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- All Subjects: Nanoparticles
- Creators: Herckes, Pierre
Description
Nanotechnology is becoming increasingly present in our environment. Engineered nanoparticles (ENPs), defined as objects that measure less than 100 nanometers in at least one dimension, are being integrated into commercial products because of their small size, increased surface area, and quantum effects. These special properties have made ENPs antimicrobial agents in clothing and plastics, among other applications in industries such as pharmaceuticals, renewable energy, and prosthetics. This thesis incorporates investigations into both application of nanoparticles into polymers as well as implications of nanoparticle release into the environment. First, the integration of ENPs into polymer fibers via electrospinning was explored. Electrospinning uses an external electric field applied to a polymer solution to produce continuous fibers with large surface area and small volume, a quality which makes the fibers ideal for water and air purification purposes. Indium oxide and titanium dioxide nanoparticles were embedded in polyvinylpyrrolidone and polystyrene. Viscosity, critical voltage, and diameter of electrospun fibers were analyzed in order to determine the effects of nanoparticle integration into the polymers. Critical voltage and viscosity of solution increased at 5 wt% ENP concentration. Fiber morphology was not found to change significantly as a direct effect of ENP addition, but as an effect of increased viscosity and surface tension. These results indicate the possibility for seamless integration of ENPs into electrospun polymers. Implications of ENP release were investigated using phase distribution functional assays of nanoscale silver and silver sulfide, as well as photolysis experiments of nanoscale titanium dioxide to quantify hydroxyl radical production. Functional assays are a means of screening the relevant importance of multiple processes in the environmental fate and transport of ENPs. Four functional assays – water-soil, water-octanol, water-wastewater sludge and water-surfactant – were used to compare concentrations of silver sulfide ENPs (Ag2S-NP) and silver ENPs (AgNP) capped by four different coatings. The functional assays resulted in reproducible experiments which clearly showed variations between nanoparticle phase distributions; the findings may be a product of the effects of the different coatings of the ENPs used. In addition to phase distribution experiments, the production of hydroxyl radical (HO•) by nanoscale titanium dioxide (TiO2) under simulated solar irradiation was investigated. Hydroxyl radical are a short-lived, highly reactive species produced by solar radiation in aquatic environments that affect ecosystem function and degrades pollutants. HO• is produced by photolysis of TiO2 and nitrate (NO3-); these two species were used in photolysis experiments to compare the relative loads of hydroxyl radical which nanoscale TiO2 may add upon release to natural waters. Para-chlorobenzoic acid (pCBA) was used as a probe. Measured rates of pCBA oxidation in the presence of various concentrations of TiO2 nanoparticles and NO3- were utilized to calculate pseudo first order rate constants. Results indicate that, on a mass concentration basis in water, TiO2 produces hydroxyl radical steady state concentrations at 1.3 times more than the equivalent amount of NO3-; however, TiO2 concentrations are generally less than one order of magnitude lower than concentrations of NO3-. This has implications for natural waterways as the amount of nanoscale TiO2 released from consumer products into natural waterways increases in proportion to its use.
ContributorsHoogesteijn von Reitzenstein, Natalia (Author) / Westerhoff, Paul (Thesis advisor) / Herckes, Pierre (Committee member) / Hristovski, Kiril (Committee member) / Arizona State University (Publisher)
Created2015
Description
Engineered nanoparticles (NPs) pose risk potentials, if they exist in water systems at significant concentrations and if they remain reactive to cause toxicity. Three goals guided this study: (1) establishing NP detecting methods with high sensitivity to tackle low concentration and small sizes, (2) achieving assays capable of measuring NP surface reactivity and identifying surface reaction mechanisms, and (3) understanding the impact of surface adsorption of ions on surface reactivity of NPs in water.
The size detection limit of single particle inductively coupled plasma spectrometry (spICP-MS) was determined for 40 elements, demonstrating the feasibility of spICP-MS to different NP species in water. The K-means Clustering Algorithm was used to process the spICP-MS signals, and achieved precise particle-noise differentiation and quantitative particle size resolution. A dry powder assay based on NP-catalyzed methylene blue (MB) reduction was developed to rapidly and sensitively detect metallic NPs in water by measuring their catalytic reactivity.
Four different wet-chemical-based NP surface reactivity assays were demonstrated: “borohydride reducing methylene blue (BHMB)”, “ferric reducing ability of nanoparticles (FRAN)”, “electron paramagnetic resonance detection of hydroxyl radical (EPR)”, and “UV-illuminated methylene blue degradation (UVMB)”. They gave different reactivity ranking among five NP species, because they targeted for different surface reactivity types (catalytic, redox and photo reactivity) via different reaction mechanisms. Kinetic modeling frameworks on the assay outcomes revealed two surface electron transfer schemes, namely the “sacrificial reducing” and the “electrode discharging”, and separated interfering side reactions from the intended surface reaction.
The application of NPs in chemical mechanical polishing (CMP) was investigated as an industrial case to understand NP surface transformation via adsorbing ions in water. Simulation of wastewater treatment showed CMP NPs were effectively removed (>90%) by lime softening at high pH and high calcium dosage, but 20-40% of them remained in water after biomass adsorption process. III/V ions (InIII, GaIII, and AsIII/V) derived from semiconductor materials showed adsorption potentials to common CMP NPs (SiO2, CeO2 and Al2O3), and a surface complexation model was developed to determine their intrinsic complexation constants for different NP species. The adsorption of AsIII and AsV ions onto CeO2 NPs mitigated the surface reactivity of CeO2 NPs suggested by the FRAN and EPR assays. The impact of the ion adsorption on the surface reactivity of CeO2 NPs was related to the redox state of Ce and As on the surface, but varied with ion species and surface reaction mechanisms.
The size detection limit of single particle inductively coupled plasma spectrometry (spICP-MS) was determined for 40 elements, demonstrating the feasibility of spICP-MS to different NP species in water. The K-means Clustering Algorithm was used to process the spICP-MS signals, and achieved precise particle-noise differentiation and quantitative particle size resolution. A dry powder assay based on NP-catalyzed methylene blue (MB) reduction was developed to rapidly and sensitively detect metallic NPs in water by measuring their catalytic reactivity.
Four different wet-chemical-based NP surface reactivity assays were demonstrated: “borohydride reducing methylene blue (BHMB)”, “ferric reducing ability of nanoparticles (FRAN)”, “electron paramagnetic resonance detection of hydroxyl radical (EPR)”, and “UV-illuminated methylene blue degradation (UVMB)”. They gave different reactivity ranking among five NP species, because they targeted for different surface reactivity types (catalytic, redox and photo reactivity) via different reaction mechanisms. Kinetic modeling frameworks on the assay outcomes revealed two surface electron transfer schemes, namely the “sacrificial reducing” and the “electrode discharging”, and separated interfering side reactions from the intended surface reaction.
The application of NPs in chemical mechanical polishing (CMP) was investigated as an industrial case to understand NP surface transformation via adsorbing ions in water. Simulation of wastewater treatment showed CMP NPs were effectively removed (>90%) by lime softening at high pH and high calcium dosage, but 20-40% of them remained in water after biomass adsorption process. III/V ions (InIII, GaIII, and AsIII/V) derived from semiconductor materials showed adsorption potentials to common CMP NPs (SiO2, CeO2 and Al2O3), and a surface complexation model was developed to determine their intrinsic complexation constants for different NP species. The adsorption of AsIII and AsV ions onto CeO2 NPs mitigated the surface reactivity of CeO2 NPs suggested by the FRAN and EPR assays. The impact of the ion adsorption on the surface reactivity of CeO2 NPs was related to the redox state of Ce and As on the surface, but varied with ion species and surface reaction mechanisms.
ContributorsBi, Xiangyu (Author) / Westerhoff, Paul K (Thesis advisor) / Rittmann, Bruce E. (Committee member) / Herckes, Pierre (Committee member) / Richert, Ranko (Committee member) / Arizona State University (Publisher)
Created2018
Description
The production and applications of engineered nanomaterials (ENM) has increased rapidly in the last decade, with release of ENM to the environment through the sewer system and municipal wastewater treatment plants (WWTPs) being of concern. Currently, the literature on ENM release from WWTPs and removal of ENM by WWTPs is insufficient and disorganized. There is little quantitative data on the removal of multi-walled carbon nanotubes (MWCNTs), graphene oxide (GO), or few-layer graphene (FLG), from wastewater onto biomass. The removal of pristine and oxidized MWCNTs (O-MWCNTs), graphene oxide (GO), few-layer graphene (FLG) and Tween™ 20-coated Ag ENM by the interaction with biomass were determined by programmable thermal analysis (PTA) and UV-Vis spectrophotometry. The removal of pristine and O-MWCNTs was 96% from the water phase via aggregation and 30-min settling in presence or absence of biomass with an initial MWCNT concentration of 25 mg/L. The removal of 25 mg/L GO was 65% with biomass concentration at or above 1,000 mg TSS/L. The removal of 1 mg/L FLG was 16% with 50 mg TSS/L. The removal of Tween™ 20 Ag ENM with concentration from 0.97 mg/L to 2.6 mg/L was from 11% to 92% with biomass concentration of 500 mg TSS/L to 3,000 mg TSS/L, respectively.
A database of ENM removal by biomass was established by analyzing data from published papers, and non-linear solid-liquid distribution functions were built into the database. A conventional activated sludge (CAS) model was built based on a membrane bioreactor (MBR) model from a previous paper. An iterative numeric approach was adapted to the CAS model to calculate the result of non-linear adsorption of ENM by biomass in the CAS process. Kinetic studies of the CAS model showed the model performance changed mostly in the first 10 days after changing influent chemical oxygen demand (COD) concentration, and reached a steady state after 11 days. Over 60% of ENMs which have distribution coefficients in the database reached higher than 50% removal by the CAS model under general operational conditions. This result suggests that traditional WWTP which include the CAS process can remove many known types of ENMs in certain degree.
A database of ENM removal by biomass was established by analyzing data from published papers, and non-linear solid-liquid distribution functions were built into the database. A conventional activated sludge (CAS) model was built based on a membrane bioreactor (MBR) model from a previous paper. An iterative numeric approach was adapted to the CAS model to calculate the result of non-linear adsorption of ENM by biomass in the CAS process. Kinetic studies of the CAS model showed the model performance changed mostly in the first 10 days after changing influent chemical oxygen demand (COD) concentration, and reached a steady state after 11 days. Over 60% of ENMs which have distribution coefficients in the database reached higher than 50% removal by the CAS model under general operational conditions. This result suggests that traditional WWTP which include the CAS process can remove many known types of ENMs in certain degree.
ContributorsYu, Zhicheng (Author) / Westerhoff, Paul (Thesis advisor) / Rittmann, Bruce (Committee member) / Herckes, Pierre (Committee member) / Arizona State University (Publisher)
Created2015
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