Thesis advisor: Lawrence T. Scott / The focus of this project was to probe the ability of various transition metal complexes to cleave carbon-carbon bonds in a C30H12 hemifullerene. The hemifullerene was synthesized in our lab from commercial 1-tetralone and bromonaphthalene in six steps. Palladium and nickel complexes were used to open the five membered rings along the periphery of the C30H12 bowl. Diphosphine complexes of nickel were capable of opening either all three five membered rings or one of the periphery five membered rings and the central six membered ring. / Thesis (BS) — Boston College, 2005. / Submitted to: Boston College. College of Arts and Sciences. / Discipline: Chemistry. / Discipline: College Honors Program.

Submitted by Erika Demachki (erikademachki@gmail.com) on 2014-09-18T18:51:43Z No. of bitstreams: 2 Dissertação Vanessa Loren Nunes.pdf: 10979785 bytes, checksum: 8efff856842f8d2962b9f8221ec1fcb5 (MD5) license_rdf: 23148 bytes, checksum: 9da0b6dfac957114c6a7714714b86306 (MD5) / Approved for entry into archive by Luciana Ferreira (lucgeral@gmail.com) on 2014-09-19T11:28:41Z (GMT) No. of bitstreams: 2 Dissertação Vanessa Loren Nunes.pdf: 10979785 bytes, checksum: 8efff856842f8d2962b9f8221ec1fcb5 (MD5) license_rdf: 23148 bytes, checksum: 9da0b6dfac957114c6a7714714b86306 (MD5) / Made available in DSpace on 2014-09-19T11:28:41Z (GMT). No. of bitstreams: 2 Dissertação Vanessa Loren Nunes.pdf: 10979785 bytes, checksum: 8efff856842f8d2962b9f8221ec1fcb5 (MD5) license_rdf: 23148 bytes, checksum: 9da0b6dfac957114c6a7714714b86306 (MD5) Previous issue date: 2012-05-04 / Conselho Nacional de Pesquisa e Desenvolvimento Científico e Tecnológico - CNPq / This work describes some studies on the preparation of unsymmetrical diaryl thioethers catalyzed by Copper(I)-Senelenophene-2-carboxylate. The results concern to the catalyzed cross-coupling reaction between aryl halides and aryl or alkylthiols using Copper(I)-Senelenophene-2-carboxylate (CuSC) a new Cu-catalyzed one-pot protocol. The products were obtained in good to excellent yields under relatively mild reaction conditions presenting chemoselectivity and functional group tolerance. Additionally, we have developed a chemio-, regio and stereoselective synthesis of vinyl chalcogenides compounds promoted by zinc chalcogenolates. In this protocol the reductive cleavage of chalcogen bond by the Zn/NH4OH system led to zinc chalcogenolates. The reaction was carried out with acids and esters propiolics afford β-chalcogenacrillic acids and esters under mild and basic conditions. The stereochemistry corresponding to anti-Markovnikov addition of the chalcogenolate constituents across the triple bond were obtained in good yields. / Este trabalho descreve o estudo das reações de acoplamento cruzado entre iodetos arílicos e tióis arílicos ou alquílicos catalisada por 2-carboxilato selenofeno de cobre (I) (CuSC). Apresentamos uma nova metodologia “ one pote” para a síntese de tioésteres arílicos obtidos em condições reacionais relativamente brandas, apresentando quimiosseletividade, tolerância a diversos grupos funcionais e rendimentos que variam entre bons a ótimos (70-100%). R1I + R2SH K3PO4, DMSO S R1 R2 Adicionalmente, desenvolvemos uma síntese quimio, régio, e estereosseletiva de compostos vinil calcogenetos promovida por calcogenolato de zinco. Neste protocolo a clivagem redutiva da ligação calcogênio feita pelo sistema Zn/NH4OH obteve os calcogenolatos de zinco. A reação foi realizada com ácidos e ésteres propiólicos formando ácidos acrílicos β-calcogênio e ésteres sob condições básicas e brandas. A estereoquímica corresponde a adição anti-Markovnikov dos constituintes calcogenolatos através da ligação tripla. Os calcogenetos vinílicos foram obtidos em bons rendimentos (40-96).

Herein we report the synthesis of an RGD-ruthenium bipyridine [Ru(Bpy)2(BpyRGD)]2+ complex aimed at the detection of angiogenesis. Angiogenesis plays a critical role in many pathophysiological processes, such as tumor growth. The αv-integrins (αv[beta]3, αv[beta]5) are currently used as molecular targeting sites for anti-angiogenic therapies. The [Ru(Bpy)2(BpyRGD)]2+ complex is an organometallic luminescent probe, which enables noninvasive, in vitro imaging of αv[beta]3 expression. Peptides containing the arginine-glycine-aspartic acid (RGD) sequence have been shown to bind strongly to the αvb3 integrin. The RuBpy probes are soluble in water, display long lifetimes, and are photochemically stable. These properties enable the Ru(tris-bpy) complexes to be useful in numerous applications in biophysical and cell biology. The [Ru(Bpy)2(BpyRGD)]2+ complex was synthesized by combining the succinimidyl ester on the RuBpy complex with the lysine of the c(RGDfK) peptide. The results of the one-photon fluorescence bioimaging showed selective binding of the cyclic RGD to αv[beta]3 integrin, which supports previous literature. The high luminescence intensity, long lifetimes, and low cell toxicity levels of dye [Ru(Bpy)2(BpyRGD)]2+, illustrates the potential usage of this probe for future biological applications.