Despite indications that they are potential contaminant transport systems and threats to groundwater quality, very little effort has been invested in comparing contaminant transport behavior of natural environmental nanocolloids and their corresponding macrocolloid fractions in the presence of As, Se, Pb, and Cu contaminants. This study involved physico-chemical, mineralogical, stability and contaminant-transport characterizations of nano- (< 100 nm) and macro-colloids (100-2000 nm) fractionated from three Kentucky soils and one biosolid waste. Particle size was investigated with SEM/TEM and dynamic light scattering. Surface reactivity was estimated using CEC and zeta potential. Mineralogical composition was determined by XRD, FTIR, and thermogravimetric analyses. Sorption isotherms assessed affinities for Cu2+, Pb2+, AsO3-, and SeO4-2 contaminants, while settling kinetics experiments of suspensions at 0, 2 and 10 mg/L contaminants determined stability and transportability potential. Undisturbed 18x30 cm KY Ashton Loam soil monoliths were also used for transport experiments, involving infusion of 50 mg L-1 colloid suspensions spiked with 2 mg L-1 mixed contaminant loads in unsaturated, steady state, unit gradient downward percolation experiments. Overall, nanocolloids exhibited greater stability over corresponding macrocolloids in the presence and absence of contaminants following specific mineralogy trends. Physicochemical characterizations indicated that extensive organic carbon surface coatings and higher Al/Fe:Si ratios may have induced higher stability in the nanocolloid fractions, in spite of some hindrance by nano-aggregation phenomena. In the transport experiments, nanocolloids eluted significantly higher concentrations of colloids, total, and colloid-bound metals than corresponding macrocolloids. Contaminant elutions varied by colloid type, mineralogy and contaminant, with the following sequences: soil-colloids>bio-colloids, smectitic>mixed≥kaolinitic>biosolid, and Se>Pb/Cu≥As. Our findings demonstrate that even though they behave more like nano-aggregates rather than individual nano-particles, nanocolloids may exhibit significantly higher mobility and contaminant transport potential over great distances in subsoil environments than their corresponding macrocolloid fractions.

The techniques of optoperforation, spectral characterization of alloy disorder, and metal-enhanced fluorescence were applied to previously unconsidered or disregarded systems in order to demonstrate that such applications are both feasible and consequential. These applications were the subject of three disparate works and, as such, are independently discussed. Despite being ostensibly restricted to mammalian cells, optoperforation was demonstrated in intact plant cells by means of successful femtosecond-laser-mediated infiltration of a membrane impermeable dextran-conjugated dye into cells of vital Arabidopsis seedling stems. By monitoring the rate of dye uptake, and the reaction of both CFP-expressing vacuoles and nanocellulose substrates, the intensity and exposure time of the perforating laser were adjusted to values that both preserved cell vitality and permitted the laser-assisted uptake of the fluorophore. By using these calibrated laser parameters, dye was injected and later observed in targeted cells after 72 hours, all without deleteriously affecting the vital functions of those cells. In the context of alloy disorder, photoluminescence of excitonic transitions in two InAsxP1-x alloys were studied through temperature and magnetic field strength dependencies, as well as compositionally-dependent time-resolved behavior. The spectral shape, behavior of the linewidths at high magnetic fields, and the divergence of the peak positions from band gap behavior at low temperatures indicated that alloy disorder exists in the x=0.40 composition while showing no considerable presence in the x=0.13 composition. The time-resolved photoluminescence spectrum for both compositions feature a fast and slow decay, with the slow decay lifetime in x=0.40 being longer than that of x=0.13, which may be due to carrier migration between localized exciton states in x=0.40. In order to achieve broadband metal-enhanced fluorescence in upconverting NaYF4:Yb,Er nanocrystals, two nanocomposite architectures were proposed that retrofit metallic nanoshells to these lanthanide-doped nanocrystals. The typical monometallic construction was rejected in favor of architectures featuring Au-Ag bimetallic concentric surfaces, a decision supported by the considerable overlap of the calculated plasmon modes of the metallic structures with the emission and absorption spectrum of the nanocrystals. Furthermore, precursors of these nanocomposites were synthesized and photoluminescence measurements were carried out, ultimately verifying that these precursors produce the requisite upconversion emissions. / Ph. D.

The potential applications of dispersed and self-assembled nanoparticles depend critically on accurate control and prediction of their phase behavior. The chemical potential is essential in describing the equilibrium distribution of all components present in every phase of a system and is useful as a building block for constructing phase diagrams. Furthermore, the chemical potential is a sensitive indicator of the local environment of a molecule or particle and is defined in a mathematically rigorous manner in both classical and statistical thermodynamics. The goal of this research is to use simulations and experiments to understand how particle size and composition affect the particle chemical potential of attractive nanoparticle-polymer mixtures. The expanded ensemble Monte Carlo (EEMC) simulation method for the calculation of the particle chemical potential for a nanocolloid in a freely adsorbing polymer solution is extended to concentrated polymer mixtures. The dependence of the particle chemical potential and polymer adsorption on the polymer concentration and particle diameter are presented. The perturbed Lennard-Jones chain (PLJC) equation of state (EOS) for polymer chains1 is adapted to calculate the particle chemical potential of nanocolloid-polymer mixtures. The adapted PLJC equation is able to predict the EEMC simulation results of the particle chemical potential by introducing an additional parameter that reduces the effects of polymer adsorption and the effective size of the colloidal particle. Osmotic pressure measurements are used to calculate the chemical potential of nanocolloidal silica in an aqueous poly(ethylene oxide) (PEO) solution at different silica and PEO concentrations. The experimental data was compared with results calculated from Expanded Ensemble Monte Carlo (EEMC) simulations. The results agree qualitatively with the experimentally observed chemical potential trends and illustrate the experimentally-observed dependence of the chemical potential on the composition. Furthermore, as is the case with the EEMC simulations, polymer adsorption was found to play the most significant role in determining the chemical potential trends. The simulation and experimental results illustrate the relative importance of the particles size and composition as well as the polymer concentration on the particle chemical potential. Furthermore, a method for using osmometry to measure chemical potential of nanoparticles in a nanocolloid-mixture is presented that could be combined with simulation and theoretical efforts to develop accurate equations of state and phase behavior predictions. Finally, an equation of state originally developed for polymer liquid-liquid equilibria (LLE) was demonstrated to be effective in predicting nanoparticle chemical potential behavior observed in the EEMC simulations of particle-polymer mixtures.

Binary mixtures of polymers and soft nanocolloids, also called as polymer nanocomposites are well known and studied for their enormous potentials on various technological fronts. In this thesis blends of polystyrene grafted gold nanoparticles (PGNPs) and polystyrene (PS) are studied experimentally, both in bulk and in thin films. This thesis comprises three parts; 1) evolution of microscopic dynamics in the bulk(chapter-3),2) dispersion behavior of PGNPs in thin and ultra thin polymer matrices (chapter-4) 3) effect of dispersion on the glass transition behavior (chapter-5). In first part, the state of art technique, x-ray photon correlation spectroscopy is used to study the temperature and wave vector dependent microscopic dy¬namics of PGNPs and PGNP-PS mixtures. Structural similarities between PGNPs and star polymers (SPs) are shown using small angle x-ray scatter¬ing and scaling relations. We find unexpected (when compared with SPs) non-monotonic dependence of the structural relaxation time of the nanoparticles with functionality (number of arms attached to the surface). Role of core-core attractions in PGNPs is shown and discussed to be the cause of anomalous behavior in dynamics. In PGNP-PS mixtures, we find evidence of melting of the dynamically arrested state of the PGNPs with addition of PS followed by a reentrant slowing down of the dynamics with further increase in polymer frac¬tion, depending on the size ratio(δ)of PS and PGNPs. For higher δ the reen¬trant behavior is not observed with polymer densities explored here. Possible explanation of the observed dynamics in terms of the presence of double-glass phase is provided. The correlation between structure and reentrant vitrifica¬tion in both pristine PGNPs and blends are derived rather qualitatively. In the second part, the focus is shifted to miscibility between PGNPs and polymers under confinement i.e., in thin films. This chapter provide a compre¬hensive study on the different parameters affecting dispersion viz., annealing conditions, fraction of the added particles, polymer-particle interface and more importantly the thickness of the films. Changes in the dispersion behavior with annealing is shown and the need for annealing the films at temperatures higher than the glass transition temperature of the matrix polymers is clearly elucidated. Irrespective of the thickness of the films( 20 and 65 nm) studied, immiscible particle-polymer blends unequivocally prove the presence of gradi¬ent in dynamics along the depth of the films. To our knowledge for the first time, we report results on confinement induced enhancement in the dispersion of the nanoparticles in thin polymer films. The enhanced dispersion is argued to be facilitated by the increased free volume in the polymer due to confinement as shown by others. Based on these results we have proposed a phase diagram for dispersibility of the nanoparticles in polymer films. The phase diagram for ultra thin films highlights an important point: In ultra thin films the particles are dispersed even with grafting molecular weight less than matrix molecular weight. In the third part, we have studied the glass transition of the thin films whose structure has been studied earlier in the earlier part. Non-monotonic variation in glass transition with the fraction of particles in thin films has increased our belief on the gradient in the dynamics of thin polymer films. En¬hanced dispersion with confinement is captured with the enhanced deviation in glass transition temperature of ultra thin films. Effect of miscibility param¬eter on Tgis studied and the results are explained with the subtle interplay of polymer-particle interface and confinement.