Phenolic compounds oxidation

Fig 1 shows the rate of p-coumaric acid solution (500ppm) and TOC removals during the phenolic compound oxidation over (Al-Fe)PILC catalyst (0.5g/l), as well as the uncatalysed reaction in slurry at 70°C. 

Tratnyek and Hoigne (1994) investigated 25 substituted phenoxide anions for QSARs that can be used to predict rate constants for the reaction of additional phenolic compounds oxidized by chlorine dioxide (OCIO). Correlating oxidation rates of phenols in aqueous solution is complicated by the dissociation of the phenolic hydroxyl group. The undissociated phenol and the phenoxide anion react as independent species and exhibit very different properties. The correlation analysis should be performed on the two sets of rate constants separately. 

Polcaro, A. M., Vacca, A., Palmas, S. and Mascia, M. (2003) Electrochemical treatment of wastewater containing phenolic compounds Oxidation at boron-doped diamond electrodes. J. Appl. 

Insufficiently clarified juices, especially those containing insolnble products of phenolic compound oxidation, can produce wines with decreased varietal aromas. On the contrary, overclarification (less than 50 NTU) also decreases the fruity aroma of dry white wines. This phenomenon has been observed with Muscat, Chardonnay, Sauvignon, Semilion, Mansengs, etc. It is exacerbated by difficult fermentation conditions, excessively slow fermentations with increased volatile acidity production. The varietal aroma of wines made from excessively clarified juices is sometimes masked by an artificial, banana, amylic or soapy aroma, linked to the presence of a significant quantity of esters. 

Ch. II., The Constituents of Essential Oils and Synthetic Perfume Bodies. — Hydrocarbons—Sesquiterpenes —Alcohols—Terpene Alcohols—Esters— Aldehydes—Ketones— Phenols and Phenolic Compounds—Oxides and Lactones— Nitrogen Compounds — Sulphur Compound—Free Acids. 

Phenolic compounds are commonplace natural products Figure 24 2 presents a sampling of some naturally occurring phenols Phenolic natural products can arise by a number of different biosynthetic pathways In animals aromatic rings are hydroxylated by way of arene oxide intermediates formed by the enzyme catalyzed reaction between an aromatic ring and molecular oxygen... 

At present, chlorine dioxide is primarily used as a bleaching chemical in the pulp and paper industry. It is also used in large amounts by the textile industry, as well as for the aching of flour, fats, oils, and waxes. In treating drinking water, chlorine dioxide is used in this country for taste and odor control, decolorization, disinfection, provision of residual disinfectant in water distribution systems, and oxidation of iron, manganese, and organics. The principal use of chlorine dioxide in the United States is for the removal of taste and odor caused by phenolic compounds in raw water supplies. 

Transition-metal complexes such as [Rh(CO)2Cl]2,204 Rh(butadiene)2Cl,205 or Cr(CO)3(NH3)312 have also been used for the deoxygenation of oxepins to give 312,204 205 and benzoxepins to give 4.12,204 Occasionally, substantial amounts of phenolic compounds have been isolated due to the competing NIH shift of the arene oxide.204 1-Benzoxepin and 3-benzoxepin resist oxygen extrusion under these conditions probably due to their inability to form arene oxi-des.133,204... 

PO performs vitally important functions in the plant cell and is mainly associated with the oxidation of phenolic compounds and with the formation and strengthening of the cell wall (Passardi et al., 2004). PO is involved in the oxidative transformation of molecules in growth-regulating or signalling activities and - as a result - can also perform regulatory functions in the cell. Plant POs are represented by genetically different proteins with the same enzymatic activity (Welinder et al., 2002). 

Therefore depending upon the conditions used to simulate either in vitro or in vivo oxidation, catechins or other phenolic compounds display differences in their antioxidant properties. Catechins also limited the consumption of a-tocopherol, allowing it to act as a scavenger within cell membranes whilst the catechins scavenged aqueous peroxyl radicals near the membrane surface (Pietta and Simonetti, 1998). 

The conclusions about the role phenol plays as an antioxidant in real food systems are often reached by comparing the oxidative behaviour of food samples with different contents of phenolic compounds. The variations in phenolics are usually obtained by using products made from different raw materials (e.g. malts containing different levels of polyphenols for production of beer (Andersen et al, 2000)). However, using different raw materials not only affects the levels of phenols, but also affects the levels of transition metals and enzymes which can have profound effects on the oxidative behaviour of the finished product. It is, therefore, often advantageous to study the oxidative behaviour of samples derived from a single batch of production where the level of phenols has either been increased by addition or decreased... 

Phenol, the simplest and industrially more important phenolic compound, is a multifunctional monomer when considered as a substrate for oxidative polymerizations, and hence conventional polymerization catalysts afford insoluble macromolecular products with non-controlled structure. Phenol was subjected to oxidative polymerization using HRP or soybean peroxidase (SBP) as catalyst in an aqueous-dioxane mixture, yielding a polymer consisting of phenylene and oxyphenylene units (Scheme 19). The polymer showed low solubility it was partly soluble in DMF and dimethyl sulfoxide (DMSO) and insoluble in other common organic solvents. 

Most phenolic compounds are readily oxidized at carbon electrodes. The oxidation potentials vary widely depending upon the number of ring hydroxyl groups and their positions on the ring. Many compounds of biomedical and industrial interest are phenolic and LCEC based trace determinations are quite popular. 

Polyphenolic compounds are present in mate. Flavanols, at least in significant quantities, are absent.9 The major phenolic compounds are chlorogenic acid and its oxidation products referred to as resinotanol , which are formed during the manufacturing process.10 The chlorogenic acid may be a mixture of three different isomers.11... 

Alnaizy R, Akgerman A (2000) Advanced oxidation of phenolic compounds. Adv Environ Res 4(3) 233-244... 

Reported redox potentials of laccases are lower than those of non-phenolic compounds, and therefore these enzymes cannot oxidize such substances [7]. However, it has been shown that in the presence of small molecules capable to act as electron transfer mediators, laccases are also able to oxidize non-phenolic structures [68, 69]. As part of their metabolism, WRF can produce several metabolites that play this role of laccase mediators. They include compounds such as /V-hvdi oxvacetan i I ide (NHA), /V-(4-cyanophenyl)acetohydroxamic acid (NCPA), 3-hydroxyanthranilate, syringaldehyde, 2,2 -azino-bis(3-ethylben-zothiazoline-6-sulfonic acid) (ABTS), 2,6-dimethoxyphenol (DMP), violuric acid, 1-hydroxybenzotriazole (HBT), 2,2,6,6-tetramethylpipperidin-iV-oxide radical and acetovanillone, and by expanding the range of compounds that can be oxidized, their presence enhances the degradation of pollutants [3]. 

MnP is the most commonly widespread of the class II peroxidases [72, 73], It catalyzes a PLC -dependent oxidation of Mn2+ to Mn3+. The catalytic cycle is initiated by binding of H2O2 or an organic peroxide to the native ferric enzyme and formation of an iron-peroxide complex the Mn3+ ions finally produced after subsequent electron transfers are stabilized via chelation with organic acids like oxalate, malonate, malate, tartrate or lactate [74], The chelates of Mn3+ with carboxylic acids cause one-electron oxidation of various substrates thus, chelates and carboxylic acids can react with each other to form alkyl radicals, which after several reactions result in the production of other radicals. These final radicals are the source of autocataly tic ally produced peroxides and are used by MnP in the absence of H2O2. The versatile oxidative capacity of MnP is apparently due to the chelated Mn3+ ions, which act as diffusible redox-mediator and attacking, non-specifically, phenolic compounds such as biopolymers, milled wood, humic substances and several xenobiotics [72, 75, 76]. 

---