Casearin X, Its Degradation Product and Other Clerodane Diterpenes from Leaves of Casearia sylvestris: Evaluation of Cytotoxicity against Normal and Tumor Human Cells

An EtOH extract of the leaves of Casearia sylvestris afforded new clerodane diterpene, casearin X, together with the known compounds casearins B, D, L, and O, and caseargrewiin F Casearin X degraded to the corresponding dialdehyde when stored in CDCl(3). The diterpenes isolated were cytotoxic to human cancer cell lines, with caseargrewiin F being the most active and the new clerodane, casearin X, the second active compound with IC(50) values comparable to the positive control doxorubicin. All isolated diterpenes showed lower activities against normal human cells than against cancer cell lines, which might indicate a possible selective action on cancer cells. Casearin X dialdehyde was not cytotoxic to cancer cells indicating that the occurrence of these CO groups at C(18) and C(19) is incompatible with the cytotoxic activity.

Penicillium expansum versus antagonist yeasts and patulin degradation in vitro

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

The influence of soil and landfill leachate microorganisms in the degradation of PVC/PCL films cast from DMF

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

FACTORS THAT AFFECT THE ENZYMATIC DEGRADATION OF NATURAL STARCH GRANULES - EFFECT OF THE SIZE OF THE GRANULES

In this study the relationship between the enzymatic susceptibility and the size of the com and cassava starch granules was studied. The starch granules were separated by size and classified according to their average diameter in: a) larger than 16 mum; b) between 15 and 10 mum and c) smaller than 10 mum. The starch granules of various sizes were hydrolyzed by bacterial alpha-amylase and fungal amyloglucosidase. The results showed a relationship between the enzymatic susceptibility and the size of the starch granules; smaller size of the starch granules resulted in a higher percentage of hydrolysis. A basic difference in the mode of action of enzymes on small and large granules was observed. Enzymatic attack on the large granules was characterized by considerable surface corrosion, mainly at the radial axis. For small granules, the enzymatic action occurred on the surface of the granules and was characterized by an erosion with solubilization of the granules. Chemical and physical analysis of the starches suggested that hydrolysis should occur mainly at the amorphous areas of the granules.

The role of chain scission and chain branching in high density polyethylene during thermo-mechanical degradation

The mechanical and thermo-oxidative degradation of high density polyethylene (HDPE) was measured in a twin-screw extruder using various processing conditions. Two types of HDPE, Phillips and Ziegler-Natta, having different levels of terminal vinyl unsaturation were analysed. Mild screw profiles, having mainly conveying elements, have short mean residence times then profiles with kneading discs and left hand elements. Carbonyl and traps-vinylene group concentrations increased, whereas vinyl group concentration decreased with number of extrusions. Higher temperature profiles intensified these effects. The thermo-mechanical degradation mechanism begins with chain scission in the longer chains due to their higher probability of entanglements. These macroradicals then react with the vinyl terminal unsaturations of other chains producing chain branching. Shorter chains are more mobile, not suffering scission but instead are used for grafting the macroradicals, increasing the molecular weight. Increase in the levels of extrusion temperature, shear and vinyl end groups content facilitates the thermo-mechanical degradation reducing the amount of both, longer chains via chain scission and shorter chains via chain branching, narrowing the polydispersity. Phillips HDPE produces a higher level of chain branching than does the Ziegler-Natta type. (C) 2004 Elsevier Ltd. All rights reserved.

TiO2 films organofunctionalized with 2-aminothiazole ligand and adsorbed Pd(II) ions applied in the photocatalytic degradation of phenol in an aqueous medium

This paper describes the preparation of thin titanium films via sol-gel route and their subsequent chemical modification by anchoring with 2-aminothiazole ligand and Pd(II) ion sorption, aiming to maximize the photocatalytic activity. The material was characterized by diffuse reflectance infrared Fourier transform spectroscopy, ultraviolet and visible spectrometry, X-ray diffractometry, and scanning electronic microscopy. The amount of palladium adsorbed on the film's surface, determined by graphite furnace atomic absorption spectrometry, showed a value of 2.69 x 10(16) atoms CM-2. The photocatalytic tests indicated that the functionalization with 2-aminothiazole and the adsorption of palladium (II) were determinants in the semiconductor's enhanced photocatalytic activity. (c) 2007 Elsevier B.V. All rights reserved.

beta(2)-Agonists and cAMP inhibit protein degradation in isolated chick (Gallus domesticus) skeletal muscle

1. The role of beta(2)-agonist and of cAMP in chick skeletal muscle proteolytic pathways and protein synthesis was investigated using an in vitro preparation that maintains tissue glycogen stores and metabolic activity for several hours.2. In extensor digitorum longus (EDL) muscle total proteolysis decreased by 15 to 20% in the presence of equimolar concentrations of epinephrine, clenbuterol, a selective beta(2)-agonist, or dibutyryl-cAMP. Rates of protein synthesis were not altered by clenbuterol or dibutyryl-cAMP.3. The decrease in the rate of total protein degradation induced by 10(-5) M clenbuterol was paralleled by a 44% reduction in Ca2+-dependent proteolysis, which was prevented by 10(-5) M ICI 118.551, a selective beta(2)-antagonist.4. No change was observed in the activity of the lysosomal, ATP-dependent, and ATP-independent proteolytic systems. Ca2+-dependent proteolytic activity was also reduced by 58% in the presence of 10(-4) M dibutyryl-cAMP or isobutylmethylxanthine.5. The data suggest that catecholamines exert an inhibitory control of Ca2+-dependent proteolysis in chick skeletal muscle, probably mediated by beta(2)-adrenoceptors, with the participation of a cAMP-dependent pathway.

Prediction of dry matter intake based on ruminal degradation from milking cows grazing coast-cross grass

Dry matter intake (DMI) of coast-cross grazing by crossbred Holstein-Zebu and Zebu lactating cows was calculated using in vitro dry matter digestibility from extrusa (four esophageal fistulated cows) and fecal output estimate with mordent chromium. Pasture was rotationally grazed with three days grazing period and 27 days testing period, adopting a stocking rate of 1.6 and 3.2 cows/ha, during the dry and rainy season respectively. Voluntary DMI was estimated from degradation characteristics using different equations. Predicted coast-cross DMI varied with models. The prediction of tropical forages dry matter intake from equations based in ruminal degradation parameters needs farther investigation before being employed in practice.

Evaluation of different electrochemical methods on the oxidation and degradation of Reactive Blue 4 in aqueous solution

The oxidation of a reactive dye, Reactive Blue 4, RB4, (C.I. 61205), widely used in the textile industries to color natural fibers, was studied by electrochemical techniques. The oxidation on glassy carbon electrode and reticulated vitreous carbon electrode occurs in only one step at 2.0 < PH < 12 involving a two-electron transfer to the amine group leading to the imide derivative. Dye solution was not decolorized effectively in this electrolysis process. Nevertheless, the oxidation of this dye on Ti/SnO2/SbOx (3% mol)/RuO2 (1% mol) electrode showed 100% of decolorization and 60% of total organic carbon removal in Na2SO4 0.2 M at PH 2.2 and potential of +2.4 V. Experiments on degradation photoelectrocatalytic were also carried out for RB4 degradation in Na2SO4 0.1 K PH 12, using a Ti/TiO2 photoanode biased at +1.0 V and UV light. After 1 h of electrolysis the results indicated total color removal and 37% of mineralization. (c) 2004 Elsevier Ltd. All rights reserved.

Thermal degradation of a composite solid propellant examined by DSC - Kinetic study

The thermal decomposition of ammonium perchlorate (AP)/hydroxyl-terminated-polybutadiene (HTPB), the AP/HTPB solid propellant, was studied at different heating rates in dynamic nitrogen atmosphere. The exothermic reaction kinetics was studied by differential scanning calorimetry (DSC) in non-isothermal conditions. The Arrhenius Parameters were estimated according to the Ozawa method. The calculated activation energy was 134.5 W mol(-1), the pre-exponential factor, A, was 2.04.10(10) min(-1) and the reaction order for the global composite decomposition was estimated in 0.7 by the kinetic Shimadzu software based on the Ozawa method. The Kissinger method for obtaining the activation energy value was also used for comparison. These results are discussed here.

Evaluation of color removal and degradation of a reactive textile azo dye on nanoporous TiO2 thin-film electrodes

The feasibility of the photobleaching of a textile azo dye, reactive orange 16 (C.I. 17757), in aqueous solution using titanium dioxide thin-film electrodes prepared by the sol-gel method was investigated. The best conditions for maximum photoelectrocatalytic degradation were found to be pH > 10 for Na2SO4 medium and pH < 6 for NaCl. In both situations, an applied potential of +1.0 V and low dye concentration are recommended, when 100% of color removal is obtained after 20 min of photoelectrocatalysis. The effects of side reaction pathway on the degradation rate of dye in sulfate and chloride medium were presented and the best performance are optimized to situations closed to that verified in the textile effluent. The influence of variables as applied potential, pH, supporting electrolyte and dye concentration on the kinetics of photoelectrochemical degradation also were investigated. Oxalic acid is identified by HPLC and UV-Vis spectrophotometric methods as the main degradation product generated after 180 min of photoelectrocatalysis of 4 x 10(-5) mol l(-1) dye in sodium sulphate pH 12 and NaCl pH 4.0 and a maximum reduction of 56 and 62% TOC was obtained, respectively. (C) 2004 Elsevier Ltd. All rights reserved.

Rapid degradation of propanil in rice crop fields

Propanil and its major degradation product, 3,4-dichloroaniline (DCA), were monitored in surface water and soil samples from two rice fields of the Ebre Delta area (Tarragona, Spain) following agricultural application. On-line solid-phase extraction (SPE) (water) and Soxhlet extraction (soil) followed by liquid chromatography/diode array detection (LC/DAD) were used for the trace determination of both compounds. Unequivocal confirmation/identification was conducted by using liquid chromatography/atmospheric pressure chemical ionization-mass spectrometry, LC/APCI/MS (using negative and positive ionization modes). Concentrations of the herbicide propanil in water samples varied from 1.9 to 55.9 mu g/L. Propanil degraded very rapidly to DCA, and high concentrations of this product were found, varying from 16.5 to 470 mu g/L in water and 119 +/- 22 mu g/kg in soil samples. No detectable DCA (<0.001%) was found in the applied pesticide formulation, indicating that DCA formation took place after propanil application. These field results compared favorably with laboratory experiments showing that humic interactions had a strong influence on the pesticide degradation. The half-lifes under real conditions for propanil and DCA, calculated using a first-order decay, were 1.2 and 1.6 days, respectively.

Degradation of the herbicide tebuthiuron using solar photo-Fenton process and ferric citrate complex at circumneutral pH

The influence of pH on the degradation of the herbicide tebuthiuron (TBH) was investigated using in situ generated Fe(III)-citrate complexes (Fe:cit) submitted to the photo-Fenton process under solar irradiation. Using Fe:cit in a wide pH range (2.5-7.5), 100-78% TBH oxidation was achieved respectively from a UV dose of 2.0 J cm(-2) (15 min). Moreover, the oxidation of TBH obtained in the presence of Fe:cit at pH 6.0 was higher than that obtained using Fe(NO3)3 at pH 2.5. A similar behavior is observed for the removal of total organic carbon (TOC) in TBH solutions. In the presence of Fe:cit, 20% and 85% of TOC was removed at pH 7.5 and 2.5, respectively, after 7.5 J cm-2 irradiation, while no mineralization was observed employing Fe(NO3)(3) for the same UV dose. Using Fe(NO3)(3), mineralization was observed only after 11 J cm-2 (8%). A higher mineralization rate was obtained with Fe(NO3)(3) only when a concentration three times higher was employed at pH 2.5. Besides the high efficiency of TBH degradation observed using the ferric citrate complex in the solar photo-Fenton process, it also offers the advantage of application at a pH of up to 7.5. (c) 2007 Elsevier B.V. All rights reserved.

Thermal degradation of geomembranes after exposure to heat

HDPE and PVC geomembranes are sensitive to changes in their properties when in contact with high temperatures. The effects of hot temperature on polymeric geomembranes are assessed by the ASTM D794 and ASTM D5721.This paper brings an analysis of degradation of the Poly Vinyl Chloride (PVC) and High Density Poly Ethylene (HDPE) geomembranes when exposed to conventional and air oven after specific periods.. Mechanical and physical properties were evaluated. OIT tests were also performanced to evaluate the level of oxidation degradation occurred on the HDPE geomembranes. Geomembranes of two thicknesses were tested: 1.0, 2.0 nun (PVC) and 0.8, 2.5 mm, (HDPE). The results obtained show, for example, that after the last period of exposure, the PVC geomembranes (1.0, 2.0 mm) were more rigid and stiffer than fresh samples. The HDPE geomembranes, on the other hand, when exposed to heat presented increases in deformation. OIT tests showed efficient to detect some level of degradation on the HDPE geomembranes.

Indirect polarographic and cathodic stripping voltammetric determination of cefaclor as an alkaline degradation product

Cefaclor is not reducible at a mercury electrode, but it can be determined polarographically and by cathodic stripping voltammetry as its initial alkaline degradation product which is obtained in high yield by hydrolysis of cefaclor in Britton-Robinson (B-R) buffer pH 10 at 50 degrees C for 30 min (reduction peak at pH 10, -0.70 V). Differential pulse polarographic calibration graphs are linear up to at least 1 x 10(-4) mol l(-1). Recoveries of 93% of the cefaclor (n = 3) were obtained from urine spiked with 38.6 mu g ml(-1) using this polarographic method with 1 ml urine made up to 10 ml with pH 10 buffer. Using cathodic stripping voltammetry and accumulating at a hanging mercury drop electrode at -0.2 V for 30 s, linear calibration graphs were obtained from 0.35 to 40 mu g ml(-1) cefaclor in B-R buffer pH 10. A relative standard deviation of 4.2% (eta = 5) was obtained, and the limit of detection was calculated to be 2.9 ng ml(-1). Direct determination of cefaclor in human urine (1 ml of urine was made up to 10 ml with pH 10 buffer) spiked to 0.39 mu g ml(-1) was made (recovery 98.6%). (C) 1999 Elsevier B.V. B.V. All rights reserved.