No description available.

No description available.

No description available.

This work examines the use of supercritical fluid extraction (SFE)as a sample introduction technique for supercritical fluid chromatography (SFC) and Fourier transform infrared spectrometry (FT-IR). In order to study the effects of a supercritical mobile phase on the resulting IR spectra, carbon dioxide was compared to xenon as a supercritical fluid mobile phase for flow cell SFC/FT-IR. A packed capillary column (30 cm x 320 μm, Deltabond® Cyano, 5 μm particle) was employed for the chromatographic portion of the study. Various samples were tested, such as an ethoxylated alcohol mixture and a unique polarity mix. The roles of temperature and density on the IR spectra were also examined as each was independently varied for the analysis of five different probe compounds. Comparisons of spectra produced in supercritical CO₂ and xenon each matched well with the Nicolet vapor phase library. CO₂ spectra matched the vapor phase spectra equally as well as did the xenon spectra, despite the fact that CO₂ spectra have blanked regions where the mobile phase absorbs in the IR. Following this study, SFE was coupled directly to FT-IR to produce the novel method of on-line SFE/FT-IR. This technique was optimized for the analysis of n-tetracosane, yielding a detection limit of 74 ng. The method was later applied to the quantitative and qualitative analysis of fiber finishes from textile matrices with equivalent success. Finish was extracted directly from the fiber or textile surface and passed through the IR flow cell as an analyte "plug". In this way, the entire finish was quickly quantified, and if desired, qualitatively analyzed as well, without need of prior chromatographic separation. The method required no organic solvent and was proven to be fairly reproducible for four fiber finish types tested. Lastly, supercritica1 fluid extraction (SFE) was examined and optimized as a sample introduction technique for on-line SFE/SFC. Trapping and recovery of analytes in SFE/SFC were studied under varying conditions using a currently marketed system. The system was replumbed using a 12 cm x 100 μm fused silica capillary (100% methyl, d_f = 0.25 μm) for trapping and increased solute focusing. These changes nearly doubled the total analyte recovery (as based on FID peak areas) and lowered the overall system recovery RSDs from 30 % to 4 %. / Ph. D.

El diagnóstico final de la mayoría de tipos de cáncer lo realiza un médico experto en anatomía patológica que examina muestras tisulares o celulares sospechosas extraídas del paciente. Actualmente, esta evaluación depende en gran medida de la experiencia del médico y se lleva a cabo de forma cualitativa mediante técnicas de imagen tradicionales como la microscopía óptica. Esta tarea tediosa está sujeta a altos grados de subjetividad y da lugar a niveles de discordancia inadecuados entre diferentes patólogos, especialmente en las primeras etapas de desarrollo del cáncer. La espectroscopía infrarroja por Transformada de Fourier (siglas FTIR en inglés) es una tecnología ampliamente utilizada en la industria que recientemente ha demostrado una capacidad creciente para mejorar el diagnóstico de diferentes tipos de cáncer. Esta técnica aprovecha las propiedades del infrarrojo medio para excitar los modos vibratorios de los enlaces químicos que forman las muestras biológicas. La principal señal generada consiste en un espectro de absorción que informa sobre la composición química de la muestra iluminada. Los microespectrómetros FTIR modernos, compuestos por complejos componentes ópticos y detectores matriciales de alta sensibilidad, permiten capturar en un laboratorio de investigación común imágenes hiperespectrales de alta calidad que aúnan información química y espacial. Las imágenes FTIR son estructuras de datos ricas en información que se pueden analizar individualmente o junto con otras modalidades de imagen para realizar diagnósticos patológicos objetivos. Por lo tanto, esta técnica de imagen emergente alberga un alto potencial para mejorar la detección y la graduación del riesgo del paciente en el cribado y vigilancia de cáncer. Esta tesis estudia e implementa diferentes metodologías y algoritmos de los campos interrelacionados de procesamiento de imagen, visión por ordenador, aprendizaje automático, reconocimiento de patrones, análisis multivariante y quimiometría para el procesamiento y análisis de imágenes hiperespectrales FTIR. Estas imágenes se capturaron con un moderno microscopio FTIR de laboratorio a partir de muestras de tejidos y células afectadas por cáncer colorrectal y de piel, las cuales se prepararon siguiendo protocolos alineados con la práctica clínica actual. Los conceptos más relevantes de la espectroscopía FTIR se investigan profundamente, ya que deben ser comprendidos y tenidos en cuenta para llevar a cabo una correcta interpretación y tratamiento de sus señales especiales. En particular, se revisan y analizan diferentes factores fisicoquímicos que influyen en las mediciones espectroscópicas en el caso particular de muestras biológicas y pueden afectar críticamente su análisis posterior. Todos estos conceptos y estudios preliminares entran en juego en dos aplicaciones principales. La primera aplicación aborda el problema del registro o alineación de imágenes hiperespectrales FTIR con imágenes en color adquiridas con microscopios tradicionales. El objetivo es fusionar la información espacial de distintas muestras de tejido medidas con esas dos modalidades de imagen y centrar la discriminación en las regiones seleccionadas por los patólogos, las cuales se consideran más relevantes para el diagnóstico de cáncer colorrectal. En la segunda aplicación, la espectroscopía FTIR se lleva a sus límites de detección para el estudio de las entidades biomédicas más pequeñas. El objetivo es evaluar las capacidades de las señales FTIR para discriminar de manera fiable diferentes tipos de células de piel que contienen fenotipos malignos. Los estudios desarrollados contribuyen a la mejora de métodos de decisión objetivos que ayuden al patólogo en el diagnóstico final del cáncer. Además, revelan las limitaciones de los protocolos actuales y los problemas intrínsecos de la tecnología FTIR moderna, que deberían abordarse para permit / The final diagnosis of most types of cancers is performed by an expert clinician in anatomical pathology who examines suspicious tissue or cell samples extracted from the patient. Currently, this assessment largely relies on the experience of the clinician and is accomplished in a qualitative manner by means of traditional imaging techniques, such as optical microscopy. This tedious task is subject to high degrees of subjectivity and gives rise to suboptimal levels of discordance between different pathologists, especially in early stages of cancer development. Fourier Transform infrared (FTIR) spectroscopy is a technology widely used in industry that has recently shown an increasing capability to improve the diagnosis of different types of cancer. This technique takes advantage of the ability of mid-infrared light to excite the vibrational modes of the chemical bonds that form the biological samples. The main generated signal consists of an absorption spectrum that informs of the chemical composition of the illuminated specimen. Modern FTIR microspectrometers, composed of complex optical components and high-sensitive array detectors, allow the acquisition of high-quality hyperspectral images with spatially-resolved chemical information in a common research laboratory. FTIR images are information-rich data structures that can be analysed alone or together with other imaging modalities to provide objective pathological diagnoses. Hence, this emerging imaging technique presents a high potential to improve the detection and risk stratification in cancer screening and surveillance. This thesis studies and implements different methodologies and algorithms from the related fields of image processing, computer vision, machine learning, pattern recognition, multivariate analysis and chemometrics for the processing and analysis of FTIR hyperspectral images. Those images were acquired with a modern benchtop FTIR microspectrometer from tissue and cell samples affected by colorectal and skin cancer, which were prepared by following protocols close to the current clinical practise. The most relevant concepts of FTIR spectroscopy are thoroughly investigated, which ought to be understood and considered to perform a correct interpretation and treatment of its special signals. In particular, different physicochemical factors are reviewed and analysed, which influence the spectroscopic measurements for the particular case of biological samples and can critically affect their later analysis. All these knowledge and preliminary studies come into play in two main applications. The first application tackles the problem of registration or alignment of FTIR hyperspectral images with colour images acquired with traditional microscopes. The aim is to fuse the spatial information of distinct tissue samples measured by those two imaging modalities and focus the discrimination on regions selected by the pathologists, which are meant to be the most relevant areas for the diagnosis of colorectal cancer. In the second application, FTIR spectroscopy is pushed to their limits of detection for the study of the smallest biomedical entities. The aim is to assess the capabilities of FTIR signals to reliably discriminate different types of skin cells containing malignant phenotypes. The developed studies contribute to the improvement of objective decision methods to support the pathologist in the final diagnosis of cancer. In addition, they reveal the limitations of current protocols and intrinsic problems of modern FTIR technology, which should be tackled in order to enable its transference to anatomical pathology laboratories in the future. / El diagnòstic final de la majoria de tipus de càncer ho realitza un metge expert en anatomia patològica que examina mostres tissulars o cel¿lulars sospitoses extretes del pacient. Actualment, aquesta avaluació depèn en gran part de l'experiència del metge i es porta a terme de forma qualitativa mitjançant tècniques d'imatge tradicionals com la microscòpia òptica. Aquesta tasca tediosa està subjecta a alts graus de subjectivitat i dóna lloc a nivells de discordança inadequats entre diferents patòlegs, especialment en les primeres etapes de desenvolupament del càncer. L'espectroscòpia infraroja per Transformada de Fourier (sigles FTIR en anglès) és una tecnologia àmpliament utilitzada en la indústria que recentment ha demostrat una capacitat creixent per millorar el diagnòstic de diferents tipus de càncer. Aquesta tècnica aprofita les propietats de l'infraroig mitjà per excitar els modes vibratoris dels enllaços químics que formen les mostres biològiques. El principal senyal generat consisteix en un espectre d'absorció que informa sobre la composició química de la mostra il¿luminada. Els microespectrómetres FTIR moderns, compostos per complexos components òptics i detectors matricials d'alta sensibilitat, permeten capturar en un laboratori d'investigació comú imatges hiperespectrals d'alta qualitat que uneixen informació química i espacial. Les imatges FTIR són estructures de dades riques en informació que es poden analitzar individualment o juntament amb altres modalitats d'imatge per a realitzar diagnòstics patològics objectius. Per tant, aquesta tècnica d'imatge emergent té un alt potencial per a millorar la detecció i la graduació del risc del pacient en el cribratge i vigilància de càncer. Aquesta tesi estudia i implementa diferents metodologies i algoritmes dels camps interrelacionats de processament d'imatge, visió per ordinador, aprenentatge automàtic, reconeixement de patrons, anàlisi multivariant i quimiometria per al processament i anàlisi d'imatges hiperespectrals FTIR. Aquestes imatges es van capturar amb un modern microscopi FTIR de laboratori a partir de mostres de teixits i cèl¿lules afectades per càncer colorectal i de pell, les quals es van preparar seguint protocols alineats amb la pràctica clínica actual. Els conceptes més rellevants de l'espectroscòpia FTIR s'investiguen profundament, ja que han de ser compresos i tinguts en compte per dur a terme una correcta interpretació i tractament dels seus senyals especials. En particular, es revisen i analitzen diferents factors fisicoquímics que influeixen en els mesuraments espectroscòpiques en el cas particular de mostres biològiques i poden afectar críticament la seua anàlisi posterior. Tots aquests conceptes i estudis preliminars entren en joc en dues aplicacions principals. La primera aplicació aborda el problema del registre o alineació d'imatges hiperespectrals FTIR amb imatges en color adquirides amb microscopis tradicionals. L'objectiu és fusionar la informació espacial de diferents mostres de teixit mesurades amb aquestes dues modalitats d'imatge i centrar la discriminació en les regions seleccionades pels patòlegs, les quals es consideren més rellevants per al diagnòstic de càncer colorectal. En la segona aplicació, l'espectroscòpia FTIR es porta als seus límits de detecció per a l'estudi de les entitats biomèdiques més xicotetes. L'objectiu és avaluar les capacitats dels senyals FTIR per discriminar de manera fiable diferents tipus de cèl¿lules de pell que contenen fenotips malignes. Els estudis desenvolupats contribueixen a la millora de mètodes de decisió objectius que ajuden el patòleg en el diagnòstic final del càncer. A més, revelen les limitacions dels protocols actuals i els problemes intrínsecs de la tecnologia FTIR moderna, que haurien d'abordar per permetre la seva transferència als laboratoris d'anatomia patològica en el futur. / Peñaranda Gómez, FJ. (2018). Application of artificial vision algorithms to images of microscopy and spectroscopy for the improvement of cancer diagnosis [Tesis doctoral]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/99748

Thesis (MSc (Chemistry and Polymer Science))--University of Stellenbosch, 2005. / Two cationic polymerizable surfactants (surfmers), (11-acryloyloxyundecyl)dimethyl-(2-hydroxyethyl)ammonium bromide (Ethanol surfmer) and (11-acryloyloxyundecyl)-dimethylethylammonium bromide (Ethyl surfmer) were synthesized and characterized. Characterization was done using, conductivity, Fourier transform infra-red spectroscopy (FT-IR), electrospray mass spectrometry (ESMS), differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), small angle X-ray scattering (SAXS) and polarized light microscopy with a heating stage. These surfmers and the commercial surfactant cetyltrimethylammonium bromide (CTAB) were used for functionalization of sodium montmorillonite (Na+-MMT), thereby forming organophilic MMT. The functionalization of MMT dispersions was carried out by ion exchange of the sodium ions in Na+-MMT by surfactants in aqueous media. Organophilic MMT clays were then dispersed in styrene and subsequently polymerized by a free radical reaction to yield polystyrene-clay nanocomposites. This in-situ intercalative polymerization process resulted in an exfoliated structure for Ethyl surfmer modified clay, a partially exfoliated structure for Ethanol surfmer modified clay and an intercalated structure for CTAB modified clay. These nanocomposite structures were confirmed by SAXS and transmission electron microscopy (TEM). The nanocomposites exhibited enhanced thermal stability. All the nanocomposites exhibited an inferior storage modulus (GI) at low clay contents relative to polystyrene. At higher clay loadings there was an increase in GI which was dependent on the level of clay dispersion and the clay content. All the nanocomposites showed an increase in glass transition temperature (Tg), regardless of the amount of clay and the level of clay dispersion. There was a shift towards higher temperatures and broadening of the tan δ peak, which was in turn dependent on the amount of clay and level of clay dispersion. Molecular masses of polystyrene-clay nanocomposites were in the range 105 g/mol for bulk polymerization relative to 103 g/mol for solution polymerization as revealed by gel permeation chromatography (GPC).

Thesis (MSc (Chemistry and Polymer Science))--University of Stellenbosch, 2005. / This thesis begins with the description of the preparation of thirteen dithioesters (of the form Z- (C=S)-S-R) which were characterized via Fourier-transform infrared spectroscopy (FT-IR), nuclear magnetic resonance spectroscopy (NMR) and ultraviolet spectroscopy (UV). The dithioesters were then used as reversible addition-fragmentation chain transfer (RAFT) mediating agents in the bulk polymerization of styrene, in order to observe differences in the kinetic behaviour of the polymerizations and, as a result, the efficiencies of the dithioesters in mediating the polymerizations.

Thesis (MSc (Wine Biotechnology))--University of Stellenbosch, 2009. / ENGLISH ABSTRACT: Fermentation is a complex process in which raw materials are transformed into high-value products, in this case, grape juice into wine. In this modern and economically competitive society, it is increasingly important to consistently produce wine to definable specifications and styles. Process management throughout the production stage is therefore crucial to achieve effective control over the process and consistent wine quality. Problematic wine fermentations directly impact on cellar productivity and the quality of wine. Anticipating stuck or sluggish fermentations, or simply being able to foresee the progress of a given fermentation, would be extremely useful for an enologist or winemaker, who could then take suitable corrective steps where necessary, and ensure that vinifications conclude successfully. Conventional methods of fermentation monitoring are time consuming, sometimes unreliable, and the information limited to a few parameters only. The current effectiveness of fermentation monitoring in industrial wine production can be much improved. Winemakers currently lack the tools to identify early signs of undesirable fermentation behaviour and to take preventive actions. This study investigated the application of Fourier transform mid infrared (FT-IR) spectroscopy in transmission mode, for the quantitative and qualitative monitoring of alcoholic fermentation during industrial wine production. The major research objectives were firstly to establish a portfolio of quantitative calibration models suitable for quantification of the major quality determining parameters in fermenting must. The second major research objective focused on a pilot study aimed at exploring the use of off-line batch multivariate statistical process control (MSPC) charts for actively fermenting must. This approach used FT-IR spectra only, for the purpose of qualitative monitoring of alcoholic fermentation in industrial wine production. Towards these objectives, a total of 284 industrial-scale, individual, actively fermenting tanks of the seven major white cultivars and blends, and nine major red cultivars, of Namaqua Wines, Vredendal, South Africa, were sampled and analysed with FT-IR spectroscopy and appropriate reference methods during vintages 2007 to 2009. For the quantitative strategy, partial least squares regression (PLS1) calibration models for determination of the classic wine parameters ethanol, pH, volatile acidity (VA), titratable acidity (TA) and the total content of glucose plus fructose, were redeveloped to provide a better fit to local South African samples. New PLS1 models were developed for the must components glucose, fructose and yeast assimilable nitrogen (YAN), all of which are frequently implicated in problem fermentations. The regression statistics, that included the standard error of prediction (SEP), coefficient of determination (R2) and bias, were used to evaluate the performance of the redeveloped calibration models on local South African samples. Ethanol (SEP = 0.15 %v/v, R2 = 0.999, bias = 0.04 %v/v) showed very good prediction and with a residual predictive deviation (RPD) of 30, rendered an excellent model for quantitative purposes in fermenting must. The models for pH (SEP = 0.04, R2 = 0.923, bias = -0.01) and VA (SEP = 0.07 g/L, R2 = 0.894, bias = -0.01 g/L) with RPD values of 4 and 3 respectively, showed that the models were suitable for screening purposes. The calibration model for TA (SEP = 0.35 g/L, R2 = 0.797, bias = -0.004 g/L) with a RPD of 2, proved unsatisfactory for quantification purposes, but reasonable for screening purposes. The calibration model for the total content of glucose plus fructose (SEP = 0.6.19 g/L, R2 = 0.993, bias = 0.02 g/L) with a RPD of 13, showed very good prediction and can be used to quantify total glucose plus fructose content in fermenting must. The newly developed calibration models for glucose (SEP = 4.88 g/L, R2 = 0.985, bias = -0.31 g/L) and fructose (SEP = 4.14 g/L, R2 = 0.989, bias = 0.64 g/L) with RPD values of 8 and 10 respectively, also proved fit for quantification of these important parameters. The new calibration models of ethanol, total glucose plus fructose; and glucose and fructose individually, showed an excellent relation to local South African samples and can be easily implemented by the wider wine industry. Two calibration models were developed to determine YAN in fermenting must by using different reference methods, namely the enzyme-linked spectrophotometric assay and Formol titration method, respectively. The results showed that enzyme-linked assays provided a good quantitative model for white fermenting must (SEP = 14.10 mg/L, R2 = 0.909, bias = -2.55 mg/L, RPD = 6), but the regression statistics for predicting YAN in red fermenting must, were less satisfactory (data not shown). The Formol titration method could be used successfully in both red- and white fermenting must (SEP = 16.37 mg/L, R2 = 0.912, bias = -1.01 mg/L, RPD = 4). A minor, but very important finding was made with respect to the storage of must samples that were taken from tanks, but that could not immediately be analysed with FT-IR spectroscopy or reference values. Principal component analysis (PCA) of frozen samples showed that must samples could be stored frozen for up to 3 months and still be used to expand the calibration sample sets when needed. Therefore, samples can be kept frozen to a later stage if immediate analyses are not possible. For the purpose of the pilot study that focused on the use of FT-IR spectroscopy for qualitative off-line monitoring of alcoholic fermentation, a total of 21 industrial-scale fermentation tanks were monitored at 8- or 12-hourly intervals, from the onset of fermentation to complete consumption of the grape sugars. This part of the work excluded quantitative data, and only used FT-IR spectra. MSPC charts were constructed on the PLS scores of all the FT-IR spectra taken at the various time intervals of the different batches, using time as the y-variable. The primary aim of this research objective was to evaluate if the PLS batch models could be used to discriminate between normal and problem alcoholic fermentations. The models that were constructed clearly showed the variations in patterns over time, between red- and white wine alcoholic fermentations. One Colombar tank that was fermented at very low temperature in order to achieve a specific wine style, was characterised by a fermentation pattern that clearly differed form the rest of the Colombar fermentations. This atypical fermentation was identified by the batch models constructed in this study. PLS batch models over all the Colombar fermentations clearly identified the normal and problem fermentations. The results obtained in this study showed that FT-IR spectroscopy showed great potential for effective quantitative and qualitative monitoring of alcoholic fermentation during industrial wine production. The work done in this project resulted in the development of a portfolio of calibration models for the most important quality determining parameters in fermenting must. The quantitative models were subjected to extensive independent test set validation, and have subsequently been implemented for industrial use at Namaqua Wines. Multivariate batch monitoring models were established that show good discriminatory power to detect problem fermentations. This is a very useful diagnostic tool that can be further developed by monitoring more normal and problem fermentations. Future work in this regard, will focus on further optimisation and expansion of the quantitative and qualitative calibration models and implementation of these in the respective wineries of Namaqua Wines. / AFRIKAANSE OPSOMMING: Fermentasie is ‘n komplekse proses waartydens rou material getransformeer word na produkte van hoë waarde, in hierdie geval, druiwesap na wyn. In die huidige ekonomies-kompeterende samelewing, is dit al hoe meer belangrik om volhoubaar wyn te produseer wat voldoen aan definieerbare spesifikasies en style. Goeie prosesbestuur tydens die wynproduksie stadium is baie belangrik om herhaalbaarheid en gehaltebeheer te verseker. Problematiese wynfermentasies het ’n direkte impak op beide kelderproduktiwiteit en wynkwaliteit. Die voorkoming van slepende- of steekfermentasies, of selfs net om probleme te voorsien, sou uiters bruikbaar wees vir ‘n wynkundige of wynmaker, wat dan die toepaslike regstellende stappe kan neem waar nodig, om te verseker dat die wynbereiding suksesvol voltooi word. Konvensionele metodes van monitering van alkoholiese fermentasie is tydrowend, soms onbetroubaar en die inligting beperk tot ‘n paar parameters. Die huidige effektiwiteit van fermentasie monitering in industriële wynproduksie kan heelwat verbeter word. Wynmakers ervaar tans ’n behoete aan tegnologië wat die vroeë tekens van ongunstige fermentasiepatrone kan identifiseer, en hul doeltreffendheid om moontlike regstellende aksies te neem, is dus beperk. Hierdie studie het die toepassing van Fourier transformasie mid-infrarooi (FT-IR) spektroskopie in transmissie, ondersoek met die oog op kwantitatiewe en kwalitatiewe monitering van alkoholiese gisting tydens industriële wynproduksie. Die vernaamste navorsingsdoelwitte was eerstens om ’n portefeulje van kwantitatiewe kalibrasiemodelle te vestig, wat geskik is om die belangrikste kwaliteitsbepalende parameters in gistende mos te kwantifiseer. Die tweede hoofnavorsingsdoelwit was ’n loodsstudie wat ondersoek ingestel het na die opstel van multiveranderlike statistiese proseskontrole grafieke van aktief-gistende mos, met die oog op aflyn-kwalitatiewe monitering van alkoholiese gisting in industriële wynproduksie. Hiervoor is slegs FT-IR spektra gebruik. Vir die doel van hierdie studie is monsters van ’n totaal van 284 individuele, aktief-gistende tenke van die sewe hoof wit kultivars en hul versnydings en nege hoof rooi kultivars van Namaqua Wyne, Vredendal, Suid Afrika, geneem. Al die monsters is met toepaslike chemiese metodes en FT-IR spektroskopie analiseer tydens die parsseisoene van 2007 tot 2009. Vir die kwantitatiewe strategie is parsiële kleinste kwadraat (PKK1) kalibrasiemodelle vir die bepaling van die klassieke wynparameters etanol, pH, vlugtige suur (VS), titreerbare suur (TS) en die totale konsentrasie van glukose plus fruktose herontwikkel, om beter te pas op plaaslike Suid-Afrikaanse monsters. Nuwe PKK1 kalibrasiemodelle is ontwikkel vir die komponente glukose, fruktose en gis-assimileerbare stikstof, aangesien hierdie komponente gereelde aanduidings van probleemgisting is. Die regressiestatistieke het die standaardvoorspellingsfout (SVF), bepalingskoëffisiënt (R2) en sydigheid ingesluit en was gebruik om die prestasie van die herontwikkelde kalibrasiemodelle vir plaaslike Suid-Afrikaanse monsters te evalueer. Etanol (SVF = 0.15 %v/v, R2 = 0.999, sydigheid = 0.04 %v/v) het baie goeie regressiestatistiek getoon en met ‘n relatiewe voorspellingsafwyking (RVA) van 30, was dit ‘n uitstekende model vir kwantifisering in gistende mos. Die modelle vir pH en VS met RVA waardes van 4 en 3 onderskeidelik, is geskik vir semi-kwantitatiewe toepassings. Die kalibrasiemodel vir TS met ‘n RVA waarde van 2, was nie geskik vir akkurate kwantifisering nie, maar wel vir semikwantitatiewe analises. Die kalibrasiemodel vir die totale glukose plus fruktose inhoud in gistende mos, met ‘n RVA waarde van 13, het uitstekende regressiestatistiek gegee en is geskik vir akkurate kwantifiseringsdoeleindes. Die nuut-ontwikkelde kalibrasiemodelle vir glukose en fruktose, met RVA waardes van onderskeidelik 8 en 10, is geskik vir akkurate kwantifisering van hierdie belangrike parameters. Die kalibrasiemodelle vir etanol, totale glukose plus fruktose, en glukose en fruktose afsonderlik, het uitstekende korrelasies getoon met plaaslike Suid-Afrikaanse monsters en is gereed om toepassing te vind in die wyer wynindustrie. Twee kalibrasiemodelle is ontwikkel om gis-assimileerbare stikstof in gistende mos te bepaal, deur gebruik te maak van verskillende verwysingsmetodes van analise; hierdie metodes was ‘n ensiem-gekoppelde spektrofotometriese toets en die Formoltitrasie metode. Resultate het getoon dat goeie regressiestatistiek vir FT-IR spektroskopie-gebaseerde kalibrasiemodelle waar data wat met die ensiem-gekoppelde toetse verkry is, as verwysingwaardes gebruik is, in wit gistende mos (SVP = 14.10 mg/L, R2 = 0.909, sydigheid = -2.55 mg/L, RVA = 6), maar nie in rooi gistende mos nie. Die Formoltitrasie metode as verwysingsmetode, was geskik vir die ontwikkeling van goeie kalibrasiemodelle in beide rooi- en wit gistende mos (SVP = 16.37 mg/L, R2 = 0.912, sydigheid = -1.01 mg/L, RVA = 4). ’n Sekondêre, maar baie belangrike bevinding is gemaak met betrekking tot die stoor van mosmonsters wat geneem is van tenke, maar wat nie dadelik met die verwysingsmetodes en FT-IR spektroskopie analiseer kon word nie. Multiveranderlike hoofkomponentanalise op vars en gevriesde sapmonsters het getoon dat gevriesde monsters gebruik kan word om die kalibrasie datastel uit te brei, wanneer benodig. Dus, sapmonsters kan gevries word tot ’n later stadium as onmiddelike analises nie moontlik is nie. Vir die doel van die tweede navorsingsdoelwit van die studie, naamlik kwalitatiewe af-lyn monitering van alkoholiese fermentasie met FT-IR spektroskopie, is ‘n totaal van 21 industriëlegrootte fermentasietenks ge-monitor deur sapmonsters met 8- tot 12-uurlikse intervalle te trek, vanaf die begin van fermentasie, totdat al die druifsuiker gemetaboliseer is. Vir hierdie deel van die werk is die kwantitatiewe data nie gebruik nie; slegs die FT-IR spektra. Multiveranderlike statistiese proseskontrole grafieke is opgestel op grond van die PKK tellings wat bereken is op al die FT-IR spektra wat gemeet is by die verskillende tydsintervalle. Vir hierdie analise is tyd as y-veranderlike gebruik. Die vernaamste doel van hierdie ondersoek was om te evalueer of die PKK-gebaseerde modelle kon onderskei tussen normale en slepende gistings. Die modelle wat verkry is, het die variasie oor tyd in die fermentasiepatrone tussen wit- en rooiwyn fermentasies tydens alkoholiese gisting, duidelik uitgewys. Een Colombar tenk wat teen baie lae temperatuur gefermenteer is om ‘n spesifieke wynstyl te verkry, se fermentasiepatroon het aansienlik verskil van die ander Colombar tenks wat gemonitor is, en hierdie atipiese patroon is ook deur die kwalitatiewe modelle identifiseer. ‘n PKK model oor al die Colombar fermentasies kon duidelik tussen normale en slepende gistings onderskei. Die resultate wat in hierdie studie verkry is, het getoon dat FT-IR spektroskopie baie goeie potensiaal toon vir die aanwending van kwantitatiewe en kwalitatiewe monitering van alkoholiese fermentasie tydens industriële wynproduksie. Die werk wat in hierdie projek gedoen is, het gelei tot die vestiging van ‘n portefeulje van kalibrasiemodelle vir die belangrikste kwaliteitsbepalende parameters in fermenterende mos. Die kwantitatiewe modelle is baie deeglik getoets met onafhanlike toets datastelle, en daarna is die kalibrasiemodelle geimplementeer vir industriële gebruik by Namaqua Wyne. Multiveranderlike statistiese proseskontrole grafieke wat baseer is op data wat vanaf 21 verskillende fermentasietenks verkry is, het baie goeie potensiaal getoon om probleemfermentasies vroeg te identifiseer. Dié grafieke is ‘n baie nuttige diagnostiese hulpmiddel wat verder ontwikkel kan word om verskillende tipes probleemfermentasies te monitor. Toekomstige navorsing in hierdie konteks, sal toegespits word op die optimisering en uitbreiding van die kwantitatiewe en kwalitatiewe modelle, sowel as toepassing van die tegnieke in die onderskeie kelders van Namaqua Wyne.

Master of Public Health / Department of Diagnostic Medicine/Pathobiology / Deon Van der Merwe / Cyanobacteria are Gram-negative photosynthetic bacteria capable of producing toxins responsible for morbidity and mortality in humans and domestic animals. Many are capable of forming concentrated blooms that impact the environment by limiting the growth of sub-surface plants and phytoplankton. Harmful algal blooms (HABs) are also capable of producing multiple types of toxins, creating a potential hazard to recreational water users and animals drinking water from or near a bloom. Characterization of HABs is necessary to prevent these human and animal exposures and includes classifying of the type of cyanobacteria present and whether or not they are capable of toxin production, and the exact type of cyanotoxin that is actually present in bloom. Current methods used to classify cyanobacteria and cyanotoxins include microscopy, bioassays, ELISA, PCR, HPLC, and LC/MS. All of these methods, however, have limitations that include time, labor intensity, or cost. Fourier-Transform Infrared Spectroscopy (FTIR) is another potential tool for cyanobacterial classification that is not limited by these factors. To examine the practicality of this method, library screening with default software algorithms was performed on diagnostic samples received at the Kansas State University Veterinary Diagnostic Lab, followed by PCA of samples meeting minimum quality requirements to produce cluster analyses and dendrograms. Both spectrometers and software packages used were successful at distinguishing cyanobacteria from green algae in clean samples with 89.13% agreement. PCA resulted in clear classification of cyanobacteria or green algae demonstrated by a large order of magnitude difference produced by average Euclidian distance dendrograms. While this method is only capable of differentiating cyanobacteria from green algae or other aquatic environmental constituents, its simple, rapid use and low cost make it a beneficial screening tool when coupled with toxin-detection methods to characterize HABs.

In the anthropological analysis of burned bone, the presence of a white heat line aids in determining a bone’s physical condition prior to burning, distinguishing between those burned fleshed or wet versus dry. However, while the relationship between this thermal signature and a bone’s physical condition has been studied, there is a lack of research concerning the chemical composition of white heat lines. The present study assessed the composition of white heat lines that form on burned bone using Fourier transform infrared spectroscopy (FTIR) with the potassium bromide (KBr) pellet method. The present study examined the effects of soft tissue and the retention of bone’s organic material, including naturally-occurring grease and water, on the development and appearance of a white heat line. Experimental remains consisted of isolated long bones from white-tailed deer (Odocoileus virginianus), elk (Cervus canadensis), sheep (Ovis aries), and pig (Sus scrofa) in five physical conditions – fleshed (fresh bones with adhering soft tissue), very wet (recently defleshed bone, greasy), partially wet (defleshed, slight grease retention), dry (defleshed, naturally degreased), and soaked (formerly dry bone immersed in water). These bones were burned over a wood fire made within a 55-gallon drum. After a visual analysis to evaluate white heat line formation, chemical composition was analyzed by determining spectral peak heights of the carbonate (CO3) ν3 (1415 cm-1), phosphate (PO4) ν3 (1035 cm-1), and amide I (1660 cm-1) vibrational bands. These thermal signatures appear to form superficially, measuring approximately 1.5 mm in depth. Results indicate that white heat lines that formed on fleshed bone contain an increased amount of CO3, PO4, and amide I in comparison to their unburned controls, while those that formed on very wet bone contain decreased amounts instead. These findings further our knowledge of how fire modifies physical remains and the effect that bone’s physical condition prior to burning has on the development of a white heat line and the resulting compositional changes. In order to build upon the results gained from the present study, continuing research is needed to investigate compositional differences between white heat lines that form on fleshed versus very wet bone and to assess bone’s fat content as a possible contributing factor. Additional FTIR research is needed to assess the other vibrational bands of CO3, PO4, and amide that are present in bone.