Thermal Behavior and Spectroscopic Study of Neutral and Cationic Mononuclear Cyclopalladated Compounds

The reactions of the precursor [Pd(N,C-dmba)(MeCN)2](NO 3) (1) (dmba = N,N-dimethylbenzylamine), with the proligands 3,5-dimethylpyrazole (Hdmpz), 2-quinolinethiol (qnSH) and 1,1′- bis(diphenylphosphine)ferrocene (dppf) afforded the compounds [Pd(N,C-dmba)(Hdmpz)(ONO2)]0.5CH2Cl2 (2), [Pd(N,C-dmba)(qnSH)(ONO2)] 0.5CH2Cl2 (3) and [Pd(N,C-dmba)(dppf)](NO3) (4), respectively. The mononuclear species 2,3 and 4 were characterized by elemental analysis, infrared spectroscopy, NMR and thermogravimetric analysis. The IR spectra show bands which are consistent with terminal monodentate nitrate group for 2-3 and ionic nitrate for 4. The 1H and 13C NMR data confirm that coordination of the organic ligands has occurred and the 31P{1H} NMR data for 4 clearly evidences the occurrence in solution of three cyclopalladated species with the dppf acting as a bridging ligand in two cases and as a chelate in one. The thermal behavior of compounds 1-4 suggests that complex 2 is the most stable. The X-ray diffractometry results show the formation of PdO from 1 and 2, Pd2OSO4 from 3, and of a mixture of PdO and Fe 2(PO4)3 from 4, as final decomposition products.

Tracing metabolic routes of feed ingredients in tissues of broiler chickens using stable isotopes

The present study aimed to quantify the proportion of 13C from energy and protein feed ingredients that follow the metabolic routing of the liver and muscle in broiler chickens. A stable isotope of carbon technique was used that is based on the isotopic discrimination that occurs in the plants during the photosynthesis process. One-day-old male chicks were subjected to treatments based on free choice of energy and protein sources. Rice bran (R) and soybean meal (S), C3 plants, have higher isotopic ratios than corn (C), a C4 plant, and corn gluten meal (G). Choices were R+S, C+G, R+G, C+S, or R+C+G+S. A complete feed (CF) was a sixth treatment. Feed intake and BW were measured at 30 d of age, when liver and breast muscle were collected for isotopic analysis. Treatments affected the amount of feed intake and the choices of energy or protein sources. Complete feed had the largest intake, differing from the other treatments that had free-choice feeding. Final BW was a direct reflection of consumption by these birds in all treatments. The isotopic results indicated that the 13C/12C ratio was generally higher in breast muscle than in liver, probably because of higher protein content. Moreover, in the liver, the proportion of 13C retained from the energy ingredient was greater than the proportion from the protein ingredient. That is in contrast to muscle, where the proportion of 13C retained from the protein ingredient was greater than from the energy ingredient that was self-selected.

Carbon isotope composition and leaf anatomy as a tool to characterize the photosynthetic mechanism of Artemisia annua L.

Leaves of Artemisia annua L. are a plentiful source of artemisinin, a drug with proven effectiveness against malaria. The aim of this study was to classify the photosynthetic mechanism of A. annua through studies of the carbon isotope composition (δ 13C) and the leaf anatomy. A. annua presented a δ 13C value of - 31.76 ± 0.07, which characterizes the plants as a typical species of the C3 photosynthethic mechanism, considering that the average δ 13C values for C3 and C4 species are -28 and -14, respectively. The leaf anatomy studies were consistent with the δ 13C results, where, in spite of the existence of parenchymatic cells forming a sheath surrounding the vascular tissue, the cells do not contain chloroplasts or starch. This characteristic is clearly different from that of the Kranz anatomy found in C4 species.

Synthesis, characterization, and biological activity of a new palladium(II) complex with deoxyalliin

Synthesis, characterization, and biological activity of a new water-soluble Pd(II)-deoxyalliin (S-allyl-L-cysteine) complex are described in this article. Elemental and thermal analysis for the complex are consistent with the formula [Pd(C6H10NO2S)2]. 13C NMR, 1H NMR, and IR spectroscopy show coordination of the ligand to Pd(II) through S and N atoms in a square planar geometry. Final residue of the thermal treatment was identified as a mixture of PdO and metallic Pd. Antiproliferative assays using aqueous solutions of the complex against HeLa and TM5 tumor cells showed a pronounced activity of the complex even at low concentrations. After incubation for 24 h, the complex induced cytotoxic effect over HeLa cells when used at concentrations higher than 0.40 mmol/L. At lower concentrations, the complex was nontoxic, indicating its action is probably due to cell cycle arrest, rather than cell death. In agreement with these results, the flow cytometric analysis indicated that after incubation for 24 h at low concentrations of the complex cells are arrested in G0/G1. © 2005 NRC Canada.

Biosynthetic origins of the isoprene units of 4-nerolidylcatechol in Potomorphe umbellata

The biosynthetic origins of the isoprene units of 4-nerolidylcatechol (1), the major constituent of Potomorphe umbellata, have been studied through feeding experiments with [14C]- and [13C]-glucose, and with precursors of the mevalonic acid and triose/pyruvate pathways, namely, [2- 14C]-mevalonolactone and [U-14C]-glyceraldehyde-3- phosphate, respectively. The pattern of incorporation of label from [1- 13C]-glucose into 1 was determined by quantitative 13C NMR spectroscopy. The labelling pattern revealed that the additive was specifically incorporated, and that the isoprene units of the sesquiterpenoid moiety of 4-nerolidylcatechol were derived from both the mevalonic acid and the triose/pyruvate pathways. The results indicate that both plastidic and cytoplasmic pathways are able to provide isopentenyl diphosphate units for the biosynthesis of 1. ©2005 Sociedade Brasileira de Química.

Carbon isotope composition as a tool to control the quality of herbs and medicinal plants

Isotope screening is a simple test for determining the photosynthetic pathway used by plants. The scope of this work was to classify the photosynthetic type of some herbs and medicinal plants through studies of the carbon isotope composition (δ13C). Also, we propose the use of carbon isotope composition as a tool to control the quality of herbs and medicinal plants. For studies of δ13C, δ 13C‰ = [R (sample)/R (standard) - 1] × 10-3, dry leaves powdered in cryogenic mill were analyzed in a mass spectrometer coupled with an elemental analyzer for determining the ratio R = 13CO2/12CO2. In investigation of δ13C of 55 species, 23 botanical families, and 44 species possessed a C3 photosynthetic type. Six species found among the botanical families Euphorbiaceae and Poaceae were C4 plants, and 5 species found among the botanical families Agavaceae, Euphorbiaceae, and Liliaceae possessed CAM-type photosynthesis. Carbon isotope composition of plants can be used as quality control of herbs and medicinal plants, allowing the identification of frauds or contaminations. Also, the information about the photosynthetic type found for these plants can help in introducing and cultivating exotic and wild herbs and medicinal plants.

Studies on carbon-13 turnover in eggs and blood of commercial layers

This paper aimed at evaluating the influence of diets containing different isotopic values of carbon-13 turnover on the half-life of egg (yolk + albumen), yolk and albumen individually, and blood of poultry using δ‰ 13C isotopic variation. Commercial layers fed four experimental isocaloric and isonitrogenous diets (RC 4, RC 3, RMC 4 and RMC 3) containing different isotopic values, during an experimental period of 56 days. Turnover of the studied tissues was influenced by the experimental diets. Blood and albumen were more influenced by dietary treatments as compared to egg and yolk. The RMC 3 diet induced better performance (better feed intake and higher egg production) due faster rate of carbon substitution than the RC 4 diet, and lower half-life for egg (yolk + albumen), yolk, and albumen.

Carbon isotope composition as a tool for quality control of herbs, spices and medicinal plants

Isotope screening is a simple and cheap test for determining the photosynthetic pathway used by plants. The scope of this work was to classify the photosynthetic type of Melissa officinalis L. and Cymbopogon citratus [DC.] Stapf, through studies of the carbon isotope composition (δ13 C), and we are proposing the use of carbon isotope composition results as a tool to control the quality of medicinal plants. For studies of δ 13C (13 C% = [R (sample)/R (standard) - 1] × 10 -3), dried, powdered leaves were analyzed in a mass spectrometer coupled with an elemental analyzer for determining the ratio R (R = 13CO2/12CO2). As results, M. officinalis presented a C3 photosynthetic type, and C. citratus presented a C4 photosynthetic type. The carbon isotope composition from this study can be used as quality control of M. officinalis adulterants.

Characterization and environmental interpretation of a floodplain Holocene paleosoil: Implications for paleohydrological reconstructions in the Upper Paraná River, Brazil

Alluvial paleosoil horizons from the 3 to 4 m high banks of the Paraná River were used to reconstruct the palaeoenvironmental history and palaeohydrological regime of the river. The bank consists of a Middle to Late Holocene sequence of sandy to silty clay layers of overbank deposits. The paleosoil horizon is located to a depth of 1.95 m from the top of the bank and is recognized as a guide horizon throughout the floodplain of the Upper Paraná River floodplain. Analyses of organic matter (δ13C and humic/fulvic acids), palynology (pollen and charcoal fragments), magnetic susceptibility, micromorphology, x-ray diffraction and 14C dating were conducted for samples from two representative profiles of the study area. Two phases were characterized in the history of the river: 1) An older phase, of stability in fluvial hydrology (stasis) with low frequency of floods, which produced conditions for soil development (14C 1700 ± 70 yr. BP). At this period, the predominance of herbaceous vegetation (determinated by pollen and δ13C analyses) suggests a climate less humid than the present one, and 2) A second phase, when climate changed to the present conditions of humidity (annual rain fall of 1600 rum) and characterized by the predominance of C3 plants. Under this new hydrological regime, the river developed an agradational floodplain, with a depositional sedimentary rate of 1.2 mm.y-1. © 2006 Gebrüder Borntraeger.

Structure and properties of Brazilian peat: Analysis by spectroscopy and microscopy

Peat was taken from the Sergipe State, Brazil and characterized by several techniques: elemental and thermal analyses; Fourier infrared (FTIR) and solid state 13C nuclear magnetic resonance (NMR) spectroscopies; scanning electron microscopy (SEM), environmental scanning electron microscopy (ESEM) and X-ray diffractometry (XRD). Also, the Sergipe State peat samples were compared with other peat sample from later from Sao Paulo State, Brazil. The lowest O/C and E 4/E 6 ratios and differential thermal analysis (DTA) curves of the Santo Amaro (SAO) sample indicated that this sample had the highest degree of decomposition. FTIR results showed that Itabaiana (ITA) and São Paulo (SAP) samples presented more prominent peak at 1086 cm -1 attributed the presence of Si-O than SAO sample spectra. The SAO sample showed two more intense peaks at 2920 cm -1 and 2850 cm -1. These results were corroborated by 13C NMR and thermal gravimetric (TG) where the relative abundance of the alkyl-C groups was greater in the SAO sample. The X-ray diffractometry (XRD) of SAO sample is characteristic of amorphous matter however, the SAP and ITA samples revealed the large presence of quartz mineral. The scanning electron microscopy (SEM) and environmental scanning electron microscopy (ESEM) showed that the surface of peat samples have porous granules of organic material. The ITA and SAP peat samples are alike while SAO peat sample is richer in organic material. Only the SAO sample has truthful characteristics of peat. The results of this study showed that the samples are very different due to variable inorganic and organic material contents. ©2007 Sociedade Brasileira de Química.

A new ent-kaurane diterpene from stems of Alibertia macrophylla K. Schum. (Rubiaceae)

Phytochemical investigations of the stems of a specimen of Alibertia macrophylla led to the isolation and characterization of the new diterpene ent-kaurane-2β,3α,16α-triol (1), along with triterpenes 2-8, iridoids 9-12, and phenolic acids 13-15. The structure of 1 was established based on spectroscopic studies (1H- and 13C-NMR, IR, and HR-ESI-MS). This is the first report of the isolation of a diterpene from the Alibertia genus in Rubiaceae. © 2007 Verlag Helvetica Chimica Acta AG.

Biosynthetic origin of the isoprene units in chromenes of Piper aduncum (Piperaceae)

Metabolic studies involving the incorporation of [1-13C]-D- glucose into intact leaves of Piper aduncum (Piperaceae) have indicated that both the mevalonate (MVA) and the pyruvate-triose (MEP) non-mevalonate pathways are implicated in the biosynthesis of isoprene moieties present in methyl 2,2-dimethyl-2H-1-chromene-6-carboxylate (1) and methyl 2,2-dimethyl-8- (3′-methyl-2′-butenyl)-2H-1-chromene-6-carboxylate (2). The pattern of incorporation of label from [1-13C]-D-glucose into these chromenes was determined by quantitative 13C NMR spectroscopy. The results confirmed that biosynthetic compartment of 1 and 2 could either be the plastid and/ or the cytosol or, possibly, an additional compartment such as the plastid inter-membrane space. ©2007 Sociedade Brasileira de Química.

Flavonóides de Calotropis procera R. Br. (Asclepiadaceae)

In this work we report the identification of two flavonol glycosides isolated from the leaves of Calotropis procera R. Br. (Asclepiadaceae), a plant species with large occurrence in Northwest of Brazil with some applications in folk medicine. Some proved pharmacological activities in this species could be attributed to the presence of flavonol glycosides. The extraction and isolation of flavonol glycosides was carried out firstly by a liquid-liquid partition, and then by elution of n-BuOH fraction with MeOH over a Sephadex LH-20 column. The identification of flavonol glycosides isorhamnetin-3-O-rutinoside (1), and isorhamnetin-3-O-robinobioside (2), was obtained by 1H and 13C NMR, one- and two-dimensional techniques.

Síntese e atividade biológica do derivado 6-formil-oxamniquina

Schistosomiasis, an important disease in Brazil, is caused by a trematode of the genus Schistosoma, reaching millions of person in one of the most endemic region of this disease in the whole globe. The main goal of this work was to syntetize the 6-formyl- oxamniquine derivative and evaluate its biological activity. The 6-formyl-oxamniquine derivative was obtained by the oxidation of oxamniquine with MnO 2, applying CH 2Cl 2 as solvent at room temperature for 24 hours. The obtaintion of 6-formyl-oxamniquine derivative compound was confirmed by IR spectroscopy and 13C NMR and 1H NMR, presenting similar activity when compared to the commercial oxamniquine (Mansil®).

Polissacarídeos de parede celular fúngica: purificação e caracterização

The cell wall is a rigid structure essential for the survival of fungi. A knowledge of its composition is therefore useful for the development of novel anti-fungal drugs. In this context, polysaccharides as main components of the fungal cell wall have been the subject of intense scientific study over the years. The information gained from the knowledge of the structure of these macrobiomolecules could therefore be valuable in elucidating the mechanisms of their biosynthesis in the cell walls of pathogenic fungi infecting plants and animals alike. Determination of the chemical structures of these polysaccharides (endo) is preceded by their extraction and purification. The extractions, generally lead to neutral and/ or alkaline soluble biopolymers in groups according to their solubilities. Mixtures of polysaccharides in these extracts can then be purified by a combination of chemical and chromatographic methods. Following purification, the polysaccharides, considered homogeneous, can be characterized structurally using conventional techniques of carbohydrate chemistry, such as hydrolysis, methylation analysis, and FT-IR, 13C- and 1H- NMR spectroscopy. This review surveys the main scientific literature that characterizes polysaccharides constituting the fungal cell wall.