Master of Science / Department of Grain Science and Industry / D.L. Wetzel / Chemical imaging enables displaying the distribution of different substances within a field of view based on their fundamental vibrational frequencies. Mid-IR bands are generally strong and feature direct correlation to chemical structure, while near IR spectra consist of overtones and combinations of mid-IR bands. Recently, mid-IR microspectroscopy has enabled determination of the relative substitution of hydroxyl groups with the modifying agent for individual waxy maize starch granules by using synchrotron source. The brightness and non-divergence of the synchrotron source and confocal masking enabled obtaining individual spectra with 5 [mu]m[superscript]2 masking and 1 [mu]m raster scanned steps. Each 1 [mu]m step results from the coaddition of hundreds of scans and lengthy data collection is required to produce data. The recent breakthrough at the Synchrotron Research Center uses a multi-beam synchrotron source combined with a focal plane array microspectrometer. This major improvement in localized detection of the modifying agent within single waxy maize starch granules is the increased efficiency of focal plane array detection and an effective spatial resolution of 0.54 [mu]m. Mixtures of granular solids represent an analytical challenge due to the range of heterogeneity and homogeneity within samples. Near IR imaging provides deeper sample penetration allowing for solid mixture analysis. However, the broad, overlapping bands present in the near IR necessitates statistical data treatment. This requires imaging specimens representative of the individual components to create spectral libraries for classification of each component. Partial least squares analysis then allows characterization and subsequent pixel analysis provides quantitative results. The primary break system for wheat milling was studied as it is key in releasing endosperm to be further ground into fine flour in subsequent processes. The mass balance of endosperm throughout individual unit processes was determined by obtaining flow rates of incoming and outgoing millstreams and calculating endosperm content through pixel identification. The feed milling industry requires the use of a tracer to determine adequate mixing and mix uniformity to limit the time and energy in processing. Near IR imaging allows individual components of a formula feed to serve as a self-tracer, eliminating the need of an inorganic tracer.

Master of Science / Food Science Institute / J. Scott Smith / Carboxymethyllysine (CML) and other advanced glycation end products (AGEs) have been shown to affect diseases such as diabetes, cancer, and Alzheimer’s by inducing oxidative stress, inflammation, and tissue damage. CML is formed in foods through Maillard browning reactions and through various mechanisms that are affected by time, temperature, pH, water activity, trace metals, and antioxidants. Natural antioxidants can be found in plant and fruit extracts, as well as in spices. The research contained herein is in two parts. The first part includes preliminary work, which examines the percent recovery of CML from various solid phase extraction columns, the analysis of CML in maple syrup, barbeque sauce, honey, and infant formula. The data show that solid phase extraction with a C-18 cartridge produced the highest percent recovery when using a CML standard at 100 ppb, with a recovery of 69%. Furthermore, the analysis of the syrups and sauces is inconclusive, due to the very low levels of CML detected in the infant formula, and the complications due to the high levels of reducing sugars. The second part of the research examines the effect that cinnamon, onion, garlic, black pepper, and rosemary have on CML levels in biscuits. The data show that all of the spices inhibit the formation of CML, at each of the 0.5%, 1%, and 2% levels used in the experiment, by a minimum of 3% in 2% onion samples and a maximum of 79% in 0.5% cinnamon samples when looking at the cumulative data. When looking subsets of the data, the CML inhibition was a minimum of 59% in 2% onion samples and a maximum of 74% in 0.5% cinnamon samples. Other trends can be observed in the chroma values in the CML color data, which suggest that chroma values decrease as the spice level increases, but these are not statistically significant. They may be due to color from the spices themselves, or to the chemical changes in the Maillard reaction.

Diss. (sammanfattning) Uppsala : Sveriges lantbruksuniv., 2003. / Härtill 4 uppsatser.

Master of Science / Department of Animal Sciences and Industry / Evan C. Titgemeyer / Two experiments analyzed effects of zilpaterol-HCl and nitrogen supplementation in the form of either dried distiller’s grains with solubles (DDGS) or urea fed to steers. In Experiment 1, steers were fed corn-based diets: control (CON; 10.2% CP), urea (UREA; 13.3% CP), or DDGS (14.9% CP). Nitrogen intake differed among treatments (99, 151, and 123 g/d for CON, DDGS, and UREA). Urea-N synthesis tended to be greater for DDGS (118 g/d) than for UREA (86 g/d), which tended to be greater than CON (52 g/d). Urinary urea-N excretion was greater ([italics]P[italics]<0.03) for DDGS (35.1 g/d) and UREA (28.6 g/d) than for CON (12.7 g/d). Gut entry of urea-N (GER) was numerically greatest for DDGS (83 g/d), intermediate for UREA (57 g/d), and least for CON (39 g/d). Urea-N returned to the ornithine cycle tended to be greater for DDGS (47 g/d) than for UREA (27 g/d) or CON (16 g/d). The percent of microbial N flow derived from recycled urea-N tended ([italics]P[italics]=0.10) to be greater for DDGS (35%) than for UREA (22%) or CON (17%). The percent of urea production captured by ruminal bacteria was greater ([italics]P[italics]<0.03) for CON (42%) than for DDGS (25%) or UREA (22%). Experiment 2 diets were identical to those used in Experiment 1. In addition, steers were also fed either 0 or 60 mg/d zilpaterol-HCl. Dietary CP was 9.6, 12.4, and 13.7% for CON, UREA, and DDGS, respectively. Zilpaterol increased ([italics]P[italics]<0.01) total DMI and N intake; however, zilpaterol did not affect urea entry rate ([italics]P[italics]=0.80) or GER ([italics]P[italics]=0.94). Urea entry rate and GER were numerically greater for DDGS than CON and UREA. In conclusion, zilpaterol did not influence urea entry rate or GER. This lack of response in the face of greater N intake was interpreted to suggest that zilpaterol may reduce urea production and GER at constant N intake.

Master of Science / Department of Grain Science and Industry / Sajid Alavi / Texturized vegetable protein (TVP) based foods offer several advantages compared to animal protein, including lower costs and improved health benefits. Wheat gluten is often processed using extrusion to produce TVP. Processing aids, such as reducing agents (example, cysteine and sodium metabisulfite) and pH modifiers (example, tetra potassium phosphate) aid in texturization. Reduction of sulfhydryl groups, cleavage of disulfide bonds, and reformation of bonds between elongated protein molecules results in protein aggregation and texturization. This study focused on development of a fundamental understanding of these mechanisms for texturization using analytical tools such as the phase transition analyzer (PTA), in combination with lab- and pilot-scale extrusion. The abovementioned three chemicals were added to four varieties of gluten. The control treatment had no additives. PTA was used to understand the operative flow properties of gluten in an environment similar to an extrusion system. Addition of sulfite (0.18%) and cysteine (0.18%) lowered the thermal softening (Ts:36.6-44.1 °C) and thermal flow (Tf:79.6-105.6 °C) temperatures of all varieties of gluten as compared to the controls (Ts:38.8-48.2 °C; Tf:91.7-112.2 °C). Phosphate (3%) did not have the same lowering effect on Ts (40.2-47.0 °C) and Tf (96.2-108.2 °C), indicating a different mechanism. Extrusion studies were conducted to gain an understanding of the reformation of disulfide bonds and texturization. Two of the varieties of gluten, a “superior” one that texturizes well and an “inferior” gluten requiring texturizing aids, were processed on a lab-scale extruder. Pilot scale extrusion was used to process the other two glutens (“superior” varieties) to obtain commercial quality products, which were evaluated for degree of texturization (hydration rate, absorption index and integrity). During lab-scale extrusion, texturization was observed only in the case of phosphate and corresponded with an increase in specific mechanical energy (SME) as compared to the control, indicating disulfide bond reformation. Phosphate also led to significantly (p<0.05) better texturization during pilot-scale extrusion, although SME trends were different due to higher in-barrel moisture and a more ideal extrusion system. Fourier Transform Infrared Spectroscopy was used to examine protein structural changes and indicated a loss of α-helix structure in TVP with an increase in β-sheet formation.

Styrene production by a (FlDAB)PdII(TFA)(η2-C2H4) complex was modeled using density functional theory (DFT). Benzene C-H activation by this complex was studied via five mechanisms: oxidative addition/reductive elimination, sigma-bond metathesis, concerted metalation deprotonation (CMD), CMD activation of ethylene, and benzene substitution of ethylene followed by CMD of the ligated benzene. Calculations provided evidence that conversion of benzene and ethylene to styrene was initiated by the fifth pathway, arylation via CMD of coordinated benzene, followed by ethylene insertion into the Ru-Ph bond, and then β-hydrogen elimination. Also, monomer (active species)/dimer equilibrium concentrations were analyzed. The results obtained from present study were compared with that of a recently reported RhI complex to help identify more suitable catalysts for the direct production of styrene from ethylene and benzene. Second, theoretical studies of heterobimetallic {Ag–Fe(CO)5}+ fragments were performed in conjunction with experiments. The computational models suggested that for this first example of a heterodinuclear, metal-only FeAg Lewis pair (MOLP) that Fe(CO)5 acts as a Lewis base and AgI as a Lewis acid. The ῡCO bands of the studied molecules showed a blue shift relative to those measured for free Fe(CO)5, which indicated a reduction in Fe→CO backbonding upon coordination to silver(I). Electrostatic interaction is predicted via DFT as the dominant mode of Fe—Ag bonding augmented by a modest amount of charge transfer between Ag+ and Fe(CO)5. Third, computational analyses of hypothetical transition metal-terminal boride [MB(PNPR)] complexes were reported. DFT, natural orbital analysis (NBO), and multiconfiguration self-consistent field (MCSCF) calculations were employed to investigate the structure and bonding of terminal boride complexes, in particular the extent of metal dπ - boron pπ bonding. Comparison of metal-boride, -borylene and –boryl bond lengths confirms the presence of metal-boron π bonds, albeit the modest shortening (~ 3%) of the metal-boron bond suggests that the π-bonding is weak. Their instabilities, as measured by free energies of H2 addition to make the corresponding boryl complexes, indicate terminal boride complexes to be thermodynamically weak. It is concluded that for the boride complexes studied, covering a range of 4d and 5d metals, that the metal-boride bond consisted of a reasonably covalent σ and two very polarized π metal-boron bonds. High polarization of the boron to metal π-bonds indicated that a terminal boride is an acceptor or Z type ligand. Finally, anti-Markovnikov addition of water to olefins has been a long-standing goal in catalysis. The [Rh(COD)(DPEphos)]+ complex was found as a general and regioselective group 9 catalyst for intermolecular hydroamination of alkenes. The reaction mechanism was adapted for intermolecular hydration of alkenes catalyzed by a [Rh(DPEphos)]+ catalyst and studied by DFT calculations. Olefin hydration pathways were analyzed for anti-Markovnikov and Markovnikov regioselectivity. On the basis of the DFT results, the operating mechanism can be summarized as follows: styrene activation through nucleophilic attack by OHδ− of water to alkene with simultaneous Hδ+ transfer to the Rh; this is then followed by formation of primary alcohol via reductive elimination. The competitive formation of phenylethane was studied via a β-elimination pathway followed by hydrogenation. The origin of the regioselectivity (Markovnikov vs anti-Markovnikov) was analyzed by means of studying the molecular orbitals, plus natural atomic charges, and shown to be primarily orbital-driven rather than charge-driven.

Master of Science / Department of Agronomy / Ganga M. Hettiarachchi / Phosphorus (P) management in reduced tillage systems has been a great concern for farmers. Conclusive results for benefits of deep banding of P fertilizers for plant yield in reduced tillage system are still lacking. Knowledge of the dominant solid P species present in soil following application of P fertilizers and linking that to potential P availability would help us to design better P management practices. The objectives of this research were to understand the influence of placement (broadcast- vs. deep band-P or deep placed-P), fertilizer source (granular- versus liquid-P), and time on reaction products of P. Greenhouse and field based experiments were conducted to study P behavior in soils. Soil pH, resin extractable P, total P, and speciation of P were determined at different distances from the point of fertilizer application at 5 weeks (greenhouse and field) and 6 months (field) after P application (at rate 75 kg/ha) to a soil system that was under long-term reduced tillage. X-ray absorption near edge structure spectroscopy technique was used to speciate reaction products of fertilizer P in the soil. The reaction products of P formed upon addition of P fertilizers to soils were found to be influenced by soil pH, P placement methods, and P sources. Acidic pH (below~5.8) tended to favor formation of Fe-P and Al-P like forms whereas slightly acidic near neutral pH soils favored formation of Ca-P like forms. Scanning electron microscope with energy dispersive X-ray analysis of applied fertilizer granules at 5-wk showed enrichment of Al, Fe and Ca in granule- indicating these elements begin to react with applied P even before granules dissolve completely. The availability of an applied P fertilizer was found to be enhanced as a result of the deep banding as compared to the surface broadcasting or deep placed methods. Deep banded liquid MAP was found to be in more adsorbed P like forms and resulted greater resin extractable P both at 5 wk and 6 month after application. Deep banding of liquid MAP would most likely result both agronomically and environmentally efficient solution for no-till farmers.