Analytical Chemistry Commons^™

Development And Application Of Liquid Chromatography-Tandem Mass Spectrometry Methods To The Understanding Of Metabolism And Cell-Cell Signaling In Several Biological Systems, Jessica Renee Gooding

Doctoral Dissertations

Liquid chromatography tandem mass spectrometry has become a powerful tool for investigating biological systems. Herein we describe the development of both isotope dilution mass spectrometry methods and targeted metabolomics methods for the study of metabolic and cell-cell signaling applications.

A putative yeast enzyme was characterized by discovery metabolite profiling, kinetic flux profiling, transcriptomics and structural biology. These experiments demonstrated that the enzyme shb17 was a sedoheptulose bisphosphatase that provides a thermodynamically dedicated step towards riboneogenesis, leading to the redefinition of the canonical pentose phosphate pathway.

An extension of metabolic profiling and kinetic flux profiling methods was developed for a set …

Advanced Techniques In Mass Spectrometry For Qualitative And Quantitative Protein Characterization, Andrew Boissy Dykstra

Doctoral Dissertations

Though mass spectrometry has earned a central role in the field of proteomics due to its versatility in a wide range of experiments, challenges and complications are still encountered when using mass spectrometry to characterize protein structures, post-translational modifications (PTMs), and abundances. In this dissertation, analytical methods utilizing mass spectrometry have been developed to address challenges associated with both qualitative and quantitative protein characterization. The effectiveness of using multiple pepsin-like proteases, both separately and in mixtures, combined with online proteolysis using a special triaxial probe has been demonstrated on an amyloid beta peptide related to the onset of Alzheimer’s disease. …

Liquid Extraction Based Surface Sampling: Liquid Microjunction Surface Sampling Probes Coupled With Mass Spectrometry, Matthew John Walworth

Doctoral Dissertations

The direct sampling of analytes from surfaces under atmospheric conditions followed by mass spectrometric analysis is an ever expanding area of scientific research. Atmospheric pressure surface sampling and ionization techniques for mass spectrometry (MS) offer the ability to interrogate samples that could not be studied under vacuum conditions required of more traditional MS surface analysis techniques. The geometry and nature of materials or surfaces that can be analyzed has been greatly expanded as a result. This dissertation characterizes and shows applications of liquid microjunction surface sampling probe (LMJ-SSP) electrospray ionization systems. The presented work compares traditional analytical work flows with …

Non-Thermal Plasma Inactivation Of Bacillus Amyloliquefaciens Spores, Yaohua Huang

Masters Theses

Bacterial spores have remarkable resistance to a variety of harsh conditions, causing spoilage in food industry and becoming the primary bacterial agent in biowarfare and bioterrorism. In this study, inactivation mechanisms of Bacillus amyloliquefaciens (BA) spores by non-thermal plasma (NTP) were investigated by using Fourier-transform infrared spectroscopy (FTIR) as a major tool to exam spores after NTP treatment. Chemometric techniques, such as multivariate classification models based on soft independent modeling of Class Analogy (SIMCA) and Principal Component Analysis (PCA), were employed to identify functional group changes in FTIR spectra. The IR absorbance bands correlated to dipicolinic acid (DPA) decreased after …

The Elucidation Of Stationary Phase Treatment Effects In Enantiomeric Separations, Joel Garrett Putnam

Doctoral Dissertations

Acid/base modifiers are sometimes used as additives in the elution on columns packed with amylose tris(3,5-dimethylphenylcarbamate) stationary phase to separate enantiomers. When modifiers are removed from the mobile phase, the stationary phase is affected in ways that are not understood because of the lack of systematic studies, making the scale-up of preparative separations difficult to predict. Once a column has been exposed to these modifiers, the selectivity of certain pairs of enantiomers may change, for the better or the worse. Numerous pairs of molecules affected by this phenomenon are listed in the literature. Five pairs of these molecules were chosen, …

Thermally Robust Ald And Silver Nanocube Based Plasmonic Probe For High Temperature And Microfluidic Sers Measurement, Joshy Francis John

Doctoral Dissertations

Raman spectroscopy is normally a non-destructive, highly selective technique that has become an ubiquitous tool for analytical chemists. One of the primary limitations of Raman spectroscopy, however, is the relatively low cross-section of the technique. With signal enhancements relative to normal Raman scattering as high as 1011, the ultra-trace detection of adsorbates down to the single molecule level has been achieved with SERS. Despite the dramatic improvement in the sensitivity and the high selectivity afforded by the SERS method, the acceptance of SERS as a general analytical tool has been hindered by a lack of stability and reproducibility in the …

Surface-Enhanced Raman Scattering: Substrate Development And Applications In Analytical Detection, Deepak Bhandari

Doctoral Dissertations

To advance the capabilities of surface-enhanced Raman scattering (SERS), we developed a silver modified polypropylene filter (AgPPF) substrate which acts as a pseudo stationary phase in harvesting SERS signatures of so called "phytochemical estrogens" and other environmentally significant chemicals. To augment electron beam lithography (EBL) in SERS research, we also introduced an interesting nanotransfer printing (nTP) technique which could circumvent the low throughput and extremely high resolution (< 10 nm) limitations of EBL in designing advanced SERS substrates. In our study, a nominal average thickness of 10 nm silver on the polypropylene microfiber produced nanoglobules of less than 100 nm in diameter. This noble metal nanoroughened layer allowed AgPPF to serve as a SERS active substrate, onto which the noted endocrine disrupting chemicals were passed through and harvested. The intense, multifeatured vibrational Raman spectra of very rarely SERS studied chemical species collected indicates the potential for useful detection via this approach of creating SERS substrates. AgPPF substrates were also used in characterizing the adsorption behavior of hydroxyl complexes of uranium. Interestingly, hydroxyl group on the uranium complexes showed slow sorption kinetics on the nanostructured silver surfaces. Understanding the adsorption behavior of aqueous solution of uranium on nanostructured silver surfaces has opened up the possibilities of SERS detection of these environmental and non-proliferation concerned species without any surface modifications. nTP is a high resolution printing technique and relies on interfacial chemistries to control the transfer of thin metal film from a "stamp" to a "substrate". In our research, high-aspect-ratio AutoCAD designed nanopatterns were created on silicon wafers using e-beam lithography and reactive ion etching. Silicon relief pillars based stamps were then used to integrate a variety of nanostructures on different dielectric materials. Thus created nanopatterns have shown their promise to hold their inherent SERS activity. For its simplicity, cost-effectiveness, and ease of operation, this hyphenated nTP-SERS technique is impressive in the selection of suitable supporting-films for better SERS enhancements and also to manipulate gap between nanodiscs (gap-plasmonic SERS effect).