Matching Items (8)
Filtering by
- All Subjects: Nanoparticles
- Creators: Phelan, Patrick
- Creators: Buttry, Daniel A
Description
Gold-silver alloy nanoparticles (NPs) capped with adenosine 5'-triphosphate were synthesized by borohydride reduction of dilute aqueous metal precursors. High-resolution transmission electron microscopy showed the as-synthesized particles to be spherical with average diameters ~4 nm. Optical properties were measured by UV-Visible spectroscopy (UV-Vis), and the formation of alloy NPs was verified across all gold:silver ratios by a linear shift in the plasmon band maxima against alloy composition. The molar absorptivities of the NPs decreased non-linearly with increasing gold content from 2.0 x 108 M-1 cm-1 (fÉmax = 404 nm) for pure silver to 4.1 x 107 M-1 cm-1 (fÉmax = 511 nm) for pure gold. The NPs were immobilized onto transparent indium-tin oxide composite electrodes using layer-by-layer (LbL) deposition with poly(diallyldimethylammonium) acting as a cationic binder. The UV-Vis absorbance of the LbL film was used to calculate the surface coverage of alloy NPs on the electrode. Typical preparations had average NP surface coverages of 2.8 x 10-13 mol NPs/cm2 (~5% of cubic closest packing) with saturated films reaching ~20% of ccp for single-layer preparations (1.0 ~ 10-12 mol NPs/cm2). X-ray photoelectron spectroscopy confirmed the presence of alloy NPs in the LbL film and showed silver enrichment of the NP surfaces by ~9%. Irreversible oxidative dissolution (dealloying) of the less noble silver atoms from the NPs on LbL electrodes was performed by cyclic voltammetry (CV) in sulfuric acid. Alloy NPs with higher gold content required larger overpotentials for silver dealloying. Dealloying of the more-noble gold atoms from the alloy NPs was also achieved by CV in sodium chloride. The silver was oxidized first to cohesive silver chloride, and then gold dealloyed to soluble HAuCl4- at higher potentials. Silver oxidation was inhibited during the first oxidative scan, but subsequent cycles showed typical, reversible silver-to-silver chloride voltammetry. The potentials for both silver oxidation and gold dealloying also shifted to more oxidizing potentials with increasing gold content, and both processes converged for alloy NPs with >60% gold content. Charge-mediated electrochemistry of silver NPs immobilized in LbL films, using Fc(meOH) as the charge carrier, showed that 67% of the NPs were electrochemically inactive.
ContributorsStarr, Christopher A (Author) / Buttry, Daniel A (Thesis advisor) / Petuskey, William (Committee member) / Jones, Anne (Committee member) / Arizona State University (Publisher)
Created2014
Description
A method of determining nanoparticle temperature through fluorescence intensity levels is described. Intracellular processes are often tracked through the use of fluorescence tagging, and ideal temperatures for many of these processes are unknown. Through the use of fluorescence-based thermometry, cellular processes such as intracellular enzyme movement can be studied and their respective temperatures established simultaneously. Polystyrene and silica nanoparticles are synthesized with a variety of temperature-sensitive dyes such as BODIPY, rose Bengal, Rhodamine dyes 6G, 700, and 800, and Nile Blue A and Nile Red. Photographs are taken with a QImaging QM1 Questar EXi Retiga camera while particles are heated from 25 to 70 C and excited at 532 nm with a Coherent DPSS-532 laser. Photographs are converted to intensity images in MATLAB and analyzed for fluorescence intensity, and plots are generated in MATLAB to describe each dye's intensity vs temperature. Regression curves are created to describe change in fluorescence intensity over temperature. Dyes are compared as nanoparticle core material is varied. Large particles are also created to match the camera's optical resolution capabilities, and it is established that intensity values increase proportionally with nanoparticle size. Nile Red yielded the closest-fit model, with R2 values greater than 0.99 for a second-order polynomial fit. By contrast, Rhodamine 6G only yielded an R2 value of 0.88 for a third-order polynomial fit, making it the least reliable dye for temperature measurements using the polynomial model. Of particular interest in this work is Nile Blue A, whose fluorescence-temperature curve yielded a much different shape from the other dyes. It is recommended that future work describe a broader range of dyes and nanoparticle sizes, and use multiple excitation wavelengths to better quantify each dye's quantum efficiency. Further research into the effects of nanoparticle size on fluorescence intensity levels should be considered as the particles used here greatly exceed 2 ìm. In addition, Nile Blue A should be further investigated as to why its fluorescence-temperature curve did not take on a characteristic shape for a temperature-sensitive dye in these experiments.
ContributorsTomforde, Christine (Author) / Phelan, Patrick (Thesis advisor) / Dai, Lenore (Committee member) / Adrian, Ronald (Committee member) / Arizona State University (Publisher)
Created2011
Description
Nanoparticles are ubiquitous in various fields due to their unique properties not seen in similar bulk materials. Among them, core-shell composite nanoparticles are an important class of materials which are attractive for their applications in catalysis, sensing, electromagnetic shielding, drug delivery, and environmental remediation. This dissertation focuses on the study of core-shell type of nanoparticles where a polymer serves as the core and inorganic nanoparticles are the shell. This is an interesting class of supramolecular building blocks and can "exhibit unusual, possibly unique, properties which cannot be obtained simply by co-mixing polymer and inorganic particles". The one-step Pickering emulsion polymerization method was successfully developed and applied to synthesize polystyrene-silica core-shell composite particles. Possible mechanisms of the Pickering emulsion polymerization were also explored. The silica nanoparticles were thermodynamically favorable to self-assemble at liquid-liquid interfaces at the initial stage of polymerization and remained at the interface to finally form the shells of the composite particles. More importantly, Pickering emulsion polymerization was employed to synthesize polystyrene/poly(N-isopropylacrylamide) (PNIPAAm)-silica core-shell nanoparticles with N-isopropylacrylamide incorporated into the core as a co-monomer. The composite nanoparticles were temperature sensitive and could be up-taken by human prostate cancer cells and demonstrated effectiveness in drug delivery and cancer therapy. Similarly, by incorporating poly-2-(N,N)-dimethylamino)ethyl methacrylate (PDMA) into the core, pH sensitive core-shell composite nanoparticles were synthesized and applied as effective carriers to release a rheological modifier upon a pH change. Finally, the research focuses on facile approaches to engineer the transition of the temperature-sensitive particles and develop composite core-shell nanoparticles with a metallic shell.
ContributorsSanyal, Sriya (Author) / Dai, Lenore L. (Thesis advisor) / Jiang, Hanqing (Committee member) / Lind, Mary L. (Committee member) / Phelan, Patrick (Committee member) / Rege, Kaushal (Committee member) / Arizona State University (Publisher)
Created2012
Description
Waste heat energy conversion remains an inviting subject for research, given the renewed emphasis on energy efficiency and carbon emissions reduction. Solid-state thermoelectric devices have been widely investigated, but their practical application remains challenging because of cost and the inability to fabricate them in geometries that are easily compatible with heat sources. An intriguing alternative to solid-state thermoelectric devices is thermogalvanic cells, which include a generally liquid electrolyte that permits the transport of ions. Thermogalvanic cells have long been known in the electrochemistry community, but have not received much attention from the thermal transport community. This is surprising given that their performance is highly dependent on controlling both thermal and mass (ionic) transport. This research will focus on a research project, which is an interdisciplinary collaboration between mechanical engineering (i.e. thermal transport) and chemistry, and is a largely experimental effort aimed at improving fundamental understanding of thermogalvanic systems. The first part will discuss how a simple utilization of natural convection within the cell doubles the maximum power output of the cell. In the second part of the research, some of the results from the previous part will be applied in a feasibility study of incorporating thermogalvanic waste heat recovery systems into automobiles. Finally, a new approach to enhance Seebeck coefficient by tuning the configurational entropy of a mixed-ligand complex formation of copper sulfate aqueous electrolytes will be presented. Ultimately, a summary of these results as well as possible future work that can be formed from these efforts is discussed.
ContributorsGunawan, Andrey (Author) / Phelan, Patrick E (Thesis advisor) / Buttry, Daniel A (Committee member) / Mujica, Vladimiro (Committee member) / Chan, Candace K. (Committee member) / Wang, Robert Y (Committee member) / Arizona State University (Publisher)
Created2015
Description
Buildings continue to take up a significant portion of the global energy consumption, meaning there are significant research opportunities in reducing the energy consumption of the building sector. One widely studied area is waste heat recovery. The purpose of this research is to test a prototype thermogalvanic cell in the form factor of a UK metric brick sized at 215 mm × 102.5 mm × 65 mm for the experimental power output using a copper/copper(II) (Cu/Cu2+) based aqueous electrode. In this study the thermogalvanic brick uses a 0.7 M CuSO4 + 0.1 M H2SO4 aqueous electrolyte with copper electrodes as two of the walls. The other walls of the thermogalvanic brick are made of 5.588 mm (0.22 in) thick acrylic sheet. Internal to the brick, a 0.2 volume fraction minimal surface Schwartz diamond (Schwartz D) structure made of ABS, Polycarbonate-ABS (PCABS), and Polycarbonate-Carbon Fiber (PCCF) was tested to see the effects on the power output of the thermogalvanic brick. By changing the size of the thermogalvanic cell into that of a brick will allow this thermogalvanic cell to become the literal building blocks of green buildings. The thermogalvanic brick was tested by applying a constant power to the strip heater attached to the hot side of the brick, resulting in various ∆T values between 8◦C and 15◦C depending on the material of Schwartz D inside. From this, it was found that a single Cu/Cu2+ thermogalvanic brick containing the PCCF or PCABS Schwartz D performed equivalently well at a 163.8% or 164.9%, respectively, higher normalized power density output than the control brick containing only electrolyte solution.
ContributorsLee, William J. (Author) / Phelan, Patrick (Thesis advisor) / El Asmar, Mounir (Committee member) / Milcarek, Ryan (Committee member) / Arizona State University (Publisher)
Created2018
Description
Neurological disorders are difficult to treat with current drug delivery methods due to their inefficiency and the lack of knowledge of the mechanisms behind drug delivery across the blood brain barrier (BBB). Nanoparticles (NPs) are a promising drug delivery method due to their biocompatibility and ability to be modified by cell penetrating peptides, such as transactivating transciptor (TAT) peptide, which has been shown to increase efficiency of delivery. There are multiple proposed mechanisms of TAT-mediated delivery that also have size restrictions on the molecules that can undergo each BBB crossing mechanism. The effect of nanoparticle size on TAT-mediated delivery in vivo is an important aspect to research in order to better understand the delivery mechanisms and to create more efficient NPs. NPs called FluoSpheres are used because they come in defined diameters unlike polymeric NPs that have a broad distribution of diameters. Both modified and unmodified 100nm and 200nm NPs were able to bypass the BBB and were seen in the brain, spinal cord, liver, and spleen using confocal microscopy and a biodistribution study. Statistically significant differences in delivery rate of the different sized NPs or between TAT-modified and unmodified NPs were not found. Therefore in future work a larger range of diameter size will be evaluated. Also the unmodified NPs will be conjugated with scrambled peptide to ensure that both unmodified and TAT-modified NPs are prepared in identical fashion to better understand the role of size on TAT targeting. Although all the NPs were able to bypass the BBB, future work will hopefully provide a better representation of how NP size effects the rate of TAT-mediated delivery to the CNS.
ContributorsCeton, Ricki Ronea (Author) / Stabenfeldt, Sarah (Thesis director) / Sirianni, Rachael (Committee member) / Harrington Bioengineering Program (Contributor) / Barrett, The Honors College (Contributor)
Created2016-05
Description
Water-soluble, adenosine triphosphate (ATP)-stabilized palladium nanoparticles have been synthesized by reduction of palladium salt in the presence of excess ATP. They have been characterized by electron microscopy, energy dispersive X-ray spectroscopy, ultraviolet-visible (UV-Vis) spectroscopy, and X-ray diffraction in order to determine particle size, shape, composition and crystal structure. The particles were then subsequently attached to a glassy carbon electrode (GCE) in order to explore their electrochemical properties with regard to hydrogen insertion in 1 M sodium hydroxide. The particles were found to be in the size range 2.5 to 4 nm with good size dispersion. The ATP capping ligand allowed the particles to be air-stable and re-dissolved without agglomeration. It was found that the NPs could be firmly attached to the working electrode via cycling the voltage repeatedly in a NP/phosphate solution. Further electrochemical experiments were conducted to investigate the adsorption and absorption of hydrogen in the NPs in 1 M sodium hydroxide. Results for cyclic voltammetry experiments were consistent with those for nanostructured and thin-film palladium in basic solution. Absorbed hydrogen content was analyzed as a function of potential. The maximum hydrogen:Pd ratio was found to be ~0.7, close the theoretical maximum value for β phase palladium hydride.
ContributorsLamb, Timothy (Author) / Buttry, Daniel A (Thesis advisor) / Yarger, Jeffery (Committee member) / Ros, Alexandra (Committee member) / Arizona State University (Publisher)
Created2013
Description
The applications utilizing nanoparticles have grown in both industrial and academic areas because of the very large surface area to volume ratios of these particles. One of the best ways to process and control these nanoparticles is fluidization. In this work, a new microjet and vibration assisted (MVA) fluidized bed system was developed in order to fluidize nanoparticles. The system was tested and the parameters optimized using two commercially available TiO2 nanoparticles: P25 and P90. The fluidization quality was assessed by determining the non-dimensional bed height as well as the non-dimensional pressure drop. The non-dimensional bed height for the nanosized TiO2 in the MVA system optimized at about 5 and 7 for P25 and P90 TiO2, respectively, at a resonance frequency of 50 Hz. The non-dimensional pressure drop was also determined and showed that the MVA system exhibited a lower minimum fluidization velocity for both of the TiO2 types as compared to fluidization that employed only vibration assistance. Additional experiments were performed with the MVA to characterize the synergistic effects of vibrational intensity and gas velocity on the TiO2 P25 and P90 fluidized bed heights. Mathematical relationships were developed to correlate vibrational intensity, gas velocity, and fluidized bed height in the MVA. The non-dimensional bed height in the MVA system is comparable to previously published P25 TiO2 fluidization work that employed an alcohol in order to minimize the electrostatic attractions within the bed. However, the MVA system achieved similar results without the addition of a chemical, thereby expanding the potential chemical reaction engineering and environmental remediation opportunities for fluidized nanoparticle systems.
In order to aid future scaling up of the MVA process, the agglomerate size distribution in the MVA system was predicted by utilizing a force balance model coupled with a two-fluid model (TFM) simulation. The particle agglomerate size that was predicted using the computer simulation was validated with experimental data and found to be in good agreement.
Lastly, in order to demonstrate the utility of the MVA system in an air revitalization application, the capture of CO2 was examined. CO2 breakthrough time and adsorption capacities were tested in the MVA system and compared to a vibrating fluidized bed (VFB) system. Experimental results showed that the improved fluidity in the MVA system enhanced CO2 adsorption capacity.
In order to aid future scaling up of the MVA process, the agglomerate size distribution in the MVA system was predicted by utilizing a force balance model coupled with a two-fluid model (TFM) simulation. The particle agglomerate size that was predicted using the computer simulation was validated with experimental data and found to be in good agreement.
Lastly, in order to demonstrate the utility of the MVA system in an air revitalization application, the capture of CO2 was examined. CO2 breakthrough time and adsorption capacities were tested in the MVA system and compared to a vibrating fluidized bed (VFB) system. Experimental results showed that the improved fluidity in the MVA system enhanced CO2 adsorption capacity.
ContributorsAn, Keju (Author) / Andino, Jean (Thesis advisor) / Phelan, Patrick (Thesis advisor) / Adrian, Ronald (Committee member) / Emady, Heather (Committee member) / Kasbaoui, Mohamed (Committee member) / Arizona State University (Publisher)
Created2019