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- All Subjects: Chemistry
- All Subjects: Microfluidics
- Genre: Academic theses
- Genre: Doctoral Dissertation
- Creators: Herckes, Pierre
- Creators: Hayes, Mark A.
Description
Bioparticles comprise a diverse amount of materials ubiquitously present in nature. From proteins to aerosolized biological debris, bioparticles have important roles spanning from regulating cellular functions to possibly influencing global climate. Understanding their structures, functions, and properties provides the necessary tools to expand our fundamental knowledge of biological systems and exploit them for useful applications. In order to contribute to this efforts, the work presented in this dissertation focuses on the study of electrokinetic properties of liposomes and novel applications of bioaerosol analysis. Using immobilized lipid vesicles under the influence of modest (less than 100 V/cm) electric fields, a novel strategy for bionanotubule fabrication with superior throughput and simplicity was developed. Fluorescence and bright field microscopy was used to describe the formation of these bilayer-bound cylindrical structures, which have been previously identified in nature (playing crucial roles in intercellular communication) and made synthetically by direct mechanical manipulation of membranes. In the biological context, the results of this work suggest that mechanical electrostatic interaction may play a role in the shape and function of individual biological membranes and networks of membrane-bound structures. A second project involving liposomes focused on membrane potential measurements in vesicles containing trans-membrane pH gradients. These types of gradients consist of differential charge states in the lipid bilayer leaflets, which have been shown to greatly influence the efficacy of drug targeting and the treatment of diseases such as cancer. Here, these systems are qualitatively and quantitatively assessed by using voltage-sensitive membrane dyes and fluorescence spectroscopy. Bioaerosol studies involved exploring the feasibility of a fingerprinting technology based on current understanding of cellular debris in aerosols and arguments regarding sampling, sensitivity, separations and detection schemes of these debris. Aerosolized particles of cellular material and proteins emitted by humans, animals and plants can be considered information-rich packets that carry biochemical information specific to the living organisms present in the collection settings. These materials could potentially be exploited for identification purposes. Preliminary studies evaluated protein concentration trends in both indoor and outdoor locations. Results indicated that concentrations correlate to certain conditions of the collection environment (e.g. extent of human presence), supporting the idea that bioaerosol fingerprinting is possible.
ContributorsCastillo Gutiérrez, Josemar Andreina (Author) / Hayes, Mark A. (Thesis advisor) / Herckes, Pierre (Committee member) / Ghrilanda, Giovanna (Committee member) / Arizona State University (Publisher)
Created2011
Description
A new challenge on the horizon is to utilize the large amounts of protein found in the atmosphere to identify different organisms from which the protein originated. Included here is work investigating the presence of identifiable patterns of different proteins collected from the air and biological samples for the purposes of remote identification. Protein patterns were generated using high performance liquid chromatography (HPLC). Patterns created could identify high-traffic and low-traffic indoor spaces. Samples were collected from the air using air pumps to draw air through a filter paper trapping particulates, including large amounts of shed protein matter. In complimentary research aerosolized biological samples were collected from various ecosystems throughout Ecuador to explore the relationship between environmental setting and aerosolized protein concentrations. In order to further enhance protein separation and produce more detailed patterns for the identification of individual organisms of interest; a novel separation device was constructed and characterized. The separation device incorporates a longitudinal gradient as well as insulating dielectrophoretic features within a single channel. This design allows for the production of stronger local field gradients along a global gradient allowing particles to enter, initially transported through the channel by electrophoresis and electroosmosis, and to be isolated according to their characteristic physical properties, including charge, polarizability, deformability, surface charge mobility, dielectric features, and local capacitance. Thus, different types of particles are simultaneously separated at different points along the channel distance given small variations of properties. The device has shown the ability to separate analytes over a large dynamic range of size, from 20 nm to 1 μm, roughly the size of proteins to the size of cells. In the study of different sized sulfate capped polystyrene particles were shown to be selectively captured as well as concentrating particles from 103 to 106 times. Qualitative capture and manipulation of β-amyloid fibrils were also shown. The results demonstrate the selective focusing ability of the technique; and it may form the foundation for a versatile tool for separating complex mixtures. Combined this work shows promise for future identification of individual organisms from aerosolized protein as well as for applications in biomedical research.
ContributorsStaton, Sarah J. R (Author) / Hayes, Mark A. (Committee member) / Anbar, Ariel D (Committee member) / Shock, Everett (Committee member) / Williams, Peter (Committee member) / Arizona State University (Publisher)
Created2011
Description
Atmospheric particulate matter has a substantial impact on global climate due to its ability to absorb/scatter solar radiation and act as cloud condensation nuclei (CCN). Yet, little is known about marine aerosol, in particular, the carbonaceous fraction. In the present work, particulate matter was collected, using High Volume (HiVol) samplers, onto quartz fiber substrates during a series of research cruises on the Atlantic Ocean. Samples were collected on board the R/V Endeavor on West–East (March–April, 2006) and East–West (June–July, 2006) transects in the North Atlantic, as well as on the R/V Polarstern during a North–South (October–November, 2005) transect along the western coast of Europe and Africa. The aerosol total carbon (TC) concentrations for the West–East (Narragansett, RI, USA to Nice, France) and East–West (Heraklion, Crete, Greece to Narragansett, RI, USA) transects were generally low over the open ocean (0.36±0.14 μg C/m3) and increased as the ship approached coastal areas (2.18±1.37 μg C/m3), due to increased terrestrial/anthropogenic aerosol inputs. The TC for the North–South transect samples decreased in the southern hemisphere with the exception of samples collected near the 15th parallel where calculations indicate the air mass back trajectories originated from the continent. Seasonal variation in organic carbon (OC) was seen in the northern hemisphere open ocean samples with average values of 0.45 μg/m3 and 0.26 μg/m3 for spring and summer, respectively. These low summer time values are consistent with SeaWiFS satellite images that show decreasing chlorophyll a concentration (a proxy for phytoplankton biomass) in the summer. There is also a statistically significant (p<0.05) decline in surface water fluorescence in the summer. Moreover, examination of water–soluble organic carbon (WSOC) shows that the summer aerosol samples appear to have a higher fraction of the lower molecular weight material, indicating that the samples may be more oxidized (aged). The seasonal variation in aerosol content seen during the two 2006 cruises is evidence that a primary biological marine source is a significant contributor to the carbonaceous particulate in the marine atmosphere and is consistent with previous studies of clean marine air masses.
ContributorsHill, Hansina Rae (Author) / Herckes, Pierre (Thesis advisor) / Westerhoff, Paul (Committee member) / Hartnett, Hilairy (Committee member) / Arizona State University (Publisher)
Created2011
Description
Bioanalytes such as protein, cells, and viruses provide vital information but are inherently challenging to measure with selective and sensitive detection. Gradient separation technologies can provide solutions to these challenges by enabling the selective isolation and pre-concentration of bioanalytes for improved detection and monitoring. Some fundamental aspects of two of these techniques, isoelectric focusing and dielectrophoresis, are examined and novel developments are presented. A reproducible and automatable method for coupling capillary isoelectric focusing (cIEF) and matrix assisted laser desorption/ionization mass spectrometry (MALDI-MS) based on syringe pump mobilization is found. Results show high resolution is maintained during mobilization and &beta-lactoglobulin; protein isoforms differing by two amino acids are resolved. Subsequently, the instrumental advantages of this approach are utilized to clarify the microheterogeneity of serum amyloid P component. Comprehensive, quantitative results support a relatively uniform glycoprotein model, contrary to inconsistent and equivocal observations in several gel isoelectric focusing studies. Fundamental studies of MALDI-MS on novel superhydrophobic substrates yield unique insights towards an optimal interface between cIEF and MALDI-MS. Finally, the fundamentals of isoelectric focusing in an open drop are explored. Findings suggest this could be a robust sample preparation technique for droplet-based microfluidic systems. Fundamental advancements in dielectrophoresis are also presented. Microfluidic channels for dielectrophoretic mobility characterization are designed which enable particle standardization, new insights to be deduced, and future devices to be intelligently designed. Dielectrophoretic mobilities are obtained for 1 µm polystyrene particles and red blood cells under select conditions. Employing velocimetry techniques allows models of particle motion to be improved which in turn improves the experimental methodology. Together this work contributes a quantitative framework which improves dielectrophoretic particle separation and analysis.
ContributorsWeiss, Noah Graham (Author) / Hayes, Mark A. (Thesis advisor) / Garcia, Antonio (Committee member) / Ros, Alexandra (Committee member) / Arizona State University (Publisher)
Created2011
Description
Black carbon (BC) is the product of incomplete combustion of biomass and fossil fuels. It is found ubiquitously in nature and is relevant to studies in atmospheric science, soil science, oceanography, and anthropology. Black carbon is best described using a combustion continuum that sub-classifies BC into slightly charred biomass, char, charcoal and soot. These sub-classifications range in particle size, formation temperature, and relative reactivity. Interest in BC has increased because of its role in the long-term storage of organic matter and the biogeochemistry of urban areas. The global BC budget is unbalanced. Production of BC greatly outweighs decomposition of BC. This suggests that there are unknown or underestimated BC removal processes, and it is likely that some of these processes are occurring in soils. However, little is known about BC reactivity in soil and especially in desert soil. This work focuses on soot BC, which is formed at higher temperatures and has a lower relative reactivity than other forms of BC. Here, I assess the contribution of soot BC to central AZ soils and use the isotopic composition of soot BC to identify sources of soot BC. Soot BC is a significant (31%) fraction of the soil organic matter in central AZ and this work suggests that desert and urban soils may be a storage reservoir for soot BC. I further identify previously unknown removal processes of soot BC found naturally in soil and demonstrate that soil soot BC undergoes abiotic (photo-oxidation) and biotic reactions. Not only is soot BC degraded by these processes, but its chemical composition is altered, suggesting that soot BC contains some chemical moieties that are more reactive than others. Because soot BC demonstrates both refractory and reactive character, it is likely that the structure of soot BC; therefore, its interactions in the environment are complex and it is not simply a recalcitrant material.
ContributorsHamilton, George (Author) / Hartnett, Hilairy E (Thesis advisor) / Herckes, Pierre (Committee member) / Hall, Sharon (Committee member) / Arizona State University (Publisher)
Created2013
Description
Complex samples, such as those from biological sources, contain valuable information indicative of the state of human health. These samples, though incredibly valuable, are difficult to analyze. Separation science is often used as the first step when studying these samples. Electrophoretic exclusion is a novel separations technique that differentiates species in bulk solution. Due to its ability to isolate species in bulk solution, it is uniquely suited to array-based separations for complex sample analysis. This work provides proof of principle experimental results and resolving capabilities of the novel technique. Electrophoretic exclusion is demonstrated at a single interface on both benchtop and microscale device designs. The benchtop instrument recorded absorbance measurements in a 365 μL reservoir near a channel entrance. Results demonstrated the successful exclusion of a positively-charged dye, methyl violet, with various durations of applied potential (30 - 60 s). This was the first example of measuring absorbance at the exclusion location. A planar, hybrid glass/PDMS microscale device was also constructed. One set of experiments employed electrophoretic exclusion to isolate small dye molecules (rhodamine 123) in a 250 nL reservoir, while another set isolated particles (modified polystyrene microspheres). Separation of rhodamine 123 from carboxylate-modified polystyrene spheres was also shown. These microscale results demonstrated the first example of the direct observation of exclusion behavior. Furthermore, these results showed that electrophoretic exclusion can be applicable to a wide range of analytes. The theoretical resolving capabilities of electrophoretic exclusion were also developed. Theory indicates that species with electrophoretic mobilities as similar as 10-9 cm2/Vs can be separated using electrophoretic exclusion. These results are comparable to those of capillary electrophoresis, but on a very different format. This format, capable of isolating species in bulk solution, coupled with the resolving capabilities, makes the technique ideal for use in a separations-based array.
ContributorsKenyon, Stacy Marie (Author) / Hayes, Mark A. (Thesis advisor) / Ros, Alexandra (Committee member) / Buttry, Daniel (Committee member) / Arizona State University (Publisher)
Created2012
Description
N-nitrosodimethylamine (NDMA) is a probable human carcinogen that has been detected in various environments including the atmosphere, clouds, surface waters, and drinking water. NDMA can form through natural reactions in the aqueous phase of the atmosphere and it can form as a disinfection byproduct in water treatment. Due to its carcinogenic nature, it is important to understand the mechanism of formation of NDMA in both engineered processes such as water treatment and in natural processes in fogs and clouds. NDMA might form through the reaction of chloramines with amines in both cases. This work analyzes polydiallyldimethyl ammonium chloride (PolyDADMAC), which is the most commonly used polymer at drinking water treatment plants and has the potential to form NDMA if free polymer is present during the chloramination (disinfection) process. The composition of industrial polyDADMAC solutions is not well understood and is difficult to analyze. This work uses 1H and 13C nuclear magnetic resonance (NMR) to analyze the polymer solution composition. Both 1H and 13C NMR allow investigation of the presence of trace impurities in the solution, gather structural information such as chain length, and inform on reaction mechanisms. The primary impurities of concern for NDMA formation were identified as dimethylamine (DMA) and short-chain oligomers of the polyDADMAC. 13C NMR was further used to confirm that NDMA likely forms from polyDADMAC via a Hofmann elimination.
Chloramines might also form in fogs and clouds although to date the potential for chloramines to form NDMA in atmospheric fog and cloud droplets has not been investigated. This work uses computational modeling to determine that at reported atmospheric conditions, the chloramine pathway contributes to less than 0.01% NDMA formation. The numerical modeling identified a need for more atmospheric HOCl measurements. This work proposes a concept of using HOCl to react to form chloramine, which can react to form NDMA as a way to quantify atmospheric HOCl.
ContributorsDonovan, Samantha Jo (Author) / Herckes, Pierre (Thesis advisor) / Westerhoff, Paul (Committee member) / Hayes, Mark (Committee member) / Arizona State University (Publisher)
Created2022
Description
Trace evidence is an essential component of forensic investigations. Anthropogenicmaterials such as fibers and glass have been well studied for use in forensic trace evidence, but the potential use of retroreflective beads found in soils for forensic investigations is largely unexplored. Retroreflective glass beads are tiny spheres mixed into pavement markings to create reflective surfaces to reduce lane departure accidents. Retroreflective glass beads are a potentially new source of trace evidence for forensic investigations.
Analysis of the spatial distribution and chemical compositions of retroreflective glass beads recovered from 17 soil samples were analyzed and compared to see if there are striking variations that can distinguish samples by source. Soil samples taken near marked roads showed significantly higher concentrations of glass beads, averaging from 0.18 bead/g of soil sample to 587 beads/g of soil, while soil samples taken near unmarked roads had average range of concentration of 0 bead/g of soil to 0.21 bead/g of soil. Retroreflective glass beads come from pavement markings, thus soil samples near marked roads are expected to have higher concentrations of glass beads. Analysis of spatial distribution of glass beads showed that as sample collection moved further from the road, concentration of glass beads decreased.
ICP-MS results of elemental concentrations for each sample showed discriminative differences between samples, for most of the elements. An analysis of variance for elemental concentrations was conducted, and results showed statistically significant differences, beyond random chance alone for half of the elements analyzed. For forensic comparisons, a significant difference in even just one element is enough to conclude that the samples came from different sources. The elemental concentrations of glass beads collected from the same location, but of varying differences, was also analyzed. ANOVA results show significant differences for only one or two elements. A pair-wise t-test was conducted to determine which elements are most discriminative among all the samples. Rubidium was found to be the most discriminative, showing significant difference for 67% of the pairs. Beryllium, potassium, and manganese were also highly discriminative, showing significant difference for at least 50% of all the pairs.
ContributorsGomez, Janelle Kate Pacifico (Author) / Montero, Shirly (Thesis advisor) / Herckes, Pierre (Thesis advisor) / Borges, Chad (Committee member) / Gordon, Gwyneth (Committee member) / Arizona State University (Publisher)
Created2023
Description
ABSTRACT
Tempe, Arizona can experience high atmospheric particulate matter episodes, both in winter and in summer. In summer, such events might be due to dust storms or wildfires, while in the wintertime, domestic wood burning (fireplaces and heating) tends to be a major contributor. In this study, it was investigated that the particulate matter concentrations and composition for select summertime and wintertime events in Tempe, expected to have high concentrations and possibly biomass burning impacts. Summertime concentrations on the selected days were low except for a dust storm event. In the winter events, across the New Year holiday, concentrations were substantial, especially on New Year's morning because of the fireworks, although precipitation impacted the concentrations. Chemical analysis of bulk organic (OC) and elemental (EC) carbon shows a high ratio of OC/EC, indicative of substantial secondary organic aerosol contributions or biomass burning. Investigation of biomass burning specific molecular markers, such as levoglucosan, using gas chromatography mass spectrometry, showed detectable concentrations during wintertime, confirming wood burning as a significant source of atmospheric particulate matter. In summer, levoglucosan was detected but during the times investigated, wood smoke was not a dominant source of particulate matter. Finally, particulate polycyclic aromatic hydrocarbons (PAH) of burning origin were also investigated because of their toxicity. PAH concentrations showed a clear dependence of temperature with lower molecular weighted (LMW) PAHs being less abundant in the summertime in the particulate matter because of their volatility. The use of diagnostic PAH ratios confirmed the importance of combustion sources for the PAH albeit different ones in summer compared to winter events.
ContributorsAbel, Parker Stephen (Author) / Herckes, Pierre (Thesis advisor) / Xu, Jie (Committee member) / Fraser, Matthew (Committee member) / Arizona State University (Publisher)
Created2024
Description
Pollen allergies are common in the United States, especially in Arizona. In addition to more people experiencing allergies, the allergies themselves are worse, with people reporting more severe and longer lasting symptoms, after moving to Arizona. Potential reasons behind this include a longer blooming season in the state, a lack of rain to wash out pollen from the atmosphere, and compounding factors of poor air quality. One significant contributor to poor air quality are high ozone levels in urban areas like Phoenix. The goal of this study is to determine if ozone and pollen interact in a way that changes pollen physically or chemically. Ragweed pollen was placed in a chamber and exposed to low, medium, and high levels of ozone for 6-72 hours corresponding to different exposure doses. Exposed and non-exposed pollen was analyzed for physical changes in the pollen grain using scanning electron microscopy (SEM). Chemical changes were investigated using Fourier Transform Infrared Spectroscopy (FT-IR). Finally, exposed and non-exposed pollen was analyzed for changes in lipid profiles using gas chromatography mass spectrometry (GC/MS). SEM analysis found that when ragweed pollen is exposed to high ozone levels (60-100 ppm, > 48 hours), pollen grains become damaged. The same exposure level results in chemical changes in the pollen that are detectable by FT-IR. A higher ozone dose results in worse physical damage and increased changes in the lipid profile. Future research should study a wider ranges of exposure doses and relate the physicochemical changes to differences in immune response.
ContributorsKing, Lily (Author) / Herckes, Pierre (Thesis advisor) / Fraser, Matthew (Committee member) / Levitus, Marcia (Committee member) / Arizona State University (Publisher)
Created2024