Rotational-translational decoupling, in which translational motion is apparently enhanced overrotational motion in violation of Debye-Stokes-Einstein predictions, has been observed in a wide variety of materials near their glass transition temperatures (Tg). This has been posited to result from ensemble averaging in the context of dynamic heterogeneity. In this thesis, single fluorescent probe molecules are tracked rotationally and translationally to interrogate this explanation. In one study, ensemble and single molecule experiments are performed in parallel on the ideal fluorescent probe N,N’-dipentyl-3,4,9,10-perylenedicarboximide (pPDI) in high molecular weight polystyrene near its Tg. Ensemble results show decoupling onset at approximately 1.15Tg, increasing to over three orders of magnitude at Tg. Single molecule measurements also show a high degree of decoupling, with typical molecules at Tg showing translational diffusion coefficients nearly 400 times higher than expected from Debye-Stokes-Einstein predictions. The same experiments were performed on a microscope with somewhat lower spatial resolution to investigate the role of localization accuracy in apparent degree of breakdown. Here similar, though slightly larger, degrees of breakdown were found, consistent with the idea that averaging across heterogeneous regions, even within a single molecule’s trajectory, is the primary driver of rotational-translational breakdown, while the lower degree of localization accuracy of the microscope additionally leads to some sub-ensemble selection that further inflates apparent breakdown. Across all single molecule experiments, higher degree of breakdown is associated with particularly mobile molecules and anisotropic trajectories, providing support for anomalous diffusion as a critical driver of rotational-translational decoupling and Debye-Stokes-Einstein breakdown. In a final study, single molecule translational simulations are performed with varying types (spatial and dynamical) and degrees of heterogeneity to assist in interpreting results of single molecule translation experiments. These reveal that fast portions of translational trajectories inflate diffusion coefficients and that, taken together with experimental results, the majority of rotational- translational decoupling in glassy systems occurs through dynamic exchange consistent with wide underlying distributions of diffusion coefficients and exchange coupled to local spatiotemporal dynamics.

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Plastic wastes released in the environment can produce microplastics (MPs, Size < 5 mm) and nanoscale plastics (NPs, Size < 100 nm) due to the environmental weathering processes. The presence of the MPs and NPs have been found worldwide in different aquatic and terrestrial environments. These tiny plastics have detrimental health impacts when they are ingested or inhaled by aquatic organisms as well as human beings. However, their occurrences including identification and quantification in the environment are still a great challenge. Particularly, quantification for NPs is a challenge, as there is no standard technique available yet that can count the NPs effectively. Therefore, this thesis was focused on two important aspects related to microplastics (MPs) and nanoscale plastics (NPs). Firstly, assess the source of MPs or NPs release and secondly, NPs quantification. Microfibers (MFs) are one of the most abundant portions of MPs in the aquatic environment, which are shed during the washing and drying of fabrics. Hence, in the first area of the study, the release pattern of MPs, in the form of acrylic MFs from portable washer and dryer during fabric washing and drying under different conditions were investigated. Additionally, the subsequent degradations behavior of these released MFs under ultraviolet light (UV-A) irradiation were explored. The results indicated that the MFs were released almost 2 times higher when the fabrics were washed for 60 min compared to 30 min due to higher mechanical stresses. In addition, MFs released were increased by 1.4 times higher when the fabrics were dried for 60 min compared to 30 min due to longer rotational forces on the fabrics. The use of detergent during washing promoted 2.7 times more MF release compared to without detergent. Moreover, MFs were released approximately 1.8 times higher from washing when washed with 40°C of water than with 20°C of water. However, subsequent washing cycles showed decreasing patterns of MF releases during washing and drying, approximately 45% less and 67% less, respectively in the 7th wash compared to the 1st wash as the fabrics approach a plateau. The released acrylic MFs were analyzed after their exposure to UV-A irradiation in the aquatic environment from 0 day to 182 days. After 182 days of UV-A irradiation, released acrylic MFs showed significant changes in the surface morphology in the form of cracks, holes, and flakes determined by scanning electron microscope (SEM). The formations of cracks, cavities, and flakes in the MF’s surface were proportional to the period of UV-A exposure. Dimensions of the formed holes and cracks on the UV-A degraded MFs suggested that MFs can turn into NPs in presence of water and UV-A exposure in the environment. Hence, a robust analytical tool must be optimized to detect these tiny degraded NPs in the aquatic environment. This brings to the second area of the study which aimed to optimize and validate a method to detect NPs through coating with synthesized gold nanoparticles (AuNPs) by Single Particle Inductively Coupled Plasma Mass Spectrometry (SP-ICP-MS). This study successfully detected the polystyrene nanoscale plastics (PS NPs, size 61 nm) by particle-by-particle analysis in single quadrupole-based SP-ICP-MS and the detection limit of particle number concentration was reached up to 8.64 × 10^7 particles/L. PS NPs were selected as a model nanoscale plastic as it is one of the most abundant plastics in the environment. The method was applied to PS NPs in deionized (DI) water which achieved a good amount of PS NP recoveries by up to 98%. This analytical technique can be further optimized and might be helpful for analyzing NPs in any environmental samples to determine their occurrences and concentrations.

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Many phenomena of interest to science and engineering occur at interfaces; however, access to, or discrimination of, interfacial interactions has been challenging, especially at buried interfaces. Vibrationally resonant sum-frequency generation (VR-SFG) spectroscopy is a powerful tool for investigating the molecular structure of free or buried interfaces, but spectral analysis has relied on many assumptions. To claim accurate new insights, practitioners must be able to make unique determinations from the data without experimental artifacts affecting the final results. For example, two independent and overlapping studies for the polystyrene/air interface were carried out, but reported different surface structures. Initially, this difference was attributed to the use of different substrates, but we have shown that the surface structure is independent of substrate by experimental suppression of the interfering nonresonant signal. These results show difficulties in SFG analysis that have led to faulty determinations of structural changes. Similar problems have been observed in systems assumed to have negligible nonresonant interference, demonstrating the need for proper experimental design instead of relying solely on post-experimental analysis of the data. We have investigated the inherent limitations imposed on the technique from the nature of the signal generation and nonresonant interference, and have developed methods to overcome such difficulties, depending on what is desired from the data. By nature of nonlinear spectroscopy, the desired frequency response is affected by overlapping interactions in the time domain, and these time domain interactions can be exploited to overcome challenges in analysis. By delaying the upconverting pulse, the nonresonant signal can be removed to enable accurate qualitative comparison or even quantify change; however this removal results in incomplete upconversion, or apodization, of the resonant signal, causing distortion in the observed resonant response. If absolute parameters are desired, additional work is necessary to correct the distortion of the resonant response. Correction can be accomplished by further exploiting time domain effects by collecting spectra at various delay times of the upconverting pulse, and this additional data also aids in interpretation of congested spectra. Many practical applications, however, only require a means to quantify change, and measurements of change are unaffected by the effects of apodization. These techniques have been used to more accurately analyze polystyrene and octadecylsilane surfaces.

This project involves the fabrication and testing of microporous, polymer membranes designed to remove minute amounts of toxic air pollutants such as formaldehyde from air streams. The hypothesis to be tested is that active, the silver contained within the porous polymer membranes results in high formaldehyde retention. Monolayers consist of different sizes of sPS particles are assembled first on the silicon wafers by spin coating method and convective assembly method, respectively. Then each kind of monolayer with one dimension of sPS particles is deposited with a nanometer scaled silver thin film with a bench top metal evaporator. The porous membranes are produced by assembly of close-packed colloidal crystals of silver capped polystyrene template particles and subsequent infiltration with polyurethane prepolymer. The prepolymer is cured by UV exposure. The sPS particles are removed from the particle polymer membrane by treatment with organic solvents resulting in the formation of inverse opal structures. Silver does not dissolve in the organic solvents and cannot leave the pores due to the small size of connecting holes in an inverse opal. All the monolayers, cylindrical colloidal crystals and microcapillaries after infiltration of polyurethane had been characterized by optical microscope, and the porous membranes had been characterized by SEM. The application of porous membranes with silver caps is to absorb formaldehyde in the air, while in fact the silver caps are oxidized and become Ag2O, which will initiate a gas-phase/solid reaction with formaldehyde. In the future, TiO2 will be applied together with Ag2O, since TiO2 is another good absorbent for formaldehyde

Plastics, due to their extensive production and inert nature, accumulate in the environment after their improper disposal. While being in the environment, these plastic-based products undergo different degradation processes resulting in smaller sized microplastics (MPs) and nanoscale plastics (NPs). MPs and NPs can adsorb various organic and inorganic contaminants due to their huge surface area to volume ratio and the presence of diverse functional groups. Hence, the presence of various contaminants in the environment can impact both the plastics and the adsorbed contaminants fate in the environment. In light of this, the current work investigates the co-transport behavior of polystyrene (PS) MPs and copper metal (Cu), as both PS MPs and Cu are commonly encountered in the environment. The co-transport behavior was observed by understanding the mobility and deposition behavior of both contaminants under various ionic strength conditions (IS) and salt types (NaCl, CaCl2). Bench scale packed column studies and batch adsorption experiments were used to observe the transport behavior. The quartz crystal microbalance (QCM) was used to determine the mechanisms responsible for the deposition behavior of MPs and NPs at the nanoscale level. Results showed that in the absence of Cu, the secondary energy minimum was responsible for the reduced PS mobility (40-60%) with increasing IS of NaCl and CaCl2 respectively. However, when Cu was present, PS mobility reduced even more (10-30%), which might result from the adsorption of PS-Cu complexes on porous media following their formation. Similarly, in the absence of PS, Cu had less mobility (nearly 10%) in all IS and salt types due to electrostatic attraction between sand and Cu. On the other hand, Cu demonstrated increasing mobility during co-transport owing to a lack of adsorption sites caused by the competing adsorption of PS and Cu. The batch adsorption results also revealed that MPs had a greater adsorption capacity on quartz sand in the presence of Cu, resulting in enhanced heavy metal mobility. QCM experiments also showed that with increasing IS and in absence of Cu, both MPs and NPs deposition on the silica surface increased due to compression of the electric double layer, following DLVO theory. However, in presence of Cu, PSMPs and PSNPs had 6.6 and 4.0-fold higher deposition respectively for NaCl and 1.5 and 4.8-fold respectively for CaCl2 under the high IS condition, than in absence of Cu. Positive metal ions can compress the electrostatic double-layer even more, lowering the energy barrier and form complexes with the PS causing greater PS deposition on the silica surfaces. Furthermore, QCM showed that regardless of the presence of heavy metals, NPs mass deposition was higher than MPs on the silica surface. According to DLVO theory, NPs had a lower energy barrier than MPs due to their smaller size, resulting in a higher deposition. In summary, the findings of this study showed that the interaction between PS and Cu can influence both their transport and deposition behaviors in the environment under different aquatic chemistry conditions. This work could be used to anticipate the fate and movement of MPs and NPs in the presence of other pollutants in the aquatic environment and allow necessary steps to be taken to prevent additional contamination and design their subsequent removal.

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<p> This project proposal is focused on the development of a novel class of Viscosity Index improvers. A bench-top method for living anionic polymerization has been set up and tested in many aspects. A new difulvene derivative, 1,4-di(6'-6'-methyl-fulvyl)benzene, was synthesized. The living anionic polymer chain was terminated on this difulvene. Cyclopentadiene groups were formed in the middle of the macromolecule chain during the termination. A doubled molecular weight of polystyrene was obtained after the termination. The cyclopentadienes were then changed to other functional groups by Diels-Alder reaction with dimethyl acetylenedicarboxylate, ozonolysis of double bonds, and bromination and reaction with amine. The infrared spectra and nuclear magnetic resonance spectra of the resulting polymers showed new peaks for the new attached groups.</p> / Thesis / Master of Science (MSc)