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The research in this dissertation presents Pulsed-Laser Excited photothermal studies of optical glasses and cylindrical sample cell. First, a study of a photothermal lens experiment and the finite element analysis modeling for commercial colored glass filters is done. The ideal situation of a semiinfinite cylinder approximate model used to describe the photothermal lens experiment requires the boundary condition that there is no transfer of heat from the glass to surrounding when the glass is excited with a laser. The finite element analysis modeling for photothermal signal with coupling heat with surrounding shows the thermal heat transfer between the glass surface and the coupling fluid. This work shows that the problem can be resolved by using pulsed laser excitation where the signal decay is faster than the heat diffusion to the surrounding, and finite element analysis modeling to correct the likely deviation from semi-infinite cylinder approximate models. Second, finite element analysis modeling of a photothermal lens signal also shows that there are slow and fast components of signals, which are detected by using a fast response detector and is explained to be due to the axial and radial transfer of heat. A semi-analytical theoretical description of the mode-mismatched continuous and pulsedlaser excitation thermal lens effect that accounts for heat coupling both within the sample and out to the surrounding is presented. The results are compared with the finite element analysis solution and found to be an excellent agreement. The analytical model is then used to quantify the effect of the heat transfer from the sample surface to the air coupling fluid on the thermal lens signal. The results showed that the air signal contribution to the total photothermal lens signal is significant in many cases. Third, surface deformation phenomena are quite common when glasses are excited by laser. Finite element analysis modeling of a surface deformation phenomenon is done. A thermal lens reflection experiment is carried out and results are compared with modeling. The effect of coupling fluid on sample is taken in to account to make more accurate measurement of thermophysical properties of solid sample. Fourth, a novel apparatus for performing photothermal lens spectroscopy is described which uses a low-volume cylindrical sample cell with a pulsed excitation laser. Finite element analysis modeling is used to examine the temperature profile and the photothermal signal. The result of finite element analysis is compared with the experimental result. The experimental photothermal lens enhancement has been found to be that predicted from theory within experimental error.

The Southern Ocean is home to two major types of fishes: endemics in the suborder Notothenioidii and representatives of oceanic fish families that are widely distributed in the midwater and benthic environments elsewhere (e.g. bathylagids, myctophids, liparids, and zoarcids) In most regions of the coastal Antarctic, e.g. the Ross Sea, there is a distinct separation in the pelagic communities at the shelf break between the oceanics (off-shelf) and the endemics (on-shelf). Coincidentally, in much of the coastal Antarctic, the shelf break also marks the boundary between a water column entirely composed of the very cold (-2°C ) Ice Shelf Water and an oceanic profile that includes warmer Circumpolar Deep Water (2°C at 200 m) at intermediate depths. The distinct separation in pelagic communities observed in most coastal regions of the Antarctic is not seen on the western Antarctic Peninsula (WAP), where circumpolar deep water intrudes to form a warmer midwater and oceanic species are strongly represented. It was hypothesized that the cold ice-shelf water, lethal to fishes without antifreeze glycoproteins (AFGP's) in their blood, was excluding the oceanic species from most of the Antarctic continental shelf waters. To test the hypothesis, nine species of fish captured in WAP shelf waters were tested for the presence of AFGP's. The oceanic fish families analyzed: Myctophidae (Electrona and Gymnoscopelus), Zoarcidae (Melanostigma), Gempylidae (Paradiplospinus), Paralepididae (Notolepsis), and Bathylagidae (Bathylagus) showed no antifreeze activity. Two endemic species captured in the same sampling program did show antifreeze activity: the important pelagic species Pleuragramma antarcticum (Nototheniidae) and the Bathydraconid (Vomeridens). The absence of AFGP's in the blood of Antarctic oceanic species makes a strong case for temperature exclusion of oceanic fishes in the coastal Antarctic.

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In this thesis, new methods that address some current limitations in nanoelectrospray mass spectrometry (nESI-MS) analysis are presented. One of the major objectives is the potential gain in sensitivity that can be obtained when employing the proposed techniques. In the first part of this thesis, a new emitter, based on the generation of electrospray from a spray orifice with variable size, is presented. Electrospray is generated from an open gap between the edges of two individually mounted, pointed tips. The fabrication and evaluation of two different types of such emitters is presented; an ESI emitter fabricated from polyethylene terephtalate (Paper I), and a high-precision silicon device (Paper II). Both emitters were surface-treated in a selective way for an improved wetting of the gap and to confine the sample solution into the gap. In the second part of this thesis, different methods for improved sensitivity of nESI-MS analysis have been developed. In Paper III, a method for nESI-MS analysis from discrete sample volumes down to 1.5 nL is presented, using commercially available nESI needles. When analyzing attomole amounts of analyte in such a small volume of sample, an increased sensitivity was obtained, compared to when analyzing equal amounts in conventional nESI-MS analysis. To be able to analyze smaller sample volumes, needles with a narrower orifice and a higher flow resistance were needed. This triggered the development of a new method for fabrication of fused silica nESI needles (Paper IV). The fabrication is based on melting of a fused silica capillary by means of a rotating plasma, prior to pulling the capillary into a fine tip. Using the described technique, needles with sub-micrometer orifices could be fabricated. Such needles enabled the analysis of sample volumes down to 275 pL, and a further improvement of the sensitivity was obtained. In a final project (Paper V), nESI-MS was used to study the aggregation behavior of Aβ peptides, related to Alzheimer’s disease. An immunoprecipitation followed by nESI-MS was employed. This technique was also utilized to study the selectivity of the antibodies utilized. / QC 20101112

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