Iron control during acidizing plays a key role in the success of matrix treatment. Ferric ion precipitates in the formation once the acid is spent and the pH exceeds 1-2. Precipitation of iron (III) within the formation can cause formation damage. Chelating agents such as EDTA and NTA are usually added to acids to minimize iron precipitation. Drawbacks of these chelating agents include limited solubility in strong acids and poor environmental profile. Hydroxy EDTA was introduced because of its higher solubility in 15 wt% HCl. However, its solubility in 28 wt% HCl is low and it is not readily biodegradable. In this study we studied the formation damage caused by iron precipitation in acidizing operations and tested the chelate L-glutamic acid, N,N-diacetic acid (GLDA). This chelant is soluble in higher concentrations of HCl. It is readily biodegradable, and is an effective iron control agent. A study was conducted to study the concentration of iron at different pHs ranging from 1-4 without the presence of any chelating agent at room temperature. A similar study was conducted in the presence of a chelating agent. To simulate field conditions, coreflood tests were conducted on Indiana Limestone, Austin Chalk and Pink Desert. Tests were conducted with and without the chelant. Samples of core effluent were collected and iron and calcium concentrations were measured using atomic absorption spectroscopy (AA). The cores were scanned using X-ray before and after acid injection. Results indicated that precipitation of iron can cause serious reduction in core permeability. The chelate was found to be very effective in chelating iron upto 300 degrees F. No permeability reduction was noted when GLDA was added to the acid. Material balance calculations show that significant amount of the iron that was added to the injected acid was produced when GLDA was used. This chelant is effective, environmentally friendly and can used up to 300 degrees F.

This work increased the value of ferrite process (FP) in three directions: firstly, changed the inferiority of FP on cost by transforming the FP sludge into a catalyst; secondly, used ERFP and elutriation to promote the performance of FP; thirdly, developed Fenton oxidation as a pretreatment step for avoiding the interference from chelating agents. Six ferrite catalysts (MxFe(3-x)O4, M = Cu, Zn, Mn, Ni, Cr or Fe) formed from FP were tested. Experimental results indicate that the Cu-ferrite catalyst with a Cu/Fe ratio of 1/2.5 can completely convert CO to CO2 at an inlet CO concentration of 4000 ppm and a space velocity of 6000 hr-1 were held at 140¢J. The catalytic performance of Cu-ferrite did not reduce even when the concentration of O2 was just 1%. This work proves that the ferrite catalysts have good potential for catalyzing oxidation. For developing FP for effectively treating almost all heavy metal waste liquid, hence an extremely difficult treating target- simulated waste liquid was designed. It contains ten heavy metals - Cd, Pb, Cu, Cr, Zn, Ag, Hg, Ni, Sn and Mn, each at a concentration of 0.002 M. Although conventional FP could not be used to treat the simulated waste liquid completely, the enhanced FP, i.e. ERFP, could be used to satisfy regulatory limits. FeSO4 can be added in the extended stage of ERFP intermittently rather than continuously. The optimum operating parameters in the initial stage are pH = 9 , FeSO4 dosage = 0.2 mol/L, temperature = 90 oC, air supply rate = 3 L/min/L and reaction time = 40 min; in the extended stage, they are intermittent dosing, adding 10 mL 1M-FeSO4 solution per liter waste liquid every 5 min, pH = 9, temperature = 90 oC, air supply rate = 3 L/min/L and reaction time = 80min. Elutriation was conducted to reduce the cost of ERFP and ensure that the sludge met Toxicity Characteristic Leaching Procedure (TCLP) standards. An operating pH from 2.88 to 4 and an elutriation time of 6 h were recommended. Used Fenton oxidation to decompose chelating agent in waste liquid and then treated heavy metal by FP, this research showed that under proper operational conditions Fenton/ ERFP could completely solve the chelating agent interference problem. The best condition for decreasing EDTA using the Fenton method was: pH = 2, ferrous ion initial concentration [Fe2+]0 = 1¡Ñ10-2M, hydrogen peroxide addition rate = 5¡Ñ10-4 mol/min/L and reaction time = 10 min. Lastly, a lot of real waste liquids were treated satisfactorily by applying the results of this study.

The use of hydroxyl radical based reaction (Fenton reaction) for the destruction of organic pollutants has been widely reported in the literature. However, the low pH requirement and rapid hydrogen peroxide consumption rate make the application of conventional Fenton reaction difficult for in-situ treatment. In this study, we conducted a modified Fenton reaction by introducing a chelating agent into the reaction system that could prevent Fe(OH)3 (s) precipitation even at a neutral pH condition and reduce the H2O2 consumption rate by controlling the Fe2+ concentration. A chelating agent (mono-chelate or poly-chelate) combines with Fe2+ or Fe3+ to form stable metal-chelate complexes in solution. This decreases the concentration of Fe2+ in the solution so that reactions can be carried for longer contact times. Experimental results (citrate was the chelating agent) for 2,4,6-trichlorophenol (TCP) showed that TCP degradations were greater than 95% after 2.5 h and 24 h reaction times at fixed pH 5 and 6, respectively. For the same reaction time, the normalized chloride formations were 85% at pH 5 and 88% at pH 6. Several other chlorinated organic compounds were also chosen as the model compounds for detoxification studies because of their chemical structures: trichloroethylene (unsaturated hydrocarbon), carbon tetrachloride (highly oxidized compound), 2,2-dichlorobiphenyl, and biphenyl (a dual-aromatic ring structure). Poly-chelating agents (such as polyacrylic acid-PAA) provide multiple Fe2+/Fe3+ binding sites in the modified Fenton reaction for the oxidation of contaminants (2,2-dichlorobiphenyl, and biphenyl) at a neutral pH environment. Numerical simulation based on the kinetic model developed from the well known Fenton reaction and iron-chelate chemistry fits experiment data well for both standard and chelate modified Fenton reactions. In this dissertation, it was proven that both monomeric (citrate) and polymeric (PAA) chelate modified Fenton reactions were effective for dechlorination of carbon tetrachloride from aqueous phase by the superoxide radical anion. On the other hand, PAA (a poly-chelating agent) can also be used for solid surface modification by polymerization of acrylic acid (monomer). The successful degradations of biphenyl and trichloroethylene by the PAA functionalized silica particles/membrane demonstrate the versatile applications of the chelate modified Fenton reaction.

A series of 2-substituted 8-hydroxyquinolines have been prepared and their reactions with a number of metal ions studied. Acid-dissociation constants and metal-chelate formation constants have been determined. 2-(2'-Hydroxyphenyl), 2-(2'-pyridyl) and 2-hydrazino-8-hydroxyquinoline function as terdentate ligands. The latter two ligands form a number of protonated complexes some of which are unusually stable. This stability is likely due to hydrogen bonding. / Thesis / Doctor of Philosophy (PhD)

Three effective solutions to dissolve the filter cake created by water-based drilling fluids weighted with Mn3O4 particles were developed. Hydrochloric acid at concentration lower than 5 wt% can dissolve most of Mn3O4-based filter cake. Dissolving the filter cake in two-stage treatment of enzyme and organic acid was effective and eliminated the associated drawbacks of using HCl. Finally, combining low and safe concentration of HCl with an organic acid in one-stage treatment was very effective. Hydrochloric acid (10-wt%) dissolved 78 wt% of Mn3O4-based filter cake at 250°F after 28 hours soaking time. However, Chlorine gas was detected during the reaction of 5 to 15-wt% HCl with Mn3O4 particles. At 190°F, 1- and 4-wt% HCl dissolved most Mn3O4 particles (up to 70-wt% solubility). Their reactions with Mn3O4 particles followed Eq. 8 at 190°F, which further confirmed the absence of chlorine gas production at HCl concentrations lower than 5-wt%. EDTA and DTPA at high pH (12) and acetic, propionic, butyric, and gluconic acids at low pH (3-5) showed very low solubilities of Mn3O4 particles. GLDA, citric, oxalic, and tartaric acids produced large amount of white precipitation upon the reactions with Mn3O4 particles. Similarly, DTPA will produce damaging material if used to dissolve Mn3O4-based filter cake in sandstone formation. At 4-wt% acid concentration, lactic, glycolic, and formic acids dissolved Mn3O4 particles up to 76 wt% solubility at 190°F. Malonic acid at lower concentration (2-wt%) dissolved 54 wt% of Mn3O4 particles at 190°F. Manganese tetraoxide particles were covered with polymeric material (starch), which significantly reduced the solubility of filter cake in organic acids. Therefore, there was a need to remove Mn3O4-based filter cake in two-stage treatment. Enzyme-A (10-wt%) and Precursor of lactic acid (12.5-wt%) dissolved 84 wt% of the filter cake. An innovative approach led to complete solubility of Mn3O4 particles when low and safe concentration of HCl (1-wt%) combined with 4-wt% lactic acid at 190°F. HCl (1-wt%) combined with lactic acid (4-wt%), dissolved 85 wt% of the Mn3O4-based filter cake after 18-22 hours soaking time at 250°F in one stage treatment.

В данной работе проведено исследование переработки мышьяксодержащих шламов нейтрализации отработанных электролитов с целью селективного извлечения ценных металлов (медь, никель). Для определения химического и фазового анализа техногенного многокомпонентного сырья применены методы спектрофотометрии (AAС) и рентгенофазовой дифрактоскопии. Предложен выщелачивающий комплексообразующий реагент Трилон Б и обоснован его выбор. Проведены литературный обзор современных методов переработки, лабораторные исследования. Исследованы и оптимизированы процессы выщелачивания шламов водным раствором Трилона Б, очистки полученного трилонатного раствора от металлов-примесей, регенерации растворителя. Так же в диссертации выбрана оптимальная схема переработки гидроксидных шламов и отражено эколого-экономическое обоснование выбранной технологии переработки. / In this paper, research arsenic-containing slimes of neutralization of waste electrolytes was carried out to selectively extract valuable metals (copper, nickel). The method of Atomic Absorption Spectroscopy (AAS), X-ray Diffraction (XRD) was applied. The chemical and phase analysis of multicomponent manmade waster was carried out, the leaching chelating reagent Trilon B was offered and its choice is reasonable. A review of modern methods of processing and laboratory studies were carried out. The processes of leaching of slimes by aqueous solution of Trilon B, purification of the obtained trilonate solution from metal-impurities and solvent regeneration were studied and optimized. Also, in the thesis the optimal scheme of processing of hydroxide sludges was chosen and the ecological and economic justification of the chosen technology of processing was represented.

Title: Bifunctional chelators for selective copper(II) binding Autor: Bc. Monika Paúrová Department: Department of Inorganic Chemistry, Faculty of Science Supervisor: doc. RNDr. Jan Kotek, Ph.D. Supervisor's e-mail: modrej@natur.cuni.cz Abstract: In this Master thesis, cyclam bifunctional derivatives bearing pendant phosphinate groups (4-methyl-11-p-aminobenzyl-1,4,8,11-tetraazacyclotetradecane-1,8- bis(methylenephosphinic acid)) and phosphonate groups (4-methyl-11-p-aminobenzyl- 1,4,8,11-tetraazacyclotetradecane-1,8-bis(methylenephosphonic acid)), were prepared and studied as potential ligands for complexation of divalent copper. These ligands are suitable for binding to a macromolecular carrier. Keywords: radiomedicine, copper, cyclam, chelating agent, phosphinate, phosphonate, kinetic inertness, kinetic lability, thermodynamic stability

Les polyazacycloalcanes sont largement utilisés pour l’élaboration de radiopharmaceutiques destinés à la médecine nucléaire. Ces structures, et plus particulièrement celles dérivées du cyclam, permettent une complexation idéale du cuivre et ainsi une application en imagerie TEP, avec l’utilisation du 64Cu, ou en radiothérapie grâce à l’isotope 67Cu. Le cyclam doit, en plus d’être N-fonctionnalisé par des bras coordinants, disposer d’une fonction supplémentaire permettant la bioconjugaison à une biomolécule pour un ciblage spécifique des cellules cancéreuses. Une première partie de cette thèse a porté sur la synthèse du cyclam monopicolinate C-fonctionnalisé par une fonction de bioconjugaison de type benzyle isothiocyanate. Cette synthèse, basée sur des travaux antérieurs du laboratoire, a nécessité la mise au point d’une méthode d’alkylation régiospécifique du cyclam C-fonctionnalisé par le biais de protections sélectives des atomes d’azote du macrocycle. Le ligand a ensuite été étudié in vitro et in vivo, par nos collaborateurs nantais du CRCINA, pour l’imagerie immuno-TEP du myélome multiple.La seconde partie de ce travail s’est consacrée à l’élaboration d’un dérivé polyfonctionnel du cyclam possédant deux fonctions permettant le ciblage des cellules tumorales. Ce composé a été synthétisé au sein du laboratoire brestois puis étudié, in vitro et in vivo, dans les locaux de la NECSA en Afrique duSud pour l’imagerie TEP du cancer du sein.Ces deux projets ont permis d’obtenir une preuve de concept en imagerie TEP ce qui confirme le potentieldes ligands dérivés de cyclam C-fonctionnalisés pour l’élaboration de radiopharmaceutiques à base de cuivre pour la médecine nucléaire. / Polyazacycloalkanes are wildly used in the conception of radiopharmaceuticals for nuclear medicine. These structures, and especially cyclam derivatives, provide ideal complexation properties of copper, which can be applied in nuclear medicine applications with the 64Cu isotope for PET imaging or with 67Cu for radiotherapy purpose. Cyclams derivatives have to be N-functionalized with coordinative arms, and moreover include an additional function especially introduced for the bioconjugation of a biomolecule in the aim to preferentially target cancer cells.The first project treated in this manuscript consisted of the synthesis of a monopicolinate cyclam C-functionalized with a benzyl isothiocyanate function for the bioconjugation. Based on precedent results obtained in the Lab, a regiospecific alkylation method has been developed for the synthesis of this ligand.This method implies the selective protection and deprotection of the macrocycle nitrogen atoms. This ligand, once obtained, has been studied in vitro and in vivo, by our collaborators of the CRCINA in Nantes, for multiple myeloma immuno-PET imaging.The second project of this work is dedicated to the conception of a radiopharmaceutical based on apolyfunctionnal cyclam which bear two different moieties allowing the targeting of cancer cells. This ligand has been synthesized in our Lab in Brest and studied, in vitro and in vivo, in the South African NECSA company for breast cancer PET imaging.These two projects were elaborated in the aim to obtain a proof of principle in PET imaging and to confirm the high potential of C-funcitonnalized cyclam derivatives for nuclear medicine applications.

Magister Scientiae - MSc (Physics) / Zinc oxide (ZnO) is a wide and direct semiconductor with a wurtzite crystal structure. Its multifunctionality as the ideal candidate in applications such as blue-UV light emitting diodes, transparent conducting oxide, selective gas sensor and efficient catalyst support among others, has attracted a significant interest worldwide. Nano-scaled ZnO has been synthesized in a plethora of shapes. A rich variety of physical and chemical methodologies have been used in the synthesis of undoped or doped ZnO. However, such methods either necessitate relatively high vacuum infrastructures, elevated temperatures, or the use of toxic reagents. The "green chemistry" synthesis of metal oxide nanoparticles which is based on using natural plant extract as an effective 'reducing agent' of metal precursor, has been reported to be a cleaner and environment-friendly alternative to the physical and chemical methods. The thesis is based on the synthesis and the main physical properties of pure ZnO nanoparticles synthesized by a completely green chemistry process using the natural extract of Aspalathus Linearis to bio-reduce the zinc acetate precursor. The obtained ZnO nanopowdered samples were annealed at different temperatures from 300 °C to 600 °C. The samples were characterized using Scanning Electron Microscopy, Energy Dispersive Spectroscopy, Transmission Electron Microscopy, X-ray Diffraction, Differential Scanning Calorimetry, Thermogravimetric Analysis and Fourier Transform Infrared. Highly pure quasi-spherical ZnO nanoparticles with an average crystallite size of 24.6 nm (at 300 °C), 27.2 nm (at 400 °C), 27.6 nm (at 500 °C), and 28.5 nm (at 600 °C) were found. The results also showed that the average crystallite size increased with an increase in annealing temperature. It was successfully demonstrated that the natural plant extract of Aspalathus Linearis can be used in the bio-reduction of zinc acetate dihydrate to prepare highly pure ZnO nanoparticles.

L'utilisation du plutonium (Pu(IV) pour des applications militaires et civiles peut engendrer des contaminations internes chez les personnes exposées. Plusieurs voies de contamination sont possibles : par ingestion, par inhalation ou par blessure. En cas d'inhalation, le plutonium se présente le plus souvent sous forme de particules d'oxyde de plutonium qui vont se localiser au sein des alvéoles pulmonaires. Par un mécanisme de phagocytose, les particules sont internalisées par les macrophages de l'épithélium pulmonaire. Actuellement, le seul agent de décorporation administré en cas de contamination au plutonium est le DTPA (l'acide diethylenetriaminepentaacetique). Il est administré en France sous forme de CaNa3-DTPA par injection intraveineuse et est efficace pour les contaminations par ingestion et par blessure. Les nanoparticules fonctionnalisées à base de polymères naturels sont un concept innovant de décorporation du Pu(IV) solubilisé dans les macrophages pulmonaires et ouvrent la voie au développement de nouvelles familles de décorporants. C'est dans ce contexte que deux stratégies ont été développées : des nanoparticules à base de N-trimethyl chitosan fonctionnalisées par le ligand DTPMP (l'acide diéthylènetriaminepentamethylene phosphonique) qui est l'analogue phosphonique du DTPA et des nanoparticules chélatantes à base de -cyclodextrines amphiphiles anioniques. Ce travail a consisté en la synthèse et la caractérisation des nano-objets puis de l'étude de leur complexation avec les actinides (Th/Pu) en utilisant la spectroscopie EXAFS. Et enfin, des tests préliminaires biologiques in vitro ont été réalisés. Les résultats obtenus, avec les nanoparticules à base de chitosan et de DTPMP montrent que les nanoparticules présentent des tailles et une stabilité compatible avec l’application visée. D’autre part, leur affinité pour les actinides (IV) (Th,Pu) est comparable à celle du chélatant de référence, le DTPA. Enfin, les tests, effectués sur deux lignées de macrophages montrent que les nanoparticules sont internalisées très rapidement et que la matrice polysaccharidique semble se dégrader, permettant le relargage du chélateur DTPMP au niveau des sites de rétention du Pu(IV). Cette thèse constitue un travail préliminaire au développement d'une nouvelle famille d’agents décorporants plus ciblés pour une contamination au plutonium par inhalation. / The use of plutonium (Pu(IV) for military and civil applications can lead to internal contamination. There are several possible routes of contamination: ingestion, inhalation or injury. In case of plutonium inhalation, the plutonium forms oxide particles that reach the pulmonary alveoli. Through a phagocytosis mechanism, the particles are internalized by the macrophages of the pulmonary epithelium and continue to exert their toxicity. Currently, the only decorporating agent administered in the event of contamination with plutonium is DTPA (diethylenetriaminepentaacetic acid). in France, it is administered as CaNa3-DTPA by intravenous injection. This standard is effective for contamination by ingestion and injury. However, it is not effective in case of contamination by inhalation. Functionalized nanoparticles based on natural polymers constitute an innovative concept for decorporating Pu(IV) solubilized in pulmonary macrophages and open the way for the development of new families of decorporants. We investigated two strategies: chitosan-based nanoparticles functionalized by the DTPMP (diethylenetriaminepentamethylene phosphonic acid) which is the phosphonic analog of DTPA and self-organized chelating β-cyclodextrin-based nanoparticles. This work was first focused on the synthesis and characterization of the nano-objects and then on the study of their complexation abilities with actinides (Th/Pu) using EXAFS spectroscopy. Finally, preliminary in vitro biological tests were carried out. Our obtained results with DTPMP and chitosan based nanoparticles showed that these aggregates exhibit size and stability compatible with the application. Furthermore, we demonstrate their affinity for the actinides(IV) (Th, Pu) is comparable to the reference DTPA. Finally, in vitro tests realized onto macrophages show that our nanoparticles are rapidly internalized through phagocytosis and that the polysaccharide matrix seems to undergo degradation which allows the DTPMP to be released and targeted right into the sequestration sites of Pu(IV). This work constitutes a first step in the development of new family of decorporating agents with a higher efficiency in case of plutonium contamination through inhalation.