Thesis (Ph. D.)--Hong Kong University of Science and Technology, 2003. / Includes bibliographical references. Also available in electronic version. Access restricted to campus users.

Thesis (Ph.D.)--Hong Kong University of Science and Technology, 2007. / Includes bibliographical references. Also available in electronic version.

Plasmonics can achieve the tight optical confinement and localization in the subwavelength domain. Surface plasmon polaritons (SPPs) are closely related to coupling to emitters in excitation and emission, waveguiding, and active modulating on the nanoscale. Due to these phenomenon, plasmonic nanostructures can be used for applications, such as light emission, photodetection, optical sensing, and spectroscopy. Conventional plasmonic nanostructures can support plasmonic modes, and it is typically optimized for a single wavelength window with planar plasmonic structures. Recent studies have reported some in-plane composite nanostructures and core-shell geometries can induce multiple plasmonic responses. However, it is challenging to achieve the control of individual plasmonic response due to the interdependent spectral tunability with changes in their in-plane geometries. In this dissertation, the concept of out-of-plane engineered nanoantenna structures is introduced, numerically calculated, and experimentally demonstrated. The nanolaminated MIM plasmonic structures show multiresonant plasmonic responses in the same antenna and each wavelength band can be tunable individually with different thicknesses of dielectric layers. The nanolaminated plasmonic structures has been reported for a scalable Surface-enhanced Raman spectroscopy (SERS) substrate for single-molecule sensitive and label-free chemical analysis. Due to the strong optical field confinement, the nanolaminated SERS substrates achieve increased SERS enhancement factor (EF) up to 1.6 x 108 with proper partial etching of dielectric layers. Furthermore, the nanolaminated MIM plasmonic structures have been successfully integrated with micro-scale pillar arrays to control the surface wettability for ultrasensitive SERS measurements. The hierarchical micro/nano plasmonic surface has densely packed intrinsic SERS-active hot spots that give rise to SERS EFs exceeding 107. This platform can take full advantage of low surface energy to control and measure the analyte in water droplets. Leidenfrost evaporation-assisted SERS sensing on the hierarchical substrates provides the way for ultrafast and ultrasensitive biochemical detections without a need for additional surface modifications and chemical treatments. / Doctor of Philosophy / The life in the 21th century has benefited from the technical revolutions of computational power that is based on the manipulation/storage of electrons. As predicted in Moore's law, the size of electronic microchip would go down, and the computational power has been enhanced due to the increase of transistor integration density. However, the two major factors, such as energy dissipation of electrons and signal delay of electronic circuit, limit the communication speed of electronics. These barriers have caused slowdown in the performance of computational power. Photonic solutions have been offered to solve the limitations based on the larger bandwidth and a rare energy dissipation, compared to electronic counterparts. Moreover, optical communications typically demand much lighter channel to deliver similar power/information than practical electrical cables do. Thus, light manipulation/enhancement techniques are envisioned to overcome the limitations and guide to the methodology of interconnections between the electronic circuits and optical platforms. Plasmonics can achieve the nanoscale light confinement and localization in the subwavelength domain. This strong confinement is originated from the coupling between the photons and the electron gas on the metal that results in surface plasmon polariton (SPP). SPPs are closely related to coupling to emitters in excitation and emission, waveguiding, and active modulating on the nanoscale. Due to these phenomenon, plasmonic nanostructures can be used for applications, such as light emission, photodetection, optical sensing, and spectroscopy. In this dissertation, the concept of out-of-plane engineered nanoantenna structures is introduced, numerically calculated, and experimentally demonstrated. This vertically stacked nanoantenna structure is composed of metal-insulator-metal (MIM) laminates fabricated by physical vapor deposition techniques. Although conventional plasmonic nanostructures can support plasmonic modes, it is typically optimized for a single wavelength window. The nanolaminated MIM nanostructures, by contrast, can induce multiresonant plasmonic response in the same antenna with several advantages: (1) reduced individual footprint size and volume of nanoantenna, (2) accurate control of layer thicknesses by thin film deposition technique for resonance tuning, (3) easier integration with other functional materials as gap layers, and (4) efficient transport of charge carriers or heat in nanolaminated layers. As a result of the tight optical field confinement, the nanolaminated plasmonic structures can be used for sensing application called Surface-enhanced Raman spectroscopy (SERS), which is a promising sensing platform for label-free biochemical analysis at the single-molecule level. Partial oxide etching process enables the analyte molecules to accommodate in strong enhancement region of the nanolaminated structures, resulting in amplified unique Raman features of molecular compounds as a finger print. The SERS enhancement factor is increased by one order of magnitude achieving 1.6x108. Furthermore, the nanolaminated plasmonic structures have been integrated with micro-scale pillar arrays to control the surface wettability for ultrasensitive SERS measurements.

Detecting lung cancer is di cult as it is hidden in the body, and current clinical methods are not elective at an early stage; the one-year survival rate after diagnosis in the World is just 29-33%. Acetyl amantadine (AcAm) is recognised as an exogeneous cancer biomarker because it is the product of a metabolic process known to be significantly up-regulated in cancerous cells. After ingestion, the an-tiparkinson and antiviral drug amantadine is acetylated in the body by the enzyme spermidine/spermine N1 acetyltransferase to give AcAm, which can be detected in patient’s urine. However, techniques previously used to quantify AcAm in urine, such as liquid chromatography-mass spectrometry (LC-MS), are undesirable for clin- ical adoption due to high costs and long run times. Further costs and delays result from the requirement for solid phase extraction (SPE). Therefore, it is highly desired to lower the costs and delays in processing by exploring different quantification approaches, ideally without the need for SPE processing. In this thesis, I investigate the use of surface enhanced Raman spectroscopy (SERS) to quantify AcAm in urinalysis. I prepare two kinds of Raman substrates with hydrophobic pocket surface capture agents beta -cyclodextrin (beta -CD) that work to extract the AcAm from the urine, followed by the surface enhanced Raman measurement using two kinds of Raman systems. The detection strategy is more economical than the currently used LC-MS approach, and enables development of an easy-to-use point-of-care tool that should provide a more rapid turnaround to the health care provider. The next step will be to use real samples. If it is achieved, it will be a promising step in early cancer diagnostics. / Graduate

As the developments in nanoscale fabrication and characterization technology, the investigation and applications of light in metal nanostructures have been becoming one of the most focused research areas. Metal materials allow to couple the incident light energy into electromagnetic waves propagating on the metal surface under certain configurations, which is called surface plasmon (SP). This feature tremendously expanded the application possibility of metals in optical regime, such as extraordinary transmission (EOT), near-field optics and surface enhanced spectroscopies. In this talk, various metal structures will be demonstrated which could control SP’s propagation, resonance andlocal field enhancement. A number of SP applications are benefited – the plasmonic bragg reflector (PBR), the frequency sensitive plasmonic microcavity, the subwavelength metallic taper, the long range surface plasmon (LRSP) waveguide and surface enhanced Raman spectroscopy (SERS). Especially for SERS, long-term effort was devoted into it to achieve the single molecule detection limit. / Graduate

Thesis (Ph. D.)--West Virginia University, 1999. / Title from document title page. Document formatted into pages; contains xvii, 169 p. : ill. Vita. Includes abstract. Includes bibliographical references.

Thesis (M.S.)--West Virginia University, 2000. / Title from document title page. Document formatted into pages; contains xi, 81 p. : ill. (some col.). Vita. Includes abstract. Includes bibliographical references.

Thesis (M.Sc.Eng.) / Sepsis is a serious medical condition in which a person becomes infected with bacteria in his or her bloodstream. The symptoms of sepsis are a result of the immune system’s interaction with the infecting agent. Currently, to diagnose a patient with sepsis, a blood sample must be collected and cultured for 24-48 hours before the infection can be confirmed. In the meantime, a broad-scope antibiotic is administered which may or may not be effective in treating the patient. If the antibiotic is ineffective, a different antibiotic must be chosen. When the results of the blood culture are available, a narrow scope antibiotic, appropriate to treat the infection is administered. However, sepsis has a mortality rate of 18-30% depending on the infecting agent and the treatment is highly time sensitive. Within 24 hours, the syndrome may progress to septic shock and mortality rates reach 50%. Therefore, it is important to quickly and correctly identify the infecting agent and provide immediate targeted treatment. Surface Enhanced Raman Spectroscopy (SERS) can be used to quickly identify and distinguish between different bacterial strains; however it requires higher bacterial concentrations than are present in the blood during the early stages of sepsis. A microfluidic evaporator chip has been developed to concentrate bacteria samples from 4μl to 100nl; the chip has been evaluated for concentration efficiency on Escherichia coli and methicillin-sensitive Staphylococcus aureus. Various blocking methods using bovine serum albumin (BSA) have been tested to reduce bacterial adhesion to the chip and have improved bacterial recovery to around 70% for both strains tested. Ongoing tests are being performed to improve bacterial recovery and sample purity for identification. / 2031-01-01

The rational combination of dielectric and metallic nano particles brings novel optical properties to conventional subwavelength structures. This thesis introduces the optoplasmonic geometries demonstrating versatile ability in both far and near field modification within nano scale. Template-assisted self-assembly approaches are applied creating nano entities with titanium dioxide and gold nano spheres. A top-bottom mono hybrid unit and interdigitated array are developed. With the examination of the elastic and inelastic response of these hybrid materials, physical models are simulated to depict the scenario of varied geometry and combination of nano particles. In contrast to solely metal or dielectric particle arrays, this type of artificial material not only enhances the near electric field intensity within the metal nano cluster hot spots, but also expands the overall volume of enhanced electric field. Further study reveals that the additional enhancement and redistribution of near field are derived from the coupling between the nano gold cluster plasmon resonance and the in-plane diffractive mode of the dielectric array. The redirected emission profile of the fluorescent dyes within the hybrid array is explored.

Raman spectroscopy is an extremely versatile technique with molecular sensitivity and fingerprint specificity. However, the translation of this tool into a deployable technology has been stymied by irreproducibility in sample preparation and the lack of complex data analysis tools. In this dissertation, a droplet microfluidic platform was prototyped to address both sample-to-sample variation and to introduce a level of quantitation to surface enhanced Raman spectroscopy (SERS). Shifting the SERS workflow from a cell-to-cell mapping routine to the mapping of tens to hundreds of cells demanded the development of an automated processing tool to perform basic SERS analyses such as baseline correction, peak feature selection, and SERS map generation. The analysis tool was subsequently expanded for use with a multitude of diverse SERS applications. Specifically, a two-dimensional SERS assay for the detection of sialic acid residues on the cell membrane was translated into a live cell assay by utilizing a droplet microfluidic device. Combining single-cell encapsulation with a chamber array to hold and immobilize droplets allowed for the interrogation of hundreds of droplets. Our novel application of computer vision algorithms to SERS maps revealed that sialic sugars on cancer cell membranes are found in small clusters, or islands, and that these islands typically occupy less than 30% of the cell surface area. Employing an opportunistic mindset for the application of the data processing platform, a number of smaller projects were pursued. Biodegradable aliphatic-aromatic copolyesters with varying aromatic content were characterized using Raman spectroscopy and principal component analysis (PCA). The six different samples could successfully be distinguished from one another and the tool was able to identify spectral feature changes resulting from an increasing number of aryl esters. Uniquely, PCA was performed on the 3,125 spectra collected from each sample to investigate point-to-point heterogeneities. A third set of projects evaluated the ability of the data processing tool to calculate spectral ratios in an automated fashion and were exploited for use with nano-pH probes and Rayleigh hot-spot normalization. / Ph. D. / How can we understand the dynamic behavior of the cell membrane? Do certain polymeric structures in biodegradable plastic favor bacterial growth and subsequent degradation? To answer these and other intriguing scientific questions, techniques and technologies must be borrowed from a diverse array of fields and combined with fundamental understanding to create innovative solutions. In this dissertation, a two-dimensional surface enhanced Raman spectroscopy (SERS) assay was translated into a live cell assay by utilizing a droplet microfluidic device. Combining single-cell encapsulation with a chamber array to hold and immobilize droplets allowed for the interrogation of hundreds of droplets. Shifting the SERS workflow from a manual cell-to-cell mapping routine to the mapping of tens to hundreds of cells demanded the development of an automated processing tool to perform basic SERS analyses such as baseline correction, peak feature selection, and SERS map generation. Our novel application of computer vision algorithms to SERS maps was able to reveal that sialic sugars on cancer cell membranes are found in small clusters, or islands, and that these islands typically occupy less than 30% of the cell surface area. With an opportunistic mindset, several smaller projects that combine Raman and SERS with extensive data analysis were also pursued. Biodegradable plastics of varying content were studied with Raman spectroscopy. The aliphatic and aromatic polymeric units within these plastics both contain esters, but it is hypothesized that enzymatic hydrolysis occurs at the units asymmetrically. For each of six different samples, five maps were collected, processed using the analysis tool, and then analyzed using a multivariate analysis toolbox. Principal component analysis (PCA) was used to distinguish the polymers and to identify spectral feature changes resulting from an increasing v number of aryl esters. Uniquely, PCA was performed on the 3,125 spectra collected from each sample to investigate point-to-point heterogeneities. A third set of projects evaluated the ability of the data processing tool to calculate spectral ratios in an automated fashion and it was exploited for use with nano-pH probes and Rayleigh hot-spot normalization