The main objectives of this research were to examine effects of protein modification (protein cleavage and crosslinking) on turkey meat gelation and to evaluate textural properties and water holding capacity of meat gels prepared from normal and PSE (pale, soft, exudative) turkey breast meat.<p>First, the effect of protein degradation on turkey breast meat gelation was studied. To create different extent of proteolysis in the meat, á-chymotrypsin (EC 3.4.21.1) was added to normal and PSE meat batters at 0, 2.5, 5 and 10 ppm levels. Sodium dodecyl sulphate-polyacrylamide gel electrophoresis (SDS-PAGE) of cooked meat gels showed progressive protein hydrolysis with increasing enzyme level. Texture profile analysis and torsional analysis of the cooked meat gels showed an incremental deterioration in texture with increasing enzyme level. This inferior texture caused by proteolysis was similar to that observed in the gels made from PSE turkey meat alone. Pearson correlation coefficients indicated gel textural properties and expressible moisture were highly correlated to the degree of proteolysis, especially to that of myosin heavy chain (p < 0.001).<p>The second study focused on modifying protein size to improve meat gelation, especially PSE meat gelation. Transglutaminase (TGase, EC 2.3.2.13) was chosen due to its ability to catalyze crosslinking of proteins. Pea protein isolate, an alternative to soy protein, was also evaluated as a meat protein extender. Textural profile and torsional gelometry analyses of the cooked meat gels showed TGase alone significantly (p < 0.05) increased gel texture, especially for those made from PSE meat. However, cook yield of the meat gels was compromised possibly due to steric effects. Addition of pea protein isolate alone improved cook yield and gel texture, especially for the gels made from PSE meat. The combination of TGase and pea protein produced the strongest meat gels, while maintaining a similar cook yield to the control. SDS-PAGE showed the disappearance of several protein bands contributed from the meat or pea protein with TGase addition, indicating that these likely were crosslinked and too large to enter the gel. Dynamic rheological analysis revealed TGase altered the viscoelastic properties of the meat or meat-pea protein mixtures and produced more elastic gels on cooling.<p>This research indicated proteolysis had a dramatic impact on textural properties of turkey breast meat gels. Crosslinking of proteins catalyzed by TGase significantly improved gel texture, especially for the gels made from PSE meat. However, TGase-assisted crosslinking of proteins resulted in greater cooking losses unless an extender/adjunct such as pea protein was added.

The compound 2,6-anthracenedicarboxylic acid is used as a comonomer for the synthesis of poly(ethylene terephthalate). The resulting copolymers are characterized and further functionalized by Diels-Alder grafting or crosslinking through the anthracenate unit. Diels-Alder reaction is used to graft small molecules and oligomers endcapped with maleimide as dienophiles on to poly(ethylene terephthalate-co-2,6-anthracenedicarboxylate),PET-co-A. Maleimide-capped poly(ethylene glycol) is grafted onto PET-co-A to improved its hydrophilicity. 2,6-Anthracenedicarboxylic acid is also incorporated into the known liquid crystalline polymer, LCP, poly(4-oxybenzoate-co-1,4-phenylene isophthalate), HIQ40. The resulting copolymer, poly(4-oxybenzoate-co-1,4-phenylene isophthalate-co-2,6-phenylene anthracenate), HIQ40-co-A, shows LCP behavior. These HIQ40-co-A copolymers are grafted with maleimide end-capped monomers and polymers andcrosslinked with bismaleimides through a Diels-Alder mechanism.

This thesis presents the first reported grafted PPE - polycaprolactone-g-PPE; the first PPE based sensing model: biotinylated grafted PPE/streptavidin coated sphere; the first photocrosslinkable PPE ¨C allyloxy PPE; and the new mechanism which demonstrates morphology control on a single molecular level

As a low cost natural polymer, starch is widely used in paper, food, adhesive, and many other industries. In order to improve the performance of starch, crosslinking is often conducted either in the processes of starch modification or during the application processes. Many crosslinkers have been developed in the past for crosslinking starch. Ammonium zirconium carbonate (AZC) is one of the common crosslinkers for crosslinking starch in aqueous solutions, having been widely used as a starch crosslinking agent in paper surface coating for more than 20 years. However, the mechanisms of starch crosslinking with AZC have not been well studied. In order to optimize the crosslinking chemistry of starch and find new paths for the utilization of starch in papermaking, a better understanding of the starch crosslinking mechanism is necessary. This thesis focuses on the fundamental study of starch crosslinking in an aqueous solution and its applications in fiber surface grafting, filler modification, and starch nanoparticle formation. Particularly, the thesis contains three major parts: (1) Mechanism study of starch crosslinking induced by AZC: In this thesis, the crosslinking (or gelation) kinetics of starch/AZC blends were investigated by using rheological measurements. The evolution of viscoelastic properties of AZC solutions and the AZC-starch blends was characterized. It was found that for both AZC self-crosslinking and AZC-starch co-crosslinking, the initial bond formation rate and the gel strength had a strong power law relationship with the concentrations of both AZC and starch. It is suggested that the development of the crosslinking network is highly dependent on the AZC concentration, while the starch concentration effect is less significant. It was determined that the activation energy of AZC self-crosslinking was approximately 145-151 kJ/mol, while the activation energy of AZC-starch co-crosslinking was 139 kJ/mol. (2) Fiber and filler modifications with starch and crosslinkers: Besides reacting with starch, AZC can react with cellulose which also contains hydroxyl groups. Theoretically, it is possible to use AZC as a crosslinker / coupling agent to graft starch onto cellulose fibers. It is believed that the grafted starch on fiber surfaces can improve the fiber bonding capability. In this thesis, a facile method to graft starch onto cellulose fiber surfaces through the hydrogen bond formation among cellulose, starch and AZC was developed. Compared with the paper sheets made of fibers with an industry refining level (420 ml CSF), the paper sheets made of fibers with a much lower refining degree but with grafted starch showed higher paper strengths, including the tensile strength, stiffness and z direction tensile; meanwhile, a faster drainage rate during web formation could also be achieved. Not only can the fiber-fiber bonding be improved by grafting starch onto fiber surfaces, but the filler-fiber bonding can also be improved if starch can be effectively coated on the filler surface. This concept has been supported by the early studies. In this thesis, the effects of the crosslinking of starch in the filler modification for the papermaking application were also studied. (3) Mechanism of starch nanoparticle formation during extrusion with crosslinkers: It was reported that starch crosslinking could facilitate the reduction of starch particle size during reactive extrusion. However, the mechanism of the particle size reduction by starch crosslinking was not illustrated. The reason that the crosslinking can cause the particle size reduction of starch during extrusion is fundamentally interesting. In this thesis, the mechanism of starch particle size reduction during extrusion with and without crosslinkers was investigated by identifying the contributions of thermal and mechanical effects. The effects of extrusion conditions, including temperature, screw speed, torque, starch water content and crosslinker addition, on the particle size were studied. It was found that the addition of crosslinkers could significantly increase the shear force (torque), and consequently facilitate the reduction of the particle size. The results indicate that for extrusion without a crosslinker, the starch particle size decreased with the increase of temperature. At 100 degree Celsius, the starch particles with a size of 300 nm could be obtained. With the addition of appropriate crosslinkers (glyoxal), the starch particle size could be reduced to around 160 nm, even at a lower extrusion temperature of 75 degree Celsius .

Compared to the conventional amine adsorption process to separate CO₂ from natural gas, the membrane separation technology has exhibited advantages in easy operation and lower capital cost. However, the high CO₂ partial pressure in natural gas can plasticize the membranes, which can lead to the loss of CH₄ and low CO₂/CH₄ separation efficiency. Crosslinking of polymer membranes have been proven effective to increase the CO₂ induced plasticization resistance by controlling the degree of swelling and segmental chain mobility in the polymer. This thesis focuses on extending the success of crosslinking to more productive asymmetric hollow fibers. In this work, the productivity of asymmetric hollow fibers was optimized by reducing the effective selective skin layer thickness. Thermal crosslinking and catalyst assisted crosslinking were performed on the defect-free thin skin hollow fibers to stabilize the fibers against plasticization. The natural gas separation performance of hollow fibers was evaluated by feeding CO₂/CH₄ gas mixture with high CO₂ content and pressure.

Includes vita. / Title from PDF of title page. / Document formatted into pages; contains 172 pages. / Thesis (PH.D.)--University of South Florida, 2003. / Includes bibliographical references. / Text (Electronic thesis) in PDF format. / ABSTRACT: Modeling methods are required for predicting the chemical stability of macromolecular materials used in critical spacecraft components of satellites orbiting in the high-energy radiation environment of near earth and deep space planetary magnetic belts. Methods for establishing degradation mechanisms and predicting and simulating the total absorbed dose and ionization for long term space missions are presented herein. This investigation evaluates cross-linking, main-chain scission and elimination products in a linear series of narrowly dispersed poly(methyl methacrylate) (PMMA) and polystyrene (PS) polymers. A comparison is made of the scission radiation yield (Gs) and crosslinking (Gx) predicted for the simulated ionization data to the results of degradation in a ground-based simulation of the space radiation environment using a 60Co source. / ABSTRACT: The influence of molecular weight on the stability of post-irradiated polymer is evident in the degree of change observed for each molecular weight series with respect to the degradation products produced by exposure to gamma radiation. The analysis of the specific polymer degradation products and changes in the average molecular weight (Mw) were performed using chemical analysis (FTIR and GPC) and thermal analysis (DSC). The analytical results for PMMA and polystyrene radiation-induced degradation products demonstrate that, depending on Mw, the amount and types of degradation products will vary with respect to crosslinking, chain scission and other oxidative pathways. The results support the preference for end group loss with free volume properties driving the observed differences in the G(s) and (Gx) values. / ABSTRACT: The cross-linking observed for polystyrene is controlled by molecular weight as well wherein the lowest molecular weight molecules display greater resistance to cross-linking. This research investigation employs proven tools of analysis (NASA AP8 and AE8) that accurately predict the amount of energy applied to spacecraft materials during a typical near-earth, aggressive mission environment . Another model (SPENVIS) is applied to determine the amount of total energy absorbed by the spacecraft materials from proton, electron and Brehmsstralung radiation throughout the mission life. Another set of models (SRIM and CASINO) are used to asses the range of penetration of particles into the materials and the extent of ionization caused by the particle spectrum and fluence. The absorption coefficients for the PS and PMMA structure are determined to ensure good correlation between ground simulation and the true space environment. / ABSTRACT: The total dose values are used to establish the total dose that is to be deposited during the ground simulation experiments. A 60Co irradiator was used as the ground simulation source. Dosimetry was used to determine the exposure time needed to deposit an equivalent amount of dose accumulation needed to simulate the total dose modeled for the space mission. Using gel permeation chromatography, previous studies have demonstrated that the characteristic Gaussian distribution of narrowly-dispersed PS and PMMA is perturbed by the accumulation of degradation products following irradiation. The change in distribution provides insight into the preferred path of degradation. The role of free volume in the glass transition temperature are reported with respect to Tg variation with molecular weight. Using differential scanning calorimetry. / ABSTRACT: The role of free volume in the determination of the mechanism of radiation-induced degradation is a primary focus of this investigation when considering the ability of the main chain to recombine or undergo abstraction as opposed to crosslinking or scission where motion is restricted in the solid state. The subtle distinction of structural changes brought about by the loss of side groups, double bond formation and crosslinking have been characterized by infrared spectroscopy. The resultant spectra of irradiated polymers offer considerable information on verifying the extent of competing reactions that involve structural features of the molecule. These instrumental methods are the tools of research that will assess the affect of molecular structure on polymer radiation resistance, and will support the rationale explaining the preference for one degradation mechanism over another. / ABSTRACT: This research investigation has yielded information on the affect of polymer molecular structure on radiation resistance. The work goes beyond previous studies that define empirical observations for a change in radiation resistance by virtue of a change in side group. The effect of free volume, stabilized intermediates and reactive intermediates are related to molecular weight and side group functionality. The understanding of the mechanistic rationale behind the effect of structural features on polymer radiation resistance are essential to the development of modeling systems for predicting polymer stability in space mission environments. / System requirements: World Wide Web browser and PDF reader. / Mode of access: World Wide Web.

This dissertation has aimed to fabricate polypeptide based biomaterial and characterize physical properties. Electrospinning is used as a tool for the sample fabrication. Project focused on determining the feasibility of electrospinning of certain synthetic polypeptides and certain elastin-like peptides from aqueous feedstocks and to characterize physical properties of polymer aqueous solution, cast film and spun fibers and fiber mats. The research involves peptide design, polymer electrospinning, fibers crosslinking, determining the extent of crosslinking, fibers protease degradation study, fibers stability and self-organization analysis, structure and composition determination by various spectroscopy and microscopy techniques and characterization of mechanical properties of individual suspended fibers. Fiber mats of a synthetic cationic polypeptide poly(L-ornithine) (PLO) and an anionic co-polypeptide of L-glutamic acid and L-tyrosine (PLEY) of defined composition have been produced by electrospinning. Fibers were obtained from polymer aqueous solution at concentrations of 20-45% (w/v) in PLO and at concentrations of 20-60% (w/v) in PLEY. Applied voltage and spinneret-collector distance were also found to influence polymer spinnability and fibers morphology. Oriented fibers were obtained by parallel electrodes geometry. Fiber diameter and morphology was analyzed by scanning electron microscopy (SEM) and atomic force microscopy (AFM). PLO fibers exposed on glutaraldehyde (GTA) vapor rendered fiber mats water-insoluble. A common chemical reagent, carbodiimide was used to crosslink PLEY fibers. Fiber solubility in aqueous solution varied as a function of crosslinking time and crosslinker concentration. Crosslink density has been quantified by a visible-wavelength dye-based method. Degradation of crosslinked fibers by different proteases has been demonstrated. Investigation of crosslinked PLEY fibers has provided insight into the mechanisms of stability at different pH values. Variations in fiber morphology, elemental composition and stability have been studied by microscopy and energy-dispersive X-ray spectroscopy (EDX), following the treatment of samples at different pH values in the 2-12 range. Fiber stability has been interpreted with reference to the pH dependence of the UV absorbance and fluorescence of PLEY chains in solution. The data show that fiber stability is crucially dependent on the extent of side chain ionization, even after crosslinking. Self-organization kinetics of electrospun PLO and PLEY fibers during solvent annealing has been studied. After being crosslinked in situ, fibers were annealed in water at 22 °C. Analysis by Fourier transform infrared spectroscopy (FTIR) has revealed that annealing involved fiber restructuring with an overall time constant of 29 min for PLO and 63 min for PLEY, and that changes in the distribution of polymer conformations occurred during the first 13 min of annealing. There was a substantial decrease in the amount of Na+ bound to PLEY fibers during annealing. Kinetic modeling has indicated that two parallel pathways better account for the annealing trajectory than a single pathway with multiple transition states. Bacteria have been engineered to make novel 250-mer elastin-like polypeptides (ELPs). Each was predicted to have an absolute net charge of less than 0.05 electron charges per amino acid residue in aqueous solution at neutral pH. Polymer structure in solution has been assessed by Circular dichroism spectroscopy (CD) and dynamic light scattering (DLS). Suitability for materials manufacture has been tested by electrospinning. Here, we have also tested the hypothesis that blending polypeptides of radically different amino acid composition will enable the realization of novel and potentially advantageous material properties. Aqueous polymer feedstock solutions consisted of pure ELP or ELP blended with a synthetic polypeptide, PLEY, which is highly ionized at neutral pH and spinnable. Morphology analysis of blended fibers by SEM has revealed the formation of a surprising variety of structures that are not seen in fibers of ELP or PLEY alone, for example, hollow beads. Analysis of blended fibers by fluorescence microscopy showed that there was little or no phase separation, despite the large difference in electrical properties between ELP and the synthetic polymers. Structure and composition of PLO, PLEY, ELPs and blends and electrospun fibers made of these polymers have been determined and compared. CD and FTIR have been utilized to obtain structural information on these polymers in aqueous solution, cast films and fibers. Fiber composition has been analyzed by EDX. Protein adsorption has been analyzed by quantitative fluorescence microscopy. The polymers adopted random coil-like conformations in aqueous feedstocks at neutral pH and in dehydrated cast films and fibers on glass, and the fibers comprised numerous counterions, according to spectral analysis. Adsorption of model proteins and serum proteins onto hydrated and crosslinked fibers depended on the electrical charge of the proteins and the fibers. The surface charge density of the fibers will be comparable to, but less than, the charge density on the outer leaflet of the plasma membrane of usual eukaryotic cells. Mechanical properties of a series of as-spun and crosslinked PLO and PLEY nanofibers with various diameters have been analyzed by using the pure bending mode and AFM technique. Aligned nanofibers were deposited on top of a microsized groove etched on a glass substrate. AFM tip was used as a probe, which could apply a measurable deflection and force onto the suspended nanofiber at a force calibration mode, so that the Young's modulus of a single nanofiber can be calculated based on the basic beam bending theories. The Young's moduli of the studied peptide nanofibers increased significantly with decreased fiber diameters. This study has also demonstrated that crosslinked electrospun PLO and PLEY fibers have a higher Young's modulus compared with their as-spun counterparts. Taken together, the results will advance the rational design of polypeptides for peptide-based materials, especially materials prepared by electrospinning. It is believed that this research will increase basic knowledge of polymer electrospinning and advance the development of electrospun materials, especially in medicine and biotechnology. The study has yielded two advances on previous work in the area: avoidance of an animal source of peptides and avoidance of inorganic solvent. The present results thus advance the growing field of peptide-based materials. Non-woven electrospun fiber mats made of polypeptides are increasingly considered attractive for basic research and technology development in biotechnology, medicine and other areas.

This dissertation presents enabling technologies to fabricate thermo-responsive polymer composite based Lab-on-a-Chip (LOC) devices. LOC devices, also known as micro-total-analytical systems (microTAS) or microfluidic devices can amalgamate miniaturized laboratory functions on a single chip. This significant size reduction decreases the amount of required fluid volumes down to nano or pico-liters. The main commercial application of LOC devices is the biomedical fields. However, these devices are anticipated to make a technological revolution similar to the way miniaturization changed computers. In fact, medical and chemical analyses are predicted to shift from room-sized laboratories to hand-held portable devices. This dissertation is divided into three technologies. First, a series of terpolymer systems were synthesized and characterized to fabricate crosslinked coatings for phototunable swelling and create chemically patterned regions in order to conjugate cationic markers, proteins, or nanoparticles to the terpolymer coating. Second, antifouling surfaces were fabricated using magnetic thermo-responsive hydrogel structures via soft lithography. The structures were remote control activated with the use of AC magnetic fields. Finally, in order for LOC devices to fulfill its promise of bringing a laboratory to a hand-held device, they will have to be integrated with CMOS technology. Packaging will play a crucial role in this process. The last section will focus on the importance of coefficient of thermal expansion (CTE) mismatch in multi-chip modules. For the first technology, multi-functionalized terpolymer systems have been developed comprising of three units: N-isopropylacrylamide (NIPAAm), a stimuli responsive monomer that swells and collapses in response to temperature; methacryloxybenzophenone (MaBP), a photo-crosslinkable monomer that is activated at λ = 365 nm; and phenacyl methacrylate (PHEm), a photolabile protected functional group that generates localized free carboxyl groups in response to deprotection at λ = 254 nm. The multifunctional terpolymers can be spin-casted to form thin films of well-defined thickness, photo-crosslinked by a long UV wavelength light (λ = 365 nm) to form distinct structural patterns, and subsequently photo-chemically modified by a short UV wavelength light (λ = 254 nm). The photocleavage reaction by UV irradiation allows the production of free carboxylic groups that can be used to conjugate cationic markers, proteins, or nanoparticles to the terpolymer coating. Furthermore, the free carboxyl groups can be used to locally tune the swelling characteristics and transition temperature of the coatings. For the second technology, when Fe3O4 magnetic nanoparticles are integrated into PNIPAAm based composite systems, their resultant hyperthermia behavior becomes an ideal mechanism for remote controlled actuation. In this work, nano Fe3O4 octopods were seeded in fabricated PNIPAAm hydrogel micro-actuators. When the magnetic hydrogel structures were exposed to a magnetic field strength of 63 kA/m at a frequency of 300 kHz, the hydrogel micro-beams underwent a buckling effect when the field was absent and an unbuckling effect when the field was present. The hydrogel micro-beams were fabricated at an approximate distance from one another developing micromanipulating surfaces that were remote control activated. The response time, heating efficiency, and magnetic behavior were thoroughly studied. Lastly, micron sized polystyrene beads were exposed to the antifouling surfaces and movement of the beads was observed as the magnetic hydrogel micro-beams underwent their physical changes. For the third technology, a major reason of device failure in multi-chip module assemblies is a CTE mismatch between the underfill encapsulant material and the integrated circuit chip. Some of the failure mechanisms of microelectronic packaging due to CTE mismatch include fractures, delamination, or cracks through the device. In this section, the CTE of a commercially available underfill material is greatly reduced by loading the polymer resin material with hollow glass beads, to realize an overall effective CTE of 6.6 ppm/°C. Furthermore, the newly developed composite material exhibited outstanding thermomechanical stability at high temperatures beyond 150°C by holding a 3X lower CTE and a higher glass transition temperature.

Natural gas feeds often contain contaminants such as CO₂, H₂S, H₂O, and small hydrocarbons. Carbon dioxide is a major contaminant reducing the heating value of the gas and causing pipeline corrosion, so CO₂ level should be lowered to below 2% to meet the United States pipeline specifications. Membrane separation technology can be advantageous over cryogenic distillation and amine adsorption in terms of cost and efficiency. The key hurdle to overcome in polymeric membrane separation technology is improvement in selectivity, productivity, and durability without introducing significant additional cost. The ultimate goal of this study is to analyze effects due to polymerization conditions and imidization methods on properties of 1,3-propanediol monoesterified crosslinkable polyimide (PDMC). Hillock, Omole, Ward, and Ma did work on PDMC synthesis; however, variability of polymer properties remains a challenge that must be overcome for industrial implementation of PDMC material. First, reaction temperature and reaction time of polymerization prior to imidization were considered as key conditions to affect molecular weight, crosslinkability and transport properties of polymer. Batches with controlled reaction temperature and time were prepared, and properties of each dense film were measured and optimized in terms of permeability, selectivity, and plasticization suppression. Second, imidization methods for PDMC were also studied. There are mainly two kinds of Imidization: chemical Imidization and thermal Imidization. Surprisingly, thermally imidized PDMC showed 70% higher permeability than chemically imidized samples with minimal acrifice in selectivity. At high reaction temperature during the thermal imidization, transamidation can occur. It is believed that the transamidation led to more randomized sequence distribution in the thermally imidized samples. We thus hypothesize that the higher permeability of the thermally imidized PDMC results from greater uniformity of the sequence distribution, as compared to the chemically imidized sample that does not experience high temperature during imidization. XRD, DSC, DMA, and permeation instruments checked and supported this hypothesis. FTIR, TGA, and NMR ruled out the possibility of an alternate hypothesis related to side reaction. Finally, effects of aggressive feed conditions on both chemically imidized PDMC and thermally imidized PDMC dense film were examined. The aggressive feed conditions include high CO₂ partial pressure, operating temperatures, and exposure to high feed pressure. Testing aggressive feed conditions for dense film should be pursued before pursuing hollow fiber applications, to decouple effects on the basic material from those on the more complex asymmetric morphology. This study enables understanding of the disparity between various previous researchers’ selectivity and permeability values. The work shows clearly that polymerization conditions and imidization methods must be specified and controlled to achieve consistently desirable polymer properties. In addition, for batch scale-up and development to a hollow fiber, this fundamental study should enable production of high molecular weight PDMC with good fiber spinnability and defect-free structure.

No description available.