extended Huckel Molecular Orbital Calculations. Electrochemical elucidation of these systems has shown that the redox potentials of the complexes are predominantly dependent on one ligand, namely the phosphine/arsine trans to the halide. The fac isomers also show two metal based one-electron couples at very different potentials from the analogous mer isomers. The reduction also produces an electroactive daughter product. The oxidation results in the isomerisation of the fac isomer to that of the mer isomer. The kinetic parameters of the reaction have been measured, and a mechanism is proposed for the isomerisation.

The purpose of this thesis is the study and characterization of 12 image of the volcano Arsia Mons captured by the Cassis camera on board of the ESA’s TGO satellite. Arsia is the second biggest volcano on Mars in terms of volume of materials erupted and is composed by a large summit caldera and 2 huge aprons on the side, one extending toward N/N-E and the other toward S/S-W. Cassis camera provides color image with a great resolution of 4.5 m/pixel covering about 3% of the martian surface. The fact that the image are colored helps understanding the different processes that have occurred during the Martian history. This study analyzed every image using different tools and programs such as QGIS for the morphological analysis, Google Mars for the general overview and HiView for small details study of the HiRISE image where it was possible. The final result present a description of every image pointing out every structure and morphology as well as the overview of the area because some of the structures cannot be analyzed on a detailed scale. At the end we described the potential genesis of some pit craters due to volcanic (such as lava tube or rill) or tectonic processes. Moreover, there are some pits that may result from different not yet described processes such as piping which is a particular type of subsurface water erosion of loose pyroclastic materials following a collapse on the surface, or magmatic dyke intrusion of mantle materials causing surface sinkholes. There are a lot of terrestrial analogues easy to study on site that will help understanding better the correlations between Earth and Mars. The conclusions needs further investigations that could be useful for future robotic and human missions to Mars and other rocky planetary bodies that experienced volcanism.

Doktorska disertacija “Model procene kvaliteta podzemne vode sapovećanim sadržajem arsena primenom fazi logike” urađena je kao rezultatpotrebe za istraživanjem mogućnosti primene fazi logike u savremenompristupu procene kvaliteta podzemnih voda. Imajući u vidu da ova tematikanije dovoljno istražena u našem okruženju i da joj nije dat odgovarajućiakcenat i težina, osnovni cilj disertacije je da se razrade optimalni modeli zaprocenu kvaliteta podzemnih voda sa povećanim sadržajem arsena.Disertacija pored teorijske dimenzije prezentuje i primenu evaluiranih fazimodela na primeru eksperimenatlno odabranog lokaliteta grada Zrenjanina.Razvijene modele je moguće transponovati na urbanim i ruralnim područjimauz odgovarajuće iteracije.
PhD Thesis “Model assessment for groundwater quality with elevated arseniccontent with application of fuzzy logic” was elaborated as a result of the needto explore the possibilities of application of fuzzy logic in the modernapproach of assessing the groundwater quality. Because this issue has notbeen sufficiently explored and it was not given proper emphasis and weight,the main aim of the dissertation is to develop optimal models for assessingthe groundwater quality with elevated arsenic content. Dissertation, besidestheoretical dimensions, presente and evaluate the implementation of thecreated models to the experimentaly selected locality of the city of Zrenjanin.The developed models can be transposed to the urban and rural areas withappropriate iteration.

Le suivi des zones côtières nécessite à la fois une bonne résolution spatiale, une bonne résolution spectraleassociée à un bon rapport signal sur bruit et enfin une bonne résolution temporelle pour visualiser deschangements rapides de couleur de l’eau.Les capteurs disponibles actuellement, et même ceux prévus prochainement, n’apportent pas à la fois unebonne résolution spatiale, spectrale ET temporelle. Dans cette étude, nous nous intéressons à la fusion de 2futurs capteurs qui s’inscrivent tous deux dans le programme Copernicus de l’agence spatiale européenne:MSI sur Sentinel-2 et OLCI sur Sentinel-3.Comme les capteurs MSI et OLCI ne fournissent pas encore d’images, il a fallu les simuler. Pour cela nousavons eu recours aux images hyperspectrales du capteur HICO. Nous avons alors proposé 3 méthodes : uneadaptation de la méthode ARSIS à la fusion d’images multispectrales (ARSIS), une méthode de fusion baséesur la factorisation de tenseurs non-négatifs (Tenseur) et une méthode de fusion basée sur l’inversion dematrices (Inversion)Ces 3 méthodes ont tout d’abord été évaluées à l’aide de paramètres statistiques entre les images obtenuespar fusion et l’image « parfaite » ainsi que sur les résultats d’estimation de paramètres biophysiques obtenuspar minimisation du modèle de transfert radiatif dans l’eau
Monitoring coastal areas requires both a good spatial resolution, good spectral resolution associated with agood signal to noise ratio and finally a good temporal resolution to visualize rapid changes in water color.Available now, and even those planed soon, sensors do not provide both a good spatial, spectral ANDtemporal resolution. In this study, we are interested in the image fusion of two future sensors which are bothpart of the Copernicus program of the European Space Agency: MSI on Sentinel-2 and OLCI on Sentinel-3.Such as MSI and OLCI do not provide image yet, it was necessary to simulate them. We then used thehyperspectral imager HICO and we then proposed three methods: an adaptation of the method ARSIS fusionof multispectral images (ARSIS), a fusion method based on the non-negative factorization tensors (Tensor)and a fusion method based on the inversion de matrices (Inversion).These three methods were first evaluated using statistical parameters between images obtained by fusionand the "perfect" image as well as the estimation results of biophysical parameters obtained by minimizingthe radiative transfer model in water

The rac- and meso- forms of “all carbon” 1,2-diphosphonium dications with the naphthalene -1,8-diyl backbone were synthesised in good yields and purity by double alkylation of the parent diphosphine (1,2-diphenyl-1,2-diphosphaacenaphthene) using strong alkylating agents. Pure rac- and meso- forms of 1,2-diphosphoniums were obtained diastereospecifically by using methyl triflate and trimethyloxonium tetrafluoroborate respectively. It was found that the equilibrium between the rac- and meso- forms at room temperature in acetonitrile solutions effectively depends on the anion present. A reaction mechanism which proceeds via a P-pentacoordinated intermediate was proposed for the epimerisation observed between the rac- and meso- forms in the presence of F⁻ donors in the solution. Reactivity of the new 1,2-dications towards a range of compounds (nucleophiles, bases) was examined and a series of new compounds including phosphine-phosphoniums and phosphonium-phosphine oxides were obtained. Cyclic and acyclic compounds belonging to a novel group of phosphine-arsine mixed peri-substituted acenaphthenes were synthesised by introducing arsenic and phosphorus to the acenaphthene ring, using stepwise lithiation and carbon-group 15 element coupling. All new compounds were fully characterised including single crystal X-ray diffraction. The effect of the peri-substitution by phosphorus moieties and mixed arsine-phosphine peri-substitution on the naphthalene ring was studied using the detailed structural data obtained for these systems.

Arsine gas is a potent hemolytic agent. Early work suggested glutathione depletion preceded, and oxygen required for hemolysis to occur. This study developed an in vitro model of arsine hemolysis, using the solubility of arsine gas in aqueous solutions. A total of 75% of the arsine was taken up into the cells within 5 minutes. Hemolysis occurred after 1-2 hours and reached 40-50%. Glutathione depletion occurred, but only after hemolysis reached its maximum. Increasing intracellular glutathione did not prevent hemolysis. The use of an intracellular chelator, monomethyldimercaptosuccinic acid did not prevent hemolysis. Hemolysis occurred in an oxygen excluding atmosphere but carboxyhemoglobin prevented hemolysis. Glutathione depletion is not a critical first step in arsine induced hemolysis. The interaction of arsine with the heme site of hemoglobin is critical to hemolysis. It is likely that a free radical intermediate of oxygen or arsine is the ultimate hemolytic agent.

A novel test system using isolated erythrocytes (red blood cells, RBCs) and arsine (AsH₃ gas dissolved in aqueous solution was characterized which allows for the quantitation of RBC exposure to AsH₃ in vitro and for in vitro study of the toxicity of AsH₃. AsH₃ was found to be rapidly and strongly associated with RBCs. Toxicity, measured as hemolysis, was time- and dose-dependent and exhibited a lag phase of about 30 minutes in both dog and rat RBCs. Hemolysis of dog RBCs was completely blocked by carbon monoxide preincubation and was reduced by pure oxygen. Sodium nitrite induction of methemoglobin (metHb) in intact rat RBCs decreased hemolysis, confirming the importance of hemoglobin in the mechanism of AsH₃-induced hemolysis. Spectrophotometric studies of the reaction of AsH₃ with purified dog hemoglobin revealed that AsH₃ reacted with reduced and oxygenated hemoglobin (HbO₂) to produce metHb and degraded Hb, characterized by gross precipitation of the protein. AsH₃ did not alter the spectrum of deoxyHb and did not cause degradation of metHb in oxygen, but bound to and reduced metHb in the absence of oxygen. Oxidative reactions as the putative cause of hemolysis were investigated. AsH₃ caused a slight decrease in cellular glutathione levels in dog RBCs, but only after hemolysis had reached maximum levels. Hydrogen peroxide (H₂O₂) was detected in aqueous solutions containing AsH₃ and HbO₂ or AsH₃ alone but not in intact red blood cells or lysates suggesting that cellular defenses were adequate to detoxify the amount formed. Additionally, high activity catalase or glutathione peroxidase added to solutions of HbO₂ and AsH₃ had little effect against AsH₃-induced damage. The differences between the visible spectra of HbO₂ treated with either AsH₃ or H₂O₂ suggest that two different degradative processes occur. Superoxide anion was not detected in AsH₃ mixtures and superoxide dismutase did not affect AsH₃-induced HbO₂ damage. Other antioxidants, mannitol, DMSO, ascorbate, and glutathione, had no effect against HbO₂ damage. These results indicate that the superoxide anion, the hydroxyl radical, and H₂O₂ are not responsible for AsH₃-induced HbO₂ damage and the subsequent hemolysis. A mechanism by which an arsenic species is the hemolytic agent is proposed.

Prisusutvo  arsena  u  podzemnim  vodama,  koje  se  primenjuju  za vodosnabdevanje stanovništva je globalan problem. Različiti  konvencionalniprocesi  se primenjuju  za  uklanjanje  arsena iz vode, uključujući koagulaciju iflokulaciju,  sorpciju,  membransku  filtraciju  i  jonsku  izmenu.  Uzimajući  uobzir relativnu nisku cenu, jednostavnu kontrolu procesa i održavanje, visokstepen uklanjanja arsena, sorpcija se smatra jednom od najpodobnijih tehnikaza uklanjanje arsena u tretmanu vode za piće. Premda su na tržištu dostupnirazličiti  sorbenti  za  uklanjanje  arsena,  postoji  potreba  za  iznalaženjem  irazvojem  novih  low-cost  sorbenata,  a  kojima  bi  se  pak  mogao  obezbeditivisok stepen uklanjanja oba oksidaciona oblika  arsena,  i  As(III) i As(V). Ciljovog rada bio je usmeren na sintezu i karakterizaciju novih sorbenata na bazigvožđa  i  mangana  odnosno  Fe-Mn  binarnog  oksida,  ispitivanje  njihovogpotencijala  za  uklanjanje  arsena  iz  vode  i  utvrđivanje  da  li  novosintetisanisorbenti po pitanju efikasnosti, mogu konkurisati postojećim komercijalnim iširoko korišćenim sorbentima u tretmanima voda.Metodom  precipitacije,  sintetisani  su  Fe-Mn  binarni  oksidi  sa  različitim Fe:Mn  molskim  odnosima  1:1,  3:1,  6:1  i  9:1,  dok  su  kombinacijom heterogene  nukleacione  tehnike  i  precipitacije,  sintetisana  i  četiri  sorbenta magnetnih  svojstava  (Mag,  Mag-Fe,  Mag-Mn,  Mag-FeMn).  Modifikacijom biopolimera  Chitosana  i  GAC,  sa  Fe-Mn  binarnim  oksidom,  razvijena  su preostala  dva  materijala  Chit-FeMn,  odnosno  GAC-FeMn.  Sintetisani sorbenti su karakterisani različitim tehnikama i metodama (SEM/EDS, XRD,FTIR, BET).Fizičko-hemijskom karakterizacijom sintetisanih sorbenata ustanovljeno je da se Fe-Mn binarni oksidi i magnetni materijali, karakterišu relativno velikim specifičnim  površinama  (109-300  m ² /g)  i  zapreminama  mezopora (0,144-0,403  cm ³ /g).  Velika  specifična  površina  i  razvijena  mikroporozna struktura uočena je kod GAC-FeMn (996 m² /g; 0,394 cm ^{3 /}g). U poređenju sa ostalim  sintetisanim  sorbentima,  Chit-FeMn  je  karakterisala  najmanja specifična  površina  i  zapremina  mezopora  (1,99  m² /g;  0,014  cm ³ /g).  XRD analiza  Fe-Mn  binarnih  oksida  ukazala  je  da  je  fazna  struktura  sintetisanih Fe-Mn  binarnih  oksida  slična  ferihidratu  dok  je  fazna  struktura  magnetnih materijala ukazala na prisustvo magemita.Ispitivanja kinetike sorpcionog procesa ukazala su da je mehanizam sorpcijeAs(III)  i  As(V)  na  sintetisanim  sorbentima  sloţena  kombinacija  površinskehemisorpcije,  koja  se  odvija  kroz  granični  sloj  čestica  sorbenata  i unutarčestične difuzije. Tome u prilog išli su i rezultati FTIR analize kojimaje potvrđeno da se sorpcija arsena na sintetisanim sorbentima ostvaruje krozinterakcije hidroksilnih grupa gvožđa prisutnih na površini sorbenata i arsena.Dodatno, pokazano je da se za razliku od sorpcije As(V), sorpcija As(III) na sorbentima  koji  pored  oksida  gvožđa  sadrže  i  okside  mangana  (Fe-Mn binarni oksidi, Mag-FeMn, Mag-Mn,Chit-FeMn i GAC-FeMn) odvija u dva koraka. U prvom koraku As(III) se oksiduje do As(V), dok u drugom koraku, oksidovani  As(V)  mehanizmom  ligandne  izmene  formira  komplekse  na površini ovih sorbenata.Afiniteti sorpcije Fe-Mn binarnih oksida (na osnovu K_d vrednosti)  za As(III) opadali su u nizu Fe-Mn 3:1 > Fe-Mn 1:1 > Fe-Mn 6:1 > Fe-Mn 9:1 odnosno kod  As(V):  Fe-Mn  6:1  >  Fe-Mn  3:1  >  Fe-Mn  9:1  >  Fe-Mn  1:1.  Kod magnetnih kompozita,  najveća K_d vrednost za As(III) i As(V) ustanovljena je kod  Mag-FeMn.  Uopšteno,  Kdvrednosti  za  As(III),  kod  magnetnih kompozita,  opadale  su  u  nizu:  Mag-FeMn  >  Mag-Mn  >  Mag  >  Mag-Fe, Slično, afinitet sorbenata za As(V), opadao je na sledeći način: Mag-FeMn > Mag  >  Mag-Fe  >  Mag-Mn.  U  poređenju  sa  neimpregniranim,  K_d vrednosti bile su daleko veće kod obloţenih materijala, Chit-FeMn i GAC-FeMn, što je ukazalo  na  značajan  doprinos  Fe-Mn  binarnog  oksida  adsorpcionom kapacitetu neimpregniranih medija za As(III) i As(V). U  odnosu  na  ostale  ispitivane  anjone,  najveći  uticaj  na  sorpciju  oba  oblika arsena  na  svim  sintetisanim  sorbentima  uočen  je  kod  fosfata,  dok  je  uticaj nitrata i hlorida, u svim slučajevima bio bez značaja. Uticaj ispitivanih anjona na  sorpciju  As(III)  i  As(V)  na  Fe-Mn  binarnim  oksidima,  magnetnim materijalima, Chit-FeMn kao i na sorpciju As(V) na GAC-FeMn, opadao je u nizu: fosfati > silikati > karbonati > sulfati > nitrati > hloridi. Slično, uticaj ispitivanih  anjona  na  sorpciju  As(III)  na  GAC-FeMn  je  opadao  na  sledeći način: fosfati > silikati > sulfati > karbonati > nitrati > hloridi.Primenom  smeše  NaCl-NaOH-NaOCl  odnosno  primenom  0,1  M  i  0,5  M  rastvora NaOH, ustanovljeno je da se sintetisani sorbenti mogu jednostavno i  efikasno  regenerisati  i  višestruko  primeniti,  što  je  od  izuzetnog  značaja  sa ekološkog i ekonomskog aspekta.  Najmanje smanjenje sorpcionog kapaciteta  i za As(III) i za As(V), nakon pet ciklusa sorpcije -desorpcije, ustanovljeno je kod binarnog oksida sa Fe:Mn molskim odnosom 3:1 i Mag-FeMn.  Na osnovu rezultata prikazanih u ovom radu, može se zaključiti da sintetisani sorbenti,  Fe-Mn  binarni  oksidi  i  magnetni  kompoziti,  posebno  Mag-FeMn, mogu  biti  efikasna  i  ekonomična  alternativa  skupim  komercijalnim sorbentima  i  drugim  sofisticiranim  tehnologijama.  Visok  oksidacioni  i sorpcioni kapacitet ovih  materijala, koji obezbeđuje istovremeno uklanjanje  oba oksidaciona oblika arsena daje veliku prednost ovim sorbentima i čini ih veoma  atraktivnim  i  obećavajućim  u  tretmanu  voda.  Dodatni  benefitmagnetnih  sorbenata,  pre  svega  Mag-FeMn,  ogleda  se  u  njegovoj jednostavnoj separaciji iz vodenog medijuma i recirkulaciji u sistemu. Glavne prednosti  sintetisanih  Chit-FeMn  i  GAC-FeMn,  ogledaju  se  u  mogućnosti  njihove primene kao efikasne filtracione ispune.
The  presence  of  inorganic  arsenic  in  groundwater  used  for  drinking  water supply  is  a  global  problem.  Different  techniques  such  as  oxidation, coagulation,  adsorption,  ion  exchange,  and  membrane  filtration  have  been developed  and  applied  for  arsenic  removal  from  aqueous  media.  Among these  technologies,   adsorption  is  regarded  as  one  of  the  most  promising approaches to remove arsenic from water because of its high efficiency, low cost, simplicity of operation. Although many sorbents for arsenic removal are available on the market, there is still a need to identify and develop new  lowcost  sorbents which are highly effective in removing both oxidation states of arsenic, As(III) and As(V). This dissertation therefore presents the synthesis and  characterization  of  ten  new  iron  and  manganese  based  sorbents specifically developed for effective As removal. The Fe- Mn binary oxides were prepared with Fe:Mn molar ratios of 1:1, 3:1,6:1 and 9:1, while four heterogeneous magnetic composites (Mag, Mag-Fe,Mag-Mn,  Mag-FeMn)  were  synthesized  by  combining  the  heterogeneous nucleation  technique  with  precipitation.  The  remaining  two  materials, Chit-FeMn  and  GAC-FeMn,  were  created  by  modifying  the  Chitosan  and GAC  biopolymers  with  Fe-Mn  binary   oxide  (Chit-FeMn  and  GAC-FeMn).Multiple  techniques  were  applied  to  determine  the  physical  and  chemical characteristics  of  the  resulting  sorbents  (including  SEM/EDS,  XRD,  FTIR and BET analyses). In order to establish which sorbents show  the greatest promise for application during  drinking  water  treatment,  the  sorption  capacity  of  the  sorbents,  theAs(III)  and  As(V)  sorption  mechanisms,  and  the  impact  of  various  factors relevant to arsenic sorption, including the regeneration potential and the reuse potential of the sorbents, were all investigated in  batch experiments. During the physical characterisation, the Fe-Mn binary oxides and magnetic materials  were  found  to  have  relatively  large  specific  surface  areas (109-300 m 2 /g) and mesopore volumes (0.144-0.403 cm 3 /g).  A large specific surface  area  and  microporous  structure  was  observed  for  GAC-FeMn  (996 m 2 /g;  0.394  cm 3 /g).  In  comparison  with  the  other  synthesized  sorbents,  Chit-FeMn has the smallest specific surface area and pore volume (1.99 m 2 /g; 0.014  cm 3 /g).  XRD  analyses  of  the  Fe-Mn  binary  oxides  indicated  that  the phase  structure  of  the  synthesized  Fe-Mn  binary  oxides  was  similar  to ferrihydrate,  while  the  phase  structure  of  the  magnetic  materials  showed  a good agreement with the XRD diffractogram of maghemite. Investigations into As sorption process kinetics have shown that the sorption mechanism  for  both  As(III)  and  As(V)  on  the  synthesized  sorbents  is  a combination  of  surface  hemisorption,  which  takes  place  through  the boundary  layer  of  sorbent  particles,  and  intracellular  diffusion.  The  FTIR analyses  confirmed  that  arsenic  sorption  was  accomplished  through  the interactions  of  the  hydroxyl  groups  of  iron  present  on  the  surface  of  the sorbents and arsenic. In contrast to the sorption of As(V), it was also shown that  As(III)  sorption  onto  sorbents  containing  manganese  oxides  (Fe-Mn binary  oxides,  Mag-FeMn,  Mag-Mn,  Chit-FeMn  and  GAC  -FeMn)  takes place in two steps. In the first step As(III) is oxidized to As(V), while in the second  step,  the  oxidized  As(V)  forms  complexes  on  the  surface  of  the sorbents via ligand exchange. The  Fe-Mn  binary  oxide  sorption  capacities  (expressed  as  Kd values)  for As(III)   followed the trend Fe-Mn 3:1 > Fe-Mn 1:1 > Fe-Mn 6:1 > Fe-Mn 9:1, whereas the  As(V) trend was Fe-Mn 6:1 > Fe-Mn 3:1 > Fe-Mn 9:1 > Fe-Mn 1:1. In the magnetic  composites, the largest  Kd value for As(III) and As(V) was  obtained  for  Mag-FeMn.  Generally,  the  Kd values  for  As(III)  in  the magnetic composites decreased in the series: Mag-FeMn > Mag-Mn > Mag > Mag-Fe.  Similarly,  the  affinity  of  the  sorbents  for  As(V)  was  as  follows: Mag-FeMn  >  Mag  >  Mag-Fe  >  Mag- Mn.  In  comparison  to  the  nonimpregnated  materials,  the  Kd values  were  much  higher  for  the   boated materials,  Chit-FeMn  and  GAC-FeMn,  demonstrating  the  significant advantage  Fe-Mn  binary  oxides  provide  in  increasing  As(III)  and  As(V)  adsorption capacities. One  of  the  most  problematic  limiting  factors  in  applying  adsorption technologies during drinking water treatment is the presence of other water constituents which interfere with the adsorption process.  Investigations into the inhibitory effect of competive anions on the adsorption of both forms of arsenic  revealed  that  phosphates  were  the  worst  offenders  in  terms  ofreducing  the  arsenic  removal  efficacy  of  sorbents  investigated.  From  the largest  to  the  smallest  negative  influence  of  the  anions  investigated,  for As(III)  and  As(V)  adsorption  on  Fe-Mn  binary  oxides,  magnetic  materials and Chit-FeMn, as well as As(V) adsorption on GAC-FeMn, the order was: phosphates > silicates > carbonates > sulfates > nitrates > chlorides, with the presence  of  the  latter  two  anions  proving  almost  irrelevant  to  the  As adsorption  process.  Similarly,  the  negative  influence  of  anions  on  As(III) sorption on GAC-FeMn was: phosphates > silicates > sulphates > carbonates > nitrates > chlorides. Another  issue  with  applying  adsorption  in  real  treatment  conditions  is  the need to regularly  regenerate and/or replace the spent sorbent. In this work, a simple  and  efficient  process  for  sorbent   rfegeneration  is  demonstrated.  This regeneration  process  can  be  applied  to  the  sorbents  investigated  multiple times, and uses an NaCl-NaOH-NaOCl mixture, or 0.1 M and 0.5 M NaOH solutions.  This  finding  is  of  great  importance  from  an  ecological  and economic point of view. The minimum reduction in the sorption capacity for both As(III) and As(V), after five sorption-regeneration cycles, was found in  the  binary  oxide  with  a  3:1  Fe:Mn  molar  ratio  and  Mag-FeMn.  Arsenic sorption  behaviour  was  also  investigated  using  real  groundwater  samples, with the results demonstrating the great potential of 3:1 Fe-Mn binary oxide and Mag- FeMn. However, Chit-FeMn and GAC-FeMn were less effective at adsorbing As from the groundwater samples.Based on the results presented in this dissertation, it can  be concluded that the synthesized  sorbents,  especially  the  Fe-Mn  binary  oxides  and  magnetic composites,  and  Mag-FeMn  in  particular,  can  be  efficient  and  economical alternatives  to  expensive  commercial  sorbents  and  other  sophisticated  As removal  technologies.  The  high  oxidation  and  sorption  capacity   of  these materials,  which  ensure  the  simultaneous  removal  of  arsenic  with  both oxidation states, is a large advantage for these sorbents and makes them very attractive  and  promising  for  application  in  drinking  water  treatment.  An additional  benefit of the magnetic sorbents, primarily Mag-FeMn, is the ease with  which  they  may  be  separated  from  the  aqueous  medium,  allowing  for simple  recirculation within a system. Similarly,  the main advantages of  the synthesized Chit- FeMn and GAC-FeMn are reflected in their application as effective filtration media.

Dans le cadre du formalisme algébrique U(p+1), nous exposons la méthode de construction d'un Hamiltonien vibrationnel lié à un ensemble de trois oscillateurs identiques. Une application aux molécules de stibine et d'arsine est entreprise. Nous introduisons un groupe supplémentaire K(3) inspiré d'un formalisme utilisé en physique nucléaire. Ce groupe K(3) fournit des étiquettes supplémentaires pour classer les niveaux d'énergie. Les valeurs propres de ses invariants distinguent alors les états locaux de la molécule. Puis nous étudions pour les molécules XY3 non planes, le couplage des modes d'élongation avec ceux de pliage. Nous présentons la construction d'un opérateur algébrique de couplage de ces différents degrés de liberté, ainsi que la confrontation de ce modèle avec les données expérimentales. Nous montrons comment l'introduction du nombre quantique de polyade K=2ne+np permet une modélisation du problème, particulièrement utile pour diagonaliser la matrice hamiltonienne.

Des dérivées des phosphine et arsine ont été caractérisées par spectroscopie de rotation et calculs ab initio. Le spectre de rotation de la méthylidynephosphine et de ses espèces isotopiques a été analysé. La constante sextique de distorsion centrifuge H a été déterminée. Une structure à l'équilibre a été calculée à partir de l'étude des spectres des états excites. Nous avons caractérisé pour la première fois un arsaalcyne non stabilise : l'éthylidynearsine. La constante de rotation b et les constantes de distorsion centrifuge jusqu'aux termes sextiques ont été déterminées. L'identification des spectres de sept espèces isotopiques a permis l'obtention d'une structure fiable. Les phosphines et arsines suivantes ont été caractérisées : vinylphosphine, vinyllarsine, éthylarsine et éthynylarsine. On montre l'utilité des calculs ab initio pour l'identification des spectres. La série complète des monohalogénophosphines a été analysée. En particulier la bromophosphine a pour la première fois été détectée. Les structures de quelques phosphines halogénées sont présentées. Enfin, le spectre de rotation du trifluorure d'arsenic AsF3 a été mesuré et le dédoublement des transitions k = 3 analysé.

Mars est un objet privilégié pour comprendre l'évolution d'une planète. Des témoins géologiques de son activité interne et des échanges surface-atmosphère sont préservés sur 4 Ga. Cette thèse étudie ces échanges au travers de la circulation des fluides dans la croûte. Le climat froid et sec de l'Amazonien (< 3 Ga) implique la condensation, sublimation et diffusion des espèces volatiles dans le régolithe. Ce paradigme est modifié par la découverte de l'importance de la convection d'air dans les sols poreux (aérothermalisme). Ce processus a été mis en évidence par l'imagerie thermique (Mars Odyssey/THEMIS) et la morphologie (e.g., Mars Express/HRSC) pour Cerberus Fossae et le volcan Arsia Mons. La période Hespérienne est marquée par la libération massive d'eau aboutissant à la formation des terrains chaotiques et des chenaux de débâcle. Nous proposons que ces objets résultent de la convection d'argiles. Cette hypothèse originale est corroborée par les détections de phyllosilicates (données CRISM et OMEGA).

Dans le cadre du formalisme U (p+1), nous construisons un Hamiltonien adapté aux modes d'élongation de molécules non planaires XY3 dont le groupe d'invariance géométrique est C3v. Cet Hamiltonien est ensuite couplé à deux Hamiltoniens possibles décrivant les modes de pliage de ces systèmes moléculaires : a) basé sur une approche du type U (p+1), un Hamiltonien de pliage est développé et l'interaction entre les modes d'élongation et de pliage est prise en compte par un opérateur de couplage de la résonance 2 :1, définit comme un opérateur de l'algèbre enveloppante de Us(4) x Ub(4) ; b) basé sur le formalisme standard des modes normaux, un Hamiltonien de pliage est formulé et l'interaction 2 :1 est prise en compte par le produit tensoriel d'un operateur de Us(4) avec un operateur standard normal pour le pliage. Ces formalismes sont alors appliqués aux molécules de stibine, phospine et d'arsine et comparés avec des études précédentes. Le nombre quantique de polyade permet une modélisation informatique du problème, particulièrement dans le processus de diagonalisation de la matrice hamiltonienne. Les programmes et les méthodes informatiques sont expliquées dans ce travail de thèse. La thèse est entièrement écrite en français avec une traduction équivalente en russe.

ROMERO, José Camilo Torres. Análise proteômica do plasma de pacientes portadores de síndrome mielodisplásica do tipo areb e arsa utilizando lectinas vegetais. 2016. 104 f. Tese (Doutorado em Bioquímica)-Universidade Federal do Ceará, Fortaleza, 2016.
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The myelodysplastic syndromes (Myelodysplastic Syndrome MDS) are diseases that occur when blood-producing cells are damaged bone marrow. This causes damage to one or moretypes of blood cells because its production is defective. MDS is considered a type of cancer and often end up being melodie acute leukemia (AML). The most common types of these syndromes are refractory anemia with ringed sideroblasts (ARSA) and anemia refractory with Excess Blasts (AREB). This study aimed to carry out the proteomic analysis of spinal cord serum of pediatric patients with any of the syndromes for the identification of proteins that are potential candidates for biological markers for evaluation, study and diagnosis of disease. The samples from ten patients with ARSA, tem with AREB and Ten healthy persons (control) were compared. These were subjected to immunodepletion, affinity chromatography with lectin galactose-linker selected by the anomeric recognition profile using chromatography in crosslinked hemicelulases, the selected lectins were subsequently immobilized in Sepharose 4B, the serum bone marrow samples were digested for subsequent analysis by mass spectrometry. The softwareExpressionE, based on protein expression levels, calculated the ratio between the selected groups, so 7 proteins have been identified as possible candidates for the biomarker syndromes. The overexpression of Vitronectin (VTN), fibrinogen (FGA), Pregnancy zone protein (PZP), Kininogen (KNG1) Immunoglobulin lambda chain (IGL), complement factor C4b (CB4) and Hemopexin (HPX) compared with the group control, seems to be an indicator of syndromes and were selected to form a panel of potential candidates for prognostic biomarkers. The only recognition by the frutalin to Clusterin (CLU) and Vitronectin in ARSA and Fibrinogen to AREB, do lectin a very useful tool to differentiate syndromes in proteomics studios.
As Síndromes Mielodisplásicas (SMD) são doenças que ocorrem quando as células produtoras de sangue são danificadas na medula óssea e esses danos podem afetar um ou mais tipos de células sanguíneas. Os tipos mais comuns de SMD são a Anemia Refratariacom Sideroblastos em Anel (ARSA) e Anemia Refratariacom Excesso de Blastos (AREB). Este trabalho teve como objetivo realizar a análise proteômica do plasmamedular de pacientes com SMD tipo ARSA e AREB, visando àidentificação de proteínas que sejam potenciais candidatas a marcadores biológicos para avaliação, estudo e diagnóstico dessas doenças. Amostras de plasmade dez pacientes com ARSA, dez com AREB e dez indivíduos saudáveis (Controle) foram selecionadas para análise proteômica. Estas foram submetidas à imunodepleção, cromatografia de afinidade com lectina α-D-galactose-ligante de sementes de Artocarpus incisa imobilizada em SepharoseTM 4B, concentradas e digeridas para posterior análise por espectrometria de massas. O programa ExpressionE, baseado nos níveis de expressão das proteínas, calculou a razão entre os grupos selecionados. Foram identificadas 7 proteínas potenciais candidatas a biomarcadores, tais como a Vitronectina (VTN), Fibrinogênio (FGA), Pregnancy zone protein (PZP), Cininogênio (KNG1), Cadeia de Imunoglobulina Lambda (IGLL1), Factor do complemento Cb4 (Cb4) e Hemopexina (HPX), por estarem super expressas no grupo de pacientes com SMD, em ambos os tipos, ao se comparar com o grupo controle (indivíduos sadios). Estas foram selecionadas para formar um painel de proteínas candidatas biomarcadoresde diagnóstico da SMD. O reconhecimento único por parte da frutalina para Clusterina (CLU) e Vitronectina em ARSA e Fibrinogenio para AREB, torna essa lectina, uma ferramenta muito útil para diferenciar as SMD em estudos proteômicos.

In this work, the doping processes of the SA type stepped Ge (100) surface by arsine (AsH3) and diborane (B2H6) gas flow have been simulated seperately by the possible adsorption and dissociation models. The most stable adsorption and dissociation models of AsH3 and B2H6 on stepped Ge(100) surface have been determined by the local minimum total energy and/or binding energy calculations based on Hartree-Fock Theory. The present calculations have shown that, the step region (both up and down terraces) of the stepped Ge (100) surface has the most attractive sites for the initial adsorption stages of the gas molecules. It has been found that the thermodynamically preferred structures in the dissociation paths of arsine and diborane are the same
AsH3 , BH3 (fragment of diborane), AsH2 and BH2 products prefer to be bounded to a single surface Ge atom, but AsH and BH prefer to be bridged between two adjacent surface Ge atoms. It has been also found that, at the first step of the adsorptions, AsH3 can only dissociate to AsH2, but BH3 can dissociate to both BH2 and BH. This remarkable result has showed that dissociation of BH3 on Ge(100) surface can be easier than AsH3&rsquo
s. According to the optimization calculations, the dissociation path has started with the adsorption of AsH3 (or BH3) on the electron deficient side (buckled down) of the Ge dimer bond and ended with the occupation of the empty Ge sites in the surface layers by As (or B) atom substitutionally. In the present work, the beginning of the n &ndash
(or p-) type doping of the stepped Ge(100) surface has been illustrated by the As (or B) electronic states obtained in the optical energy gap of Ge very close to HOMO (or LUMO) energy edge.

Organoarsenicals such as methylarsenical methylarsenate (MAs(V)) and aromatic arsenicals including roxarsone (4-hydroxy-3-nitrophenylarsenate or Rox(V)) have been extensively used as an herbicide and growth enhancers in animal husbandry, respectively. They undergo environmental degradation to more toxic inorganic arsenite (As(III)) that contaminates crops and drinking water. We previously identified a bacterial gene (arsI) responsible for aerobic MAs(III) demethylation. The gene product, ArsI, is a Fe(II)-dependent extradiol dioxygenase that cleaves the carbon-arsenic (C-As) bond in MAs(III) and trivalent aromatic arsenicals. The objective of this study was to elucidate the ArsI mechanism. Using isothermal titration calorimetry, we determined the dissociation constants (Kd) and ligand-to-protein stoichiometries (N) of ArsI for Fe(II), MAs(III) and aromatic phenyl arsenite. Using a combination of methods including chemical modification, site-directed mutagenesis, and fluorescent spectroscopy, we demonstrated that amino acid residues predicted to participate in Fe(II)-binding (His5-His62-Glu115) and substrate binding (Cys96-Cys97) are all involved in catalysis. Finally, the products of Rox(III) degradation were identified as As(III) and 4-hydroxy-2-nitrophenol, demonstrating that ArsI is a dioxygenase that incorporates one oxygen atom from dioxygen into the carbon and the other to the arsenic to catalyze the cleavage of the C-As bond. These results augment our understanding of the mechanism of this novel C-As lyase.

Recurrence rate is often used to describe volcanic activity. There are numerous documented ex- amples of non-constant recurrence rate (e.g. Dohrenwend et al., 1984; Condit and Connor, 1996; Cronin et al., 2001; Bebbington and Cronin, 2011; Bevilacqua, 2015), but current techniques for calculating recurrence rate are unable to fully account for temporal changes in recurrence rate. A local–window recurrence rate model, which allows for non-constant recurrence rate, is used to calculate recurrence rate from an age model consisting of estimated ages of volcanic eruption from a Monte Carlo simulation. The Monte Carlo age assignment algorithm utilizes paleomagnetic and stratigraphic information to mask invalid ages from the radiometric date, represented as a Gaussian probability density function. To verify the age assignment algorithm, data from Heizler et al. (1999) for Lathrop Wells is modeled and compared. Synthetic data were compared with expected results and published data were used for cross comparison and verification of recurrence rate and volume flux calculations. The latest recurrence rate fully constrained by the data is reported, based upon data provided in the referenced paper: Cima Volcanic Field, 33 +55/-14 Events per Ma (Dohren- wend et al., 1984), Cerro Negro Volcano, 0.29 Events per Year (Hill et al., 1998), Southern Nevada Volcanic Field, 4.45 +1.84/-0.87 (Connor and Hill, 1995) and Arsia Mons, Mars, 0.09 +0.14/-0.06 Events per Ma (Richardson et al., 2015). The local–window approach is useful for 1) identifying trends in recurrence rate and 2) providing the User the ability to choose the best median recurrence rate and 90% confidence interval with respect to temporal clustering.

Kyoto University (京都大学)
0048
新制・課程博士
博士(地域研究)
甲第10992号
地博第9号
新制||地||3(附属図書館)
UT51-2004-G839
京都大学大学院アジア・アフリカ地域研究研究科アフリカ地域研究専攻
(主査)助教授 重田 眞義, 教授 島田 周平, 助教授 木村 大治
学位規則第4条第1項該当

The purpose of this study was to explore the effects of acculturation on the parent and teacher ratings of non-clinical Mexican American children's behavior, using the BASC Parent Rating Scale-C (PRS-C ) and the Teacher Rating Scale-C (TRS-C ). One hundred twenty-three children of Mexican descent (ages 6-11) attending Texas public schools were rated by their parents and teachers. Parent acculturation level was measured using the Acculturation Rating Scale for Mexican Americans-II. Parents were assigned to High, Medium or Low acculturation groups based on a combination of linear acculturation levels (Part 1) and obtained typologies (Part 2). Parent acculturation level was then assigned to TRS-C data creating matched-rater pairs (PRS-C and TRS-C of same child) for use in this study. Internal consistency reliabilities for the Total Mexican American sample's Teacher Rating Scale-C (TRS-C) were more similar to the published BASC general norms than the Total Mexican American sample's Parent Rating Scale-C (PRS-C ) on six of the nine clinical scales investigated and on all three of the shared adaptive scales. The most striking internal consistency result emerged when the sample was subdivided by acculturation, the High acculturation TRS-C Conduct Problems scale showed no cohesion of items for this sample (.00). Comparison of the Total, High, Medium, and Low groups' obtained distributions on each of the 16 selected scales of the PRS-C and TRS-C to the published BASC general norms revealed: 1) six significant differences of potential clinical relevance on the PRS-C scales, and 2) thirteen significant differences of potential clinical relevance on the TRS-C scales. Both parents and teachers rated the children as demonstrating less maladaptive symptoms on the Aggression, Depression, Hyperactivity, and Behavioral Symptom Index. Only parents reported lower Adaptability and Adaptive Skills scores. And only teachers of the High acculturation group reported higher Adaptability scores. No systematic influence of acculturation was present among any of the 16 selected scales. However, the parents and teachers of the High acculturation subgroup did have more moderate correlations than the Medium and Low groups combined.

Dans un programme de recherche de nouveaux heterocycles intercalants de l'adn, nous avons observe une totale regioselectivite de substitution electrophile en position 4 de la 3-aminoacridine. Ce resultat a ete utilise pour la synthese de bases de troger derivees d'aminoacridine. Les acridines etant connues pour leur affinite pour l'adn, les bases de troger correspondantes pourraient egalement interagir avec l'adn et grace a leur chiralite, leurs enantiomeres pourraient presenter differents modes d'association avec la macromolecule. Un enantiomere de la molecule pourrait alors reconnaitre specifiquement une conformation b ou z de l'adn. Une serie de bases de troger polyfonctionnalisees a ete synthetisee. Les proprietes physico-chimiques (rx, uv, rmn, pka) des composes les plus interessants ont ete etudiees. Le dedoublement partiel de deux bases de troger, 1 et 2, a ete partiellement realise par cristallisation de sels diastereomeres, donnant 80% d'exces enantiomerique. L'etude de l'interaction du compose 2 avec l'adn de thymus de veau a ete realisee par partition eau-butanol. L'enantiomere 2 (+) est extrait dans la phase butanolique avec des exces enantiomeriques atteignant 70% pour 15% de produit extrait. L'enantiomere (-) reste dans la phase aqueuse complexe a l'adn (etude par dichroisme circulaire). Cette etude a clairement montre une association preferentielle de l'enantiomere 2 (-) a l'adn

The purpose of this study was to determine relationships between acculturation level, generational status, and gender with acculturative stress. Acculturation level was determined by the Acculturation Rating Scale for Mexican Americans-II (ARSMA-II) and acculturative stress was determined by the Societal, Attitudinal, Familial and Environmental Acculturative Stress Scale-Children's Version (SAFE-C). Subjects included 1268 Hispanic children ages 11-15. In order to validate the usefulness of the ARSMA-II with this sample, analyses were conducted between acculturation level and generational status. The Pearson product moment correlation (r=.44) and the ANOVA between the mean acculturation score and generational status were significant. However, the mean acculturation score from this study was considerably lower than the ARSMA-II score; therefore, new acculturation levels were developed to establish local adolescent norms for the ARSMA-II. All analyses involving acculturation levels were conducted using both the ARSMA-II and new acculturation levels because 300 subjects were reclassified with the new norms. Significant results were similar using both acculturation levels; however, there were more between group differences using the new acculturation levels. It was hypothesized that as acculturation level increased toward the Anglo culture, acculturative stress would decrease. The one-way ANOVA confirmed this relationship. It was also hypothesized that as generational status increased, acculturative stress would decrease. A one-way ANOVA also supported this hypothesis. In order to replicate previous findings on gender, a one-way ANOVA was conducted with acculturative stress and acculturation level. Results for both were non-significant. Overall findings indicate that generational status and acculturation level have a significant impact on acculturative stress in Hispanic children; however, gender does not seem to be a factor. Findings emphasize the importance of addressing cultural issues in the assessment, intervention, and treatment of acculturating Hispanic children. Furthermore, the ARSMA-II appears to be a useful instrument in assessing acculturation level in young adolescent Hispanics though new local adolescent norms for the ARSMA-II were developed from this study.

L'énergie éolienne est une des composantes d'une politique énergétique permettant de réaliser un développement durable. Ces dernières années, des parcs éoliens offshore ont été installés. Ces parcs bénéficient d'un vent plus fort et plus régulier en mer que sur terre. Pour un choix judicieux des lieux d'implantation des parcs éoliens, il est nécessaire de disposer d'une cartographie du potentiel éolien. Ces cartes doivent être à haute résolution spatiale pour détecter les variations du potentiel à l'échelle d'un parc éolien. La cartographie du potentiel éolien se fait au travers de la description de la variation spatiale des paramètres statistiques caractérisant la climatologie du vent. Pour une estimation précise de ces paramètres statistiques, il est nécessaire d'avoir des mesures de vitesse et de direction du vent à haute résolution temporelle. Cependant, aucune source de données, actuelle, n'allie la haute résolution spatiale et la haute résolution temporelle. On propose une méthode de fusion de données permettant de tirer profit de la haute résolution spatiale de certains instruments de télédétection (les radars à ouverture synthétiques) et de la haute résolution temporelle d'autres instruments de télédétection (les radars diffusomètres). La méthode de fusion est appliquée à un cas d'étude et les résultats sont évalués. Les résultats montrent la pertinence de la fusion de données pour la cartographie du potentiel éolien offshore.

Critiques of the new technology in agriculture have expressed its class, technological, regional and crop bias. They call for expanded research to cover more crops suited to ecologically marginal areas, agrarian reform to distribute its benefits and the generation of mechanical technology and institutions amenable to the poor. Ethiopia experienced both the dissemination of the new technology (first in 1967 in the Arsi Region and as of 1970 in limited parts of the country as a whole) and a radical redistributive agrarian reform (since 1975) aiming at a socialist transition in agriculture. A micro level analysis of output and input in 30 farms disaggregated into the pre and post technology period on the one hand and poor/lower middle and rich peasants on the other is built upon to assess the effect of the new technology on production, factor productivity, the social differentiation of the peasantry, changes in the form and extent of the marketed surplus and prices in 1966-1975 (post technology, pre-agrarian reform) and 1975-1980 (post new technology and post agrarian reform) in the Arsi Region. This is further extended to Ethiopian agriculture as a whole including the countrywide redistributive impact of the reform, government intervention in marketing and the terms of trade. The study argues that given the non-feudal, non-capitalist agrarian class formation in rainfed single cropping 'land surplus' agrarian economy, redistributive agrarian reform, state intervention with high marketing cost and the accumulation of merchant capital not reinvested into agriculture meet neither the redistributive nor the accumulation objectives of development.

Chez les ruminants, l’Acidose Ruminale SubAiguë (ARSA) est une maladie d’origine nutritionnelle qui fait suite à une perturbation des fermentations microbiennes et à une acidité anormale du compartiment ruminal. L’installation chronique de ce dysfonctionnement digestif peut avoir une incidence néfaste sur l’efficacité de production et la santé des animaux. À l’échelle de l’individu ou du troupeau, elle aura pour conséquences des retombées économiques négatives pour l’éleveur. Un des problèmes majeurs de cette maladie est qu’elle ne se manifeste pas par des signes cliniques spécifiques. A l’heure actuelle, seul le pH ruminal permet d’objectiver la maladie même si aucun indicateur de pH ne fait l’unanimité, notamment du fait des variabilités importantes liées à la technique de mesure du pH d’une part et à la susceptibilité des animaux d’autre part. Dans ce contexte, cette thèse a eu pour objectif d’améliorer le diagnostic individuel de l’ARSA chez la vache laitière en développant une approche multiparamétrique applicable sur le terrain. Nous proposons de nouveaux indicateurs issus de cinétiques de pH mesuré de façon non-invasive avec des bolus intra-ruminaux. Ces nouveaux indicateurs relatifs, calculés quotidiennement sur les cinétiques normalisées sur 0 (NpH), sont le temps passé sous NpH <-0,3, l’écart type et l’amplitude. Ils permettent de pallier les fortes sources de variabilité et présentent l’intérêt d’être transposables entre études et sont plus précis pour caractériser l’ARSA. Parallèlement, nous avons développé des modèles multiparamétriques composés de plusieurs paramètres mesurés simultanément dans différents compartiments biologiques (lait, fèces, salive, sang, urine) ou sur l’animal (comportement). Leur capacité de prédiction de l’ARSA a ensuite été évaluée en élevage. Certains modèles incluant des paramètres périphériques au rumen et simples à mesurer sur le terrain présentent une bonne sensibilité (concentration en urée dans le lait, en bicarbonate dans le sang, pH salivaire), et d’autres ont une bonne spécificité (nombre de buvées de l’animal, pH fécal, concentration en urée dans le lait). Néanmoins, aucun modèle ne renferme un couple sensibilité et spécificité satisfaisant. A l’issue de ce travail nous proposons une stratégie diagnostique fondée sur 4 étapes : 1) l’analyse du contexte de diagnostic de l’ARSA, 2) l’évaluation des facteurs de risques, 3) l’évaluation des modèles multiparamétriques et 4) le calcul d’indicateurs NpH ruminaux des individus à risque
In ruminants, subacute ruminal acidosis (SARA) is a nutritional disease that induces an abnormal acidity of the rumen compartment as well as disturbance in microbial fermentation. When the disease becomes chronic, it can lead to negative effects on production efficiency and animal health at the individual or the herd scales, with negative economic consequences for the farmer. One of the major problems of SARA is that there are no obvious clinical signs. Presently, the only benchmark to define SARA is rumen pH. However, no pH indicator is unanimous due to the important variability related both to the measurement technique itself and to the animal susceptibility. In this context, this thesis aimed to improve the individual diagnosis of SARA in dairy cows by developing a multiparametric approach that could be used on field. We propose new indicators of pH kinetics measured noninvasively with intra-ruminal boluses. These new relative indicators, calculated daily (kinetic normalised on 0, NpH), consist of the time spent under NpH < - 0.3, the NpH standard deviation and the NpH range. These indicators make it possible to overcome the strong sources of variability and have the advantage of being transposable while being more accurate to characterize SARA. At the same time, we have developed multiparametric models including a number of parameters measured simultaneously in various biological compartments (milk, faeces, saliva, blood, urine) or on animal behaviour. The models ability to predict SARA has been evaluated on field. Some models including rumen peripheral parameters (concentration of urea in milk, of bicarbonate in blood, salivary pH) have a proficient sensitivity while others have a proficient specificity (number of drinking acts, faecal pH, and urea concentration in milk). However, no model developed is both sensitive and specific enough. The diagnostic strategy we propose is based on 4 steps: 1) analysis of the SARA diagnostic context, 2) assessment of risk factors, 3) evaluation of multiparametric models and (4) determination of ruminal NpH indicators for individuals presenting a high risk of SARA

Studies have identified perceived racism as one type of social stress that is believed to contribute to hypertension, though no studies to date have examined the relationship between perceived racism and blood pressure among foreign-born Mexicans living in the United States (U.S.). In addition, studies have shown that acculturation may increase levels of perceived discrimination among foreign-born Mexicans living in the U.S. The primary purpose of this study was to examine the relationship between perceived racism and ambulatory blood pressure among a convenience sample of 332 foreign-born Mexicans living in Utah County, Utah controlling for age, gender, body mass index (BMI), and acculturation. This was done through the use of several multiple regression analyses using archival data collected at Brigham Young University. The Perceived Ethnic Discrimination Questionnaire—Community Version (Brief PEDQ—CV) was used to measure perceived racism. The Acculturation Rating Scale for Mexican Americans (ARSMA-II) was used to measure both language and general acculturation. Four blood pressure variables, including waking systolic blood pressure (WSBP), waking diastolic blood pressure (WDBP), sleeping systolic blood pressure (SSBP), and sleeping diastolic blood pressure (SDBP) were used as outcome variables in the regression analyses. A relationship between perceived racism and any of the ambulatory blood pressure variables used in this study was not found. In addition, English-language acculturation was not found to moderate the relationship between perceived racism and blood pressure in the sample of first generation Mexicans participating in this study. A moderating effect of general acculturation on the relationship between perceived racism and blood pressure was found when controlling for age, BMI, and gender, though this moderating effect disappeared when WDBP was included in the regression model. Implications of findings, limitations, and directions for future research are discussed.

Les satellites de type SPOT, Ikonos ou Quickbird fournissent des images possédant des caractéristiques différentes: d'une part des images de basse résolution spectrale et de haute résolution spatiale, et d'autre part, des images de caractéristiques opposées, c'est-à-dire de haute résolution spectrale combinée à une basse résolution spatiale. De nombreuses applications nécessitent de combiner ces hautes résolutions spatiales et spectrales. Ce travail s'insère dans la synthèse d'images multispectrales à haute résolution au moyen de la fusion d'images. La constatation de lacunes dans la littérature à propos de l'évaluation de la qualité, a mené à l'établissement d'un protocole d'évaluation de la qualité, correspondant à une généralisation de deux travaux précédents. Une étude empirique sur l'évolution de la qualité des produits de fusion dans les échelles complète ce protocole. Une catégorisation des nombreuses distances de la littérature est proposée. Nous ajoutons une nouvelle distance pour caractériser la qualité géométrique des produits de fusion basée sur la fonction de transfert de modulation, que nous avons validée grâce à l'imagerie Ikonos et à son application à quelques méthodes de fusion connues. La sélection d'une série de distances sous forme de bilan de qualité est discutée dans le but d'obtenir une idée de la qualité qui soit la plus complète possible. Puisque nous disposons des outils nécessaires à l'évaluation de la qualité, nous pouvons désormais les exploiter pour le développement de nouvelles méthodes de fusion. Nous avons choisi le concept ARSIS comme cadre de développement car, d'une part, ses différentes implantations donnent généralement de bons bilans de qualité, d'autre part, leur qualité visuelle a été parfois controversée. Une campagne d'évaluation de la qualité visuelle des produits de fusion a permis de répertorier, de classer puis d'expliquer la formation des artefacts de quelques implantations ARSIS. L'étude critique de ces méthodes a mené au développement de trois nouvelles méthodes de fusion qui s'appuient aussi sur des outils extérieurs au concept. Ces nouvelles méthodes sont testées lors d'une seconde campagne d'expérimentation. Une des nouvelles méthodes offre de meilleurs résultats que la méthode de référence choisie. Les expérimentateurs l'ont déclarée acceptable et recommandable pour une utilisation dans le cadre d'une exploitation opérationnelle au sein du ministère de la défense.

Studies have identified metabolic health factors to be a major concern in Mexican-Americans, including Mexican immigrants to the United States (U.S.). Acculturation stress has been hypothesized to be a factor in the development of many health-related concerns in this population. Specifically, previous studies have shown that acculturation stress contributes to health concerns, including metabolic health concerns (e.g., diabetes, metabolic syndrome). The primary purpose of this study was to examine the relationship between cultural orientation, a measure of acculturation designed to provide more information than traditional acculturation measures, and metabolic health outcomes. Specific acculturation-related stressors (social support, job-related stress, and depression) were hypothesized mediators in this relationship among a convenience sample of 98 foreign-born Mexicans living in Utah County, Utah controlling for age, gender, socio-economic status (SES), and years in the U.S. Data were collected twice with a three year interval to examine change over time. Changes in these constructs were examined through the use of Growth Modeling with Bayesian estimation. The Acculturation Rating Scale for Mexican-Americans (ARSMA-II) was used to measure Anglo Cultural Orientation and Mexican Cultural Orientation. Standard blood analyses were used to measure metabolic health outcomes, which included glycosylated hemoglobin (HbA1c), insulin, and glucose. The Interpersonal Support Evaluation List (ISEL-12) was used to measure social support, the Job Content Questionnaire (JCQ) was used to measure job-related stress, and the Center for Epidemiological Studies-Depression Scale (CES-D) was used to measure depression. No change was identified in Anglo Cultural Orientation or Mexican Cultural Orientation over time in the majority of subjects. A positive relationship between Anglo Cultural Orientation and HbA1c was found, as was a negative relationship between Mexican Cultural Orientation and HbA1c. Mediation analyses showed a mediation effect of depression on the relationship between Anglo Cultural Orientation and glucose. Implications of findings, limitations, and directions for future research are discussed.

Metachromatic leukodystrophy (MLD) and Gaucher disease (GD) are caused by a deficiency of arylsulphatase A (ASA) and b-glucocerebrosidase (GBA), respectively. They are lysosomal storage disorders with a heterogeneous clinical spectrum encompassing visceral, skeletal and neurologic involvement resulting in high morbidity and mortality. The overall aim of this study is to elucidate the genetic component/s of high ASA and GBA enzyme activity in normal healthy individuals with the ultimate goal of using this information to produce greater protein activity from a recombinant protein. A wide variation in ASA and GBA enzyme activity levels has been observed in the normal population. The first objective of this project was to identify and characterise single nucleotide polymorphisms (SNPs) in the arylsulphatase A (ARSA) and glucocerebrosidase (GBA) genes that are responsible for determining the levels of expressed enzyme activity in the normal population. The second objective was to assess the contribution of transcriptional regulation and TCP80 mediated translational control to normal enzyme variation. TCP80, a translational control protein that interacts with the GBA coding region, is a splice variant of the interleukin binding factor 3 (ILF3) gene. Ten samples from individuals with high ASA activity and twenty samples from individuals with high GBA activity were screened for polymorphisms via denaturing high pressure liquid chromatography (dHPLC) and sequencing. The frequency of these polymorphisms in the normal population was determined using dot-blot hybridisation. Fifteen ARSA polymorphisms (4 promoter, 5 coding, 5 intronic and 1 poly(A) signal) and two GBA polymorphisms (1 intronic and 1 in 3¢-UTR) were identified. Two low frequency ASA polymorphisms (2723A > G, W193C) were found to be correlated with low activity, while another low frequency ASA polymorphism (1101+123C > T) was found to be correlated with high activity in a population of 113 individuals. Real time PCR was used to measure mRNA levels of GBA, ASA and LF3 along with enzyme activity levels of GBA and ASA in two cell types (leucocytes and skin fibroblasts) from four healthy individuals and seven cell lines (HL60, THP1, Huh7, U118, SW1353, Hep G2, and B-cells). Transcriptional control was evident for all three genes with GBA mRNA levels varying over 30 fold, ASA mRNA levels varying over seven fold and ILF3 levels varying more than 24 fold. The 5¢-flanking region of GBA was investigated for the cis-elements responsible for tissue-specific expression. However, it was not possible to demonstrate that the cis-element region was influencing GBA expression. Translational efficiency was measured using the magnitude of the mRNA:enzyme activity ratio as an indicator. GBA translational inefficiency was most pronounced in B cells which require four times more mRNA molecules than hepatocytes (Hep G2) and over 25 times more mRNA molecules than chondrocytes (SW1353) to produce one unit of GBA enzyme activity. Except in B-cells, GBA translational efficiency appears to increase as ILF3 mRNA levels decrease. The tissue-specific variation observed in the protein levels of the ILF3 splice variants, TCP80 and DRBP76, may play a role. The correlation of several low frequency SNPs with low ASA enzyme activity or high ASA activity indicates a role in determining the distribution of enzyme activity levels in the normal population. However, there do not appear to be any common high activity polymorphisms. Knowledge of the exact mechanisms responsible for the observed transcriptional and translational control of these lysosomal genes will greatly enhance the understanding of genotype-phenotype correlation and the contribution of genetic variants to natural variation.

Les satellites d'observation de la Terre (Quickbird, Ikonos, SPOT-5, PLÉIADES) fournissent des images de deux types : soit une image panchromatique à haute résolution spatiale mais basse résolution spectrale, soit une image multispectrale dont la résolution spatiale est inférieure d'un rapport 2 ou 4, mais avec une bonne résolution spectrale. Des méthodes permettant la fusion de ces deux types d'images existent, cependant il est encore possible d'améliorer la qualité des images synthétisées. Nos travaux visent à améliorer la qualité des images synthétisées par une meilleure prise en compte des caractéristiques de l'imageur comme ; la Fonction de Transfert de Modulation (FTM) et l'échantillonnage. Les travaux que nous avons menés sur l'impact du repliement de spectre présent dans les images MS ont mis en évidence que l'absence de repliement permet la suppression des artefacts visuels importants, mais les outils usuels d'évaluation de la qualité des images de fusion ne permettent pas la quantification des performances. La FTM caractérise la capacité de l'instrument à représenter un contraste en fonction de la fréquence spatiale. Celle-ci diffère entre les images PAN et MS. Nous avons proposé à partir de méthodes existantes, deux méthodes de fusion permettant de mieux prendre en compte la FTM et ainsi d'améliorer la qualité et les caractéristiques de l'image synthétisée.

碩士
國立臺灣大學
食品科技研究所
107
4-acetylantroquinonol B (4-AAQB) and Antroquinonol (AQ) are two of the most iconic ubiquinones from the mycelium of Antrodia cinnamomea (AC). 4-AAQB has been proven to be more effective in inhibiting the growth of liver cancer cells than AQ. Therefore, the objective of this study was to increase the yield of 4-AAQB during cultiva-tion of AC. The dividing step in the biosynthetic pathways of 4-AAQB and AQ is farne-sylation of benzoquinone rings. The benzoquinone rings are either farnesylated with far-nesylpyrophosphate (FPP) or FPPB, the suffix B represents γ-lactone modification at the end of FPP. The hypothesis of this study was that FPPB are formed by lactonization of FPP. Hence, we supposed that if the lactonization process could be accelerated, then the yield of 4-AAQB would be increased and the yield of AQ decreased. Since acidic condi-tion favors the formation of γ-lactone, the effect of pH adjustment of the culture medium on the yields of 4-AAQB and AQ were investigated, and the effect of addition of farnesol as a precursor to FPP and FPPB was also studied. We expected that combination of these two treatment would further increase the yield of 4-AAQB. UPLC quantitative analysis has shown that adjusting the pH of the broth to 2.75 at the 14th day during fermentation could significantly increase the yield of 4-AAQB and decrease the yield of AQ. Further analyses of the biosynthetic intermediates by LC MS/MS revealed that farnesylation and O-methylation of the intermediates for the biosynthesis of both 4-AAQB and AQ were promoted by pH adjustment, but ketone group reduction and acetylation of benzoquinone rings were not affected. This phenomenon could mean that the reaction of FPP lactonized to FPPB was promoted. LC MS/MS analyses also showed that addition of 0.1% farnesol could increase farnesylation steps for the synthesis of both 4-AAQB and AQ, but it strongly inhibited the benzoquinone rings modification on AQ side of biosynthetic path-way, especially the conversion of CoQ3 to AQ. On the other hand, addition of farnesol did not affect too much on 4-AAQB side of biosynthetic pathway. Consequently, addition of farnesol during fermentation significantly reduced the yield of AQ but did not affect the yield of 4-AAQB. The results of this study suggested that pH adjustment could promote lactonization of FPP to formed FPPB. It seems promising to find a proper way to adjust pH and add farnesol at the same time to further increase the yield of 4-AAQB.