L'élaboration de méthodes de synthèse, basées sur l’utilisation d’espèces métalliques a été un sujet de tous les instances en chimie organique. Malgré l’efficacité des métaux utilisés en catalyse homogènes, leurs procédures de recyclage restent limitées. Ce pourquoi, une contrainte supplémentaire a été placée dans la conception de catalyseurs, pouvant offrir à la fois l'efficacité de la catalyse homogène et le recyclage de l’hétérogène. Dans ce contexte, les nanoparticules métalliques sont apparues comme objet phare, en raison de leurs propriétés physico-chimiques inégalées. On a découvert que les nanoparticules de métaux nobles présentaient des propriétés catalytiques similaires dans certains cas, aux complexes monoatomiques. De plus, les Au NPs ont montré une activité catalytique remarquable dans l'oxydation d’alcools activés sous O2. Nous avons donc envisagé des procédures multicatalytiques, basées sur les NPs d’Au. Notre choix d'utiliser des catalyseurs solides était pertinent, puisque les nano-catalyseurs, pour lesquels la fraction de sites actifs se trouve en surface, limitent les risques de cross-quenching. Ici, nous présentons trois nouveaux procédés bicatalytiques permettant l’accès, à des chromenes/quinoléines (53-93%) via une oxydation / Michael Addition/ aldolisation, combinant nanocatalyse et catalyse basique, l’accès à des ortho-THC (50-81%) via oxydation / arylation / cyclisation, combinant nanocatalyse et catalyse supportée, ainsi qu’une une oxydation / hydrolyse en cascade, pour accéder à l’HMLA (86%, sel 93%), un grand panel de produits d'activité biologique reconnue, utilisé en parfumerie ou visant une pré-industrialisation via la chimie en flux continu. / Elaboration of synthetic methods based on metal-catalyzed reactions has been a hot topic in organic chemistry. Despite good efficiency, catalysis proceeding homogeneously, are limited in the operation of recovering/recycling of the catalysts. An important stress was placed to design catalysis, offering both the efficiency of homogeneous catalysts and the recyclability of heterogeneous catalysts. In this context, metal nanoparticles merged as a key tool, due to their unique physical and chemical properties. Notably, Au NPs have shown remarkable catalytic activity in the oxidation of activated alcohols under O2 atmosphere. Since now, the access to more complex molecules is the next step forward for this field, we envisioned multicatalytic roads, based on the oxidation of activated alcohols via supported Au NPs. Our choice of using solid catalysts was relevant, since nanostructured catalysts for which the fraction of active sites are located on the surface, limit the risk of cross-quenching. The latter carbonyl formed, could be further converted in situ, via tandem protocol. Herein, we developed novel, atom- and step-economical bicatalytic one-pot processes, to access substituted chromenes/quinolines (53-93%) by tandem oxidation/hetero-Michael addition/aldolisation combining nanocatalysis and base catalysis, ortho-THCs (50-81%) via tandem oxidation/arylation/cyclisation combining nanocatalysis and supported catalysts and a tandem cascade oxidation/hydrolysis to access HMLA (86%, sel 93%). A large panel of products of biological activity relevance, pertaining to the fragrance chemistry or aiming in some cases, pre-industrial scalability via continuous flow applications.

Com o desenvolvimento de novos nanomateriais têm-se descoberto propriedades eletrônicas, elétricas, ópticas e catalíticas únicas para aplicações nanotecnológicas. Entre estes nanomateriais com caraterísticas singulares, estão as nanopartículas (Np) CoreαShell, as quais combinam propriedades físico-químicas de dois materiais diferentes, provendo maior eficiência em aplicações como nanoeletrônica, sensoreamento, biossensoreamento e biomédicas. Neste trabalho, Np CoreαShell são sintetizada com núcleo (Core) de Np Fe₃O₄ e com casca (Shell) de Np Au, formando as Nps Fe₃O₄αAu na presença do dendrímero poli(amidoamina) geração 4.0 (Pamam G4). As propriedades físico-químicas do nanomaterial core-shell são estudadas através de análises espectroscópicas, microscopias e eletroquímicas, além de medidas de magnetização. Essas técnicas revelam a formação das Nps Au nas cavidades do Pamam G4 e as interações eletrostáticas entre os grupos funcionais do Pamam G4 e os grupos OH ⁻ e H ⁺ da superfície das Nps magnéticas, as quais dão uma forte estabilidade na configuração da Np Fe₃O₄αAu. Evidencia-se propriedades óticas da Np Au e propriedades superparamagnéticas da Np Fe ₃ O ₄, as quais podem ser usadas para aplicações em nanomedicina. As propriedades electrocatalíticas das Nps são utilizadas na detecção de dopamina (DA). Foram fabricados sensores eletroquímicos das Nps Fe₃O₄αAu, Nps Fe₃O₄ e Nps Au, e caracterizados por técnicas de voltametria cíclica e voltametria de pulso diferencial. A fabricação dos sensores consistiu na deposição de camadas alternadas entre as nanopartículas com o poliânion poly(ácido vinil sulfônico) (PVS) no eletrodo de ITO, levando à configuração de três arquiteturas; ITO - (Fe₃O₄αAu ⁄ PV S), ITO - (Fe₃O₄ ⁄ PV S) e ITO - (Au ⁄ PV S). Um problema encontrado na detecção de DA é que esta tem potenciais de oxidação aproximadamente iguais ao ácido ascórbico (AA) e ao ácido úrico (AU). Portanto, os sensores utilizados na detecção de DA, devem ser altamente seletivos a DA em relação a seus interferentes. Os sensores desenvolvidos aqui mostraram uma boa seletividade e velocidade de resposta na detecção de DA, sendo o sensor ITO - (Fe₃O₄αAu ⁄ PV S) o mais eficiente. As Nps Fe₃O₄αAu revelam maior citotoxicidade nas células cancerígenas comparadas com as células saudáveis, já que as células cancerígenas são mais sensíveis ao estresse oxidativo produzido pelas nanopartículas no interior da célula. / Along with the development of nanomaterials came the knowledge and design of their unique eletronic, optical and catalitycal properties which may be used for a variety of nanotecnological applications. A special class of nanomaterials with interesting characteristics is represented by the CoreαShell nanoparticles, which combine the physicochemical properties of two differerent nanomaterials (including oxides, metals, semiconductors or polymers). This combination provides greater efficiency in applications such as nanoelectronics, sensing, biosensing and biomedical areas. This study reports the synthesis of Fe₃O₄ Np, which in the presence of the polyamido amine generation 4.0 (Pamam G4), is covered with Au Np forming the Fe₃O₄αAu Nps. The nanomaterials had been characterized using spectroscopic, microscopic and electrochemical techniques. The results revealed the formation of Au Nps in the cavities of PAMAM G4 and showed that the electrostatic interactions between the PAMAM functional groups and the OH ⁻ and H ⁺ groups on the surface of the magnetic nanoparticles lead to a strong stability in the configuration of Fe₃O₄αAu Nps. The optical properties of the Au Np (namely the Plasmon resonance band at 542 nm) as well as the superparamagnetic properties of the Fe₃O₄ Np were present in the core-shell nanostrutures. Due to their electrocatalytical properties, the core-shell nanoparticles were employed as active elements for dopamine (DA) detection. The fabrication of the modified electrodes for DA detection consisted in the deposition by LbL technique of alternating layers of nanoparticles and poly(vinyl sulfonic acid) (PVS) on the ITO eletrode, in three distinct architectures: ITO - (Fe₃O₄αAu Fe₃O₄ PV S), ITO - (Fe₃O₄ ⁄ PV S) and ITO - (Au ⁄ PV S). We found a good selectivity and rapid response toward the detection of DA, being the sensor ITO - (Fe₃O₄αAu ⁄ PV S) the most efficient. The effect of Fe₃O₄αAu Nps showed a higher cytotoxicity in cancer cells compared to healthy cells, because cancer cells are more sensitive to oxidative stress produced by the nanoparticles.

Com o desenvolvimento de novos nanomateriais têm-se descoberto propriedades eletrônicas, elétricas, ópticas e catalíticas únicas para aplicações nanotecnológicas. Entre estes nanomateriais com caraterísticas singulares, estão as nanopartículas (Np) CoreαShell, as quais combinam propriedades físico-químicas de dois materiais diferentes, provendo maior eficiência em aplicações como nanoeletrônica, sensoreamento, biossensoreamento e biomédicas. Neste trabalho, Np CoreαShell são sintetizada com núcleo (Core) de Np Fe₃O₄ e com casca (Shell) de Np Au, formando as Nps Fe₃O₄αAu na presença do dendrímero poli(amidoamina) geração 4.0 (Pamam G4). As propriedades físico-químicas do nanomaterial core-shell são estudadas através de análises espectroscópicas, microscopias e eletroquímicas, além de medidas de magnetização. Essas técnicas revelam a formação das Nps Au nas cavidades do Pamam G4 e as interações eletrostáticas entre os grupos funcionais do Pamam G4 e os grupos OH ⁻ e H ⁺ da superfície das Nps magnéticas, as quais dão uma forte estabilidade na configuração da Np Fe₃O₄αAu. Evidencia-se propriedades óticas da Np Au e propriedades superparamagnéticas da Np Fe ₃ O ₄, as quais podem ser usadas para aplicações em nanomedicina. As propriedades electrocatalíticas das Nps são utilizadas na detecção de dopamina (DA). Foram fabricados sensores eletroquímicos das Nps Fe₃O₄αAu, Nps Fe₃O₄ e Nps Au, e caracterizados por técnicas de voltametria cíclica e voltametria de pulso diferencial. A fabricação dos sensores consistiu na deposição de camadas alternadas entre as nanopartículas com o poliânion poly(ácido vinil sulfônico) (PVS) no eletrodo de ITO, levando à configuração de três arquiteturas; ITO - (Fe₃O₄αAu ⁄ PV S), ITO - (Fe₃O₄ ⁄ PV S) e ITO - (Au ⁄ PV S). Um problema encontrado na detecção de DA é que esta tem potenciais de oxidação aproximadamente iguais ao ácido ascórbico (AA) e ao ácido úrico (AU). Portanto, os sensores utilizados na detecção de DA, devem ser altamente seletivos a DA em relação a seus interferentes. Os sensores desenvolvidos aqui mostraram uma boa seletividade e velocidade de resposta na detecção de DA, sendo o sensor ITO - (Fe₃O₄αAu ⁄ PV S) o mais eficiente. As Nps Fe₃O₄αAu revelam maior citotoxicidade nas células cancerígenas comparadas com as células saudáveis, já que as células cancerígenas são mais sensíveis ao estresse oxidativo produzido pelas nanopartículas no interior da célula. / Along with the development of nanomaterials came the knowledge and design of their unique eletronic, optical and catalitycal properties which may be used for a variety of nanotecnological applications. A special class of nanomaterials with interesting characteristics is represented by the CoreαShell nanoparticles, which combine the physicochemical properties of two differerent nanomaterials (including oxides, metals, semiconductors or polymers). This combination provides greater efficiency in applications such as nanoelectronics, sensing, biosensing and biomedical areas. This study reports the synthesis of Fe₃O₄ Np, which in the presence of the polyamido amine generation 4.0 (Pamam G4), is covered with Au Np forming the Fe₃O₄αAu Nps. The nanomaterials had been characterized using spectroscopic, microscopic and electrochemical techniques. The results revealed the formation of Au Nps in the cavities of PAMAM G4 and showed that the electrostatic interactions between the PAMAM functional groups and the OH ⁻ and H ⁺ groups on the surface of the magnetic nanoparticles lead to a strong stability in the configuration of Fe₃O₄αAu Nps. The optical properties of the Au Np (namely the Plasmon resonance band at 542 nm) as well as the superparamagnetic properties of the Fe₃O₄ Np were present in the core-shell nanostrutures. Due to their electrocatalytical properties, the core-shell nanoparticles were employed as active elements for dopamine (DA) detection. The fabrication of the modified electrodes for DA detection consisted in the deposition by LbL technique of alternating layers of nanoparticles and poly(vinyl sulfonic acid) (PVS) on the ITO eletrode, in three distinct architectures: ITO - (Fe₃O₄αAu Fe₃O₄ PV S), ITO - (Fe₃O₄ ⁄ PV S) and ITO - (Au ⁄ PV S). We found a good selectivity and rapid response toward the detection of DA, being the sensor ITO - (Fe₃O₄αAu ⁄ PV S) the most efficient. The effect of Fe₃O₄αAu Nps showed a higher cytotoxicity in cancer cells compared to healthy cells, because cancer cells are more sensitive to oxidative stress produced by the nanoparticles.

MESHWR / Department of Hydrology and Water Resources / This research involves the investigation of the interaction of different sized Nano Gold particles released into municipal drinking water and municipal waste water. Waste water was collected from Malamulele waste water treatment plant and the municipal water was collected at Mintek in Johannesburg, Randburg, South Africa. The waste water was analysed using ICP-MS to detect the metals and anions in it. The results showed the abundance of Sulphur (464 ppm), Calcium (28 ppm), Chloride (27.8 ppm), Iron (20 ppm), Magnesium (8.2 ppm), silicon (6.192 ppm) in descending order and other trace elements, including gold, that were immeasurable (<0.1). The simulated situation was created by adding 20nm gold and 40nm gold nanoparticles into municipal drinking water and waste water and kept at different environmental conditions (light, light and agitation, dark, dark and agitation) under aerobic and anaerobic conditions over a period of two months. Physico-chemical properties (pH and chemical oxygen demand) of the solutions were checked once in a month. The pH fluctuated between the acceptable ranges (5.5 – 9.5) for the two month period. Both municipal water and waste water, with and without gold nanoparticles, under aerobic condition showed an increase in chemical oxygen demand. The gold content in waste water under anaerobic condition showed an increase while under aerobic condition the decline in gold content was evident. The zeta potential of gold nanoparticles in waste water in light and agitation showed (-30 mV) while waste water on other environmental condition (light, dark and dark with agitation) presenting unstable (-18 mV) charge, but the charge shifted positively on the second month rendering them also unstable. Dynamic light scattering and TEM were used to check any possible aggregation or agglomeration of nanoparticles in the waste water. There were some few discrepancies where TEM and DLS contradict, but overall there was no significant probability of any aggregation of gold nanoparticles. The EDX was used to confirm the presence of Au0 in the waste water (with added gold nanoparticles). The research did show that the gold nanoparticles would exist as Au0 in the waste water and thus the discharge of Au-NPs to the sewer system is not recommended, but rather recycle them.