Yes / Thermal desolvation of poly(N‐isopropylacrylamide) (PNIPAM) in the presence of a low concentration of gold nanoparticles incorporates the nanoparticles resulting in suspended aggregates. By covalently incorporating <1% acenaphthylene into the polymerization feed this copolymer is enabled to be used as a model to study the segmental mobility of the PNIPAM backbone in response to gold nanoparticles both below and above the desolvation temperature, showing that there is a physical conformational rearrangement of the soluble polymer at ultralow nanoparticle loadings, indicating low affinity interactions with the nanoparticles. Thermal desolvation is capable of extracting >99.9% of the nanoparticles from their solutions and hence demonstrates that poly(N‐isopropylacrylamide) can act as an excellent scrubbing system to remove metallic nanomaterial pollutants from solution. / Science Foundation Ireland's ETS. Grant Number: 11/W.I/12085; MRC. Grant Number: MR/N501888/2

Yes / Developing new methods to treat heart diseases is always a focus for basic research and clinical applications. Existing drugs have strong side-effects and also require lifetime administration for patients. Recent attempts of using nanoparticles (NPs) in treating atherosclerosis in animals and some heart diseases such as heart failure and endocarditis have provided hopes for better drug delivery and reducing of drug side-effects. In this mini-review, we summarize the present applications of using gold nanoparticles (GNPs) as a new drug delivery system in diseased hearts and of the assessment of toxicity in using GNPs. We suggest that conjugating existing clinical drugs with GNPs is a favorable choice to provide “new and double-enhanced” potentiality to those existing drugs in treating heart diseases. Other applications of using NPs in the treatment of heart diseases including using drugs in nano-form and coating drugs with a surface of relevant NP are also discussed.

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.

The favorable interaction between proteins and nanoparticles has sparked potential applications of nanotechnology in medicine, and the unique electronic and chemical properties of nanoparticles also provide novel strategies for protein-related therapeutics. The formation of the biocorona has attracted substantial interest over the past decades. For instance, as a potential drug delivery mechanism, protein-coated nanoparticles can improve biocompatibility and increase targeting ability. However, the mechanistic details of protein-nanoparticle interactions remain poorly understood. For example, it is currently impossible to predict the orientation and structure of proteins on the nanoparticle surface, as well as the fate of the biocorona in vivo. Since the composition of the biocorona determines the biological response, identifying and stabilizing the biocorona seems critical for the further development of applications in biological system. In this study, we investigated the physicochemical properties of protein interactions with gold nanoparticles (AuNPs). Firstly, we developed an NMR-based approach for measuring the stoichiometry of protein adsorption to AuNPs, which can be generally applied to globular proteins of different size. Quantitative analysis enabled us to create a protein binding model that involves an initial association, structure reorientation and irreversible adsorption. Secondly, we measured the protein hydrogen-deuterium exchange rates and found that they were unperturbed in the presence of AuNPs, suggesting that proteins retain their globular structure upon adsorption. Finally, we investigated the electrostatic contribution to binding, and we identified a dynamically changing surface in which the factors of net charge, binding affinity and protein size play distinct roles at different phases.

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Polymer matrices doped with a dispersion of noble metal nanoparticles combine the strong plasmon resonance-based optical signatures of the latter with the flexibility and processability of the former. We have developed a nonlinear lithographic technique to generate large populations of epoxide waveguides containing a uniform dispersion of Au nanoparticles. The method is based on the self-trapping of multiple beams of white light propagating through a catonic polymerizable matrix doped with a gold salt, initiating the polymerization of epoxide moieties and simultaneously the in situ synthesis of elemental Au nanoparticles. Each white light filament inscribes a cylindrical waveguide, leading to an array of metallodielectric waveguides. Field of view (FOV) measurements indicate that the metallodielectric waveguide array has a nearly 59 % increase in FOV relative to its all-dielectric counterparts and can be tuned through the concentration of Au nanoparticles and the optical intensities employed to generate waveguides. / Thesis / Master of Science (MSc)

Emerging technologies in the healthcare industry encompass revolutionary devices or drugs that have the potential to change how healthcare will be practiced in the future. While there are several emerging healthcare technologies in the pipeline, a few key innovations are slated to be implemented clinically sooner based on their mass appeal and potential for healthcare breakthroughs. This thesis will focus on specific topics in the emerging technological fields of nanotechnology for photothermal cancer therapy, 3D printing for irreversible electroporation applications, and imageable biomaterials. While these general areas are receiving significant attention, we highlight the potential opportunities and limitations presented by our select efforts in these fields. First, in the realm of nanomedicine, we discuss the optimization and characterization of sodium thiosulfate facilitated gold nanoparticle synthesis. While many nanoparticles have been examined as agents for photothermal cancer therapy, we closely examine the structure and composition of these specific nanomaterials and discuss key findings that not only impact their future clinical use, but elucidate the importance of characterization prior to preclinical testing. Next, we examine the potential use of 3D printing to generate unprecedented multimodal medical devices for local pancreatic cancer therapy. This additive manufacturing technique offers exquisite design detail control, facilitating tools that would otherwise be difficult to fabricate by any other means. Lastly, in the field of imageable biomaterials, we demonstrate the development of composite catheters that can be visualized with near infrared imaging. This new biomaterial allows visualization with near infrared imaging, offering potentially new medical device opportunities that alleviate the use of ionizing radiation. This collective work emphasizes the need to thoroughly optimize and characterize emerging technologies prior to preclinical testing in order to facilitate rapid translation. / Master of Science

The emergence of novel electronic, optical and magnetic properties in ordered two-dimensional (2D) nanoparticle ensembles, due to collective dipolar interactions of surface plasmons or excitons or magnetic moments have motivated intense research efforts into fabricating functional nanostructure assemblies. Such functional assemblies (i.e., highly-integrated and addressable) have great potential in terms of device performance and cost benefits. Presently, there is a paradigm shift from lithography based top-down approaches to bottom-up approaches that use self-assembly to engineer addressable architectures from nanoscale building blocks. The objective of this dissertation was to develop appropriate processing tools that can overcome the common challenges faced in fabricating floating gate memory devices using self-assembled 2D metal nanoparticle arrays as charge storage nodes. The salient challenges being to synthesize monodisperse nanoparticles, develop large scale guided self-assembly processes and to integrate with Complementary Metal Oxide Semiconductor (CMOS) memory device fabrication processes, thereby, meeting the targets of International Technology Roadmap for Semiconductors (ITRS) – 2017, for non-volatile memory devices. In the first part of the thesis, a simple and robust process for the formation of wafer-scale, ordered arrays using dodecanethiol capped gold nanoparticles is reported. Next, the results of ellipsometric measurements to analyze the effect of excess ligand on the self-assembly of dodecanethiol coated gold nanoparticles at the air-water interface are discussed. In a similar vein, the technique of drop-casting colloidal solution is extended for tuning the interparticle spacing in the sub-20 nm regime, by altering the ligand length, through thiol-functionalized polystyrene molecules of different molecular weights. The results of characterization, using the complementary techniques of Atomic Force Microscopy (AFM) and Field-Emission Scanning Electron Microscopy (FESEM), of nanoparticle arrays formed by polystyrene thiol (average molecular weight 20,000 g/mol) grafted gold nanoparticles (7 nm diameter) on three different substrates and also using different solvents is then reported. The substrate interactions were found to affect the interparticle spacing in arrays, changing from 20 nm on silicon to 10 nm on a water surface; whereas, the height of the resultant thin film was found to be independent of substrate used and to correlate only with the hydrodynamic diameter of the polymer grafted nanoparticle in solution. Also, the mechanical properties of the nanoparticle thin films were found to be significantly altered by such compression of the polymer ligands. Based on the experimental data, the interparticle spacing and packing structure in these 2D arrays, were found to be controlled by the substrate, through modulation of the disjoining pressure in the evaporating thin film (van der Waals interaction); and by the solvent used for drop casting, through modulation of the hydrodynamic diameter. This is the first report on the ability to vary interparticle spacing of metal nanoparticle arrays by tuning substrate interactions alone, while maintaining the same ligand structure. A process to fabricate arrays with square packing based on convective shearing at a liquid surface induced by miscibility of colloidal solution with the substrate is proposed. This obviates the need for complex ligands with spatially directed molecular binding properties. Fabrication of 3D aggregates of polymer-nanoparticle composite by manipulating solvent-ligand interactions is also presented. In flash memory devices, charges are stored in a floating gate separated by a tunneling oxide layer from the channel, and the tunneling oxide thickness is scaled down to minimize power consumption. However, reduction in tunneling oxide thickness has reached a stage where data loss can occur due to random defects in the oxide. Using metal nanoparticles as charge-trapping nodes will minimize the data loss and enhance reliability by compartmentalizing the charge storage. In the second part of the thesis, a scalable and CMOS compatible process for fabricating next-generation, non-volatile, flash memory devices using the self-assembled 2D arrays of gold nanoparticles as charge storage nodes were developed. The salient features of the fabricated devices include: (a) reproducible threshold voltage shifts measured from devices spread over cm2 area, (b) excellent retention (>10 years) and endurance characteristics (>10000 Program/Erase cycles). The removal of ligands coating the metal nanoparticles using mild RF plasma etching was found, based on FESEM characterization as well as electrical measurements, to be critical in maintaining both the ordering of the nanoparticles and charge storage capacity. Results of Electrostatic Force Microscope (EFM) measurements are presented, corroborating the need for ligand removal in obtaining reproducible memory characteristics and reducing vertical charge leakage. The effect of interparticle spacing on the memory characteristics of the devices was also studied. Interestingly, the arrays with interparticle spacing of the order of nanoparticle diameter (7 nm) gave rise to the largest memory window, in comparison with arrays with smaller (2 nm) or larger interparticle spacing (20 nm). The effect of interparticle spacing and ligand removal on memory characteristics was found to be independent of different top-oxide deposition processes employed in device fabrication, namely, Radio-frequency magnetron sputtering (RF sputtering), Atomic Layer Deposition (ALD) and electron-beam evaporation. In the final part of the thesis, a facile method for transforming polydisperse citrate capped gold nanoparticles into monodisperse gold nanoparticles through the addition of excess polyethylene glycol (PEG) molecules is presented. A systematic study was conducted in order to understand the role of excess ligand (PEG) in enabling size focusing. The size focusing behavior due to PEG coating of nanoparticles was found to be different for different metals. Unlike the digestive ripening process, the presence of PEG was found to be critical, while the thiol functionalization was not needed. Remarkably, the amount of adsorbed carboxylate-PEG mixture was found to play a key role in this process. The stability of the ordered nanoparticle films under vacuum was also reported. The experimental results of particle ripening draw an analogy with the well-established Pechini process for synthesizing metal oxide nanostructures. The ability to directly self-assemble nanoparticles from the aqueous phase in conjunction with the ability to transfer these arrays to any desired substrate using microcontact printing can foster the development of applications ranging from flexible electronics to sensors. Also, this approach in conjunction with roll-to-roll processing approaches such as doctor-blade casting or convective assembly can aid in realizing the goal of large scale nanostructure fabrication without the utilization of organic solvents.

This thesis summarizes the methods of preparation and optical properties of hybrid assemblies of Au NPs and cadmium selenide (CdSe) QDs. First chap-ter deals with the literature survey and theoretical aspects of plasmonics and discussions on optical excitations of metal (plasmons) and semiconducting QDs (excitons). Variation of energy levels of CdSe QDs and its optical properties i e. absorption and emission properties under strong confinement regime have been discussed with respect to effective mass approximation (EMA) model. This is followed by the discussion on optical properties of Au NPs and rods, describing absorption properties, based on Mie theory. Size and shape depen-dent variation of absorption properties. Theoretical discussions of collective effects in QDs assemblies and plasmonic interactions with the QDs assemblies i.e. plasmonic Dicke effect and metal nanoantenna interaction with CdSe QDs arrays is provided. In the second chapter a discussion on experimental techniques used for the study is provided. It starts with a discussion on the synthesis methods for CdSe QDs and Au NPs/rods with different capping ligands. Different techniques of preparation of CdSe QDs assemblies and their hybrid with metallic nanoparti-cles has been discussed. Further discussion on optical microscopy techniques, confocal, near field scanning microscopy (NSOM), Brewster angle microscopy and electron microscopy techniques i. e transmission electron microscopy and scanning electron microscopy and thermogravimetry analysis of the samples is provided. In the third chapter the details of the different self-assembly methods of preparation of hybrid assemblies of CdSe QDs and Au NPs /rods are given. The different strategies are used for different type of hybrids. In first method of Langmuir-Blodgett (LB) , effect of different capping agents, core size, and number ratios of Au NPs/rods to CdSe QDs, effect of anisotropy of Au NPs on the LB films of CdSe QDs assemblies is discussed. In another method of dip coating several control parameters like dip time, concentration of the solution and dip speed of transferring an aligned GNRs is given. Finally a combination of LB and dip coating methods is described for transferring aligned GNRs over a compact layer of CdSe QDs. At the end, a section is devoted to hit and trials of self-assemblies of hybrid of GNRs and CdSe QDs using LB method, the failures of which resulted in devising a method which uses a combination of LB and dip coating. In fourth chapter effects of plasmons on the collective emission of CdSe QDs assemblies are investigated. A plasmonic tuning of photoluminescence from semiconducting QD assemblies using Au NP in different ratio and different packing density has been discussed. We have described how the emission from a closed pack assemblies, prepared with different packing densities depends on the packing density and extent of spectral overlap between QD photolumi-nescence and the metal nanoparticle absorbance. We have provided possible evidence for plasmon mediated coherent emission enhancement from some of these assemblies from the case of strong spectral overlap between CdSe QDs and Au nanoparticle. In fifth chapter, we have demonstrated non local far field enhancement of PL in QDs assemblies induced by isolated and partially aligned GNRs nano-antenna located on such assemblies. It is shown that the emission is also anisotropic with the maxima being near such GNRs assembly which decays to finite, nonzero and significantly large values even away from the vicinity of any such assemblies. For this novel effect it is shown to have a clear spec-tral dependence. It is shown to be maximum when the longitudinal surface plasmon resonance absorption maxima is resonant with the CdSe QD photolu-minescence maxima and the excitation wavelength and is always non-existent for the off resonant case. We have also shown that finite difference time do-main simulations could model some of the observed near field effects but the far field effects could not be modelled in such simulations.