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Cyanobacterial blooms are of great concern to the drinking water treatment industry due to their capacity to produce microcystins and other cyanotoxins that are deadly to humans, livestock, pets, and aquatic life at low doses. Unfortunately, the strategies currently employed for cyanotoxin detection involve laborious analyses requiring significant expertise or bioassay kits that are subject to numerous false positives and negatives. These methods are incapable of providing rapid, inexpensive, and robust information to differentiate between the >80 cyanotoxin variants potentially present in an aqueous sample. The use of Raman spectroscopy for identification and quantification of the ubiquitous cyanotoxin microcystin-LR (MC-LR) was examined. Raman spectra readily reflect minute changes in molecular structure, spectra can be collected through water or glass, portable Raman spectrometers are increasingly available, and through surface enhanced Raman spectroscopy (SERS) it is possible to achieve femto or picomolar detection limits for a variety of target species. Drop coating deposition Raman (DCDR) was successfully implemented for quantitation of 2-100 ng of MC-LR deposited in 2 ?L of aqueous sample, even without the use of a specifically designed DCDR substrate or Raman signal enhancements. Reproducible MC-LR Raman spectra were observed for both fresh and aged DCDR samples, and the MC-LR Raman spectrum remained identifiable through a matrix of >80% DOM by mass. DCDR methods show tremendous potential for the rapid, simple, and economical detection of cyanotoxins in environmental matricies at environmentally relevant concentrations. / Master of Science

Parts of human telomere sequences containing at least 4 guanine subsequences show the ability to form intrastrand quadruplexes of remarkable conformational diversity. Former studies using conventional Raman spectroscopy have revealed that the sequence G3(TTAG3)3 at milimolar concentrations in phosphate buffer solution doped with Na+ ions (ionic strength 150 mM) adopts antiparallel conformation regardless of the length of standing at room temperature or annealing, whereas K+ ions cause gradual transition to "3+1" or even parallel conformation. On the other hand, measurements carried out upon sequence AG3(TTAG3)3 at similar concentrations using Photonic Crystal Fibre-enhanced Raman Spectroscopy (PCFRS) suggest that in the respective presence of both Na+ and K+ (ionic strength 100 mM), a parallel structure is adopted. The hereby presented work employs conventional Raman spectroscopy and Drop Coating Deposition Raman spectroscopy to examine the sequence AG3(TTAG3)3 at concentrations ranging from units to hundreds of milimoles in strands. It concludes that the structure adopted in the presence of Na+, resp. K+ ions is antiparallel, resp. "3+1", and doesn't change over time despite both long standing and annealing. Two hypotheses about the cause of the differences between the results obtained by PCFRS and...

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Due to an ever-increasing global population and limited resource availability, there is a constant need for detection of both natural and anthropogenic hazards in water, air, food, and material goods. Traditionally a different instrument would be used to detect each class of contaminant, often after a concentration or separation protocol to extract the analyte from its matrix. Raman spectroscopy is unique in its ability to detect organic or inorganic, airborne or waterborne, and embedded or adsorbed analytes within environmental systems. This ability comes from the inherent abilities of the Raman spectrometer combined with concentration, separation, and signal enhancement provided by drop coating deposition Raman (DCDR) and surface-enhanced Raman spectroscopy (SERS). Herein the capacity of DCDR to differentiate between cyanotoxin variants in aqueous solutions was demonstrated using principal component analysis (PCA) to statistically demonstrate spectral differentiation. A set of rules was outlined based on Raman peak ratios to allow an inexperienced user to determine the toxin variant identity from its Raman spectrum. DCDR was also employed for microcystin-LR (MC-LR) detection in environmental waters at environmentally relevant concentrations, after pre-concentration with solid-phase extraction (SPE). In a cellulose matrix, SERS and normal Raman spectral imaging revealed nanoparticle transport and deposition patterns, illustrating that nanoparticle surface coating dictated the observed transport properties. Both SERS spectral imaging and insight into analyte transport in wax-printed paper microfluidic channels will ultimately be useful for microfluidic paper-based analytical device (𝜇PAD) development. Within algal cells, SERS produced 3D cellular images in the presence of intracellularly biosynthesized gold nanoparticles (AuNP), documenting in detail the molecular vibrations of biomolecules at the AuNP surfaces. Molecules involved in nanoparticle biosynthesis were identified at AuNP surfaces within algal cells, thus aiding in mechanism elucidation. The capabilities of Raman spectroscopy are endless, especially in light of SERS tag design, coordinating detection of analytes that do not inherently produce strong Raman vibrations. The increase in portable Raman spectrometer availability will only facilitate cheaper, more frequent application of Raman spectrometry both in the field and the lab. The tremendous detection power of the Raman spectrometer cannot be ignored. / Ph. D.