Tannin reactivity

Niobic Acid. Niobic acid, Nb20 XH2O, includes all hydrated forms of niobium pentoxide, where the degree of hydration depends on the method of preparation, age, etc. It is a white insoluble precipitate formed by acid hydrolysis of niobates that are prepared by alkaH pyrosulfate, carbonate, or hydroxide fusion base hydrolysis of niobium fluoride solutions or aqueous hydrolysis of chlorides or bromides. When it is formed in the presence of tannin, a volurninous red complex forms. Freshly precipitated niobic acid usually is coUoidal and is peptized by water washing, thus it is difficult to free from traces of electrolyte. Its properties vary with age and reactivity is noticeably diminished on standing for even a few days. It is soluble in concentrated hydrochloric and sulfuric acids but is reprecipitated on dilution and boiling and can be complexed when it is freshly made with oxaHc or tartaric acid. It is soluble in hydrofluoric acid of any concentration. 

As tannins contain many phenolic -type subunits (Fig. 3), one may be tempted to think that they will exhibit a similar reactive potential to that of phenol, and that therefore procedures used in standard PF production can be transferred to those containing tannin. This, however, is not the case. The real situation is that tannin is far more reactive than unsubstituted phenol due to the resorcinol and catchecol rings present in the tannin. This increase in hydroxyl substitution on the two aromatic rings affords an increase in reactivity to formaldehyde by 10 to 50... 

Chemical analyses and fractionations. Freeze-dehydrated cotton tissue was analyzed for condensed tannin (heated n-BuOH-HCl), gossypol (phlorogluclnol-HCl), and anthocyanlns-anthocyanldlns (ale. HCl at 540 nm). Other analyses performed but not reported here were for catechin, total phenols, (tannin), and aniline reactive terpenes (gossypol). 

Tangerine oil. see Citrus Orange Tannins, structure of. see also Polyphenolics Taste, see Flavor analysis TBA. see 2-Thiobarbituric acid TBARS. see 2-Thiobarbituric acid reactive substances... 

In addition to the variations in the LHC composition that occur from species to species, each species has its extractives, which include resins and waxes. These constituents are capable of interfering with cellulose hydrolysis because of their hydrophobic nature. Tannins and other highly reactive materials are constituents of some woody species. When LHC is obtained from nonwoody (herbaceous) species, the range of interfering constituents increases greatly. Sugars, starches, dextran, carotenoids, and many isoprenoids are to be found. Operators of a cellulose hydrolysis process that uses municipal solid waste as its biomass resource may experience seasonal variations in composition and chance inclusion of crankcase oil and other products that inhibit enzymes or kill yeast. 

Each of the barks used in the present investigation was analyzed for extractive content and the results are summarized in Table I. Table U shows the tannin and reactive polyphenols formaldehyde-hydrochloric acid contents (5). 

As indicated by the structures of these molecules, the A ring contains resorcinol phenolic hydroxyls, while the B ring contains the catechol or adjacent phenolic hydroxy groups, both of which would be expected to be highly reactive in resin formation. This high reactivity would also hold for the condensed tannins present in the bark extract, since they are polymeric flavonoids (14). 

Attempts to make adhesive formulations by direct reaction of formaldehyde or its equivalent resulted in products that were excessively viscous, and the working time was too short for commercial application (57). It was concluded that formaldehyde, although readily reactive with the tannin molecule, provided much too short linkages to connect the bulky tannin molecules. This problem was circumvented by the preparation of a polymethylolphenol reagent that, when put in solution with the bark extract, formed a combination that was stable for several weeks at room temperature. When heated, the polymethylolphenol and bark extract reacted rapidly to form an infusible resin. Commercial trials were made to produce exterior-grade Douglas-fir plywood. Widespread use of the extracts for this purpose, however, was inhibited by a drop in the price of phenol below what the bark extracts could be manufactured for. (The best extract for adhesive purposes was an ammonia extract of hemlock bark converted to a sodium derivative prior to spray drying, a more costly extraction procedure than simple sodium hydroxide extraction of bark.)... 

The reactivity of resorcinol with formaldehyde is essential for developing the cohesive strength of the interlayer and its bonding characteristics. Condensed tannins are known to be very reactive with formaldehyde (7-0), so these renewable phenolic polymers are good candidates as resorcinol replacements. Indeed, condensed tannins from wattle and pine bark extracts have been successfully used in cold-setting, wood-laminating adhesives, and the former are used extensively in the commercial production of laminated timbers in South Africa (Pizzi, A., National Timber Research Institute, Pretoria, South Africa, personal communication, 1982) (10-13). 

Progress in the use of condensed tannins in adhesive formulations might be expected to be more rapid than is the case for lignins because of the impetus provided by the commercialization of wattle tannin-based adhesives and because of the extraordinarily high reactivity of tannins in reactions with formaldehyde. This reactivity offers an opportunity to substitute tannin for resorcinol (currently priced at about 1.80/lb) instead of phenol (about 0.40/lb). Now that wattle tannins have been successfully introduced, their application can be expected to continue to expand. The situation remains difficult, on the other hand, for use of conifer bark tannins in adhesives. Herb Hergert is certainly... 

TMS production involves one specific functional group (-OH, -COOH, =NH, -NH2, or -SH), which loses an activated hydrogen and is replaced by a trimethylsilyl group (Proestos et ah, 2006). To achieve silylation, some authors have used BSTFA (N,0-hA(trimethyl-silyl)trifluoroacetamide) and TMCS (trimethylchlorosilane) successfully in several matrices (e.g. aromatic plants, cranberry fixiit) (Zuo et ah, 2002 Proestos et ah, 2006). Using silylated derivatives is advantageous for several reasons phenols and carboxylic acids are prone to silylation, these compounds can be derivatized in the same part of the process, and the minor products do not impede analysis and are well documented (Little, 1999 Stalikas, 2008). A two-step methylation procedure was used to analyze catechins and tannins in plant extracts. The first step used trimethylsilyl diazomethane (TMS-diazomethane) to pre-methylate the sample, and the second step used thermally assisted hydrolysis and methylation (THM). The pre-methylation step with TMS-diazomethane stabilized the dimer molecule m/z 540) by minimizing isomerization and reducing reactivity. (Shadkami et ah, 2009). 

The small experimental reactor was able to clarify apple juice. However its life was severely limited when used for this purpose. Decline in activity probably resulted from precipitated solids clogging the reactive sites in the module or through nonspecific inactivation of the bound lyase by tannins in the circulating juice (199). 

Cisplatin has also been shown to induce ROS in cultured proximal tubular cells and antioxidants such as green tea tannin can dose dependency protect against cisplatin-induced nephrotoxicity in vitro and in vivo [126]. Bragado and colleagues have recently demonstrated that cisplatin-induced apoptosis requires the onset of p53-mediated p38alpha MARK via the generation of reactive oxygen species [127]. 

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