Yes / In order to improve the frequency-dependent dielectric properties of the immiscible polymeric blends which were melt-compounded by composing poly (vinylidene fluoride) (PVDF) and low density polyethylene (LDPE), the layer multiplication and the solid phase orientation technologies were respectively adopted as two effective strategies to optimize the dispersion state and the orientation of internal microstructure, aiming at reducing physical porosity and improving the barrier performance as well as crystal phase of the polymer extrudates. Results comparison showed the dielectric properties were greatly dependent on the crystal type and the physical porosity density which were also emphasized as the interfacial effect in the previous work [ref. 29: Lin X et al, J Appl Polym Sci 2015; 132(36), 42507]. It was found that the multilayer-structure manipulation could substantially improve the dispersion state between the two immiscible components, enhance the mechanical performance and reduce the internal defects and increase the dielectric constant while keeping the dielectric loss stable. By uniaxial stretching the sample sheets at a rubber state temperature of ca. 10-20˚C below the melting point, crystal transformation was induced by increasing molecular chains orientation degree which was also contributed to the enhancement of the dielectric properties. These techniques implied the potential as a promising way for inducing functional structures of polymeric blends.

No / Simply melt blended polypropylene/carbon nanotubes composites (PP/CNTs) usually present mechanical deterioration. In this work, multilayered sheet of PP/CNTs with improved tensile property was obtained by solid-phase orientation and hot compression. The initially blended PP/CNTs were highly orientated by employing a constrained slit die and hot compressed under a certain temperature and pressure by stacking eight layers together. The effects of compression temperature and pressure on the tensile property and AC conductivity of the multilayered sheets were examined to explore the evolution of hierarchical crystallization morphology and CNT networks. The multilayered sheet which was hot compressed at 184°C and 5 MPa demonstrated an optimum tensile strength of ∼132.5 MPa and an elongation at break ∼52.7%, respectively, raised by almost 3-fold compared with those initially blended PP/CNTs. By increasing compression temperature and decreasing pressure, the AC conductivity showed an increase of 2 to 4 orders of magnitude. / China Scholarship Council. Grant Number: 201806465028.

Preventing flavor fade requires an understanding of the relationship between carbonyl amine and lipid oxidation reactions. The polyunsaturated fatty acid content of lipids in peanuts makes them more susceptible to lipid oxidation. The major by-products of the oxidation reaction are nonanal, hexanal, octanal, and decanal. These chemicals are associated with cardboardy, painty, and oxidized flavors associated with flavor fade. The carbonyl-amine reaction yields a variety of pyrazines with positive flavor attributes. Initial flavor notes were explored through sensory work, Gas Chromatography-Olfactometry, and chemical analysis. The fresh roasted volatiles produced from roasted peanuts and the aldehydes resulting from oxidation were also evaluated using GC-FID to quantify and identify the pyrazines and hexanal over a 21 day storage period. Electronic Nose was used to determine differences between storage periods. Gas chromatography-Olfactometry identified potent pyrazines contributing to fresh roasted peanutty aroma in fresh peanuts. Using GC-FID a significant decrease (p<.05) in 2-ethylpyrazine and 2,3-diethylpyrazine concentration was found over a 21-day period. No significant difference (p>0.05) was noted in the other pyrazines evaluated. A significant increase (p<0.05) was noted in the hexanal concentration over a 21-day period. The peroxide values and sensory analysis correlated directly with the GC-FID results with a significant increase (p<0.05) in peroxide value at Day 14 and Day 21, and a significant decrease (p<0.05) in fresh roasted peanuty flavor from days 0-21 and a significant increase (p<.05) in painty, cardboardy and bitter from days 7-21. The electronic nose successfully separated Day 0 and Day 21 samples from Day 7 and 14, which were also separated, but with minimal overlap. / Ph. D.

Solid phase extraction (SPE) has become a popular sample preparation method for the extraction of analytes from complex matrices. Solid phase extraction overcomes such disadvantages as large solvent usage and waste, large amounts of time spent in sample preparation and labor intensive methods with little hope of automation. In this report, SPEC®⋅ Microcolumns are evaluated for the extraction of Zantac® (ranitidine hydrochloride) from urine for high performance liquid chromatography (HPLC) analysis. SPEC®⋅Microcolumns are rigid disc structures with glass fiber impregnated with silica gel. These microcolumns look like packed-bed SPE cartridges but have the advantages of low void volumes and low bed mass that give clean extracts with the use of small amounts of solvents. An SPE method was developed and evaluated for the recovery of Zantac® from water and spiked urine. Percent recoveries and matrix interferences are reported. The limit of detection and analytical range tor the HPLC method of analysis with ultraviolet detection will be presented. / Master of Science

The effect of wine matrix ingredients and conditions on the headspace (HS) sampling of 3-alkyl-2-methoxypyrazines was investigated with solid-phase microextraction (SPME) and capillary gas chromatography, using a nitrogen phosphorus detector. Changes in the recovery of 3-ethyl-, isopropyl-, sec-butyl-, and isobutyl-2-methoxypyrazines from the static headspace of synthetic wine matrices spiked with 5mg/L of each analyte were investigated and reported as a function of SPME fiber type, extraction time, and temperature. The influence of pH, ethanol, phenolics, and ground oak was studied. DVB/Carboxen?/PDMS SPME fibers at an extraction temperature of 50°C for 30 minutes with 30% (w/v) added sodium chloride resulted in the highest analyte recoveries. Although, PDMS (100 micron) SPME fibers at an extraction temperature of 35°C for 30 minutes with 30% (w/v) added sodium chloride resulted in the lower analyte recoveries, the fiber remained functional after 50 to 75 analyses after other coatings deteriorated. Changing the sample ethanol concentration from 0 to 20% (v/v) resulted in an exponential decrease in the recovered analytes. Below pH 2, there was extensive loss of the analytes in the headspace. No measurable impact on alkylmethoxypyrazine headspace concentrations was observed with exposures to selected phenolics and to ground oak. / Master of Science

A significant issue affecting the aquaculture and water industries is the presence of off-flavour compounds in water, which cause problems by imparting an undesirable earthy/musty flavour and smell to water and fish. Two predominant off-flavour compounds are geosmin (GSM) and 2-methylisoborneol (MIB). These compounds are produced by several varieties of cyanobacteria and actinomycetes as metabolic products and can be detected by humans at concentrations as low as 0.015 mg L-1. Removal of GSM and MIB from potable waters has proven to be inefficient using standard water treatment such as filtration, coagulation, flocculation, sedimentation and chlorination. Activated carbon and membrane processes can physically remove GSM and MIB, but do not destroy them, and ozone treatment can be expensive. Titanium dioxide (TiO2) photocatalysis has recently been demonstrated to rapidly degrade GSM and MIB. When the semiconductor catalyst is illuminated with ultraviolet light simultaneous oxidation and reduction reactions occur. Pollutants are broken down into mineral acids, carbon dioxide and water. This study was conducted to determine if TiO2 photocatalysis, using a pelleted form of TiO2 called Hombikat K01/C, was a suitable method for the treatment of potable water. Additionally an analytical method was developed to rapidily analyse the large number of samples generated. Two reactors, a bench scale batch reactor and pilot scale flow reactor, were developed and used to evaluate the efficacy of Hombikat K01/C TiO2 photocatalysis in degrading GSM. The batch reactor, containing Hombikat K01/C, was used to investigate the effect of numerous experimental variables on the photocatalysis of GSM, including initial substrate concentration, pH, light intensity, aeration rate, the presence of additional reactants, and catalysis conducted in deuterated water. GSM was rapidly degraded using the TiO2 batch reactor, with the rate of GSM degradation most affected by light intensity and additional reactants, though pH also had a notable effect. A kinetic isotope effect of 1.61 was observed for the destruction of GSM using Hombikat K01/C TiO2. The flow reactor was also found to efficiently degrade GSM in raw waters. The rate of GSM destruction was found to be significantly lowered by UV shielding of the catalyst, caused by constituents of raw the water used, and the presence of additional reactants. The pilot scale flow reactor was also successfully evaluated in Denmark using gesomin contaminated water from an eel farm

<p>Different sample preparation steps prior to a detection method are often essential in analytical chemistry. In this thesis, both static extractions and on-line coupled solid-phase extractions have been studied in combination with different detection techniques. Aspects of performing sample preparations in miniaturized analytical devices and the development of poly(dimethylsiloxane) (PDMS) microchips are discussed. Polypyrrole was also evaluated as an electrochemically controllable stationary phase for solid-phase microextraction (SPME) and solid-phase extraction (SPE).</p><p>The first part of this thesis describes the extraction of an organic compound from a very complex solid matrix utilizing the pressurized-fluid extraction (PFE) technique. The presented results show that PFE is easily optimized and enables rapid extractions and extracts relatively free from interferences.</p><p>An integrated three-electrode device, which enabled electrochemical (EC) SPME under potential control, was developed. With this device, both anions and cations could be extracted employing two types of polypyrrole films. Planar micro band electrodes positioned at the end of a capillary were also used to electrochemically extract and detect anions in a miniaturized flow system. Different analyte concentrations and preconcentration times were examined, and good linear correlations were found between the extraction time and the detection response. The on-line coupling of a thin layer EC cell, with a polypyrrole coated working electrode, to different mass spectrometric (MS) techniques is also described and evaluated. The results show that EC-SPE, employing polypyrrole as stationary phase, can be used as a preconcentration step prior to detection.</p><p>In addition, this thesis describes the development and on-line coupling of a microelectrode array equipped PDMS microchip with an integrated graphite electrospray emitter to electrospray ionization (ESI) MS. The system enabled short transfer times and an EC conversion efficiency of 30% at a flow rate of 0.5 μL/min. The on-line EC/ESI-MS experiments were significantly simplified using a wireless Bluetooth battery-powered EC instrument.</p>

Different sample preparation steps prior to a detection method are often essential in analytical chemistry. In this thesis, both static extractions and on-line coupled solid-phase extractions have been studied in combination with different detection techniques. Aspects of performing sample preparations in miniaturized analytical devices and the development of poly(dimethylsiloxane) (PDMS) microchips are discussed. Polypyrrole was also evaluated as an electrochemically controllable stationary phase for solid-phase microextraction (SPME) and solid-phase extraction (SPE). The first part of this thesis describes the extraction of an organic compound from a very complex solid matrix utilizing the pressurized-fluid extraction (PFE) technique. The presented results show that PFE is easily optimized and enables rapid extractions and extracts relatively free from interferences. An integrated three-electrode device, which enabled electrochemical (EC) SPME under potential control, was developed. With this device, both anions and cations could be extracted employing two types of polypyrrole films. Planar micro band electrodes positioned at the end of a capillary were also used to electrochemically extract and detect anions in a miniaturized flow system. Different analyte concentrations and preconcentration times were examined, and good linear correlations were found between the extraction time and the detection response. The on-line coupling of a thin layer EC cell, with a polypyrrole coated working electrode, to different mass spectrometric (MS) techniques is also described and evaluated. The results show that EC-SPE, employing polypyrrole as stationary phase, can be used as a preconcentration step prior to detection. In addition, this thesis describes the development and on-line coupling of a microelectrode array equipped PDMS microchip with an integrated graphite electrospray emitter to electrospray ionization (ESI) MS. The system enabled short transfer times and an EC conversion efficiency of 30% at a flow rate of 0.5 μL/min. The on-line EC/ESI-MS experiments were significantly simplified using a wireless Bluetooth battery-powered EC instrument.

Described herein are three projects centered on the synthesis of conducting polymer derivatives for various applications. The first is the novel synthesis of 9,9-dioctylfluorene-co-benzothiadiazole [F8BT] oligomers through solid phase synthesis for the study of the thermodynamics and kinetics of electron transfer in the polymer. The second endeavor involves the synthesis of a series of 4”,3’’’-dialkyl-2,2’:5’,2”:5”,2’’’:5’’’,2’’’’:5’’’’,2’’’’’-sexithiophenes for the studies on crystal packing and surface deposition of organic p-type semiconducting materials. Lastly is described the development of a conducting metallopolymer based on the ligand 2,6-Bis(4-(2,2’-bithiophen-5-yl)-1H-pyrazol-1-yl)pyridine for use in a drug delivery system. / text

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