The theoretical model of Beratan and Onuchic predicts a large attenuation of ET rates through hydrogen bonds; however, the effect of individual hydrogen bond on electron transfer reaction has not been systematically studied. The organic complexes in this study are a series of crown ether/ammonium salt, which incorporate a redox partner on each component of the complex. The dimethoxynaphthalene redox donor was attached to the crown ether and a series of ammonium salts was synthesized which bear substituted quinone and naphthoquinone acceptor. The complexes characterization and preliminary electron transfer rate measurement were completed with UV/Vis and steady-state emission spectroscopy.

Two types of nitrogen have been studied in this report, nitrate and ammonium. Nitrate mainly originates from incomplete combustion like fossil fule combustion from sea traffic, land traffic and energy use. Ammonium mainly origins from farming like fertilizers and animal waste. Nitrate and ammonium are water soluble and can be transported long distances in the atmosphere before depositing with precipitation. In order to record the nitrogen deposition, precipitation was collected and the amount of nitrogen was measured. This was done in 6 places in Eastern Svealand over a two month period, middle of March to middle of May 2014. The source regions of the precipitation was studied and it was found out that if the precipitation originated from areas north of Sweden the amount of deposited nitrogen was significantly lower then if the air masses originated from areas south, south east and south west of Sweden. The results from the measurements shows a decrease in nitrogen deposition with distance from the pollution source and that there is a higher amount of nitrogen in the precipitation in urban areas. / I denna rapport har två typer av kväve studerats, nitrat och ammonium. Nitrat har främst sitt ursprung från förbränningar, till exempel förbränning av fossila bränslen från sjöfart, fordonstrafik och energiförbrukning. Ammonium har framför allt källor från jordbruk, till exempel gödsling och djuravföring. Nitrat och ammonium är vattenlösliga och kan transporteras långa sträckor för att sedan deponera med nederbörden. Genom att samla in nederbörd och mäta halterna av nitrat och ammonium i proverna kunde depositionen av kväve beräknas. Detta gjordes över en tvåmånaders period, mitten av mars till mitten av maj 2014, på 6 platser i östra Svealand. Luftmassornas ursprung undersöktes och det visade sig att när luftmassorna och nederbörden hade sitt ursprung norr om Sverige innehöll den betydligt lägre halter kväve än när de kom från söder, sydöst och sydväst. Resultaten från mätningarna visade att det är en tydlig minskning av kvävehalten i nederbörden med avståndet från källan och att det är en förhöjd kvävehalt i nederbörden i städerna.

The drawbacks of nonactin, the current commercial standard receptor for ammonium ion necessitate the development of new ammonium ionophores. We have designed and attempted to synthesize fluoroionophores, I- III. Molecular modeling of I suggests superior selectivity over that of nonactin. III was synthesized as a selective ionophore for optical detection of ammonium ion. The synthetic strategies for III are two-fold: solid phase and solution phase. Solution phase synthesis was performed with two different protecting groups (t-butyl ester and benzyl ester). A methyl-amino substituted anthracene molecule will be covalently coupled to the secondary amine group to provide an optical signaling moiety that operates on the basis of an“off-on" fluorescence emission mechanism. Compound IV was also synthesized in order to provide a sample reaction for the covalent coupling of the chromophore and to provide a fast route to an ammonium fluoroionophore.

L’objectif de la thèse était de développer un procédé de traitement des lisiers de porc par zone humide artificielle (ZHA) adapté aux contraintes du climat méditerranéen ainsi qu’à celles des éleveurs porcins. Le lisier de porc présentant des teneurs en ammonium (NH4+) toxiques pour les espèces végétales, il a été nécessaire de prétraiter le lisier. Des expérimentations sur le prétraitement du lisier de porc par aération continue (30 jours) à petite (12 litres) et moyenne échelles (300 litres) ont donc été conduites, et ont permis une diminution des concentrations en NH4+ en dessous des seuils de tolérance végétale. Cependant, la volatilisation de l’ammoniac semble avoir été le processus majoritairement à l’origine des abattements observés (phénomène d'ihnibition). Afin d’améliorer la diminution du NH4+, des produits d’ensemencement microbiens commerciaux ont été utilisés sans que leur effet n'ait pu être mis en évidence. Lors des expérimentations à moyenne échelle, le lisier prétraité a été amendé en ZHA (mésocosmes constitués d’un filtre à écoulement vertical suivi d’un filtre à écoulement horizontal). La forte variabilité phénotypique en système expérimental des macrophytes sélectionnés et prélevés dans le milieu naturel environnant (Carex hispida, Typha latifolia, Carex cuprina, Iris pseudacorus, Alisma lanceolatum et Juncus effusus), a été illustrée. Lors des apports en lisier dans la ZHA, les espèces végétales ont répondu différement, soulignant l’intérêt des cortèges multi-spécifiques. Les premiers résultats épuratoires ont été probants. Cependant l’étude des processus épuratoires a mis en lumière la problématique de leur durabilité. / The aim of the thesis was to develop a treatment process of pig manure by constructed wetland (CW) and designed in order to be adapted to the Mediterranean climate constraints and those of pig farmers. However hog manure has concentrations above 2 g.l-1 of ammonium (NH4+), toxic to the plants. It is therefore necessary to establish a slurry pre-treatment step. The thesis has included experiments including pre-treatment of pig slurry by continuous aeration (30 days) to small (12 liters) and medium scale (300 liters). Commercial products for microbial seeding were also used. The results showed that the aeration of pig manure did allow lower concentrations of NH4+ below plant tolerance threshold. However, the ammonia volatilization process appears to be the leading cause behind the observed reductions (inhibition phenomenom). No effect could be demonstrated for microbial treatments. During meso-scale experiments, the CW was amended with the pre-treated slurry (mesocosms made of a vertical flow filter followed by a horizontal flow filter). As a first step, the high phenotypic variability of macrophytes (taken from the natural environment) in experimental system was illustrated and discussed. After manure application, the selected plant species (Carex hispida, Typha latifolia, Carex cuprina Iris pseudacorus, Alisma lanceolatum and Juncus effusus) have presented different responses, emphasizing the importance of multi-species selection for the CW. Finally, the first purifying results were conclusive. However the study of the underlying purifying processes has highlighted the issue of sustainability of these phenomena.

En raison d’une abondante matrice extracellulaire chondrogénique, peu vascularisée et hypoxique, le chondrosarcome, cancer du cartilage, est une tumeur chimio et radiorésistante. Une stratégie bispécifique s’appuyant sur deux caractéristiques spécifiques du chondrosarcome, une forte densité de charges négatives, ainsi qu’une hypoxie chronique sévère de la matrice extracellulaire, est actuellement développée au laboratoire et consiste à fonctionnaliser une prodrogue activée en hypoxie avec un ammonium quaternaire (AQ). Sur la base de résultats précliniques, une prodrogue, ICF05016, a été identifiée et fait actuellement l’objet d’une étude d’optimisation.Ce projet vise à identifier des relations structure-activité dans une série de moutardes phosphorodiamidates vectorisées par une fonction AQ. Dans une première partie, nous nous sommes intéressés à faire varier la nature des substituants de la fonction ammonium quaternaire ainsi que la longueur du bras espaceur séparant cette dernière de la moutarde. Ainsi, 27 dérivés ont été synthétisés par une séquence commune multi-étapes impliquant la phosphorylation d’un dérivé 2-nitro-5-hydroxyméthylimidazole.Un screening par résonance plasmonique de surface a permis de mettre en évidence 12 composés plus affins envers l’aggrécane que le composé de référence ICF05016. Cette étude a révélé une dépendance importante entre l’affinité à l’aggrécane et la nature de l’ammonium quaternaire, les composés benzyléspossédant tous des affinités supérieures. In vitrosur cultures cellulaires HEMC-SS, les composés ont affichés des ratios de cytotoxicité normoxie vs hypoxie (HCR)supérieurs à celui du lead ICF05016, et notamment le composé benzylé31f.Avec une constante de dissociation à l’aggrécane de 2,10 µM et un différentiel de cytotoxicité normoxie/hypoxie équivalent à celui de l’évosfosfamide en étude clinique, la composé 31f a été évalué en termes de stabilité et de clivage en conditions réductrices, mimant l’hypoxie tumorale. Démontrant une excellente stabilité sur 24 heures dans un tampon phosphate, le composé 31f s’est révélé être réduit par réduction chimique ou enzymatique via une nitroréductase, et ce avec une cinétique rapide. Ce dernier a été ainsi identifié au terme de l’évaluation in vitro et de cet axe de recherche comme un nouveau « lead ».Dans une seconde partie, nous avons choisi de moduler l’halogène et la position des bras alkylants portés par la moutarde phosphorodiamidate. Compte tenu de l’instabilité des composés de la série bromée, par rapport à la série chlorée, les analogues bromés des composés ICF05016 et 31f n’ont pu faire l’objet d’une évaluation in vitro. Pour les isomères de type moutarde ifosfamide, l’instabilité des précurseurs phosphoramidiques et les difficultés de synthèse inhérentes à l’introduction d’une fonction amine secondaire sur un chlorure de phosphoryle préalablement fonctionnalisé, nous ont contraints à réorienter nos travaux vers des structures issues d’une étape de chimie de click, permettant d’introduire le bras vecteur portant la fonction amine tertiaire indépendamment de l’étape de phosphorylation. Cette séquence réactionnelle pourrait être étendue à la synthèse de nouveaux analogues du composé 31f, identifié lors de ces travaux. / Due to an abundant chondrogenic, poorly vascularized and particularly hypoxic extracellular matrix, chondrosarcoma, a malignant cartilaginous tumour, is chemo- and radio-resistant. A dual targeted therapy leveraging specific chondrosarcoma hallmarks, an extensive cartilaginous extracellular matrix, namely the high negative fixed charge density and severe chronic hypoxia,was investigatedby conjugation of a hypoxia-activated prodrug (HAP) to quaternary ammonium (QA) functions. Based on preclinical results, animidazole prodrug, ICF05016, was identified and provided the basis for a lead optimization study.This project was designed to identify structure-activity relationships in a series of QA-targeted phosphorodiamidate mustard conjugates. In a first part, a series of 27 conjugates, with different QA function and length of the alkyl linker, was synthesizedvia a common multi-step sequence involvingphosphorylation of a key 2-nitroimidazole alcohol intermediate. Then, biomolecular interactions between these QA derivatives and aggrecan were assessed using thesurface plasmon resonance technology. This screeningrevealed that the affinity depends more on the natureof the QA function, rather than on the linker length. The most promising results were obtainedwith QA bearing a benzyle group. Twelves compounds were then evaluated in terms of hypoxia selective cytotoxicityonthe HEMC-SS cell line. For all prodrugs, an overall improvement in hypoxic selectivity compared with the ICF05016 was obtained and the positive impact of thebenzyle QA function was again highlighted. With a dissociation constant of 2.10 µM in the SPR experiment and an attractive hypoxic selectivity, compound 31fwas further selected for a stability and reductive activation study. Activation of the prodrug and phosphoramide mustard release under reductive chemical conditions, and nitroreductase-based activation were demonstrated. From this study, compound 31f emerged as the most effective PG-targeted HAPs. In a second part, the nature of the halogen and the position of the alkylating arms carried by the phosphorodiamidic mustard were modified. Given the high instability of the final compounds of the brominated series, compared to the chlorinated series, brominated analogs of the compounds ICF05016 and 31fcould not be obtained with sufficient purity to be evaluated in vitro.For ifosfamide-like isomers, the design of the prodrugs was modified due to the instability of the phosphoramidic precursors or difficulties of introducing a secondary amine function on a phosphoryl chloride previously functionalized.A click chemistry approach was developed to tether the spacer arm carrying the tertiary amine function independently of the phosphorylation step and could be extended to the synthesis of triazoleanalogues of the new lead 31f.

Quaternary ammonium compounds (QACs) are widely used in commercial and consumer applications as disinfectants, fabric softeners, hair conditioners, and emulsifying agents. The massive production and utilization of QACs has led to their extensive discharge into the environment, raising concerns globally. Several studies have reported on potential risks and detrimental effects of QACs on the natural environment and public wastewater treatment plants. Biological treatment has been found to be an effective way to remove QACs and especially aerobic treatment processes can provide rapid biodegradation via a consortium of bacteria. Although extensive research has been conducted on the fate and effect of QACs, relatively little is known about their effect on aerobic biological treatment processes, especially on nitrification. Research was conducted on the fate and effect of alkyl benzyl dimethyl ammonium chloride (AB), a QAC widely used as disinfectant, in mixed aerobic and nitrifying cultures. The results of this study demonstrated that up to 50 mg/L AB was efficiently degraded in a mixed aerobic culture fed with dextrin and peptone, although trace residual AB levels were observed. Nitrification of the produced ammonia was complete at an AB concentration of 20 mg/L after an acclimation period, but was almost completely inhibited at 50 mg/L. Mixed aerobic cultures maintained only with AB as external nitrogen and carbon source achieved a high degree of AB degradation at both 20 and 50 mg/L. Ammonia oxidation by a nitrifying culture, enriched with ammonium chloride and sodium bicarbonate, was inhibited with increasing AB concentration and completely ceased at 15 mg/L AB. Degradation or utilization of AB was not observed for all tested AB concentrations between 2 to 20 mg/L. Based on these experimental results, and assuming non-competitive inhibition, a relatively low value of the AB inhibition coefficient was obtained, which indicates a relatively high susceptibility of the ammonia oxidizers to AB. The results of this study have significant implications for both engineered and natural systems relative to the fate and effect of QACs.

Quaternary ammonium compounds (QACs) are ubiquitous contaminants found worldwide in both engineered and natural systems. QACs are toxic to aquatic organisms and cause co-selection for antibiotic resistance, thus providing a reservoir of antibiotic-resistant bacteria, as well as antibiotic resistance genes in QAC-polluted environments. The objectives of the research presented here were to: a) systematically assess the fate and toxicity of QACs using quantitative structure-activity relationships (QSAR); b) evaluate the biotransformation potential of QACs under aerobic, anoxic and anaerobic conditions; and c) assess the potential toxicity of QACs biotransformation products. Nine QACs, belonging to three homologous groups -- monoalkonium, dialkonium and benzalkonium chlorides -- were the target QACs. The QACs critical micelle concentration (CMC) was determined. Then, the CMC was used as a descriptor to derive relationships between QAC structure and partitioning to biosolids as well as acute Microtox® toxicity. QACs with low CMCs had a relatively high adsorption affinity for biosolids and a lower toxicity than QACs with higher CMCs, which suggests that QACs that are more mobile and more (bio)available are more toxic. The biotransformation potential of benzalkonium chlorides (BAC) -- the most commonly used QACs found in engineered and natural biological systems -- under aerobic, methanogenic, nitrate reducing, and fermentative conditions was evaluated using bioenergetics and batch bioassays. The aerobic BAC biotransformation involved sequential dealkylation and debenzylation steps resulting in the formation of benzyl dimethyl amine, and dimethyl amine, respectively. The bacterial community involved in the aerobic BAC degradation was mainly composed of species belonging to the Pseudomonas genus. All QACs tested were recalcitrant under methanogenic conditions and inhibited methanogenesis at and above 25 mg QAC/L. Under nitrate reducing and fermentative conditions, BAC was transformed to alkyldimethyl amines via an abiotic reaction known as modified Hofmann degradation and a biotic reaction known as fumarate addition, respectively. Both reactions are based on a mechanism known as nucleophilic substitution. The discovery of BAC transformation by the above mentioned two reactions is the first ever report to document QAC transformation under anoxic/anaerobic conditions and delineate the transformation pathway.

Thesis (M. Sc.)--Carleton University, 2001. / Includes bibliographical references (p. 84-90). Also available in electronic format on the Internet.

Th.--Sci.--Bordeaux 1, 1979. N°: 632.

Orientador: Marcelo Andreotti / Banca: Salatiér Buzetti / Banca: Aloísio Costa Sampaio / Resumo: O abacaxizeiro é classificado como uma cultura exigente em fertilidade do solo, sendo o N o nutriente mais importante para o desenvolvimento da planta e aumento do tamanho e massa dos frutos. O objetivo deste trabalho foi avaliar quantitativamente e qualitativamente os frutos de abacaxi cv. Smooth Cayenne na região noroeste do estado de São Paulo, utilizando fontes e doses de N, aplicado antes e após a indução do florescimento, em solo corrigido quanto ao teor de potássio. O trabalho foi conduzido na Fazenda Água Limpa, no município de Guaraçaí-SP, em um solo Latossolo Vermelho-Amarelo. As mudas foram plantadas em sulcos na superfície do solo, no dia 17/03/2009, com espaçamento de 1,10m entrelinhas, 0,40m entre fileiras e 0,40m entre plantas, com densidade aproximada de 33.000 plantas ha-1, sendo cada parcela composta por quatro fileiras duplas com 56 plantas/parcela no total. A indução floral foi realizada em duas épocas, em virtude da pouca porcentagem de plantas induzidas na primeira, ou seja, nos dias 21/02/2009 e 05/05/2009, com as respectivas colheitas dos frutos realizada nos dias 12/09/2009 (203 dias após a indução) e 27/11/2009 (206 dias após a indução). As avaliações realizadas foram duas análises nutricionais da folha "D", uma antes e outra após a indução floral, e duas análises dos frutos, devido à realização de duas colheitas. O delineamento experimental adotado foi o de blocos ao caso com quatro repetições, em esquema fatorial 3x5 (para 1ª análise foliar sem efeito de época) e 2x3x4 (para a 2ª análise da folha e as duas análises dos frutos), sendo composto por duas épocas de aplicação de N: toda a dose aplicada no dia 06/10/2008 (antes da indução floral) ou toda no dia 12/06/2009 (após a indução floral), 3 fontes de N, sulfato de amônio, uréia e nitrato de amônio, e quatro doses de N (7,5; 15; 22,5 e 30 g planta-1) ... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: Pineapple plant is demanding in fertility of soil, and N is the most important nutrient for the development of plant and increase of size and mass of fruits. The objective of this work was to evaluate quantity and quality of fruits of pineapple cv. Smooth cayenne in the northwest area of São Paulo State, using sources and doses of N, applied before and after the flowering induction, in soil fertilized with potassium. The work was conducted at Água Limpa farm, in Guaraçaí-SP, in a Red-yellow Latosol. The seedlings were planted in furrows at soil surface, in 03/17/2009, with spacing of 1.10m between double lines, 0.40m between single lines and 0.40m among plants, with approximate density of 33,000 plants ha-1, being each plot composed of four double lines with 56 plants/plot in the total. The flowering induction was accomplished in two times, due to little percentage of plants induced in the first time, in other words, in 02/21/2009 and 05/05/2009, with the respective crops of the fruits accomplished in 09/12/2009 (203 days after the induction) and 11/27/2009 (206 days after the induction). The evaluations were: two nutritional analyses in "D" leaf, one before and other after the flowering induction, and two analyses of fruits, due to the accomplishment of two crops. A randomized block design with four repetitions in a factorial scheme 3x5 (for 1st leaf analysis without time effect) and 2x3x4 (for 2nd leaf analysis and two fruit analyses), being composed by two times of N application: the total dose accomplished in 10/06/2008 (before the floral induction) or total dose in 06/12/2009 (after the floral induction), 3 sources of N, ammonium sulfate, urea and ammonium nitrate, and four N doses (7.5; 15; 22.5 and 30 g plant-1) was used. Ammonium sulfate provided higher leaf N and S content as applied on pineapple plant before or after the floral induction. For the fruits harvested ... (Complete abstract click electronic access below) / Mestre