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Arsenic and selenium capture by fly ashes at low temperature.

Arsenic and selenium compounds may be emitted to the environment during coal conversion processes, although some compounds are retained in the fly ashes, in different proportions depending on the characteristics of the ashes and process conditions. The possibility of optimizing the conditions to achieve better trace element retention appears to be an attractive, economical option for reducing toxic emissions. This approach requires a good knowledge of fly ash characteristics and a thorough understanding of the capture mechanism involved in the retention. In this work the ability of two fly ashes, one produced in pulverized coal combustion and the other in fluidized bed combustion, to retain arsenic and selenium compounds from the gas phase in coal combustion and coal gasification atmospheres was investigated. To explore the possible simultaneous retention of mercury, the influence of the unburned coal particle content was also evaluated. Retention capacities between 2 and 22 mg g(-1) were obtained under different conditions. The unburned coal particle content in the fly ash samples does not significantly modify retention capacities.

Air Pollution↗

Isoflavone transformation during soybean koji preparation and subsequent miso fermentation supplemented with ethanol and NaCl.

Soybeans were soaked with water for 4 h, steam-cooked, inoculated with the conidia of Aspergillus oryzae, and incubated for 3 days for koji preparation. The koji was then mixed with water-soaked and steam-cooked soybeans (1:2, w/w), ground into paste, and supplemented with 15% ethanol and 12.5% NaCl or 3% ethanol and 6% NaCl for miso fermentation at 30 degrees C. Daidzin, genistin, daidzein, and genistein contents were extracted from the lyophilized and pulverized soybean powder or from the miso homogenate by a developed one-tube procedure and analyzed with an HPLC. After water soaking, daidzein and genistein contents increased markedly, whereas daidzin and genistin contents decreased. Further increases of daidzein and genistein contents and decreases of daidzin and genistin contents were observed after koji mold growth. During fermentation, fungal and lactic acid bacterial (LAB) growth in the miso products was inhibited, whereas soluble protein contents increased much more rapidly in the low-salt miso products supplemented with 3% ethanol and 6% NaCl than the other products. When the 4- and 8-week-fermented miso products were cooked with tofu for sensory evaluation, flavor ratings of the low-salt products were higher than that of a popular commercial product. In both products, the most daidzins and genistins were hydrolyzed after 4 weeks of fermentation. The hydrolytic enzymes contributing to isoflavone transformation originated from soybeans after water soaking and from koji with mold growth. It was of merit that the low-salt fermented products were fairly acceptable in flavor rating and rich in daidzein and genistein contents after 4 weeks of fermentation.

Aspergillus oryzae↗

Comparative characterization of peanuts grown by aquatic floating cultivation and field cultivation for seed and resveratrol production.

Peanut pods (Tainan 12, a Spanish cultivar, Arachis hypogaea L.) have been obtained from peanuts grown in a newly developed aquatic floating cultivation system without artificial aeration or periodic renewal of the solution. The system provided a convenient status for examination of root and pod development. Compared to field-grown peanuts of the same cultivar, the aquatic-cultivated peanut pods and seeds were smaller, whereas seed/pod weight ratios, crude fat and protein contents, and SDS-PAGE protein patterns varied within similar ranges. During cultivation, the highest detected temperature of the aquatic solution was higher than the field-soil temperature. After gas chromatographic analysis of the fatty acid compositions, the oleic acid/linoleic acid ratio of the aquatic-cultivated seeds was higher than that of field-cultivated ones. When the peanut roots were collected, cleaned, dried, weighed, pulverized, and subjected to resveratrol analysis, dry root weights were 4.2 +/- 0.1 and 2.2 +/- 1.1 g/plant and resveratrol contents were 0.074 +/- 0.009 and 0.114 +/- 0.212 mg/g for the aquatic- and field-cultivated peanut roots, respectively. This indicates that the aquatic-cultivated peanut roots could be a potent and consistent source of resveratrol.

Agriculture↗

Effects of dose and glycosylation on the transfer of genistein into the eggs of the Japanese quail (Coturnix japonica).

Soy isoflavones have been associated with several beneficial effects of soy in human diets. However, most soy is consumed by livestock in the Western countries. It is possible that isoflavones could be transferred and/or accumulated into animal products, which could become additional sources of dietary isoflavones for humans. Our objectives were to determine whether dietary isoflavone genistein could be transferred and/or accumulated into the eggs of Japanese quail (Coturnix japonica) and how the supplementation dosage and glycosylation of the isoflavone would affect this transfer. Adult reproductive female Japanese quail were randomly assigned to treatment groups that received encapsulated 50 or 100 mg genistein or 80 mg genistin per day (four quail per treatment) for 5 days. A control group (two quail) received placebo capsules. Eggs were collected prior to treatment and then daily for 15 days. The egg, separated into yolk and white, and pulverized quail diet were extracted in 80% methanol for 2 h and either centrifuged or filtered before evaporation of the solvent. The extracts were redissolved in 16% acetonitrile for high-performance liquid chromatography (HPLC) analyses. Genistein and genistein metabolites were detected in the egg yolks of treated quail. Trace concentrations of genistein were detected in the control group, due to the presence of genistein derivatives in the diet. Neither genistein nor its metabolites were found in egg white. Levels of genistein in the eggs increased significantly from the 3rd day of supplementation and reached the maximum about 2 days after the supplementation stopped. The higher dose of genistein supplementation resulted in higher genistein concentrations in egg yolks. Glycosylation decreased the transfer and accumulation of genistein into the egg yolks.

Animals↗

RP-HPLC analysis of the phenolic compounds of plant extracts. investigation of their antioxidant capacity and antimicrobial activity.

Extracts of aromatic plants of Greek origin were examined as potential sources of phenolic compounds. RP-HPLC with UV detection was employed for the identification and quantification of the phenolic antioxidants, present in methanolic extracts. The most abundant phenolic acids were ferulic acid (1.1-280 mg/100 g of dry sample) and caffeic acid (1.2-60 mg/100 g of dry sample). (+)-Catechin and quercetin were the most abundant flavonoids. Apigenin and luteolin were detected in high amounts in Menta pulegium and Thymus vulgaris, respectively. The antioxidant capacity was determined, in dried ground plants and in their methanol extracts, with the Rancimat test using sunflower oil as substrate. Both pulverized plants and extracts showed antioxidant capacity. Total phenolic content in the extracts was determined spectrometrically according to the Folin-Ciocalteu assay and ranged from 1 to 21 mg of gallic acid/100 g of dry sample. Antimicrobial activity of the extracts against selected microbes was also conducted in this study.

Anti-Bacterial Agents↗

Antiinflammatory properties of the muscadine grape (Vitis rotundifolia).

The muscadine grape possesses one of the highest antioxidant levels among fruits; yet, the effect of this fruit on mammalian metabolic systems has not received significant attention. To examine the antiinflammatory properties of the muscadine, grape skins were dried, pulverized, and extracted (10% w/v) with 50% ethanol. The extract was then tested in two different assays: the release of superoxide in phorbol myristate acetate-activated neutrophils and the release of cytokines [tumor necrosis factor-alpha (TNF-alpha), interleukin-1beta (IL-beta), and interleukin-6 (IL-6)] by lipopolysaccharide-activated peripheral blood mononuclear cells. The release of superoxide and cytokines was inhibited by increasing concentrations of the extract. A 1:100 dilution of the extract inhibited superoxide release by approximately 60% while the release of TNF-alpha and IL-1beta was reduced at a dilution of 1:200 by approximately 15 and 90%, respectively (all P < 0.05). The inhibition pattern on the release of IL-6 was similar to that seen with TNF-alpha. In a related in vivo study, rats were fed a diet containing 5% (wt/wt) dried muscadine grape skins for 14 days and then were injected with carrageenan in the foot pad. After 3 h, paw edema was measured and the rats on the grape skin diet had approximately 50% less paw edema than controls (P < 0.05). These results demonstrate that the muscadine grape skin powder possesses significant in vitro and in vivo antiinflammatory properties.

Animals↗

Nondestructive determination of lignans and lignan glycosides in sesame seeds by near infrared reflectance spectroscopy.

Sesame (Sesamum indicum L.) contains abundant lignans including lipid-soluble lignans (sesamin and sesamolin) and water-soluble lignan glycosides (sesaminol triglucoside and sesaminol diglucoside) related to antioxidative activity. In this study, near infrared reflectance spectroscopy (NIRS) was used to develop a rapid and nondestructive method for the determination of lignan contents on intact sesame seeds. Ninety-three intact seeds were scanned in the reflectance mode of a scanning monochromator. This scanning procedure did not require the pulverization of samples, allowing each analysis to be completed within minutes. Reference values for lignan contents were obtained by high-performance liquid chromatography analysis. Calibration equations for lignans (sesamin and sesamolin) and lignan glycosides (sesaminol triglucoside and sesaminol diglucoside) contents were developed using modified partial least squares regression with internal cross-validation (n = 63). The equations obtained had low standard errors of cross-validation and moderate R2 (coefficient of determination in calibration). The prediction of an external validation set (n = 30) showed significant correlation between reference values and NIRS predicted values based on the SEP (standard error of prediction), bias, and r2 (coefficient of determination in prediction). The models developed in this study had relatively higher values (more than 2.0) of SD/SEP(C) for all lignans and lignan glycosides except for sesaminol diglucoside, which had a minor amount, indicating good correlation between the reference and the NIRS estimate. The results showed that NIRS, a nondestructive screening method, could be used to rapidly determine lignan and lignan glycoside contents in the breeding programs for high quality sesame.

Calibration↗

Toward a better understanding of the lignin isolation process from wood.

The recently developed protocol for isolating enzymatic mild acidolysis lignins (EMAL) coupled with the novel combination of derivatization followed by reductive cleavage (DFRC) and quantitative (31)P NMR spectroscopy were used to better understand the lignin isolation process from wood. The EMAL protocol is shown to offer access at lignin samples that are more representative of the overall lignin present in milled wood. The combination of DFRC/(31)P NMR provided a detailed picture on the effects of the isolation conditions on the lignin structure. More specifically, we have used vibratory and ball milling as the two methods of wood pulverization and have compared their effects on the lignin structures and molecular weights. Vibratory-milling conditions cause substantial lignin depolymerization. Lignin depolymerization occurs via the cleavage of uncondensed beta-aryl ether linkages, while condensed beta-aryl ethers and dibenzodioxocins were found to be resistant to such mechanical action. Condensation and side chain oxidations were induced mechanochemically under vibratory-milling conditions as evidenced by the increased amounts of condensed phenolic hydroxyl and carboxylic acid groups. Alternatively, the mild mechanical treatment offered by ball milling was found not to affect the isolated lignin macromolecular structure. However, the overall lignin yields were found to be compromised when the mechanical action was less intense, necessitating longer milling times under ball-milling conditions. As compared to other lignin preparations isolated from the same batch of milled wood, the yield of EMAL was about four times greater than the corresponding milled wood lignin (MWL) and about two times greater as compared to cellulolytic enzyme lignin (CEL). Molecular weight distribution analyses also pointed out that the EMAL protocol allows the isolation of lignin fractions that are not accessed by any other lignin isolation procedures.

Carbohydrates↗

Validation of a method to quantify copper and other metals in olive fruit by ETAAS. Application to the residual metal control after olive tree treatments with different copper formulations.

An electrothermal atomization atomic absorption spectrometry method was validated to quantify residues of copper, aluminum, cadmium, chromium, iron, lead, and nickel in olive fruit. The linearity ranges under the optimized conditions were 0.19-20.0, 1.11-50.0, 0.02-2.0, 0.15-20.0, 0.80-20.0, 0.35-50.0, and 0.60-50.0 microg/L, respectively. The limits of quantification were, expressed in nanograms per gram of dry weight, 12.6, 74.0, 1.34, 10.0, 53.4, 23.4, and 40.0, respectively. For all of the metals the precision of the instrumental method was <6.3% and that of the analytical method was always <10%, except for aluminum, for which the precision was 12%. The accuracy of the method was evaluated according to the standard additions method, the recoveries being >90% for all of the added concentrations. An interference study was also carried out in a simulated matrix, and it was verified that the deviations of the expected values were <6% for all of the metals. The method was applied to the monitoring of the residues of the referred metals in olive fruits collected from trees pulverized with three different copper formulations available on the market to control fungal diseases.

Copper↗

Determination of whole-body rotenone residues in the brown tree snake (Boiga irregularis).

The brown tree snake (Boiga irregularis) is an introduced pest in Guam, responsible for extensive agricultural damage, the extinction of several bird species, and severe and frequent electrical power outages. Rotenone, a naturally occurring pesticide, has been investigated as a possible chemical control agent. An analytical method was developed to assess whole body rotenone residues ranging in concentration from 0.035 to 250 microg g(-)(1) in snakes. The method employed ethyl acetate extraction of 2 g samples of cryogenically frozen, pulverized snakes, followed by silica and Florisil solid-phase extraction cleanup. Extract analysis was performed using a high-performance liquid chromatography system employing a cyanopropyl analytical column. Tissues fortified to concentrations of 0.035, 4.82, and 250 microg g(-)(1) yielded analyte recoveries of 85.1, 85.6, and 83.5%, respectively. The linear response of rotenone standard solutions was assessed from 0. 025 to 0.25 microg mL(-)(1) (r(2) = 0.9968) and from 0.250 to 125 microg mL(-)(1) (r(2) = 0.9999). The method was simple, rugged, and reliable.

Animals↗

Isolation and quantification of volatiles in fish by dynamic headspace sampling and mass spectrometry.

A dynamic headspace sampling method for isolation of volatiles in fish has been developed. The sample preparation involved freezing of fish tissue in liquid nitrogen, pulverizing the tissue, and sampling of volatiles from an aqueous slurry of the fish powder. Similar volatile patterns were determined by use of this sample preparation method and for samples chewed for 10 s. Effects of sampling time, temperature, and purge flow on level of volatiles were tested. Purging at 340 mL/min for 30 min at 45 degrees C was found to be optimal. Detection limits for a number of aldehydes were 0.2-2.7 microg/kg. Levels of volatiles are given for fresh salmon, cod, saithe, mackerel, and redfish.

Aldehydes↗

A comparative study of unrelaxed surfaces on quartz and kaolinite, using the periodic density functional theory.

To investigate surface properties of fractured silica particles, which are commonly connected to the etiology of silica toxicity, models of low-index unrelaxed surfaces of quartz and kaolinite were constructed and analyzed using the periodic density functional theory calculations. The models were used to investigate surface sites that emerge in the processes of heterolytic and homolytic cleavage of quartz. It is found that the quartz surface is stabilized by two types of interactions. One, due to a more even charge distribution of sites, was characterized by surface energies of up to 0.025 eV x A(-2) and the other, due to a more even oxygen distribution between complementary surfaces, was up to 0.036 eV x A(-2). The total specific surface energies of unrelaxed surfaces ranged from 0.161 to 0.200 eV x A(-2) for quartz and from 0.017 to 0.158 eV x A(-2) for kaolinite. For the conchoidal fracture of quartz an average specific surface energy of 0.187 eV x A(-2) was obtained. These results provide a foundation for further characterization of the surface properties of mechanically comminuted respirable silica particulate and for reduction of occupational health hazards due to pulverized silica.

Chemistry, Physical↗

Development of an empirical force field for silica. Application to the quartz-water interface.

Interactions of pulverized crystalline silica with biological systems, including the lungs, cause cell damage, inflammation, and apoptosis. To allow computational atomistic modeling of these pathogenic processes, including interactions between silica surfaces and biological molecules, new parameters for quartz, compatible with the CHARMM empirical force field were developed. Parameters were optimized to reproduce the experimental geometry of alpha-quartz, ab initio vibrational spectra, and interactions between model compounds and water. The newly developed force field was used to study interactions of water with two singular surfaces of alpha-quartz, (011) and (100). Properties monitored and analyzed include the variation of the density of water molecules in the plane perpendicular to the surface, disruption of the water H-bond network upon adsorption, and space-time correlations of water oxygen atoms in terms of Van Hove self-correlation functions. The vibrational density of states spectra of water in confined compartments were also computed and compared with experimental neutron-scattering results. Both the attenuation and shifting to higher frequencies of the hindered translational peaks upon confinement are clearly reproduced by the model. However, an upshift of librational peaks under the conditions of model confinement still remains underrepresented at the current empirical level.

Adsorption↗

Modification of physical characteristics of microcrystalline cellulose by codrying with beta-cyclodextrins.

In an attempt to modify the physical properties of microcrystalline cellulose (MCC), the slurry form of this material was codried with beta-cyclodextrin (beta-CD). MCC slurry was blended with beta-CD at concentrations of 10%-50% w/w as a dried mass relative to MCC. The mixtures were then granulated with water and codried at 60 degrees C for 12 h or until a constant weight was reached. Codried granules were pulverized, and the fraction between 61 and 150 microns in size was reserved. The powder and tableting properties of the codried products were compared to those of various grades of MCC and the corresponding components and physical mixtures. The results showed that the products of MCC codried with beta-CD significantly improved the flowability of MCC powder. It is probable that the improved flowability was due to the more rounded shape of particles formed with this codried process, which was confirmed by SEM photographs. Moreover, the compactibility and disintegration properties of tablets produced from the codried products were even better than those using MCC alone, physical mixtures, or various grades of MCC. MCC in a slurry form was more efficient than the existing MCC products in achieving these results, which is postulated to be due to the greater amount of water required and the higher solubility of beta-CD in water promoting the interaction between beta-CD and MCC during granulation. In conclusion, MCC codried with beta-CD provides a useful excipient for direct compression.

Cellulose↗

Chemical defense in the zebra swallowtail butterfly, Eurytides marcellus, involving annonaceous acetogenins.

Few herbivores feed on the foliage of the North American paw paw tree, Asimina triloba; notable exceptions are the larvae of the zebra swallowtail butterfly, Eurytides marcellus. Toxic annonaceous acetogenins, produced by A. triloba, are responsible for the relative unpalatability of the leaves. Acetogenins found in A. triloba extracts are potent pesticidal and antineoplastic agents and have emetic activity in vertebrates. In this study, partitioned aqueous MeOH fractions of the bioactive CH2Cl2 extracts, of freeze-dried and pulverized larvae, and of mature butterflies revealed acetogenin content through the use of HPLC coupled to tandem MS (LC-MS/MS). This sensitive technique provides an uncomplicated method for the detection of trace compounds and, in this instance, has confirmed tissue presence of acetogenins that serve a probable role as chemical defense agents against bird predation in zebra swallowtail larvae and adults.

Animals↗

The potential of mining slag as a substrate for microbial growth and the microbiological analysis of slag and slag seepage.

The potential of a Cu/Ni mining slag to act as a substrate for the growth of the bacteria Thiobacillus ferrooxidans, Thiobacillus thiooxidants, and Thiobacillus thioparus was examined. As well, slag and slag seepage samples were screened for the presence of the Thiobacillus species. For the 28 samples employed in the environmental recovery studies, T. ferrooxidans was recovered in 25 samples, T. thiooxidans in 19 samples, and T. thioparus in 27 samples. For R. ferrooxidans, the development of a colour change in the medium corresponded with the presence of motile bacilli as detected microscopically. For T. thiooxidans and T. thioparus, a decrease in culture pH of greater than 0.2 units usually corresponded with the presence of motile bacilli. The potential for growth on slag was determined by adding slag samples to media (devoid of an electron donor) appropriate for the growth of the three Thiobacillus species. All pulverized slag samples supported the growth of the three species.

Acidithiobacillus thiooxidans↗

Characterization of free and glyceride-esterified long chain fatty acids in different skeletal muscle types of the rat.

The plasma-borne long-chain free fatty acids (FFA) enter skeletal muscle cells. Upon entering they are oxidized or esterified and a fraction remains free (non-esterified). The data on free fatty acids in skeletal muscles remain highly controversial. Furthermore, the composition of individual fatty acids in various lipid fractions including free fatty acids, monoglyceride and diglyceride in muscles has not been characterized. Also data on the composition of fatty acids esterified into muscle triglycerides and phospholipids are incomplete. The present study was undertaken to examine a composition of fatty acids in lipid fractions of different skeletal muscle types. For this purpose, samples of the rat soleus, red and white portions of gastrocnemius were excised, trimmed of visible fat and fascias and immediately frozen in liquid nitrogen. Samples were then pulverized and, lipids were extracted and fractionated by thin-layer chromatography. Individual long-chain fatty acids in different fractions were identified, characterized and quantitated by gas-liquid chromatography. FFA composition in the plasma was also determined. The total FFA content in the soleus, red and white gastrocnemius was 69.1 +/- 10.8, 49.0 +/- 13.6 and 22.7 +/- 8.6 nmol/g, respectively. Palmitic and oleic acids were the major fatty acids in the muscles FFA fraction. Monoglyceride fraction of each muscle contained palmitic, stearic and linoleic acid as the major fatty acids, Diglyceride fraction contained mostly palmitic and oleic acid whereas triglyceride fraction mostly palmitic and linoleic acid.. The fraction of phospholipids was composed mostly of palmitic and linoleic acid but contained also considerable percentage of archidonic acid. Total plasma FFA/muscle FFA ratio depended on a muscle type and was: 2.4 in the soleus, 3.5 in the red and 7.4 in the white gastrocnemius. This assured transport of FFA to the myocytes. However, there were great differences in the ratio between particular FFA within the same muscle as well between the muscles. It indicates that individual FFA are either selectively transported from the plasma to the muscles or selectively used within the myocytes or both.

Animals↗

Effect of tannic acid solution on collagen structures for dental restoration.

This study examined the effect of tannic acid solution on dissolution of dentine collagen and morphological aspects of tendon collagen. Using root dentine, which was cut off from bovine anterior tooth, dentine powders were obtained by the pulverization and lyophilization. They were subject to an application of 1, 3, 5 or 10% tannic acid (TA) solution for 1, 3, 6, 12 or 24 h. TA-treated dentine powders were treated with 40% phosphoric acid (PA) for 30 s at 20 degrees C and additionally with trypsin. Released hydroxyproline in Woessner's assay after a hydrolysis in 6 N HCl at 110 degrees C for 20 h was assumed to be dissolved dentine collagen. Released hydroxyproline in a control sample without acid treatment decreased from 100 to about 60% with increased TA concentration of 1 to 10%, and decreased with increased incubation times of 1 to 24 h when applied by 5% TA solution. Scanning electron microscopy results established the morphological effect of their surface characteristics due to such treatments as 40% PA for 30 s and 5% TA for 6 h, or 40% PA after 5% TA treatment, yielding collagen structures protected by TA to attack from phosphoric acid.

Journal Article↗