Matching Items (139)
Description
An imaging measurement technique is developed using surface plasmon resonance. Plasmonic-based electrochemical current imaging (P-ECi) method has been developed to image the local electrochemical current optically, it allows us to measure the current density quickly and non-invasively [1, 2]. In this thesis, we solve the problems when we extand the P-ECi technique to the field of thin film system. The P-ECi signal in thin film structure was found to be directly proportional to the electrochemical current. The upper-limit of thin film thickness to use the proportional relationship between P-ECi signal and EC current was discussed by experiment and simulation. Furthermore, a new algorithm which can calculate the current density from P-ECi signal without any thickness limitation is developed and tested. Besides, surface plasmon resonance is useful phenomenon which can be used to detect the changes in the refractive index near the gold sensing surface. With the assistance of pH indicator, by applied EC potential on the gold film as the working electrode, the detection of H2 evolution reaction can be enhanced. This measurement technique is useful in analyzing local EC information and H2 evolution. References [1] S. Wang, et al., "Electrochemical Surface Plasmon Resonance: Basic Formalism and Experimental Validation," Analytical Chemistry, vol. 82, pp. 935-941, 2010/02/01 2010. [2] X. Shan, et al., "Imaging Local Electrochemical Current via Surface Plasmon Resonance," Science, vol. 327, pp. 1363-1366, March 12, 2010 2010.
ContributorsZhao, Yanjun (Author) / Tao, Nongjian (Thesis advisor) / Wang, Shaopeng (Committee member) / Tsow, Tsing (Committee member) / Arizona State University (Publisher)
Created2013
Description
Nitrate is the most prevalent water pollutant limiting the use of groundwater as a potable water source. The overarching goal of this dissertation was to leverage advances in nanotechnology to improve nitrate photocatalysis and transition treatment to the full-scale. The research objectives were to (1) examine commercial and synthesized photocatalysts, (2) determine the effect of water quality parameters (e.g., pH), (3) conduct responsible engineering by ensuring detection methods were in place for novel materials, and (4) develop a conceptual framework for designing nitrate-specific photocatalysts. The key issues for implementing photocatalysis for nitrate drinking water treatment were efficient nitrate removal at neutral pH and by-product selectivity toward nitrogen gases, rather than by-products that pose a human health concern (e.g., nitrite). Photocatalytic nitrate reduction was found to follow a series of proton-coupled electron transfers. The nitrate reduction rate was limited by the electron-hole recombination rate, and the addition of an electron donor (e.g., formate) was necessary to reduce the recombination rate and achieve efficient nitrate removal. Nano-sized photocatalysts with high surface areas mitigated the negative effects of competing aqueous anions. The key water quality parameter impacting by-product selectivity was pH. For pH < 4, the by-product selectivity was mostly N-gas with some NH4+, but this shifted to NO2- above pH = 4, which suggests the need for proton localization to move beyond NO2-. Co-catalysts that form a Schottky barrier, allowing for localization of electrons, were best for nitrate reduction. Silver was optimal in heterogeneous systems because of its ability to improve nitrate reduction activity and N-gas by-product selectivity, and graphene was optimal in two-electrode systems because of its ability to shuttle electrons to the working electrode. "Environmentally responsible use of nanomaterials" is to ensure that detection methods are in place for the nanomaterials tested. While methods exist for the metals and metal oxides examined, there are currently none for carbon nanotubes (CNTs) and graphene. Acknowledging that risk assessment encompasses dose-response and exposure, new analytical methods were developed for extracting and detecting CNTs and graphene in complex organic environmental (e.g., urban air) and biological matrices (e.g. rat lungs).
ContributorsDoudrick, Kyle (Author) / Westerhoff, Paul (Thesis advisor) / Halden, Rolf (Committee member) / Hristovski, Kiril (Committee member) / Arizona State University (Publisher)
Created2013
Description
Human breath is a concoction of thousands of compounds having in it a breath-print of physiological processes in the body. Though breath provides a non-invasive and easy to handle biological fluid, its analysis for clinical diagnosis is not very common. Partly the reason for this absence is unavailability of cost effective and convenient tools for such analysis. Scientific literature is full of novel sensor ideas but it is challenging to develop a working device, which are few. These challenges include trace level detection, presence of hundreds of interfering compounds, excessive humidity, different sampling regulations and personal variability. To meet these challenges as well as deliver a low cost solution, optical sensors based on specific colorimetric chemical reactions on mesoporous membranes have been developed. Sensor hardware utilizing cost effective and ubiquitously available light source (LED) and detector (webcam/photo diodes) has been developed and optimized for sensitive detection. Sample conditioning mouthpiece suitable for portable sensors is developed and integrated. The sensors are capable of communication with mobile phones realizing the idea of m-health for easy personal health monitoring in free living conditions. Nitric oxide and Acetone are chosen as analytes of interest. Nitric oxide levels in the breath correlate with lung inflammation which makes it useful for asthma management. Acetone levels increase during ketosis resulting from fat metabolism in the body. Monitoring breath acetone thus provides useful information to people with type1 diabetes, epileptic children on ketogenic diets and people following fitness plans for weight loss.
ContributorsPrabhakar, Amlendu (Author) / Tao, Nongjian (Thesis advisor) / Forzani, Erica (Committee member) / Lindsay, Stuart (Committee member) / Arizona State University (Publisher)
Created2013
Description
Surface plasmon resonance (SPR) has emerged as a popular technique for elucidating subtle signals from biological events in a label-free, high throughput environment. The efficacy of conventional SPR sensors, whose signals are mass-sensitive, diminishes rapidly with the size of the observed target molecules. The following work advances the current SPR sensor paradigm for the purpose of small molecule detection. The detection limits of two orthogonal components of SPR measurement are targeted: speed and sensitivity. In the context of this report, speed refers to the dynamic range of measured kinetic rate constants, while sensitivity refers to the target molecule mass limitation of conventional SPR measurement. A simple device for high-speed microfluidic delivery of liquid samples to a sensor surface is presented to address the temporal limitations of conventional SPR measurement. The time scale of buffer/sample switching is on the order of milliseconds, thereby minimizing the opportunity for sample plug dispersion. The high rates of mass transport to and from the central microfluidic sensing region allow for SPR-based kinetic analysis of binding events with dissociation rate constants (kd) up to 130 s-1. The required sample volume is only 1 μL, allowing for minimal sample consumption during high-speed kinetic binding measurement. Charge-based detection of small molecules is demonstrated by plasmonic-based electrochemical impedance microscopy (P-EIM). The dependence of surface plasmon resonance (SPR) on surface charge density is used to detect small molecules (60-120 Da) printed on a dextran-modified sensor surface. The SPR response to an applied ac potential is a function of the surface charge density. This optical signal is comprised of a dc and an ac component, and is measured with high spatial resolution. The amplitude and phase of local surface impedance is provided by the ac component. The phase signal of the small molecules is a function of their charge status, which is manipulated by the pH of a solution. This technique is used to detect and distinguish small molecules based on their charge status, thereby circumventing the mass limitation (~100 Da) of conventional SPR measurement.
ContributorsMacGriff, Christopher Assiff (Author) / Tao, Nongjian (Thesis advisor) / Wang, Shaopeng (Committee member) / LaBaer, Joshua (Committee member) / Chae, Junseok (Committee member) / Arizona State University (Publisher)
Created2013
Description
Contaminants of emerging concern (CECs) present in wastewater effluent can threat its safe discharge or reuse. Additional barriers of protection can be provided using advanced or natural treatment processes. This dissertation evaluated ozonation and constructed wetlands to remove CECs from wastewater effluent. Organic CECs can be removed by hydroxyl radical formed during ozonation, however estimating the ozone demand of wastewater effluent is complicated due to the presence of reduced inorganic species. A method was developed to estimate ozone consumption only by dissolved organic compounds and predict trace organic oxidation across multiple wastewater sources. Organic and engineered nanomaterial (ENM) CEC removal in constructed wetlands was investigated using batch experiments and continuous-flow microcosms containing decaying wetland plants. CEC removal varied depending on their physico-chemical properties, hydraulic residence time (HRT) and relative quantities of plant materials in the microcosms. At comparable HRTs, ENM removal improved with higher quantity of plant materials due to enhanced sorption which was verified in batch-scale studies with plant materials. A fate-predictive model was developed to evaluate the role of design loading rates on organic CEC removal. Areal removal rates increased with hydraulic loading rates (HLRs) and carbon loading rates (CLRs) unless photolysis was the dominant removal mechanism (e.g. atrazine). To optimize CEC removal, wetlands with different CLRs can be used in combination without lowering the net HLR. Organic CEC removal in denitrifying conditions of constructed wetlands was investigated and selected CECs (e.g. estradiol) were found to biotransform while denitrification occurred. Although level of denitrification was affected by HRT, similar impact on estradiol was not observed due to a dominant effect from plant biomass quantity. Overall, both modeling and experimental findings suggest considering CLR as an equally important factor with HRT or HLR to design constructed wetlands for CEC removal. This dissertation provided directions to select design parameters for ozonation (ozone dose) and constructed wetlands (design loading rates) to meet organic CEC removal goals. Future research is needed to understand fate of ENMs during ozonation and quantify the contributions from different transformation mechanisms occurring in the wetlands to incorporate in a model and evaluate the effect of wetland design.
ContributorsSharif, Fariya (Author) / Westerhoff, Paul (Thesis advisor) / Halden, Rolf (Committee member) / Fox, Peter (Committee member) / Herckes, Pierre (Committee member) / Arizona State University (Publisher)
Created2013
Description
Understanding charge transport in single molecules covalently bonded to electrodes is a fundamental goal in the field of molecular electronics. In the past decade, it has become possible to measure charge transport on the single-molecule level using the STM break junction method. Measurements on the single-molecule level shed light on charge transport phenomena which would otherwise be obfuscated by ensemble measurements of groups of molecules. This thesis will discuss three projects carried out using STM break junction. In the first project, the transition between two different charge transport mechanisms is reported in a set of molecular wires. The shortest wires show highly length dependent and temperature invariant conductance behavior, whereas the longer wires show weakly length dependent and temperature dependent behavior. This trend is consistent with a model whereby conduction occurs by coherent tunneling in the shortest wires and by incoherent hopping in the longer wires. Measurements are supported with calculations and the evolution of the molecular junction during the pulling process is investigated. The second project reports controlling the formation of single-molecule junctions by means of electrochemically reducing two axial-diazonium terminal groups on a molecule, thereby producing direct Au-C covalent bonds in-situ between the molecule and gold electrodes. Step length analysis shows that the molecular junction is significantly more stable, and can be pulled over a longer distance than a comparable junction created with amine anchoring bonds. The stability of the junction is explained by the calculated lower binding energy associated with the direct Au-C bond compared with the Au-N bond. Finally, the third project investigates the role that molecular conformation plays in the conductance of oligothiophene single-molecule junctions. Ethyl substituted oligothiophenes were measured and found to exhibit temperature dependent conductance and transition voltage for molecules with between two and six repeat units. While the molecule with only one repeat unit shows temperature invariant behavior. Density functional theory calculations show that at higher temperatures the oligomers with multiple repeat units assume a more planar conformation, which increases the conjugation length and decreases the effective energy barrier of the junction.
ContributorsHines, Thomas (Author) / Tao, Nongjian (Thesis advisor) / Li, Jian (Thesis advisor) / Mujica, Vladimiro (Committee member) / Allee, David (Committee member) / Arizona State University (Publisher)
Created2013
Description
This work demonstrates the integration of a wearable particulate detector and a wireless chemical sensor into a single portable system. The detection philosophy of the chemical sensor is based on highly selective and sensitive microfabricated quartz tuning fork arrays and the particle detector detects the particulate level in real-time using a nephelometric (light scattering) approach. The device integration is realized by carefully evaluating the needs of flow rate, power and data collection. Validation test has been carried out in both laboratory and in field trials such as parking structures and highway exits with high and low traffic emissions. The integrated single portable detection system is capable of reducing the burden for a child to carry multiple devices, simplifying the task of researchers to synchronize and analyze data from different sensors, and minimizing the overall weight, size, and cost of the sensor. It also has a cell phone for data analysis, storage, and transmission as a user-friendly interface. As the chemical and particulate levels present important exposure risks that are of high interests to epidemiologists, the integrated device will provide an easier, wearable and cost effective way to monitor it.
ContributorsGao, Tianle (Author) / Tao, Nongjian (Thesis advisor) / Chae, Junseok (Committee member) / Tsow, Tsing (Committee member) / Arizona State University (Publisher)
Created2012
Description
Advances in miniaturized sensors and wireless technologies have enabled mobile health systems for efficient healthcare. A mobile health system assists the physician to monitor the patient's progress remotely and provide quick feedbacks and suggestions in case of emergencies, which reduces the cost of healthcare without the expense of hospitalization. This work involves development of an innovative mobile health system with adaptive biofeedback mechanism and demonstrates the importance of biofeedback in accurate measurements of physiological parameters to facilitate the diagnosis in mobile health systems. Resting Metabolic Rate (RMR) assessment, a key aspect in the treatment of diet related health problems is considered as a model to demonstrate the importance of adaptive biofeedback in mobile health. A breathing biofeedback mechanism has been implemented with digital signal processing techniques for real-time visual and musical guidance to accurately measure the RMR. The effects of adaptive biofeedback with musical and visual guidance were assessed on 22 healthy subjects (12 men, 10 women). Eight RMR measurements were taken for each subject on different days under same conditions. It was observed the subjects unconsciously followed breathing biofeedback, yielding consistent and accurate measurements for the diagnosis. The coefficient of variation of the measured metabolic parameters decreased significantly (p < 0.05) for 20 subjects out of 22 subjects.
ContributorsKrishnan, Ranganath (Author) / Tao, Nongjian (Thesis advisor) / Forzani, Erica (Committee member) / Yu, Hongyu (Committee member) / Arizona State University (Publisher)
Created2012
Description
In today's world there is a great need for sensing methods as tools to provide critical information to solve today's problems in security applications. Real time detection of trace chemicals, such as explosives, in a complex environment containing various interferents using a portable device that can be reliably deployed in a field has been a difficult challenge. A hybrid nanosensor based on the electrochemical reduction of trinitrotoluene (TNT) and the interaction of the reduction products with conducting polymer nanojunctions in an ionic liquid was fabricated. The sensor simultaneously measures the electrochemical current from the reduction of TNT and the conductance change of the polymer nanojunction caused from the reduction product. The hybrid detection mechanism, together with the unique selective preconcentration capability of the ionic liquid, provides a selective, fast, and sensitive detection of TNT. The sensor, in its current form, is capable of detecting parts per trillion level TNT in the presence of various interferents within a few minutes. A novel hybrid electrochemical-colorimetric (EC-C) sensing platform was also designed and fabricated to meet these challenges. The hybrid sensor is based on electrochemical reactions of trace explosives, colorimetric detection of the reaction products, and unique properties of the explosives in an ionic liquid (IL). This approach affords not only increased sensitivity but also selectivity as evident from the demonstrated null rate of false positives and low detection limits. Using an inexpensive webcam a detection limit of part per billion in volume (ppbV) has been achieved and demonstrated selective detection of explosives in the presence of common interferences (perfumes, mouth wash, cleaners, petroleum products, etc.). The works presented in this dissertation, were published in the Journal of the American Chemical Society (JACS, 2009) and Nano Letters (2010), won first place in the National Defense Research contest in (2009) and has been granted a patent (WO 2010/030874 A1). In addition, other work related to conductive polymer junctions and their sensing capabilities has been published in Applied Physics Letters (2005) and IEEE sensors journal (2008).
ContributorsDiaz Aguilar, Alvaro (Author) / Tao, Nongjian (Thesis advisor) / Tsui, Raymond (Committee member) / Barnaby, Hugh (Committee member) / Yu, Hongbin (Committee member) / Arizona State University (Publisher)
Created2012
Description
Studying charge transport through single molecules tethered between two metal electrodes is of fundamental importance in molecular electronics. Over the years, a variety of methods have been developed in attempts of performing such measurements. However, the limitation of these techniques is still one of the factors that prohibit one from gaining a thorough understanding of single molecule junctions. Firstly, the time resolution of experiments is typically limited to milli to microseconds, while molecular dynamics simulations are carried out on the time scale of pico to nanoseconds. A huge gap therefore persists between the theory and the experiments. This thesis demonstrates a nanosecond scale measurement of the gold atomic contact breakdown process. A combined setup of DC and AC circuits is employed, where the AC circuit reveals interesting observations in nanosecond scale not previously seen using conventional DC circuits. The breakdown time of gold atomic contacts is determined to be faster than 0.1 ns and subtle atomic events are observed within nanoseconds. Furthermore, a new method based on the scanning tunneling microscope break junction (STM-BJ) technique is developed to rapidly record thousands of I-V curves from repeatedly formed single molecule junctions. 2-dimensional I-V and conductance-voltage (G-V) histograms constructed using the acquired data allow for more meaningful statistical analysis to single molecule I-V characteristics. The bias voltage adds an additional dimension to the conventional single molecule conductance measurement. This method also allows one to perform transition voltage spectra (TVS) for individual junctions and to study the correlation between the conductance and the tunneling barrier height. The variation of measured conductance values is found to be primarily determined by the poorly defined contact geometry between the molecule and metal electrodes, rather than the tunnel barrier height. In addition, the rapid I-V technique is also found useful in studying thermoelectric effect in single molecule junctions. When applying a temperature gradient between the STM tip and substrate in air, the offset current at zero bias in the I-V characteristics is a measure of thermoelectric current. The rapid I-V technique allows for statistical analysis of such offset current at different temperature gradients and thus the Seebeck coefficient of single molecule junctions is measured. Combining with single molecule TVS, the Seebeck coefficient is also found to be a measure of tunnel barrier height.
ContributorsGuo, Shaoyin (Author) / Tao, Nongjian (Thesis advisor) / Bennett, Peter (Committee member) / Ning, Cun-Zheng (Committee member) / Yu, Hongbin (Committee member) / Arizona State University (Publisher)
Created2012