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- Title
- Development of enzyme-free hydrogen peroxide biosensor using cerium oxide and mechanistic study using in-situ spectro-electrochemistry.
- Creator
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Saraf, Shashank, Seal, Sudipta, Cho, Hyoung Jin, Zhai, Lei, Heinrich, Helge, Harper, James, University of Central Florida
- Abstract / Description
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During recent development, it has been demonstrated that cerium oxide nanoparticles (CNPs) have exhibited catalytic activity which mimics naturally existing enzymes such as superoxide dismutase (SOD) and catalase. The underlying mechanism is attributed to the modulation of oxygen vacancies on CNPs lattice by dynamic switching of the oxidation states between Ce3+ and Ce4+ due to the electron transfer resulting from the redox reaction between CNPs and reactive oxygen species such as hydrogen...
Show moreDuring recent development, it has been demonstrated that cerium oxide nanoparticles (CNPs) have exhibited catalytic activity which mimics naturally existing enzymes such as superoxide dismutase (SOD) and catalase. The underlying mechanism is attributed to the modulation of oxygen vacancies on CNPs lattice by dynamic switching of the oxidation states between Ce3+ and Ce4+ due to the electron transfer resulting from the redox reaction between CNPs and reactive oxygen species such as hydrogen peroxide (H2O2). Thereby the redox potential of CNPs is dependent on the surface chemistry i.e. the surface concentration of Ce3+ and Ce4+ Currently, the ratio of Ce3+/ Ce4+ in CNPs is characterized ex-situ using XPS or TEM which involves sample drying and exposure to high energy X-rays and electron beam, respectively. Sample drying and high energy beam exposure could lead to sample deterioration. The goal of the study is to explore a technique to characterize CNPs in-situ and identify the surface chemistry of CNPs. The in-situ investigation of CNPs was carried using spectroelectrochemistry wherein the electrochemical and optical measurements are carried out simultaneously. Detailed optical characterization of two different CNPs having different catalytic activity were carried under oxidation and reduction environments. Analysis of spectra revealed widely different redox potential for CNPs which was a function of pH and composition of buffer solution. In second part of dissertation a suitable surface chemistry of CNPs is investigated to replace the enzyme in biosensor assembly to allow amperometric detection of H2O2 in physiological conditions. Upon electrochemical investigation of the physio-chemical properties of CNPs, it was found that CNPs having higher surface concentration of Ce4+ as compared to Ce3+ oxidation states, demonstrated increased catalytic activity towards H2O2. The addition of CNPs resulted in 5 orders of increment in amperometric current with a response time of 400 msec towards detection of H2O2 and exhibited excellent selectivity in presence of interfering species. Additionally, cerium oxide was successfully integrated into the biosensor assembly through the anodic electrodeposition, which allowed the transfer of electron generated from the CNPs in the redox reaction to the electrode and demonstrated successful sensing of H2O2. Furthermore, to achieve detection of H2O2 in physiological conditions, CNPs were integrated with nanoporous gold (NPG) which exhibited anti-biofouling properties. The anti-biofouling property of NPG was investigated using electrochemical techniques and showed excellent signal retention in physiological concentration of albumin proteins. The novel study targets at developing robust enzyme free biosensor by integrating the detection ability of CNPs with the anti-biofouling activity of NPG based electrode.
Show less - Date Issued
- 2016
- Identifier
- CFE0006498, ucf:51404
- Format
- Document (PDF)
- PURL
- http://purl.flvc.org/ucf/fd/CFE0006498
- Title
- INVESTIGATING THE QUANTITY AND TYPES OF MICROPLASTICS IN THE ORGANIC TISSUE OF OYSTERS AND CRABS IN THE INDIAN RIVER LAGOON.
- Creator
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Waite, Heidi, Walters, Linda J., University of Central Florida
- Abstract / Description
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Microplastics are widespread and abundant. Few studies have examined the diversity and abundance of microplastics in wild organisms. This study determined the microplastic quantity and types in the organic tissues of the eastern oyster Crassostrea virginica and Atlantic mud crab Panopeus herbstii from the Indian River Lagoon (IRL). This study also investigated whether location affected the microplastic abundance and variety. Organisms were collected from three sites across Mosquito Lagoon in...
Show moreMicroplastics are widespread and abundant. Few studies have examined the diversity and abundance of microplastics in wild organisms. This study determined the microplastic quantity and types in the organic tissues of the eastern oyster Crassostrea virginica and Atlantic mud crab Panopeus herbstii from the Indian River Lagoon (IRL). This study also investigated whether location affected the microplastic abundance and variety. Organisms were collected from three sites across Mosquito Lagoon in the northern IRL. Oysters were frozen after collection. Crabs were placed in containers for 5 days before freezing. The soft organic tissue was chemically digested using hydrogen peroxide, filtered, and examined for microplastics. Water samples collected from each study site had an average of 23.1 microplastic pieces per liter and fibers were the most common type. There was a significant interaction for microplastic type and site for both oysters and crabs (p
Show less - Date Issued
- 2017
- Identifier
- CFH2000157, ucf:46042
- Format
- Document (PDF)
- PURL
- http://purl.flvc.org/ucf/fd/CFH2000157
- Title
- MICROMACHINED ELECTROCHEMICAL SENSORS FOR HYDROGEN PEROXIDE AND CHLORINE DETECTION.
- Creator
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Mehta, Anjum, Cho, Hyoung (Joe), University of Central Florida
- Abstract / Description
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Hydrogen peroxide and chlorine detection is critical for many biological and environmental applications. Hydrogen peroxide plays important roles in a variety of fields including plant physiology, medical, environmental and biochemical applications. Its role in plant defense and signal transduction, diseases such as Parkinson's and Alzhemier's, industrial processes such as disinfection and wastewater treatment and biochemical enzymatic reactions is critical. Given the gamut of areas that...
Show moreHydrogen peroxide and chlorine detection is critical for many biological and environmental applications. Hydrogen peroxide plays important roles in a variety of fields including plant physiology, medical, environmental and biochemical applications. Its role in plant defense and signal transduction, diseases such as Parkinson's and Alzhemier's, industrial processes such as disinfection and wastewater treatment and biochemical enzymatic reactions is critical. Given the gamut of areas that hydrogen peroxide is a key component of; its detection assumes great importance. Similarly chlorine has long been used as a disinfectant for making drinking water safe, but excessive chlorination is an environmental and health hazard in itself. In this work, micromachining techniques have been used to design, fabricate and test electrochemical sensors and microneedle structure that can be integrated for detection of hydrogen peroxide and free chlorine. A novel nanomaterial has been integrated with the hydrogen peroxide microsensor, which greatly increases the sensor lifetime and robustness. Miniaturization, low detection limits, high sensitivity and selectivity, as well as ease of fabrication are some of the other advantages of this work.
Show less - Date Issued
- 2005
- Identifier
- CFE0000895, ucf:46627
- Format
- Document (PDF)
- PURL
- http://purl.flvc.org/ucf/fd/CFE0000895
- Title
- CHARACTERIZATION OF HEMERYTHRIN-LIKE PROTEIN RV2633C.
- Creator
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Cherne, Michelle D, Self, William, University of Central Florida
- Abstract / Description
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Hemerythrin-like protein Rv2633c is a small 18 kDa protein that is expressed in Mycobacterium tuberculosis (Mtb). Sequence analysis of Rv2633c predicts the presence of a hemerythrin-like domain, which binds dioxygen using a �-oxo-bridge (Fe-O-Fe), rather than a heme group. Though it is noticeably upregulated during macrophage infection and during in vitro acidification, the role of Rv2633c in Mtb survival has yet to be elucidated. This project aims to characterize the function of Rv2633c by...
Show moreHemerythrin-like protein Rv2633c is a small 18 kDa protein that is expressed in Mycobacterium tuberculosis (Mtb). Sequence analysis of Rv2633c predicts the presence of a hemerythrin-like domain, which binds dioxygen using a �-oxo-bridge (Fe-O-Fe), rather than a heme group. Though it is noticeably upregulated during macrophage infection and during in vitro acidification, the role of Rv2633c in Mtb survival has yet to be elucidated. This project aims to characterize the function of Rv2633c by studying the in vitro response of the recombinant protein to conditions present in the macrophage lysosome, such as reduced oxygen levels or the presence of reactive oxygen species. UV-visible spectroscopy is used to observe these changes, as the spectrum shows a characteristic peak at 330 nm that likely corresponds to the diiron cofactor in its native state. Our results show this spectrum shifts in response to hydrogen peroxide addition, showing the proposed environmental conditions can affect the active site. Bioinformatics techniques, such as the 3D modeling program SWISS-MODEL, have been used to hypothesize possible structure and function. Determining the function of Rv2633c may help explain how Mtb so readily evades the human immune system to reside in the macrophage.
Show less - Date Issued
- 2016
- Identifier
- CFH2000011, ucf:45581
- Format
- Document (PDF)
- PURL
- http://purl.flvc.org/ucf/fd/CFH2000011
- Title
- SURFACE CHEMISTRY OF APPLICATION SPECIFIC PADS AND COPPER CHEMICAL MECHANICAL PLANARIZATION.
- Creator
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Deshpande, Sameer Arun, Seal, Sudipta, University of Central Florida
- Abstract / Description
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Advances in the interconnection technology have played a key role in the continued improvement of the integrated circuit (IC) density, performance and cost. Copper (Cu) metallization, dual damascenes processing and integration of copper with low dielectric constant material are key issues in the IC industries. Chemical mechanical planarization of copper (Cu-CMP) has emerged as an important process for the manufacturing of ICs. Usually, Cu-CMP process consists of several steps such as the...
Show moreAdvances in the interconnection technology have played a key role in the continued improvement of the integrated circuit (IC) density, performance and cost. Copper (Cu) metallization, dual damascenes processing and integration of copper with low dielectric constant material are key issues in the IC industries. Chemical mechanical planarization of copper (Cu-CMP) has emerged as an important process for the manufacturing of ICs. Usually, Cu-CMP process consists of several steps such as the removal of surface layer by mechanical action of the pad and the abrasive particles, the dissolution of the abraded particles in the CMP solution, and the protection of the recess areas. The CMP process occurs at the atomic level at the pad/slurry/wafer interface, and hence, slurries and polishing pads play critical role in its successful implementation. The slurry for the Cu-CMP contains chemical components to facilitate the oxidation and removal of excess Cu as well as passivation of the polished surface. During the process, these slurry chemicals also react with the pad. In the present study, investigations were carried out to understand the effect of hydrogen peroxide (H2O2) as an oxidant and benzotriazole (BTA) as an inhibitor on the CMP of Cu. Interaction of these slurry components on copper has been investigated using electrochemical studies, x-ray photoelectron spectroscopy (XPS) and secondary ion mass spectroscopy (SIMS). In the presence of 0.1M glycine, Cu removal rate was found to be high in the solution containing 5% H2O2 at pH 2 because of the Cu-glycine complexation reaction. The dissolution rate of the Cu was found to increase due to the formation of highly soluble Cu-glycine complex in the presence of H2O2. Addition of 0.01M BTA in the solution containing 0.1M glycine and 5% H2O2 at pH 2 exhibited a reduction in the Cu removal rate due to the formation of Cu-BTA complex on the surface of the Cu further inhibiting the dissolution. XPS and SIMS investigations revealed the formation of such Cu-glycine complex, which help understand the mechanism of the Cu-oxidant-inhibitor interaction during polishing. Along with the slurry, pads used in the Cu-CMP process have direct influence an overall process. To overcome problems associated with the current pads, new application specific pad (ASP) have been developed in collaboration with PsiloQuest Inc. Using plasma enhanced chemical vapor deposition (PECVD) process; surface of such ASP pads were modified. Plasma treatment of a polymer surface results in the formation of various functional groups and radicals. Post plasma treatment such as chemical reduction or oxidation imparts a more uniform distribution of such functional groups on the surface of the polymer resulting in unique surface properties. The mechanical properties of such coated pad have been investigated using nano-indentation technique in collaboration with Dr. Vaidyanathan's research group. The surface morphology and the chemistry of the ASP are studied using scanning electron microcopy (SEM), x-ray photoelectron spectroscopy (XPS), and fourier transform infrared spectroscopy (FTIR) to understand the formation of different chemical species on the surface. It is observed that the mechanical and the chemical properties of the pad top surface are a function of the PECVD coating time. Such PECVD treated pads are found to be hydrophilic and do not require being stored in aqueous medium during the not-in-use period. The metal removal rate using such surface modified polishing pad is found to increase linearly with the PECVD coating time. Overall, this thesis is an attempt to optimize the two most important parameters of the Cu-CMP process viz. slurry and pads for enhanced performance and ultimately reduce the cost of ownership (CoO).
Show less - Date Issued
- 2004
- Identifier
- CFE0000125, ucf:46191
- Format
- Document (PDF)
- PURL
- http://purl.flvc.org/ucf/fd/CFE0000125
- Title
- DETERMINATION OF THE HYDROGEN PEROXIDE CONCENTRATION IN ROTENONE INDUCED DOPAMINERGIC CELLS USING CYCLIC VOLTAMMETRY AND AMPLEX® RED.
- Creator
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Patel, Kishan, Kim, Yoon, University of Central Florida
- Abstract / Description
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Parkinson's disease (PD) is a neurodegenerative condition that affects millions of people worldwide. The exact etiology of PD is unknown. However, it is well established that environmental factors contribute to the onset of PD. In particular, chemicals such as the insecticide Rotenone have been shown to increase the death of dopaminergic (DA) neurons by increasing levels of reactive oxygen species (ROS). ROS such as hydrogen peroxide (H2O2) have been shown to be elevated above basal levels in...
Show moreParkinson's disease (PD) is a neurodegenerative condition that affects millions of people worldwide. The exact etiology of PD is unknown. However, it is well established that environmental factors contribute to the onset of PD. In particular, chemicals such as the insecticide Rotenone have been shown to increase the death of dopaminergic (DA) neurons by increasing levels of reactive oxygen species (ROS). ROS such as hydrogen peroxide (H2O2) have been shown to be elevated above basal levels in PD patients. Currently, to measure H2O2 concentrations, a commercially available (Amplex® Red) fluorescent assay is used. However, the assay has limitations: it is not completely specific to hydrogen peroxide and can only measure extracellular ROS concentrations. This research focuses on testing an electrochemical sensor that uses cyclic voltammetry to quantitatively determine concentrations of H2O2 released from a cell culture. The sensor was first tested in normal cell culture conditions. Next, chemical interference was reduced and the sensor was optimized for accuracy by altering protein concentrations in the media. Finally, Rotenone was added to a cell culture to induce H2O2 production. Near real-time measurements of H2O2 were taken using the sensor and comparisons made to the fluorescent assay method. Overall, we are trying to determine if the electrochemical sensor can selectively and quantitatively measure H2O2 released from cells. Being able to track the production, migration and concentration of H2O2 in a cell can help researchers better understand its mechanism of action in cell death and oxidative damage, thus getting closer to finding a cure for PD.
Show less - Date Issued
- 2012
- Identifier
- CFH0004222, ucf:44921
- Format
- Document (PDF)
- PURL
- http://purl.flvc.org/ucf/fd/CFH0004222
- Title
- Development of Novel Redox Sensors and Processes Towards Biological Applications.
- Creator
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Patel, Jigna, Yestrebsky, Cherie, Clausen, Christian, Hampton, Michael, Harper, James, Diaz, Diego, University of Central Florida
- Abstract / Description
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Research on the cure and early detection of diseases such as diabetes, Alzheimer's, and Parkinson's is becoming of great interest due to the increasing number of people affected by them every year. An accurate and quick detection of various damaging species is highly critical in treatments of such diseases not only for exploring possible cures but also for early detection. If these diseases are detected during the initial stages than the possibility of curing them is much higher. Motivated by...
Show moreResearch on the cure and early detection of diseases such as diabetes, Alzheimer's, and Parkinson's is becoming of great interest due to the increasing number of people affected by them every year. An accurate and quick detection of various damaging species is highly critical in treatments of such diseases not only for exploring possible cures but also for early detection. If these diseases are detected during the initial stages than the possibility of curing them is much higher. Motivated by this, many researchers today have developed numerous types of sensing devices that can detect various physiological and biological compounds. However, most of these sensors are enzyme based. They have several setbacks such as the lack of sensitivity, restricted selectivity, short shelf life, and biological fouling. To overcome these obstacles, we examine the use of nanoceria modified Pt and Au electrodes for the detection of glucose and reactive oxygen species such as hydrogen peroxide. Amperometric detection of glucose and hydrogen peroxide is critical for biological applications for diabetes and possible Alzheimer's and Parkinson's patients. This dissertation focuses on the exploration of non-enzymatic detection of glucose and reactive oxygen species which has the prospective to be used for biological applications, in addition to an investigation of an odor control technology that uses these reactive oxygen species for the treatment of wastewater plants. The combination of bi-metallic composites with nanoceria showed increased oxidation ability towards glucose and hydrogen peroxide. The following dissertation expands on the relationship between bi-metallic nanoceria composite materials and its electro-oxidation of glucose and hydrogen peroxide towards biological sensing along with an investigation of an odor control technology that utilizes generates hydroxyl radical fine particle mist for the degradation of hydrogen sulfide odor in wastewater treatment plants.
Show less - Date Issued
- 2013
- Identifier
- CFE0005227, ucf:50585
- Format
- Document (PDF)
- PURL
- http://purl.flvc.org/ucf/fd/CFE0005227