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.

CpG methylation is an essential requirement for the normal development of mammals, but aberrant changes in the methylation can lead to tumor progression and cancer. An in-depth understanding of this phenomenon can provide insights into the mechanism of gene repression. We present a study comparing methylated DNA and normal DNA wrt its persistence length and contour length. Although, previous experiments and studies show no difference between the physical properties of the two, the data collected and interpreted here gives a different picture to the methylation phenomena and its effect on gene silencing. The study was extended to the artificially reconstituted chromatin and its interactions with the methyl CpG binding proteins were also probed.

Air pollution is one of the biggest challenges people face today. It is closely related to people's health condition. The agencies set up standards to regulate the air pollution. However, many of the pollutants under the regulation level may still result in adverse health effect. On the other hand, it is not clear the exact mechanism of air pollutants and its health effect. So it is difficult for the health centers to advise people how to prevent the air pollutant related diseases. It is of vital importance for both the agencies and the health centers to have a better understanding of the air pollution. Based on these needs, it is crucial to establish mobile health sensors for personal exposure assessment. Here, two sensing principles are illustrated: the tuning fork platform and the colorimetric platform. Mobile devices based on these principles have been built. The detections of ozone, NOX, carbon monoxide and formaldehyde have been shown. An integrated device of nitrogen dioxide and carbon monoxide is introduced. Fan is used for sample delivery instead pump and valves to reduce the size, cost and power consumption. Finally, the future work is discussed.

Single molecules in a tunnel junction can now be interrogated reliably using chemically-functionalized electrodes. Monitoring stochastic bonding fluctuations between a ligand bound to one electrode and its target bound to a second electrode ("tethered molecule-pair" configuration) gives insight into the nature of the intermolecular bonding at a single molecule-pair level, and defines the requirements for reproducible tunneling data. Importantly, at large tunnel gaps, there exists a regime for many molecules in which the tunneling is influenced more by the chemical identity of the molecules than by variability in the molecule-metal contact. Functionalizing a pair of electrodes with recognition reagents (the "free analyte" configuration) can generate a distinct tunneling signal when an analyte molecule is trapped in the gap. This opens up a new interface between chemistry and electronics with immediate implications for rapid sequencing of single DNA molecules.

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.

Windows based mobile application for m-health and environmental monitoring sensor devices were developed and tested. With the number of smartphone users exponentially increasing, the applications developed for m-health and environmental monitoring devices are easy to reach the general public, if the applications are simple, user-friendly and personalized. The sensing device uses Bluetooth to communicate with the smartphone, providing mobility to the user. Since the device is small and hand-held, the user can put his smartphone in his pocket, connected to the device in his hand and can move anywhere with it. The data processing performed in the applications is verified against standard off the shelf software, the results of the tests are discussed in this document. The user-interface is very simple and doesn't require many inputs from the user other than during the initial setting when they have to enter their personal information for the records. The m-health application can be used by doctors as well as by patients. The response of the application is very quick and hence the patients need not wait for a long time to see the results. The environmental monitoring device has a real-time plot displayed on the screen of the smartphone showing concentrations of total volatile organic compounds and airborne particle count in the environment at the location of the device. The programming was done with Microsoft Visual Studio and was written on VB.NET platform. On the applications, the smartphone receives data as raw binary bytes from the device via Bluetooth and this data is processed to obtain the final result. The final result is the concentration of Nitric Oxide in ppb in the Asthma Analyzer device. In the environmental monitoring device, the final result is the concentration of total Volatile Organic Compounds and the count of airborne Particles.

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.

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.

Hydrogenases catalyze the interconversion of protons, electrons, and hydrogen according to the reaction: 2H+ + 2e- <-> H2 while using only earth abundant metals, namely nickel and iron for catalysis. The enzymatic turnover of Clostridium acetobutylicum [FeFe]-hydrogenase has been investigated through the use of electrochemical and scanning probe techniques. Scanning tunneling microscopy (STM) imaging revealed sub-monolayer surface coverage. Cyclic voltammetry yielded a catalytic, cathodic hydrogen production signal similar to that observed for a platinum electrode. From the direct observation of single enzymes and the macroscopic electrochemical measurements obtained from the same electrode, the apparent turnover frequency (TOF) per single enzyme molecule as a function of potential was determined. The TOF at 0.7 V vs. Ag/AgCl for the four SAMs yielded a decay constant for electronic coupling (β) through the SAM of ~ 0.82 Å -1, in excellent agreement with published values for similar SAMs. One mechanism used by plants to protect against damage is called nonphotochemical quenching (NPQ). Triggered by low pH in the thylakoid lumen, NPQ leads to conversion of excess excitation energy in the antenna system to heat before it can initiate production of harmful chemical species by photosynthetic reaction centers. Here a synthetic hexad molecule that functionally mimics the role of the antenna in NPQ is described. When the hexad is dissolved in an organic solvent, five zinc porphyrin antenna moieties absorb light, exchange excitation energy, and ultimately decay by normal photophysical processes. However, when acid is added, a pH-sensitive dye moiety is converted to a form that rapidly quenches the first excited singlet states of all five porphyrins, converting the excitation energy to heat and rendering the porphyrins kinetically incompetent to perform useful photochemistry. Charge transport was also studied in single-molecule junctions formed with a 1,7-pyrrolidine-substituted 3,4,9,10-Perylenetetracarboxylic diimide (PTCDI) molecule. A reduction in the highest occupied (HOMO) and lowest unoccupied (LUMO) molecular orbitals energy gap due to the electronic properties of the substituents is seen when compared to an unsubstituted-PTCDI. The small HOMO-LUMO energy gap allows for switching between electron- and hole-dominated charge transport with a gate voltage, thus demonstrating a single-molecule ambipolar field effect transistor.

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).