Browsing by Subject "Nanoparticle"

Traditional small molecule chemotherapeutics show limited effectiveness in the clinic as their poor pharmacokinetics lead to rapid clearance from circulation and their exposure to off-target tissues results in dose-limiting toxicity. The objective of this dissertation is to exploit a class of recombinant chimeric polypeptides (CPs) to actively target drugs to tumors as conjugation to macromolecular carriers has demonstrated improved efficacy by increasing plasma retention time, reducing uptake by healthy tissues, and enhancing tumor accumulation by exploiting the leaky vasculature and impaired lymphatic drainage characteristic of solid tumors. CPs consist of two principal components: (1) a thermally responsive elastin-like polypeptide (ELP) that displays a soluble-to-aggregate phase transition above a characteristic transition temperature (Tt); and (2) a cysteine-rich peptide fused to one end of the ELP to which small molecule therapeutics can be covalently attached (the conjugation domain). This work describes the development of CP drug-loaded nanoparticles that can be targeted to solid tumors by the external application of mild regional hyperthermia (39-43°C).

Highly repetitive ELP polymers were assembled by Plasmid Reconstruction Recursive Directional Ligation (PRe-RDL), in which two halves of a parent plasmid, each containing a copy of an oligomer, were ligated together to dimerize the oligomer and reconstitute the functional plasmid. Chimeric polypeptides were constructed by fusing the ELP sequence to a (CGG)8 conjugation domain, expressed in Escherichia coli, and loaded with small molecule hydrophobes through site specific attachment to the conjugation domain. Drug attachment induced the assembly of nanoparticles that retained the thermal responsiveness of the parent ELP in that they experienced a phase transition from soluble nanoparticles to an aggregated phase above their Tt. Importantly, the Tt of these nanoparticles was near-independent of the CP concentration and the structure of the conjugated molecule as long as it displayed an octanol-water distribution coefficient (LogD) > 1.5.

A series of CP nanoparticles with varying ratios of alanine and valine in the guest residue position was used to develop a quantitative model that described the CP transition temperature in terms of three variables - sequence, chain length, and concentration - and the model was used to identify CPs of varying molecular weights that displayed transition temperatures between 39°C and 43°C. A murine dorsal skin fold window chamber model using a human tumor xenograft was used to validate that only the thermoresponsive CP nanoparticles (and not the controls) exhibited a micelle-to-aggregate phase transition between 39-43°C in vivo. Furthermore, quantitative analysis of the biodistribution profile demonstrated that accumulation of these thermoresponsive CP nanoparticles was significantly enhanced by applying heat in a cyclical manner. It is hoped that this work will provide a helpful resource for the use of thermoresponsive CP nanoparticles in a variety of biomedical applications.

Cadmium sulfide (CdS) is one of the most commonly used II/VI semiconductor materials because of its electron energy band edge positions. CdS nanoparticles (NPs) are widely used in applications such as photodegradation of organic molecules, photocatalysis of water splitting, and as building blocks of photovoltaic devices. Bacterial precipitation of CdS NPs provides an innovative, environmentally friendly route for the synthesis of NPs with controllable electronic properties. Our previous research shows that CdS NPs can be extracellularly precipitated with tunable CdS crystallite sizes ranging from 5 nm to over 15 nm in diameter. In this thesis, I investigated the potential application of these bacterially precipitated CdS NPs for photodegradation of organic molecules, photocurrent generation, and for photoelectrochemical (PEC) hydrogen evolution. The results show that the bacterially precipitated CdS NPs and their devices performed competitively when compared with their counterparts that were synthesized via chemical bath deposition (CBD). In photodegradation experiments, the bacterially precipitated CdS NPs showed a slower rate of degradation than CBD CdS. In transient photocurrent response experiments, the devices incorporating bacterially precipitated CdS NPs showed a higher current response to visible light. Furthermore, in electrochemical hydrogen generation experiments, the bacterially precipitated CdS NP device showed a lower onset potential to trigger the reaction when irradiated with light. Collectively, the preliminary results show that biosynthesized CdS NPs have potentially promising applications for the photodegradation of organic molecules and for the photoelectrochemical hydrogen generation.

The electromagnetic properties of various plasmonic nanostructures are investigated. These nanostructures, which include random clusters, controlled clusters and particle-film hybrids are applied to surface-enhanced Raman scattering (SERS). A variety of techniques are utilized to fabricate, characterize, and model these SERS-active structures, including nanoparticle functionalization, thin film deposition, extinction spectroscopy, elastic scattering spectroscopy, Raman scattering spectroscopy, single-assembly scattering spectroscopy, transmission electron microscopy, generalized Mie theory, and finite element method.

Initially, the generalized Mie theory is applied to calculate the near-field of the small random clusters to explain their SERS signal distribution. The nonlinear trend of SERS intensity versus size of clusters is demonstrated in experiments and near-field simulations.

Subsequently, controlled nanoparticle clusters are fabricated for quantitative SERS. A 50 nm gold nanoparticle and 20nm gold nanoparticles are tethered to form several hot spots between them. The SERS signal from this assembly is compared with SERS signals from single particles and the relative intensities are found to be consistent with intensity ratios predicted by near-field calculation.

Finally, the nanoparticle/film hybrid structure is studied. The scattering properties and SERS activity are observed from gold nanoparticles on different substrates. The gold nanoparticle on gold film demonstrates high field enhancement. Raman blinking is observed and implies a single molecule signal. Furthermore, the doughnut shape of Raman images indicates that this hybrid structure serves as nano-antenna and modifies the direction of molecular emission.

In additional to the primary gap dipole utilized for SERS, high order modes supported by the nanoparticle/film hybrid also are investigated. In experiments, the HO mode show less symmetry compared to the gap dipole mode. The simulation indicates that the HO modes observed may be comprised of two gap modes. One is quadrupole-like and the other is dipole-like in terms of near-field profile. The analytical treatment of the coupled dipole is performed to mimic the imaging of the quadrupole radiation.

The properties of nanoparticle sensors intended for real- time monitoring of low concentration of elemental mercury (Hg) vapor and volatile organic compounds (VOCs) are presented and discussed. This sensor for mercury vapors is composed of gold (Au) nanoparticles on single-walled carbon nanotubes (SWNTs) networks. Surface topography was determined by scanning electron microscopy (SEM). The electrical resistance of Au-SWNTs networks drastically increased upon exposure to mercury vapor. The experiment result shows that higher deposition amounts of Au nanoparticles on SWNTs lead to higher sensing responses. A detection limit of this senor to vapor mercury concentrations in the parts-per billion (ppb) was seen. Response features of current mercury sensors are discussed concerning sensitivity, reproducibility and regeneration at room temperature (25°C).

Nanosensors made of conducting polypyrrole (PPY) and tin dioxide (SnO2) on SWNTs were tested for the detection of volatile organics such as benzene, methyl ethyl ketone (MEK), hexane and xylene. The greater sensitivity of these two sensors to lower analytes concentrations compared to previous research studies was demonstrated. Experiments were conducted at room temperature, and the response was shown to be fast and highly sensitive to low concentration of VOCs. Using PPY and SnO2 sensors in a sensor array can identify polar and nonpolar analytes. Sensing mechanisms of these two sensors to analytes are discussed in this thesis.

Further work to improve the sensors that were tested was identified. The main challenge of this sensor is that the response and regeneration time is relatively slow at room temperature, especially for Au nanoparticle sensors. Also, with respect to PPY and SnO2 nanosensors, a high reproducibility in the making of sensors is desired. This improvement can help PPY and SnO2 sensors to have consistency. Finally, since nanosensors that can detect VOCs are not very specific, array sensing and numerical methods that can be used to quantify individual compounds in mixture from nanosensors array data are needed.

Recent advances in nanotechnology have led to the application of nanoparticles in a wide variety of fields. In the field of nanomedicine, there is great emphasis on combining diagnostic and therapeutic modalities into a single nanoparticle construct (theranostics). In particular, anisotropic nanoparticles have shown great potential for surface-enhanced Raman scattering (SERS) detection due to their unique optical properties. Gold nanostars are a type of anisotropic nanoparticle with one of the highest SERS enhancement factors in a non-aggregated state. By utilizing the distinct characteristics of gold nanostars, new plasmonic materials for diagnostics, therapy, and sensing can be synthesized. The work described herein is divided into two main themes. The first half presents a novel, theranostic nanoplatform that can be used for both SERS detection and photodynamic therapy (PDT). The second half involves the rational design of silver-coated gold nanostars for increasing SERS signal intensity and improving reproducibility and quantification in SERS measurements.

The theranostic nanoplatforms consist of Raman-labeled gold nanostars coated with a silica shell. Photosensitizer molecules for PDT can be loaded into the silica matrix, while retaining the SERS signal of the gold nanostar core. SERS detection and PDT are performed at different wavelengths, so there is no interference between the diagnostic and therapeutic modalities. Singlet oxygen generation (a measure of PDT effectiveness) was demonstrated from the drug-loaded nanocomposites. In vitro testing with breast cancer cells showed that the nanoplatform could be successfully used for PDT. When further conjugating the nanoplatform with a cell-penetrating peptide (CPP), efficacy of both SERS detection and PDT is enhanced.

The rational design of plasmonic nanoparticles for SERS sensing involved the synthesis of silver-coated gold nanostars. Investigation of the silver coating process revealed that preservation of the gold nanostar tips was necessary to achieve the increased SERS intensity. At the optimal amount of silver coating, the SERS intensity is increased by over an order of magnitude. It was determined that a majority of the increased SERS signal can be attributed to reducing the inner filter effect, as the silver coating process moves the extinction of the particles far away from the laser excitation line. To improve reproducibility and quantitative SERS detection, an internal standard was incorporated into the particles. By embedding a small-molecule dye between the gold and silver surfaces, SERS signal was obtained both from the internal dye and external analyte on the particle surface. By normalizing the external analyte signal to the internal reference signal, reproducibility and quantitative analysis are improved in a variety of experimental conditions.

Although various proof-of-concept studies have demonstrated the eventual potential of a multifunctional SERS-active metallic nanostructures for biological applications such as single cell analysis/measurement and drug delivery, the actual development and testing of such a system in vitro has remained challenging. One key point at which many potentially useful biomethods encounter difficulty lies in the translation of early proof-of-concept experiments in a clean, aqueous solution to complex, crowded, biologically-active environments such as the interior of living cells. The research hypotheses for this work state that multifunctional nanoconstructs can be fabricated and used effectively in conjunction with surface-enhanced Raman scattering (SERS) spectroscopy and other photonics-based methods to make intracellular measurements in and deliver treatment to single cells. The results of experimental work address the specific research aims, to 1) establish temporal and spatial parameters of nanoprobe uptake and modulation, 2) demonstrate targeting of functionalized nanoparticles to the cytoplasm and nucleus of single cells, 3) deliver to and activate drug treatment in cells using a multifunctional nanosystem, and 4) make intracellular measurements in normal and disease cells using external nanoprobes,

Raman spectroscopy and two-dimensional Raman imaging were used to identify and locate labeled silver nanoparticles in single cells using SERS detection. To study the efficiency of cellular uptake, silver nanoparticles were functionalized with three differently charged SERS/Raman labels and co-incubated with J774 mouse macrophage cell cultures for internalization via normal cellular processes. The surface charge on the nanoparticles was observed to modulate uptake efficiency, demonstrating a dual function of the surface modifications as tracking labels and as modulators of cell uptake.

To demonstrate delivery of functionalized nanoparticles to specific locations within the cell, silver nanoparticles were co-functionalized with the HIV-1 TAT (49-57) peptide for cell-penetrating and nuclear-targeting ability and p-mercaptobenzoic acid (pMBA) molecules as a surface-enhanced Raman scattering (SERS) label for tracking and imaging. Two-dimensional SERS mapping was used to track the spatial and temporal progress of nanoparticle uptake in PC-3 human prostate cells and to characterize localization at various time points, demonstrating the potential for an intracellularly-targeted multiplexed nanosystem. Silver nanoparticles co-functionalized with the TAT peptide showed greatly enhanced cellular uptake and nuclear localization as compared with the control nanoparticles lacking the targeting moiety.

The efficacy of targeted nanoparticles as a drug delivery vehicle was demonstrated with development and testing of an anti-cancer treatment in which novel scintillating nanoparticles functionalized with HIV-1 TAT (49-57) for cell-penetrating and nuclear-targeting ability were loaded with tethered psoralen molecules as cargo. The experiments were designed to investigate a nanodrug system consisting of psoralen tethered to a nuclear targeting peptide anchored to UVA-emitting, X-ray luminescent yttrium oxide nanoparticles. Absorption of the emitted UVA photons by nanoparticle-tethered psoralen has the potential to cross-link adenine and thymine residues in DNA located in the nucleus. Such cross-linking by free psoralen following activation with UVA light has previously been shown to cause apoptosis in vitro and an immunogenic response in vivo. Experimental results using the PC-3 human prostate cancer cell line demonstrate that X-ray excitation of these psoralen-functionalized Y2O3 nanoscintillators yields concentration-dependent reductions in cell number density when compared to control cultures containing psoralen-free Y2O3 nanoscintillators.

The development and demonstration of a small molecule-sensitive SERS-active fiber-optic nanoprobe suitable for intracellular bioanalysis was demonstrated using pH measurements in single living human cells. The proof-of-concept for the SERS-based fiber-optic nanoprobes was illustrated by measurements of intracellular pH in MCF-7 human breast cancer, HMEC-15/hTERT immortalized normal human mammary epithelial, and PC-3 human prostate cancer cells. Clinical relevance was demonstrated by pH measurements in patient biopsy cell samples. The results indicated that that fiber-optic nanoprobe insertion and interrogation provide a sensitive and selective means to monitor biologically relevant small molecules at the single cell level.

The refractive index sensitivity of plasmonic nanoparticles is utilized in the development of real-time, label-free biodetection. Analyte molecules that bind to receptor-conjugated nanoparticles cause an increase in local refractive index that in turn induces an energy shift in the optical resonance of the particle. Biomolecular binding is quantified by quantitatively measuring these resonance shifts. This work describes the application and optimization of a biomolecular detection system based on gold nanorods as an optical transducer.

A microspectroscopy system was developed to collect scattering spectra of single nanoparticles, and measure shifts of the spectra as a function of biomolecular binding. The measurement uncertainty of LSPR peak shifts of the system was demonstrated to be 0.3 nm. An analytical model was also developed that provides the optimal gold nanorod geometry for detection with specified receptor-analyte pair. The model was applied to the model biotin-streptavidin system, which resulted in sensing system with a detection limit of 130 pM - an improvement by four orders of magnitude over any other single-particle biodetection previously presented in the literature.

Alternative optical detection schemes were also investigated that could facilitate mulitplexed biosensing. A theoretical model was built to investigate the efficacy of using a multi-channel detector analogous to a conventional RGB camera. The results of the model indicated that even in the best case, the detection capabilities of such a system did not provide advantages over the microspectroscopic approach.

We presented a novel hyperspectral detection scheme we term Dual-Order Spectral Imaging (DOSI) which is capable of simultaneously measuring spectra of up to 160 individual regions within a microscope's field of view. This technique was applied to measuring shifts of individual nanoparticles and was found to have a peak measurement uncertainty of 1.29 nm, at a measurement rate of 2-5 Hz.

The ability of photocatalytic nanoparticles (NPs) to produce reactive oxygen species (ROS) has inspired research into several new applications and technologies, including water purification, contaminant remediation, and self-cleaning surface coatings. As a result, NPs continue to be incorporated into a wide variety of increasingly complex products. With the increased use of NPs and nano-enabled products and their subsequent disposal, NPs will make their way into the environment. Currently, many unanswered questions remain concerning how changes to the NP surface chemistry that occur in natural waters will impact reactivity. This work seeks to investigate potential influences on photoreactivity – specifically the impact of functionalization, the influence of anions, and interactions with biological objects - so that ROS generation in natural aquatic environments may be better understood.

To this aim, titanium dioxide nanoparticles (TiO2) and fullerene nanoparticles (FNPs) were studied in terms of their reactive endpoints: ROS generation measured through the use of fluorescent or spectroscopic probe compounds, virus and bacterial inactivation, and contaminant degradation. Physical characterization of NPs included light scattering, electron microscopy and electrophoretic mobility. These systematic investigations into the effect of functionalization, sorption, and aggregation on NP aggregate structure, size, and reactivity improve our understanding of trends that impact nanoparticle reactivity.

Engineered functionalization of FNPs was shown to impact NP aggregation, ROS generation, and viral affinity. Fullerene cage derivatization can lead to a greater affinity for the aqueous phase, smaller mean aggregate size, and a more open aggregate structure, favoring greater rates of ROS production. At the same time however, fullerene derivatization also decreases the 1O2 quantum yield and may either increase or decrease the affinity for a biological surface. These results suggest that the biological impact of fullerenes will be influenced by changes in the type of surface functionalization and extent of cage derivatization, potentially increasing the ROS generation rate and facilitating closer association with biological targets.

Investigations into anion sorption onto the surface of TiO2 indicate that reactivity will be strongly influenced by the waters they are introduced into. The type and concentration of anion impacted both aggregate state and reactivity to varying degrees. Specific interactions due to inner sphere ligand exchange with phosphate and carbonate have been shown to stabilize NPs. As a result, waters containing chloride or nitrate may have little impact on inherent reactivity but will reduce NP transport via aggregation, while waters containing even low levels of phosphate and carbonate may decrease “acute” reactivity but stabilize NPs such that their lifetime in the water column is increased.

Finally, ROS delivery in a multicomponent system was studied under the paradigm of pesticide degradation. The presence of bacteria or chlorpyrifos in solution significantly decreased bulk ROS measurements, with almost no OH detected when both were present. However, the presence of bacteria had no observable impact on the rate of chlorpyrifos degradation, nor chlorpyrifos on bacterial inactivation. These results imply that investigating reactivity in simplified systems may significantly over or underestimate photocatalytic efficiency in realistic environments, depending on the surface affinity of a given target.

This dissertation demonstrates that the reactivity of a system is largely determined by NP surface chemistry. Altering the NP surface, either intentionally or incidentally, produces significant changes in reactivity and aggregate characteristics. Additionally, the photocatalytic impact of the ROS generated by a NP depends on the characteristics of potential targets as well as on the characteristics of the NP itself. These are complicating factors, and the myriad potential exposure conditions, endpoints, and environmental systems to be considered for even a single NP highlight the need for functional assays that employ environmentally relevant conditions if risk assessments for engineered NPs are to be made in a timely fashion so as not to be outpaced by, or impede, technological advances.

Methylmercury is a bioaccumulative neurotoxin that severely endangers human health. Humans are exposed to methylmercury through consumption of contaminated aquatic fish. To date, effective strategies for preventing and remediating methylmercury contamination have remained elusive, mainly due to the lack of knowledge in regard to how methylmercury is generated and degraded in the aquatic environment. The goal of this dissertation was to study the mechanisms of two transformation processes that govern the fate of methylmercury in natural settings: microbial mercury methylation and methylmercury photodegradation. The role of mercury speciation (influenced by environmental conditions) in determining the reactivity of mercury in these biological and photochemical reactions was the focus of this research.

Methylmercury production in the aquatic environment is primarily mediated by anaerobic bacteria in surface sediments, particularly sulfate reducing bacteria (SRB). The efficiency of this process is dependent on the activity of the methylating bacteria and the availability of inorganic divalent mercury (Hg(II)). In sediment pore waters, Hg(II) associates with sulfides and dissolved organic matter (DOM) to form a continuum of chemical species that include dissolved molecules, polynuclear clusters, amorphous nanoparticles and after long term aging, bulk-scale crystalline particles. The methylation potential of these mercury species were examined using both pure cultures of SRB and sediment slurry microcosms. The results of these experiments indicated that the activity of SRB was largely determined by the supply of sulfate and labile carbon, which significantly influenced the net methylmercury production in sediment slurries. The availability of mercury for methylation decreased during aging. Dissolved Hg-sulfide (added as Hg(NO3)2 and Na2S) resulted in the highest methylmercury production. Although the methylation potential of humic-coated HgS nanoparticles decreased with an increase in the age of nanoparticle stock solutions, nano-HgS was substantially more available for microbial methylation relative to microparticulate HgS, possibly due to the smaller size, larger specific surface area and more disordered structure of the nanoparticles. Moreover, the methylation of mercury derived from nanoparticles cannot be explained by equilibrium speciation of mercury in the aqueous phase (<0.2 fÝm, the currently-accepted approach for assessing mercury bioavailability for methylation). Instead, the methylation potential of mercury sulfides appeared to correlate with the extent of dissolution and their reactivity in thiol ligand exchange. Additionally, partitioning of mercury to a diverse group of bulk-scale mineral particles and colloids (especially FeS) may be an important process controlling the mercury speciation and subsequent methylmercury production in natural sediments.

In surface waters, sunlight degradation is believed to be the predominant pathway for the decomposition of methylmercury. The mechanism of this process was investigated in a series of photodegradation experiments under natural sunlight and UV-A radiation, and in the presence of DOM and selective quenchers for photo-generated reactive intermediates. The results suggested that singlet oxygen generated from photosensitization of DOM drove the photodecomposition of methylmercury. The rate of methylmercury degradation depended on the type of methylmercury (CH3Hg+) binding ligand present in the water. CH3Hg -thiol (e.g., glutathione, mercaptoacetate, DOM) complexes were significantly more reactive in photodegradation compared to other methylmercury complexes (CH3HgCl or CH3HgOH), which may be because thiol-binding can effectively decrease the activation energy and thus enhance the reactivity of methylmercury molecules toward the Hg-C bond breaking process. These findings challenge the long-accepted view that water chemistry characteristics do not affect the kinetics of methylmercury sunlight degradation, and help explain recent field observation that methylmercury photodegradation occurred rapidly in freshwater lakes (where CH3Hg-DOM dominate methylmercury speciation) but relatively slowly in sea water (where CH3Hg-Cl control methylmercury speciation).

Overall, this dissertation has demonstrated that chemical speciation of inorganic mercury and methylmercury determines their availability for microbial methylation and sunlight degradation, respectively. The abundance of these available mercury species is influenced by a variety of environmental parameters (e.g., DOM). This dissertation work contributes mechanistic knowledge toward understanding the occurrence of methylmercury in the aquatic environment. This information will ultimately help construct quantitative models for accurately predicting and assessing the risks of mercury contamination.

Expanding the role of plasmonics in tomorrow's technology requires a broader knowledge base from which to develop such applications today. Several limitations to the current plasmonics field limit progress to incremental advances within a narrow set of materials and techniques rather than developing non-traditional metals and flexible growth and characterization methods. The work described herein will provide an introduction to the burgeoning field of spectroscopic ellipsometry for plasmonic characterization; in particular, the power of its real-time monitoring capabilities and flexibility will be demonstrated. More importantly, a novel plasmonic metal, gallium, is investigated in detail. Critical characteristics of gallium for an array of applications include its tunability over a wide spectral range, phase stability across a wide temperature range, plasmon stability even after air exposure, and an ultra high vacuum evaporation growth process enabling simple, alloyed nanostructure development. Deeper scientific investigation of the underlying ripening mechanisms driving gallium nanoparticle formation and in concert with in situ alloying paves the way for future work contributing to the development of advanced nanostructured alloys. Finally, this work demonstrates the first example of gallium nanoparticle-enhanced Raman spectroscopy - an area craving materials innovation. While the specific application of gallium for SERS detection is interesting, the far-reaching implication lies in the demonstrated potential for plasmonic gallium nanoparticles' ultimate use in a wider variety of applications enhanced by nanoscale materials.

While anisotropic nanoparticles provide unique building blocks for self-assembling useful nanodevices and nanomaterials ranging from plasmonic sensors to chiral metamaterials, controlling their self-assembly process to achieve targeted structure remains challenging. Recently, surface functionalization of nanoparticles with polymer grafts was shown to be a powerful strategy for tuning the orientation-dependent interactions of the nanoparticles. This technique allows modulation of the interaction between nanoparticles as grafted polymers can provide both repulsive interactions arising from their steric hindrance as well as attractive interactions due to their adsorption to the particle surfaces. Utilizing this approach, experiments have successfully assembled nanoparticles into large structures with highly uniform interparticle orientations. However, many challenges remain in fabricating desired nanostructures with the polymer-grafted anisotropic nanoparticles. First, much of the underlying physics governing assembly of such nanoparticles is not well understood and is difficult to discern using experimental techniques due to the nanoscopic nature of the self-assembly process. Second, the relevant parameter space that affects the particle assembly is vast and investigation of such large parameter space is costly in terms of both time and expenses. Third, computationally investigating the behavior of anisotropic nanoparticles is difficult as calculation of their interaction energies is computationally expensive due to the lack of analytical expressions for these energies.In this dissertation, I tackle these challenges in self-assembly of anisotropic nanoparticles through computational modeling, focusing specifically on polymer-grafted nanocubes and DNA-grafted nanorods. For both systems, computational methods and analytical models for efficiently calculating the interaction energies between the anisotropic nanoparticles are first developed. Using such methods as well as advanced Monte Carlo simulations and atomistic calculations, free-energy landscapes describing the assembly of these anisotropic nanoparticles are obtained. Analysis of the free-energy landscapes demonstrates that understanding the interplay between the different interaction components of the systems as well as their dependencies on the relative configurations of the assembled particles is crucial. Specifically for the nanocubes, the competition between the attractive interactions between the inorganic particle cores lead to face-face type of configurations while the repulsive interactions due to the polymer corona induce edge-edge configurations. For the DNA-grafted nanorods, the competition between attractive and repulsive interactions interplay with the chirality of the bridging DNA to induce chiral assembly of the nanorods. Based on these results, material design rules for assembling both the nanocubes and the nanorods into desired configurations are suggested. These results were not only in agreement with many previous experimental studies but also provided the underlying mechanism that explain such assembly behaviors. In summary, the results presented in this dissertation should both aid in fabrication of nanodevices with precisely controlled particle assemblies as well as provide efficient computational methods for future investigation of anisotropic nanoparticles.

Nanoceria, or cerium (IV) oxide, is used widely in industry for its catalytic and physical properties, thus its release into the environment is eminent. The environmental risk of nanoceria is still unclear, but understanding its environmental fate could help to inform future studies. To understand its fate, large scale simulated wetlands were constructed and dosed weekly. Nanoceria of primary particle sizes ~4nm (sm-CeO2) and ~140nm (lg-CeO2) were dosed into these mesocosms, 750 mg total over nine months. Single particle ICP-MS (spICP-MS) was employed with microsecond dwell times (0.1ms) to understand particulate cerium in surface water. spICP-MS proved ineffective as a comparison tool between treatments, since sm-CeO2 was below instrument detection, and further data processing could not amend the issue. However, comparisons between nanoceria stocks and mesocosm samples could be conducted. Mesocosm water dosed with lg-CeO2 exhibited some aggregation of its smaller fraction.

At the end of 9-months, elemental analyses showed that nanoceria size did not affect the mass of cerium in surface water, as mesocosms treated with lg-CeO2 contained 4.0 ± 1.4 mg of Ce and sm-CeO2 treated waters contained 5.6± 6.7mg Ce. Greater biological uptake did occur when treated with smaller particles, as shown in elevated root concentration (sm-CeO2: 67 ± 14 ng g-1 ; lg-CeO2: 21 ± 10 ng g-1) and total Ce in Egeria densa biomass (sm-CeO2: 22 ± 1.4 ; lg-CeO2: 2.9 ± 0.5 mg). The environmental compartments in this study accounted for a small fraction of dosed nanoceria (< 5%), so assumed nanoceria fate is the sediment.

Increasing demands on energy resources have largely constrained the future development of modern society. Currently, people rely strongly on the combustion of fossil fuels creating massive CO2 and causing severe greenhouse effects. Hence, the expansion of renewable energy technologies becomes necessary for the next generation of industrialization. In many novel approaches for solving these growing concerns, converting earth-abundant chemicals into chemical fuels and utilizing generated fuels in fuel cells with cost-effective electrocatalysts have been considered as a substitution of fossil fuels. In Chapters 1 and 2, recent progress and research methods of electrocatalysis for the electrochemical energy conversion and storage in liquid solution have been summarized in detail. It has been widely recognized that the electrocatalyst surface and interface structure play a deceive role in their electrocatalytic performance. However, the studies on the surface and interface of electrocatalyst are still at their very early stage, and the advancements in new materials need to be made available in large quantities at low cost while satisfying various harsh industry conditions is a key part of developing electrochemical energy conversion and storage technology. Chapter 3 describes the development of partial oxidation methods to synthesize δ-MnO2/Mn3O4 nanocomposites with a tunable surface electronic structure. The δ-MnO2/Mn3O4 nanocomposites exhibit significantly improved ORR activity with a half-wave potential of 750 mV vs. RHE, which is ~110 mV and ~90 mV lower than those of the Mn3O4 nanocrystal and the δ-MnO2 nanoflakes in their pure forms, respectively. Chapter 4 focuses on improving the selectivity of CO2 reduction by the atomically dispersive Ni active atoms. The Ni single atom electrocatalyst possesses the maximum CO FE of over 95% at −1600 mV vs. Ag/AgCl, which is about 30% higher than the standard Ni nanoparticles on the nitrogen-doped carbon nanofiber. In Chapter 5, we develop an electrocatalyst of metal nitride nanosheets by controlling the composition, atomic and electronic structure, and morphology for efficient ammonia oxidation reaction (AOR). The AOR onset overpotential of NiCo2N nanosheets is 550 mV, which is about 250 mV lower than that of the Pt/C electrocatalyst. Our ultraviolet-visible and mass spectroscopy results reveal that the NiCo2N nanosheets bypass the formation of the soluble metal-amine complex and preferentially oxidize ammonia to environmentally friendly diatomic nitrogen with a Faradic efficiency of over 90%. Moreover, High entropy material offers a surface atomic structure that cannot be obtained previously by virtue of engineering surface through directly controlling element compositions. These materials represent a new direction in materials research because their diverse compositions can resolve some of the long-standing all-in-one bottlenecks to tune the multiple chemical reaction process in the electrocatalyst industry. In Chapter 6, we report that the high entropy (Mn, Fe, Co, Ni, Cu)3O4 oxides can achieve a high electrocatalytic activity for AOR in non-aqueous solutions. In Chapter 7, I summarize the main scientific achievement and contribution of this dissertation is that we have introduced several well-defined surfaces and interface structures of nanomaterials to significantly enhance their electrocatalytic performance, which paves the way for efficient energy conversion technology and beyond.

Nanomaterials often exhibit enhanced reactivity relative to their larger colloidal counterparts because of the high specific surface area and number of imperfections on the crystal lattice at the nanoscale. Management of ecosystems, remediation of contaminated waters, and assessment of the potential risks from the industrial use on nanomaterials requires an understanding of the environmental factors that control the reactivity and bioavailability of natural and manufactured nanomaterials. Dissolved organic matter (DOM) acts as a moderator of reactivity and bioavailability for dissolved and particulate moieties in natural waters. DOM consists of a range of low and high molecular weight species that are complex and heterogeneous. It has been historically categorized based on operational definitions, rather than physical properties. In order to understand the effect of DOM on nanomaterials, there is an urgent need for information regarding specific properties of DOM, such as ligand groups.

The goal of this research was to study how cysteine, a low molecular weight metal-binding ligand, affects the composition and reactivity of nanoparticulate zinc sulfide and metallic silver. Zinc sulfide was used as a representative of nanoparticulate metal sulfide which occurs naturally in sulfidic environments. Metallic silver nanoparticles were also studied because of its wide use in consumer products. Both types of nanomaterials contain metal constituents (zinc and silver) that are expected to strongly bind to sulfhydryl-containing ligands (such as cysteine) in the environment. Serine is structurally similar to cysteine, with the only difference of a hydroxyl group in the place of the sulfhydryl group of cysteine. Therefore, serine was used for comparison as a hydroxyl-containing analogue to cysteine.

The aggregation kinetics of zinc and other metal sulfide nanoparticles in the presence of cysteine and serine were investigated using dynamic light scattering. Cysteine decreased aggregation rates of the particles, while serine had no effect on their aggregation behavior. Further experiments revealed that the mechanism of stabilization occurred through the adsorption of cysteine on zinc sulfide, which induced electrostatic charge on the particles surface. A direct link was established between the amount of cysteine sorbed and attachment efficiency, an indicator of the tendency of particles to aggregate. These results shed light on discrepancies in the literature between metal sulfide precipitation experiments conducted in our lab and work on the formation and aggregation of zinc sulfide nanoparticles on biofilms of sulfate reducing bacteria.

The early-stage growth and aggregation kinetics of zinc sulfide nanoclusters in the presence of cysteine was studied in detail using a suite of complementary techniques. Growth and aggregation experiments have been traditionally difficult to conduct due to instrumental precision issues, but newly developed analytical tools and software products have made it possible to study the early-stage formation of nanoclusters. Experiments with small angle X-ray scattering, X-ray diffraction, dynamic light scattering, and X-ray absorption spectroscopy at the extended fine structure range showed that cysteine controlled the growth and aggregation of zinc sulfide nanoclusters. The molar ratio between zinc, sulfide, and cysteine was a determining factor in the precipitation process. When zinc and sulfide were in equimolar concentrations with cysteine, very small nanoclusters of about 2.5 nm formed within 12 hours and aggregated to structures with hydrodynamic diameter larger than 100 nm. When cysteine was in excess of zinc and sulfide, aggregation was held to a minimum, but monomer nanoclusters were able to grow to about 5 nm in 12 hours. Overall, these results indicate the importance of thiol ligands on the monomer size, extent of aggregation, and aggregate structure of zinc sulfides.

The effect of metal ligands on metal bearing particle surfaces is of particular interest for manufactured nanoparticles, because they are typically coated with an organic coating during the production process. These coatings are sorbed on the particles surface and are likely to interfere between the metallic surface and the ligand. Dissolution experiments using citrate and polyvinylpyrrolidone (PVP) coated zero valent silver nanoparticles in the presence of cysteine and serine showed that cysteine dissolved both types of particles, while serine did not. Dissolution rates depended on the aggregation state of the particles exposed to cysteine. As indicated by zeta potential and adsorption measurements, cysteine replaced the coating on the particles surface and altered their aggregation pattern. X-ray absorption spectroscopy near the absorption edge showed partial oxidation of silver and formation of Ag(+I)-sulfur bonds, indicating that the thiol group in cysteine formed chemical bonds with oxidized surface silver atoms. A comparison between the two coatings showed that citrate coated particles dissolved approximately three times faster than PVP coated particles. Overall, these results show that metal binding ligands can drastically change the fate of manufactured silver nanoparticles in the environment and that this effect is moderated by surface coatings.

The results of this study suggest that cysteine, a metal binding ligand was able to induce and control transformations, such as growth, aggregation, dissolution, and surface reactivity of zinc sulfide and metallic silver nanoparticles. Cysteine adsorbed on metal sites on both ZnS and Ag particles, inducing changes on their surface charge. Aggregation of ZnS particles was slowed because of a net decrease in zeta potential compared to the bare particles. On the contrary, cysteine enhanced the aggregation of Ag particles, by replacing the citrate and PVP coatings on the particles surface. Finally, the cysteine-Ag(+I) bonds caused strong polarization on the particles surface and lead to the oxidative dissolution of the particles.

Overall, this research provides a better understanding of the fate of natural and manufactured nanoparticles in anaerobic waters, where thiols are present in significant amounts. It may also be used for risk assessment of manufactured nanomaterials and the production of safer and environmentally responsible materials.