Hydroxymethylnitrofurazone:Dimethyl-beta-cyclodextrin Inclusion Complex: A Physical-Chemistry Characterization

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

APPLICATIONS OF ARTIFICIAL-INTELLIGENCE IN ORGANIC-CHEMISTRY .17. NEW PROGRAMS IN THE SISTEMAT PROJECT

This work describes the new improvements of the SISTEMAT project, one system for structural elucidation mainly in the field of Natural Products Chemistry. Some examples of the resolution of problems using C-13 Nuclear Magnetic Resonance and Mass Spectroscopy are given. Programs to discover new heuristic rules for structure generation are discussed. The data base contains about 10000 C-13 NMR spectra.

Chemistry of Fe(II) in the presence of organic exudates from phytoplankton and of copper in seawater

Programa de doctorado de Oceanografía ; 2006-2008

Sulfanyl Radical Addition to Alkynes: Revisiting an Old Reaction to Enter the Novel Realms of Green Chemistry, Bioconjugation, and Material Chemistry

In the last decade considerable attention has been devoted to the rewarding use of Green Chemistry in various synthetic processes and applications. Green Chemistry is of special interest in the synthesis of expensive pharmaceutical products, where suitable adoption of “green” reagents and conditions is highly desirable. Our project especially focused in a search for new green radical processes which might also find useful applications in the industry. In particular, we have explored the possible adoption of green solvents in radical Thiol-Ene and Thiol-Yne coupling reactions, which to date have been normally performed in “ordinary” organic solvents such as benzene and toluene, with the primary aim of applying those coupling reactions to the construction of biological substrates. We have additionally tuned adequate reaction conditions which might enable achievement of highly functionalised materials and/or complex bioconjugation via homo/heterosequence. Furthermore, we have performed suitable theoretical studies to gain useful chemical information concerning mechanistic implications of the use of green solvents in the radical Thiol-Yne coupling reactions.

Sulfoxides as an intramolecular sulfenylating agent for indoles and diverse applications of the sulfide-sulfoxide redox cycle in organic chemistry

This dissertation involves study of various aspects of sulfoxide chemistry. Specifically designed t-butyl and propanenitrile sulfoxides tethered to indole-2-carboxamide were used as a source of intramolecular sulfenylating agents to synthesize novel indolo[3,2-b]-1-5-benzothiazepinones which are structurally analogous to the other biologically active benzothiazepinones. This study reveals that the intramolecular cyclization of sulfoxide follows an electrophilic sulfenylation (Sulfoxide Electrophilic Sulfenylation, SES) reaction pathway. Evidence of the absence of sulfenic acid as a transient reactive intermediate in such intramolecular cyclization is also provided. In another study, sulfoxide was used as a “protecting group” of thioether to synthesize 8-membered, indole substituted, thiazocine-2-acetic acid derivative via Ring Closing Metathesis (RCM). Protection (oxidation) of inert (to RCM) sulfide to sulfoxide followed by RCM produced cyclized product in good yields. Deprotection (reduction) of sulfoxide was achieved using Lawessons Reagent (L.R.). Application of the sulfide-sulfoxide redox cycle to solve the existing difficulties in using RCM methodology to thioethers is illustrated. A new design of a “molecular brake”, based on the sulfide-sulfoxide redox cycle is described. N-Ar rotation in simple isoindolines is controlled by the oxidation state of the proximate sulfur atom. Sulfide [S(II)] shows “free” [brake OFF] N-Ar rotation whereas sulfoxide displayed hindered [brake ON] N-Ar rotation. The semi-empirical molecular orbital (PM3) calculations revealed concerted pyramidalization of amidic nitrogen with N-Ar rotation.

(Table 1) Maceral composition and organic carbon chemistry of ODP Leg 104 samples

The Cenozoic sediments sampled in ODP Leg 104 on the Vøring Plateau show a distinct variability of the total organic carbon content (TOC) and the accumulation rates of TOC. Based on the geochemical and organic-petrographic characterization of the sedimentary organic matter (OM), the allochthonous and autochthonous proportion of the OM could be quantified. The results clearly demonstrate that high TOC percentages and TOC accumulation rates in Cenozoic sediment sections display a generally high input of allochthonous organic matter. Oxidized and partly well-rounded organic particles built up the main portion of OM within the Miocene, TOC-rich sediments. The most probable source of this oxidized OM are reworked sediments from the Scandinavian shelf. Changes in the input of these organic particles are to some degree correlative with sea-level changes. The Cenozoic accumulation of autochthonous OM is low and does not reveal a clear variation during the Miocene and early Pliocene. In spite of a high accumulation rate of biogenic opal during the Early Miocene, the accumulation rate of autochthonous TOC is low. The autochthonous particle assemblage is dominated by relatively inert OM, like dinoflagellate cysts. This points to an intensive biological and/or early diagenetic degradation of the marine OM under well oxidized bottom water conditions during the last 23 Myr. Nevertheless, a continuation of marine OM degradation during later stages of diagenesis cannot be excluded. A prominent dominance of allochthonous OM over autochthonous is documented with the beginning of the Pliocene. At 2.45 Ma the episodic occurrence of ice-rafted, thermally mature OM reflects the onset of the glacial erosion of Mesozoic, coal and black shale bearing sediments on the Scandinavian and Barents Sea shelves. The first occurrence of these, in view of the actual burial depth, thermally overmature OM particles is, therefore, a marker for the beginning of the strong Scandinavian glaciation and the advance of the glacial front toward the shelves.

(Table 2) Chemistry of the organic matter at DSDP Leg 62 Holes

The wide distribution of sapropelic deposits in the sedimentary cover of the oceans, their Cretaceous age, and their possible oil- and gas-generating characteristics allow us to regard these deposits as a regular global stage in the history of oceanic sedimentation. So, Cretaceous sapropelic deposits are a unique object for study. Cretaceous sapropelic deposits of DSDP Sites 463, 465, and 466, as well as similar sediments of the Atlantic and Indian Oceans, are characterized by enrichment in organic matter, which sometimes reaches 33% (Cape Verde Basin, DSDP Sites 367 and 368). The objective of this study is the elucidation of genesis, paleogeographic environment of sedimentation, and oil-generating potential of Cretaceous sapropelic deposits at these sites. Attention is given to petrographic composition and distribution of the organic matter.

Stable isotope organic chemistry of ODP Leg 105 sites

Stable carbon and nitrogen isotopic compositions as well as organic carbon and total nitrogen contents are reported for Site 645 in Baffin Bay and Sites 646 and 647 in the Labrador Sea. Both low-resolution analyses (1 sample/section) and high-resolution results (up to 7 samples/section) are presented. These records indicate that large-scale changes in productivity since the middle Miocene have occurred in Baffin Bay. Such changes are not evident in samples from the Labrador Sea. Isotopic records of all the sites are influenced strongly by rapidly changing influxes that combine terrigenous debris with planktonic production. In parts of the cores, relationships to other phenomena, such as ice stages, are present. However, these correlations are not common and indicate that these events were masked by the dynamic changes in sources of organic matter occurring in this complex system.