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Enhancing phosphate removal from wastewater by using polyelectrolytes and clay injection.

Aluminum sulfate, alum, is a common chemical coagulant used for coagulation. Recently, polymers have been utilized in coagulation/flocculation processes for water purification. In this study, the ability of two organic polymers, tannin (natural polyelectrolyte) and AN913 (synthetic anionic polyelectrolyte), and clay to act as coagulant aids was tested, in the removal of phosphate from synthetic wastewater. Contaminants in synthetic waters were coagulated using alum, alum+clay, alum+tannin, alum+AN913, alum+tannin+clay and alum+AN913+clay. Alum together with polymers as coagulant aids yielded a significant improvement in phosphate removal compared with alum alone, for initial phosphate concentrations of 5-15 mg/l PO(4)(3-). The use of clay and polyelectrolytes improved the efficiency of phosphate removal and lowered the required alum dose. Fourier transform infrared (FTIR) spectroscopy was used for the identification and characterization of the aluminum species formed during dephosphorization of the synthetic wastewater with and without tannin, AN913 and clay. Evidence from FTIR spectroscopy showed the formation of aluminum hydroxyphosphate, hydroxy-Al-tannate and aluminum complexes containing phosphorus, tannin and AN913.

Alum Compounds↗

Effects of four tanniferous plant extracts on the in vitro exsheathment of third-stage larvae of parasitic nematodes.

The anthelmintic properties of tanniferous plants and of their secondary metabolites represent one possible alternative to chemotherapy that is currently being explored as a means of achieving sustainable control of gastrointestinal nematodes in ruminants. Previous in vivo and in vitro results suggest that tanniferous plants can have direct anti-parasitic effect against different stages of nematodes. However, the mode of action of the bioactive plant compounds remains obscure. The objectives of the current study were (1) to examine the hypothesis that extracts of tanniferous plants might interfere with the exsheathment of third-stage infective larvae (L3); (2) to assess the role of tannins in the process by examining the consequence of adding an inhibitor of tannins (polyethylene glycol: PEG) to extracts. The effects of 4 tanniferous plant extracts on exsheathment have been examined on L3 of Haemonchus contortus and Trichostrongylus colubriformis. Artificial exsheathment was induced in vitro by adding hypochloride solution to larval suspension. The evolution of exsheathment with time was measured by repeated observations at 10-min interval for 60 min. The selected plants were: genista (Sarothamnus scoparius), heather (Erica erigena), pine tree (Pinus sylvestris), and chestnut tree (Castanea sativa), with tannin contents ranging from 1.5 to 24.7% of DM. Extracts of a non-tanniferous plant (rye grass, tannin content: 0.3% of DM) were included in the assay as negative controls. The extracts were tested at the concentration of 600 microg/ml and the effects were compared to the rate of exsheathment of control larvae in PBS. No statistical differences in the pattern of exsheathment was observed after addition of rye grass or genista extracts for both nematode species and with heather extracts for T. colubriformis. In contrast, pine tree extracts on larvae of both species and heather extracts with H. contortus induced a significant delay in exsheathment. Last, contact with chest nut extracts led to a total inhibition of the process for both nematodes. These results suggest that extracts of tanniferous plants might affect a key process in the very early stages of larval invasion of the host. In most cases, the addition of PEG led to a total or partial restoration towards control values. This suggests that tannins are largely involved in the inhibitory process. However, other secondary metabolites may also interfere with the process that would help to explain some of the differences in response observed between the two nematode species.

Animals↗

Antioxidative activity of green tea treated with radical initiator 2, 2'-azobis(2-amidinopropane) dihydrochloride.

This study investigated the antioxidative activity of green tea extract, and a green tea tannin mixture and its components, under conditions of radical generation using the hydrophilic azo compound, 2,2'-azobis(2-amidinopropane) dihydrochloride (AAPH) to generate peroxyl radicals at a constant and measurable rate in the cultured renal epithelial cell line, LLC-PK(1), which is susceptible to oxidative damage. Treatment with AAPH decreased cell viability and increased the formation of thiobarbituric acid-reactive substances. However, green tea extract, and the tannin mixture and its components, comprising (-)-epigallocatechin 3-O-gallate (EGCg), (-)-gallocatechin 3-O-gallate (GCg), (-)-epicatechin 3-O-gallate (ECg), (-)-epigallocatechin (EGC), (+)-gallocatechin (GC), (-)-epicatechin (EC), and (+)-catechin (C), showed protective activity against AAPH-induced cellular damage. The tannin mixture and its components exhibited higher antioxidative activity than the green tea extract. Furthermore, EGCg and GCg had higher activity than EGC and GC, respectively. In particular, EGCg exerted the most significant cellular protective activity against AAPH. These results indicate that green tea tannin may inhibit cellular loss and lipid peroxidation resulting from the peroxyl radical generated by AAPH, and that the chemical structure of tannin is also involved in the activity, suggesting that the O-dihydroxy structure in the B ring and the galloyl groups are important determinants for radical scavenging and antioxidative potential.

Amidines↗

Interactions between yeast lees and wine polyphenols during simulation of wine aging. II. Analysis of desorbed polyphenol compounds from yeast lees.

In the first part of this work, the analysis of the polyphenolic compounds remaining in the wine after different contact times with yeast lees during simulation of red wine aging was undertaken. To achieve a more precise view of the wine polyphenols adsorbed on lees during red wine aging and to establish a clear balance between adsorbed and remnant polyphenol compounds, the specific analysis of the chemical composition of the adsorbed polyphenolic compounds (condensed tannins and anthocyanins) after their partial desorbtion from yeast lees by denaturation treatments was realized in the second part of the study. The total recovery of polyphenol compounds from yeast lees was not complete, since a rather important part of the initial wine colored polyphenols, especially those with a dominant blue color component, remained strongly adsorbed on yeast lees, as monitored by color tristimulus and reflectance spectra measurements. All anthocyanins were recovered at a rather high percentage (about 62%), and it was demonstrated that they were not adsorbed in relation with their sole polarity. Very few monomeric phenolic compounds were extracted from yeast lees. With the use of drastic denaturing treatments, the total recovery of condensed tannins reached 83%. Such tannins extracted from yeast lees exhibited very high polymeric size and a rather high percentage of galloylated residues by comparison with initial wine tannins, indicating that nonpolar tannins were preferentially desorbed from yeast lees by the extraction treatments.

Adsorption↗

Trade-off between chemical and biotic antiherbivore defense in the South East Asian plant genus Macaranga.

The plant genus Macaranga is known for its manifold mutualistic associations with ants. The plants provide food for the ants and in turn get protection from herbivores. Depending on the strength of the plant-ant interaction, the plant's investment in ants and the biotic defense derived from them is more or less effective. We conducted a comparative study on tannin content in 12 Macaranga species that were selected based on their associations with ants (three nonmyrmecophytes and nine myrmecophytes, three of which start their ontogeny as nonmyrmecophytes). Different developmental stages were investigated in three Macaranga species. Extracts of every individual plant analyzed for tannins were also tested for their effects on larval growth employing larvae of the common cutworm (Spodoptera littoralis). The studied Macaranga species differed significantly in their tannin contents as well as in the effects of their leaf extracts on the growth of S. littoralis larvae. A correlation analysis shows a connection between tannin contents and larval growth. High tannin contents and, thus more effective chemical defense, were observed in nonmyrmecophytic Macaranga species associated only facultatively with ants as compared to obligate myrmecophytes. Our study supports the hypothesis of a trade-off between chemical and biotic defense in the genus Macaranga.

Adaptation, Physiological↗

The enhancement of the nutritive value of mango seed kernels for poultry by thermal treatment and radiation processing.

Raw seed kernels of local mango varieties (Magnifera indica L.) were analyzed for composition, levels of trypsin inhibitors, tannins, cyanogenetic glucosides, in vitro protein digestibility and apparent metabolizable energy (AMEN) as being effected by boiling, autoclaving as well as irradiation at 5, 10, 15, and 20 kGy. The air-dry mango seed kernels (MSK) contained CP 70 g kg-1, EE 128 g kg-1, and tannins 67 g kg-1. Compared with raw kernels the contents of trypsin inhibitory activity (30 TIU g-1) and cyanogenetic glucosides, measured as hydrocyanic acid (71 mg kg-1), were lowered by boiling, autoclaving and radiation treatments. Tannin content (67.2 g kg-1 in raw kernels) was decreased only by boiling or autoclaving, but irradiation did not introduce any effect. The low in vitro protein digestibility and AMEN values of raw MSK were enhanced by processing. The improvements were paralleled to reductions in trypsin inhibitory activity, cyanogenetic glucosides and tannin contents. Greater improvements were noticed with boiling and autoclaving than with irradiation alone. Autoclaving for 30 min plus irradiation treatment up to 20 kGy increased the in vitro protein digestibility and AMEN by 139% and 72%, respectively. These results indicate that tannins, trypsin inhibitors and cyanogenetic glucosides are responsible for the poor nutritive value of MSK. The effects of feeding 200 g kg-1 raw or processed MSK on the performance of broiler chicks were examined. The inclusion of raw kernel affected body weight gain and feed consumption, while weight gain of birds fed the autoclaved (30 min) plus irradiated (20 kGy) kernels was significantly more improved than by the other treatments. However, feed conversion ratio was not significantly different between groups fed the processed MSK. The results showed that the combination of autoclaving for 30 min plus irradiation up to 20 kGy upgraded the nutritive value more than the other tested treatments and that this method is most effective in processing MSK to be used as animal feed.

Anacardiaceae↗

Nitrogen metabolism of sheep and goats consuming Acacia brevispica and Sesbania sesban.

We described the effects of two East African browses, Acacia brevispica and Sesbania sesban, on nitrogen metabolism of sheep and goats. The A. brevispica had a substantial amount of proanthocyanidins (condensed tannins); S. sesban did not. The browses were fed at three levels in combination with vetch (Vicia dasycarpa) and teff straw (Eragrostis abyssinica). Fecal N, N balance, and plasma urea N (PUN) were estimated with intact animals. Ruminal ammonia (RuA) and VFA concentrations were estimated with ruminally fistulated animals. Urinary N loss, PUN, RuA, and VFA concentrations were higher for S. sesban diets than for A. brevispica diets. Fecal N was highest with diets including A. brevispica due to high levels of fecal neutral-detergent insoluble N. Nitrogen retention was highest for diets including S. sesban. Nitrogen retention was adequate for A. brevispica diets because low urinary N compensated for high fecal N. Four hypotheses describe possible effects of tannins on N metabolism: 1) escape of protein from the rumen to the lower tract; 2) increased microbial yield; 3) increase in N-containing endogenous products; and 4) protein made indigestible in tannin-protein complexes. The effect of tannins in A. brevispica on N metabolism can best be described by the formation of indigestible tannin-protein complexes, although increased production of endogenous products is also possible.

Acacia↗

The composition and dissolution of phytobezoars.

The plant fiber content (cellulose, hemicellulose, lignin, and tannins) in phytobezoars was determined. Phytobezoars were found to have a high concentration of polymerized tannins composed mainly of leucoanthocyanins and catechins. Unripe fruit was found to have a high concentration of the tannin monomers. It is concluded that the formation of phytobezoars is due to the polymerization of these tannin monomers. On the ingestion of unripe fruit, the hydrochloric acid of the stomach initiates the polymerization, resulting in a tannin-cellulose-hemicellulose-protein complex. This complex disintegrated in a crude preparation of cellulase. Cellulase is a simple and effective method of treating human gastric phytobezoars.

Bezoars↗

Roles of peritrophic membranes in protecting herbivorous insects from ingested plant allelochemicals.

Four mechanisms by which peritrophic membranes (PMs) potentially protect herbivorous insects from ingested allelochemicals are reviewed: adsorption, ultrafiltration, polyanion exclusion, and the capacity of PMs to act as antioxidants. Most of the research on the protective roles of PMs against ingested allelochemicals has focused on their impermeability to tannins. Adsorption of tannins by the PMs in grasshoppers may limit their permeability, but ultrafiltration of tannin complexes in the caeca is an alternative explanation. Polyanion exclusion does not explain the impermeability of caterpillar PMs to tannins (polyphenolate anions). Ultrafiltration remains the most likely mechanism by which tannins, and other tested allelochemicals, are retained in the endoperitrophic space. Although the pores in PMs are too large to impede the passage of most free allelochemicals, large allelochemical complexes are retained. Such complexes form in the gut fluid of caterpillars between tannic acid, proteins, lipids, and polyvalent metal cations, and also in the gut fluid of grasshoppers (Melanoplus sanguinipes) between some amphiphilic allelochemicals (digitoxin) and surfactant micelles. Further work is needed to examine the role of PMs as antioxidants in vivo, such as their potential to bind catalytically-active metal ions.

Animals↗

Highly concentrated phenolic wastewater treatment by the photo-Fenton reaction, mechanism study by FTIR-ATR.

Phenol degradation by Photo-Fenton reaction has been studied in highly concentrated wastewaters and most intermediate species have been identified by Fourier Transform IR-Spectroscopy with ATR device. During the photodegradation of highly concentrated phenol solutions, the formation of dissolved and precipitate tannin has been observed. The possibility of a Fe3+-Pyrogallol complex formation, previous to the tannin formation, has been proposed too. The complex formation involving Fe3+ ions could be related to the observed Photo-Fenton activity decrease. Tannin formation inhibits the complete mineralization of phenol because *OH radicals attack will produce further condensation steps and the polymer size increase. This fact limits the applicability of the process for highly concentrated phenolic wastes mineralization. However, the tannin precipitation allows its separation from the solution by conventional filtration, and reduction of the corresponding dissolved organic carbon. These observations have been proved from the identification of primary degradation products, catechol and hydroquinone. Catechol is considered to be the first step for the formation of tannins. Degradation process for phenol, catechol and hydroquinone have been monitored by total organic carbon (TOC) measurements along the reaction time span. From these results, a global mechanism for the Photo-Fenton degradation of phenol is proposed.

Environmental Monitoring↗

Biological treatments affect the chemical composition of coffee pulp.

Biological treatments were applied to fresh coffee pulp (CoP) to improve its nutritive value for monogastric animals by reducing its content of cellulose and antinutritional factors (ANFs) such as total phenols, tannins and caffeine. Treatments were: (1) ensiling with 0, 50 and 100 gkg(-1) molasses for 2 and 3 months, (2) aerobic decomposition for 0, 7, 14, 21, 28, 35 and 42 days, (3) aerobic bacterial inoculation (Bacillus sp.) for 0, 7, 14, 21 and 28 days. Ensiled CoP (E-CoP) showed higher fat and ash contents than oven-dried-CoP (OD-CoP; P<0.05). Similarly, true protein values tended to increase. The cellulose and total phenols levels of E-CoP were lower than OD-CoP (P<0.05). The E-CoP tannins levels tended to be lower than OD-CoP whereas caffeine levels remained unaffected. Improvement in the nutritional quality of E-CoP was associated with higher fat and protein contents and reduction of cellulose, total phenols and tannins. The aerobic decomposition treatment improved the nutritional quality of CoP by increasing true protein and fat contents. In addition, total phenols, tannins, caffeine and cellulose contents were reduced by an increase in treatment time (P<0.05). Bacterial treatment increased the protein content of CoP after 21 days (from 137 to 392 gkg(-1)) and decreased it after 28 days. Cellulose, total phenols, tannins and caffeine contents reduced with an increase in time of bacterial degradation. Bacterial treatment improved the CoP quality by increasing protein content and reducing cellulose and ANFs, especially after 21 days of treatment. Both the aerobic decomposition (after 21-28 days) and the aerobic bacterial degradation of CoP (after 21 days) appeared more suitable to improve the nutritional quality of CoP than the ensiling.

Aerobiosis↗

Effects of elevated concentrations of atmospheric CO2 and tropospheric O3 on leaf litter production and chemistry in trembling aspen and paper birch communities.

Human activities are increasing the concentrations of atmospheric carbon dioxide ([CO2]) and tropospheric ozone ([O3]), potentially leading to changes in the quantity and chemical quality of leaf litter inputs to forest soils. Because the quality and quantity of labile and recalcitrant carbon (C) compounds influence forest productivity through changes in soil organic matter content, characterizing changes in leaf litter in response to environmental change is critical to understanding the effects of global change on forests. We assessed the independent and combined effects of elevated [CO2] and elevated [O3] on foliar litter production and chemistry in aspen (Populus tremuloides Michx.) and birch-(Betula papyrifera Marsh.) aspen communities at the Aspen free-air CO2 enrichment (FACE) experiment in Rhinelander, WI. Litter was analyzed for concentrations of C, nitrogen (N), soluble sugars, lipids, lignin, cellulose, hemicellulose and C-based defensive compounds (soluble phenolics and condensed tannins). Concentrations of these chemical compounds in naturally senesced litter were similar in aspen and birch-aspen communities among treatments, except for N, the C:N ratio and lipids. Elevated [CO2] significantly increased C:N (+8.7%), lowered mean litter N concentration (-10.7%) but had no effect on the concentrations of soluble sugars, soluble phenolics and condensed tannins. Elevated [CO2] significantly increased litter biomass production (+33.3%), resulting in significant increases in fluxes of N, soluble sugars, soluble phenolics and condensed tannins to the soil. Elevated [O3] significantly increased litter concentrations of soluble sugars (+78.1%), soluble phenolics (+53.1%) and condensed tannins (+77.2%). There were no significant effects of elevated [CO2] or elevated [O3] on the concentrations of individual C structural carbohydrates (cellulose, hemicellulose and lignin). Elevated [CO2] significantly increased cellulose (+37.4%) input to soil, whereas elevated [O3] significantly reduced hemicellulose and lignin inputs to soil (-22.3 and -31.5%, respectively). The small changes in litter chemistry in response to elevated [CO2] and tropospheric [O3] that we observed, combined with changes in litter biomass production, could significantly alter the inputs of N, soluble sugars, condensed tannins, soluble phenolics, cellulose and lignin to forest soils in the future.

Betula↗

Desirable characteristics of forage legumes for improving protein utilization in ruminants.

Forages help meet the protein requirements of ruminants by providing degraded CP for microbial protein synthesis plus protein that escapes ruminal degradation. Evidence from numerous feeding studies with lactating dairy cows indicates that excessive ruminal protein degradation may be the most limiting nutritional factor in higher-quality temperature legume forages. Hence, there is interest in identifying factors that influence the rate and extent of ruminal degradation of forage proteins. Condensed tannins found in legumes are known to decrease protein degradation, either by altering the forage proteins or by inhibiting microbial proteases. Quadratic regressions of degradation rate and estimated protein escape on tannin concentration reached minimal rate (.048/h) and maximal escape (56%) at 27 g of tannic acid equivalents/kg of DM. Although most tannin-containing forages are not well-adapted to growing conditions in North America, biotechnology has been used to inject genes for tannins into adapted germplasm. The CP in red clover, which has no detectable tannins, was found to be less degradable than that in alfalfa, both in the silo and in the rumen. Small differences in protein degradability also were detected among alfalfa germplasm. Protein in alfalfa harvested as hay, rather than as silage, was used more efficiently for milk protein synthesis when fed to lactating cows; degraded CP from hay was captured more efficiently by ruminal microbes for protein synthesis in vitro. A ruminal escape of approximately 35% for total dietary CP is recommended by the NRC for lactating dairy cows fed mixed diets with 1.6 to 1.7 Mcal of NE1/kg of DM. Ruminal degradation of CP from the forage portion of the diet can exceed 65% when forages are the major source of degradable protein. When ruminants obtain most or all of their nutrients from forage, the ruminal escape for forage protein should approximate 35%.

Animals↗

Antioxidant capacity of flavanols and gallate esters: pulse radiolysis studies.

Reactivities of several proanthocyanidins (monomers of condensed tannins) and gallate esters (representing hydrolyzable tannins) with hydroxyl radicals, azide radicals, and superoxide anions were investigated using pulse radiolysis combined with kinetic spectroscopy. We determined the scavenging rate constants and the decay kinetics of the aroxyl radicals both at the wavelength of the semiquinone absorption (275 nm) and the absorption band of the gallate ester ketyl radical (400-420 nm). For most compounds second-order decay kinetics were observed, which reflect disproportionation of the semiquinones. In the case of the oligomeric hydrolysable tannins, pentagalloyl glucose and tannic acid, the decay kinetics were more complex involving sequential first-order and second-order reactions, which could only be resolved by kinetic modeling. A correlation of the reaction rates with hydroxyl radicals (k*OH) with the number of adjacent aromatic hydroxyl groups (i.e., representing catechol and/or pyrogallol structures) was obtained for both condensed and hydrolyzable tannins. Similar correlation for the reactions with azide radicals and superoxide anions are less obvious, but exist as well. We consider proanthocyanidins superior radical scavenging agents as compared with the monomeric flavonols and flavones and propose that these substances rather than the flavonoids proper represent the antioxidative principle in red wine and green tea.

Anions↗

[Growth inhibition of Entamoeba histolytica and E. invadens produced by pomegranate root (Punica granatum L.)].

The purpose of the present work has been to evaluate the biological activity of alkaloids and tannins extracted from roots of Punica granatum L. on axenic cultures from Entamoeba histolytica and E. invadens, strains. Initially, the total aqueous extract and later some of its components obtained by thin layer chromatography were tested. These compounds were identified by chromatography as alkaloids or tannins. The density of amebic cultures was determined with a hemocytometer after 48 and 96 hours of incubation, which was calculated by the difference between number of trophozoites obtained at the times chosen and the number of amoebae inoculated. Two milliliters of aqueous extract had higher activity on cultures from E. histolytica than E. invadens strains, producing growth inhibitions of about 100 and 40 per cent respectively. Alkaloid concentrations of 1 mg/ml had no amebicide activity, however tannins at concentrations of 10 micrograms/ml for E. histolytica, and 100 micrograms/ml for E. invadens were sufficient to produce an growth inhibition about 100 per cent. Tannic acid was also tested on the cultures of E. histolytica observing an high inhibitory activity on the growth, this effect was produced at 0.01 mg/ml was similar to that observed with the tannins mixture.

Alkaloids↗

A modified method for determining protein binding capacity of plant polyphenolics using radiolabelled protein.

A modified radiochemical protein binding method for determining the protein binding capacity of plant polyphenolics (tannins) is described. Purified tannin or unfractionated plant extracts were immobilised on filter paper discs and incubated with the 125I-labelled bovine serum albumin. Protein bound to the disc was proportional to the amount of tannin applied to the disc, although at high concentrations of polyphenolics the discs became saturated and the relationship was no longer applicable. The method was validated using purified procyanidin from Sorghum grain and has been applied to crude polyphenolic extracts from maple, white oak, black oak, walnut and tulip poplar leaves. Specific chemical assays for the determination of proanthocyanidins (acid butanol method) and hydrolysable tannins (modified potassium iodate method) were employed to validate the new protein binding method with the complex plant extracts.

Chemical Precipitation↗

Study on the composition and structure of commercial chestnut tanning agent.

Current research has focused on the composition of commercially used chestnut tannin extracts so as to provide a quantitative basis for studies of reactions, structure-property relationships, and applications of chestnut tannin extract. Two chestnut tannins, vescalagin and castalagin, have been isolated using chromatography on Sephadex LH-20 and cellulose. The structures of these compounds have been established by means of nuclear magnetic resonance and fast atom bombardment mass spectroscopy. Some other components have been found and analyzed by chromatography and spectroscopy, but their structures have not as yet been completely defined. These structural features, together with quantitative results for each component, provide a better understanding of the mode of action of complex commercial chestnut tannin extracts.

Chromatography↗

[Polyphenols in brewing (author's transl)].

Analytical methods for the determination of polyphenols of malt, barley, hop, wort, and beer are described. Malt or barley tannins has hitherto not received as much study as hop tannin. Polyphenols or tannins are classified. Studies on non-biological hazes are discussed in relation to the haze problem in brewing. The leucoanthocyanins of malt differ from those of hops in ability to form hazes. Subfractionation of polyphenol concentrates on sephadex columns allows isolation of individual tannins.

Anthocyanins↗