L'oxyde de zinc dopé de type n est un excellent candidat pour la réalisation de films transparents et isolants thermiques grâce à ses propriétés d'absorption et de réflexion limitées aux domaines UV et IR. La synthèse en milieu polyol de particules nanostructurées d'oxyde de zinc dopé par du gallium a été utilisée afin de maîtriser la morphologie des cristallites. Il a été démontré expérimentalement et théoriquement que le maximum d'efficacité d'absorption IR est atteint pour un taux de dopant de 2,6 % molaire. Des suspensions de haute transmission dans le visible et absorption infrarouge significative ont été obtenues par l'encapsulation des particules avec un matériau fluoré d'indice de réfraction intermédiaire entre l'oxyde et le milieu dispersant, ainsi que par l'optimisation de l'état de dispersion de suspensions colloïdales grâce à l'adsorption de thioalcanes en surface des cristallites de ZnO dopés.

Pelchem, a commercial subsidiary of Necsa (South African Nuclear Energy Corporation), produces a range of commercial fluorocarbon products while driving research and development initiatives to support the fluorine product portfolio. One such initiative is to develop improved analytical techniques to analyse product composition during development and to quality assure produce. Generally the C–F type products produced by Necsa are in a solution of anhydrous HF, and cannot be directly analyzed with traditional techniques without derivatisation. A technique such as vibrational spectroscopy, that can analyze these products directly without further preparation, will have a distinct advantage. However, spectra of mixtures of similar compounds are complex and not suitable for traditional quantitative regression analysis. Multivariate data analysis (MVA) can be used in such instances to exploit the complex nature of spectra to extract quantitative information on the composition of mixtures. A selection of fluorocarbon alcohols was made to act as representatives for fluorocarbon compounds. Experimental design theory was used to create a calibration range of mixtures of these compounds. Raman and infrared (NIR and ATR–IR) spectroscopy were used to generate spectral data of the mixtures and this data was analyzed with MVA techniques by the construction of regression and prediction models. Selected samples from the mixture range were chosen to test the predictive ability of the models. Analysis and regression models (PCR, PLS2 and PLS1) gave good model fits (R2 values larger than 0.9). Raman spectroscopy was the most efficient technique and gave a high prediction accuracy (at 10% accepted standard deviation), provided the minimum mass of a component exceeded 16% of the total sample. The infrared techniques also performed well in terms of fit and prediction. The NIR spectra were subjected to signal saturation as a result of using long path length sample cells. This was shown to be the main reason for the loss in efficiency of this technique compared to Raman and ATR–IR spectroscopy. It was shown that multivariate data analysis of spectroscopic data of the selected fluorocarbon compounds could be used to quantitatively analyse mixtures with the possibility of further optimization of the method. The study was a representative study indicating that the combination of MVA and spectroscopy can be used successfully in the quantitative analysis of other fluorocarbon compound mixtures. / Thesis (M.Sc. (Chemistry))--North-West University, Potchefstroom Campus, 2012.

Pelchem, a commercial subsidiary of Necsa (South African Nuclear Energy Corporation), produces a range of commercial fluorocarbon products while driving research and development initiatives to support the fluorine product portfolio. One such initiative is to develop improved analytical techniques to analyse product composition during development and to quality assure produce. Generally the C–F type products produced by Necsa are in a solution of anhydrous HF, and cannot be directly analyzed with traditional techniques without derivatisation. A technique such as vibrational spectroscopy, that can analyze these products directly without further preparation, will have a distinct advantage. However, spectra of mixtures of similar compounds are complex and not suitable for traditional quantitative regression analysis. Multivariate data analysis (MVA) can be used in such instances to exploit the complex nature of spectra to extract quantitative information on the composition of mixtures. A selection of fluorocarbon alcohols was made to act as representatives for fluorocarbon compounds. Experimental design theory was used to create a calibration range of mixtures of these compounds. Raman and infrared (NIR and ATR–IR) spectroscopy were used to generate spectral data of the mixtures and this data was analyzed with MVA techniques by the construction of regression and prediction models. Selected samples from the mixture range were chosen to test the predictive ability of the models. Analysis and regression models (PCR, PLS2 and PLS1) gave good model fits (R2 values larger than 0.9). Raman spectroscopy was the most efficient technique and gave a high prediction accuracy (at 10% accepted standard deviation), provided the minimum mass of a component exceeded 16% of the total sample. The infrared techniques also performed well in terms of fit and prediction. The NIR spectra were subjected to signal saturation as a result of using long path length sample cells. This was shown to be the main reason for the loss in efficiency of this technique compared to Raman and ATR–IR spectroscopy. It was shown that multivariate data analysis of spectroscopic data of the selected fluorocarbon compounds could be used to quantitatively analyse mixtures with the possibility of further optimization of the method. The study was a representative study indicating that the combination of MVA and spectroscopy can be used successfully in the quantitative analysis of other fluorocarbon compound mixtures. / Thesis (M.Sc. (Chemistry))--North-West University, Potchefstroom Campus, 2012.

This dissertation describes the advantages and feasibility of newly synthesized near-infrared (NIR) bis-heptamethine cyanine (BHmC) dyes for non-covalent labeling schemes. The NIR BHmCs were synthesized for biomolecule assay. The advantages of NIR BHmCs for biomolecule labeling and the instrumental advantages of the near-infrared region are also demonstrated. Chapter 1 introduces the theory and applications of dye chemistry. For bioanalysis, this chapter presents covalent and non-covalent labeling. The covalent labeling depends on the functionality of amino acids and the non-covalent labeling relies on the binding site of a protein. Due to the complicated binding process in non-covalent labeling, this chapter also discusses the binding equilibria in spectroscopic and chromatographic analyses. Chapter 2 and 3 evaluate the novel BHmCs for non-covalent labeling with human serum albumin (HSA) and report the influence of micro-environment on BHmCs. The interesting character of BHmCs in aqueous solutions is that the dyes exhibit non- or low-fluorescence compared to their monomer counterpart, RK780. It is due to their H-type closed clam-shell form in the solutions. The addition of HSA or organic solvents opens up the clam-shell form and enhances fluorescence. The binding equilibria are also examed. Chapter 4 provides a brief introduction that summaries the use of capillary electrophoresis (CE), and offers a detailed instrumentation that discusses the importance and advantage of a detector in NIR region for CE separation. Chapter 5 focuses on the use of NIR cyanine dyes with capillary electrcophoresis with near-infrared laser induce fluorescence (CE-NIR-LIF) detection. The NIR dyes with different functional groups show that RK780 is a suitable NIR dye for HSA labeling. The use of BHmCs with CE-NIR-LIF reduces signal noises that are commonly caused by the interaction between NIR cyanine dyes and negatively charged capillary wall. In addition, bovine carbonic anhydrase II (BCA II) is applied to study the influence of hydrophobicity on non-covalent labeling. Finally, chapter 6 presents the conformational dependency of BHmCs on the mobility in capillary and evaluates the further possibility of BHmCs for small molecule detection. Acridine orange (AO) is used as a sample and it breaks up the aggregate and enhances fluorescence. The inserted AO into BHmC changes the mobility in capillary, owing to the conformational changes by AO.

Μετά την πρώτη ενεργειακή κρίση την δεκαετία του ’70 κατά την οποία τα περιορισμένα αποθέματα ενέργειας προκάλεσαν την πρώτη σημαντική αύξηση στην τιμή της ενέργειας, η χρήση ενέργειας στα θερμοκήπια έχει γίνει κύριο ερευνητικό ζήτημα. Η ανάγκη για μείωση του ενεργειακού κόστους είναι σημαντική, γιατί η ενέργεια αποτελεί σημαντικό κλάσμα του συνολικού κόστους παραγωγής. Στις Μεσογειακές χώρες έχει υπολογιστεί ότι η χρήση ενέργειας για έλεγχο των συνθηκών περιβάλλοντος και ειδικότερα για τη θέρμανση, είναι 20% - 30% του συνολικού κόστους παραγωγής, ποσοστό το οποίο στις βορειότερες χώρες αυξάνεται. Ταυτόχρονα, με το έντονο ενδιαφέρον για το παγκόσμιο φαινόμενο του θερμοκηπίου και τις κλιματικές αλλαγές, η χρήση των συμβατικών καυσίμων είναι και πάλι στην πολιτική ατζέντα. Έτσι και η βιομηχανία θερμοκηπίων είναι αντιμέτωπη με οικονομική, πολιτική και κοινωνική πίεση για μείωση της χρήσης ενέργειας και βελτίωση της ενεργειακής απόδοσης των θερμοκηπίων μέσω τεχνολογικών καινοτομιών. Η κατανάλωση ενέργειας για τη θέρμανση του θερμοκηπίου αποτελεί ένα πολύ σοβαρό πρόβλημα διότι οι απώλειες του θερμοκηπίου σε θερμότητα λόγω των λεπτών τοιχωμάτων του και της κατασκευής του, είναι πολύ μεγάλες, 6-12 φορές μεγαλύτερες από εκείνες ενός συνήθους κτίσματος ίσου όγκου. Η θερμότητα παρέχεται στο θερμοκήπιο κυρίως μέσω συμβατικών συστημάτων θέρμανσης (συστήματα σωληνώσεων θερμού νερού, συστήματα θερμού αέρα) και σε περιορισμένη έκταση με χρήση ανανεώσιμων πηγών ενέργειας (ηλιακή, γεωθερμία, βιομάζα). Για να επιτευχθεί με αυτές τις μεθόδους η απαραίτητη θερμοκρασία στο επίπεδο των φυτών, το εσωτερικό του θερμοκηπίου πρέπει να θερμανθεί στην ίδια ή υψηλότερη θερμοκρασία από την επιθυμητή θερμοκρασία των φυτών με αποτέλεσμα την δημιουργία ισοθερμοκρασιακού κλίματος σε ολόκληρο το θερμοκήπιο (όλον κλίμα). Το αποτέλεσμα αυτής της πρακτικής σε όλες τις μελέτες που διεξάγονται είναι ότι, τα θερμοκήπια καταναλώνουν απαράδεκτα υψηλά ποσά ενέργειας σε σχέση με την ενέργεια που απορροφάται από τα φυτά, για να καλύπτουν τις αυξημένες ενεργειακές απώλειες που λόγω κατασκευής παρουσιάζουν. Στην παρούσα διατριβή αναπτύσσεται μια ολοκληρωμένη πρόταση για την δημιουργία ενός "ψυχρού θερμοκηπίου" στο οποίο τα φυτά θα λαμβάνουν απευθείας την ενέργεια που χρειάζονται προκειμένου να φτάσουν και να διατηρήσουν την επιθυμητή για την ανάπτυξή τους θερμοκρασία χωρίς να υπάρχει ανάγκη για αύξηση της θερμοκρασίας του αέρα του θερμοκηπίου. Για τον σκοπό αυτό χρησιμοποιείται σύστημα θέρμανσης με μικρού μήκους υπέρυθρη ακτινοβολία (NIR). Σε αυτά τα συστήματα η θερμότητα μεταδίδεται απευθείας από την πηγή στον δέκτη, στην προκειμένη περίπτωση στα φυτά και το έδαφος και το αποτέλεσμα είναι η δημιουργία ισοθερμοκρασιακού κλίματος μόνο στην περιοχή του φυτικού θόλου (τοπικό κλίμα). Ειδικότερα η παρούσα εργασία αντιμετωπίζει τη θερμική συμπεριφορά του θερμοκηπίου λαμβάνοντας υπόψη όλα τα ουσιαστικά θερμικά φαινόμενα που συμβαίνουν κατά την διάρκεια θέρμανσης (με συμβατικό και με σύστημα θέρμανσης με ακτινοβολία) και παρουσία καλλιέργειας. Γι αυτό τον λόγο δίνεται ιδιαίτερη βαρύτητα στην ανάπτυξη ενός μαθηματικού μοντέλου που προσομοιάζει επαρκώς τις κύριες διαδικασίες μεταφοράς θερμότητας μέσα στο θερμοκήπιο, το οποίο περιλαμβάνει ένα σύνολο λειτουργικών συνθηκών, και στο οποίο καθορίζονται με σχετική ακρίβεια οι παράγοντες που επηρεάζουν την θερμική συμπεριφορά του θερμοκηπίου. Το μοντέλο προσομοίωσης δίνει την δυνατότητα αξιόπιστης περιγραφής του περιβάλλοντος του θερμοκηπίου, και σαφούς εκτίμησης των ενεργειακών αναγκών του και με τις δυο τεχνικές θέρμανσης. Ετσι προσδιορίζεται το εξοικονομούμενο ενεργειακό όφελος που προκύπτει με τη χρήση συστήματος θέρμανσης με ακτινοβολία. Ο έλεγχος της ποιότητας του μοντέλου προσομοίωσης και η περαιτέρω βελτίωσή του γίνεται με σύγκριση των θεωρητικών αποτελεσμάτων με πειραματικά δεδομένα, η συλλογή και επεξεργασία των οποίων αποτελεί τον πυρήνα της έρευνας. Τα πειραματικά δεδομένα προέρχονται από πειράματα που διεξήχθησαν σε δύο πειραματικά θερμοκήπια συζευγμένα με αυτόματο μετεωρολογικό σταθμό, στα οποία εφαρμόζεται συμβατικό σύστημα θέρμανσης και θέρμανση με υπέρυθρη ακτινοβολία αντίστοιχα. Αυτό δίνει την δυνατότητα πιστοποίησης των δυνατοτήτων της θέρμανσης με ακτινοβολία και ποσοτικοποίησης του ενεργειακού οφέλους που επιτυγχάνεται. Συμπερασματικά, η συστηματική θεωρητική και πειραματική μελέτη ενός "ψυχρού" θερμοκηπίου με χρήση μικρού μήκους υπέρυθρης ακτινοβολίας (NIR) και ενός "θερμού θερμοκηπίου" με χρήση συμβατικού συστήματος θέρμανσης αναδεικνύουν το κύριο πλεονέκτημα της υπέρυθρης ακτινοβολίας, δηλαδή η θερμότητα να μεταδίδεται απευθείας από το σύστημα ακτινοβολίας στα φυτά και το έδαφος χωρίς να παρεμβάλεται ο αέρας του εσωτερικού περιβάλλοντος του θερμοκηπίου. Αυτό οδηγεί σε ομοιομορφία θέρμανσης του φυτικού θόλου και ταυτόχρονα σε σημαντική εξοικονόμηση ενέργειας της τάξεως του 40-50%. / After the first energy crisis in the seventies during which limited energy supplies led to an important increase in energy prices, greenhouse energy consumption has again become a major research issue. The energy cost reduction need is significant, since energy forms a substantial fraction of the total production costs. In Mediterranean countries it has been estimated that energy consumption for environment conditions control and more specifically for heating, consists 20% - 30% of total production cost, a percentage that is higher in northern countries. Moreover, due to the recent pronounced interest in the global greenhouse effect and climatic change, the use of fossil fuels is once again in the political agenda. Therefore the greenhouse industry is confronted with economical, political and social pressure to reduce energy usage and improve the greenhouse energy efficiency via technological innovations. Energy consumption for greenhouse heating represents a serious concern because greenhouse heat losses due to thin covers and construction specifics are 6-12 times higher than those of a common building of equal volume. Traditionally, thermal energy is transmitted to the greenhouse mainly through conventional heating systems (either by hot water circulation through a piping system or by air heaters) and, in a limited scale, through renewable energy sources (solar, geothermal, biomass). In order for the plants to reach required temperature through these methods, the greenhouse interior has to be heated to the same or even to a slightly higher temperature than the value targeted for the plants (entire climate). This practice results in extremely increased heat losses compared to the energy absorbed by plants, because of the increased energy losses due to construction specifications. The present thesis formulates a complete proposal for the creation of a "cold greenhouse" where plants will directly receive the needed energy in order to reach and preserve the desirable growth temperature without having to increase the internal greenhouse air temperature. The near infrared radiation (NIR) is used for this purpose. In the radiation system, heating is transmitted straight from the source to the receiver, in this particular case plants and soil. The result is an isothermal climate formation in the plant canopy (local climate). Specifically this study investigates the greenhouse thermal performance taking into account all the essential thermal phenomena that take place during heating (conventional and IR heating) and cultivation. For this reason, emphasis is given to the development of a mathematical model that simulates the main heating transfer procedures inside the greenhouse, takes into account a sum of operational conditions and determines all factors influencing the greenhouse thermal performance with relevant accuracy. The simulation model allows a credible description of greenhouse environment as well as a clear estimation of its energy needs with both heating systems. Thus the resulting energy saving by IR heating usage is determined. Quality control of the simulation model and its forward improvement is done by comparing the theoretical results with experimental data. Collecting and processing these data forms the research kernel. The experimental data correspond to experiments that took place in two experimental greenhouse connected with automatic meteorological station where conventional and IR heating have been used respectively. This method makes possible the identification of IR heating potential and quantification of energy saving. Concluding, the systematic theoretical and experimental study of a "cold" greenhouse using near IR heating, and of a "warm" greenhouse using conventional heating, proves the main advantage of IR heating that is that, the heat is directly transferred from the radiation system to the plants and the soil without interference of the internal greenhouse air. This leads to uniform heating of the plant canopy and at the same time to a significant energy saving of 40-50%.

Thesis (MSc Food Sc )--Stellenbosch University, 2000. / ENGLISH ABSTRACT: This study shows Fourier transform near infrared (FT-NIR) spectroscopy's application on wine, fruit and dried fruit for quantitative determinations or as a discriminative method for classification purposes. During wine production optimum yeast growth, resulting in healthy alcohol fermentation rates, is monitored by the amount of free amino nitrogen (FAN) present in the must. The status of malolactic fermentation (MLF) in Chardonnay wines is monitored by determining the degree of conversion of malic to lactic acid. Ethyl carbamate (EC), a suspected carcinogen, is mainly formed during ageing of wine and is restricted by legislation in some countries. It is therefore necessary to determine the EC content in wine. Fourier transform near infrared spectroscopy can be used on wine as a rapid method to measure the °Brix (residual sugars) content of must and to discriminate between different must samples in terms of their FAN values. It can also be used as a rapid method to discriminate between Chardonnay wine samples in terms of the MLF status and between table wine samples in terms of the EC content. Calibrations were derived and it was found that a very strong correlation existed in the sample set for the FT-NIR spectroscopic predictions for °Brix (r = 0.99, SEP = 0.31%), but poorer correlations for the FAN (r = 0.405, SEP = 275%), malic acid (r = 0.64, SEP = 1.02%), lactic acid (r = 0.61, SEP = 1.35%) and EC predictions (r = 0.47, SEP = 3.6%). When soft independent modelling by class analogy (SIMCA) was applied as a discriminative method, the must and wine samples were classified in terms of their FAN and EC values and MLF status, respectively, obtaining results with recognition rates exceeding 80%. The canning of peaches has become a significant industry in South Africa, producing approximately 4.1 million cartons per year. Fourier transform near infrared spectroscopy was applied as an alternative non-destructive method for the quantitative determination of the total soluble solid (TSS) content of whole fresh peaches. The TSS content of fresh clingstone peaches is an indication of the internal quality, maturity and perceived sweetness of the fruit for the peach canning industry. By determining the TSS, fresh peaches can be graded and the farmers compensated accordingly. Results obtained by building QUANT+™calibrations for the TSS content (r = 0.96, SEP = 0.55%) showed acceptable accuracy and can replace the present destructive methods. Peak periods during the harvesting season necessitate storage of peaches for up to three weeks before canning. Approximately 5 - 10% of the peaches stored, disintegrate during canning due to loose skin, large stone cavities, soft flesh and rot. The storage potential of fresh clingstone peaches can be successfully predicted with FT-NIR and SIMCA models, using subjective internal quality evaluations. Results with recognition rates exceeding 80% were obtained in most cases and this method proved useful as a non-destructive method of quality assessment. By applying this method, losses caused when storing peaches with poor storage quality will be reduced. The golden sultana industry plays an important role in the dried fruit exporting market of South Africa. Due to the large numbers of consignments that must be checked upon arrival, and the need for rapid decision making during processing, it is essential to replace the present time-consuming analytical methods. Fourier transform near infrared spectroscopy was used as a rapid, analytical technique to determine whether the S0₂ and moisture contents of sultanas are within specifications upon arrival at the factory and during processing. High positive correlation was found between the measured values and those predicted by FT-NIR spectroscopy for S0₂ (r = 0.99, SEP = 24.09%) and moisture (r = 0.99, SEP = 0.051 %) contents. / AFRIKAANSE OPSOMMING: Hierdie studie dui op Fourier transformasie naby-infrarooi (FT-NIR) spektroskopie se toepassing op wyn, vrugte en droëvrugte vir die uitvoer van kwantitatiewe bepalings of vir klassifikasie doeleindes om as 'n diskriminasie metode te dien. Gedurende wynproduksie word die optimum groei van giste wat lei tot 'n gesonde alkohol fermentasie gemonitor deur die hoeveelheid vry-aminostikstof (VAS) wat in die mos teenwoordig is te bepaal. Die status van appelmelksuurgisting (AMG) in Chardonnay wyne word gemonitor deur die mate van omskakeling van appelsuur na melksuur te bepaal. Etielkarbamaat (EK), 'n vermoede karsinogeen wat hoofsaaklik in verouderde wyne voorkom, word in sekere lande deur wetgewing beperk en dus die bepaling van die EK inhoud van wyne noodsaak. Fourier transformasie naby-infrarooi spektroskopie kan op mos toegepas word as 'n vinnige metode vir die bepaling van °Brix (residuele suiker) en om tussen die monsters te onderskei in terme van hulle VAS inhoud. FT-NIR kan ook gebuik word as 'n vinnige metode om tussen Chardonnay monsters te onderskei op grond van die status van AMG en tussen tafelwyn monsters op grond van die EK inhoud. Kalibrasies is ontwikkel en daar is gevind dat baie sterk korrelasies bestaan in die monsterstel vir die FT-NIR spektroskopiese voorspelling van °Brix (r = 0.99, SEP = 0.31%), maar swakker korrelasies vir die VAS (r = 0.405, SEP = 275%), appelsuur (r = 0.64, SEP = 1.02%), melksuur (r = 0.61, SEP = 1.35%) en EK voorspellings (r = 0.47, SEP = 3.6%). Met die toepassing van soft independent modelling by class analogy (SIMCA) as diskriminasie metode, is die mos- en wynmonsters geklassifiseer op grond van hul VAS en EK waardes en die status van AMG, en herkenningswaardes van bo 80% is onderskeidelik behaal. Die inmaak van perskes het 'n beduidende industrie in Suid-Afrika geword en produseer jaarliks ongeveer 4.1 miljoen kartonne. Fourier transformasie nabyinfrarooi spektroskopie is toegepas as alternatiewe, nie-beskadigende metode om kwantitatiewe bepalings van die totale oplosbare vastestowwe (TOV) inhoud van heel vars perskes, te doen. Vir die perske inmaak-industrie is die TOV inhoud van vars taaipitperskes 'n aanduiding van interne kwaliteit, rypheid en die soetheid van die vrugte. Vars perskes kan gradeer word deur die TOS te bepaal en sodoende kan boere oreenkomstige vergoeding ontvang. Resultate' wat verkry is deur QUANT+™ kalibrasies vir TOS inhoud te ontwikkel (r = 0.96, SEP = 0.55%), dui op aanvaarbare akkuraatheid en kan die huidige metodes vervang. Tydens oestyd kom piektye voor wanneer dit soms nodig is om perskes vir tot drie weke op te berg voordat dit ingemaak kan word. Ongeveer 5 tot 15% van hierdie opgebergte perskes disintegreer tydens inmaak omdat opberging lei tot defekte in die perskes soos skille wat loskom, groot pitholtes, sagte vleis en vrot. Die opbergingspotentiaal van vars taaipitperskes kan suksesvol voorspel word deur FTNIR en SIMCA modelle te bou en subjektiewe interne kwaliteitsevaluerings daarop toe te pas. Herkenningsresultate wat 80% in die meeste gevalle oorskry, is behaal wat hierdie metode as 'n suksesvolle nie-beskadigende kwaliteitbepalingsmetode bewys. Hierdie metode sal verliese kan beperk wat voorkom as gevolg van opberging van perskes met swak opbergingskwaliteit. Die goue sultana industrie speel 'n belangrike rol in die droë vrugte uitvoermark van Suid-Afrika. As gevolg van die hoeveelheid monsters wat gelyktydig getoets moet word en besluite wat vinnig geneem moet word tydens prosessering, is dit belangrik om die huidige tydrowende analitiese metodes te vervang. Fourier transformasie naby-infrarooi spektroskopie is gebruik as 'n vinnige, analitiese tegniek om tydens ontvangs by die fabriek en gedurende prosessering te bepaal of die S0₂- en voginhoud van goue sultanas binne die spesifikasies val. Goeie positiewe korrelasie is gevind tussen die bepaalde en voorspelde FT-NIR spektroskopiese waardes vir SO₂- (r = 0.99, SEP = 24.09%) en voginhoud (r = 0.99, SEP = 0.051 %).

>Magister Scientiae - MSc / In this study PbSe quantum dots (QDs) were successfully synthesized via the organometallic and aqueous routes. Optical characterization was carried out using photoluminescence (PL) spectroscopy, structural and morphological characterization were carried out using X-ray diffraction (XRD) and transmission electron microscopy (TEM). Energy-dispersive X-ray spectroscopy (EDS) was used to determine the composition of the QDs. All the synthesized QDs were found to have emissions within the near-infrared region of the spectrum (≥1000 nm) with most of them being less than 5 nm in size. The aqueous synthesized QDs had a perfect Gaussian emission spectrum with a FWHM of ~23 nm indicating pure band gap emission and narrow size distribution respectively. The QDs were determined to have a cubic rock-salt crystal structure consistent with bulk PbSe. The aqueous synthesized QDs were however not stable in solution with the QDs precipitating after approximately 48 h. The organometallic synthesized QDs were transferred into the aqueous phase by exchanging the surface oleic acid ligands with 11-mercaptoundecanoic acid ligands. The ligand exchanged QDs were however stable in solution for over two weeks. The effects of reaction parameters on the optical and structural properties of the organometallic synthesized QDs were investigated by varying the reaction time, temperature, ligand purity, lead and selenium sources. It was observed that larger QDs were formed with longer reaction times, with reactions proceeding faster at higher reaction temperatures than at lower temperatures. Varying the ligand purity was found to have minimal effects on the properties of the synthesized QDs. The lead and selenium sources contributed largely to the properties of the QDs with lead oxide producing spherical QDs which were smaller compared to the cubic QDs produced from lead acetate. TBPSe was seen to produce smaller QDs as compared to TOPSe. The cytotoxity of the synthesized QDs was determined following the WST-1 cell viability assay with the QDs being found to be non-toxic at all the tested concentrations

Hand-held optical imagers are developed towards clinical breast cancer imaging. Herein, a Gen-2 hand-held optical imager has been developed with unique features: (i) image curved breast tissues with ~86% surface contact, and (ii) perform reflectance and transillumination imaging using the novel forked probe heads. Extensive phantom studies were performed using 1% Liposyn solution (background, ~ 300 ml and 1000 ml volumes) and 0.45 cc India Ink (absorption) targets, under different target:background contrast ratios and target depths. Two-dimensional surface images detected target(s) up to 2.5 cm deep via reflectance imaging, and up to 5 cm deep via transillumination imaging. Preliminary studies on gel-based breast phantoms (~700 ml) detected targets via reflectance and transillumination imaging. Preliminary in-vivo reflectance studies on normal and cancerous breast tissues also detected targets, although with artifacts. In future, the portable Gen-2 imager has potential for clinical breast imaging via reflectance and transillumination approach after extensive in-vivo studies.

The present thesis deals with different aspects of the chemistry of oxovanadium(IV) complexes, their interaction with DNA and protein and photo-induced DNA and protein cleavage activity and photocytotoxicity. Chapter I presents a general introduction on various modes of interactions of organic compounds and transition metal complexes capable of targeting DNA leading to DNA strand scission, emphasizing particularly the photo-induced DNA cleavage activities for their potential application in PDT. The mechanistic pathways associated with the DNA cleavage are discussed. A comparison has been made on the advantages of photoactive metal complexes over organic conjugates. Objective of the present investigation is also dealt in this Chapter. Chapter II of the thesis deals with the synthesis, characterization, DNA binding and photo-induced DNA cleavage activity of ternary oxovanadium(IV) complexes of N-salicylidene-S-methyldithiocarbazate (salmdtc) and phenanthroline bases to explore the photo-induced DNA cleavage activity in UV-A light of 365 nm. Chapter III presents the synthesis, characterization, DNA binding and photo-induced DNA cleavage activity of ternary oxovanadium(IV) complexes containing N-salicylidene-L-methionate (salmet) and N-salicylidene-L-tryptophanate (saltrp) Schiff bases and phenanthroline bases. The objective of this work is to investigate the photo-induced DNA cleavage activity in near-IR light and to see the effect of pendant thiomethyl and indole moieties in the DNA cleavage reactions. Chapter IV deals with the synthesis, characterization, DNA binding, red-light induced DNA cleavage activity and photocytotoxicity of ternary oxovanadium(IV) complexes having N-salicylidene-L-arginine (sal-argH) and N-salicylidene-L-lysine (sal-lysH) Schiff bases and phenanthroline bases. The important results include the visible light-induced DNA cleavage activity and photocytotoxicity of the complexes in human cervical HeLa cancer cells. Chapter V describes the synthesis, characterization, DNA binding and photo-induced DNA and protein cleavage activity and photocytotoxicity of oxovanadium(IV) complexes containing bis(2-benzimidazolylmethyl)amine and phenanthroline bases. The significant results include DNA cleavage activity in near-IR light and photocytotoxicity of the dppz complex in non-small cell lung carcinoma/human lung adenocarcinoma A549 cells in visible light. Further, we have studied the protein cleavage activity of the complexes in UV-A light of 365 nm by using bovine serum albumin (BSA) and lysozyme. Finally, Chapter VI presents the binary oxovanadium(IV) complexes of phenanthroline bases. We have studied their synthesis, characterization, DNA binding and photo-induced DNA and protein cleavage activity and photocytotoxicity. Photocytotoxicity of dppz complex has been studied in human cervical HeLa cancer cells in visible light. Photo-induced protein cleavage activity of the complexes has been studied in UV-A light of 365 nm by using BSA and lysozyme. The references have been compiled at the end of each chapter and indicated as superscript numbers in the text. The complexes presented in this thesis are represented by bold-faced numbers. Crystallographic data of the complexes, characterized structurally by single crystal X-ray crystallography, are given in CIF format in the enclosed CD (Appendix-I). Due acknowledgements have been made wherever the work described is based on the findings of other investigators. Any omission that might have happened due to oversight or mistake is regretted.

We present an overview of the current and future adaptive optics systems at the LBTO along with the current and planned science instruments they feed. All the AO systems make use of the two 672 actuator adaptive secondary mirrors. They are (1) FLAO (NGS/SCAO) feeding the LUCI NIR imagers/spectrographs; (2) LBTI/AO (NGS/SCAO) feeding the NIR/MIR imagers and LBTI beam combiner; (3) the ARGOS LGS GLAO system feeding LUCIs; and (4) LINO-NIRVANA - an NGS/MCAO imager and interferometer system. AO performance of the current systems is presented along with proposed performances for the newer systems taking into account the future instrumentation.