>Magister Scientiae - MSc / A novel 3-mercaptopropionic acid capped iridium selenide quantum dots based label free impedimetric immunosensor was successfully constructed. The 3-mercaptopropionic acid capped iridium selenide quantum dots synthesized were studied using HRTEM, revealing the formation of very small sizes, of about 3 nm. The optical Uv-Vis absorption wavelength of the quantum dots is blue-shifted, a phenomenon explained by the effective mass approximation (EMA) for semiconducting materials with sizes below 10 nm. Using cyclic voltammetry it is noted that the quantum dots have interesting electro-catalytical properties. The immunosensor proved to be sensitive towards nodularin, with a very low detection limit of 0.009 ng/mL and is significantly lower than the recent anti-nodularin ELISA kit developed by (Zhou et al., 2011) which has a detection limit of 0.16 ng/mL.Also the dection limit of the immunosensor is below the South African guideline value for microcystin-LR (0-0.8) μg/L (DWAF; 1996). The calibration curve of the 3MPA-GaSe nanocrystal based biosensor was successfully constructed, which exhibited a trend described by Michaelis-Menten, a typical behaviour of enzymatic biosensors. The detection limit of the biosensor is 0.004 nM and is significantly lower than the action limit of 17beta-estradiol, (1.47 x 10-10 M).

The synthesis, spectroscopic characterization, and studies of the photophysicochemical behaviour of selective anionic, cationic and neutral metallophthallocyanine (MPc) complexes were carried out and the results are presented herein. Studies on the effect of the central metal ion, the solvent used and the presence of nanoparticles on the photophysicochemical properties were conducted. The findings showed that the photophysicochemical parameters were mostly enhanced in the presence of central metal ions of high atomic numbers and also in the presence of nanoparticles. It was also observed that solvents that encouraged the monomericity of the MPc complexes also lead to improved photophysical and photochemical behaviour. CdTe quantum dots (QDs) stabilized with mercaptocarbonic acids were also observed to cause stimulated emission of the MPcs through Förster resonance energy transfer (FRET) thus acting as energy donors while the respective MPc acted as energy acceptors in all the FRET studies. FRET was observed following the photoexcitation of QDs for all monomeric anionic MPcs but it was also shown to occur for some cationic MPcs in organic media. Both the substituent and solvent used were found to exert a strong influence on the occurrence of FRET. Other cationic MPcs however showed different behaviour in the presence of the meraptocarbonic stabilized CdTe QDs; with the cationic porphyrazine giving clear indications of Pc ring reduction. The rest of the cationic MPcs did not give clear evidence of Pc ring reduction, instead they showed signs of aggregate formation possibly from the assembly of electrostatic ion pair complexes which could result in reduction of the quaternized pyridinium ring of the substituent. Both the QDs and the MPc complex emission spectra were significantly quenched for each in the presence of the other. Stern-Volmer quenching studies indicated that both static and dynamic quenching of the QDs in the presence of MPcs took place. The fluorescence lifetimes of the mercaptopropionic acid (MPA) capped CdTe QDs in the presence of various MPc complexes showed quenching of mostly the longer lifetimes of the QDs in the presence of MPcs suggesting that the surface defects and states are involved in the interaction of the QDs and MPcs. An MPc complex terminating in thio tethers was employed in the conjugation to AuNPs. Spectroscopic and microscopic studies confirmed the formation of the MPc-AuNP conjugate which was also shown to exhibit improved photophysicochemical properties compared to the free MPc.

The potential toxicity of seven different types of quantum dots without shell (L-cysteine-CdTe, TGA-CdTe, MPA-CdTe, TGA-CdSe) and with the shell (GSH-CdSe@ZnS, GSH-CdTe@ZnS,) with different capping agents were evaluated. The growth inhibitory effects of the various quantum dots on human pancreatic BON cancerous cells were determined. The least cytotoxic of the various quantum dots synthesized and the one displaying the lowest growth inhibitory potential and no embryotoxicity was determined to be the GSH-CdSe@ZnS quantum dots. The GSH-CdSe@ZnS quantum dots were then conjugated to gallium, aluminium and indium octacarboxy phthalocyanine and the photophysical behaviour of the conjugates studied for potential use in photodynamic therapy and imaging applications. The sizes, morphology, thermal stability and confirmation of successful conjugation was determined using X-ray diffraction (XRD), transmission electron microscopy (TEM), thermogravimetric analysis (TGA) and Fourier transform infrared spectroscopy (FTIR), respectively. The study was extended by conjugating amino functionalized magnetic nanoparticles (Fe₃O₄) to indium octacarboxy phthalocyanine to study the photophysical behaviour of the conjugate as a potential bi-functional anti-cancer agent (hyperthermia and photodynamic therapy applications). A three-in-one multifunctional nanocomposite comprising of the quantum dots, magnetic nanoparticles and indium octacarboxy phthalocyanine was developed with the aim of developing a multifunctional composite that is able detect, monitor and treat cancer. All conjugates showed improved and enhanced photophysical behaviour. Finally, GSH-CdSe@ZnS conjugated to aluminium octacarboxy phthalocyanine was applied in human pancreatic carcinoid BON cells. The conjugates induced cell death dose-dependently.

The synthesis, characterization and amphiphilic self-assembly of polymer brush functionalized nanoparticles (PBNPs) using a block copolymer template is described herein. To study the effect of polymer brush composition on self-assembly, four samples were created using a mixture of PS-b-PAA (polystyrene-block-polyacrylic acid) and PMMA-b-PAA (poly(methyl methacrylate)-block-polyacrylic acid) diblock copolymers to create PBNPs with a CdS quantum dot (QD) core and different ratios of PS and PMMA in the coronal brush. Static light scattering showed that despite differences in brush composition, the PBNPs formed nanoparticles of similar aggregation number and chain density but showed evidence of asymmetric structure in a common solvent for both blocks at higher PS contents. After subsequent hydrolysis of the hydrophobic PMMA to hydrophilic poly(methacrylic acid) (PMAA), these amphiphilic particles were then self-assembled in THF/H2O solution in which it was determined that increasing the hydrophobic content of the brush composition, the initial nanoparticle concentration (c0) or the added salt content (RNaCl), would cause the assembly of low curvature assemblies. Compilation of this data allowed for the construction of phase diagrams for PBNP systems based on brush composition and c0 at different salt contents. Lastly, PS-b-PAA-b-PMMA triblock copolymers with variable PMMA chain length were assembled into PBNPs around a CdS QD core using a block copolymer template approach. Light scattering showed these particles also had similar aggregation number and chain density despite the difference in PMMA chain length. After hydrolysis of PMMA to PMAA these particles were then self-assembled in THF/H2O mixtures to determine the role of PMAA block length on the produced morphological structures. The resulting assemblies suggest that chain length played a minimal role in their self-assembly / Graduate / 2018-09-15

Submitted by Heitor Rapela Medeiros (heitor.rapela@ufpe.br) on 2015-03-03T18:07:38Z No. of bitstreams: 2 DISSERTAÇÃO DE ANTONIO_VERSÃO_FINAL.pdf: 2621194 bytes, checksum: 63f0412f30f9e4e90794017db0616113 (MD5) license_rdf: 1232 bytes, checksum: 66e71c371cc565284e70f40736c94386 (MD5) / Made available in DSpace on 2015-03-03T18:07:38Z (GMT). No. of bitstreams: 2 DISSERTAÇÃO DE ANTONIO_VERSÃO_FINAL.pdf: 2621194 bytes, checksum: 63f0412f30f9e4e90794017db0616113 (MD5) license_rdf: 1232 bytes, checksum: 66e71c371cc565284e70f40736c94386 (MD5) Previous issue date: 2012-02-28 / CAPES / Os Quantum dots (QDs) ou ponto quânticos vem sendo cada vez mais aplicados na área de diagnóstico por fluorescência como uma alternativa mais estável em comparação com os corantes orgânicos usualmente aplicados. Em comparação a estes, os QDs têm características ópticas peculiares que os dão vantagens como: resistência ao fotoescurecimento, possuírem um estreito espectro de emissão e uma larga banda de absorção. Uma vez recobertos, estas nanoestruturas podem ser bioconjugadas a alvos biológicos ou mesmo a anticorpos tornando-se fluoroimunoensaios com grande especificidade. Este foi o objetivo deste manuscrito, onde CdS/Cd(OH)2 - emissão no verde - tendo como agente estabilizante o polifosfato de sódio ([(NaPO3)]n) e CdTe sintetizados com telúrio metálico, Cd(ClO4)2, ácido mercaptosuccínico (AMS) - emissão no laranja - e ácido mercaptopropiônico (AMP) - emissão no verde - como agentes estabilizantes, foram bioconjugados por formação de bases de Shiff e por adsorção a anticorpos do sistema sanguíneo ABO e, posteriormente, usados na marcação simples (A e B) e dupla (AB) de eritrócitos previamente fenotipados sendo o tipo O foi usado como controle negativo. Os QDs foram caracterizados opticamente através de espectroscopias de absorção e emissão e estruturalmente através de técnicas de microscopias eletrônica de transmissão, pela qual pode ser confirmada a sua cristalinidade, e também a difração de raio-X, revelando diâmetros médios de ~3 nm para o QD-AMS, ~2 nm para o QD-AMP e ~7,5 nm para o CdS/Cd(OH)2. Através da Citometria de Fluxo, os sistemas QDs-anitocorpos demonstraram especificidade obtendo-se valores de 28,4% para os bioconjugados com CdS/Cd(OH)2-anti-A, 70,64% para o tipo A com o sistema CdTe/CdS-anti-A em FL2 (canal laranja), 37,73% para o tipo B com o sistema CdTe/CdS-anti-B em FL1 (canal verde) e 58,24% de dupla marcação detectada em ambos os canais. Os resultados dos QDs CdS/Cd(OH)2, QD-AMS e QD-AMP bioconjugados a anticorpos do sistema ABO mostram especificidade da técnica e abrem a possibilidade de determinação de fenótipos fracos desse sistema. Além disso, serve de modelo para a bioconjugação com outros anticorpos e consequentemente, para o diagnóstico de várias doenças.

Single spins confined in semiconductor quantum dots - artificial atoms in the solid-state - are attractive candidates for quantum mechanical bits, the fundamental units and building blocks of a quantum computer. The ability to address quantum dot spins optically allows us to initialise and manipulate the state of the quantum bit. Gaining information on the qubit, for example by reading out its state, not only requires state-selective optical excitation, but also access to the single photons scattered in response by the quantum dot. Further, for a distributed computer architecture where nodes of few quantum bits are interlinked via optical communication channels photonic quantum bits are required to faithfully transmit the quantum information. In this thesis we advocate resonant excitation of quantum dot transitions and collection of the resonance fluorescence to address two outstanding challenges: generating dephasing-free single photons for use as flying quantum bits and single-shot spin readout. To this end we investigate the spectral and first-order coherence properties of quantum dot resonance fluorescence. In particular, we directly observe highly coherent scattering in the low Rabi frequency limit which has remained unexplored for solid-state single photon emitters so far. At the same time, interactions with the semiconductor environment are revealed and quantified through their optical signatures: exciton-phonon coupling, nuclear spin dynamics and local electric field fluctuations signal a departure from the ideal atom-like behaviour. Taking advantage of the laser-like coherence of single phase-locked quantum dot photons in the Heitler regime, we demonstrate near-ideal two-photon quantum interference. This benchmark measurement is a precursor for the photonic entanglement of distant quantum dot spins in a quantum optical network, and the results here predict a high fidelity operation. Finally, moving to tunnel-coupled quantum dot molecules we show that the overlap of carrier wave functions in two closely spaced quantum dots forms new spin-selective optical transitions not available in single quantum dots. Then, the presence or absence of scattered photons reveals the electron spin. Intermittency in the quantum dot resonance fluorescence allowed us, for the first time, to observe spin quantum jumps in real-time. Both achievements - highly coherent photons and spin readout - provide the missing link to attempt creation of a small-scale quantum network now.

Indiana University-Purdue University of Indianapolis (IUPUI) / A Near-field Scanning Optical Microscope (NSOM) is used to study the resonant energy transfer between different size CdSe/ZnS quantum dots (QDs). The NSOM system is used to bring the small QDs which are 6 nm in diameter close to 8 nm diameter QDs which are embed with PMMA on a cover glass. The PMMA is used to prevent the 8 nm QDs from aggregation, which allows us to locate one dot on the cover slide and have the potential to get the interaction of two individual dots. A systematic methodology is used to localize a single QD on the cover glass and align the small and large QDs. Since the ground energy state of the small QDs match the excitation energy level of the large QDs. When the small dots get excited, part of the energy transfers to the large QDs. As the separation between small and large QDs is changed in near-field range (20-50nm), the transition probability is observed, indicating that the FRET level changes as a function of separation between small and large QDs. Possible future improvements are also discussed.

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