Avalia����o da express��o da cicloxigenase-2 de macr��fagos em diferentes graus histol��gicos de mastocitoma canino

Funda����o de Amparo �� Pesquisa do Estado de S��o Paulo (FAPESP)

S��ntese e caracteriza����o de h��bridos org��nico-inorg��nicos luminescentes para aplica����o em ensaios biol��gicos

P��s-gradua����o em Qu��mica - IBILCE

Imunolocaliza����o do fator de crescimento semelhante �� insulina (IGF-I) e do fator de crescimento epidermal (EGF) em ov��rios caninos e seus efeitos sobre a matura����o in vitro de o��citos: avalia����o nuclear

Conselho Nacional de Desenvolvimento Cient��fico e Tecnol��gico (CNPq)

Influ��ncia do ��ndice apopt��tico e da imuno-express��o da survivina no progn��stico de pacientes com mola hidatiforme completa

P��s-gradua����o em Ginecologia, Obstetr��cia e Mastologia - FMB

NANO(BIO)SENSORES ELECTROQUIMICOS Y PLASM��NICOS: DISE��O, CARACTERIZACI��N Y APLICACIONES PARA LA CUANTIFICACION DE BIOMARCADORES DE ALTO IMPACTO

En Argentina, en consonancia con el resto del mundo, la Nanotecnolog��a es considerada un ��rea estrat��gica. Sin embargo, las investigaciones en Nanobiotecnolog��a todav��a constituyen un ��rea de vacancia. El uso de nanomateriales para desarrollar plataformas bioanal��ticas que permitan la construcci��n de biosensores ofrece m��ltiples ventajas y una promisoria perspectiva de aplicaci��n en diversas ��reas. En la actualidad, los laboratorios de an��lisis cl��nicos, la industria farmac��utica y alimentaria, y los laboratorios de control bromatol��gico y ambiental requieren de metodolog��as anal��ticas que proporcionen resultados exactos, reproducibles, r��pidos, sensibles y selectivos empleando peque��os vol��menes de muestra, con un m��nimo consumo de reactivos y una producci��n de deshechos limpia y escasa. Las investigaciones en nanobiosensores se encuentran dirigidas hacia el logro de estas metas. Uno de los grandes desaf��os es lograr biosensores miniaturizados con potencialidad para el desarrollo de dispositivos de medici��n descentralizada (���point of care���) y la detecci��n simult��nea de multianalitos. A��n cuando se han hecho innumerables desarrollos en los casi 50 a��os de vida de los biosensores, todav��a hay numerosos interrogantes por dilucidar. La modificaci��n con nanomateriales juega un rol preponderante en los transductores tanto en los electroqu��micos como en los plasm��nicos. El uso de pel��culas delgadas de Au para SPR modificadas con grafeno u ��xido de grafeno, es un campo de una enorme potencialidad y sin embargo es muy poco explotado, por lo que reviste gran importancia. En lo referido a la capa de biorreconocimiento, se trabajar�� con mol��culas capaces de establecer interacciones de bioafinidad, como los anticuerpos y tambi��n mol��culas que son muy poco usadas en nuestro pa��s y en Latinoam��rica como ADN, apt��meros, PNA y lectinas. RESUMEN: El Objetivo general de este proyecto es desarrollar nuevas plataformas bioanal��ticas para la detecci��n de diferentes eventos de bioafinidad a partir de la integraci��n de transductores electroqu��micos (EQ) y plasm��nicos con materiales nanoestructurados (nanotubos de carbono, nanol��minas de grafeno, nanoalambres met��licos); biomol��culas (ADN, ���peptide nucleic acid��� (PNA), apt��meros, anticuerpos, lectinas) y pol��meros funcionalizados con mol��culas bioactivas. Las arquitecturas supramoleculares resultantes estar��n dirigidas al desarrollo de biosensores EQ y plasm��nicos para la cuantificaci��n de biomarcadores de relevancia cl��nica y medioambiental. Se funcionalizar��n CNT, grafeno, ��xido de grafeno, nanoalambres met��licos empleando homop��ptidos y prote��nas con alta afinidad por cationes met��licos, los que se integrar��n a transductores de carbono y oro y biomol��culas de reconocimiento capaces de formar complejos de afinidad (ant��geno-anticuerpo, apt��mero-mol��cula blanco, ADN-ADN, PNA-ADN, lectinas-hidratos de carbono, ligandos-cationes met��licos y avidina-biotina). Se sintetizar��n y caracterizar��n nuevos mon��meros y pol��meros funcionalizados con mol��culas bioactivas y/o grupos r��dox empleando diferentes rutas sint��ticas. Se desarrollar��n genosensores para la detecci��n del evento de hibridaci��n de secuencias de inter��s m��dico (c��ncer de colon y de mama, tuberculosis); aptasensores para la detecci��n de marcadores proteicos de T. cruzi, enfermedades cardiovasculares y contaminantes cati��nicos; inmunosensores para la detecci��n de biomarcadores proteicos relacionados con enfermedades cardiovasculares y c��ncer; y biosensores de afinidad con lectinas para la detecci��n de hidratos de carbono. La caracterizaci��n de las plataformas y las se��ales anal��ticas se obtendr��n empleando las siguientes t��cnicas: voltamperometr��as c��clica, de pulso diferencial y de onda cuadrada; stripping; resonancia de plasm��n superficial; espectroscop��a de impedancia electroqu��mica; microscop��as de barrido electroqu��mico, SEM, TEM, AFM,SNOM, espectroscop��as: UV-vis, FTIR,Raman;RMN, TGA y DSC.

Complessi tetrazolici di Re(I): design e preparazione di una nuova classe di probes luminescenti

In this experimental work we report the design, the synthesis and characterization of a new class of Re(I) complexes of the general formula fac-[Re(CO)3(N^N)(2-QTZ)], where N^N = 2,2��� bipyridine or 1,10 phenantroline, whereas 2-QTZ is the anion 2-quinolyl-tetrazolate. The complexes and, in particular, the tetrazolate ligand 2-QTZ were designed in order to investigate their specific interaction with biologically and toxicologically relevant metal ions, as Zn(II), Cd(II) e Cu(II). The addition of such ions led to substantial variations of the photophysical properties of these complexes, suggesting their application as luminescent sensors. The photophysical performance of the complexes proved to remain unchanged inside cellular substrates, as Yarrowia Lipolytica cultures. Within these yeasts, the complexes show unchanged ability to perform luminescent sensing towards Zn(II) and Cd(II) ions.

Sintesi di leganti ciclopentadienonici e piridilimidazolici per complessi metallici. Metodo classico e microonde a confronto

In questo elaborato �� stata messa a punto una procedura sintetica, semplice e veloce che sfrutta la tecnica microonde per la sintesi di tetraarilciclopentadienoni variamente sostituiti mediante una condensazione bis-aldolica tra 1,3 difenilacetone con dichetoni aromatici variamente sostituiti. Questa nuova tecnica consente di ottenere tetraarilciclopentadienoni con rese da basse a buone in 25 minuti a 70��C. La stessa procedura sintetica �� stata valutata per ottenere leganti piridilimidazolici, usando come fonte di azoto NH4OAc. Basse rese e la formazione di svariati sottoprodotti ha diretto lo studio verso un approccio classico per la sintesi di questi sistemi. I leganti piridilimidazolici sono stati poi impiegati per la sintesi di complessi di Zn(II) luminescenti, i quali sono stati caratterizzati anche da un punto di vista fotofisico.

Da Laodice I a Laodice III: l'orizzonte politico delle regine seleucidi

Questo studio indaga la tradizione storiografica sulle regine seleucidi di III secolo a.C. - da Laodice I fino all���ascesa al trono di Laodice III - alla luce delle testimonianze documentarie. L���intento �� stabilire l���orizzonte politico dell���azione delle regine nel momento meno conosciuto e pi�� buio della storia del regno di Siria. Il III secolo seleucidico �� infatti un periodo caratterizzato da incertezza nella ricostruzione evenemenziale e nell���analisi delle dinamiche sociopolitiche, soprattutto a causa dell���interesse relativo e limitato delle fonti storiografiche antiche a noi giunte relativamente alle vicende della monarchia seleucidica precedenti l���avvento di Antioco III il Grande. In questo panorama rappresenta un���eccezione il caso di Laodice I, che �� al centro di un rilevante numero di testimonianze. Tenendo conto della differente natura delle fonti e della complessit�� del contesto evenemenziale, non sempre ricostruibile, �� stata studiata la figura di Laodice I nell���intento di comprendere il paradigma di regalit�� femminile stabilito dalle azioni della regina, e quindi l���influenza di tale paradigma sulla generazione seleucide successiva. La ricerca si articola in tre sezioni, legate agli eventi principali del III secolo seleucide che vedono coinvolta la regina. La prima parte �� dedicata all���attivit�� di Laodice I dopo il secondo matrimonio di Antioco II con la tolemaica Berenice. La seconda parte riguarda il ruolo di Laodice nei complessi eventi che seguirono la morte del marito Antioco II nel 246 e nella Terza Guerra Siriaca, che vide la regina a fianco del figlio Seleuco II contrapporsi a Tolemeo III e Berenice Sira. La terza sezione si occupa dell���azione di Laodice I nella Guerra Fraterna al fianco di Antioco Ierace contro Seleuco II e Laodice II. Nella conclusione si riflette sull���influenza delle azioni politiche di Laodice I sulla scelta di Antioco III di sposare la cugina Laodice III, prima principessa del Ponto entrata nella dinastia regnante.

New dimeric supramolecular structure of mixed (phthalocyaninato)(porphyrinato)-europium(III) sandwiches : preparation and spectroscopic characteristics

The mixed double-decker Eu\[Pc(15C5)4](TPP) (1) was obtained by base-catalysed tetramerisation of 4,5-dicyanobenzo-15-crown-5 using the half-sandwich complex Eu(TPP)(acac) (acac = acetylacetonate), generated in situ, as the template. For comparative studies, the mixed triple-decker complexes Eu2\[Pc(15C5)4](TPP)2 (2) and Eu2\[Pc(15C5)4]2(TPP) (3) were also synthesised by the raise-by-one-story method. These mixed ring sandwich complexes were characterised by various spectroscopic methods. Up to four one-electron oxidations and two one-electron reductions were revealed by cyclic voltammetry (CV) and differential pulse voltammetry (DPV). As shown by electronic absorption and infrared spectroscopy, supramolecular dimers (SM1 and SM3) were formed from the corresponding double-decker 1 and triple-decker 3 in the presence of potassium ions in MeOH/CHCl3.

Electrochemistry of Heteroleptic Tris(phthalocyaninato) Rare Earth(III) Complexes

The electrochemical characteristics of a series of heteroleptic tris(phthalocyaninato) complexes with identical rare earths or mixed rare earths (Pc)M(OOPc)M(OOPc) [M = Eu...Lu, Y; H2Pc = unsubstituted phthalocyanine, H2(OOPc) = 3,4,12,13,21,22,30,31-octakis(octyloxy)phthalocyanine] and (Pc)Eu(OOPc)Er(OOPc) have been recorded and studied comparatively by cyclic voltammetry (CV) and differential pulse voltammetry (DPV) in CH2Cl2 containing 0.1 M tetrabutylammonium perchlorate (TBAP). Up to five quasi-reversible one-electron oxidations and four one-electron reductions have been revealed. The half-wave potentials of the first, second and fifth oxidations depend on the size of the metal center, but the fifth changes in the opposite direction to that of the first two. Moreover, the difference in redox potentials of the first oxidation and first reduction for (Pc)M(OOPc)M(OOPc), 0.85���0.98 V, also decreases linearly along with decreasing rare earth ion radius, clearly showing the rare earth ion size effect and indicating enhanced ������� interactions in the triple-deckers connected by smaller lanthanides. This order follows the red-shift seen in the lowest energy band of triple-decker compounds. The electronic differences between the lanthanides and yttrium are more apparent for triple-decker sandwich complexes than for the analogous double-deckers. By comparing triple-decker, double-decker and mononuclear [ZnII] complexes containing the OOPc ligand, the HOMO���LUMO gap has been shown to contract approximately linearly with the number of stacked phthalocyanine ligands.

The ageing of alumina hydrolysates synthesized from sec-butoxyaluminium(III)

A combination of X-ray diffraction, thermal analysis and Raman spectroscopy was employed to characterise the ageing of alumina hydrolysates synthesised from the hydrolysis of anhydrous tri-sec-butoxyaluminium(III). X-Ray diffraction showed that the alumino-oxy(hydroxy) hydrolysates were pseudoboehmite. For boehmite the lamellar spacings are in the b direction and multiple d(020) peaks are observed for the un-aged hydrolysate. After 4 h of ageing, a single d(020) peak is observed at 6.53 ��. Thermal analysis showed five endotherms at 70, 140, 238, 351 and 445��C. These endotherms are attributed to the dehydration and dehydroxylation of the boehmite-like hydrolysate. Raman spectroscopy shows the presence of bands for the washed hydrolysates at 333, 355, 414, 455, 475, 495, 530 and 675 cm���1. These bands are attributed to pseudoboehmite. Ageing of the hydrolysates results in an increase in the crystallite size of the pseudoboehmite.

Comparative Electrochemical Study of Unsubstituted and Substituted Bis(phthalocyaninato) Rare Earth(III) Complexes

The electrochemistry of homoleptic substituted phthalocyaninato rare earth double-decker complexes M(TBPc)2 and M(OOPc)2 [M = Y, La...Lu except Pm; H2TBPc = 3(4),12(13),21(22),30(31)-tetra-tert-butylphthalocyanine, H2OOPc = 3,4,12,13,21,22,30,31-octakis(octyloxy)phthalocyanine] has been comparatively studied by cyclic voltammetry (CV) and differential pulse voltammetry (DPV) in CH2Cl2 containing 0.1 M tetra-n-butylammonium perchlorate (TBAP). Two quasi-reversible one-electron oxidations and three or four quasi-reversible one-electron reductions have been revealed for these neutral double-deckers of two series of substituted complexes, respectively. For comparison, unsubstituted bis(phthalocyaninato) rare earth analogues M(Pc)2 (M = Y, La...Lu except Pm; H2Pc = phthalocyanine) have also been electrochemically investigated. Two quasi-reversible one-electron oxidations and up to five quasi-reversible one-electron reductions have been revealed for these neutral double-decker compounds. The three bis(phthalocyaninato)cerium compounds display one cerium-centered redox wave between the first ligand-based oxidation and reduction. The half-wave potentials of the first and second oxidations and first reduction for double-deckers of the tervalent rare earths depend on the size of the metal center. The difference between the redox potentials of the second and third reductions for MIII(Pc)2, which represents the potential difference between the first oxidation and first reduction of [MIII(Pc)2]���, lies in the range 1.08���1.37 V and also gradually diminishes along with the lanthanide contraction, indicating enhanced ������� interactions in the double-deckers connected by the smaller, lanthanides. This corresponds well with the red-shift of the lowest energy band observed in the electronic absorption spectra of reduced double-decker [MIII(Pc���)2]��� (Pc��� = Pc, TBPc, OOPc).

Vibrational spectroscopy of phthalocyanine and naphthalocyanine in sandwich-type (na)phthalocyaninato and porphyrinato rare earth complexes: Part 14. The infrared and Raman characteristics of phthalocyanine in ���pinwheel-like��� homoleptic bis[1,8,15,22-tetrakis(3-pentyloxy)phthalocyaninato] rare earth(III) double-decker complexes

The infrared (IR) spectroscopic data and Raman spectroscopic properties for a series of 13 ���pinwheel-like��� homoleptic bis(phthalocyaninato) rare earth complexes M[Pc(��-OC5H11)4]2 [M = Y and Pr���Lu except Pm; H2Pc(��-OC5H11)4 = 1,8,15,22-tetrakis(3-pentyloxy)phthalocyanine] have been collected and comparatively studied. Both the IR and Raman spectra for M[Pc(��-OC5H11)4]2 are more complicated than those of homoleptic bis(phthalocyaninato) rare earth analogues, namely M(Pc)2 and M[Pc(OC8H17)8]2, but resemble (for IR) or are a bit more complicated (for Raman) than those of heteroleptic counterparts M(Pc)[Pc(��-OC5H11)4], revealing the decreased molecular symmetry of these double-decker compounds, namely S8. Except for the obvious splitting of the isoindole breathing band at 1110���1123 cm���1, the IR spectra of M[Pc(��-OC5H11)4]2 are quite similar to those of corresponding M(Pc)[Pc(��-OC5H11)4] and therefore are similarly assigned. With laser excitation at 633 nm, Raman bands derived from isoindole ring and aza stretchings in the range of 1300���1600 cm���1 are selectively intensified. The IR spectra reveal that the frequencies of pyrrole stretching and pyrrole stretching coupled with the symmetrical CH bending of ���CH3 groups are sensitive to the rare earth ionic size, while the Raman technique shows that the bands due to the isoindole stretchings and the coupled pyrrole and aza stretchings are similarly affected. Nevertheless, the phthalocyanine monoanion radical Pc������ IR marker band of bis(phthalocyaninato) complexes involving the same rare earth ion is found to shift to lower energy in the order M(Pc)2 > M(Pc)[Pc(��-OC5H11)4] > M[Pc(��-OC5H11)4]2, revealing the weakened ������� interaction between the two phthalocyanine rings in the same order.

Tris[4,4,4-trifluoro-1-(2-thienyl)butane-1,3-dionato]aluminium(III)-tris[4,4,4-trifluoro-1-(2-thienyl)butane-1,3-dionato]iron(III) (3/1)

In the title compound, [Al(C8H4F3O2S)3]3[Fe(C8H4F3O2S)3], the metal centre is statistically occupied by AlIII and FeIII cations in a 3:1 ratio. The metal centre is within an octahedral O6 donor set defined by three chelating substituted acetoacetonate anions. The ligands are arranged around the periphery of the molecule with a mer geometry of the S atoms.