Urea aqueous solution is ubiquitously used to denature protein. Regardless of its extensive use, the mechanism is still unclear and remains an active field of study. There have been two proposed mechanisms, the direct and indirect. The indirect mechanism, which attributes the ability of urea of changing water structure, is susceptible since many research works show that there is little effect of urea on water structure. The current study provided evidence for the indirect mechanism by demonstrating that the introduction of urea slightly changes the water structure in the hydrophobic interfacial areas. In the current study, the urea aqueous solution systems with either gas-liquid or hydrophobic interface are studied by MD simulations, and the structures of water near the interfacial areas are analyzed in terms of density, orientation and number of hydrogen bonds. For each kind of interface, systems with four different urea concentrations are included, ranging from 0M to 8M. The results show slight change of water structure by the urea solute on the hydrophobic interface in terms of the orientation and number of hydrogen bonds per water molecule.

Twenty-four Quarter horse weanlings (120 d +/- 10 d) were blocked by age into 4 groups (n = 6) for a 56 d trial to evaluate the influence of methionine on growth and nitrogen retention. Weanlings were housed by block and individually fed 1 of 4 concentrate diets twice daily at 1.5% BW (as fed). Weanlings were randomly assigned to 1 of 4 treatments: basal (0.20 MET), basal + 0.03% methionine (0.23 MET), basal + 0.07% methionine (0.27 MET), and basal + 0.11% methionine (0.31 MET). Diets were formulated to be isonitrogenous, isocaloric, and contain equal amounts of LYS and THR. Coastal bermudagrass hay was individually fed at 0.75% BW (as fed). Growth measurements, body weight, rump fat, and plasma were obtained every 7 d. The final 4 days consisted of total collection of urine and feces. Feed, fecal, and urine samples were analyzed for nitrogen content and nitrogen balance was calculated. Urine was analyzed for urea and ammonia concentration. Plasma was analyzed for urea concentration. Grain, hay, and fecal samples were analyzed for nutrient composition. Data were analyzed using the PROC MIX procedure of SAS. Linear, quadratic, and cubic effects were tested in the form of contrasts. There was no influence of treatment on growth measurements, nitrogen balance, or urinary urea or ammonia. Intake of LYS and THR (g/d) did not differ among treatments (P = 0.78 and P = 0.38 respectively). Plasma urea nitrogen (PUN) was influenced by treatment (P = 0.005) exhibiting quadratic (P = 0.04) and cubic (P = 0.002) effects. An unexpected peak in PUN was observed with 0.27 MET. Upon analysis, 0.20 MET contained more lysine than formulated, and 0.27 MET contained the least lysine. Treatments 0.20 MET and 0.31 MET contained more threonine compared to formulations. These differences may explain unexpected values of PUN concentration. Results suggest future studies that more closely isolate methionine as the only dietary variable are necessary to better explain the methionine requirements of weanling horses.

In the present study, a new "anti-Bredt" bicyclic urea, 1,3-diazabicyclo[3·3·1]nonan-2-one, and an isomeric bond-bridged reference compound 1,8-diazabicyclo[4·3·0]nonan-9-one, were synthesized. The [3·3·1] urea was prepared in two ways. 3-Aminomethylpiperidine was reacted with phosgene. Deprotonation of the precipitated ammonium salt with triethylamine gave the urea. In another method, thermal depolymerization (in vacuo) of a glassy product arising from the reaction of 3-aminomethylpiperidine with diphenyl carbonate afforded the urea. The [4·3·0] urea was obtained through the reaction of diphenyl carbonate with 2-aminomethylpiperidine. No glassy intermediate was observed. The [4·3·0] and [3·3·1] ureas resisted hydrolysis. The former would not polymerize either in bulk or in solution at any temperature with or without initiator catalysts. At 120° and above the [3·3·1] urea bulk polymerized within 30 minutes with or without catalysts. The uncatalysed thermal polymerization gave lower molecular weight polymers in lower yield than the catalysed one. Cationic initiator, phenylphosphonic acid, and anionic potassium tertiary butoxide catalysts gave highest molecular weight polymers. Comparatively, the anionic initiator generated a higher molecular weight polymer than the cationic one. Dibutyltin oxide which is a coordination metal catalyst was also effective in generating high polymer but the yield compared favorably only with the uncatalysed thermal polymerization. The bulk polymerization of the [3·3·1] urea is one of the rare cases of polymerization of a bicyclo [3·3·1] nonan derivative. The mechanism proposed for the thermal polymerization of [3·3·1] urea involved the dissociation of the urea to an aminoisocyanate which then propagated the polymerization. The reaction of 3-aminopiperidine with diphenyl carbonate afforded a urea which was proposed to be a dimer of the desired urea, 1,6-diazabicyclo[3·2·1]octan-7-one. The unsuccessful syntheses of two ureas possessing two nitrogen bridgehead atoms, 1,5-diazabicyclo[3·2·1]octan-8-one, and 1,5-diazabicyclo[3·3·1]nonan-9-one, and another which was seven-membered, 1,3-diazabicyclo[3·2·2]nonan-2-one, were explained in terms of their canonical forms violating Wiseman's rule. However, a nuclear magnetic resonance (NMR) spectrum evidence of the formation of 1,5-diazabicyclo[3·2·1]octan-8-one in the NMR tube was presented.

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No description available.

The use of urea fertiliser has been associated with relatively poor nitrogen (N) use efficiency (NUE) due to heavy N losses such as gaseous emissions of ammonia (NH₃) and nitrous oxide (N₂O) and nitrate (NO₃⁻) leaching into surface and ground waters. Improving N use-efficiency of applied urea is therefore critical to maximise its uptake and to minimise its footprint on the environment. The study was conducted under laboratory-glasshouse conditions (Chapter 2-4)and lysimiter-field plot studies (Chapter 5). In chapter 2, Two glasshouse-based experimentswere conducted to investigate the potential of incorporating urea fertiliser with ureaseinhibitor, (N-(n-butyl) thiophosphoric triamide (nBTPT) or ‘Agrotain’) to enhance fertiliser N uptake efficiency. Urea, with or without Agrotain, was applied to Ryegrass (Lolium perenne L.) grown in standard plant trays maintained at soil moisture contents of 75–80% field capacity, at rates equivalent to 25 or 50 kg Nha⁻¹. These treatments were compared with other common forms of N fertilisers (ammonium nitrate, ammonium sulphate and sodium nitrate). In a separate pot experiment, granular ¹⁵N urea (10 atom %) with or without Agrotain, was applied at 25 kg Nh⁻¹ to track N use-efficiency and the fate of ¹⁵N-labelled fertiliser. In both experiments, Agrotain-treated urea improved bioavailability (defined as the fraction of total soil N that can interact with a biological target in the plant or that can be taken up by plant) of added N and resulted in significantly higher herbage DM yield and N uptake than urea alone or other forms of N fertilisers. Results from the ¹⁵N experiment support the suggestion that a delay in urea hydrolysis by Agrotain provided an opportunity for direct plant uptake of an increased proportion of the applied urea-N than in the case of urea alone. In chapter 3, two more glasshouse-based experiments were conducted to investigate if urea applied in fine particle application (FPA), with or without Agrotain, had any effect on fertiliser-N uptake efficiency (defined as the difference in N uptake between the fertiliser treatment and the control as a percentage of the amount of N applied) under optimum soil moisture (75-80% field capacity) and temperature (25 °C) conditions, in comparison with other common forms of N fertilisers applied, either in FPA or in granular form. In a separate pot experiment, ¹⁵N urea (10 atom %), with or without Agrotain, was applied to either shoots or leaves only or to the soil surface (avoiding the shoots and leaves) to determine urea hydrolysis, herbage DM and ¹⁵N uptake. In both experiments, herbage DM yield and N uptake were significantly greater in the FPA treatments than in those receiving granular application. Agrotain-treated urea FPA resulted in significantly higher N response efficiency (difference between the dry matter produced by the various fertiliser treatments and the control, divided by the amount of N applied) than urea FPA alone or other forms of N fertilisers. Results from the ¹⁵N experiment support the idea that Agrotain treatment improves the N response of urea applied in FPA form due to a delay in hydrolysis of urea, thus providing herbage an extended opportunity to absorb added urea directly through leaves, cuticles and roots. A further glasshouse-based study was conducted to investigate the effect of Agrotain and irrigation on urea hydrolysis and its movement in a Typic Haplustepts silt loam soil (Chapter 4). A total of 72 repacked soil cores (140 mm inner diameter and 100 mm deep) were used - half (36) of these cores were adjusted to soil moisture contents of 80% field capacity (FC) and the remaining 36 cores to 50% FC. Granular urea, with or without Agrotain, was applied at a rate equivalent to 100 kg N ha⁻¹. Twelve pots were destructively sampled at each day after 1, 2, 3, 4, 7, and 10 days of treatment application to determine urea hydrolysis and its lateral and vertical movement in different soil layers. Agrotain-treated urea delayed urea hydrolysis compared with urea alone during the first 7 days of its application. This delay in urea hydrolysis by Agrotain enabled added urea to disperse and move away from the surface soil layer to the sub-surface soil layer both vertically and laterally. In contrast, most urea in the absence of Agrotain hydrolysed within 2 days of its application. Irrigation after 1 day resulted in further urea movement from the surface soil layer (0-10 mm) to the sub-soil layer (30-50 mm) in Agrotain-treated urea. These results suggest that Agrotain delayed urea hydrolysis and allowed more time for rainfall or irrigation to move the added urea from the surface layer to sub-soil layers where it is likely to make good contact with plant roots. This distribution of urea in the rooting zone (0-200 mm) has the potential to enhance N use efficiency and minimise N losses via ammonia (NH₃) volatilisation from surface-applied urea. Finally, a field study using lysimeters (300 mm inner diameter and 400 mm deep), and small field plots (1 m² in area) was established using a silt loam Typic Haplustepts soil (Soil Survey Staff 1998) to investigate the effect of FPA and granular applications of urea, with or without Agrotain, on N losses and N use efficiency (Chapter 5). The five treatments were: control (no N) and ¹⁵N-labelled urea (10 atom %), with or without Agrotain, applied to lysimeters or mini plots (un-labelled urea), either in granular form to the soil surface or in FPA form (through a spray) at a rate equivalent to 100 kg N ha⁻¹. Gaseous emissions of NH₃ and N₂O, NO₃⁻ leaching, herbage production, N response efficiency, total N uptake and total recovery of applied ¹⁵N in the plant and soil were determined up to 63 days. Urea-alone and urea with Agrotain, applied in FPA form, was more effective than its granular form and reduced N2O emissions by 5-12% and NO3- leaching losses by 31-55%. Urea-alone applied in FPA form had no significant effect in reducing NH₃ losses compared with granular form. However, urea with Agrotain applied in FPA form reduced NH₃ emissions by 69% compared with the equivalent granular treatment. Urea-alone and with Agrotain applied in FPA form increased herbage dry matter production by 27% and 38%, and N response efficiency compared with the equivalent granular urea application, respectively. Urea applied in FPA form resulted in significantly higher ¹⁵N recovery in the shoots compared with granular treatments – this was improved further when urea in FPA form was applied with Agrotain. Thus, treating urea with Agrotain in FPA under field conditions has the potential to delay its hydrolysis, minimise N losses and improve N use efficiency and herbage production. The lower dry matter production and N-response efficiency to urea applied in FPA form in Chapter 3 are probably because of additional factors such as lower application rates (25 kg N ha⁻¹ ) or lack of interception of urea by the leaves. Applying urea in FPA form is a good management strategy and I conclude that combining FPA urea with Agrotain has the potential to increase N use efficiency and herbage production further.

Thesis (Ph. D.)--University of Nevada, Reno, 2006. / "May, 2006." Includes bibliographical references. Online version available on the World Wide Web.

Thesis (M.S.)--Auburn University, 2007. / Title from title screen (viewed on Jan. 31, 2008). Abstract. Vita. Includes bibliographic references (ℓ. 47-51)

Thesis (Ph. D.)--University of Adelaide, 1987. / Includes bibliographical references (leaves 132-147).

Thesis (Ph.D.)--University of Western Sydney, Nepean, 1994. / Bibliography: leaves 227-256.