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This thesis investigates the biodistribution and toxicological effects of amphiphilic polymer coated CdSe/ZnS quantum dots (QDs) in two aquatic species, Daphnia magna (daphnia) and Danio rerio (zebrafish). The use of QDs in the life sciences has become common practice over the past decade. In addition QDs are being incorporated in commercially available light emitting diodes and photovoltaic solar cells. As the widespread commercial use of QDs increases, environmental release is inevitable, and water will contain the highest environmental concentrations based on life cycle assessments. Despite increased attention to the aquatic toxicology of nanomaterials in recent years, little information exists on the biological fate of QDs in aquatic organisms. Quantitative data on the uptake and excretion of QDs from daphnia and zebrafish were collected using fluorescence imaging paired with metal analysis. First, daphnia were examined after aqueous and dietary exposure to amphiphilic polymer coated CdSe/ZnS QDs. Surface coating influenced QD acute toxicity and high particle aggregation correlated with daphnia mortality. QDs were readily ingested by daphnia and accumulated in the intestines. High body burdens of 150-200 μg/g were found in the daphnia, with intestinal QD concentrations significantly elevated above the exposure media concentration. The slow elimination observed in daphnia suggested that trophic transfer of QDs to higher organisms may occur. Using daphnia and zebrafish as a model food chain revealed that QDs can transfer to zebrafish through dietary exposure with body burdens of 8-9.5 μg/g found. However, no biomagnification between daphnia and zebrafish was observed and the biomagnification factor (BMF = 0.04) was significantly less than one. This work demonstrates that aqueous and dietary exposures to QDs can result in high total body concentrations in aquatic organisms with little to no gross toxicity. The low acute toxicity observed for some surface coated QDs encourages further design optimization to improve the biocompatibility and reduce the environmental impact of QDs.

Thesis (M.S.)--University of Missouri, School of Mines and Metallurgy, 1928. / The entire thesis text is included in file. Typescript. Illustrated by author. Title from title screen of thesis/dissertation PDF file (viewed October 21, 2009) Includes bibliographical references (p. 103).

Thesis (M.Sc.)--City University of Hong Kong, 2005. / At head of title: City University of Hong Kong, Department of Physics and Materials Science, Master of Science in materials engineering & nanotechnology dissertation. On t.p. the "x" of "CdxZn₁-xS" are subscript. Title from title screen (viewed on Sept. 4, 2006) Includes bibliographical references.

The optical propagation losses resulting from the internal microstructure of ZnS thin films were investigated using a wavelength technique. Waveguide losses were determined by measuring the scattered light as a function of propagation distance along the film. Accurate measurements were obtained by using a technique we developed that employees a coherent fiber bundle to transfer the scattered light streak to a remote image plane that was scanned with an apertured photomultiplier tube. Microstructure effects on losses were found to dominate effects caused by substrate surface finish. The magnitude of the loss was found to depend upon two independent parameters: the average grain size of the polycrystalline films and the refractive index difference between ZnS and the interstitial material. Increasing the H₂O partial pressure led to lower losses as a result of reduced crystallite size, and a change in preferential crystallite orientation. A similar change in orientation was observed for films deposited onto heated substrates. Increasing the O₂ partial pressure during deposition also resulted in slightly lower waveguide losses, possibly as a result of void filling with ZnO. The modal dependence of the losses for ZnS films deposited at ambient temperature suggests that volume losses dominate surface losses for the lowest order mode while the ratio of surface to volume losses increases for higher order modes. By depositing ZnS onto substrates cooled with liquid nitrogen, adatom surface mobility was reduced which resulted in amorphous films. Losses were minimized (≤0.5 dB/cm at λ = 633 nm) for a substrate temperature of -50°C. These losses are lower than any previously reported for ZnS. However, further reduction of the substrate temperature resulted in an increase in tensile stress which eventually led to higher waveguide losses and crazing. The films deposited onto cooled substrates exhibited a low refractive index which indicates a low packing density and increased porosity. Differential water desorption, which is further evidence of increased porosity, was most noticeable in films with lower refractive indices when nonlinear prism coupling was attempted.

<p>Mercury contamination in aquatic ecosystems is a concern as anaerobic aquatic sediments are the primary regions of methylmercury production in freshwater and coastal regions. Methlymercury is a bioaccumulative neurotoxin, and human exposure to methylmercury can result in impaired functioning of the central nervous system and developmental disabilities in children. To minimize the risk of human exposure to methylmercury, it is important to be knowledgeable of the various sources which can supply mercury to aquatic ecosystems as well as have a complete understanding of the biogeochemical processes which are involved in methylmercury production in aquatic systems. In this dissertation work, both mercury biogeochemical speciation in anaerobic aquatic sediments and sources of mercury to aquatic systems were addressed. </p><p>The biogeochemical speciation of mercury is a critical factor which influences the fate and transformation of mercury in aquatic environments. In anaerobic sediments, mercury chemical speciation is controlled by reduced sulfur groups, such as inorganic sulfide and reduced sulfur moieties in dissolved organic matter (DOM). The formation of mercury sulfide nanoparticles through stabilization by dissolved organic matter (DOM) was investigated in precipitation studies using dynamic light scattering. Mercury sulfide nanoparticles (particle diameter < 100 nm) were stabilized through precipitation reactions that were kinetically hindered by DOM. To further investigate the interaction between DOM and metal sulfides, similar precipitation studies were performed using zinc sulfide and a number of DOM isolates (humic and fulvic acids) representing a range of DOM properties. The results of these experiments suggest that the mechanism of metal sulfide particle stabilization may be electrostatic or electrosteric, depending on the nature of the DOM molecule.</p><p>The mercury that is methylated in aquatic systems enters these environments via a number of sources, including atmospheric deposition, landscape runoff and other industrial and municipal activities. In two separate field studies, two potential sources of mercury to aquatic systems were investigated: landscape runoff and coal combustion products. The mercury loading to aquatic environments from these sources and their potential for transformation to methylmercury were investigated.</p><p>Landscape runoff from a Duke University campus catchment (Durham, NC) was identified as a source of mercury to a stream-wetland. The source of mercury to the runoff was likely from a `legacy' source of mercury; the historic application of mercury fungicide compounds to turf grass during the 20th century. Downstream of the point where the runoff was discharged to the stream-wetland, methylmercury concentrations were detected in stream sediments (up to 11% of total mercury), suggesting that this legacy mercury could be transformed to methylmercury. </p><p>The environmental impact of coal combustion products (CCPs) with respect to mercury and methylmercury was also investigated in a river system (Roane County, TN) that was inundated with fly ash and bottom ash from the Tennessee Valley Authority Kingston coal ash spill in 2008. Elevated total mercury and methylmercury sediment concentrations (relative to upstream sediments) were detected in regions impacted by the ash spill, and our biogeochemical data suggested that the ash may have stimulated methylmercury production in river sediments.</p><p>The results of this dissertation work address the formation of mercury sulfide (along with zinc sulfide) nanoparticles in anaerobic aquatic sediments. In the current mercury methylation paradigm, dissolved mercury species such as Hg(SH)02(aq) and HgS0(aq) are assumed to be the only mercury species that are available for methylation. The results of this dissertation work suggests that in previous studies, HgS0(aq) may have been mistaken as mercury sulfide nanoparticles which may be formed in under supersaturated conditions (with respect to HgS(s)) where DOM is present. Mercury sulfide nanoparticles are a mercury biogeochemical species that has been largely ignored in the research literature and whose role in the mercury biogeochemical cycle and in mercury methylation remains to be investigated.</p><p> This dissertation work also identifies potential sources of mercury to aquatic systems, namely, landscape runoff and CCPs. Atmospheric deposition is currently considered to be the major source of mercury to inland aquatic water bodies compared to sources such as landscape runoff and CCPs. However, in the watershed studied in this dissertation, landscape runoff was identified as a larger source of mercury than atmospheric deposition, suggesting that these so-called `minor' sources may actually be major sources of mercury to watersheds depending on land usage, and should be considered in watershed models. Furthermore, the environmental hazards of mercury-associated with CCPs has typically been determined through leaching experiments, such as the Toxicity Characteristic Leaching Procedure (TCLP), which are not representative of environmental conditions and do not predict that CCPs may influence mercury methylation in aquatic sediments. Thus, in this dissertation work, we suggest that leaching protocols such as the TCLP should be re-evaluated. </p><p>Overall, this dissertation work will be useful in future studies examining mercury speciation and bioavailability to methylating bacteria in aquatic sediments, and the formation of metal sulfide nanoparticles in aquatic systems. Additionally, data on sources of mercury will be useful in developing policies for the regulation of these sources and in assessing the risk to human health from mercury methylation.</p> / Dissertation

The structure and properties of chemical vapor deposited zinc sulfide (CVD ZnS) were assessed before and after heat treatments, involving different annealing and hot isostatic pressing (HIPing) profiles. Samples were characterized using optical microscopy, SEM, TEM, electron diffraction, polycrystalline and powder x-ray diffraction, x-ray chemical microanalysis, photoluminescence, ultraviolet through longwave infrared transmission, and mechanical testing. Before heat treatment, CVD ZnS consists of lamellar twinned structures in 10 to 100 nm layers aggregated into domains which compose grains typically 5 to 10 μm in diameter with an overall crystallographic texture on the {100} planes. The scattering behavior of CVD ZnS was investigated and described by a surface scattering model based on internal surface roughness and refractive index variations due to onedimensional stacking disorder. The two to five percent hexagonality measured by x-ray diffraction is believed to form due to oxygen impurities at the twin boundaries which cause nanostructural polytypism and result in differential refractive index and scattering. CVD ZnS variants in low temperature deposited red ZnS and sulfur precursor elemental ZnS are examined as well. Color in CVD ZnS is believed to be due to band edge position, probably due to oxygen content, and not directly related to the hydride absorption at 6 μm. After annealing or hot isostatic pressing above 850 °C for sufficient time, CVD ZnS recrystallizes and becomes strongly textured on the {111} planes. This recrystallization is required to remove stacking disorder, resulting in a structure with less than half a percent hexagonality and low visible scattering. The recrystallization is believed to proceed by diffusing the oxygen at the nano-twin boundaries back into the lattice, thus unpinning the boundaries and allowing them to move and grow into the tabular recrystallized morphology by polytype induced exaggerated grain growth. The presence of active metals like platinum, silver, copper, or nickel during hot isostatic pressing causes a reaction with sulfur and lowers the temperature required for recrystallization. The optical scattering model is consistent in describing standard CVD ZnS, elemental ZnS, and multispectral recrystallized ZnS as having successively lower birefringence at internal surfaces.

Thesis (Ph.D.)--McMaster University (Canada), 1991. / Source: Dissertation Abstracts International, Volume: 54-02, Section: B, page: 1040.

Colloidal semiconductor nanocrystals exist at the interface of inorganic chemistry, solid-state physics, and materials applications. The highly tunable and size-dependent properties position them as prime candidates for advancing a range of technologies, including improving efficiency in solid-state lighting devices and high color-purity displays. To be successful in these endeavors, quantum dots require excellent optical properties, such as bright emission. Optimization of a zinc sulfide coating is widely regarded as a key requirement to achieving these necessary performances. Even so, zinc sulfide nanocrystal chemistry remains underdeveloped. This dissertation addresses these shortcomings and provides comprehensive synthetic and analytical tools to harness the potential of zinc sulfide containing nanocrystals. Chapter 1 introduces semiconductor nanocrystals, also referred to as quantum dots, and begins with a description of the size-dependent optical properties. Factors that lead to poorer emission properties, such as undercoordinated surface atoms are discussed. Methods to alleviate these issues, including controlling the surface coordination environment, and design and growth of heterostructures are introduced. Lastly, synthetic approaches and nanocrystal formation mechanisms are described. Chapter 2 covers the synthesis and size-dependent optical properties of zinc sulfide nanocrystals. We find that commonly used solvents in nanocrystal reactions lead to the formation of polymeric byproducts that are challenging to purify away, and thus design the zinc sulfide synthesis such that these can be avoided. Leveraging a library of rate tunable thioureas the final nanocrystal size can be carefully controlled. The reactions follow a thermally activated growth process, with larger zinc sulfide nanocrystals accessible at higher temperatures. Most relevantly for later chapters, the surface coordination environment is highly important; bulkier zinc carboxylate ligands that cannot achieve high surface coverages result in higher growth rates. These results represent the most tunable size controls reported for zinc sulfide nanocrystals. Chapter 3 uses high resolution electron microscopy techniques to study the shape (morphology) of zinc sulfide nanocrystals, synthesized using the methods developed in the second chapter. Irregular, anisotropic growth is commonly seen in zinc sulfide shell growth and is attributed to core/shell interfacial strain. We find that this growth also occurs in the binary zinc sulfide system. Synthetic conditions favoring fast growth result in unselective, isotropic growth of spherical zinc sulfide. Conversely, slower conditions can lead to irregular, anisotropic shapes. The shape is also highly dependent on the coordination environment during growth. Small, sterically unencumbered ligands stabilize specific crystal facets, leading to selective, anisotropic growth. These findings are translated to shelling procedures in Chapter 6, and further emphasize the need to understand and characterize zinc sulfide surfaces. Chapter 4 establishes an empirical relationship between the band gap energy of a zinc sulfide nanocrystal and its diameter. The literature reports a wide spread of diameters for a given energy, meaning zinc sulfide sizes could not previously be easily calculated from their optical properties. Leveraging the size- and shape-control discussed in Chapters 2 and 3, we assess the utility of a range of nanocrystal characterization techniques for accurately sizing quantum confined zinc sulfide. Using electron microscopy and X-ray scattering methods we present an updated energy-size (“sizing curve”) relationship for zinc sulfide. These results represent the most comprehensive zinc sulfide nanocrystal sizing study and enable the rapid size characterization of zinc sulfide from its absorbance spectrum. This provided crucial insight into the reaction progressions described in Chapter 2. Chapter 5 covers our endeavors to characterize and quantify the zinc sulfide nanocrystal surface chemistry, which we believe is imperative to improving shelling procedures and optical properties in zinc sulfide heterostructures. With no published extinction coefficient, the surface coverages of zinc sulfide cannot be obtained. Using the size- and shape-controlled syntheses, in conjunction with optical absorption spectroscopy and elemental analysis, we calculate extinction coefficients for a range of zinc sulfide nanocrystal sizes. The size-dependence is well described by a power law, and this represents the first reported extinction coefficient for zinc sulfide. Using this, we report the first surface coverages of zinc sulfide nanocrystals and assess the binding affinity of zinc carboxylates to the surface by monitoring their displacement by L-type ligands. Chapter 6 widens the zinc sulfide synthetic methods developed in earlier chapters to deposit zinc sulfide shells onto blue-emitting II-VI and red-emitting III-V nanocrystals. The reaction shows versatility, shelling nanocrystals over a wide range of temperatures. We demonstrate morphology control over the zinc shell by altering the deposition kinetics and coordination environment. Usually, thick, homogenous shells are desired by the nanocrystal field. However, by correlating the shell morphology to its optical properties, we see that the anisotropic shells generally achieve higher photoluminescence quantum yields (PLQYs). We also report progress towards cadmium-free quantum dot downconverters for use in solid-state lighting applications. Among other things, the photoluminescence intensity evolution throughout the shelling procedure is highly dependent on the initial surface termination of the nanocrystal core. Application of surface treatments allows brighter zinc sulfide shelled III-V heterostructures to be accessed.

Large amounts of money are being applied to the construction of the next generation of spallation sources for neutron scattering. Neutron powder diffraction instruments will be an important element of these facilities and the incorporation of detectors into these instruments with a high neutron capture efficiency is desirable. A new detector design named the Flexible Embedded Fiber Detector (FEFD) has been developed and tested for this thesis. This detector is based on wavelength shifting fibers embedded in a zinc-sulfide lithium-fluoride based scintillator. The virtue of this design is that the detecting surface can be curved around the Debye-Scherrer rings. This virtue is lacking in other detector designs, making them more complex and poorer in performance than our FEFD detectors. Monte Carlo calculations were performed to determine the neutron capture efficiencies of our FEFD detectors, which proved to be much higher than those of the proposed powder diffractometer design for the Spallation Neutron Source and about equal with the efficiency for the ISIS powder diffractometer design. Four FEFD detector prototypes were then fabricated and tested at the Intense Pulsed Neutron Source at Argonne National Laboratory. We find that our measured and calculated relative efficiencies are in good agreement.