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The mystery surrounding high concentrations of Cr(III) in plants has been uncovered. It is attributed to the presence of low molecular weight organic acids (LMWOA) in soil in which the plants are growing. Apart from that, the factors influencing solubility of Cr(VI) in soil have also been investigated. It was found that the solubility of Cr(VI) species is governed by the presence of CO3 2− ions in a soil solution that resulted when atmospheric CO2 dissolves in soil–water. Concentrations of Cr(VI) and Cr(III) were determined in plants, collected on unpolluted soils in different geographical areas. It was found that the concentration of Cr(VI) in plants correlated with the soluble fraction of Cr(VI) in soil, while Cr(III) concentration in plants is limited by concentration LMWOA in soil. It can therefore be concluded that the high level of Cr(III) in plants is also due to the direct absorptions of the species from soil rich in organic acids.

Health benefits of high molecular weight (MW) β-glucans are well documented. Therefore, understanding and controlling depolymerization of β-glucan in baked products, would increase the effectiveness of β-glucan to confer health benefits. In this study we demonstrated that endogenous β-glucanase in wheat kernels are responsible for the depolymerization of β-glucans. A protocol was developed based on the Megzayme procedure to detect low levels of β-glucanase activity in wheat flour. This was confirmed by using HPLC-Calcofluor detection to monitor molecular weight changes. The distribution of β-glucanase in wheat kernels was also investigated. The effect of genotype, location, planting season and environmental factors on the level of endogenous β-glucanase in selected wheat cultivars was investigated using different wheat varieties planted under different condition and different seasons. Furthermore, kinetics of β-glucan depolymerization by endogenous glucanase in two dough systems with different moisture content was investigated. The results demonstrated that enzymes with β-glucanase activity are concentrated primarily in the outer layer of wheat kernels. Also genotype, environmental conditions and agronomic practice all had significant effects on the β-glucanase activity in wheat flours and poor harvesting conditions can significantly increase β-glucanase activity level in wheat. The kinetics results demonstrated that moisture content, incubation time and levels of endogenous β-glucanase activity of the system had significant impact on the final MW of β-glucan in the dough. Among all factors investigated, moisture content had the greatest impact. This study presents opportunities for industry to fortify baked products with high molecular weight β-glucan. / Ontario Ministry of Agricultural Food and Rural Affairs

This thesis presents the optical trapping of various nanometric particles (both biological and non-biological) and methods that can be used to extract information about the trapped particle from the signal transmitted through a nanoaperture trap. These methods are used to detect the excitation of vibrational modes in trapped particles due to the presence of a beat signal between two tunable trapping lasers and the molecular weight of the particle by examining the transmitted signal. Optical trapping has long been used to trap ever smaller particles in gentle non-destructive ways. In its infancy, only the optical trapping of micron sized particles was feasible. Due to various limitations, changes to the optical trapping scheme were needed to push its limits into the nanometric regime. Nanoaperture assisted optical trapping has allowed for the optical trapping of particles as small as 5 nm in diameter. By making use of specially chosen nanoapertures in gold films higher trapping strengths with lower incident laser powers have become possible. While this is an accomplishment in and of itself there are several issues associated with working with such small systems. Most notably, the ability to observe such systems is very limited. Traditional optical trapping of micron sized particles could make easy use of optical inspection, however in the nanometric regime this is not possible. It has since become a focus of the trapping community to find sophisticated ways to use the limited data available to probe these systems and their trapped targets. Once a particle is trapped the only information available about the particle is contained in the signal transmitted through the nanoaperture. The first main area of research in this thesis covers using this information to extract the molecular weight of the trapped particles for identification. In the same vein, Raman has been a tool widely used in the past to identify and probe systems of large ensembles of particles. While this is incredibly effective in some situations, it is not effective at the single particle limit. To form an analog that can be used within an optical trapping setup a new method of exciting Raman active vibrational modes with twin trapping lasers is presented. The low wavenumber vibrational spectra are presented for several different particles as well as a wide array of globular proteins. / Graduate

In wheat (Triticum aestivum L), high molecular weight glutenin subunits (HMW -GS) are synthesized by the loci Glu-A1, Glu-B1, and Glu-D1 on the long arm of group 1 chromosome, and their variants play a significant role in the functional properties of flour; hence dough properties and tortilla quality. This study was conducted to understand the effects of HMW-GS on dough properties and tortilla quality using 40 different wheat lines from two different locations; Texas Agrilife Experiment Station at McGregor, and at Castroville, Texas, in 2010. Wheat lines in which one or more of these loci were absent (deletion lines) and non-deletion lines were used. Flours were evaluated for insoluble polymeric protein (IPP) content and mixograph properties. Dough properties; compression force, stress relaxation test, and dough extensibility, were determined using a texture analyzer. Tortillas were produced by hot-pressed method and evaluated for physical properties and textural change during 16 days of storage. Flour from deletion lines had lower average IPP content (38.4%) than non-deletion lines (41.9%). Dough from deletion lines were more extensible (44.8 mm) and required lower equilibrium force from stress relaxation test (4.91 N) compared to non-deletion lines (34.2 mm, and 6.56 N, respectively). Deletion lines produced larger diameter tortillas (177 mm) than non-deletion lines (165 mm) and had lighter color (L* = 82.3) than tortillas from non-deletion lines (L* = 81.0). Most of the deletion lines interestingly produced tortillas with acceptable flexibility scores on day 16 of storage (>= 3.0). Flour IPP content (r = -0.57) and equilibrium force (r = -0.80) were negatively correlated with tortilla diameter, but positively correlated with 16 day flexibility scores (r = 0.72, and r = 0.68, respectively). In general, deletion at Glu-A1 or Glu-D1 or presence of 2+12 instead of 5+10 allelic pair at Glu-D1 locus produced large diameter tortillas, but with poor day 16 flexibility. However, combination of 7+9 at Glu-B1 locus with deletions at Glu-A1 or Glu-D1 or 2+12 at Glu-D1 consistently produced tortillas that had large diameter and retained good flexibility scores during 16 days of storage. The results indicate the presence of 7+9 at Glu-B1 may play a crucial role in selection of wheat varieties for tortilla making.

Doctor of Philosophy (PhD), Engineerig / Free radical emulsion polymerization (FRP) is widely adopted in industry due to its applicability to a wide range of monomers. Despite its many benefits and wide spread use, the fast chain growth and the presence of rapid irreversible termination impose limitations with respect to the degree of control in FRP. Furthermore, producing block copolymers and polymers with complex structures via FRP is not feasible. Closer control of macromolecular chain structure and molar mass, using novel polymerization techniques, is required to synthesize and optimize many new polymer products. Reversible addition fragmentation chain transfer (RAFT)-mediated polymerization is a novel controlled living free radical technique used to impart living characters in free radical polymerization. In combination with emulsion polymerization, the process is industrially promising and attractive for the production of tailored polymeric products. It allows for the production of particles with specially-tailored properties, including size, composition, morphology, and molecular weights. The mechanism of RAFT process and the effect of participating groups were discussed with reviews on the previous work on rate retardation. A mathematical model accounting for the effect of concentrations of propagating, intermediate, dormant and dead chains was developed based on their reaction pathways. The model was combined with a chain-length dependent termination model in order to account for the decreased termination rate. The model was validated against experimental data for solution and bulk polymerizations of styrene. The role of the intermediate radical and the effect of RAFT agent on the chain length dependent termination rate were addressed theoretically. The developed kinetic model was used with validated kinetic parameters to assess the observed retardation in solution polymerization of styrene with high active RAFT agent (cumyl dithiobenzoate). The fragmentation rate coefficient was used as a model parameter, and a value equal to 6×104 s-1 was found to provide a good agreement with the experimental data. The model predictions indicated that the observed retardation could be attributed to the cross termination of the intermediate radical and, to some extent, to the RAFT effect on increasing the average termination rate coefficient. The model predictions showed that to preserve the living nature of RAFT polymerization, a low initiator concentration is recommended. In line with the experimental data, model simulations revealed that the intermediate radical prefers fragmentation in the direction of the reactant. The application of RAFT process has also been extended to emulsion polymerization of styrene. A comprehensive dynamic model for batch and semi-batch emulsion polymerizations with a reversible addition-fragmentation chain transfer process was developed. To account for the integration of the RAFT process, new modifications were added to the kinetics of zero-one emulsion polymerization. The developed model was designed to predict key polymer properties such as: average particle size, conversion, particle size distribution (PSD), and molecular weight distribution (MWD) and its averages. The model was checked for emulsion polymerization processes of styrene with O-ethylxanthyl ethyl propionate as a RAFT based transfer agent. By using the model to investigate the effect of RAFT agent on the polymerization attributes, it was found that the rate of polymerization and the average size of the latex particles decreased with increasing amount of RAFT agent. It was also found that the molecular weight distribution could be controlled, as it is strongly influenced by the presence of the RAFT based transfer agent. The effects of RAFT agent, surfactant (SDS), initiator (KPS) and temperature were further investigated under semi-batch conditions. Monomer conversion, MWD and PSD were found to be strongly affected by monomer feed rate. With semi-batch mode, Mn and <r> increased with increasing monomer flow rate. Initiator concentration had a significant effect on PSD. The results suggest that living polymerization can be approached by operating under semi-batch conditions where a linear growth of polymer molecular weight with conversion was obtained. The lack of online instrumentation was the main reason for developing our calorimetry-based soft-sensor. The rate of polymerization, which is proportional to the heat of reaction, was estimated and integrated to obtain the overall monomer conversion. The calorimetric model developed was found to be capable of estimating polymer molecular weight via simultaneous estimation of monomer and RAFT agent concentrations. The model was validated with batch and semi-batch emulsion polymerization of styrene with and without RAFT agent. The results show good agreement between measured conversion profiles by calorimetry with those measured by the gravimetric technique. Additionally, the number average molecular weight results measured by SEC (GPC) with double detections compare well with those calculated by the calorimetric model. Application of the offline dynamic optimisation to the emulsion polymerization process of styrene was investigated for the PSD, MWD and monomer conversion. The optimal profiles obtained were then validated experimentally and a good agreement was obtained. The gained knowledge has been further applied to produce polymeric particles containing block copolymers. First, methyl acrylate, butyl acrylate and styrene were polymerized separately to produce the first block. Subsequently, the produced homopolymer attached with xanthate was chain-extended with another monomer to produce block copolymer under batch conditions. Due to the formation of new particles during the second stage batch polymerization, homopolymer was formed and the block copolymer produced was not of high purity. The process was further optimized by operating under semi-batch conditions. The choice of block sequence was found to be important in reducing the influence of terminated chains on the distributions of polymer obtained. It has been found that polymerizing styrene first followed by the high active acrylate monomers resulted in purer block copolymer with low polydispersity confirmed by GPC and H-NMR analysis.

Diss. (sammanfattning) Stockholm : Karol. inst. / Härtill 6 uppsatser.

Thesis (Ph. D.)--Technische Universiteit Eindhoven, 1993. / Includes bibliographical references.

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