Nous utilisons un microscope à effet tunnel (STM) associé à un microscope optique inversé pour l’excitation et la détection des plasmons de surface propagatifs et/ou localisés. L’excitation de ces plasmons est assurée par passage d’un courant tunnel inélastique entre la pointe du STM et la surface d’un film métallique mince (épaisseur de 50 nm) d’or ou d’argent déposé sur une lamelle de verre. Les fuites radiatives des plasmons de surface propagatifs et la lumière émise par les plasmons localisés dans le substrat de verre sont collectées par un microscope optique via un objectif à immersion. Il est alors possible de déterminer à la distribution spatiale et angulaire des émissions issues de ces plasmons de surface excités par STM, ainsi qu’à leur distribution en longueurs d’onde. Dans cette thèse, nous nous sommes intéressés au fonctionnement et à l’émission de lumière sous la pointe d’un microscope à effet tunnel fonctionnant à l’air. Nous montrons que la présence d’eau adsorbée au sein de la jonction tunnel, associée à la boucle d’asservissement du STM induit un mode de fonctionnement oscillant et périodique du STM sans lequel il serait difficile d’exciter les plasmons de surface. Ensuite, nous avons montré qu’il est possible de contrôler la directivité des plasmons de surface propagatifs excités par STM en excitant localement un nanofil d’or déposé sur le film d’or. L’étude détaillée de cette directivité nous a permis de démontrer que, contrairement au cas du nanofil d’or déposé sur verre, un nanofil d’or déposé sur film d’or ne se comporte pas comme un résonateur Fabry Pérot. Nous avons proposé un modèle simple dans lequel le nanofil est assimilé à un réseau linéaire d’antennes. Ce modèle permet de rendre compte des structurations spectrales et spatiales des plasmons de surface sur le film d’or résultant de l’ajout du nanofil d’or. Puis, nous avons étudié le couplage entre des nanofibres organiques fluorescentes (structures excitoniques) et les plasmons de surface propagatifs d’un film métallique d’or ou d’argent sur lequel ces nanofibres sont déposées. Nous avons ainsi montré que (i) la fluorescence de la nanofibre peut exciter des plasmons de surface à la surface du film d’or, (ii) la nanofibre organique agit comme un guide d’onde plasmonique et (iii) qu’il est possible d’injecter des plasmons de surface propagatifs du film excités par STM dans ces modes guidés par la nanofibre. D’autre part, en étudiant la figure d’interférences dans le plan de Fourier, nous avons pu confirmer que l’émission du dipôle sous la pointe STM et les plasmons de surface propagatifs excités par STM sont cohérents, donc issus du même événement tunnel. Enfin, nous discutons les effets du couplage entre des nanocristaux semiconducteurs (quantum dots) individuels et un monofeuillet de graphène. Nous montrons que la présence du graphène réduit d’un facteur ~10 la durée de vie de l’état excité des quantum dots déposés sur graphène par rapport aux quantum dots déposés sur verre. Pour les quantum dots déposés sur graphène, il résulte de cette réduction de la durée de vie de l’état excité, une baisse de l’intensité de fluorescence et une réduction du phénomène de scintillement avec un temps de résidence dans un état brillant globalement plus long que pour les quantum dots déposés sur verre. Les différents résultats obtenus au cours de cette thèse permettent de mieux comprendre l’excitation de plasmons de surface avec un microscope à effet tunnel, le couplage entre nanostructures plasmoniques et le couplage entre une structure plasmonique et une nanostructure excitonique. Ils ouvrent des perspectives intéressantes pour le développement de nanodispositifs hybrides plus complexes liants plasmons et excitons et contrôlés électriquement / We use a scanning tunnelling microscope (STM) to excite propagating and/or localised surface plasmons on a thin metallic film (50 nm thick) made of gold or silver deposited on a glass substrate. The leakage radiation of these STM-excited propagating surface plasmons, and the light emitted by localized plasmons into the glass substrate are collected by an inverted optical microscope equipped with an oil immersion objective. Using this setup, it is possible to image both the spatial and angular distribution of the light emitted into the glass substrate on a cooled-CCD. Sending this light to a spectrometer, it is also possible to obtain the wavelength distribution of these STM-excited plasmons. In this manuscript, we discuss the different operation modes of an STM in air. We show that the thin water layers adsorbed on both the STM tip and sample, along with the STM feedback loop, may give rise to an oscillatory mode of operation. Moreover, this mode turns out to be the most efficient one for plasmon excitation with a STM in air. We then show that, when the STM tip is used to locally excite plasmons on a gold nanowire deposited on a gold film, propagating surface plasmons may be preferentially launched along the nanowire axis. Precise understanding of this directivity allows us to demonstrate that, when deposited on a gold film, gold nanowires do not behave as Fabry-Perot resonators, but may be described quite accurately with a one dimensional antenna array model. With this model, it is thereby possible to explain the complex spatial and spectral characteristics of the STM-excited plasmons on the gold film after the addition of the nanowire. Next, we focus on the coupling between fluorescent organic nanofibres (excitonic nanostructures) and propagating surface plasmons on a metallic film (either gold or silver). We show that when the nanofibres are deposited on the metallic film, (i) their fluorescence can excite propagating surface plasmon, (ii) the nanofibre can act as a plasmonic waveguide, and (iii) it is possible to inject surface plasmons propagating onto the metallic film into the guided plasmonic modes of the nanofibre. Moreover, by studying Fourier space images, we confirmed that the vertical dipole localised under the STM tip and the STM-excited propagating surface plasmons are coherent. We finally study the coupling between individual semiconducting nanocrystals (quantum dots) and a graphene monolayer deposited on a glass substrate. We show that, when deposited on graphene, the fluorescence lifetime of the quantum dots is about 10 times shorter than for the quantum dots deposited on bare glass. This leads to a weaker fluorescence signal and reduced blinking behaviour with longer time spent into a bright state. These results improve our understanding of the STM excitation of surface plasmons. They also provide information on the coupling between plasmonic nanostructures and between plasmonic and excitonic entities. in particular, these results are a promising step toward the conception and the realisation of complex electrically driven hybrid plasmonic/excitonic nanodevices

Submitted by LAÍS GALVÃO CAETANO null (laisgalvao@iq.unesp.br) on 2017-02-06T13:41:04Z No. of bitstreams: 1 Dissertação Mestrado Laís Galvão Caetano.pdf: 2178003 bytes, checksum: 2239574ffc48afbca6a43b06084d326b (MD5) / Approved for entry into archive by LUIZA DE MENEZES ROMANETTO (luizamenezes@reitoria.unesp.br) on 2017-02-09T17:06:10Z (GMT) No. of bitstreams: 1 caetano_lg_me_arafo.pdf: 2178003 bytes, checksum: 2239574ffc48afbca6a43b06084d326b (MD5) / Made available in DSpace on 2017-02-09T17:06:10Z (GMT). No. of bitstreams: 1 caetano_lg_me_arafo.pdf: 2178003 bytes, checksum: 2239574ffc48afbca6a43b06084d326b (MD5) Previous issue date: 2016-12-21 / A fibroína da seda extraída dos casulos do bicho-da-sêda é um co-polímero particularmente atraente para aplicações em dispositivos fotônicos e opticoeletrônicos devido a sua transparência óptica, biocompatibilidade e propriedades mecânicas. Esta tese apresenta a obtenção de suspensões e filmes iridescentes-luminescentes de fibroína contendo nanopartículas luminescentes de carbono (“carbon dots”) obtidos a partir de carvão vegetal. As nanopartículas luminescentes de carbono apresentam biocompatibilidade, baixa toxicidade, propriedades de fotoluminescência interessantes e possibilidade de modificação da superfície. Redes de difração foram produzidas nestes filmes utilizando como molde um DVD comercial. Os materiais obtidos foram caracterizados por um conjunto de técnicas de análise: Microscopia de Força Atômica (AFM), Microscopia Eletrônica de Varredura (MEV), Microscopia Eletrônica de Transmissão (MET), Espectroscopia de absorção na região do UVVis, Espectrofotometria de absorção molecular na região do infravermelho com transformada de Fourier (FTIR) e Luminescência. Medidas de luminescência mostram que os carbon dots emitem múltiplas cores entre toda a região do visível. Planos cristalinos foram observados nas imagens de MET das nanopartículas, no qual foram asssociadas a estrutura do grafite. Pela análise de UV-Vis dos carbon dots observou-se que a absorção óptica decai gradualmente à medida em que ocorre deslocamento para o vermelho e para os filmes de fibroína observou-se um ombro referente a transição eletrônica da tirosina (aminoácido de sua composição). A partir dos espectros de FTIR observou-se que não houve mudança na estrutura da fibroína após a adição dos carbon dots. As imagens de AFM e MEV comprovam a presença dos micropadrões periódicos na superfície dos filmes. Os resultados mostraram que os filmes de fibroína contendo carbono dots tem um grande potencial para a biomedicina, principalmente devido os seus parâmetros de luminescência se extenderem em toda a região do visível e por apresentar uma matriz sustentável, com excelentes propriedades ópticas e mecânicas. / Silk fibroin extracted from silkworm cocoons is a particularly attractive copolymer for applications in photonics and optoelectronics devices due its optical transparency, biocompatibility and high mechanical strength. This thesis presents the preparation of suspensions and iridescent-luminescent films of silk fibroin containing luminescent carbon nanoparticles (carbon dots) obtained from vegetal coal. Luminescent carbon nanoparticles present high biocompatibility, low toxicity, interesting photoluminescence properties and possibility of surface modification. Diffraction gratings were produced in these films using a commercial DVD as a template. The materials obtained were characterized by a set of analysis techniques: Atomic-Force Microscopy (AFM), Scanning Electron Microscopy (SEM), Transmission Electron Microscopy (TEM), UV-Visible Spectroscopy, Fourier transform infrared spectroscopy (FTIR), and Luminescence. Luminescence measurements show that carbon dots emit light at the entire visible region. Crystalline planes were observed in the TEM images of the nanoparticles, where upon the graphite structure was associated. By analyzing the UV-Vis spectra of the carbon dots it was observed that the optical absorption gradually decreases as the red shift occurs. In the UV-Vis spectra of the silk fibroin films it was observed a shoulder referring to the electronic transition of the tyrosine (amino acid of its composition). From the FTIR spectra it was observed that there was no change in the silk fibroin structure after addition of the carbon dots. The AFM and SEM images confirm the presence of the periodic micro-patterns on the surface of the films. The results showed that the silk fibroin films containing carbon dots have a great potential for biomedicine, mainly due to its luminescence parameters extending throughout the visible region and due to a sustainable platform with excellent optical and mechanical properties.

Darbo tikslas. Išsiaiškinti slaugytojo vaidmenį mokant aktyvia plaučių TB sergančius pacientus ir tiesiogiai kontroliuojant prieštuberkuliozinių vaistų vartojimą. Darbo uždaviniai: 1. Įvertinti pacientų požiūrį ir žinias apie savo ligą. 2. Įvertinti pacientų higieninius įgūdžius ir socialines problemas. 3. Išsiaiškinti slaugytojo vaidmenį mokant aktyvia plaučių TB sergančius pacientus. 4. Tyrimo metodai. 1. Anoniminė anketinė apklausa. 2. Aprašomoji statistinė analizė. Tyrimo objektas – pacientai, sergantys aktyvia plaučių tuberkulioze ir besigydantys ambulatoriškai. Anketinė apklausa raštu buvo pateikta minėtiems pacientams bei slaugytojoms, tiesiogiai kontroliuojančioms vaistų vartojimą. Tyrimas atliktas 2008 m. rugsėjo 2 d. – gruodžio 20 d. Gauta informacija buvo sisteminama naudojant SPSS 13.0 ir MS Excel programą. Statistinė duomenų analizė atlikta taip pat naudojantis šiomis programomis. Požymių nepriklausomumui nustatyti naudotas χ² kriterijus. Skirtumai tarp atitinkamų duomenų (dominančių grupių, pavyzdžiui, vyrų ir moterų ar pacientų ir slaugytojų) laikomi reikšmingi (arba požymiai yra priklausomi), kai klaidos tikimybė p<0,05. Tyrimo duomenys aprašyti, interpretuoti rezultatai. Tyrimo metu apibūdinama anketinė apklausa, lentelių ir paveikslų pagalba analizuojamos sergančiųjų aktyvia plaučių tuberkulioze turimos žinios ir higieniniai įpročiai tuberkuliozės klausimais. Analizuojamas tuberkulioze sergančių asmenų gyvenimo būdas ir kylančios socialinės bei... [toliau žr. visą tekstą] / Idea of the job: To sort out the role of the nurse in teaching the patients and directly controlling the usage of anti-tuberculosis medicine. The task of the job: 1. Evaluate the oppinion of patients and their knowledge about the disease. 2. Evaluate the sanitary skills of patients and social problems. 3. To sort out the role of nurse in teaching patients, whose are ailing by active tuberculosis of lungs. Methods of the analysis: 1. Questionnairable poll in the written form. 2. Descriptive statistical analysis. Subject of anglysis – patients, whose are ailing by active tuberculosis of lungs and treating ambulantly. Questionnairable poll in written form was adduced for above-mentioned patients and nurses, directly controlling usage of medicine. Analysis was done on 2 of September – 20 of December of 2008 years. The data was systemized by using SPSS 13.0 and MS Excel program. Statistical analysis of data was done by using these programmes too. To estimate the independence of features χ² criterion was used. Differences between corresponding data (between groups of interest, eg., women and men, patients and nuries) are reputed important (or features are dependent), when error probability is p<0,05. The data of analysis are described, results interpreted, conclusions and recommendations are given. During the analysis questionnairable poll is characterized, with the help of tables and pictures there is analysed knowledge and sanitary mannerism for questions of tuberculosis of... [to full text]

This study shows a detailed report on the morphological, structural and optical properties of CdSe QDs synthesised by the hot injection method. Cadmium acetate dihydrate and Se powder were used as cadmium and selenide precursors, respectively. Various QD sizes were achieved by synthesizing in temperature range of 150ºC, 175ºC, 200ºC, 225ºC, 250ºC, 275ºC and 300ºC, respectively. The as synthesized QDs by the hot injection method were cross-examined for their morphological, structural and optical using HRTEM, FTIR, XRD, RS, and UV-Vis spectroscopy techniques respectively. FTIR analysis has revealed vibrations at 738, 738, 738, 738, 735, 735 and 733 cm-1 for the QDs synthesized at various temperatures of 150, 175, 200, 225, 250, 275, and 300℃, respectively. The presence of the above mentioned peaks confirms the presence of Cd-Se bond in our samples. XRD analysis of CdSe QDs revealed diffraction peaks at 2 angles of 16.66 , 25.20 , 34.77 , 40.9 , 45.39 and 49.1 for 150 17.4 , 25.22 , 34.85 , 41.7 , 44.45 and 47.5 for the QDs synthesized at various temperatures of 175 17.07 , 25.19 , 34.85 , 41.34 , 44.41 and 48.86 for 200 ; 16.34 , 25.20 , 34.76 , 40.6 , 44.74 and 49.48 for 225 ; 17.44 , 25.17 , 34.19 , 41.7 , 44.45 , 49.24 for 250 ; 16.70 , 25.16 , 34.85 , 40.32 , 45.1 and 49.1 7 for 275 ;and 17.35 , 25.18 , 35.13 , 41.63 , 45.7 , 49.48 for 300 . These XRD peaks relate to crystal planes of (100), (002), (102), (220), (103) and (112) which belong to hexagonal Wurtzite CdSe crystal structure. Additionally XRD analysis has revealed a general peak shift to higher 2 values was observed for CdSe QDs. HRTEM analysis showed that the synthesised CdSe QDs have a spherical shape and are monodispersed. Moreover, HRTEM analysis has revealed CdSe QDs modal crystallite size of 1.79 nm, 1.81 nm, 2.06 nm, 2.08 nm, 2.11 nm, 3.10 nm and 3.12 nm for the QDs synthesized at various temperatures of 150ºC, 175ºC, 200ºC, 225ºC, 250ºC, 275ºC and 300ºC, respectively. HRTEM results were in mutual agreement with XRD results. Additionally, the SAED images showed intense electron diffraction rings, which confirmed that the as-synthesised CdSe QDs have a Wurtzite crystal structure. RS analysis showed that CdSe QDs have LO and 2LO vibrational modes which are characteristic peaks for CdSe. The presence of these peaks in Raman spectra further supports our previous observation from XRD analysis and HRTEM analysis that the synthesized CdSe QDs have a Wurtzite crystal structure. The effect of synthesis temperature Raman peak shift, FHWH and peak intensity has been cross examined in this work, Moreover, the effect of increasing temperature on the peak shift, FWHM and peak intensity is discussed in detail below. UV-Vis analysis revealed an absorbance of CdSe QDs in higher wavelengths as temperature was increased. Furthermore, the Yu et al 2003 relation was used to calculate QD size and band gap energy of CdSe QDs. The results showed that QD size increases with increasing synthesis temperature, which is in agreement with HRTEM and XRD results.

Submitted by Irene Nascimento (irene.kessia@ufpe.br) on 2016-06-28T16:52:16Z No. of bitstreams: 2 license_rdf: 1232 bytes, checksum: 66e71c371cc565284e70f40736c94386 (MD5) Dissertação Denilson Digital.pdf: 4230195 bytes, checksum: 254e94141d3bf5cb07e451a017faacd5 (MD5) / Made available in DSpace on 2016-06-28T16:52:16Z (GMT). No. of bitstreams: 2 license_rdf: 1232 bytes, checksum: 66e71c371cc565284e70f40736c94386 (MD5) Dissertação Denilson Digital.pdf: 4230195 bytes, checksum: 254e94141d3bf5cb07e451a017faacd5 (MD5) Previous issue date: 2015-04-10 / FACEPE / A necessidade de metodologias sintéticas verdes vem aumentando significativamente nos últimos anos. O uso de materiais tóxicos e de metodologias caras vem sendo evitadas, sendo necessário o desenvolvimento de novas metodologias de síntese para Quantum Dots (QDs). Portanto, com o objetivo de baratear e diminuir a toxicidade dos QDs formados, devido à presença de agentes redutores presentes nas metodologias de síntese tradicionais, nesse trabalho foi desenvolvida uma metodologia de síntese eletroquímica para síntese de QDs de CdTe e CdSe estabilizados pelo ácido tioglicólico (TGA). A metodologia de síntese eletroquímica desenvolvida consiste na redução eletroquímica de alguns calcogênios (telúrio e selênio) em solução aquosa de NaOH 0,2 mol L-1 (pH = 13) e atmosfera inerte, para posterior reação com o precursor metálico,CdCl2/TGA. Os QDs obtidos a partir dessa metodologia apresentaram boa estabilidade e alta luminescência, com tamanhos médios de 3,9 nm para o CdTe e de 2,6 nm para o CdSe. Também foi avaliada a fluorescência dos QDs na presença do íon Hg2+, sendo observado que estas nanopartículas podem ser considerados promissores sensores químicos para determinação analítica de íons metálicos. / The demand for green synthetic methodologies has increased significantly in recent years. The use of toxic materials and expensive methodologies has been avoided, requiring the development of new methods of synthesis for Quantum Dots (QDs). Therefore, in order to cheapen and reduce the toxicity of QDs sintetizados, due to the need of reducing agents in the traditional synthetic methods, in this work we developed an electrochemical method for the synthesis of CdSe and CdTe QDs, stabilized by thioglycolic acid (TGA ). The electrochemical methodology developed involves the electrochemical reduction of some chalcogenes (tellurium and selenium) in aqueous solution (pH = 13) and inert atmosphere, for subsequent reaction with the metal precursor, CdCl2/TGA. The QDs obtained from this methodology showed good stability and high luminescence, with average sizes 3.9 nm for CdTe and 2.6 nm for CdSe. The fluorescence of the QDs in the presence of Hg2+ ion was also evaluated. It was observed that the electrochemically synthesized nanoparticles can be considered promising chemical sensors for analytical determination of metal ions.

This dissertation addresses the delicate problem of aging in complex systems characterized by non-Poissonian statistics. With reference to a generic two-states system interacting with a bath it is shown that to properly describe the evolution of such a system within the formalism of the continuous time random walk (CTRW), it has to be taken into account that, if the system is prepared at time t=0 and the observation of the system starts at a later time ta>0, the distribution of the first sojourn times in each of the two states depends on ta, the age of the system. It is shown that this aging property in the fractional derivative formalism forces to introduce a fractional index depending on time. It is shown also that, when a stationary condition exists, the Onsager regression principle is fulfilled only if the system is aged and consequently if an infinitely aged distribution for the first sojourn times is adopted in the CTRW formalism used to describe the system itself. This dissertation, as final result, shows how to extend to the non-Poisson case the Kubo Anderson (KA) lineshape theory, so as to turn it into a theoretical tool adequate to describe the time evolution of the absorption and emission spectra of CdSe quantum dots. The fluorescence emission of these single nanocrystals exhibits interesting intermittent behavior, namely, a sequence of "light on" and "light off" states, departing from Poisson statistics. Taking aging into account an exact analytical treatment is derived to calculate the spectrum. In the regime fitting experimental data this final result implies that the spectrum of the "blinking" quantum dots must age forever.

published_or_final_version / abstract / toc / Physics / Master / Master of Philosophy

published_or_final_version / abstract / Physics / Doctoral / Doctor of Philosophy

Quantum dots (QDs) CdS and CdSe were synthesized in three different media including reverse micelles, aqueous solution, and trioctylphosphine oxide/trioctylphosphine (TOPO/TOP). Transmission electron microscope (TEM), X-ray diffraction (XRD), UV-VIS, fluorescence spectroscopy and microscopy were used to characterize the QDs and their nanoassemblies. CdS QDs synthesized in reverse micelles showed broad emission spectra. CdSe-CdS QDs with core shell structure synthesized in aqueous solution showed more than 30% emission quantum yield. CdSe-CdS QDs of different emission colors were prepared. CdSe and CdSe-ZnS QDs were also synthesized in TOPO/TOP media. This synthesis route produced highly luminescent CdSe QDs with over 50% emission quantum yield. The application of QDs as ions probes and methods to encapsulate QDs in nanospheres including micelles, glyconanospheres and silica nanospheres and the use of these nanospheres in bioassays are described. CdS QDs capped with different ligands such as thioglycerol, cysteine and polyphosphate showed different responses to biological relevant ions. The emission intensity of polyphosphate capped CdS QDs was affected by all the tested ions and did not show a selective response. On the other hand, the emission of thioglycerol capped CdS QDs was selectively quenched by copper ions while the emission of cysteine capped CdS QDs was selectively enhanced by zinc ions. Stern-Volmer equation was applied to correlate the emission intensity of the CdS QDs and the copper ion concentration. A Lagmuir isotherm binding equation was used to describe the relation between the emission intensity of cysteine capped CdS QDs and zinc ion concentration. The possible mechanism to explain the effects of capping ligands on CdS QDs responses to ions is also discussed. CdSe QDs synthesized in TOPO/TOP media were encapsulated in nanospheres for bioassay applications. The glyconanospheres contained a large number of glucose residues on their surface and showed high binding activity towards the lectinic protein Concanavalin A (Con A). Silica nanospheres containing hundreds of CdSe QDs were functionalized with thiol groups to enable the conjugation of streptavidin to the nanospheres. The streptavidin modified silica nanospheres were used as luminescent indicators in a sandwich immunoassay for the detection of antiprotein A antibody. The advantages and disadvantages of the nanospheres based bioassay are discussed.

Thesis advisor: Torsten Fiebig / This dissertation examines the chemistry and photophysics of semiconductor quantum dots with the intent of studying their capabilities and limitations as they pertain to photovoltaic technologies. Specifically, experiments are presented detailing the first time-resolved measurements of electron transfer in electronically coupled quantum rods. Electron transfer from the conduction band of CdTe was measured to occur on the 400 fs timescale (<italic>k_ET</italic> = 2.5 x 10<super>12</super> s<super>-1</super>), more than 500x faster than previously believed. Additionally, the direct optical promotion of an electron from the valence band of CdTe was observed, occurring on the timescale of the pump pulse (~50 fs). Based on the determined injection rates, a carrier separation efficiency of > 90% has been calculated suggesting these materials are sufficient for use in solar energy capture applications where efficient carrier separation is critical. To this end, model photovoltaic cells were fabricated, and their power conversion efficiency and photon-to-current generation efficiency characterized. In devices based of CdSe and heteromaterial quantum rods we observed fill-factors on the order of 10-20% though with power conversion efficiencies of < 0.02%. It was discovered that using a high temperature annealing step, while critical to get electrochemically stable photoelectrodes, was detrimental to quantum confinement effects and likely removed any hQR specific capabilities. Additionally, a detailed study on the role of nucleotide triphosphate chemistry in stabilizing emissive CdS nanoparticles is presented. Specifically it was observed that in a neutral pH environment, GTP selectively stabilizes CdS quantum dots with diameters of ~4 nm while the other naturally occurring ribonucleotides do not yield emissive product. The selectivity is dependent on the presence of the nucleophilic N-7 electrons near a triphosphate pocket for Cd<super>2+</super> complexation as well as an exocyclic amine to stabilize the resulting product particles. However, in an elevated pH environment, the nucleobase specificity is relaxed and all NTPs yield photo-emissive quantum dots with PLQEs as high as 10%. / Thesis (PhD) — Boston College, 2009. / Submitted to: Boston College. Graduate School of Arts and Sciences. / Discipline: Chemistry.