Crops grown in sandy soils require frequent irrigation. As a result, nitrogen (N) fertilizers. such as ammonium sulfate((NH4)2SO4), are leached from the rooting zone of crops. This loss of N increases N fertilizer use and the potential for nitrate (NO3-) contamination of water. Ammonium-loaded clinoptilolite (NH4+-Cp) may reduce this N leaching, increase N fertilizer use-efficiency, and prevent NO3- contamination of water while sustaining normal crop growth. The potential of NH4+-Cp as a N fertilizer was assessed in three leaching experiments without plants and two leaching experiments with plants. Pots containing rounded quartz sand were amended with (NH4)2SO4 and one of three NH4+-Cp size fractions: small ( Finally, in two leaching studies, pots containing the sandy soil were planted with sweet corn and grown for 35 d and 42 d, respectively. No differences were found among N sources in corn relative growth rates, leaf area ratios, and net assimilation rates, even though the corn plants that were fertilized with NH4+-Cp assimilated significantly more N than the (NH4)2SO4-fertilized plants. The pots fertilized with NH5+-Cp leached In the greenhouse, NH4+-Cp is a slow-release fertilizer that will reduce N leaching while maintaining normal plant growth. However, field studies are needed to confirm the suitability of NH4+-Cp as a slow-release fertilizer under field conditions.

Hydrogels have successfully proved themselves useful for drug delivery applications and several delivery routes have been developed over the years. The particular interest in this work was to design, synthesise and evaluate in situ forming drug eluting hydrogels, which have the potential to ameliorate the healing of cardiovascular diseases. With this aim the anti-inflammatory and immunosuppressant drugs rapamycin (Ra) and dexamethasone (Dex) were made water soluble by conjugation with polyethylene glycol (PEG). Ra was attached pendant from the terminal of PEGs while Dex was incorporated into dendritic structures grown from PEGs. These conjugates were further crosslinked into hydrogels by either conjugate or thiol-ene addition. The gel degradation was tuned to take between 5 and 27 days by using gel building block combinations that induced either 2 or 4 hydrolytically labile bonds per crosslink or by varying the number of crosslinking sites of the building blocks. The use of thiol-ene addition prolonged the degradation time nearly seven folded compared to conjugate addition as a more stable crosslink was formed. Two different formulations for gelling via conjugate addition were used (acrylate-thiol or vinyl sulphone-thiol) to deliver Ra, which was carried by either a 4- or 2-armed PEG. The elution kinetic for the respective gel formulation was of zero order during 15 and 19 days of gel degradation. In addition, Ra was PEGylated via esters, with a distance of either one or two carbons to a nearby thio-ether functionality. The difference in ester conjugation resulted in a slight but significant change in drug-PEG conjugate stability, which was mirrored by the increased time to reach the half amount of total drug elution; from 9.3 to 10.2 days and from 5.1 to 9.7 days for the two gel formulations, respectively. Dexamethasone was incorporated via an ester into dendrons of first and second generation pending from 2- and 4-armed PEGs at loadings of 2, 4 or 6 Dex molecules per carrier molecule. The resulting elution kinetic was of zero order during degradation periods of 5-27 days. Released Dex still possessed biological activity as determined by an in vitro cell assay. The novelties in this thesis are: (A) slow release of rapamycin obtained by covalent incorporation into hydrogels, (B) the use of unique PEG-based dendrimers to incorporate dexamethasone into a hydrogel and (C) zero order sustained release of dexamethasone at physiological pH. / Hydrogeler har framgångsrikt visat sig användbara för att leverera läkemedel och ett flertal metoder har utvecklats de senaste 20 åren. Fokuset i den här avhandlingen ligger på att designa, framställa och utvärdera läkemedelsutsöndrande hydrogeler som spontanhärdar in situ, vilka har potential att förbättra läkningen efter kardiovaskulär sjukdom. Med det syftet gjordes de anti-inflammatoriska och immunsänkande läkemedlen rapamycin (Ra) och dexametason (Dex) vattenlösliga genom att konjugeras med polyetylenglygol (PEG). Ra fästes kovalent längst ut på PEGar medans Dex inkluderades i dendritiska strukturer vilka byggdes från ändpunkten av PEGar. De här konjugaten tvärbands till hydrogeler via antingen konjugerad addition eller radikal polymerisation. Nedbrytningen av gelerna trimmades till att ta mellan 5 och 27 dagar genom att använda kombinationer av gelbyggstenar som bildar antingen 2 eller 4 hydrolyserbara estrar per tvärbindning eller genom att variera antalet tvärbindningspunkter hos byggstenarna. Användandet av radikal polymerisation i sig ledde till att nedbrytningen av geler tog nära sju gånger längre tid jämfört med geler gjorda via konjugerad addition eftersom stabilare tvärbindningar då formas. Två olika kombinationer för härdning via konjugerad addition (akryl-tiol eller vinylsulfon-tiol) användes för att leverera Ra som bars av antingen en 4- eller 2-armad PEG. Utsöndringskinetiken av Ra för de två kombinationerna var av nollte ordningen under de 15 och 19 dagar som gelerna degraderade. Dessutom, Ra PEGylerades via estrar med ett avstånd på antingen ett eller två kol till en närliggande tioeter. Skillnaden i avstånd ledde till en liten men signifikant skillnad i stabiliteten hos Ra-PEG konjugaten, vilket speglades i den förlängda tiden att nå halva mängden av den totala läkemedelsutsöndringen; från 9.3 till 10.2 dagar och från 5.1 till 9.7 dagar för de två respektive gelkombinationerna. Dex kopplades in via en esterbindning till dendroner av första och andra generationen byggda från PEGar med 2 eller 4 armar, vilket resulterade i att 2, 4 eller 6 Dex levererades per bärarmolekyl. Dex eluerade med nollte ordningens kinetik under degraderingsperioder på mellan 5 och 27 dagar. Vidbehålllen biologisk aktivitet av eluerad Dex bekräftades genom cellexperiment in vitro. Nyheterna i den här avhandlingen består av: (A) kontrollerad utsöndring av rapamycin uppnådd genom kovalent inbindning till hydrogeler, (B) användandet av unika PEGbaserade dendrimerer för kovalent inbindning av dexametason till hydrogeler och (C) nollte ordningens utsöndring av dexametason vid fysiologiskt pH. / <p>QC 20130204</p>

The cow/calf phase of production represents a large expense in the production of beef, and efficient beef cows use fewer resources to obtain the same outcome in a sustainable environment. The objective of study 1 was to utilize a mechanistic nutrition model to estimate metabolizable energy requirement (MER) of grazing cows based on changes in cow body weight (BW) and fatness measurements (body condition score, BCS) along with calf age and BW, as well as forage quality and quantity. In addition, an energy efficiency index (EEI), computed as MER of the cow and calf divided by calf weaning BW, was used to rank cows within a herd based on their efficiency of utilizing available forage to meet their maintenance requirements and support calf growth. Data were collected from one herd of approximately 140 Santa Gertrudis cows over a four-year period, and analyzed per calving cycle, conception to weaning. The model's estimation of EEI appears to be moderately heritable and repeatable across years, and efficient cows might have greater peak milk and be leaner. In typical feedlot diets, the rates of ruminal fermentation of highly processed grains and the hydrolysis rate of urea may not match. Asynchronous utilization of carbohydrate and protein would result in some portion of the urea unknot being utilized by the ruminal microbes and ultimately the animal. The use of slow-release urea (SRU) products offers a unique opportunity to synchronize ruminal fermentation of carbohydrate with non-protein nitrogen (NPN) release rate. Two experiments were conducted to examine the impact of source, urea or SRU, and level of dietary NPN on 1) performance and carcass characteristics and 2) N balance of finishing cattle. Steers had lower initial F:G when SRU was used as the only source of feed N (treatment 3), suggesting that SRU may replace both NPN and true protein feeds in finishing cattle diets. High levels of either NPN source had greater N intake and urinary N excretion, as well as N absorption and no major differences were observed between SRU and urea, suggesting that SRU can replace urea at different levels of N intake.

No description available.

No description available.

O nitrogênio é um dos nutrientes mais importante para o desenvolvimento vegetal e o mais aplicado em diversos cultivos agrícolas. Dentre as fontes nitrogenadas disponíveis, a ureia se destaca pela alta concentração de nitrogênio que remete a diversas vantagens econômicas e operacionais no sistema de produção agrícola. Porém, além da alta propensão a perdas, principalmente por volatilização do gás amônia, tem-se a necessidade do aumento da produtividade de modo ao suprimento da demanda crescente de alimentos, fibras e energia. Considerando estes fatores, uma nova vertente de pesquisa está voltada a aplicação de tecnologias à ureia, os fertilizantes com tecnologia agregada, estes vêm se destacando e disponibilizando alternativas de novos produtos no mercado. Com base no exposto, buscou-se elucidar os seguintes questionamentos: As novas tecnologias aplicadas a ureia possibilitam a redução de perdas por volatilização? As novas tecnologias aplicadas a ureia modificam suas transformações inorgânicas e orgânicas no solo e, em caso de modificação, estas são positivas? O uso de tecnologias aplicadas à ureia reflete em maior longevidade na liberação do nutriente ao solo e, em caso positivo, esta longevidade é vantajosa? A combinação entre produtos de ureia convencional e com tecnologia agregada, pode trazer mais benefícios à cultura do milho do que a aplicação destes isoladamente? A substituição do uso/aplicação da ureia em sua forma tradicional pela ureia com tecnologia agregada, na cultura do milho, é viável economicamente ao produtor? Para responder a estes questionamentos, foram conduzidos três experimentos: análise das frações do nitrogênio provenientes da ureia com inibidores de urease; caracterização da dinâmica de liberação e longevidade de fertilizantes recobertos com polímero e enxofre e; análise da produtividade da cultura do milho submetida a adubação com ureia recoberta com polímero e enxofre. O primeiro experimento permitiu concluir que o uso dos inibidores de urease tem potencial para a redução das perdas por volatilização da amônia, foi possível verificar as transformações sofridas pelo nitrogênio desde a aplicação do grânulo até a disponibilidade das formas minerais, passando a incorporação do nutriente na matéria orgânica. No segundo experimento concluiu-se que os fertilizantes recobertos com polímero e enxofre possuem dinâmica exponencial de liberação, o recobrimento é dependente da temperatura, umidade do solo, tipo de material de recobrimento e processo de recobrimento (espessura), que afetam diretamente a liberação e longevidade destes fertilizantes. O último experimento mostrou que uso dos fertilizantes recobertos com polímero e enxofre aumenta a produtividade, os parâmetros biométricos, os parâmetros nutricionais e a qualidade do grão da cultura do milho. As combinações realizadas entre os produtos recobertos com a ureia convencional são alternativas para o aumento da produtividade resultando em valores superiores a aplicação dos insumos de forma isolada. A combinações de produtos recobertos com a ureia convencional é opção para a redução do investimento e, consequentemente, custo de produção resultante da adoção destas novas tecnologias. / Nitrogen is one of the most important nutrient for plant development and the most applied nutrient in several agricultural crops. Among the available nitrogen sources, urea differ due to the high concentration of nitrogen that result to several economic and operational advantages in the agricultural production system. However, in addition to the high propensity for losses, mainly due to the ammonia volatilization, the need to increase yield in order to supply the growing demand for food, fiber and energy emerge. Considering these factors, a new research area is focused to aggregate technologies to the urea, they call fertilizers with aggregate technology, this type of fertilizers emerges and brings new alternatives about new products available in the market. Based on the above, it was tried to answer the following questions: Does the new technologies applied to urea fertilizer enable the reduction of losses by volatilization? The new technologies applied to urea modify their inorganic and organic transformations in the soil and, if modified, are these positive? Does the use of technologies applied to urea reflect in a longer longevity in the release of the nutrient to the soil and, if so, is this longevity advantageous? Can the combination of conventional urea and aggregate technology products brings more benefits to cons than the application of these alone? Is the substitution of urea in its traditional form by urea with aggregate technology in the maize crop economically viable to the producer? In order to answer these questions, three experiments were conducted: analysis of nitrogen fractions from urea and urea mixed with inhibitors; Dynamics of release and longevity of polymer sulfurcoated fertilizers; Analysis of maize yield submitted to fertilization with polymer and sulfur coated urea. The first experiment allowed concluding that the use of the urea inhibitors has potential to reduce losses by ammonia volatilization, it was possible to verify all the changes undergone by the nitrogen fertilization since the granule until the availability of the mineral forms, including the immobilization of the nutrient in organic matter. In the second experiment, it was concluded that the polymer and sulfur coated fertilizers have exponential dynamics of release, the coating depends on the temperature, soil moisture, type of coating material and coating process (thickness), which directly affects the release and longevity of these fertilizers. The last experiment showed that the use of the coated fertilizers with polymer and sulfur increases the yield, the biometric parameters, the leaf concentration and the quality of grain to the maize crop. The combinations performed between the coated products with conventional urea are alternatives for increasing the yield resulting in higher application values of the inputs in an isolated way. Combinations of coated products with conventional urea is an alternative to reduce investment and consequently the production costs, it will result the adoption of these new technologies.

Praguicidas são substancias capazes de prevenir, destruir, repelir ou mitigar uma praga e por isso desempenham um papel de grande importância na agricultura moderna. A elevada utilização destes compostos visa atender à crescente demanda de produção de alimentos, e para isso pesquisas vem sendo realizadas para o desenvolvimento de novas formulações. Entretanto a utilização descontrolada destes compostos pode levar à contaminação de alimentos, solo, águas superficiais e subterrâneas. Os Hidróxidos Duplos Lamelares (HDL) ou argilas aniônicas apresentam estrutura lamelar na qual uma variedade de ânions podem ser intercalados entre as lamelas através de interações eletrostáticas, incluindo praguicidas ácidos. Estes materiais apresentam propriedades interessantes como blindagem das moléculas intercaladas e capacidade de liberação lenta das mesmas. Assim, os principais objetivos deste trabalho foram: estudar a intercalação dos herbicidas ácidos Triclopir, Fluroxipir e Quinclorac, utilizados na agricultura nacional, em HDL de dois sistemas diferentes; estudar a liberação dos herbicidas intercalados em soluções aquosas e em suspensões solo/água; estudar o comportamento dos materiais obtidos quanto à lixiviação em colunas de solo; e comparar a eficácia herbicida dos híbridos com os herbicidas livres através de bioensaios com plantas. Os resultados obtidos demonstraram que os herbicidas ácidos foram intercalados nos HDL dos sistemas Mg/Al e Zn/Al, resultando em sólidos lamelares com boa organização estrutural ainda desconhecidos da literatura. Os híbridos liberaram os herbicidas de forma lenta e contínua para a solução aquosa, diferentemente do observado para o caso dos herbicidas livres, que apresentaram liberação praticamente instantânea para a solução. O tipo de solo também não interferiu na liberação dos princípios ativos. Os estudos de lixiviação em colunas de solo demonstraram que os HDL são bons suportes para a liberação dos herbicidas, pois apresentam liberação lenta do ingrediente ativo, atrasando sua passagem através do solo e diminuindo as concentrações obtidas nos lixiviados. Os híbridos apresentaram a mesma eficácia herbicida que os princípios ativos em forma livre, regulando o crescimento das plantas de agrião nos testes de bioensaios, utilizando as doses de aplicação recomendadas no campo. / Pesticides are substances that prevent, destroy, repel, or mitigate a plague; hence, they play a crucial role in modern agriculture. The widespread use of these compounds aims to meet the growing demand for food production, and this research has focused on the development of new pesticides formulations. However, the uncontrolled use of these compounds can lead to food, soil, surface, and groundwater contamination. Layered Double Hydroxides (LDH) or anionic clays present a lamellar structure in which a variety of anions can intercalate via electrostatic interactions, including acid pesticides. These materials offer interesting properties such as shielding and slow release of intercalated molecules. In this contest, the main objectives of this work were: to study the intercalation of the acid herbicides Triclopyr, Fluroxypyr, and Quinclorac, employed in the Brazilian agriculture, into LDH of two different systems; to study the release of these herbicides into aqueous solutions and soil/water suspensions; to study the behavior of the obtained materials as to their leaching in soil columns; and to compare the herbicidal efficacy of the hybrids with free herbicides through bioassays with plants. Our results showed that acidic herbicides intercalated into the Mg/Al and Zn/Al LDH systems, to yield in lamellar solids with good structural organization, which are yet unknown in the literature. The hybrids released the herbicides slowly and continuously into the aqueous solution, in contrast with free herbicides, which presented virtually instantaneous release into the solution. The soil type did not interfere in the release of active ingredients. Leaching studies in soil columns showed that the LDH are good carriers for herbicides release - they feature slow release of the active ingredient, delaying its passage through the soil and decreasing the concentrations obtained in the leachate. The hybrids displayed the same herbicide effectiveness as the active ingredients in the free form; they regulated the growth of plants in bioassays, when the doses recommended for field use were applied.

Orientador: Leonardo Fernandes Fraceto / Resumo: Considerando os danos causados pelas arboviroses disseminadas pelo vetor Aedes aegypti, o Brasil vem sofrendo, porém buscando estratégias de combate a tal realidade, uma vez que teve um custo total de R$ 2,3 bilhões, apenas no ano de 2016, distribuídos no combate ao vetor, em inseticidas e larvicidas e nos custos diretos e indiretos. Valor esse, correspondente a cerca de 2 % do montante investido na Saúde no mesmo ano. Esse quadro ressalta a necessidade de novas ações e táticas na procura de minimizar a situação, como a elaboração de repelentes que possuam um sistema mais efetivo no combate do vetor responsável pela disseminação do vírus Zika, da Dengue, do Chikungunya e da Febre Amarela. Hoje, sabe-se que um dos ativos repelentes mais eficientes é a icaridina, porém, ela pode causar intoxicação nos organismos não alvos. Também, tem-se o geraniol, que é um ativo de origem botânica, bastante eficaz em sua atuação repelente. E, na busca de aprimorar a ação dos ativos, existe a opção da utilização de sistemas de liberação lenta, o que resulta no aumento da faixa de efeito biológico do ativo de interesse, devido ao prolongamento da liberação do mesmo. No entanto, nota-se a existência de intensa preocupação e responsabilidade na elaboração de sistemas que, além de se mostrarem mais eficientes, sejam, também, focados na diminuição de possíveis mecanismos de resistência que o vetor possa desenvolver. Dessa forma, o presente estudo teve por objetivo o desenvolvimento de sistemas de l... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: Considering the damage caused by arboviruses disseminated by the vector Aedes aegypti, Brazil has been suffering, but seeking strategies to combat this reality, since it had a total cost of R$ 2.3 billion, only in the year 2016, distributed in combat to the vector, in insecticides and larvicides and in direct and indirect costs. This amount corresponds to approximately 2 % of the amount invested in Health in the same year. This scenario highlights the need for new actions and tactics in order to minimize the situation, such as the elaboration of repellents that have a more effective system in the fight against the vector responsible for the spread of the Zika virus, Dengue, Chikungunya and Yellow Fever. It is now known that one of the most effective repellent actives is icaridin, but it can cause intoxication in non-target organisms. Also, one has the geraniol, that is an active of botanical origin, quite effective in its action repellent. And, in the search to improve the action of the assets, there is the option of using slow release systems, which results in the increase of the biological effect range of the asset of interest, due to the prolongation of the release of the same. However, we note the existence of intense concern and responsibility in the elaboration of systems that, in addition to being more efficient, are also focused on the reduction of possible mechanisms of resistance that the vector can develop. Thus, the present study aimed at the development of sustai... (Complete abstract click electronic access below) / Mestre

As key components of flexible organic electronics, the synthesis of polythiophenes via less toxic and more cost-effective routes is demanded. An efficient synthetic route for the production of thienyl-containing homopolymers and copolymers has been developed. The synthetic approach consists of: i) the synthesis in high yield and high purity of thienyl borane monomers protected with N-methyliminodiacetic acid (MIDA) via C-H electrophilic borylation. This reaction uses a combination of inexpensive reagents BCl3, AlCl3, and 2,6-dichloropyridine (Cl2Py) for the regioselective electrophilic aromatic substitution of thiophenes, followed by addition of a second aprotic amine pre-esterification to reduce the Brønsted acidity of the reaction mixture. In situ esterification provided the desired thienyl MIDA boronateester monomers in one-pot at room temperature. ii) Subsequent Suzuki-Miyaura polymerisation of the synthesised monomers to produce well defined thienyl containing pie-conjugated polymers in high molecular weight and high yields. Key reaction parameters for successful Suzuki-Miyaura polymerisation of thienyl-derived MIDA boronate esters under mild temperatures (i.e., 55 °C in THF) were found: a) an optimal monomer:H2O:base ratio, which enables controlled hydrolysis of the BMIDA moiety into its corresponding boronic acid at appropriate rates for high fidelity polymerisation. b) Nature of the base, where K3PO4 provided the best results for production of homopolymers (e.g., rr-P3HT), or KOH which gave excellent results for the formation of copolymers across a range of electronically different comonomers (e.g., pCPDT-BT). Thus, it is demonstrated that the approach is a general strategy for the highly efficient production of thienyl containing pie-conjugated regioregular, regiosymmetric and Donor-Acceptor polymers.

Background: Abdominal solid organ transplantation has evolved from an experimental procedure to a well-established therapy within a few decades. This success is largely due to the introduction of calcineurin inhibitor immunosuppression. Tacrolimus is the most widely used calcineurin inhibitor but has a narrow therapeutic range which requires close drug monitoring to prevent both toxicity and inadequate immunosuppression. Previous studies in renal transplantation have shown that genetic polymorphisms, CYP3A5, CYP3A4*22 and ABCB1 can influence the bioavailability and pharmacokinetics of tacrolimus. These polymorphisms are closely linked to ethnicity and have never been studied in a Scottish population before. Additionally, increasing evidence suggests that high variability of tacrolimus is linked to increased graft loss in kidney transplant patients. Methods: 5889 subjects were genotyped for the genetic polymorphisms CYP3A5 A > G allele transition, CYP3A4*22 C > T and ABCB1 C > T transition. This included 4899 healthy individuals from Generation Scotland bio-resource and 990 patients who underwent renal, liver, or simultaneous pancreas kidney transplants or were organ donors. Tacrolimus dose, trough level and renal function were measured at 11 time points from date of transplant up to and including 12 months post-transplant. Clinical data including episodes of acute rejection, graft and patient survival were compared between the different genotypes. Separate analyses were undertaken for kidney, SPK transplants, as well as liver transplants, the latter looking at recipient and liver donor genotype. A separate cohort of 103 renal transplant patients converted from twice-daily to once-daily tacrolimus had their tacrolimus variability calculated and compared with graft survival. Results: The distribution of the 3 different genotypes of CYP3A5, CYP3A4*22 and ABCB1 were comparable with other Caucasian populations studied previously. In renal transplant recipient expression of the A allele (GA/AA) led to significantly increased dose requirements of tacrolimus and initially lower tacrolimus trough levels. The different genotypes of ABCB1 had no effect. Expression of a CYP3A4*22 T allele trended towards a lower tacrolimus dose requirement but this was not significant. There was no difference in renal function, graft survival or patient survival with any of the polymorphisms. SPK patients had comparable results. In the liver transplant patients, the donor genotype had a greater influence than the recipient one. The donors with CYP3A5 A allele expression had significantly higher tacrolimus dose requirements and lower initial tacrolimus levels. This was apparent to a lesser extent with the recipient expression of CYP3A5 and did not reach statistical significance at all time points. There was no significant difference in tacrolimus dose requirements or level with either donor or recipient expression of ABCB1 or CYP3A4*22. There was a significantly higher incidence of acute rejection in donor CYP3A5 A allele expressers of liver transplant patients in univariate and multivariate analysis. There was no significant different in acute rejection with ABCB1 or CYP3A4*22 genotype. No differences in graft or patient survival with either donor or recipient genotype of any of the 3 polymorphisms were noted. Conversion from twice-daily to once-daily tacrolimus in the first 12 months post-transplant reduced tacrolimus variability. Patients with high tacrolimus variability pre and post conversion had significantly greater graft loss than patients with low tacrolimus variability. Conclusion: CYP3A5 expression results in increased tacrolimus requirements to achieve adequate immunosuppression in renal transplant and SPK patients. Donor rather than recipient CYP3A5 expression is relevant for liver transplantation and dose requirements. There may be an association with donor CYP3A5 expression in liver transplant patients and acute rejection which needs further evaluation. ABCB1 and CYP3A4*22 do not appear to have a significant impact in any of the organ transplants. High tacrolimus variability is associated increased graft loss in renal transplant patients.