Neste trabalho a metaloporfirina de segunda geração Me(TFPP)Cl (Me=Fe e Mn) [cloreto de 5, 10, 15, 20 ? tetrakis(pentafluorofenil)porfirina de ferro (III) ou manganês (III)] foi ancorada covalentemente a suportes aminofuncionalizados, através da substituição nucleofílica dos átomos para-flúor dos grupos meso-arilas do pentafluorofenil, com o objetivo de se obter catalisadores sólidos seletivos para reações de oxidação de moléculas orgânicas. Os suportes montmorilonita (modificada com aminopropiltrietoxissilano, Mont1, e cloropropiltrietoxissilano e em seguida com 1,6-diaminoexil, Mont2) e sílica modificada com 1,6-diaminoexil (DAHS) foram inicialmente sintetizados; poliestireno aminofuncionalizado, PS, foi cedido pelo Prof. Dr. John Lindsay Smith, York-Inglaterra, filossilicatos híbridos de magnésio, Silx e Talx, foram sintetizados previamente pelo grupo do Prof. Dr. Cláudio Airoldi, UNICAMP-Campinas; e 3-aminopropilssílica, APS, foi adquirida da Aldrich. Primeiramente foi realizada a síntese e caracterização dos suportes Mont1, Mont2 e DAHS e das metaloporfirinas, seguida das reações de ancoragem. Os catalisadores sólidos foram caracterizados por UV/Vis, IV, EPR, TGA, Raio-x. A atividade catalítica destes catalisadores sólidos foi investigada na oxidação do cicloocteno, cicloexano e estireno, utilizando como oxidante PhIO e o H2O2. Estes sistemas permitiram estudar as variáveis: distância entre a metaloporfirina e a superfície do suporte (tamanho de ?braço?); diferença de polaridade; tipo de estrutura do suporte (amorfo ou lamelar, orgânico ou inorgânico, rígido ou flexível); metal central da metaloporfirina; proteção dos grupos NH2 livre no suporte. De maneira geral os sistemas investigados mostraram ser catalisadores eficientes para todos os substratos, principalmente utilizando PhIO como oxidante. Em nenhum caso se observou lixiviação da metaloporfirina do suporte, provando que a ligação covalente é um método muito eficiente para preparar catalisadores ancorados. A estabilidade destes sistemas também foi comprovada realizando-se quatro ciclos de reação com o mesmo catalisador sólido, sendo que os rendimentos de produtos foram reprodutíveis. As FeP foram catalisadores mais eficientes que as MnP, mesmo quando se utilizou imidazol como co-catalisador para as MnP. Os melhores catalisadores foram os FeAPS, FeMont1, FeDAHS, FeTal2 e FeSil2. Todos estes catalisadores sólidos são rígidos e inertes, com um tamanho de ?braço? intermediário (4-7 átomos). A proteção dos grupos amino livres no suporte é fundamental para melhorar a eficiência catalítica de metaloporfirinas ancoradas em suportes aminofuncionalizados, pois evita a bis-coordenação dos NH2 ao metal, responsável pelo bloqueio do sítio catalítico. Embora os rendimentos dos produtos de oxidação utilizando o H2O2 tenham sido menores do que aqueles com o PhIO, alguns sistemas foram mais eficientes quando comparados com a metaloporfirina em solução, tanto do ponto de vista de rendimentos como de seletividade. Estes resultados abrem a possibilidade de aplicação desses sistemas para a oxidação de fármacos e poluentes. / In this work the second generation metalloporphyrin Me(TFPP)Cl (Me = Fe and Mn) [5,10, 15, 20 ? tetrakis(pentafluorophenyl) porphyrin iron (III) or manganese (III) chloride] was covalently anchored to aminofunctionalyzed supports, through nucleophilic substituition of the para-fluorine atoms of the pentafluorophenyl meso-aryl groups, with the objective of obtaining selective solid catalysts for oxidation reactions of organic molecules. The supports montmorillonite (modified with aminopropyltrietoxysilane, Mont1, and chloropropyltrietoxysilane followed by 1,6 ? diaminohexil, Mont2) and silica modified with 1,6 ? diaminohexil (DAHS) were initially synthesized; aminofunctionalyzed polystyrene, PS, was given by Prof. Dr. John Lindsay Smith, York ? England; hybrid magnesium phyllosilicates, Silx and Talx, were previously synthesized by Prof. dr. Cláudio Airoldi´s research group, UNICAMP ? Campinas; and 3 ? aminopropylsilica, APS, was purchased from Aldrich. The supports Mont1, Mont2, DAHS and metalloporphyrins were firstly synthesized and characterized, followed by the anchoring reactions. The solid catalysts were characterized by UV/Vis, IR, EPR, TGA, X-ray. The catalytic activity of these solid catalysts was investigated in the oxidation of cyclooctene, cyclohexane and styrene, using PhIO and H2O2, as oxidants. These systems possibilities the study of the effects: distance between the metalloporphyrin and the supports surface (?arm? size); polarity; support?s structures (amorphous or lamellar, organic or inorganic, rigid or flexible); metalloporphyrin´s central metal ion; protection of the free NH2 on the support. In general way, the investigated systems show to be efficient catalysts for all substrates, mainly from the supports, proving that the covalent bond is an efficient method for the preparing of anchored catalysts. The stability of these systems was also investigated through developing four reaction cycles with the same solid catalyst, with reproducible products yields. The FeP were more efficient catalysts than the MnP, even using imidazole as co-catalyst for the MnP. The better catalysts were FeAPS, FeMont1, FeDAHS, FeTal2 and FeSil2. All these solid catalysts are rigid and inert, with an intermediary ?arm? size (4-7 atoms). The protection of the support?s free NH2 groups is fundamental to improve the catalytic efficiency of metalloporphyrins anchored on aminofunctionalized supports, because it avoids the bis-coordenation of the NH2 groups to the metal ion, effect responsible for the blocking of the catalytic site. Although the oxidation products yields using H2O2 have been lower than these using PhIO, some systems were more efficient when compared to the homogeneous systems both in product yield and selectivity. These results open the possibility for utilization of the system for drugs and poluents oxidation.

Neste trabalho a metaloporfirina de segunda geração Me(TFPP)Cl (Me=Fe e Mn) [cloreto de 5, 10, 15, 20 ? tetrakis(pentafluorofenil)porfirina de ferro (III) ou manganês (III)] foi ancorada covalentemente a suportes aminofuncionalizados, através da substituição nucleofílica dos átomos para-flúor dos grupos meso-arilas do pentafluorofenil, com o objetivo de se obter catalisadores sólidos seletivos para reações de oxidação de moléculas orgânicas. Os suportes montmorilonita (modificada com aminopropiltrietoxissilano, Mont1, e cloropropiltrietoxissilano e em seguida com 1,6-diaminoexil, Mont2) e sílica modificada com 1,6-diaminoexil (DAHS) foram inicialmente sintetizados; poliestireno aminofuncionalizado, PS, foi cedido pelo Prof. Dr. John Lindsay Smith, York-Inglaterra, filossilicatos híbridos de magnésio, Silx e Talx, foram sintetizados previamente pelo grupo do Prof. Dr. Cláudio Airoldi, UNICAMP-Campinas; e 3-aminopropilssílica, APS, foi adquirida da Aldrich. Primeiramente foi realizada a síntese e caracterização dos suportes Mont1, Mont2 e DAHS e das metaloporfirinas, seguida das reações de ancoragem. Os catalisadores sólidos foram caracterizados por UV/Vis, IV, EPR, TGA, Raio-x. A atividade catalítica destes catalisadores sólidos foi investigada na oxidação do cicloocteno, cicloexano e estireno, utilizando como oxidante PhIO e o H2O2. Estes sistemas permitiram estudar as variáveis: distância entre a metaloporfirina e a superfície do suporte (tamanho de ?braço?); diferença de polaridade; tipo de estrutura do suporte (amorfo ou lamelar, orgânico ou inorgânico, rígido ou flexível); metal central da metaloporfirina; proteção dos grupos NH2 livre no suporte. De maneira geral os sistemas investigados mostraram ser catalisadores eficientes para todos os substratos, principalmente utilizando PhIO como oxidante. Em nenhum caso se observou lixiviação da metaloporfirina do suporte, provando que a ligação covalente é um método muito eficiente para preparar catalisadores ancorados. A estabilidade destes sistemas também foi comprovada realizando-se quatro ciclos de reação com o mesmo catalisador sólido, sendo que os rendimentos de produtos foram reprodutíveis. As FeP foram catalisadores mais eficientes que as MnP, mesmo quando se utilizou imidazol como co-catalisador para as MnP. Os melhores catalisadores foram os FeAPS, FeMont1, FeDAHS, FeTal2 e FeSil2. Todos estes catalisadores sólidos são rígidos e inertes, com um tamanho de ?braço? intermediário (4-7 átomos). A proteção dos grupos amino livres no suporte é fundamental para melhorar a eficiência catalítica de metaloporfirinas ancoradas em suportes aminofuncionalizados, pois evita a bis-coordenação dos NH2 ao metal, responsável pelo bloqueio do sítio catalítico. Embora os rendimentos dos produtos de oxidação utilizando o H2O2 tenham sido menores do que aqueles com o PhIO, alguns sistemas foram mais eficientes quando comparados com a metaloporfirina em solução, tanto do ponto de vista de rendimentos como de seletividade. Estes resultados abrem a possibilidade de aplicação desses sistemas para a oxidação de fármacos e poluentes. / In this work the second generation metalloporphyrin Me(TFPP)Cl (Me = Fe and Mn) [5,10, 15, 20 ? tetrakis(pentafluorophenyl) porphyrin iron (III) or manganese (III) chloride] was covalently anchored to aminofunctionalyzed supports, through nucleophilic substituition of the para-fluorine atoms of the pentafluorophenyl meso-aryl groups, with the objective of obtaining selective solid catalysts for oxidation reactions of organic molecules. The supports montmorillonite (modified with aminopropyltrietoxysilane, Mont1, and chloropropyltrietoxysilane followed by 1,6 ? diaminohexil, Mont2) and silica modified with 1,6 ? diaminohexil (DAHS) were initially synthesized; aminofunctionalyzed polystyrene, PS, was given by Prof. Dr. John Lindsay Smith, York ? England; hybrid magnesium phyllosilicates, Silx and Talx, were previously synthesized by Prof. dr. Cláudio Airoldi´s research group, UNICAMP ? Campinas; and 3 ? aminopropylsilica, APS, was purchased from Aldrich. The supports Mont1, Mont2, DAHS and metalloporphyrins were firstly synthesized and characterized, followed by the anchoring reactions. The solid catalysts were characterized by UV/Vis, IR, EPR, TGA, X-ray. The catalytic activity of these solid catalysts was investigated in the oxidation of cyclooctene, cyclohexane and styrene, using PhIO and H2O2, as oxidants. These systems possibilities the study of the effects: distance between the metalloporphyrin and the supports surface (?arm? size); polarity; support?s structures (amorphous or lamellar, organic or inorganic, rigid or flexible); metalloporphyrin´s central metal ion; protection of the free NH2 on the support. In general way, the investigated systems show to be efficient catalysts for all substrates, mainly from the supports, proving that the covalent bond is an efficient method for the preparing of anchored catalysts. The stability of these systems was also investigated through developing four reaction cycles with the same solid catalyst, with reproducible products yields. The FeP were more efficient catalysts than the MnP, even using imidazole as co-catalyst for the MnP. The better catalysts were FeAPS, FeMont1, FeDAHS, FeTal2 and FeSil2. All these solid catalysts are rigid and inert, with an intermediary ?arm? size (4-7 atoms). The protection of the support?s free NH2 groups is fundamental to improve the catalytic efficiency of metalloporphyrins anchored on aminofunctionalized supports, because it avoids the bis-coordenation of the NH2 groups to the metal ion, effect responsible for the blocking of the catalytic site. Although the oxidation products yields using H2O2 have been lower than these using PhIO, some systems were more efficient when compared to the homogeneous systems both in product yield and selectivity. These results open the possibility for utilization of the system for drugs and poluents oxidation.

Η δυνατότητα να συνδυαστούν οι ιδιότητες οργανικών και ανόργανων συστατικών σε ένα μοναδικό νανοδομημένο υβριδικό υλικό αποτελεί μία σημαντική επιστημονική πρόκληση στο σχεδιασμό υλικών, τα οποία μπορούν να εμφανίζουν νέες βελτιωμένες ιδιότητες και να τύχουν προηγμένων εφαρμογών. Τα υβριδικά υλικά, γενικά, μπορούν να ταξινομηθούν σε δύο μεγάλες κατηγορίες: στην κατηγορία I (class I), όπου οι δύο φάσεις συνδυάζονται μέσω ασθενών αλληλεπιδράσεων, και στην κατηγορία II (class II), όπου οι δύο φάσεις είναι σταθερά συνδεδεμένες. Στην παρούσα εργασία διερευνήθηκε η δυνατότητα εφαρμογής νανοδομημένων υβριδικών υλικών ως ετερογενείς καταλύτες στη διεργασία παραγωγής βιοντίζελ από διαφόρων ειδών έλαια. Κατά τη διεργασία αυτή, η οποία καλείται μετεστεροποίηση ή μεθανόλυση, τριγλυκερίδια αντιδρούν με μια αλκοόλη παρουσία ισχυρού οξέος ή βάσης προς παραγωγή εστέρων και γλυκερίνης. Σε πρώτη φάση, εστιάσαμε στη σύνθεση και το χαρακτηρισμό class I και class II υβριδικών οργανικών/ανόργανων υλικών αποτελούμενων από έναν ανόργανο πυρήνα διοξειδίου του πυριτίου (silica), ο οποίος θα περιβάλλεται από πολυμερικές αλυσίδες. Έτσι, στην προσπάθεια σύνθεσης υβριδικών υλικών class I αξιοποιήθηκαν οι πιθανές αλληλεπιδράσεις καθαρών και αμινοτροποποιημένων νανοσωματιδίων διοξειδίου του πυριτίου με υδατοδιαλυτά συμπολυμερή P(SSΗ-co-MA) του στυρενοσουλφονικού οξέος (SSH), με το μηλεϊνικό οξύ (ΜΑ), τα οποία φέρουν τόσο καρβοξυλικές όσο και σουλφονικές ομάδες. Ως αποτέλεσμα του όξινου χαρακτήρα των πολυμερών, τα υβριδικά νανοσωματίδια θα μπορούσαν δυνητικά να χρησιμοποιηθούν ως όξινοι καταλύτες κατά την παραγωγή του βιοντίζελ. Στην προσπάθεια σύνθεσης class II υβριδικών υλικών αξιοποιήθηκε κυρίως ο πολυμερισμός ελευθέρων ριζών μέσω μεταφοράς ατόμου (ATRP), μονομερών όπως στυρενοσουλφονικό νάτριο (SSNa), Ν-ισοπροπυλακρυλαμίδιο (NIPAM) και 2-(διμεθυλαμινο)μεθακρυλικός αιθυλεστέρας (DMAEMA). Για την εκκίνηση του πολυμερισμού χρησιμοποιήθηκαν νανοσωματίδια silica χημικά τροποποιημένα με 3-αμινοπροπυλοτριαιθοξυσιλάνιο και ακολούθως με 2-χλωροπροπιονυλοχλωρίδιο. Εναλλακτικά, χρησιμοποιήθηκαν νανοσωματίδια silica χημικά τροποποιημένα με 3-χλωροπροπυλoτριαιθοξυσιλάνιο (ATRP πολυμερισμός), ή βινυλοτριμεθοξυσιλανιο (πολυμερισμός ελευθέρων ριζών, FRP). Ο χαρακτηρισμός των δειγμάτων κατά περίπτωση έγινε με φασματοσκοπία πυρηνικού μαγνητικού συντονισμού υδρογόνου (1H NMR), φασματοσκοπία υπερύθρου με μετασχηματισμό Fourier (FTIR), θερμοσταθμική ανάλυση (TGA) και τιτλοδότηση οξέος-βάσεως. Στο τελευταίο μέρος της εργασίας ελέγχθηκε η καταλυτική δράση κάποιων εκ των συντεθέντων υλικών στην αντίδραση μεθανόλυσης της τριοξικής γλυκερόλης, χρησιμοποιώντας την τεχνική 1H NMR. Διαπιστώθηκε πως τα αμινοτροποποιημένα νανοσωματιδία silica εμφανίζουν σημαντική καταλυτική δράση. Αντίθετα η ικανότητα των υβριδικών οργανικών/ανόργανων υλικών silica-NH2(B)/P(SSH50-co-MA50), silica-NH2(D)/P(SSH75-co-MA25), και silica-VTMS-PDMAEMA να δρουν ως όξινοι ή βασικοί καταλύτες της ίδιας αντίδρασης είναι πολύ περιορισμένη. / The possibility to combine the properties of organic and inorganic components in a unique nanostructured hybrid material is a major scientific challenge in designing novel materials exhibiting improved properties and finding advanced applications. Hybrid materials generally can be classified into two categories: class I, where the two phases are combined through weak interactions, and class II, where the two phases are covalently connected. The aim of the present study was to develop novel hybrid organic/inorganic nanomaterials, potentially applied as heterogeneous catalysts in the biodiesel production process. In this process, called transesterification or methanolysis, triglycerides from various oils react with an alcohol in the presence of a strong acid or base to produce the respective esters and glycerin. In the first part of this work, we focused on the synthesis and characterization of class I and class II hybrid organic/inorganic nanomaterials consisting of an inorganic silicon dioxide (silica) core and a polymer shell. Thus, for the class I hybrid materials we took advantage of the weak interactions between net or amino-functionalized silica nanoparticles and water-soluble P(SSH-co-MA) copolymers of styrene sulfonic acid (SSH), with maleic acid (MA), carrying both carboxyl and sulfonic groups. These hybrid nanoparticles could potentially be used as acidic catalysts in the production of biodiesel, as a consequence of the acidic nature of the polymer used. For the class II hybrid materials, we mostly applied atom transfer radical polymerization (ATRP) of monomers such as sodium styrene sulfonate (SSNa), N-isopropylacrylamide (NIPAM) and 2-(dimethylamino) ethyl methacrylate (DMAEMA). To initiate the polymerization, silica nanoparticles chemically modified with 3-aminopropyltriethoxysilane and subsequently with 2-chloropropionylchloride were used. Alternatively, we also used silica nanoparticles chemically modified with 3-chloropropyltriethoxysilane (ATRP polymerization), or vinyltrimethoxysilane (free radical polymerization, FRP). In all cases, the products were characterized through a combination of techniques, such as proton nuclear magnetic resonance spectroscopy (1H NMR), Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA) and acid-base titration. In the latter part of this work, the catalytic activity of some materials in the methanolysis process of glycerol triacetate was investigated, using the 1H NMR technique. It was found that the aminofunctionalized silica nanoparticles exhibit significant catalytic activity, whereas the ability of the hybrid materials silica-NH2(B)/P(SSH50-co-MA50), silica-NH2(D)/P(SSH75-co-MA25) and silica-VTMS-PDMAEMA to act as acidic or basic catalysts is very limited.