Characterization of organic matter from composting of different residues by physicochemical and spectroscopic methods

Chemical and spectroscopic methods were used to characterize organic matter transformations during the composting process. Four different residue mixtures were studied: P1 - garden trimmings (GT) only, P2 - GT plus fresh cattle manure, P3 - GT plus orange pomace and P4 - GT plus filter cake. The thermophilic phase was not reached in PI compost, but the P2, P3 and P4 composts showed all three typical process phases. The thermophilic phase and CEC/C ratio stabilized after 90 days, while C/N ratio and the ash content stabilized after 60 days. The increasing E(4)/E(6) ratio indicated oxidation reactions occurring during the process in the material from P2, P3 and P4. The (13)C NMR and FTIR results suggested extraction of both pectin and lignin in the HA-like fraction. The CEC/C ratio, temperature and E(4)/E(6) ratio showed that within 90 days P2, P3 and P4 composts were humified. However, material from P1 did not show characteristics of humified compost. From these data, it is apparent that C/N ratio and ash content are not reliable methods for monitoring the composting process. (C) 2009 Elsevier Ltd. All rights reserved.

Chemical and spectroscopic studies of a new palladium(II) complex with N-acetyl-L-cysteine

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

Azaphilones from the Endophyte Chaetomium globosum

Six new azaphilones, 5`-epichaetoviridin A (7), 4`-epichaetoviridin F (9), 12 beta-hydroxychaetoviridin C (10), and chaetoviridins G-I (11-13), and six known azaphilones, chaetoviridins A E (1-5) and 4`-epichaetoviridin A (8), were isolated from the endophytic fungus Chaetomium globosum cultivated in PDB medium for 21 days. The structure elucidation and the assignment of the relative configurations of the new natural products were based on detailed NMR and MS spectroscopic analyses. The structure of compound 1 was confirmed by single-crystal X-ray diffraction analysis. were determined using Mosher`s method. The antibiotic activity of the elegans infection model. The absolute configurations of compounds 4, 7, 8, and 12 compounds was evaluated using an in vivo Caenorhabditis elegans infection model.

Biotransformation using Mucor rouxii for the production of oleanolic acid derivatives and their antimicrobial activity against oral pathogens

The goal of this study is to produce oleanolic acid derivatives by biotransformation process using Mucor rouxii and evaluate their antimicrobial activity against oral pathogens. The microbial transformation was carried out in shake flasks at 30A degrees C for 216 h with shaking at 120 rpm. Three new derivatives, 7 beta-hydroxy-3-oxo-olean-12-en-28-oic acid, 7 beta,21 beta-dihydroxy-3-oxo-olean-12-en-28-oic acid, and 3 beta,7 beta,21 beta-trihydroxyolean-12-en-28-oic acid, and one know compound, 21 beta-hydroxy-3-oxo-olean-12-en-28-oic acid, were isolated, and the structures were elucidated on the basis of spectroscopic analyses. The antimicrobial activity of the substrate and its transformed products was evaluated against five oral pathogens. Among these compounds, the derivative 21 beta-hydroxy-3-oxo-olean-12-en-28-oic acid displayed the strongest activity against Porphyromonas gingivalis, which is a primary etiological agent of periodontal disease. In an attempt to improve the antimicrobial activity of the derivative 21 beta-hydroxy-3-oxo-olean-12-en-28-oic acid, its sodium salt was prepared, and the minimum inhibitory concentration against P. gingivalis was reduced by one-half. The biotransformation process using M. rouxii has potential to be applied to the production of oleanolic acid derivatives. Research and antimicrobial activity evaluation of new oleanolic acid derivatives may provide an important contribution to the discovery of new adjunct agents for treatment of dental diseases such as dental caries, gingivitis, and periodontitis.

Phorbasin B and C: Novel diterpenes from a southern Australian marine sponge, Phorbas species

A southern Australian Phorbas sp. has yielded the novel diterpenes phorbasin B (2) and phorbasin C (3). Phorbasins B and C possess a hitherto unknown carbon skeleton, and their structures were assigned on the basis of detailed spectroscopic analyses.

Sulfated galactans from Australian specimens of the red alga Phacelocarpus peperocarpos (Gigartinales, Rhodophyta)

Polysaccharides from the red alga Phacelocarpos peperocarpos were extracted with hot water, clarified, and precipitated with 2-propanol. The native preparation was highly sulfated (36.2% w/w). Alkali modification decreased the sulfate content by 2.0% w/w. The alkali-modified polysaccharide is composed mostly of galactose (Gal, 51 mol%) and 3,6-anhydrogalactose (AnGal, 41 mol%), with minor amounts of a mono-O-methylgalactose (MeGal, 1 mol%), xylose (Xyl, 6 mol%), and glucose (Glc, 1 mol%). The FTIR spectrum of the alkali-modified polysaccharide resembled K-carrageenan with absorption at 930 cm(-1) (indicative of AnGal) and 850 cm(-1) (Gal ii-sulfate). However, an additional, major band of absorption occurred at 820 cm(-1) indicating the presence of equatorial sulfate ester substitution at O-6 of Gal residues, A combination of linkage and C-13 NMR spectroscopic analyses showed that the polysaccharide was composed predominantly of a novel repeating-unit, O-beta-D-galactopyranosyl 4,6-disulfate)-(1 --> 4)-3,6-anhydro-alpha-D-galactopyranose. Minor structural variations also occurred, including alternative patterns of sulfation and the presence of terminal Xylp, The location of the terminal Xylp residues was not certain but evidence supported their attachment at O-3 of some 4-linked Galp residues. The cell-wall galactans remain unchanged during the life cycle of the alga. (C) 1996 Elsevier Science Ltd.

Antileishmanial and antitrypanosomal activity of bufadienolides isolated from the toad Rhinella jimi parotoid macrogland secretion

Amphibian skin secretions are considered a rich source of biologically active compounds and are known to be rich in peptides, bufadienolides and alkaloids. Bufadienolides are cardioactive steroids from animals and plants that have also been reported to possess antimicrobial activities. Leishmaniasis and American Trypanosomiasis are parasitic diseases found in tropical and subtropical regions. The efforts toward the discovery of new treatments for these diseases have been largely neglected, despite the fact that the only available treatments are highly toxic drugs. In this work, we have isolated, through bioguided assays, the major antileishmanial compounds of the toad Rhinella jimi parotoid macrogland secretion. Mass spectrometry and (1)H and (13)C NMR spectroscopic analyses were able to demonstrate that the active molecules are telocinobufagin and hellebrigenin. Both steroids demonstrated activity against Leishmania (L.) chagasi promastigotes, but only hellebrigenin was active against Trypanosoma cruzi trypomastigotes. These steroids were active against the intracellular amastigotes of Leishmania, with no activation of nitric oxide production by macrophages. Neither cytotoxicity against mouse macrophages nor hemolytic activities were observed. The ultrastructural studies with promastigotes revealed the induction of mitochondrial damage and plasma membrane disturbances by telocinobufagin, resulting in cellular death. This novel biological effect of R. jimi steroids could be used as a template for the design of new therapeutics against Leishmaniasis and American Trypanosomiasis. (C) 2008 Elsevier Ltd. All rights reserved.

Tauroursodeoxycholic acid prevents Bax-induced membrane perturbation and cytochrome C release in isolated mitochondria

Biochemistry, 2003, 42 (10), pp 3070–3080 DOI: 10.1021/bi026979d

Field testing of arsenic in groundwater samples of Bangladesh using a test kit based on lyophilized bioreporter bacteria.

A test kit based on living, lyophilized bacterial bioreporters emitting bioluminescence as a response to arsenite and arsenate was applied during a field campaign in six villages across Bangladesh. Bioreporter field measurements of arsenic in groundwater from tube wells were in satisfying agreement with the results of spectroscopic analyses of the same samples conducted in the lab. The practicability of the bioreporter test in terms of logistics and material requirements, suitability for high sample throughput, and waste disposal was much better than that of two commercial chemical test kits that were included as references. The campaigns furthermore demonstrated large local heterogeneity of arsenic in groundwater, underscoring the use of well switching as an effective remedy to avoid high arsenic exposure.

Reaction Kinetics and Viscosity Modelling in the Fusion Syntheses of Ca- and Ca/Mg-resinates

Rosin is a natural product from pine forests and it is used as a raw material in resinate syntheses. Resinates are polyvalent metal salts of rosin acids and especially Ca- and Ca/Mg- resinates find wide application in the printing ink industry. In this thesis, analytical methods were applied to increase general knowledge of resinate chemistry and the reaction kinetics was studied in order to model the non linear solution viscosity increase during resinate syntheses by the fusion method. Solution viscosity in toluene is an important quality factor for resinates to be used in printing inks. The concept of critical resinate concentration, c crit, was introduced to define an abrupt change in viscosity dependence on resinate concentration in the solution. The concept was then used to explain the non-inear solution viscosity increase during resinate syntheses. A semi empirical model with two estimated parameters was derived for the viscosity increase on the basis of apparent reaction kinetics. The model was used to control the viscosity and to predict the total reaction time of the resinate process. The kinetic data from the complex reaction media was obtained by acid value titration and by FTIR spectroscopic analyses using a conventional calibration method to measure the resinate concentration and the concentration of free rosin acids. A multivariate calibration method was successfully applied to make partial least square (PLS) models for monitoring acid value and solution viscosity in both mid-infrared (MIR) and near infrared (NIR) regions during the syntheses. The calibration models can be used for on line resinate process monitoring. In kinetic studies, two main reaction steps were observed during the syntheses. First a fast irreversible resination reaction occurs at 235 °C and then a slow thermal decarboxylation of rosin acids starts to take place at 265 °C. Rosin oil is formed during the decarboxylation reaction step causing significant mass loss as the rosin oil evaporates from the system while the viscosity increases to the target level. The mass balance of the syntheses was determined based on the resinate concentration increase during the decarboxylation reaction step. A mechanistic study of the decarboxylation reaction was based on the observation that resinate molecules are partly solvated by rosin acids during the syntheses. Different decarboxylation mechanisms were proposed for the free and solvating rosin acids. The deduced kinetic model supported the analytical data of the syntheses in a wide resinate concentration region, over a wide range of viscosity values and at different reaction temperatures. In addition, the application of the kinetic model to the modified resinate syntheses gave a good fit. A novel synthesis method with the addition of decarboxylated rosin (i.e. rosin oil) to the reaction mixture was introduced. The conversion of rosin acid to resinate was increased to the level necessary to obtain the target viscosity for the product at 235 °C. Due to a lower reaction temperature than in traditional fusion synthesis at 265 °C, thermal decarboxylation is avoided. As a consequence, the mass yield of the resinate syntheses can be increased from ca. 70% to almost 100% by recycling the added rosin oil.

Constituintes químicos de Zanthoxylum ekmanii (URB.) Alain

Chemical investigation of Z. ekmanii resulted in the isolation of skimmianine, dictamnine, tembamide, sesamin, lupeol and beta-sitosterol. The structures were established by spectroscopic analyses. This is the first report on the phytochemical study of the roots and leaves of Z. ekmanii.

Constituintes químicos e atividade antioxidante de Sida galheirensiS Ulbr. (Malvaceae)

The phytochemical investigation of Sida galheirensis led to the isolation of 5,4'-dihydroxy-3,7,3´-trimethoxyflavone, 17³-ethoxyphaeoforbide, a rare natural product, 6,7-dimethoxycoumarin, ortho-hydroxybenzoic acid, sitosterol-3-O-beta-D-glucopyranoside, stigmasterol-3-O-beta-D-glucopyranoside, 5,7,4'-trihydroxyflavone, 5,7,3',4'-tetrahydroxyflavone, kaempferol-3-O-beta-D-(6"-E-p-coumaroyl) glucopyranoside and luteolin 7-O-beta-D-glucopyranoside. Their structures were assigned based on spectroscopic analyses, including two-dimensional NMR techniques. Antioxidant activities of hexane, CHCl3, EtOAc, BuOH and EtOH extracts of Sida galheirensis were measured using the 1,2-diphenyl-2-picryl-hydrazyl (DPPH) free radical scavenging assay. This is also the first work reporting the chemical investigation of Sida galheirensis.

Constituintes químicos das flores de Pterogyne nitens (Caesalpinioideae)

The phytochemical investigation of the flowers of Pterogyne nitens (Caesalpinioideae) resulted in the isolation and identification of nine phenolic derivatives, quercetin 3-O-sophoroside, taxifolin, astilbin, ourateacatechin, caffeic, ferulic, sinapic, chlorogenic and gallic acid, besides two guanidine alkaloids, pterogynine, pterogynidine. This is the first time these compounds have been reported in P. nitens flowers. As this is a monospecific genus, these secondary metabolites may have taxonomical significance. Their structures were assigned on the basis of spectroscopic analyses, including two-dimensional NMR techniques.

Alcalóides e outros metabólitos do caule e frutos de Zanthoxylum tingoassuiba A. St. Hil

Phytochemical investigation of this species, popularly known as tinguaciba and used in traditional medicine to various diseases, resulted in the isolation of 15 substances: 2 alkaloids - norchelerythrine and arnottianamide; 1 lignan - sesamin; 4 terpenoids - citronellyl acetate, lupeol, α-bisabolol and spatulenol; 5 coumarins described for the first time - xanthotoxin, isopimpinelin, O-prenylumbelliferone, imperatorin and aurapten, 1 protoalkaloid - methyl N-methylanthranilate and 2 steroids - stigmasterol and β-sitosterol. The structures of the compounds were elucidated by spectroscopic analyses and compared with literature data.

Alcaloides e outros constituintes de Xylopia langsdorffiana (Annonaceae)

The phytochemical investigation of Xylopia langsdorffiana led to the isolation of corytenchine, xylopinine, discretamine, xylopine, ent-atisan-16α-hydroxy-18-oic acid, 13² (S) hydroxy-17³-ethoxyphaephorbide and quercetin-3-α-rhamnoside. Their structures were assigned based on spectroscopic analyses, including two-dimensional NMR techniques. Antioxidant activities of discretamine were measured using the 1,2-diphenyl- 2-picryl-hydrazyl (DPPH) free radical scavenging assay.