Combined (13)C NMR and DFT/GIAO studies of the polyketides Aurasperone A and Fonsecinone A

Structural characterization by NMR spectroscopy and DFT calculations was performed for two dimeric naptho-gamma-pyrones, the polyketides Aurasperone A and Fonsecinone A. Experimental data ((13)C NMR chemical shifts and interatomic geometries) were found to be in reasonable agreement with theoretical ones, obtained at B3LYP level for three different basis sets (6-31G/6-31G(d)/6-31G(d,p)). Additionally, the dipolar moments calculation allowed explaining the different solubility for these molecules. The (13)C NMR theoretical chemical shifts were calculated with the GIAO method and the solvent effects were taken into account by means of the PCM approximation. In this work, the DFT/GIAO methodology shows to be a reliable tool in the assignment of experimental NMR chemical shifts of similar molecules. (C) 2008 Wiley Periodicals, Inc. Int J Quantum Chem 108: 2408-2416, 2008.

Poultry offal meal in chicken: Traceability using the technique of carbon (C-13/C-12)- and nitrogen (N-15/N-14)-stable isotopes

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Stable carbon (delta(13)C) and nitrogen (delta(15)N) isotopes as natural indicators of live and dry food in Piaractus mesopotamicus (Holmberg, 1887) larval tissue

This study proposed the use of the stable isotope technique to track the type of food utilized by pacu Piaractus mesopotamicus larvae during their development, and to identify the moment when the larvae start using nutrients from the dry diet by retaining its carbon and nitrogen atoms in their body tissues. Five-day-old pacu larvae at the onset of exogenous feeding were fed Artemia nauplii or formulated diet exclusively; nauplii+formulated diet during the entire period; or were weaned from nauplii to a dry diet after 3, 6 or 12 days after the first feeding. delta(13)C and delta(15)N values for Artemia nauplii were -15.1 parts per thousand and 4.7 parts per thousand, respectively, and -25.0 parts per thousand and 7.4 parts per thousand for the dry diet. The initial isotopic composition of the larval tissue was -20.2 parts per thousand and 9.5 parts per thousand for delta(13)C and delta(15)N respectively. Later, at the end of a 42-day feeding period, larvae fed Artemia nauplii alone reached values of -12.7 parts per thousand and 7.0 parts per thousand for delta(13)C and delta(15)N respectively. Larvae that received the formulated diet alone showed values of -22.7 parts per thousand for delta(13)C and 9.6 parts per thousand for delta(15)N. The stable isotope technique was precise, and the time at which the larvae utilized Artemia nauplii, and later dry diet as a food source could be clearly defined.

DIODE-LASER AND FOURIER-TRANSFORM SPECTROSCOPY OF THE (CH3OH)-C-13 C-O STRETCHING MODE

In this work we present high resolution Doppler limited absorption spectra measurements of the C-O stretching mode of (CH3OH)-C-13, obtained from diode laser spectroscopy, and the Fourier Transform spectrum obtained at 0. 12 cm-1 resolution. By using these data and previously known spectroscopic information, we determined the frequency and the J quantum number for the multiplets of the P and R(J) branches of the C-O stretching fundamental band. Infrared transitions in coincidence with emission lines of the regular CO2 laser and some of its isotope parents are pointed out.

Rastreabilidade da farinha de vísceras de aves em codornas submetidas a longo período de criação utilizando a técnica dos isótopos estáveis 'delta' 'intpot. 13 c' e 'delta' 'intpot. 15 N'

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Rastreabilidade de farinhas de origem animal em ovos de poedeiras comerciais pela técnica dos isótopos estáveis do carbono 'delta' 'INTPOT.13 C' do nitrogênio 'delta' 'INTPOT.15 N'

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Chemical Modification of Botryosphaeran: Structural Characterization and Anticoagulant Activity of a Water-Soluble Sulfonated (1 -> 3)(1 -> 6)-beta-D-Glucan

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

Polymeric precursor method to the synthesis of XWO(4) (X = Ca and Sr) thin films-Structural, microstructural and spectroscopic investigations

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

Chemical constituents and antioxidant activity from leaves extracts of terminalia fogiafolia mart. et zucc

CHEMICAL CONSTITUENTS and ANTIOXIDANT ACTIVITY FROM LEAVES EXTRACTS of Terminalia fagifolia Mart. et Zucc. Phytochemical investigation of ethanolic leaves extracts of T. fagifolia led to the isolation of (+)-catechin, sitosterol-3-O-beta-D-glucopyranoside, alpha- and beta-tocopherol, a mixture of lupeol, alpha- and beta-amyrin, sitosterol and a mixture of glicosid flavonoids (CP-13). The structures of these compounds were identified by (1)H and (13)C NMR spectral analysis and comparison with literature data. Absolute configuration of the catechin was determinate by circular dichroism. Antioxidant activity (EC(50)), evaluated by 2,2-diphenyl-1-picrylhidrazyl (DPPH) assay system, decreased in the order: (+)-catechin > hydroalcoholic fraction > CP-13 > aqueous fraction > EtOH extract.

Activity of Mo(II) allylic complexes supported in MCM-41 as oxidation catalysts precursors

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

Three exopolysaccharides of the beta-(1 -> 6)-D-glucan type and a beta-(1 -> 3;1 -> 6)-D-glucan produced by strains of Botryosphaeria rhodina isolated from rotting tropical fruit

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

Reaction pathway to the synthesis of anatase via the chemical modification of titanium isopropoxide with acetic acid

Anatase nanoparticles were obtained through a modified sol-gel route from titanium isopropoxide modified with acetic acid in order to control hydrolysis and condensation reactions. The modification of Ti(O(i)Pr)(4) with acetic acid reduces the availability of groups that hydrolyze and condense easily through the formation of a stable complex whose structure was determined to be Ti(OCOCH(3))(O(i)Pr)(2) by means of FTIR and (13)C NMR. The presence of this complex was confirmed with FTIR in the early stages of the process. A doublet in 1542 and 1440 cm(-1) stands for the asymmetric and symmetric stretching vibrations of the carboxylic group coordinated to Ti as a bidentate ligand. The gap of 102 cm(-1) between these signals suggests that acetate acts preferentially as a bidentate rather than as a bridging ligand between two titanium atoms. The use of acetic acid as modifier allows the control of both the degree of condensation and oligomerization of the precursor and leads to the preferential crystallization of TiO(2) in the anatase phase. A possible reaction pathway toward the formation of anatase is proposed on the basis of the intermediate species present in a 1:1 Ti(O(i)Pr)(4):CH(3)COOH molar system in which esterification reactions that introduce H(2)O into the reaction mixture were seen to be negligible. The Rietveld refinement and TEM analysis revealed that the powder is composed of isotropic anatase nanocrystallites.

Carbon nuclear magnetic resonance spectroscopic fingerprinting of commercial gasoline: Pattern-recognition analyses for screening quality control purposes

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

An Unprecedented Neolignan Skeleton from Chimarrhis turbinata

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

Biosynthetic origins of the isoprene units of gaudichaudianic acid in Piper gaudichaudianum (Piperaceae)

The biosynthesis of (2S)-2-methyl-2-(4'-methyl-3-pentenyl)-8-(3-methyl-2-butenyl)-2H-1-benzopyran-6-carboxylic acid (gaudichaudianic acid), the major metabolite in leaves and roots of Piper gaudichaudianum Kunth (Piperaceae), has been investigated employing [1(-13) C]-D-glucose as precursor. The labelling pattern in the isolated gaudichaudianic acid was determined by quantitative 13 C NMR spectroscopy analysis and was consistent with involvement of both mevalonic acid and 2-C-methyl-D-erythritol-4-phosphate pathways in the formation of the dimethylallyl- and geranyl-derived moieties. The results confirmed that both plastidic and cytoplasmic pathways are able to provide isopentenyl diphosphate units for prenylation of p-hydroxybenzoic acid. (c) 2007 Elsevier Ltd. All rights reserved.