Estudos experimentais e teórico-computacionais de novos complexos nanozeólitas-enzimas empregados na produção de biocombustíveis

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Caracterização da liga Ti-30Ta após tratamento biomimético associado à incorporação de antibiótico

Surface treatments have been used to modify the surface of titanium alloys. The purpose of this study is to evaluate the surface of Ti-30Ta alloy after biomimetic approach associated to antibiotic incorporation. The ingots were obtained in arc melting furnace, treated and cold-worked by swaging. The surface treatment was performed in two steps: biomimetic treatment and antibiotic incorporation. For biomimetic treatment, first an alkaline treatment (NaOH 1M at 60ºC) was performed, followed by heat treatment and immersion in SBFx5 (Simulated Body Fluid) for a period of 24 hours. In order to incorporate the antibiotic, samples were immersed in a solution formed by drugs plus SBFx5 for 48 hours. The sample surfaces were analyzed by scanning electron microscopy (SEM), X-Ray diffraction (XRD), atomic force microscopy (AFM) and contact angle measurements. The release of antibiotic from coated implants was measured in phosphate buffer saline at pH 7.4 by using UV/VIS spectrometry. Results have shown changes on the surface after incorporating the drug, which is gradually co-precipitated with the Ca-P crystals, forming a uniform and rough layer on the metal surface

Caridean Shrimps Associated with the Slimy Sea Plume (Pseudopterogorigia americana) in Midsummer at Guana Island, British Virgin Islands, West Indies

Fifty-one slimy sea plumes (Pseudopterogorgia americana Gmelin, 1791) were sampled for caridean shrimps at Guana Island, British Virgin Islands, during one week in July 1992. Sam- pling depth ranged from 3-22 m. Nine species were collected: Hippolyte nicholsoni Chace, 1972; Latreutes sp.; Neopontonides chacei Heard, 1986; Perclimenes cf. patae Heard and Spotte, 1991; Periclimenes cf. pauper Holthuis, 1951; Periclimenes sp.; Pseudocoutierea antillensis Chace, 1972; Tozeuma cf. cornutum Milne Edwards, 1881; and Trachycaris rugosa (Bate, 1888). A total of 1,418 specimens (including fragments) was obtained. The number of shrimp species per gorgonian ranged from 1-5; one gorgonian harbored 156 shrimps. The two predominant species, N. chacei and H. nicholsoni, occupy different mean depths (12.6 and 8.2 m, respectively). Sexual dimorphism assessed with Mann-Whitney U-tests was not apparent in the specimens of N. chacei (P > 0.05), but females of H. nicholsoni were significantly larger than males (P < 0.001). Minimum carapace length (CL, the tip of the rostrum to the posterior dorsal margin of the carapace) at which male N. chacei acquire a single appendix masculina spine is 1.25 mm; male H. nicholsoni can acquire a single spine at 0.9 mm CL. Histological sections of male N. chacei showed that shrimp with 0 or 1 spine are least likely to be mature. Female N. chacei can become ovigerous at 1.9 mm CL and female H. nicholsoni at 1.2 mm CL. The taxonomic status of 5 of the 9 species collected is uncertain.

Caracterização da liga Ti-30Ta após tratamento biomimético associado à incorporação de antibiótico

Surface treatments have been used to modify the surface of titanium alloys. The purpose of this study is to evaluate the surface of Ti-30Ta alloy after biomimetic approach associated to antibiotic incorporation. The ingots were obtained in arc melting furnace, treated and cold-worked by swaging. The surface treatment was performed in two steps: biomimetic treatment and antibiotic incorporation. For biomimetic treatment, first an alkaline treatment (NaOH 1M at 60ºC) was performed, followed by heat treatment and immersion in SBFx5 (Simulated Body Fluid) for a period of 24 hours. In order to incorporate the antibiotic, samples were immersed in a solution formed by drugs plus SBFx5 for 48 hours. The sample surfaces were analyzed by scanning electron microscopy (SEM), X-Ray diffraction (XRD), atomic force microscopy (AFM) and contact angle measurements. The release of antibiotic from coated implants was measured in phosphate buffer saline at pH 7.4 by using UV/VIS spectrometry. Results have shown changes on the surface after incorporating the drug, which is gradually co-precipitated with the Ca-P crystals, forming a uniform and rough layer on the metal surface

Influence of the use of Aliquat 336 in the immobilization procedure in sol-gel of lipase from Bacillus sp ITP-001

Aliquat 336, a liquid hydrophobic material, was used at different concentrations (0.5-3.0%, w/v) as an additive in the preparation of encapsulated lipase from Bacillus sp. ITP-001 on sol-gel silica matrices using tetraethoxysilane (TEOS) as the precursor. The resulting hydrophobic matrices and immobilized lipases were characterized with regard to specific surface area (BET method), adsorption-desorption isotherms, pore volume (Vp) and size (dp) by nitrogen adsorption (BJH method) and scanning electron microscopy (SEM). The catalytic activities and the corresponding coupling yields were assayed in the hydrolysis of olive oil. In comparison with pure silica matrices, the immobilization process in the presence of Aliquat 336 decreased the values for specific surface area and increased the values for pore specific volume (Vp) and mean pore diameter (dp). This behavior may be related to the partial adsorption of the enzyme on the external surface of the hydrophobic matrix as indicated by scanning electron microscopy. Aliquat 336 concentrations in the range from 0.5 to 1.5% (w/v) provided immobilized derivatives with higher coupling yields and better substrate affinity. The highest coupling yield (Y-A = 71%) was obtained for the immobilized enzyme prepared in the presence of 1.5% Aliquat which gave the following morphological properties: specific surface area = 183 m(2)/g, pore specific volume (Vp) = 0.36 cc/g and mean pore diameter (dp)= 91 angstrom. (c) 2012 Elsevier B.V. All rights reserved.

Lipase-catalyzed kinetic resolution of beta-borylated carboxylic esters

The kinetic resolution of chiral beta-borylated carboxylic esters via lipase-catalyzed hydrolysis and transesterification reactions was studied. The enantioselective hydrolysis catalyzed by CAL-B furnished the beta-borylated carboxylic acid with reasonable enantiomeric excess (62% ee), while both methyl and ethyl beta-borylated carboxylic esters were recovered with excellent ee (>99%). Meanwhile, the transesterification reaction of beta-borylated carboxylic esters and several alcohols, catalyzed by CAL-B, only indicated a high selectivity when ethanol and methyl-(beta-pinacolylboronate)-butanoate were used as substrates, which gave ethyl-(beta-pinacolylboronate)-butanoate with >99% ee. (C) 2012 Elsevier Ltd. All rights reserved.

Evaluation of immobilized lipases on poly-hydroxybutyrate beads to catalyze biodiesel synthesis

Five microbial lipase preparations from several sources were immobilized by hydrophobic adsorption on small or large poly-hydroxybutyrate (PHB) beads and the effect of the support particle size on the biocatalyst activity was assessed in the hydrolysis of olive oil, esterification of butyric acid with butanol and transesterification of babassu oil (Orbignya sp.) with ethanol. The catalytic activity of the immobilized lipases in both olive oil hydrolysis and biodiesel synthesis was influenced by the particle size of PHB and lipase source. In the esterification reaction such influence was not observed. Geobacillus thermocatenulatus lipase (BTL2) was considered to be inadequate to catalyze biodiesel synthesis, but displayed high esterification activity. Butyl butyrate synthesis catalyzed by BTL2 immobilized on small PHB beads gave the highest yield (approximate to 90 mmol L-1). In biodiesel synthesis, the catalytic activity of the immobilized lipases was significantly increased in comparison to the free lipases. Full conversion of babassu oil into ethyl esters was achieved at 72 h in the presence of Pseudozyma antarctica type B (CALB), Thermomyces lanuginosus lipase (Lipex (R) 100L) immobilized on either small or large PHB beads and Pseudomonas fluorescens (PFL) immobilized on large PHB beads. The latter preparation presented the highest productivity (40.9 mg of ethyl esters mg(-1) immobilized protein h(-1)). (C) 2012 Elsevier B.V. All rights reserved.

Caracterização de uma floresta estacional semidecidual em Varginha, MG. E comparação com remanescentes da região.

Foi realizado o levantamento florístico e fitossociológico na porção mais extensa de mata no Parque Florestal Municipal São Francisco de Assis, na cidade de Varginha, sul de Minas Gerais. A área tem cerca de 10 ha e é cortada por um pequeno córrego. Foram lançadas 25 parcelas de 20m x 20m e medidos e cadastrados todos os indivíduos arbóreos com DAP > 5cm. Foram encontrados 1568 indivíduos que, juntos, somaram área basal de 23,65 m2, sendo registrados 102 espécies, 72 gêneros e 42 famílias no levantamento fitossociológico e 111 espécies, 77 gêneros e 43 famílias no levantamento florístico. As famílias com maior número de espécies foram Myrtaceae, Fabaceae e Melastomataceae. As espécies de maior valor de importância foram Casearia arborea, Copaifera langsdorffii, Tachigali rugosa e Myrcia splendens. Os resultados encontrados são os esperados para as Florestas Estacionais Semideciduais da região.

Planktonic foraminifera in the latest Maastrichtian of Walvis Ridge, South Atlantic

An abrupt global warming of 3-4°C occurred near the end of the Maastrichtian at 65.45-65.10 Ma. The environmental effects of this warm event are here documented based on stable isotopes and quantitative analysis of planktonic foraminifera at the South Atlantic DSDP Site 525A. Stable isotopes of individual species mark a rapid increase in temperature and a reduction in the vertical water mass stratification that is accompanied by a decrease in niche habitats, reduced species diversity and/or abundance, smaller species morphologies or dwarfing, and reduced photosymbiotic activity. During the warm event, the relative abundance of a large number of species decreased, including tropical-subtropical affiliated species, whereas typical mid-latitude species retained high abundances. This indicates that climate warming did not create favorable conditions for all tropical-subtropical species at mid-latitudes and did not cause a massive retreat in the local mid-latitude population. A noticeable exception is the ecological generalist Heterohelix dentata Stenestad that dominated during the cool intervals, but significantly decreased during the warm event. However, dwarfing is the most striking response to the abrupt warming and occurred in various species of different morphologies and lineages (e.g. biserial, trochospiral, keeled globotruncanids). Dwarfing is a typical reaction to environmental stress conditions and was likely the result of increased reproduction rates. Similarly, photosymbiotic activity appears to have been reduced significantly during the maximum warming, as indicated by decreased delta13C values. The foraminiferal response to climate change is thus multifaceted resulting in decreased species diversity, decreased species populations, increased competition due to reduced niche habitats, dwarfing and reduced photosymbiotic activity.

Chemobiostratigraphy of the Cretaceous/Paleocene boundary at ODP Hole 120-750A

An integrated biostratigraphic and stable isotope investigation was conducted on a high-latitude sequence across the Cretaceous/Paleogene (K/P) boundary recovered in Hole 750A in the southern Indian Ocean. The sequence consists of nannofossil chalk and is discontinuous across the boundary; missing is an estimated 0.3-m.y. late Maestrichtian and early Danian interval. Nonetheless, because calcareous nannofossil Zones NP1 and NP2 are well-developed, micropaleontological studies of the sequence have yielded a detailed record of Danian high-latitude microplankton evolution. In addition, stable carbon isotope analyses of planktonic and benthic foraminifer and bulk samples provide a record of late Maestrichtian and early Danian surface- and deep-water carbon isotope variations. Together, the carbon isotope and carbonate accumulation records serve as an index of regional marine net productivity across the boundary. Earliest Danian nannoplankton assemblages consisted mainly of persistent genera that were generally rare or absent in the Upper Cretaceous at Hole 750A. However, by 0.5-0.6 m.y. after the boundary, newly evolving Danian taxa became dominant. The turnover in nannofossil assemblages was accompanied by significant changes in rates of net productivity as gauged by carbon isotope distributions and carbonate accumulation rates. During the period dominated by persistent taxa, net productivity was extremely low, as reflected by the absence of vertical delta13C gradients and reduced carbonate accumulation rates. Later in the Danian, as new species evolved and flourished, vertical delta13C gradients reappeared and carbonate accumulation rates increased, signaling partial recovery of net productivity in this region. The absolute timing and magnitude of late Maestrichtian and early Danian biotic and geochemical changes in the southern Indian Ocean were similar to those recorded in other pelagic K/P boundary sequences from low- and mid-latitude Atlantic and Pacific sites, indicating that these events were ubiquitous.

Living benthic foraminifera of the western and southern Arabian Sea

Sediments from the western and southern part of the Arabian Sea were collected periodically in the spring intermonsoon between March and May 1997 and additionally at the end of the Northeast Monsoon in February 1998. Assemblages of Rose Bengal stained, living deep-sea benthic foraminifera, their densities, vertical distribution pattern, and diversity were analysed after the Northeast Monsoon and short-time changes were recorded. In the western Arabian Sea, foraminiferal numbers increased steadily between March and the beginning of May, especially in the smaller size classes (30-63 µm, 63-125 µm). At the same time, the deepening of the foraminiferal living horizon, variable diversity and rapid variations between dominant foraminiferal communities were observed. We interpret these observations as the time-dependent response of benthic foraminifera to enhanced organic carbon fluxes during and after the Northeast Monsoon. In the southern Arabian Sea, constant low foraminiferal abundances during time, no distinctive change in the vertical distribution, reduced diversity, and more stable foraminiferal communities were noticed, which indicates no or little influence of the Northeast Monsoon to benthic foraminifera in this region.

Planktonic foraminifers in DSDP Holes 30-289 and 33-315A

The work is based on samples from Deep-Sea Drilling in the Pacific Ocean and from natural sections in its continental setting. Species composition of planktonic foraminifera from Maastrichtian sediments of the Pacific and South Atlantic oceans, as well as from marginal seas of Australia and New Zealand and epicontinental basins of the northern hemisphere has been analysed. Two main issues: reconstruction of Maastrichtian climatic zonality, and reconstruction of Maastrichtian paleodepths. Four bipolar climatic zones have been distinguished. According to preservation of planktonic foraminifera and composition of their complexes three levels of dissolution have been identified.