Photon Upconverting Nanophosphors: Unique Reporters for Optical Biosensing

Upconversion photoluminescence is a unique property of mostly certain inorganic materials, which are capable of converting low-energy infrared radiation into a higher-energy emission at visible wavelengths. This anti-Stokes shift enables luminescence detection without autofluorescence, which makes the upconverting materials a highly suitable reporter technology for optical biosensing applications. Furthermore, they exhibit long luminescence lifetime with narrow bandwidths also at the optical window of biomaterials enabling luminescence measurements in challenging sample matrices, such as whole blood. The aim of this thesis was to study the unique properties and the applicability of nano-sized upconverting phosphors (UCNPs) as reporters in biosensing applications. To render the inorganic nanophosphors water-dispersible and biocompatible, they were subjected to a series of surface modifications starting with silica-encapsulation and ending with a bioconjugation step with an analyte-recognizing biomolecule. The paramagnetism of the lanthanide dopants in the nanophosphors was exploited to develop a highly selective separation method for the UCNP-bioconjugates based on the magnetic selectivity of the high gradient magnetic separation (HGMS) system. The applicability of the nano-sized UCNPs as reporters in challenging sample matrices was demonstrated in two homogeneous sensing applications based on upconversion resonance energy transfer (UC-RET). A chemosensor for intracellular pH was developed exploiting UC-RET between the UCNP and a fluorogenic pH-sensitive dye with strongly increasing fluorescence intensity in decreasing pH. The pH-independent emission of the UCNPs at 550 nm was used for referencing. The applicability of the pH-nanosensor for intracellular pH measurement was tested in HeLa cells, and the acidic pH of endosomes could be detected with a confocal fluorescence microscope. Furthermore, a competitive UC-RET-based assay for red blood cell folic acid was developed for the measurement of folate directly from a whole blood sample. The optically transparent window of biomaterials was used in both the excitation and the measurement of the UC-RET sensitized emission of a near-infrared acceptor dye to minimize sample absorption, and the anti-Stokes detection completely eliminated the Stokes-shifted autofluorescence. The upconversion photoluminescence efficiency is known to be dependent on crystallite size, because the increasing surface-to-volume ratio of nano-sized UCNPs renders them more susceptible to quenching effects of the environment than their bulk counterpart. Water is known to efficiently quench the luminescence of lanthanide dopants. In this thesis, the quenching mechanism of water was studied using luminescence decay measurements. Water was found to quench the luminescence of UCNPs by increasing the non-radiative relaxation of the excited state of Yb3+ sensitizer ion, which had a very strong quenching effect on upconversion luminescence intensity.

Oxidation of Aqueous Thiosulfate Solutions by Pulsed Corona Discharge

The aim of this Master’s thesis focused on the oxidation of sodium thiosulfate using non thermal plasma technology as an advance oxidation process (AOP). By using this technology we can degrade certain toxic chemical compounds present in mining wastewaters as pollutants. Different concentrations of thiosulfate and pulse frequencies were used in the PCD experiments and the results in terms of various delivered energies (kWh/m3) and degradation kinetics were compared. Pulsed corona discharge is an energy efficient process compared to other oxidation processes using for the treatment of waste water pollutants. Due to its simplicity and low energy costs make it attractive in the field of waste water treatment processes. This technology of wastewater treatment has been tested mainly on pilot scale level and in future the attempts are to be focus on PCD investigations on larger process scale. In this research work of oxidation of thiosulfate using pulsed corona discharge, the main aim of this research was to study degradation of a studied toxic and not environmental friendly chemical compound. The focus of this research was to study the waste waters coming from the gold mines containing leachate compound thiosulfate. Literature review contained also gold leaching process when cyanide is used as the leachate. Another objective of this work was to compare PCD process with other processes based on their energy efficiencies. In the experimental part two concentrations of sodium thiosulfate, 1000ppm and 400ppm, were used. Two pulse generator frequencies of 833 and 200 pulses per second (pps) were used. The chemical analyses of the samples taken during semi-batch PCD oxidation process were analyzed by ion chromatographic (IC). It is observed after the analyses that among different frequencies and concentrations, the most suitable ones for the process is 200pps and 1000ppm respectively because the pollutants present in the waste water has more time to react with the OH radicals which are the oxidants and the process is energy efficient compared to other frequencies.

Kaukolämpöliiketoiminnan kehittäminen Mäntsälän Sähkö osakeyhtiössä

Tämän diplomityön tarkoitus oli selvittää Mäntsälän Sähkö Oy:n kaukolämpöliiketoiminnan nykytila ja kehityskohteet. Tutkimuskysymykset olivat: 1) Millaisilla toimenpiteillä varmistetaan kaukolämpöliiketoiminnan kannattavuus tulevaisuudessa? ja 2) Millaisia mahdollisuuksia älykäs kaukolämpö tuo kaukolämpöliiketoiminnalle? Tutkimus suoritettiin perehtymällä aiheen kirjallisuuteen ja uutisiin. Takaisinmaksuajan menetelmällä arvioitiin maakaasun korvaamisen kannattavuutta. Työn tuloksena voitiin todeta, että kaukolämmön hinnoittelua kannattaa kehittää kustannusvastaavampaan suuntaan. Nykyinen kaukolämmön energiankulutukseen painottuva hinnoittelu ei sovi uusille rakennuksille, jotka kuluttavat vähän energiaa. Yleistyvät hybridilämmitysjärjestelmät on otettava huomioon hinnoittelussa. Kaukolämmön kausihinnoittelu toisi etuja asiakkaalle, kaukolämpöyhtiölle sekä ympäristölle. Kaukolämmön kulutuksen tuntimittaus mahdollistaisi siirtymisen kaukolämpötehoon perustuvaan hinnoitteluun. Kaukolämmön hinta on ollut Mäntsälän Sähkö Oy:llä suhteellisen korkea. Korkea hinta johtuu enimmäkseen maakaasulla tuotetun kaukolämmön korkeista tuotantokustannuksista. Kaukolämmön tuotantoa voidaan kehittää kannattavammaksi, vaikka lämmöntalteenottolaitoksen oletettu lämmöntuotanto kattaa Mäntsälän lämmöntarpeesta noin puolet ja vähentää tuotantokustannuksia. Nykyisten maakaasukattiloiden käyttäminen pelletin pölypolttoon olisi teknisten muutoksien avulla mahdollista. Pölypolton kannattavuus riippuu erityisesti puupelletin ja maakaasun hintaerosta. Älykäs kaukolämpöjärjestelmä voisi automaattisesti tasoittaa kaukolämmön kysyntää yhdessä lämpövaraston kanssa. Tällöin huippulämpölaitosten käyttö vähentyisi ja lämmöntuotannon kustannukset pienentyisivät. Älykäs kaukolämpöjärjestelmä ja kaukolämpötehon tuntimittaus mahdollistaisivat myös kaksisuuntaisen kaukolämpökaupan.

Onondaga chert : geological and palynological studies as applied to archaeology /

Cherts from the Middle Devonian Onondaga Formation of the Niagara Peninsula in Southern Ontario and Western New York State can now be distinguished from those of the Early Devonian Bois Blanc Formation of the same area based on differences in petrology, acritarchs, spores, and "Preservation Ratio" values. The finely crystalline, carbonate sediments of the Bois Blanc Formation were deposited under shallow, low energy conditions characterised by the acritarchs Leiofusa bacillum and L. minuta and a high relative abundance of the spore, Apiculiretusispora minor. The medio crystalline and bioclastic carbonate sediments of the Onondaga Formation were deposited under shallow, high energy conditions except for the finely crystalline lagoonal sediments of the Clarence Member which is characterised by the acritarchs Leiofusa navicula, L. sp. B, and L. tomaculata . The author has subdivided and correlated the Clarence Member of the Onondaga Formation using the "Preservation Ratio" values derived from the palynomorphs contained in the cherts. Clarence Member cherts were used by the Archaic people of the Niagara Peninsula for chipped-stone tools. The source area for the chert is considered to be the cobble beach deposits along the north shore of Lake Erie from Port Maitland to Nanticoke

Transmission measurements using a new far-infrared set-up

A system comprised of a Martin-Puplett type polarizing interferometer and a Helium-3 cryostat was developed to study the transmission of materials in the very-far-infrared region of the spectrum. This region is of significant interest due to the low-energy excitations which many materials exhibit. The experimental transmission spectrum contains information concerning the optical properties of the material. The set-up of this system is described in detail along with the adaptations and improvements which have been made to the system to ensure the best results. Transmission experiments carried out with this new set-up for two different varieties of materials: superconducting thin films of lead and biological proteins, are discussed. Several thin films of lead deposited on fused silica quartz substrates were studied. From the ratio of the transmission in the superconducting state to that in the normal state the superconducting energy gap was determined to be approximately 25 cm-1 which corresponds to 2~/kBTc rv 5 in agreement with literature data. Furthermore, in agreement with theoretical predictions, the maximum in the transmission ratio was observed to increase as the film thickness was increased. These results provide verification of the system's ability to accurately measure the optical properties of thin low-Tc superconducting films. Transmission measurements were carried out on double deionized water, and a variety of different concentrations by weight of the globular protein, Bovine Serum Albumin, in the sol, gel and crystalline forms. The results of the water study agree well with literature values and thus further illustrate the reproducibility of the system. The results of the protein experiments, although preliminary, indicate that as the concentration increases the samples become more transparent. Some weak structure in the frequency dependent absorption coefficient, which is more prominent in crystalline samples, may be due to low frequency vibrations of the protein molecules.

Polyglutamine monomer structure and its implications for molecular self-assembly

Polyglutamine is a naturally occurring peptide found within several proteins in neuronal cells of the brain, and its aggregation has been implicated in several neurodegenerative diseases, including Huntington's disease. The resulting aggregates have been demonstrated to possess ~-sheet structure, and aggregation has been shown to start with a single misfolded peptide. The current project sought to computationally examine the structural tendencies of three mutant poly glutamine peptides that were studied experimentally, and found to aggregate with varying efficiencies. Low-energy structures were generated for each peptide by simulated annealing, and were analyzed quantitatively by various geometry- and energy-based methods. According to the results, the experimentally-observed inhibition of aggregation appears to be due to localized conformational restraint placed on the peptide backbone by inserted prolines, which in tum confines the peptide to native coil structure, discouraging transition towards the ~sheet structure required for aggregation. Such knowledge could prove quite useful to the design of future treatments for Huntington's and other related diseases.

Bio-inspired optimization & sampling technique for side-chain packing in MCCE

The prediction of proteins' conformation helps to understand their exhibited functions, allows for modeling and allows for the possible synthesis of the studied protein. Our research is focused on a sub-problem of protein folding known as side-chain packing. Its computational complexity has been proven to be NP-Hard. The motivation behind our study is to offer the scientific community a means to obtain faster conformation approximations for small to large proteins over currently available methods. As the size of proteins increases, current techniques become unusable due to the exponential nature of the problem. We investigated the capabilities of a hybrid genetic algorithm / simulated annealing technique to predict the low-energy conformational states of various sized proteins and to generate statistical distributions of the studied proteins' molecular ensemble for pKa predictions. Our algorithm produced errors to experimental results within .acceptable margins and offered considerable speed up depending on the protein and on the rotameric states' resolution used.

The convergence of psychopathy, self-rated vulnerability, and other-rated vulnerability

Previous research has found that victims of crime tend to exhibit asynchronous movement (e.g. Grayson & Stein, 1981), and the fact that victims display different body language suggests that they may be sending inadvertent signals to their own vulnerability (e.g. Murzynski & Degelman, 1996). Body language has also be en linked with s e l f identification as a victim (Wheeler et aI., 2009), and self-identification has be en found to act as a proxy for more severe victimization (Baumer, 2002) and greater fear of crime (Greenberg & Beach, 2004). The first prediction in the present study, then, was that self-perceived vulnerability would be correlated with body language, while number of previous victimizations mayor may not show the same relationship. Findings from the present study indicate that self-perceived vulnerability exhibits a positive correlation with the body language cues that approaches significance r (10) = .45,p =.07, one-tailed. Different types of victimization, however, were not significantly correlated with these cues. A second goal of the study was to examine the relationship between psychopathic traits and accuracy in judgments of vulnerability. Seventy male participants rated the vulnerability of 12 female targets filmed walking down a hallway who had provided selfratings of vulnerability. Individuals scoring higher on Factor 2 and total psychopathy were significantly less discrepant from target self-rat~ngs of vulnerability, r (64) = - .39,p < .001; r (64) = - .29,p >.01, respectively. The final purpose of this study was to determine which body language cues were mos t salient to raters when making judgments of vulnerability. Participants rated the apparent vulnerability of a target in 7 video clips portraying each body language cue in isolation and a natural walk. Results of repeated measures analyses indicate that the videos rated as most vulnerable to victimization were those displaying low energy and l a ck of synchrony, followed by wide stride, short stride, and stiffknees, while the video displaying ne ck stiffness did not receive significantly different ratings from the mode l ' s natural walk. Replication with a larger sample size is necessary to increase confidence in findings and implications.

Évaluation de la reconstruction des ligaments croisés post luxation aiguë du genou avec l’utilisation des ligaments synthétiques

La luxation du genou, bien que très rare, demeure une blessure dévastatrice car elle entraîne de multiples complications en raison de la nature complexe du traumatisme associé à cette lésion. La luxation peut résulter d'un traumatisme à haute ou basse énergie. Les blessures sévères aux ligaments et aux structures associées donnent à la luxation du genou un potentiel élevé d'atteinte fonctionnelle. Le traitement conservateur, qui était considéré comme acceptable auparavant, est maintenant réservé à un très faible pourcentage de patients. La reconstruction chirurgicale est maintenant préconisée dans la plupart des cas, mais de nombreuses options existent et le traitement chirurgical optimal à préconiser reste controversé. Certains chirurgiens recommandent la reconstruction complète de tous les ligaments endommagés le plus tôt possible, tandis que d'autres, craignant l’établissement d’arthrofibrose, limitent l'intervention chirurgicale immédiate à la reconstruction du ligament croisé postérieur et de l'angle postéro-externe. En raison des multiples structures endommagées lors d’une luxation du genou, les chirurgiens utilisent couramment la combinaison des autogreffes et des allogreffes pour compléter la reconstruction ligamentaire. Les complications associées au prélèvement de la greffe, l'allongement de la greffe, l’affaiblissement précoce du greffon ainsi que les risques de transmission de maladies ont poussé les chirurgiens à rechercher différentes options d’intervention. L'utilisation de matériaux synthétiques pour le remplacement du ligament lésé a été proposée dans les années ´80. Après une première vague d'enthousiasme, les résultats décevants à long terme et les taux élevés d'échec ont diminué sa popularité. Depuis lors, une nouvelle génération de ligaments artificiels a vu le jour et parmi eux, le Ligament Advanced Reinforced System (LARS) a montré des résultats prometteurs. Il a été utilisé récemment dans les reconstructions isolées du ligament croisé antérieur et du ligament croisé postérieur pour lesquelles il a montré de bons résultats à court et moyen termes. Le but de cette étude rétrospective était d'évaluer la fonction et la stabilité du genou après la luxation aiguë suivant la reconstruction des ligaments croisés avec le ligament artificiel de type LARS. Cette étude a évalué 71 patients présentant une luxation du genou et qui ont subi une chirurgie de reconstruction du ligament croisé antérieur et du ligament croisé postérieur à l'aide du ligament LARS. Suite à la chirurgie le même protocole intensif de réadaptation a été suivi pour tous les patients, où la mise en charge progressive était permise après une période d’environ 6 semaines pendant laquelle la force musculaire et la stabilité dynamique se rétablissaient. Les outils d’évaluation utilisés étaient le score Lysholm, le formulaire de «l’International Knee Documentation Committee», le «Short Form-36», les tests cliniques de stabilité du genou, l'amplitude de mouvement articulaire à l’aide d’un goniomètre et la radiographie en stress Telos à 30° et 90° de flexion du genou. Le même protocole d’évaluation a été appliqué au genou controlatéral pour des fins de comparaison. Les résultats subjectifs et objectifs de cette étude sont satisfaisants et suggèrent que la réparation et la reconstruction combinées avec ligaments LARS est une alternative valable pour le traitement des luxations aiguës du genou. Ces résultats démontrent que ces interventions produisent des effets durables en termes d’amélioration de la fonction et révèlent la durabilité à long terme des ligaments artificiels LARS. Les patients sont à la fois plus autonomes et plus satisfaits avec le temps, même si la luxation du genou est considérée comme une catastrophe au moment où elle se produit. Des études prospectives randomisées sont maintenant nécessaires afin de comparer la sélection de la greffe et le délai de reconstruction chirurgicale.

Implémentation de la répartition de charge et du mode TOT pour la simulation d’un détecteur Timepix à pixels

Les détecteurs à pixels Medipix ont été développés par la collaboration Medipix et permettent de faire de l'imagerie en temps réel. Leur surface active de près de $2\cm^2$ est divisée en 65536~pixels de $55\times 55\um^2$ chacun. Seize de ces détecteurs, les Medipix2, sont installés dans l'expérience ATLAS au CERN afin de mesurer en temps réel les champs de radiation produits par les collisions de hadrons au LHC. Ils seront prochainement remplacés par des Timepix, la plus récente version de ces détecteurs, qui permettent de mesurer directement l'énergie déposée dans chaque pixel en mode \textit{time-over-threshold} (TOT) lors du passage d'une particule dans le semi-conducteur. En vue d'améliorer l'analyse des données recueillies avec ces détecteurs Timepix dans ATLAS, un projet de simulation Geant4 a été amorcé par John Id\'{a}rraga à l'Université de Montréal. Dans le cadre de l'expérience ATLAS, cette simulation pourra être utilisée conjointement avec Athena, le programme d'analyse d'ATLAS, et la simulation complète du détecteur ATLAS. Sous l'effet de leur propre répulsion, les porteurs de charge créés dans le semi-conducteur sont diffusés vers les pixels adjacents causant un dépôt d'énergie dans plusieurs pixels sous l'effet du partage de charges. Un modèle effectif de cette diffusion latérale a été développé pour reproduire ce phénomène sans résoudre d'équation différentielle de transport de charge. Ce modèle, ainsi que le mode TOT du Timepix, qui permet de mesurer l'énergie déposée dans le détecteur, ont été inclus dans la simulation afin de reproduire adéquatement les traces laissées par les particules dans le semi-conducteur. On a d'abord étalonné le détecteur pixel par pixel à l'aide d'une source de $\Am$ et de $\Ba$. Ensuite, on a validé la simulation à l'aide de mesures d'interactions de protons et de particules $\alpha$ produits au générateur Tandem van de Graaff du Laboratoire René-J.-A.-Lévesque de l'Université de Montréal.

Prompt electron emission and collisional ionization of ambient gas during pulsed laser ablation of silver

A silver target kept under partial vacuum conditions was irradiated with focused nanosecond pulses at 1:06 mm from a Nd:YAG laser. The electron emission monitored with a Langmuir probe shows a clear twin-peak distribution. The first peak which is very sharp has only a small delay and it indicates prompt electron emission with energy as much as 60 5 eV. Also the prompt electron emission shows a temporal profile with a width that is same as that for the laser pulse whereas the second peak is broader, covers several microseconds, and represents the low-energy electrons (2 0:5 eV) associated with the laser-induced silver plasma as revealed by time-of-flight measurements. It has been found that prompt electrons ejected from the target collisionally excite and ionize ambient gas molecules. Clearly resolved rotational structure is observed in the emission spectra of ambient nitrogen molecules. Combined with time-resolved spectroscopy, the prompt electrons can be used as excitation sources for various collisional excitation–relaxation experiments. The electron density corresponding to the first peak is estimated to be of the order of 1017 cm?--3 and it is found that the density increases as a function of distance away from the target. Dependence of probe current on laser intensity shows plasma shielding at high laser intensities.

Overtone spectra of styrene and polystyrene in the visible and near infrared regions

Vibrational overtone spectra of styrene (liquid) and polystyrene (solid), studied by the laser-induced thermal lens (for ΔV=6) and the conventional near infrared absorption (for ΔV=3–5) techniques, are reported. For polystyrene, the overtone energy-bond length correlation predicts that the aryl CH bonds are ∼0.0005 Å longer than that in benzene, while no such conclusions could be drawn on styrene. Thesp 3 CH overtones in polystyrene are observed on the low energy side of the aryl CH overtones.

Transverse dipole spin modes in quantum dots

We have carried out a systematic analysis of the transverse dipole spin response of a large-size quantum dot within time-dependent current density functional theory. Results for magnetic fields corresponding to integer filling factors are reported, as well as a comparison with the longitudinal dipole spin response. As in the two-dimensional electron gas, the spin response at high-spin magnetization is dominated by a low-energy transverse mode.

Texture, composition and provinance of innershelf sediments between Narakkal and Purakkad, Kerala with special reference to the formation of Mud Banks

The continental shelf of southwest coast of India (Kerala) is broader and . flatter compared to that of the east coast. The unique characteristic feature of the study area (innershelf between Narakkal and Purakkad) is the intermittent appearance of 'mud banks' at certain locations during southwest monsoon. The strong seasonality manifests significant changes in the wind, waves, currents, rainfall, drainage etc., along this area. Peculiar geomorphological variation with high, mid and lowlands in the narrow strip of the hinterland, the geological formations mainly consisting of rocks of metamorphic origin and the humid tropical weathering conditions play significant role in regulating the shelf sedimentation. A complementary pattern of distri bution is observed for clay that shows an abundance in the nearshore. Silt, to a major extent, depicts semblance with clay distribution . Summation of the total asymmetry of grain size distribution are inferred from the variation of skewness and kurtosis.Factor I implies a low energy regime where the transportation and deposition phases are controlled mostly by pelagic suspension process as the factor loadings are dominant on finer phi sizes. The second Factor is inferred to be the result of a high energy regime which gives higher loadings on coarser size fractions. The third Factor which might be a transition phase (medium energy regime) representing the resultant flux of coastal circulation of the re-suspension/deposition and an onshoreoffshore advection by reworking and co-deposition of relict and modern sediments. The spatial variations of the energy regime based on the three end-member factor model exhibits high energy zone in the seaward portion transcending to a low energy one towards the coast.From the combined analysis of granulometry and SEM studies, it is concluded that the sandy patches beyond 20 m depth are of relict nature. They are the resultant responses of beach activity during the lower stand of sea level in the Holocene. Re-crystallisation features on the quartz grains indicate that they were exposed to subaerial weathering process subsequent to thei r deposition

Gill Nets of Kerala

The fishing industry the world over is passing through a critical situation.The landings of marine fishes seemed to have reached saturation in major fishing areas of the world.As a general rule fisheries employing fishing gear and techniques used by small scale and artisanal fishermen either from shore or from onboard small fishing craft come under small-scale fisheries.This study on gill nets of Kerala, the fishing method depended upon by maximum fishermen of the state focuses on the importance of this selective and low energy fishing method in the marine fishing sector of the state.The study opens with the conceptual framework by briefly reviewing the crisis in the marine fisheries sector. Maximum fishermen depend upon gill net, which is, an important selective and low energy fishing gear. A review of relevant literature on aspects such as material, selectivity and techno-economic efficiency together with scope and main objectives of the study form the major part of the compass of the introductory chapter.This survey provided the inputs for selection of centres. The chapter presents the basis for selection of sample centres, sample units and methodology for field and experimental study.The subject matter of the fourth chapter is a basic study on gear aterials. The weathering resistance, which is an important criterion to assess the material performance, was studied for polyamide monofilament in comparison to polyamide multifilament and polyethylene twisted monofilament.The study provides supporting evidence of oxidation and characteristic C-O stretching in polyethylene and cyclic lactam .formation and presence of OH in polyamide.The study indicates that small mesh gill netting can be encouraged as a selective fishing method in the inshore waters with restrained use of 30 and 32 mm mesh sizes. The economic efficiency was assessed using standard indices such as rate of return, internal rate of return, pay back period, fishery income, energy efficiency and factor productivity. The effect of size and cost of capital and cost of production on the economics of operation is also discussed in this chapter. It was observed that level of technology did not have direct effect on economic performance.