Orientador: Vinicius Castro Souza / Tese (doutorado) - Universidade Estadual de Campinas, Instituto de Biologia / Made available in DSpace on 2018-08-14T10:53:10Z (GMT). No. of bitstreams: 1 Silveira_DanielaSampaio.pdf: 13077358 bytes, checksum: 444d6c94d072cef289968c110c821bf3 (MD5) Previous issue date: 2009 / Resumo: Elaeocarpaceae inclui 15 gêneros, com aproximadamente 500 espécies distribuídas em regiões tropicais e subtropicais do globo, em com exceção dos continentes africano e europeu. O gênero Sloanea reúne 120 táxons, dos quais cerca de 40 ocorrem no Brasil em diversos tipos de vegetação, principalmente na Floresta Amazônica e na Floresta Atlântica. O presente trabalho refere-se à revisão taxonômica das espécies neotropicais extra-amazônicas de Sloanea. A realização deste estudo constou de levantamento bibliográfico, consulta aos acervos dos principais herbários nacionais e estrangeiros, e expedições de coleta em áreas de ocorrência natural dos táxons do gênero. De um modo geral, com base na morfologia externa, a caracterização de Sloanea compreende árvores de grande porte dotadas de sapopemas, folhas simples, flores com sépalas que podem ou não cobrir órgãos reprodutivos na fase pré-antese, estames com prolongamento do conectivo conspícuo, que pode ser agudo, acuminado ou filiforme, frutos cobertos por cerdas rígidas ou flexíveis, algumas vezes inermes. Na revisão foram definidas 19 lectotipificações aqui desginadas, quatro novas sinonimizações, um nome duvidoso e a constatação de cinco nomes ilegítimos e seis nomes nus. Foram identificadas 17 espécies na área de estudo, sendo seis desconhecidas para a ciência: S. fasciculate, S. filiforms, S. hatschbachii, S. petala, S. subssesilis, S. uniflora. / Abstract: Elaeocarpaceae includes 15 genera, witch approximately 500 species distributed in tropical and subtropical regions of the globe, except for African and European continents. Sloanea comprises 120 taxa, of witch about 40 occur in Brazil in several vegetation types, but mainly in the Amazon Forest and in the Atlantic Forest. This thesis revises the taxonomy of the neotropical species of extra-amazon Sloanea genus. This study consisted of literature review, consultation with the collections of major Brazilian and foreign herbaria, and collection expeditions in areas of natural occurrence of taxa of the genus. In general, based on external morphology, the characterization of Sloanea comprises large trees endowed with buttressed roots, simple leaves, flowers witch sepals that may cover or not the reproductive organs in pre-anthesis phasis, stamens with the connective continued into a small knob, acuminate, acute or filiform awn, fruit covered with rigid or flexible bristles, sometimes unarmed. In this thesis 19 lectotypes her designated were defined, and four new synonyms, one doubtful name, five illegitimate names and six nude names were found. From the 17 species that were identified in the studied area, six of them were unknown to science: S. fasciculate, S. filiforms, S. hatschbachii, S. petala, S. subssesilis, S. uniflora. / Universidade Estadual de Campi / Biologia Vegetal / Doutor em Biologia Vegetal

A phytochemical survey to detect alkaloids was performed on extracts of 339 discrete plants parts from a total of 77 species from five genera of Elaeocarpaceae, including 30 species from Queensland, 38 from PNG, and nine from China. An alkaloid detecting reagent, bismuth (III) tetraiodide (Dragendorff's reagent) was used in a preliminary test for alkaloids, with positive ESIMS used to confirm the presence of alkaloids. A total of 35 extracts of various plant parts produced positive results with Dragendorff's reagent. Positive ESIMS detected alkaloids in only 13 of these extracts. Bismuth (III) tetraiodide was demonstrated to produce false positive results with the new non-alkaloidal poly-oxygenated compounds 112 and 113, which were purified from the extract of Sloanea tieghemii. Two new alkaloid producing species, Elaeocarpus habbeniensis, and E. fuscoides were detected from the survey. These species were chemically investigated for the first time. Two other previously investigated species, E. grandis and Peripentadenia mearsii, were also studied. A total of 16 alkaloids, 11 of which are new, were purified from the extracts of these four species. The novel pyrrolidine alkaloids habbenine (114) and peripentonine (123), were isolated from the leaves of E. habbeniensis and Peripentadenia mearsii, respectively. Both of these compounds were purified as inseparable mixtures of diastereomers. The new pyrrolidine alkaloid mearsamine 1 (124), and the novel amino alkaloid mearsamine 2 (125), were also purified from the leaves of P. mearsii. The known pyrrolidine alkaloid peripentadenine (81), was purified from the bark of P. mearsii. Peripentonine (123) was reduced to peripentadenine (81) upon reaction with Pd/C. Four aromatic indolizidine alkaloids were isolated from the extract of the leaves of E. fuscoides. One new compound, elaeocarpenine (122), was isolated from this New Guinean plant. Three known Elaeocarpus alkaloids, isoelaeocarpicine (62), elaeocarpine (60) and isoelaeocarpine (61) were also purified from E. fuscoides. Elaeocarpenine (122) was demonstrated to produce the epimeric compounds elaeocarpine and isoelaeocarpine via reaction with ammonia. The chemical investigation of the Queensland plant E. grandis by two separate purification procedures was performed. An SCX/C18 isolation protocol was used to purify the new indolizidine alkaloids grandisine C (127), D (126), and E (128), in conjunction with the known tetracyclic indolizidine isoelaeocarpiline (63). The second purification of E. grandis was achieved with the use of ammonia in an acid/base partitioning protocol. Grandisine F (129) and G (130), and compounds 131a and b were purified by this procedure, as were 63, 126 and 127. Grandisine F and G were proposed to be ammonia adducts of grandisine D (126). Compound 131a and b were isolated as a mixture of diastereomers. The reduction of grandisine D (126) with Pd/C yielded a mixture of isoelaeocarpine (61) and elaeocarpine (60), whereas the reduction of isoelaeocarpiline (63) produced isoelaeocarpine (61). All of the alkaloids isolated from the Elaeocarpaceae, except grandisine E (128) and 131a and b, were evaluated for binding affinity against the human ? opioid receptor. Every compound except mearsamine 2 (125) possessed a binding affinity of less than 100 ?M. The most active compounds were grandisine F (129), D (126), C (127), elaeocarpenine (122), isoelaeocarpine (61), isoelaeocarpiline (63) and peripentadenine (81). The IC50 values for these compounds were 1.55, 1.65, 14.6, 2.74, 13.6, 9.86 and 11.4 ?M, respectively. The SAR of the active compounds was compared. These observations indicated that the indolizidine alkaloids were more active than the pyrrolidine alkaloids, and a phenol or ketone at position C-12 of the indolizidine alkaloids produced better binding affinity. All of these alkaloids, except 129, were proposed to interact with two of the three binding domains of the ? opioid receptor. Grandisine F (129) was proposed to have a different mode of action than the other alkaloids in the series. Synthetic modifications to isoelaeocarpine (61) and peripentadenine (81) were investigated in an attempt to incorporate an extra aromatic group into these molecules. An extra aromatic group was proposed to provide increased binding affinity to the ? opioid receptor by interaction with the third binding domain of the receptor. Two different aromatic amines were successfully attached to peripentadenine (81) by a reductive amination reaction using NaBH(OAc)3 and a titanium catalyst. The reductive amination of the ketone in isoelaecarpine (61) with various amines and NaBH(OAc)3 or NaBH4 proved unsuccessful.