Thesis (Ph. D.)--University of Missouri-Columbia, 1998. / Typescript. Vita. Includes bibliographical references (leaves 134-139). Also available on the Internet.

Thesis (M.S.)--Worcester Polytechnic Institute. / Keywords: clean extinguishing agent; c₆f-ketone; novec 1230; thermal decomposition products; halon alternative. Includes bibliographical references.

MicroNIR is a portable near-infrared diffuse reflection spectroscope. Its suitability for identifying environmental plastic polymers was evaluated through a series of performance tests. The plastic samples were collected during a beach survey in the Caribbean. First a reference database was built by analysing a series of reference plastic polymers. Prediction models were constructed by using principal component analysis (PCA) and cluster analysis on 2D- and 3D-scatterplots. Measurements of samples with a surface area down to 1 mm2 were successfully identified with the prediction models. Blend spectra were created by measuring two polymers simultaneously, from which each polymer NIR-fingerprint were able to be individually extracted from the blend spectra by subtracting the NIR-fingerprint of the opposite polymer. Prediction models were used to identify the samples in the tests with household plastics and the environmental plastic samples, collected in the Caribbean. Out of the forty-eight samples collected forty (83%) were identified. Twenty-seven were identified as polyethylene (56%), eleven as polypropylene (23%), one as polystyrene (2%), and one as polyamide (2%).

This report is exploring the possibility of characterizing hot Jupiter atmospheres using ground-based high-resolution spectroscopy. The ESO CRIRES infrared spectrometer is selected as the observing tool. Simulated observations are computed for known transiting systems. The properties of observations (noise, spectral coverage, resolution) are estimated with the CRIRES Exposure Time Calculator. An inverse method is used for reconstructing the transmission spectra of exoplanetary atmospheres and identifying spectral features. The possibility of using this method for non-transiting systems is examined. Three exoplanets are deemed possible to reconstruct the spectrum of. / Den här rapporten studerar möjligheten att karaktärisera heta Jupiter atmosfärer genom att använda markbaserad högupplöst spektroskopi. ESO:s CRIRES infraröda spektrometer används som observeringsvektyg. Simulerade observationer beräknas för kända system där planeten genomgår en transit. Flera aspekter kring observationer (brus, våglängdstäckning, upplösning) uppskattas med CRIRES Exposure Time Calculator. En invers metod används för att rekonstruera exoplanetatmosfärers transmissionsspektrum och för att identifiera spektraldrag. Möjligheten att använda den här metoden för system utan transit utforskas. Tre exoplaneter antas vara möjliga att rekonstruera spektrat från.

This thesis details research undertaken in the investigation of the open-shell open-shell Van der Waals complexes between nitric oxide (NO) and oxygen (O₂) and between nitrogen dioxide (NO₂ ) and oxygen (O</sub>2</sub> ). The Fourier transform microwave spectroscopy technique was used during the experimental work. Spectra were recorded for a mixture of NO and O₂ over the frequency range 7.0 to 18.2 GHz. Detailed ab initio calculations have been performed on the potential energy surface of both NO-O₂ and NO₂-O₂ using Multi-reference Rayleigh Schrodinger Second Order Perturbation Theory. These calculations were performed for the four distinct states of NO-O₂, ²A", ⁴A", ²A' and ⁴A', and for the two distinct states of NO,sub>2</sub>-O₂, ²A and ⁴A. Predicted rotational spectra have been generated by modelling the systems with a rigid-rotor Hamiltonians. The effective Hamiltonians included the rotational Hamiltonian, ℋ_rot, fine structure terms and hyperfine structure terms. It was not possible, for rationalizable reasons, to fit the predicted spectra for NO-O₂ to the experimental observations. Experimental details, calculation methods and rotational theory are discussed in the main body of the thesis. Predicted spectra, relevant calculations and other data is presented in the appendices.

Η υδροχλωρική δονεπεζίλη (Donepezil.HCl, DPZ) είναι ένα φάρμακο που λαμβάνεται για τη θεραπεία της νόσου Altzheimer. Δρα ως ανασολέας της ακετυλοχοληστερινάσης, ενός ενζύμου υπεύθυνου για την καταστροφή του νευροδιαβιβαστή ακετυλοχολίνη, αυξάνοντας το ποσό της ακετυλοχολίνης στον εγκέφαλο. Παρουσιάζει διάφορες κρυσταλλικές μορφές, συμπεριλαμβανομένων δύο ένυδρων, καθώς και μια άμορφη φάση. Τα δισκία Υδροχλωρικής Δονεπεζίλης λαμβάνονται από το στόμα και μπορεί να αποθηκευθούν για κάποιο χρονικό διάστημα πριν χρησιμοποιηθούν. Τα δισκία DPZ ισχύος 10 mg περιέχουν 3.6 % API, ενώ στις περιπτώσεις όπου λαμβάνει χώρα πολυμορφική μετατροπή, η επιμέρους περιεκτικότητα κάθε πολυμόρφου είναι ακόμα μικρότερη. Η ταυτοποίηση και ποσοτική ανάλυση των πολυμόρφων ή ένυδρων μορφών είναι δυνατή μόνο με τη χρήση περίθλασης ακτίνων Χ και δονητικών φασματοσκοπικών τεχνικών. Λόγω του μικρού ποσοστού της δραστικής ουσίας στα δισκία και της πιθανής παρουσίας περισσοτέρων του ενός πολυμόρφου αλλά και του μεγάλου σχετικά ορίου ανίχνευσης αυτών των τεχνικών η ταυτοποίηση και ποσοτική ανάλυση είναι μια αναλυτική πρόκληση. Στην παρούσα εργασία έγινε προσπάθεια ταυτοποίησης των κρυσταλλικών μορφών του DPZ σε δισκία και έλεγχος της σταθερότητάς τους μετά από διάφορες διαδικασίες παρασκευής των δισκίων, καθώς και μετά από αποθήκευση σε διάφορες συνθήκες υγρασίας και θερμοκρασίας, χρησιμοποιώντας τις πειραματικές τεχνικές XRD, FT-IR και FT-Raman. Παρατηρήθηκε ότι η προέλευση του API, οι συνθήκες αποθήκευσης και κυρίως η μέθοδος παρασκευής των δισκίων επηρεάζουν τη σταθερότητα των φαρμακευτικών σκευασμάτων. Με στόχο τη διερεύνηση της δυνατότητας ανάπτυξης ποσοτικών αναλυτικών μεθόδων προσδιορισμού των πολυμόρφων Ι και ΙΙΙ του DPZ σε δισκία, οι παραπάνω τεχνικές χρησιμοποιήθηκαν για τον υπολογισμό των ορίων ανίχνευσης των δύο πολυμόρφων (0.35% κ.β. για το πολύμορφο Ι και 0.44 % κ.β. για το πολύμορφο ΙΙΙ με την τεχνική Raman, 0.95% κ.β. για το πολύμορφο Ι και 1.3 % κ.β. για το πολύμορφο ΙΙΙ με την τεχνική XRD, 1.2% κ.β. για τη μορφή Ι και 1.0 % κ.β. για τη μορφή ΙΙΙ με την τεχνική IR, όπως προέκυψαν μετά από στατιστική επεξεργασία των πειραματικών δεδομένων των διαφόρων τεχνικών), καθώς και για τον ποσοτικό τους προσδιορισμό. Η τεχνική Raman φαίνεται να μπορεί χρησιμοποιηθεί για ποσοτική ανάλυση των πολυμόρφων Ι και ΙΙΙ του DPZ σε δισκία, ενώ επιπλέον η ποσοτική μέθοδος που παρουσιάσθηκε εδώ είναι απλή και μη καταστροφική για τα δείγματα. Η μέθοδος XRD μπορεί πιθανόν να χρησιμοποιηθεί για την ποσοτική ανάλυση δισκίων DPZ, με μεγαλύτερο όμως σφάλμα σε σύγκριση με την τεχνική Raman, ενώ η μέθοδος FT-IR ATR, παρέχει τα λιγότερο καλά ποσοτικά αποτελέσματα, ακόμα και στην περίπτωση που το δισκίο περιέχει αποκλειστικά το ένα από τα δύο πολύμορφα. Τέλος, με στόχο την ερμηνεία των φασμάτων δόνησης που καταγράφησαν στην παρούσα εργασία, υπολογίστηκαν η σταθερή δομή του μορίου της Δονεπεζίλης και της ένυδρης Δονεπεζίλης (με ένα μόριο νερού ανά μόριο Δονεπεζίλης) και τα φάσματα δόνησης (IR και Raman) με τις μεθόδους Hartree-Fock ab-initio και DFT (Density Functional Theory) και χρήση του υπολογιστικού πακέτου Gaussian09. / Donepezil hydrochloride (DPZ) is a medication used to treat Altzheimer’s disease. It acts as an inhibitor of acetylcholisterinase, an enzyme responsible for the destruction of the neurotransmitter acetylcholine, thus increasing the level of acetylcholine in the brain. As most of the pharmaceutical solids, DPZ exhibits polymorphism. Donepezil hydrochloride has different crystalline forms, including two hydrates, as well as an amorphous phase. DPZ is available for oral administration in tablets which can be stored for some time before use. In the present study, an effort was made to identify the crystal form of DPZ in tablets, as well as to test its stability against time, temperature and humidity, after various manufacturing processes, using XRD, FT-IR and FT-Raman techniques. The data showed that the origin of the API, the storing conditions and mainly the manufacturing process of the tablets affect the stability of the API. Quantitative determination of polymorphs I and III of DPZ in tablets was also attempted using the above experimental methods. Calibration models were constructed and applied in DPZ tablets. The detection limits of polymorphs I and III of DPZ for each technique, derived after statistical treatment of the experimental data, were calculated. Raman spectroscopy exhibited the lower detection limit (0.35 weigh % for polymorph Ι and 0.44 % weigh % for polymorph ΙΙΙ) compared with XRD (0.95% weigh % for polymorph Ι and 1.3 % weigh % for polymorph ΙΙΙ) and IR spectroscopy (1.2% weigh % for polymorph Ι and 1.0 % weigh % for polymorph ΙΙΙ). The data suggest that Raman spectroscopy could be applied to quantify polymorphs I and III in DPZ tablets; moreover, the Raman quantitative method presented in this work is simple and non-destructive for the tablets. The application of the X ray diffraction method for the quantitative analysis of polymorphs I and III in tablets yielded larger errors compared with Raman spectroscopy, while the FT-IR ATR technique yielded poor quantitative results, even in the case that only one polymorph was present in DPZ tablets. Finaly, in order to facilitate the assignment of the vibrational spectra recorded in this study, the optimized structure and the vibrational spectra (IR and Raman) of Donepezil and Donepezil hydrate (Donepezil:H20 = 1:1) molecules were calculated at the Hartree-Fock and DFT (Density Functional Theory) level of theory using the Gaussian 09 program package. The weigh % of the API in the tablets containing 10 mg of DPZ is 3.6 %. In cases where two or more polymorphs are present, the weigh % of each polymorphic form is lower. The difficulty in the identification and quantification of the crystal phase of DPZ is stemming from the small percentage of the API in the tablets, the considerable overlapping of DPZ XRPD patterns and IR and Raman spectra of the polymorphs and the excipients and the availability of various polymorphs.

The potential applicability of Fourier transform infrared (FM) spectroscopy for the study of biomolecules, has been investigated through the investigation of three specific applications. Two of the applications selected involve the classification of whole cells, whereas the third concerns the study of peptides and proteins isolated from tissues as well as synthetic peptides. In the microbiological application, for the differentiation of bacteria on the basis of their FTIR spectra, it has been found that classification is most efficiently achieved through the utilisation of artificial neural networks, and that a wide, variety of bacteria can be correctly identified with minimal sample preparation after being grown on a single growth medium. The suitability of low-cost, disposable materials as supports for the deposition of bacteria samples has also been demonstrated. In contrast to the successful classification of bacteria, it has been found that the examination of cytological smears by FTIR spectroscopy does not allow the classification of cervical cell populations into the recognised diagnostic categories. In a microscopic investigation of the same cell populations utilising infrared imaging, localised areas of the smear were found to exhibit distinct characteristics not observed in the spectra of the entire population. This indicates that infrared imaging system may be required for this type of application because the infrared spectrum recorded from a whole cervical smear does not allow the detection of the small spectral features arising from the molecular changes associated with a localised pathological state. Finally, the investigation of factors affecting the stability of peptides related to amyloidosis has shown that temperatures above 70°C, hydrostatic pressure greater than 6 kbar, and alkaline pH promote the disaggregation of the typical intermolecular beta-sheet structure of amyloid peptides. Peptides utilised as model systems for amyloidosis showed

Infrared light (IR) was first discovered by Friedrich Wilhelm Herschel in 1800. However, until 1940’s, molecular IR studies involved only water and small organic molecules, because of the long measurement times. Development Fourier transform infrared spectroscopy (FTIR) has minimized the time required to obtain data, making it possible to investigate bigger biological systems, e.g. proteins and nucleic acids.This thesis concentrates on the applications of different IR spectroscopic techniques to a variety of biological systems and development of new approaches to study complicated biological events. The first paper in this work concerns using so-called caged compounds to study the aggregation of Alzheimer’s Aβ-peptide which is linked to the formation of neurotoxic fibrils in the brain. By adding caged-sulfate to the Aβ samples we were able to change the pH of the sample, while recording IR data and study fibril formation in a time-resolved manner. Then we used caged–ADP to study the production of ATP and creatine, mediated by creatine kinase (CK). Using CK as a helper enzyme we studied the effects of the phosphate binding on the secondary structure of SR Ca2+ATPse and determined the structural differences between two similar states Ca2E1ADP and Ca2E1ATP. In the second part of the thesis we used ATR-FTIR spectroscopy and a specially designed dialysis setup, to develop a general method to detect ligand binding events by observing the IR absorbance changes in the water hydration shell around the molecules. The same method was used to determine the binding of DNA to the transcription factors of the E2F family. E2F proteins play main part in the gene regulatory networks that control cell development. However how they recognize their DNA-binding sites and the mechanism of binding is not well understood. By using ATR-FTIR, we observed the changes in the secondary structure of the proteins, as well as the distortions to the DNA upon E2F-DNA complex formation. / <p>At the time of the doctoral defense, the following paper was unpublished and had a status as follows: Paper 4: Manuscript.</p>

This thesis presents the design, fabrication, and testing of a micromixing device intended for use in investigating protein dynamics on a microsecond timescale by Fourier transform infrared (FTIR) spectroscopy. Numerical modeling of flow was implemented to predict the influence of flow rates and geometric variations on mixing performance in three passive mixers. The simulation models were validated by experimental measurements using optical and infrared detection. The optimum level of mixing was observed in a multi-lamination mixer that combined thin filaments of differing fluids in an alternating manner. The multi-laminates were transferred onto polished calcium fluoride infrared-transparent optical windows by lithographic processing of an Epon-based polymer, SU-8. A rigid seal between two microchannels was accomplished through thermal bonding of an unexposed resist layer, which acted as a thermal epoxy under the influence of temperature. The multi-lamination mixer was used to study the changes in the secondary structure of beta-Lactoglobulin in deuterated phosphate buffer under varying physicochemical conditions by time-resolved FTIR spectroscopy using focal plane array detection. Upon a pH jump from pH 2 to neutral pH, a gradual loss of alpha-helical content, accompanied by an increase in random coils and turns was observed within 2 ms of mixing. In a second kinetic experiment, mixing of a neutral-pH solution of beta-Lactoglobulin with a 60% trifluoroethanol solution resulted in the formation of an alpha-helical intermediate with an accompanying increase in intramolecular beta-sheet structure within 500 mus of mixing. These results indicate that the multi-lamination mixer designed and fabricated in this study is well suited for investigations of protein dynamics on the micro- to millisecond timescale by time-resolved FTIR spectroscopy.

Despite the documented sensitivity of polar environments, long-term monitoring data are especially sparse in these regions. Diatom-based paleolimnology has contributed significantly to understanding the response of Arctic lakes to climate change, but most studies have been conducted in regions with relatively high lakewater buffering capacity. As such, Pim Island (Nunavut, Canada) is a region of limnological interest because, due to the local geology, its surface waters are of relatively lower pH and previous research suggests that such softwater lakes may be especially responsive to climate fluctuations and therefore provide the best paleoclimate records. This thesis has two separate but related chapters, as well as an exploratory study included in appendix. First, a novel approach using visible-near-infrared spectroscopy (VNIRS) was used to infer lakewater dissolved organic carbon (DOC), from a 160-lake calibration set from the Canadian Arctic. Historically sound and similar trends were reconstructed when compared against a Canadian diatom-based DOC and Swedish VNIRS-based total organic carbon (TOC) model on Arctic Holocene sediment records. Second, a diatom and spectroscopically-based multi-proxy approach was utilized on Holocene sedimentary records from two lakes on Pim Island to assess long-term environmental change from this region. Benthic and epiphytic diatom taxa dominated the pre-19th century assemblages, although marked shifts in dominant species were recorded during the mid-Holocene. The mid-Holocene diatom assemblages underwent an abrupt ecological shift from alkaliphilous Fragilaria sensu lato to slightly acidophilous Achnanthes and Navicula. The post-19th century was characterized by an increase in the planktonic species (Cyclotella radiosa), indicating marked lakeice reductions. Third, the limnological properties and modern diatom assemblages of ponds and lakes surveyed from 1979 to 2009 on Pim Island were examined as part of an exploratory study. The ponds and lakes displayed typical characteristics observed in high Arctic lacustrine environments (i.e. oligotrophic, very dilute) but with overall relatively low alkalinity. Poorly-buffered sites had diatom assemblages that were distinct from well-buffered lakes elsewhere in the High Arctic. Our findings contribute to an improved understanding of the interactions between local environments and limnological changes, and also provide insight on the biological responses of lakes to Holocene environmental change and allow us to compare responses to those in more alkaline sites. / Thesis (Master, Biology) -- Queen's University, 2010-12-22 19:53:45.03