<div>In fire-prone forests, tree taxa and burn temperature are the major controllers of the chemical and physical properties of pyrogenic organic matter (PyOM), the aromatic carbon-rich product of the incomplete combustion of plant biomass, that accumulates in soil in such settings. These controls also dictate how soil microbes can degrade plant C once it enters into soil as previous studies demonstrate that increased fire temperature results in low PyOM degradability but also impacts the decomposition of the original soil. However, we know little about how taxa and temperature of C-inputs impact the production and accumulation of cellular residues from soil microbes, which can be the dominant source of stabilized soil organic matter in many ecosystems. </div><div>This work presents the results of the analysis of soil microbial amino sugars, as proxies for soil microbial necromass, from long-term soil incubation experiments, 180 and 600 days, that were amended with jack pine (JP) and red maple (RM) wood or their PyOM produced at 300°C or 450°C. Both wood taxa amendments resulted in an increase in microbial sugar residues compared to non-amended soils but RM, the taxa with the highest proportion of soluble sugars and low tannin content, exhibited the highest percentage increase. Soils amended with PyOM exhibited lower amino sugar content as compared to their wood but no difference compared to controls (non-amended soils). There was no difference in soil amino sugars observed between the PyOM derived from the two taxa nor between the temperature of pyrolysis, possibly due to only small amounts of bioavailable C and N in the PyOM. Total amino sugar concentrations varied significantly between PyOM and fresh wood treatments, with PyOM treatments yielding 659 – 730 μg/ g soil while wood treatments yielded 757 – 930 μg/ g soil early in incubations. While fungal-derived amino sugars were dominated in all treatments, longer soil incubation time, 600 days vs 180 days, resulted in a proportionately greater decrease bacterial-derived amino sugars. Overall, at 180 days, PyOM treatments exhibited 19-27% of soil N and 4-5% of soil C quantifiable as amino sugars while wood treatments exhibited 27-28% of total soil N and 6-7% of total soil C as amino sugars. This work shows, for the first time, that on a per C or per N basis, PyOM versus fresh wood addition to soils will result in a net depletion of microbial residues. The variable response in amino sugars between treatments and incubation time highlights the importance and dynamic nature of the physicochemical characteristics of organic matter input to soil in controlling the contribution of soil microbial residues to that soil. </div><div><br></div>

This thesis is concerned with the development of methodology for the asymmetric synthesis of a range of amino polyol containing compounds. Chapter 1 highlights the abundance of the amino polyol motif in nature, the wide range of biological activities displayed by amino polyol containing compounds, and their occurrence in drug molecules. A variety of different methods for the synthesis of stereodefined amino polyols is then discussed. Chapter 2 details a full investigation into the doubly diastereoselective conjugate addition reactions of the antipodes of lithium N-benzyl-N-(alpha-methylbenzyl)amide to enantiopurealpha,beta-unsaturated esters which contain a dioxolane unit. The “matched” conjugate addition reactions were further coupled with a highly diastereoselective in situ enolate oxidation using camphorsulfonyloxaziridine for the synthesis of keyalpha-hydroxy-beta-amino ester intermediates. Subsequent cyclisation and further elaboration allowed access to a range of amino polyol containing compounds including imino sugars, amino sugars, and amino acids. Chapter 3 extends the investigation into the doubly diastereoselective lithium amide conjugate addition reaction to enantiopure alpha,beta-unsaturated esters which contain two dioxolane units. A full assessment into the conjugate addition of the antipodes of lithium N-benzyl-N-(alpha-methylbenzyl)amide to a series of D-pentose derived alpha,beta-unsaturated esters is reported. Subsequent elaboration of thebeta-amino ester products of these conjugate addition reactions resulted in the synthesis of (2'S,3'S,4'R)-dihydroxyhomoproline and (2'S,3'R,4'S)-dihydroxyhomoproline. Chapter 4 describes the asymmetric syntheses of protected forms of APTO and AETD, the 2,4,5-trihydroxy substitutedbeta-amino acid residues found within the hexapeptide marine natural products microsclerodermins C, D and E. The optimised synthetic routes to APTO and AETD involved three key steps: a diastereoselective aminohydroxylation [via conjugate addition of lithium (R)-N-benzyl-N-(alpha-methylbenzyl)amide to an achiralalpha,beta-unsaturated ester followed by in situ enolate oxidation with camphorsulfonyloxaziridine], a diastereoselective dihydroxylation, and an olefination. Chapter 5 contains full experimental procedures and characterisation data for all compounds synthesised in chapters 2, 3 and 4.

A disponibilidade de nitrogênio no solo e o fornecimento de doses de potássio podem alterar a nutrição do capim-marandu, com reflexos diretos na morfologia, atividade de enzimas e acúmulo de poliaminas nas plantas. Objetivou-se: i) identificar a forma de nitrogênio e a dose de potássio que promovem a maximização dos atributos morfológicos da parte aérea e das raízes e, consequentemente, a produção de forragem do capim-marandu (Brachiaria brizantha cv. Marandu); ii) avaliar as concentrações de nitrogênio, nitrato, amônio, potássio, prolina, poliaminas e clorofila, além do valor SPAD e da redutase do nitrato nas folhas diagnósticas, em função da adubação de formas de nitrogênio com doses de potássio e iii) quantificar as transformações do nitrogênio do solo, em função da aplicação de formas de nitrogênio e adição de material vegetal de capim-marandu. Os experimentos foram realizados em duas etapas: a) em casa de vegetação onde as plantas de capim-marandu foram cultivadas em solo classificado como Neossolo Quartzarênico. Quatro formas de nitrogênio (nitrato, amônio, 70%nitrato+30%amônio e amídica) mais controle e quatro doses de potássio (0, 150; 300 e 450 mg dm-3) foram combinados em um fatorial completo 5x4. As unidades experimentais consistiram em 80 vasos e o delineamento experimental foi o de blocos inteiramente casualizados, com quatro repetições; b) em laboratório, seis combinações envolvendo formas de nitrogênio (nitrato e amônio enriquecidos com 15N e controle) e presença/ausência de material vegetal de capim-marandu foram avaliados em incubação aeróbica. Cada combinação foi repetida três vezes e todos foram incubados por oito períodos de avaliação (0, 1, 2, 4, 8, 12, 16 e 20 semanas) com o Neossolo Quartzarênico, em delineamento completamente causalizado. Os resultados demonstraram que o fornecimento de nitrogênio associado ao de potássio foi fundamental para elevar a produção de forragem e das raízes e a concentração desses elementos nas folhas diagnósticas do capim-marandu. A forma nitrato+amônio, na dose de potássio de 450 mg dm-3, proporcionou mais elevada área foliar, a qual foi determinante no incremento da produção de forragem. O fornecimento das formas de nitrato, nitrato+amônio e amídica, associados à máxima dose de potássio proporcionaram incrementos nos números de perfilhos e folhas, área foliar, e consequentemente na produção de forragem. O não fornecimento de nitrogênio e a aplicação na forma de amônio proporcionaram as mais baixas produções de forragem. O incremento das doses de potássio reduziu os sintomas de toxicidade de amônio nas plantas de capim. Os atributos produtivos do sistema radicular foram alterados positivamente pelas formas nitrato, nitrato+amônio e amídica e pelas doses de potássio. O valor SPAD foi incrementado pelas formas nitrato, nitrato+amônio e amídica e a aplicação de potássio de 336 mg dm-3 que resultou em 38 unidades SPAD. A concentração de clorofila de 35 ?g g-1 correspondeu à de nitrogênio total de 22,5 g kg-1. A enzima redutase do nitrato teve sua atividade aumentada com o incremento das doses de potássio e o fornecimento de nitrato+amônio. As concentrações de putrescina, espermidina, espermina e prolina aumentaram mediante o fornecimento de amônio e diminuíram com incremento das doses de potássio. Os baixos teores de 15NH4 + no solo após a segunda semana permitiram verificar que todo amônio foi imobilizado pelos microrganismos do solo, em todas as combinações. A aplicação de amônio, com material vegetal de capimmarandu, resultou nos mais elevados teores de amônio, aminoácido, aminoaçúcar e nitrogênio total hidrolisados. / Soil nitrogen availability and potassium supply rates can influence Marandu palisadegrass nutrition, with direct effect on the morphology, enzyme activity and polyamines accumulation in plants. This study aimed to: i) identify the nitrogen form and the potassium rate that maximizes the morphological attributes of shoots and roots, and consequently, the forage production of Marandu palisadegrass (Brachiaria brizantha cv. Marandu), ii) evaluate the nitrogen, nitrate, ammonium, potassium, proline, polyamines and chlorophyll concentration, as well as the SPAD value and the nitrate reductase activity in diagnostic leaves, as a function of nitrogen forms and potassium rates, and iii) quantify the soil nitrogen changes according to different forms of nitrogen and addition of Marandu residue. The experiments were carried out in two stages: a) in a greenhouse, where Marandu plants were grown in an Entisol. Four nitrogen forms (nitrate, ammonium, 70% nitrate+30% ammonium, urea) plus the control (no nitrogen) and four potassium rates (0, 150, 300 and 450 mg dm-3) were arranged in a 5x4 complete factorial design. The experimental units consisted on 80 pots. The twenty combinations were evaluated in a completely randomized block design with four replications; b) in the laboratory experiment, six combinations involving three forms of N (nitrate and ammonium enriched with15N atoms 1% and no nitrogen) and Marandu residue (presence/absence) were evaluated using aerobic incubation. Each combination was replicated three times and incubated under eight incubation periods (0, 1, 2, 4, 8, 12, 16 and 20 weeks) in an Entisol. In total, 144 experimental units were evaluated using a completely randomized design. The results from the first experiment showed that nitrogen supply associated with potassium rates were important for increasing the forage and roots biomass and the concentration of these elements in the diagnostic leaves. Nitrate+ammonium and potassium at 450 mg dm-3 provided with the largest leaf area, which was decisive for high forage production. The supply of nitrate, nitrate+ammonium and urea, associated with the maximum potassium rate resulted in increased number of tillers, leaves, leaf area, and consequently, increased forage production. Combinations involving ammonium and no nitrogen provided with the lowest forage production. High potassium rates were associated with less ammonium toxicity symptoms on the plants. The productive attributes of the root system were positively modified by nitrate, nitrate+ammonium and urea and by the high potassium rates. The SPAD value increased with nitrate, nitrate+ammonium and urea and potassium at 336 mg dm-3 resulted in 38 SPAD units. Chlorophyll concentration of 35 mg g-1 corresponded to a total nitrogen concentration of 22.5 g kg-1. Nitrate reductase activity increased with higher potassium rates and nitrate+ammonium supply. Higher concentrations of putrescine, spermidine, spermine and proline were observed with ammonium supply, but they decreased with higher potassium rates. The low concentration of 15NH4 + in the soil after the second week indicates that all ammonium was immobilized by soil microorganisms, for all combinations. The application of ammonium in combination with Marandu residue resulted in higher concentration of ammonium, amino acid, amino sugar and total nitrogen hydrolysates.

A disponibilidade de nitrogênio no solo e o fornecimento de doses de potássio podem alterar a nutrição do capim-marandu, com reflexos diretos na morfologia, atividade de enzimas e acúmulo de poliaminas nas plantas. Objetivou-se: i) identificar a forma de nitrogênio e a dose de potássio que promovem a maximização dos atributos morfológicos da parte aérea e das raízes e, consequentemente, a produção de forragem do capim-marandu (Brachiaria brizantha cv. Marandu); ii) avaliar as concentrações de nitrogênio, nitrato, amônio, potássio, prolina, poliaminas e clorofila, além do valor SPAD e da redutase do nitrato nas folhas diagnósticas, em função da adubação de formas de nitrogênio com doses de potássio e iii) quantificar as transformações do nitrogênio do solo, em função da aplicação de formas de nitrogênio e adição de material vegetal de capim-marandu. Os experimentos foram realizados em duas etapas: a) em casa de vegetação onde as plantas de capim-marandu foram cultivadas em solo classificado como Neossolo Quartzarênico. Quatro formas de nitrogênio (nitrato, amônio, 70%nitrato+30%amônio e amídica) mais controle e quatro doses de potássio (0, 150; 300 e 450 mg dm-3) foram combinados em um fatorial completo 5x4. As unidades experimentais consistiram em 80 vasos e o delineamento experimental foi o de blocos inteiramente casualizados, com quatro repetições; b) em laboratório, seis combinações envolvendo formas de nitrogênio (nitrato e amônio enriquecidos com 15N e controle) e presença/ausência de material vegetal de capim-marandu foram avaliados em incubação aeróbica. Cada combinação foi repetida três vezes e todos foram incubados por oito períodos de avaliação (0, 1, 2, 4, 8, 12, 16 e 20 semanas) com o Neossolo Quartzarênico, em delineamento completamente causalizado. Os resultados demonstraram que o fornecimento de nitrogênio associado ao de potássio foi fundamental para elevar a produção de forragem e das raízes e a concentração desses elementos nas folhas diagnósticas do capim-marandu. A forma nitrato+amônio, na dose de potássio de 450 mg dm-3, proporcionou mais elevada área foliar, a qual foi determinante no incremento da produção de forragem. O fornecimento das formas de nitrato, nitrato+amônio e amídica, associados à máxima dose de potássio proporcionaram incrementos nos números de perfilhos e folhas, área foliar, e consequentemente na produção de forragem. O não fornecimento de nitrogênio e a aplicação na forma de amônio proporcionaram as mais baixas produções de forragem. O incremento das doses de potássio reduziu os sintomas de toxicidade de amônio nas plantas de capim. Os atributos produtivos do sistema radicular foram alterados positivamente pelas formas nitrato, nitrato+amônio e amídica e pelas doses de potássio. O valor SPAD foi incrementado pelas formas nitrato, nitrato+amônio e amídica e a aplicação de potássio de 336 mg dm-3 que resultou em 38 unidades SPAD. A concentração de clorofila de 35 ?g g-1 correspondeu à de nitrogênio total de 22,5 g kg-1. A enzima redutase do nitrato teve sua atividade aumentada com o incremento das doses de potássio e o fornecimento de nitrato+amônio. As concentrações de putrescina, espermidina, espermina e prolina aumentaram mediante o fornecimento de amônio e diminuíram com incremento das doses de potássio. Os baixos teores de 15NH4 + no solo após a segunda semana permitiram verificar que todo amônio foi imobilizado pelos microrganismos do solo, em todas as combinações. A aplicação de amônio, com material vegetal de capimmarandu, resultou nos mais elevados teores de amônio, aminoácido, aminoaçúcar e nitrogênio total hidrolisados. / Soil nitrogen availability and potassium supply rates can influence Marandu palisadegrass nutrition, with direct effect on the morphology, enzyme activity and polyamines accumulation in plants. This study aimed to: i) identify the nitrogen form and the potassium rate that maximizes the morphological attributes of shoots and roots, and consequently, the forage production of Marandu palisadegrass (Brachiaria brizantha cv. Marandu), ii) evaluate the nitrogen, nitrate, ammonium, potassium, proline, polyamines and chlorophyll concentration, as well as the SPAD value and the nitrate reductase activity in diagnostic leaves, as a function of nitrogen forms and potassium rates, and iii) quantify the soil nitrogen changes according to different forms of nitrogen and addition of Marandu residue. The experiments were carried out in two stages: a) in a greenhouse, where Marandu plants were grown in an Entisol. Four nitrogen forms (nitrate, ammonium, 70% nitrate+30% ammonium, urea) plus the control (no nitrogen) and four potassium rates (0, 150, 300 and 450 mg dm-3) were arranged in a 5x4 complete factorial design. The experimental units consisted on 80 pots. The twenty combinations were evaluated in a completely randomized block design with four replications; b) in the laboratory experiment, six combinations involving three forms of N (nitrate and ammonium enriched with15N atoms 1% and no nitrogen) and Marandu residue (presence/absence) were evaluated using aerobic incubation. Each combination was replicated three times and incubated under eight incubation periods (0, 1, 2, 4, 8, 12, 16 and 20 weeks) in an Entisol. In total, 144 experimental units were evaluated using a completely randomized design. The results from the first experiment showed that nitrogen supply associated with potassium rates were important for increasing the forage and roots biomass and the concentration of these elements in the diagnostic leaves. Nitrate+ammonium and potassium at 450 mg dm-3 provided with the largest leaf area, which was decisive for high forage production. The supply of nitrate, nitrate+ammonium and urea, associated with the maximum potassium rate resulted in increased number of tillers, leaves, leaf area, and consequently, increased forage production. Combinations involving ammonium and no nitrogen provided with the lowest forage production. High potassium rates were associated with less ammonium toxicity symptoms on the plants. The productive attributes of the root system were positively modified by nitrate, nitrate+ammonium and urea and by the high potassium rates. The SPAD value increased with nitrate, nitrate+ammonium and urea and potassium at 336 mg dm-3 resulted in 38 SPAD units. Chlorophyll concentration of 35 mg g-1 corresponded to a total nitrogen concentration of 22.5 g kg-1. Nitrate reductase activity increased with higher potassium rates and nitrate+ammonium supply. Higher concentrations of putrescine, spermidine, spermine and proline were observed with ammonium supply, but they decreased with higher potassium rates. The low concentration of 15NH4 + in the soil after the second week indicates that all ammonium was immobilized by soil microorganisms, for all combinations. The application of ammonium in combination with Marandu residue resulted in higher concentration of ammonium, amino acid, amino sugar and total nitrogen hydrolysates.

No description available.

The emerging evidence of preferential accumulation and long residence time of proteinaceous compounds in soil are counter to the traditional view that their structure is readily broken down through microbial activity. The shift in thinking of their residence time is, however, heavily influenced by physical and chemical protections in soil, representing an important change for understanding global biogeochemical carbon and nitrogen cycling. We investigated the accumulation patterns of proteinogenic amino acids for a long term (thousands of years) related to their sources and sinks. We found clear patterns of change in the amino acids in a 4000 year-chronosequence adjacent to Lake Michigan, USA (Michigan chronosequence) and they were tightly related to the shifts in their biological sources, namely aboveground vegetative community (r2=0.66, p<0.0001) and belowground microbial community (r2=0.71, p<0.0001). Results also showed great variations of approximately 49% between seasons (summer and winter). Moreover, seasonal dynamic patterns (22% variations) of the amino acids in soil mineral associated fraction were rather counter to the conceptual view that it represents a slow soil organic pool with long residence times. The amino acids enriched in the mineral associated fraction, (e.g., positively charged, aromatic, and sulfur containing amino acids), tended to preferentially accumulate in whole soil pool during the 4000 years of ecosystem development. Their interaction with soil minerals, therefore, may play a critical role in the long-term sink and selective accumulation of proteinaceous compounds with some degree of the displacement. This was further confirmed by another chronosequence system near Haast River, New Zealand, which is geologically separated and climatically- and ecologically- different from the Michigan chronosequence. Common trends between two chronosequences suggested that either polar interactions or redox reactions may be relatively more important in the mineral interaction of amino acids than non-polar interactions. The consistency of results at two disparate locations in the southern and northern hemispheres is strong evidence that the processes of pedogenesis and ecosystem development are parsimonious and predictable. Our research demonstrated fundamental understanding of behavior of proteinaceous compounds at the molecular species level, and further provided their partitioning mechanisms associated with soil components. / Ph. D.