A minha mae, AntOnia Zumak Brant - USP · 2008. 10. 2. · A Romilda Rachel Soares Silva,...

DEDICATbRIAS

A minha mae, AntOnia Zumak Brant (in memoriam), que foi urn exemplo de

espirito de luta, persisténcia e humildade. Ela é para mim uma eterna saudade.

A Esther Trindade Ramos (in memoriam), como uma segunda mae, sempre

trocando comigo correspondèncias criativas e alegres, ern prosa e verso, ao longo

de muitos anos. Apelidei-a de poetisa de Ouro Fino, onde nasceu.

Aos meus Irmäos, corn carinho fraternal:

Maria Jose Caldeira Brant

Ant6nio Edson Caldeira Brant ( in memoriam)

Edna Brant Pessoa

Whitery Caldeira Brant

A Romilda Rachel Soares Silva, ex-professora de Quimica Geral e Inorg5nica

do Institute de Ciências Exatas (ICEx) da UFMG, cujas aulas brilhantes e incentivo

pessoal me motivaram a abracar a Quimica como futura profissäo. Alêm de grande

mestra, Romilda era extremamente sensivel a qualquer problema que urn de seus

alunos viesse a ter e fosse procura-la para urn conselho, diblogo. Ela sempre tinha

uma palavra amiga e de Anima Sou-lhe muito grato e sempre seu admirador.

"E o girassol vai girando dia afora...

0 girassol e o carrossel das abelhas".

(Vinicius de Moraes)

AGRADECIMENTOS

Ao Dr. Vicente de Paulo Emerenciano, pela acolhida em seu grupo de

pesquisa, orientacao para a realizacäo deste trabalho, e pela amizade.

Ao Dr. Joao Pedro Simon Farah, pela ajuda e incentivo em estudos

fundamentais de Estatistica.

A Dra. Liliana Marzorati, pelo incentivo em dar continuidade a este trabalho

futuramente.

Ao Dr. Luiz Henrique Catalani, por seu apoio todo especial em relacäo ao

suporte parcial de meu trabalho pelo CNPq.

A todos os professores do IQ-USP, em especial Dra. Helena Maria Carvalho

Ferraz , pelos ensinamentos valiosos e pela amizade.

Aos colegas de pesquisa, Marcelo Jose Pena Ferreira e Alessandra Rodrigues

Rufino, alêm da amizade, pela paciencia e empenho de ajudar-me no projeto

diretamente na parte de digitacao, desenho de estruturas quimicas e diagramas, e

passando-me tambem inOmeras dicas de use correto de programas computacionais.

Nä° posse deixar de mencionar tambem a nossa ex-estagiaria, Tanja Schwabe, que

me conferiu inUmeras tabelas e tambem desenhou algumas estruturas quimicas

relativas ao meu trabalho.

Ao Sr. Jose Rubens de Toledo Barros, cujo trabalho paciente de xerocopiar

vasto acervo literario pertinente a Asteraceae foi de extrema valia para a busca de

muitos dados necessarios para a realizacäo desta dissertacao.

Ao Prof. Dr. Waldir Mantovani, do Departamento de Ecologia Geral do Institute

de Biociéncias-USP, pelos seus comentarios valiosos e esclarecedores sobre

diversos clusters obtidos ao longo de meu trabalho, que lhe apresentei para sanar

algumas dOvidas de interpretacão dos respectivos resultados.

Aos amigos e colegas de outros laboraratários do IQ-USP , pela atencao e

amizade.

A todos os funcionarios do IQ —USP, com gratidao especial a Cibele Rosani

Carlos (Secretaria de POs-Graduacao), pelo apoio e incentivo dispensado a minha

pessoa.

RESUMO

Este trabalho descreve as ocorrências naturais de flavonóides, cumarinas e

benzofuranos na família de plantas, Asteraceae / Compositae. Tem como objetivo

principal classificar os referidos metabólitos secundários como possíveis

marcadores quimiotaxonômicos da fami'lia bem como fazer previsões de suas

ocorrências naquela. Para sua realização, foi montado um banco de dados de

ocorrências desses produtos naturais a partir da literatura especializada. Os

números de ocorrências das três classes químicas (flavonóides, 4369;cumarinas,

961 ; benzofuranos, 628) foram avaliados através de programas computacionais.

Com estes foram feitas matrizes de correlações, regressões lineares múltiplas, e

gráficos variados. Foram também correlacionados os números de oxidação

(NOXs) médios de cada classe química (exceto os dos benzofuranos, devido a

algumas dúvidas suscitadas de sua rota biogenética) com a finalidade de estudos

de passos evolutivos de táxons. Os resultados do estudo apontam alguns

esqueletos carbônicos de cumarinas e benzofuranos que podem provavelmente

servir como marcadores químicos em nível de tribos e subtribos da família.

Quanto aos flavonóides, já são considerados, em nível infrafamiliar, como

marcadores químicos alguns tipos de esqueletos carbônicos com padrões de

substituição mais específicos. Foram montadas algumas equações empiricas

capazes de prever ocorrências e NOXs das classes químicas envolvidas neste

trabalho para as tribos e subtribos da família, com um grau de confiabilidade de

95%. Para este estudo usou-se como base taxonômica a classificação de

Asteraceae mais recente de Bremer (1 994).

This work describes ,the natural occurrences of flavonoids, coumarins and

benzofurans in the family of plants, Asteraceae / Compositae. It has as main

purpose to classify the referred secondary metabolites as possible

chemotaxonomic markers of the family as well as to do predictions of occurrences

of the latter. For its accomplishment, a database of occurrences of those natural

products was set up from the specialized literature. The numbers of occurrences of

the three chemical classes (flavonoids, 4369; coumarins, 961; benzofurans, 628)

were appraised with use of statistical computacional programs. With aid of these

were made correlation matrices of the occurrences, multiple linear regressions,

numerous diverse diagrams. The average oxidation numbers (OXNs) of each

chemical class (except the ones of the benzofurans, due to some doubts raised on

their biogenetical route) were also correlated with the purpose of studies on

evolutionary steps of the taxa. The results of the study point some carbon

skeletons of coumarins and benzofurans that can probably serve as chemical

markers at tribe and subtribe levels of the family. In relation to the flavonoids, these

are already considered, at infrafamilial level, as chemical markers, especially some

types of carbon skeletons bearing more specific substitution patterns. Were also

mounted some empirical equations capable of predicting occurrences and average

OXNs of the chemical classes involved in this work for the tribes and subtribes of

the family, with a 95% reliability degree. For this work was also ulilized as

taxonomic base the most recent classification of the Asteraceae of Bremer

(1 994a).

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9L

78

Regressão linear mUltipla passo a passo para tras, tomando como vari 'dye, dependenteOCCUMA em funcdo de NOs de diversas classes quimicas em tribos de Asteraceae

2

R=0,8342%93 F1= 0,6931E70 R ajudado ,45964392F(79)=29443 p<006718 Err. padr. da eAirmativa. 61,335

Err. padr. Err. padr.BETA de BETA B de B t(9) nivel-p

Intercepto 23,23353 22,15217 0,913253 0,384921OCMONO 0,132961 0,X29587 0,059548 0,026777 2,223874 0,053726

OCSELA -022743 0,4332E6 -003211 0,061167 -0524E9 0,612345OCDITE 0,3E6907 0,3E8319 0,059463 0,05E68 0,9E63E4 0,345106OCTRIT 0,3J/487 0,214504 0,531578 0,34168 1,5/3339 0,1E091

OCPOU -00736-7 0,333949 -001165 0,048121 -024233 0,814181OCFLAV 0,1E319 0,349223 0,02E9C6 0,092756 0,313335 0,761387

OCBENZ -023114 0,413325 -029339 0,424591 -057921 0,51409

Passo 0

R =0 83310945 R2= 0,69407136 Rzajustado =051061417 Passo 1

F(6,10) = 37812 p<003134 Err. path. da estimatia a . 48E69Err. padr. Err. padr.

BETA de BETA B de B t(10) nivel-pIntercepto 21 23,44827 1,06227 0,317016()MONO 0,77670 0,2621E8 0,063107 0,021299 2,662846 0,014219

OCSELA 43287E6 0,33752 -044061 8047648 -0,85234 0,413974OCDITE 0,348113 0,336635 0,0E3501 0,051737 1,084096 0,325451OCTRIT 0,347442 0,2336E8 0,553435 0,319164 1,734016 0,1177OCFLAV 0,034164 0,317318 0,019345 0,076196 0,265237 0,7%214OCBENZ -024339 0,364909 -024966 8374312 -068637 0,519381

R=0133181676 R2= 0,69191913 R2ajutado-=055188237 Passo 2

F(6,11) =4,9410 p<0,01231 Err. padr. da estimativ a: 46,749

Err. path. Err. padr.BETA de BETA B de B t(11)

Intercepto 23,55094 18,16608 1,296424 0,221367OCMONO 0,807868 0,22435 0,C65634 0,018227 3,E0C929 0034163

OCSELA -0,24E91 0,2532766 -003E2B 0,041333 -065356 0,411557OCDITE 13,4908 0,23348 0,0315E9 0,040343 1,537563 0,152408OCTRIT 0,329497 0,183455 0,524851 0,287444 1829924 0,035103OCBENZ -02E61 0,311384 -027E6 0,344745 -0,80222 0,433414

Tabela 17. Sumario de regressào linear mi'lltipla passo a passo para fres (passo 0 -

passo 6) para a variavel dependente OCCUMA , em tribos de Asteraceae.

.(oeJped

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A minha mae, AntOnia Zumak Brant - USP · 2008. 10. 2. · A Romilda Rachel Soares Silva,...

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