Organodithiols including para-aryl dithiols (PADTs, HS-(C6H4)n-SH, n = 1, 2 and 3) and alpha, omega-alkanedithiols (ADTs, HS-(CH2)n-SH, n = 2, 4, …) with two distal thiols have been used extensively in molecular electronics, surface-enhanced Raman spectroscopy (SERS), and quantum electron tunneling between two gold or silver nanoparticles (AuNPs and AgNPs). The popular belief is that these dithiols cross-link noble metal nanoparticles (NPs) as monolayer dithiolate spacers. Reported is the finding that PADTs predominantly exist as monothiolate forms on AuNPs or AgNPs. No PADT-induced NP cross-linking was observed regardless of NP/PADT concentration ratios. 1,4-benzenedimethanethiol (HS-CH2-(C6H4)-CH2-SH) and ADT can be completely deprotonated, forming dithiolates on AuNPs and AgNPs, while only one PADT thiol can be deprotonated even when PADTs are treated with concentrated NaOH or AgNO3. AuNP localized surface plasmon resonance (LSPR) measurement provides conclusive evidence that ADT in AuNP junctions primarily consisted of dithiolate monomers in which the two sulfides are either attached to the same AuNP, or cross-link two adjacent AuNPs as single-molecular spacers. However, ADT molecules most likely in the area surrounding the AuNP junction are monothiolate with their distal thiols either remaining intact or forming disulfide cross-links with neighboring adsorbed ADTs. The possibility for ADT to cross-link two AgNPs as single molecular linker is excluded on the basis of TEM measurements that showed ADT-induced AgNP disintegration. This work highlights the difference between organothiol interactions with AgNPs and AuNPs and should be of broad importance for plasmonic NP research given the popularity of PADTs in molecular electronics and SERS applications.

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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Due to their small size and large surface area-to-volume ratios, nanoparticles (particles with limiting dimensions smaller than 100 nm) have been widely applied as catalysts. Metal nanoparticles are typically produced in suspensions from metal ion precursors, reducing agents, and organic ligands called capping agents. Capping agents help prevent particle agglomeration, fix nanoparticle size, and promote monodispersity. However, capping agents also affect the morphology and the physico-chemical surface properties of nanoparticles, which can influence catalytic properties in unpredictable ways. While there have been extensive studies focused on examining the relationship between nanoparticle size, shape, composition and catalytic activity, relatively few have investigated the effects of capping agent properties on catalysis, and most studies involving nanoparticle catalysts have been conducted on collections, ensembles, or arrays of particles rather than single nanoparticles. Results obtained for systems composed of multiple nanoparticles dispersed on solid surfaces can be difficult to interpret due to variations in particle loading and interparticle distance, which are often challenging or impossible to control and characterize. The complexity of these unavoidable experimental variables may explain some of the seemingly inconsistent conclusions that have been drawn between nanoparticle properties and catalytic activity in recent reports. Single nanoparticle studies should help overcome limitations associated with investigations based on collections of nanoparticles by helping uncover direct relationships between nanoparticle size, surface properties, and catalytic activity that are unobscured by complex factors such as interparticle distance and particle loading. In this work, we aim to use nitrided carbon fiber ultramicroelectrodes to examine electrocatalytic properties of bare (uncapped) and capped gold nanoparticles at the single nanoparticle level.

A novel synthetic methodology has been developed for attaching fluorene derivatives, containing different types of electron donating and accepting groups at the 2 and 7 positions, to gold nanoparticles of different sizes by exploiting the affinity of the thiol functional group for gold. The distance between the dye and nanoparticles was varied by introducing two alkyl chains containing different number of carbon atoms at the 9 position on the fluorene ring system. The methodology that was developed gave enough scope for performing Radiative Decay Engineering (RDE) studies, in order to investigate the impact of gold nanoparticles on the singlet oxygen quantum yields of fluorene dyes that already exhibit high singlet oxygen quantum yields as well as high two photon absorption (2PA) cross-sections. The dialkylation of the fluorene derivatives was accomplished by reacting the dye with [alpha], [omega]-dibromoalkanes containing different number of carbon atoms in a biphasic reaction mixture containing toluene and aqueous sodium hydroxide solution in the presence of tetrabutylammonium bromide (TBAB) as a phase transfer catalyst. The bromine atom on the alkyl chains was converted to thioester by reaction with potassium thioacetate. This was followed by the hydrolysis of the thioester to form the thiol moiety. The compounds synthesized were characterized using 1H and 13C nuclear magnetic resonance (NMR) spectroscopy and elemental analysis. Functionalization of gold nanoparticles was attempted by bringing into contact a solution of the thiol compound in toluene and an aqueous gold nanoparticles solution. UV-vis absorbance spectroscopy was used to monitor the progress of the attachment. Surface Enhanced Raman Scattering (SERS) spectroscopy was used to probe the enhancement of Raman signal by the metallic nanoparticles.

Gold nanoparticles (AuNPs) with their unique sizes, shapes, and properties have generated much enthusiasm over the last two decades, and have been explored for many potential applications. The successful application of AuNPs depends critically on the ability to modify and functionalize their surface to provide stability, compatibility, and special chemical functionality. This dissertation is aimed at exploring the chemical synthesis and surface modification of AuNPs with the effort to (1) control the number of functional groups on the particle surface, and to (2) increase the colloidal stability at the physiological conditions. To control the functionality on the particle surface, a solid phase place exchange reaction strategy was developed to synthesize the 2 nm AuNPs with a single carboxylic acid group attached on the particle surface. Such monofunctional AuNPs can be treated and used as molecular nanobuilding blocks to form more complex nanomaterials with controllable structures. A "necklace"-like AuNP/polymer assembly was obtained by conjugating covalently the monofunctional AuNPs with polylysine template, and exhibited an enhanced optical limiting property due to strong electromagnetic interaction between the nanoparticles in close proximity. To improve the colloidal stability in the psychological condition, biocompatible polymers, polyacrylic acid (PAA), and polyethylene glycol (PEG) were used to surface modify the 30 nm citrate-stabilized AuNPs. These polymer-modified AuNPs are able to disperse individually in the high ionic strength solution, and offer as the promising optical probes for bioassay applications. The Prostate specific antigen (PSA) and target DNA can be detected in the low pM range by taking advantages of the large scattering cross section of AuNPs and the high sensitivity of dynamic light scattering (DLS) measurement. In addition to the large scattering cross section, AuNPs can absorb strongly the photon energy at the surface plasmon resonance wavelength and then transform efficiently to the heat energy. The efficient photon-thermal energy conversion property of AuNPs has been used to thermal ablate the Aβ peptide aggregates under laser irradiation toward Alzheimer's disease therapy.

Numerous biological phenomena occur as a result of macromolecular interactions. Metal-ion-biomolecule binding account for a large portion of these reactions, and unsurprisingly, a vast amount of new research in this area is constantly emerging. Gaining insight into the characteristics that define these interactions; including equilibrium fluctuations, metal center formation, global stability perturbation, cooperativity, allostery, and site-specific binding are all significant. As with all chemical reactions, biological interactions are regulated by thermodynamics; and the development of novel tools and methods by which to study these interactions becomes highly relevant. In this dissertation, three systems involving macromolecular binding are studied using well established biophysical techniques in conjunction with a critical look at appropriate uses for mathematical modeling. The first system studied is that of the serpin plasminogen activator inhibitor-1 (PAI-1). PAI-1 is a protease inhibitor that specifically effects fibrinolysis, or the process that prevents the formation of blood clots, and misregulation of this enzyme leads to uncontrollable hemorrhaging. ITC was utilized to investigate the thermodynamics of copper binding to PAI-1. Human carbonic anhydrase II (CA) was the second system investigated. Studies were conducted on zinc(II) and copper(II) binding to CA, a metalloenzyme responsible for acid-base balances in the blood and the transport of carbon dioxide. Interestingly, CA binds two copper(II) ions, one at the active site, and one at a higher affinity N-terminal site. Temperature dependent ITC, CD and GdnHCl denaturation studies were performed to explore the impact of copper(II) binding, particularly at the higher affinity N-terminal site. Finally, protein binding to inorganic gold nanoparticles (AuNPs) was investigated. AuNPS are utilized in areas of diagnostics, biological sensing and drug delivery. We studied binding of nanoparticles to a set of six biologically relevant proteins; glutathione, wild-type GB3, K19C GB3 (a variant at position 19), bovine CA, bovine serum albumin, and fibrinogen. Nanoparticle-protein binding was monitored via UV-Visible extinction and polarized resonance synchronous spectroscopy (PRS2). The UV extinction maxima wavelength shifts were fit with two models, a Langmuir isotherm model and a mass action-derived model. The models fit the data equally well, however, they predict very different Kd values, specifically for smaller sized AuNPs.

Plasmonic photothermal therapy (PPTT) has a rising promise for treating different cancer cells such as lymphoma or stomach cancer. Technique development of PPTT using metallic nanoparticles is developed upon a modification of the irradiation therapy using two major changes: using a less harmful visible amber light (excluding blue light) and using gold-loaded biocompatible nanoparticles. Acrylate nanoparticles were loaded with desired types of gold nanoparticles at different sizes. The gold-loaded gold nanoparticles were conjugated to cancer cells. By selectively delivering the gold nanoparticles into cancer cells, irradiating a harmless amber visible light will achieve thermal ablation of the cancer cells. Based on imaging spectroscopy, flow cytometry, and cell viability assays, results showed reduction of gold-loaded viable cancer cells upon irradiating with amber visible light, no change in the number of cancer cells with irradiating with light only. On the other hand, DNA intercalation of a trinuclear gold(I), [Au(3-CH3,5-COOH)Pz]3 (Au3) is contrasted with the standard organic intercalators ethidium and ellipticine, as investigated computationally. Frontier molecular orbital energies of intercalators and DNA base pairs were determined and found that all intercalators are good electron acceptors with Au3 being the best electron acceptor having the lowest LUMO. DNA base pairs are better electron donors having the lowest HOMO values, and from the intercalators and base pairs' HOMO/LUMO energies, it is evident the intercalators will overlap with the HOMO of DNA stabilizing the intercalators. Interaction energies (kcal/mol) were obtained as a function of distance, r (angstroms). Results show that the theoretical treatment SDD-WB97XD outperforms SDD-LSDA in both adenine-thymine (AT) systems with ethidium and Au3 intercalators. In both guanine-cytosine (GC) and AT pairs, the Au3 has the lowest interaction energies among these common intercalators, suggesting a potential intercalating drug. Experimental DNA intercalation studies were attempted and methods of finding intercalation binding constants were established, showing gold complexes have better binding constants to DNA than common intercalators to support the computational results.

This report presents evidence that in-situ reduction of metal ions bound to a cross-linked polymer surface does not always result in nanoparticle formation solely at the interface, as is commonly assumed, but also as much as 40 nm deep within the polymer matrix. Tetrachloroaurate ions were bound using a variety of multi-functional amines to cured films of SU-8 -- a cross-linkable epoxide frequently used for micro- and nanofabrication -- and then treated using one of several reducing agents. The resulting gold-nanoparticle decorated films were examined by X-ray photoelectron spectroscopy and by plan-view and cross-sectional transmission electron microscopy. Reduction using sodium borohydride or sodium citrate generates bands of interspersed particles as much as 40 nm deep within the polymer, suggesting both the Au(III) complex and the reducing agent are capable of penetrating the surface and affecting reduction and formation of nanoparticles within the polymer matrix. It is shown that nanoparticle formation can be confined nearer to the polymer interface by using hydroquinone, a sterically bulkier and less flexible reducing agent, or by reacting the surface in aqueous media with high molecular-weight multifunctional amines, that presumably confine Au(III) nearer to the true interface. These finding have important implications for technologies that apply surface bound nanoparticles, including electroless metallization, catalysis, nano-structure synthesis, and surface enhanced spectroscopy.