Photodegradation is a major degradation mechanism for many environmental contaminants, both in indoor environments as well as in outdoor environments, and many of the contaminants are persistent and toxic. However, there is a lack of knowledge about the exact degradation process for many of them. It is important to not only monitor and study environmental contaminants that are commonly found. But it is also important to be able to identify their degradation products, however, due to lack of standards there is a difficulty to conduct identification. There is also the drawback with most spectral libraries used for identification being recorded at low resolution, when new instruments are being developed for using high resolution. This makes it challenging to identify compounds with spectral peaks that differ only slightly in their mass-to-charge ratio (m/z). Thus, the aim of this study was to determine potential degradation products from different compounds commonly found in indoor environments and then add these findings to a spectral library for high resolution mass spectrometry. This was conducted by first exposing the standards to ultraviolet (UV) light, and then the chemical analysis was performed using a gas chromatography coupled with a high resolution mass spectrometer. All data was then processed in different software in order to determine potential products. Many of the compounds did not indicate any degradation using the experimental settings, and for some not even the parent compound could be identified. In total, four potential degradation products were found in this study; degradation products were identified for hexabromobenzene (HBB) with penta-, tetra-, and tribromobenzene, as well as one potential product for 2-ethylhexyl-2,3,4,5-tetrabromobenzoate (EHTBB).

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The development of future electronics depends on the availability of suitable functional materials. Printed electronics, for example, relies on access to highly conductive, inexpensive and printable materials, while strong light absorption and low carrier recombination rates are demanded in photocatalysis industry. Despite all efforts to develop new materials, it still remains a challenge to have all the desirable aspects in a single material. One possible route towards novel functional materials, with improved and unprecedented physical properties, is to form composites of different selected materials. In this work, we report on hydrothermal growth and characterization of graphene/zinc oxide (GR/ZnO) nanocomposites, suited for electronics and photocatalysis application. For conductive purposes, highly Al-doped ZnO nanorods grown on graphene nanoplates (GNPs) prevent the GNPs from agglomerating and promote conductive paths between the GNPs. The effect of the ZnO nanorod morphology and GR dispersity on the nanocomposite conductivity and GR/ZnO nanorod bonding strength were investigated by conductivity measurements and optical spectroscopy. The inspected samples show that growth in high pH solutions promotes a better graphene dispersity, higher doping and enhanced bonding between the GNPs and the ZnO nanorods. Growth in low pH solutions yield samples characterized by a higher conductivity and a reduced number of surface defects. In addition, different GR/ZnO nanocomposites, decorated with plasmonic silver iodide (AgI) nanoparticles, were synthesized and analyzed for solar-driven photocatalysis. The addition of Ag/AgI generates a strong surface plasmon resonance effect involving metallic Ag0, which redshifts the optical absorption maximum into the visible light region enhancing the photocatalytic performance under solar irradiation. A wide range of characterization techniques including, electron microscopy, photoelectron spectroscopy and x-ray diffraction confirm a successful formation of photocatalysts. Our findings show that the novel proposed GR-based nanocomposites can lead to further development of efficient photocatalyst materials with applications in removal of organic pollutants, or for fabrication of large volumes of inexpensive porous conjugated GR-semiconductor composites.

Advanced oxidation of organic pollutants with TiO2 photocatalysts is limited due to the wide bandgap of TiO2, 3.2 eV, which requires ultraviolet (UV) radiation. When nanosized TiO2 is modified by carbon doping, charge recombination is inhibited and the bandgap is narrowed, allowing for efficient photodegradation under visible light. Here, we propose a flame spray pyrolysis (FSP) technique to create TiO2. The facile process of FSP has been successful in preparing highly crystalline TiO2 nanoparticles. Using the same procedure to deposit TiO2 onto biochar, the photocatalyst was doped by the carbonaceous material. The morphology, crystalline and electronic structure of the FSP TiO2 and TiO2-decorated biochar (TiO2-BC) were characterized by SEM, XRD, TGA, DLS, and diffuse reflectance UV-vis spectroscopy. Photocatalytic performance of TiO2 and TiO2-BC was investigated for model organic contaminants in an aqueous solution under UV and visible light, which will be compared to that of Degussa P25 TiO2 as a control.

Natamycin is an antimycotic compound that is widely used in the cheese industry to increase the shelf life of cheeses, especially shredded cheeses, by inhibiting the growth of molds. Natamycin is applied to the surface of cheese as an aqueous suspension or as a powder. However, natamycin is not readily water soluble making it harder to distribute evenly over shredded cheese Natamycin is degraded by ultraviolet (UV) light at wavelengths of 350 nm and below. Typical packaging applications do not provide adequate UV protection causing natamycin to degrade. This work was undertaken to determine the efficacy of UV absorber film to prevent UV light degradation of natamycin on the surface of shredded cheese. Current accepted methods to determine concentration of natamycin were evaluated for appropriateness in natamycin degradation studIes. The use of cyclodextrins to increase water solubility was tested to see if a uniform distribution of natamycin over the shredded cheese could be done effectively. Furthermore, a known application of mold was performed to see how well natamycin and each of its applications could prevent visible mold growth from occurring. The International Dairy Federation recognizes two methods to quantify natamycin on shredded cheese: high performance liquid chromatography (HPLC) and spectrophotometry. Concentrations of natamycin in aqueous suspensions were determined using both methods. Results show that spectrophotometry is flawed when quantifying the amount of active natamycin because the method gives erroneously high results. The amount of active natamycin is not accurately quantified using spectrophotometric techniques because it cannot separate the active form from the inactive form of natamycin. Polymer packages containing a UV absorber (11.4% light transmission at 350 nm) allow significantly less UV-associated degradation of natamycin than those packages that lacked a UV protectant (90.0% light transmission at 350 nm) (p<0.05). Incorporating a UV absorber into a package helps protect natamycin and its various complexes from UV light degradation, which can increase the shelf life of shredded cheese. However, even with a UV absorber, natamycin is still able to degrade. Natamycin was complexed with different cyclodextrins to help better solubilize natamycin â β-cyclodextrin, hydroxy-propyl β-cyclodextrin and γ-cyclodextrin. Using cyclodextrins to apply natamycin more uniformly onto shredded cheese did not significantly increase the consistency of distribution (p<0.05). Variability was uniform throughout all treatments with the exception of HPBCD complex. After 27 days, all of the UV packages treated with each of the cyclodextrin treatments containing shredded cheese began to show visible mold growth. Those packages stored in total darkness remained mold free through the duration of the experiment ending on day 62. When untreated with natamycin and an initial concentration of 101-102 spores/gram of Penicillium roqueforti, shredded cheese remained free from visible mold growth for 24 days in total darkness at 4°C. Samples treated with one of the natamycin treatments were able to remain mold free for at least 9 more days, showing visible signs of mold growth at day 33. There was no statistical difference between the treatments of dry natamycin, aqueous suspension natamycin, β-cyclodextrin-natamycin complex, and γ-cyclodextrin-natamycin complex (p<0.05). However, there was a difference with the use of hydroxy-propyl β-cyclodextrin-natamycin complex. Hydroxy-propyl β-cyclodextrin-natamycin complex allowed the shredded cheese to last for 41 days, 17 days longer than the control sample. / Master of Science

Natamycin is an antimycotic with very low water solubility and extremely high photosensitivity, which is used to extend the shelf life of shredded cheese products. The objectives of this research are: (a) to find a new delivery system for natamycin, which increases its aqueous solubility and (b) to increase the chemical stability of natamycin so that it has a prolonged antifungal effect on the surface of the shredded cheese. Molecular inclusion complexes of natamycin were formed with β-, hydroxypropyl β-, and γ- cyclodextrins (CDs) which allowed large increases in aqueous solubility without the use of organic co-solvents or surfactants. The water solubility of natamycin was increased 16-fold, 73- fold, and 152-fold with β-CD, γ-CD, and hydroxypropyl β-CD, respectively. The natamycin:CD inclusion complexes resulted in nearly equivalent in vitro antifungal activity as natamycin in its free state. Nuclear magnetic resonance (NMR) was utilized to prove the formation of true inclusion complexes. 1H NMR shift titrations of N-(3 -N-dimethylaminosuccimido) natamycin with β- and γ-CDs enabled determination of the stoichiometry of both complexes as 1:1. Aqueous solutions of natamycin (20 mg/L) were found by quantitative HPLC to be completely degraded after 24 hours of exposure to 1000 lux fluorescent lighting at 4 °C. After 14 days of storage in darkness at 4 °C, 92.2% of natamycin remained in active form. Aqueous solutions of natamycin:β-CD complex and natamycin:γ-CD complex were significantly more stable (p < 0.05) than natamycin in its free state when stored in darkness at 4 °C. Clear poly(ethylene terephthalate) packaging with an ultraviolet light absorber allowed 85.0% natamycin to remain after 14 days of storage under 1000 lux fluorescent lighting at 4 °C. Such dramatic increases in water solubility and light stability will enable natamycin to function as a more effective antimycotic in the food industry. / Master of Science

The ubiquity of particulate contamination requires dust mitigation techniques to provide low-scatter surfaces and edges on sensitive optical devices in space. Poly(olefin sulfone)s have been shown to photodegrade with the assistance of a photobase generator when exposed to UV light (254 nm) and heat (120 °C). These polymers may be useful for minimizing dust on optical surfaces for space applications. However, their behavior in vacuum has not been fully characterized. We synthesized poly(2-methyl-1-pentene sulfone) (PMPS) and poly(1-hexene sulfone) (PHS) with and without a photobase generator. We studied the photodegradation (172 nm or 254 nm) of thin films in vacuum. Spectroscopic ellipsometry was used to quantify film thickness over time. The PMPS and PHS films both degraded when exposed to UV light in vacuum, though PHS to a lesser degree. We found that heat was not required to cause degradation, and that degradation occurred with UV irradiation even without a photobase generator. We also found that the degradation process removes dust particles as the film disappears. This investigation shows that poly(olefin sulfone)s could be used to protect optical surfaces until after their deployment in space.

El propósito de la presente tesis doctoral es estudiar el efecto de la degradación térmica, biológica y fotolítica en la polilactida (PLA) para contribuir a la caracterización de este polímero biodegradable bajo diferentes condiciones o entornos. Este polímero procede de fuentes renovables y está considerado un excelente candidato para sustituir a otros materiales poliméricos con escasa degradabilidad. En este estudio se describen los mecanismos que regulan cada tipo de degradación y, lo que es más importante, cómo cada uno de ellos afecta a la variación de la masa molar del PLA. La monitorización del descenso de masa molar de polilactida se realizó tanto mediante Cromatografía de Permeación en Gel (GPC) como por Viscosimetría. Adicionalmente se utilizó la Espectroscopía Infrarroja con Transformada de Fourier (FTIR) para establecer los mecanismos que controlan la degradación y su efecto en la estructura química de la polilactida. Asimismo, se ha determinado el impacto de cada tipo de degradación en la morfología y en las propiedades térmicas y mecánicas del PLA. La Termogravimetría (TGA) permitió monitorizar los cambios en la estabilidad térmica del material debidos a los diferentes tipos degradación, ulilizando parámetros como la temperatura de máxima velocidad de degradación térmica o la energía de activación. El resultado de la bio y la foto degradación en la superficie del material fue evaluado mediante Microscopía Electrónica de Barrido (SEM), observándose únicamente cambios debidos a la degradación biológica. Las propiedades viscoelásticas y térmicas se analizaron mediante Análisis Dinámico-Mecánico-Térmico (DMTA), Calorimetría Diferencial de Barrido (DSC) y Microscopía Óptica (OM). Se ha obtenido que los parámetros más relevantes para discernir las diferencias entre los tres procesos de degradación son los relativos al fenómeno de cristalización. Los resultados muestran que cada degradación está controlada por un mecanismo que afecta de diferente forma a la / Santonja Blasco, L. (2012). Contribution to the study of thermal, biological and photo degradation of polylactide [Tesis doctoral]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/16470

No / Photo-irradiation of poly para-phenylene terephthalamide (PPTA) fibre is normally associated with deterioration of physical properties. Nonwoven fabrics produced from 100% photo-irradiated PPTA fibres might therefore be expected to yield fabrics with poorer mechanical properties compared to those produced from non-irradiated fibres. To test this hypothesis, the bursting strength of hydroentangled fabrics manufactured from photo-irradiated PPTA fibres was explored. Prior to fabric manufacture, virgin PPTA staple fibres were photo-irradiated under controlled lighting conditions (xenon short arc lamp with a luminous flux of 13,000 lm) for 0, 5, 10, 20, 40, 60 and 100 h. The photo-irradiated fibres were then hydroentangled to produce nonwoven fabrics. Photo-irradiation exposure of PPTA fibre up to 30 MJ m 2 was not found to be detrimental to fabric bursting strength and at irradiation energies of 5e10 MJ m 2 a small, but statistically significant increase in fabric bursting strength was observed compared to fabrics manufactured from non-irradiated fibre. This may be linked to a change in the surface and skin properties of the PPTA photo-irradiated fibres identified by atomic force microscopy (AFM) following photoirradiation.