Plasmonic resonances are characterized by enhanced optical near field and subwavelength power confinement. Light is not only scattered but also simultaneously absorbed in the metal nanostructures. With proper structural design, plasmonic-enhanced light absorption can generate nanoscopically confined heat power in metallic nanostructures, which can even be temporally modulated by varying the pump light. These intrinsic characters of plasmonic nanostructures are investigated in depth in this thesis for a range of materials and nanophotonic applications.   The theoretical basis for the photothermal phenomenon, including light absorption, heat generation, and heat conduction, is coherently summarized and implemented numerically based on finite-element method. Our analysis favours disk-pair and particle/dielectric-spacer/metal-film nanostructures for their high optical absorbance, originated from their antiparallel dipole resonances.   Experiments were done towards two specific application directions. First, the manipulation of the morphology and crystallinity of Au nanoparticles (NPs) in plasmonic absorbers by photothermal effect is demonstrated. In particular, with a nanosecond-pulsed light, brick-shaped Au NPs are reshaped to spherical NPs with a smooth surface; while with a 10-second continuous wave laser, similar brick-shaped NPs can be annealed to faceted nanocrystals. A comparison of the two cases reveals that pumping intensity and exposure time both play key roles in determining the morphology and crystallinity of the annealed NPs.   Second, the attempt is made to utilize the high absorbance and localized heat generation of the metal-insulator-metal (MIM) absorber in Si thermo-optic switches for achieving all-optical switching/routing with a small switching power and a fast transient response. For this purpose, a numerical study of a Mach-Zehnder interferometer integrated with MIM nanostrips is performed. Experimentally, a Si disk resonator and a ring-resonator-based add-drop filter, both integrated with MIM film absorbers, are fabricated and characterized. They show that good thermal conductance between the absorber and the Si light-guiding region is vital for a better switching performance.   Theoretical and experimental methodologies presented in the thesis show the physics principle and functionality of the photothermal effect in Au nanostructures, as well as its application in improving the morphology and crystallinity of Au NPs and miniaturized all-optical Si photonic switching devices. / <p>QC 20140331</p>

Thesis (M.S.) in Biological Engineering--University of Maine, 2008. / Includes vita. Includes bibliographical references (leaves 39-42).

Thesis (Ph. D.)--Chemistry and Biochemistry, Georgia Institute of Technology, 2008. / Committee Chair: El-Sayed, Mostafa A.; Committee Member: Perry, Joseph W.; Committee Member: Srinivasarao, Mohan; Committee Member: Whetten, Robert L.; Committee Member: Zhang, Z. John.

In this work the synergy between a polymer containing chelate sites and gold ions was explored by the fabrication of a polymeric membrane with embedded gold nanoparticles inside its matrix and by developing a process to recover gold from acidic solutions. After realizing that the thiosemicarbazide groups present in the monomeric unit of poly-thiosemicarbazide (PTSC) formed strong complexes with Au ions, membrane technology was used to exploit this property to its maximum. The incorporation of metal nanoparticles into polymeric matrices with current technologies involves either expensive and complicated procedures or leads to poor results in terms of agglomeration, loading, dispersion, stability or efficient use of raw materials. The fabrication procedure described in this thesis solves these problems by fabricating a PTSC membrane containing 33.5 wt% in the form of 2.9 nm gold nanoparticles (AuNPs) by a three step simple and scalable procedure. It showed outstanding results in all of the areas mentioned above and demonstrated catalytic activity for the reduction of 4-Nitrophenol (4−NP) to 4-Aminophenol (4−AP). The current exponential demand of gold for electronics has encouraged the development of efficient processes to recycle it. Several adsorbents used to recover gold from acidic solutions can be found in the literature with outstanding maximum uptakes,yet, poor kinetics leading to an overall inefficient process. The method developed in this dissertation consisted in permeating the gold-containing solution through a PTSC membrane that will capture all the Au ions by forming a metal complex with them. Forcing the ions through the pores of the membrane eliminates the diffusion limitations and the adsorption will only depended on the fast complexation kinetics, resulting in a very efficient process. A flux as high as 1868 L/h m2 was enough to capture >90% of the precious metal present in a solution of 100 ppm Au. The maximum uptake achieved without sacrificing the mechanical stability was 5.4 mmol/g. The selectivity between gold and copper (the most common unwanted metal present along with gold) was 6.7 for 100 ppm initial concentration of both metals and 14.6 for 500 ppm.

Magister Scientiae (Medical Bioscience) - MSc(MBS) / Recently nanoparticles (NPs) have been introduced and used in combination with therapeutic approaches to develop nanotechnology-enabled medicine. These nanostructures allow for the exploitation of the physiochemical properties which may be beneficial in cancer treatment. The use of NPs in nanomedicine has proven successful in modern chemotherapeutics and has demonstrated promising potential in in vivo and in vitro radiosensitization studies. This is a baseline study aimed to determine the cytotoxic effects of AuNPs for potential radiosensitization analysis. The study analysed the effects of different AuNP sizes (30, 50 and 80nm), concentrations (5, 10 and 15 μg/ml) over various time periods in CHOK1 and A549 cells.

In this paper, the electrochemical behaviors of a single gold nanoparticle attached on a nanometer sized electrode have been studied. The single nanoparticle was characterized by using electrochemical methods. Since there is only one nanoparticle on the electrode, unarguable information for that sized particle could be obtained. Our preliminary results show that it becomes more difficult to oxidize gold nanoparticle or reduce gold nanoparticle oxide as the radius of the particle becomes smaller. Also, the peak potential of the reduction of gold nanoparticle oxide is proportional to the reciprocal of the radius of the particle.

Multicomponent ligand interactions are involved in essentially all nanoparticle (NP) applications. However, the ligand conformation and ligand binding mechanisms on NPs are highly controversial. The research reported here is focused on deepening the fundamental understanding of multicomponent ligand interactions with gold and silver nanoparticles (AuNPs and AgNPs) in water. We demonstrated that AuNPs passivated by saturated layer of poly(ethylene glycol) (PEG-SH) have large fractions of AuNP surface area available for ligand adsorption and exchange. The fraction of AuNP surface area passivated by PEG-SH with molecular weights of 2000, 5000, and 30000 g/mol was calculated to be ~ 25%, ~20%, and ~9% using 2-mercaptobenzimidazole and adenine as model ligands. The effect of both reduced and oxidized protein cysteine residues on protein interactions with AgNPs was investigated. The model proteins included wild-type and mutated GB3 variants with 0, 1, or 2 reduced cysteine residues. Bovine serum albumin containing 34 oxidized (disulfide-linked) and 1 reduced cysteine residues was also included. Protein cysteine content that were found to have no detectable effect on kinetics of protein/AgNP binding. However, only proteins that contain reduced cysteine induced significant AgNP dissolution. We further demonstrated that organothiols can induce both AgNP disintegration and formation under ambient conditions by simply mixing organothiols with AgNPs or AgNO3, respectively. Surface plasmon- and fluorescence-active AgNPs formed by changing the concentration ratio between Ag+ and organothiol. Organothiols also induced AuNP formation by mixing HAuCl4 with organothiols, but no AuNP disintegration occured. Finally, we proposed that multicomponent ligand binding to AuNPs can be highly dependent on the sequence of ligand mixing with AuNPs. Quantitative studies revealed that competitive adenine and glutathione adsorption onto both as-synthesized and PEG-SH functionalized AuNPs is predominantly a kinetically controlled process. Besides providing new insights on multicomponent ligand interactions with colloidal AuNPs and AgNPs, this study opens a new avenue for fabrication of novel nanomaterials in biological/biomedical applications.

>Magister Scientiae - MSc / Different nanoparticles have the ability to improve plant tolerance to drought stress. In the study we report for the first time novel morpholin-4-ium 4-methoxyphenyl (morpholino) phosphinodithioate capped- gold nanoparticles (GYY4137-capped AuNPs). The GYY4137 is a slow releasing hydrogen sulfide (H2S) donor. The GYY4137 AuNPs compared to preliminary experiments of L-serine and L-threonine gold nanoparticles. The nanoparticles were prepared using a simple reflux reduction method in a rolling boil flask at 80 oC. The uncapped GYY4137-AuNPs were relatively stable and had surface plasmon resonance at 562 nm compared to 524 nm and 560 nm of serine-AuNPs and threonine-AuNPs. The nanoparticles were capped with different concentrations (0.1-5 %) of water-soluble poly (ethylene) glycol (PEG) (Mw300) and 0.2% chitosan. The PEG did not fully encapsulate the gold nanoparticles, while the chitosan successfully produced positively charged gold nanoparticles. The formation of chitosan capped GYY4137-AuNPs were verified with UV-Visible spectroscopy (UV-Vis), High Resolution Transmission electron microscopy (HRTEM), Dynamic Light scattering (DLS) and the Zetasizer. The UV-Vis, HRTEM and STEM verified chitosan capped nanoparticles had a surface plasmon resonance peak at 560 nm, with icosahedral, tetrahedron and spherical shaped nanoparticles as the serine-AuNPs that absorb at 560 nm. The agglomerated threonine-AuNPs had a maximum absorbance peak at 524 nm. The chitosan GYY4137-AuNPs had hydrodynamic size of 347.9 nm and zeta potential of + 47 mV, while serine-AuNPs and threonine-AuNPs had hydrodynamic size of 110 nm, zeta potential of -2.9 mV and -230 mV respectively. The polydispersity index (PDI) of the chitosan capped gold nanoparticles was 0.357 compared to 0.406 of both the amino acid gold nanoparticles. The polydispersity index (PDI) showed that the nanoparticles were polydispersed nanoparticles with broad size range as confirmed by the HRTEM and STEM results/ of chitosan capped GYY4137-AuNPs. The sizes of the nanoparticles were 100 nm and 60 nm for GYY4137-AuNPs while the size serine-AuNPs were 60 nm. The gold nanoparticles structural compositions were further confirmed by energy-dispersive X-ray spectrometry (EDX) and Attenuated total reflection infrared spectroscopy (ATR-IR). EDX results proved successful gold nanoparticles synthesis by presence of the element Au in all three nanoparticles and the chitosan GYY4137-AuNPs had 48. 56 wt. % of gold. The FTIR-ATR new bands formation shows that new chemical bonds are formed between the reducing agents, the precursor gold salt solution and capping agents. The shifts showed successful encapsulation with chitosan in GYY4137-AuNPs. The chitosan encapsulation improved surface charge and reactivity of the gold nanoparticles to improve delivery of the hydrogen sulfide donor GYY4137 for later applications to plants.

Over the past few decades, tremendous efforts have been made to develop nanomaterials for biotechnological applications such as therapeutics. Understanding and engineering interfaces between biomacromolecules and nanomaterials is a key to the creation of successful therapeutic systems. My research has been oriented toward developing therapeutic systems using gold nanoparticles (AuNPs) incorporating material science, organic synthesis, and biology. For this purpose, mixed monolayer protected AuNPs (~2 nm core size) with various functional groups have been employed for triggering therapeutic effects. Several strategies have been accomplished using anticancer drugs that non-covalently and covalently incorporate onto AuNPs as a drug delivery carrier. Alternatively, AuNPs were developed by regulating host-guest complexation processes inside the cell, allowing control of the therapeutic effect of the AuNP. In addition, by using host-guest chemical events on the AuNPs, exocytosis of the AuNPs was controlled, enabling their prolonged retention inside of the cells, providing new strategies for improving conventional drug delivery systems. Therefore, engineering of the AuNP surface can afford new pathways for designing and improving therapeutics.

<p>This thesis has exploited the use of gold nanoparticles (AuNPs)/DNA conjugates towards 1) the development of simple colorimetric assays to monitor DNA functions and relevant biological processes, and 2) the control the nanoassembly of AuNPs using biomolecules and biological processes.</p> <p>DNA has a number of attractive functions including specific biorecognition, catalysis and being manipulated by protein enzymes, etc. These characteristics were exploited to permit nanoassembly to be responsive to a specific stimulus and also ensure the specificity and precision in the construction of well-defined 3D nanostructures. Meanwhile, the assembly or disassembly of AuNPs, which results in distinct color changes due to the localized surface plasmon resonance, provides an excellent platform for the colorimetrically monitoring the DNA functions and the relevant biological processes.</p> <p>We have specifically investigated how the surface charges, the length and conformations of surface-tethered DNA polymers affect the assembly of AuNPs. We found that the colloidal stability of AuNPs can be well-tuned by nucleotides (small charged molecules) with various binding affinity to AuNP surface and/or different number of negatively-charged phosphate groups. This relies on the fact that nucleotides can bind to AuNP surface via nucleobase-Au interaction, and negatively charged phosphates stabilize AuNPs via electrostatic repulsion. This investigation allowed us to monitor protein enzymatic reactions where nucleotides are modified by alkaline phosphatase and to control the growth of AuNPs using nucleotides as capping ligands.</p> <p>We then investigated the effect of the length of DNA polymers on AuNP surface on AuNP colloidal stability. DNA-modified AuNPs are stabilized electrosterically at a relatively high salt concentration; the removal (or shortening) of the DNA molecules by enzymatic cleavage or the dissociation of DNA aptamers from AuNP surface upon binding to their target destabilizes AuNPs and results in AuNP aggregation. We attribute this to the loss of negatively-charged polymeric DNA molecules that initially served as colloidal stabilizers. This has been applied to the monitoring of enzyme (both protein enzyme and DNA enzyme) cleavage of DNA molecules, and DNA aptamer binding event to its target, respectively.</p> <p> We also studied how DNA polymer conformational changes influence AuNP colloidal stability, which has been employed to monitor DNA aptamer folding events on the AuNP surfaces. We found that AuNPs to which folded aptamer/target complexes are attached are more stable towards salt induced aggregation than those tethered to unfolded aptamers. Experimental results suggested that the folded aptamers were more extended on the surface than the unfolded (but largely collapsed) aptamers in salt solution. The folded aptamers therefore provide higher stabilization effect on AuNPs from both the electrostatic and steric stabilization points of view.</p><p> Finally, we demonstrated the well-defined assembly of AuNPs using long (hundred nanometers to microns) single-stranded (ss) DNA molecules as template in a three-dimensional (3D) fashion. Specifically, these long ssDNA containing repeating units are generated by protein enzymatic reaction (DNA extension through rolling circle amplification) on AuNP surface. The resultant product provides a 3D-like scaffold that can be subsequently used for periodical assembly of complementary DNA-attached nanospecies. </p> <p> We also expect that the facile colorimetric biosensing assays developed in this thesis work provide an attractive means to study biomolecular behaviors (e.g, biorecognition and conformational changes) on the surface, and to investigate other common DNA (or RNA) structural (e.g., triplex, G-quadruplex, hairpin, i-motif) and protein structural transitions.</p> <p> Finally, this thesis work provides some novel and general strategies for the control of nanoassemblies by tuning surface charges and surface-tethered polymers. We expect these principles can also be applied in other AuNP-based sensing platforms that exploit interparticle interactions and in the construction of well-defined nanostructures which involves other types of nano-scaled materials (e.g., quantum dots, nanotubes, nanowires, etc).</p> / Thesis / Doctor of Philosophy (PhD)