abstract / Physics / Doctoral / Doctor of Philosophy

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The primary focus of the work was to evaluate the capability of intravascular photoacoustic (IVPA) imaging in combination with intravascular ultrasound (IVUS) to detect and differentiate atherosclerotic plaques. The composition rather than structural narrowing of the arteries is a major indicator of the propensity of a vascular lesion to rupture. Consequently, intravascular imaging of these high-risk plaques is required to exactly determine the vulnerable plaque constituents for appropriate follow-up therapy. Our multi-modality imaging approach aims to utilize the high resolution structural assessment abilities of IVUS and the optical contrast of IVPA imaging and is capable of differentiating the lipid, fibrous and fibro-cellular components of an inflammatory lesion. To test the hypothesis, we developed an IVUS catheter based laboratory prototype of a combined IVUS/IVPA imaging system. The performance of the synergistic combination of IVUS and IVPA imaging was evaluated through tissue mimicking phantom studies. Further, to test the ability of the combined imaging to detect plaques, excised samples of an aorta were utilized from a specifically designed animal model of atherosclerosis. Ex-vivo IVPA imaging studies were performed using a 532 nm laser excitation to detect the lipids in the plaque. In addition, multi-wavelength spectroscopic IVPA imaging studies were evaluated to differentiate plaques. Finally, an ultrasound based temperature estimation method was utilized to demonstrate and confirm safety of IVPA imaging for clinical intravascular applications. Upon analysis of the results of our investigation, we believe that IVPA imaging offer numerous potential advantages when integrated with clinical IVUS imaging. The IVUS imaging system with integrated IVPA imaging capability could play a major role in interventional cardiology. / text

M. Tech. Chemistry / Recently, traditional electro-thermal atomic absorption spectrometry has lost its popularity to other multi-element spectrometric techniques. Limited linear determination range, which is usually two orders of magnitude, is one of the reasons for the loss. As a result, tens of calibration standards and diluted samples have become an indispensable part of the electro-thermal atomic absorption spectrometric analysis, particularly if numerous samples containing a broad concentration range of analytes are to be analysed. The objective of this work was to establish the mechanism of absorption signals for high concentrations of analyte atoms in the absorption volume. Secondly, to employ the findings for HR-CS ET-AAS data quantification, within a broad range of analyte concentrations. It was expected that the sought algorithm would permit the use of the most sensitive analytical lines or those less prone to interferences, independent of the concentration of the respective analyte in the sample.

Vibrational spectra techniques such as IR, Raman and SFG all carry molecular orientation information. Extracting the orientation information from the vibrational spectra often involves creating model spectra with known orientation details to match the experimental spectra. The running time for the exhaustive approach is O(n!). With the help of linear programming, the running time is pseudo O(n). The linear programming approach is with out a doubt far more superior than exhaustive approach in terms of running time. We verify the accuracy of the answer of the linear programming approach by creating mock experimental data with known molecular orientation distribution information of alanine, isoleucine, methionine, lysine, valine and threonine. Linear programming returns the correct orientation distribution information when the mock experimental spectrum consisted of different amino acids. As soon as the mock experimental spectrum consisted of same amino acids, different conformer with different orientation distribution, linear programming fails to give the correct answer albeit the species population is roughly correct. / Graduate

Conjugated polymers are widely used and rapidly developed in practical polymer-based light-emitting electronic devices. Understanding the electrochemical reaction of conjugated polymer has become essential in the design and operation of devices such as electrochemical light-emitting diodes. In particular, we have studied the dynamics and kinetics of oxidation/reduction behavior of conjugated polymer single-molecules and nanoparticles in order to obtain the molecular level properties of deeply trapped holes in organic semiconductor devices. Theoretical calculations suggest the penetration of ions and solvent molecules effectively stabilizes the injected charges, which allows homogeneous charge distribution and further hole injection. The formation and decay of deep traps have been explored by changing the charging rate and duration. We found that the laser excitation significantly promotes the untrapping of deep holes. Electrogenerated chemiluminescence of single nanoparticles has been investigated to unravel the effects due to particle heterogeneity, which are masked in bulk electrochemical studies of nanoparticles. Bigger particles showed more intense light and longer duration time than smaller ones. Co-reactant, tripropylamine can facilitate the formation of electrogenerated chemiluminescence as well as alleviate the polymer oxidation and following irreversible electrochemical reaction. Electrochemically generated light waves from the conjugated polymer thin films have been visualized to obtain microscopic level understanding on the complex reaction mechanism. Electrochemical reaction occurs at local defects and propagates isotropically over macroscopic distances with a sharp wave front. The initially injected holes (oxidized polymers) drag counter-ions into the film, thereby induce a phase-transition-like swelling that enhances transport of ions and solvent and move forward the double layer and corresponding propagation of the wave. / text

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published_or_final_version / abstract / toc / Applied Geosciences / Master / Master of Science