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A stereoselective oxidative free-radical cyclization of beta-keto ester polyenes 7 and 19 has been accomplished as a one-step entry to the tricarbocyclic synthons 8and 21 which contain five and six stereogenic centers, respectively. These key synthons possessing an axial carboethoxy group at C-4 were ultimately converted to the spongian skeleton (8--> 14 and 21 --> 25 -->14). The synthesis of d,l-isospongiadiol (3) from the common intermediate 14 was realized after introduction of the 2alpha-hydroxy group in the spongian A-ring via epoxidation of silyl enol ether 28 and subsequent desilylation. 相似文献
23.
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Silva Silvio S. Ribeiro JoÃo D. Felipe Maria G. A. Vitolo Michelle 《Applied biochemistry and biotechnology》1997,(1):557-564
Batch fermentations of sugar cane bagasse hemicellulosic hydrolysate treated for removing the inhibitors of the fermentation
were performed byCandida guilliermondii FTI20037 for xylitol production. The fermentative parameters agitation and aeration rate were studied aiming the maximization
of xylitol production from this agroindustrial residue. The maximal xylitol volumetric productivity (0.87 g/L h) and yield
(0.67 g/g) were attained at 400/min and 0.45 v.v.m. (KLa 27/h). According to the results, a suitable control of the oxygen input permitting the xylitol formation from sugar cane
bagasse hydrolysate is required for the development of an efficient fermentation process for large-scale applications. 相似文献
25.
Pedro A. Fernandes Elsa S. Henriques Vineet Pande Maria. J. Ramos Ana R. R. Maia André A. S. Almeida Bruno F. B. Silva Carla M. S. Ribeiro César F. B. Ribeiro David S. M. Ribeiro Diana A. P. Fonseca Eva M. S. Cunha Filipe R. N. C. Maia Joana A. A. Pereira João P. G. Pacheco Joaquim A. A. D. Ferreira Liliana R. C. Matos Manuel A. B. P. Pinto Maria C. S. Borges Paulo J. C. R. Magalhães Pedro F. R. D. Teixeira Pedro N. B. C. Veloso Ricarte J. F. Ferreira Sandro S. Gomes Tiago F. Barros Tiago S. J. T. Selão Virgínia M. M. C. Fernandes 《Theoretical chemistry accounts》2005,113(4):197-204
We present a series of new inhibitors of the association between nuclear factor kappa B (NF-B) and the corresponding B site in DNA. They were designed using the lead compound 15-deoxy-12,14 -prostaglandin J2 (PGJ2), which is a natural product with demonstrated inhibitory efficiency for this system. First, the binding mode of PGJ2 to NF-B was unraveled by GOLD docking calculation. Subsequently, substitutions were made to PGJ2 to optimize its association with NF-B. Care was taken not to strongly increase the reactivity of the new compounds, and to keep the overall shape, size and hydrophilicity of the lead compound, which should render them a similar bioavailability. Molecular mechanics calculations were performed to decide on the suitability of the substitutions, and to evaluate the energies of association with NF-B. Density functional theory calculations were performed also to study the overall reactivity of the substituted drugs towards NF-B. Important general conclusions were obtained, concerning the improvement of these natural inhibitors; namely, a set of rational methodologies were deduced to improve the association between the PGJ2 derivatives and NF-B, and their efficiency demonstrated by generating a set of substituted complexes, some of them with a very much increased affinity for NF-B, opening new doors to enlarge the therapeutic capabilities of this class of drugs. 相似文献
26.
Fátima Nunes Serralha José Madeira Lopes Francisco Lemos Duarte Prazeres Maria Aires-Barros Joo Rocha Joaquim Cabral Fernando Ramôa Ribeiro 《Reaction Kinetics and Catalysis Letters》2000,69(2):217-222
Novel [CrIII(amp)(bipy)(Cl)] (1) (H2amp = N-(hydroxyphenyl)salicyldimine; bipy = 2,2-bipyridyl) and [CrIII(app)(bipy)(Cl)]+ (2) (H2app = N-(hydroxyphenyl)pyridine-2-carboxaldimine; bipy = 2,2-bipyridyl) complexes have been synthesized and characterized by physico-chemical methods. Complexes 1 and 2 have been employed as catalysts in the oxidation of both saturated and unsaturated hydrocarbons using tert-butylhydroperoxide (t-BuOOH). The significance of the results with respect to oxo-functionalization of C-H bonds both in unsaturated and saturated hydrocarbons is noted. 相似文献
27.
Maria Merces Marques C. Costa F. Lemos F. Ram?a Ribeiro A. R. Dias 《Reaction Kinetics and Catalysis Letters》1997,62(1):9-15
In this paper we present a kinetic approach to the analysis of steady-state homogeneous Ziegler-Natta polymerization activity
data. The influence of the number of monomeric species that are coordinated to the active site on the apparent rate law is
discussed and the equations are fitted to the experimental results. 相似文献
28.
S. Calvelo N. Baccala M. A. Arribere S. Ribeiro Guevara D. Bubach 《Journal of Radioanalytical and Nuclear Chemistry》1997,222(1-2):99-104
The elemental composition of lichens from remote southern South America regions has been studied with analytical and statistical techniques to determine if the values obtained reflect species, growth forms or habitat characteristics. The enrichment factors are calculated discriminated by species and collection site and compared with data available in the literature. The elemental concentrations are standardized and compared for different species. The information was statistically processed, a cluster analysis was performed using the three first principal axes of the PCA; the three groups formed are presented. Their relationship with the species, collection sites and the lichen growth forms are interpreted. 相似文献
29.
de Souza BM Marques MR Tomazela DM Eberlin MN Mendes MA Palma MS 《Rapid communications in mass spectrometry : RCM》2004,18(10):1095-1102
The social wasp P. paulista is relatively common in southeast Brazil causing many medically important stinging incidents. The seriousness of these incidents is dependent on the amount of venom inoculated by the wasps into the victims, and the characteristic envenomation symptoms are strongly dependent on the types of peptides present in the venom. In order to identify some of these naturally occurring peptides available in very low amounts, an analytical protocol was developed that uses a combination of reversed-phase and normal-phase high-performance liquid chromatography (HPLC) of wasp venom for peptide purification, with matrix-assisted laser desorption/ionization time-of-flight post-source decay mass spectrometry (MALDI-Tof-PSD-MS) and low-energy collision-induced dissociation (CID) in a quadrupole time-of-flight tandem mass spectrometry (QTof-MS/MS) instrument for peptide sequencing at the sub-picomole level. The distinction between Leu and Ile was achieved both by observing d-type fragment ions obtained under CID conditions and by comparison of retention times of the natural peptides and their synthetic counterparts (with different combinations of I and/or L at N- and C-terminal positions). To distinguish the isobaric residues K and Q, acetylation of peptides was followed by Q-Tof-MS analysis. The primary sequences obtained were INWLKLGKMVIDAL-NH(2) (MW 1611.98 Da) and IDWLKLGKMVMDVL-NH(2) (MW 1658.98 Da). Micro-scale bioassay protocols characterized both peptides as presenting potent hemolytic action, mast cell degranulation, and chemotaxis of polymorphonucleated leukocyte (PMNL) cells. The primary sequences and the bioassay results suggest that these toxins constitute members of a new sub-class of mastoparan toxins, directly involved in the occurrence of inflammatory processes after wasp stinging. 相似文献
30.
Lupane Pentacyclic Triterpenes Isolated from Stems and Branches of Maytenus imbricata (Celastraceae)
Silvia Ribeiro deSouzaeSilva GraciaDivina deFtimaSilva LucaCludio deAlmeidaBarbosa LucienirPains Duarte SidneyAugustoVieira Filho 《Helvetica chimica acta》2005,88(5):1102-1109
Four lupane pentacyclic triterpenes were isolated from the hexane extract of stems and branches of Maytenus imbricata Mart. ex Reissek : 3‐oxolup‐20(30)‐en‐29‐al ( 1 ), 30‐hydroxylup‐20(29)‐en‐3‐one ( 2 ), (11α)‐11‐hydroxylup‐20(29)‐en‐3‐one ( 3 ), and (3β)‐lup‐20(30)‐ene‐3,29‐diol ( 4 ). The structural identification of 1 – 4 was achieved by 1H‐ and 13C‐NMR techniques, including 2D experiments (HSQC, HMBC, and NOESY). 相似文献