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Phenoxy Radicals (phenoxy + radical)
Selected AbstractsRe-evaluation of intramolecular long-range electron transfer between tyrosine and tryptophan in lysozymesFEBS JOURNAL, Issue 17 2003Evidence for the participation of other residues One-electron oxidation of six different c-type lysozymes from hen egg white, turkey egg white, human milk, horse milk, camel stomach and tortoise was studied by gamma- and pulse-radiolysis. In the first step, one tryptophan side chain is oxidized to indolyl free radical, which is produced quantitatively. As shown already, the indolyl radical subsequently oxidizes a tyrosine side chain to the phenoxy radical in an intramolecular reaction. However this reaction is not total and its stoichiometry depends on the protein. Rate constants also vary between proteins, from 120·s,1 to 1000·s,1 at pH 7.0 and room temperature [extremes are hen and turkey egg white (120·s,1) and human milk (1000·s,1)]. In hen and turkey egg white lysozymes we show that another reactive site is the Asn103,Gly104 peptidic bond, which gets broken radiolytically. Tryptic digestion followed by HPLC separation and identification of the peptides was performed for nonirradiated and irradiated hen lysozyme. Fluorescence spectra of the peptides indicate that Trp108 and/or 111 remain oxidized and that Tyr20 and 53 give bityrosine. Tyr23 appears not to be involved in the process. Thus new features of long-range intramolecular electron transfer in proteins appear: it is only partial and other groups are involved which are silent in pulse radiolysis. [source] First evidence of catalytic mediation by phenolic compounds in the laccase-induced oxidation of lignin modelsFEBS JOURNAL, Issue 17 2003Francesca D'Acunzo The sulfonephthalein indicator, phenol red, exhibits an unusually slow rate of oxidation by laccase from Poliporus pinsitus, in spite of the fact that it is a phenol and therefore a natural substrate for this phenoloxidase enzyme. Nevertheless, after prolonged exposure to laccase (24 h) phenol red is oxidized by more than 90%. We found that phenol red, which can be oxidatively converted into a resonance-stabilized phenoxy radical, performs as a mediator in the laccase-catalyzed oxidation of a nonphenolic substrate (4-methoxybenzyl alcohol) and also of a hindered phenol (2,4,6-tri- tert -butylphenol). In particular, phenol red was found to be at least 10 times more efficient than 3-hydroxyanthranilate (a reported natural phenolic mediator of laccase) in the oxidation of 4-methoxybenzyl alcohol. Other phenols, which do not bear structural analogies to phenol red, underwent rapid degradation and did not perform as laccase mediators. On the other hand, several variously substituted sulfonephthaleins, of different pK2 values, mediated the laccase catalysis, the most efficient being dichlorophenol red, which has the lowest pK2 of the series. The mediating efficiency of phenol red and dichlorophenol red was found to be pH dependent, as was their oxidation Ep value (determined by cyclic voltammetry). We argue that the relative abundance of the phenoxy anion, which is easier to oxidize than the protonated phenol, may be one of the factors determining the efficiency of a phenolic mediator, together with its ability to form relatively stable oxidized intermediates that react with the desired substrate before being depleted in undesired routes. [source] Torsional Barriers in Aromatic Molecular Clusters as Probe of the Electronic Properties of the ChromophoreCHEMPHYSCHEM, Issue 11 2004Christoph Jacoby Dr. Abstract We present a computer program that is capable of fitting n -fold torsional barriers Vn(n=2,6) and torsional constants F simultaneously to high- and low-resolution spectroscopic data of different isotopomeric internal rotors. The program has been utilized to fit independently barriers and torsional constants for both electronic states of several aromatic clusters. The constant F of the ammonia moiety in the phenol,ammonia cluster is shown to decrease upon electronic excitation, thus imaging the formation of a hydrogen-bonded complex between the phenoxy radical and the NH4 radical in the excited state. In contrast, for the naphthol,ammonia 1:1 clusters no change of F of ammonia could be found. For phenol,methanol cluster we found a decrease of F upon excitation which points to a stronger hydrogen bond between phenol and methanol in the excited state. A strong reduction of the torsional barrier upon excitation points to the formation of a methoxonium radical in a similar photoreaction as in phenol,ammonia cluster. For the phenol,water system we postulate the same mechanism, a photoreaction, which leads to a translocated hydrogen atom in the S1 state what can be deduced from the change of the torsional constant upon electronic excitation. [source] Role of phenoxy radicals in PCDD/F formationINTERNATIONAL JOURNAL OF CHEMICAL KINETICS, Issue 9 2002Sukh Sidhu In this work, the role of phenoxy radicals in polychlorinated dibenzo- p -dioxins and polychlorinated dibenzofurans (PCDD/F) formation was investigated by studying the slow oxidation of 2-chlorophenol (2-CP) and 2-chloroanisole (2-CA) at a gas-phase concentration of 4 ppm (,2.1 × 104 ,g/m3) over a temperature range of 400,800°C. Residence times were maintained at 2.0 ± 0.10 s. PCDD/F reaction products were dibenzofuran, dibenzo- p -dioxin, 4-chlorodibenzofuran, 1-chlorodibenzo- p -dioxin, 4,6-dichlorodibenzofuran, and 1,6-dichlorodibenzo- p -dioxin (1,6-DCDD). Major products observed in these experiments were 2,6-dichlorophenol, 3-phenyl-2-propenal, 1-indanone, 1,3-isobenzofurandione, and 3-phenyl-2-propenoyl chloride. The 2-CP and 2-CA experiments, along with the variable concentration 2-CA experiments, showed that the concentration of radicals present in the oxidation system has a significant effect on the PCDD/F product distribution and ultimately the PCDD/PCDF ratio. Also, the observation of dichlorinated phenoxy phenol and dichlorinated dihydroxybiphenyl, the proposed intermediate species in the radical,radical mechanism, suggests that radical,radical mechanism dominates gas-phase PCDD/F formation. This information will be helpful in constructing a detailed kinetic mechanism of PCDD/F formation/destruction in combustor postcombustion zone. © 2002 Wiley Periodicals, Inc. Int J Chem Kinet 34: 531,541, 2002 [source] Studies on dimerisation of tocopherols under the influence of methyl linoleate peroxidesMOLECULAR NUTRITION & FOOD RESEARCH (FORMERLY NAHRUNG/FOOD), Issue 2 2003Marek Gogolewski Abstract The stability of plant oils is related to the level of polyunsaturated fatty acids and the presence of native antioxidants , especially tocopherols. During storage, lipids or the fat products undergo oxidation and tocopherol dimers and trimers are formed. These compounds possess reducing and antioxidant properties and participate in oxidation clearly inhibiting this process. In the present study, the correlation between levels of peroxides formed during autoxidation of methyl linoleate and simultaneous decomposition of tocopherols was examined. The peroxide value was investigated. Quantities of decomposed tocopherols and formation of their dimers were determined by high-performance liquid chromatography (HPLC). Mass spectrum analysis confirmed that the analysed compounds were dimers. Dimerisation of ,-T begins at the smaller quantity of the methyl linoleate peroxides than dimerisation of ,-T. At the beginning of methyl linoleate autoxidation dimerization of ,-T in relation to its loss was smaller. The quantity of ,-T dimers with ether bonds in total dimers pointed to faster binding of phenoxy radicals than transformation into the phenyl ones. ,-T dimers with phenyl bonds constitute about 65% of the total. The quantity of peroxides in methyl linoleate, necessary for quantitative and qualitative changes of homologous tocopherols, decreased from ,-T to ,-T. [source] Preserving boiled eggs with a sterilization system employing microbial laccase and wood vinegarANIMAL SCIENCE JOURNAL, Issue 6 2007Hiromichi SAKAGUCHI ABSTRACT A combination of a microbial laccase and wood vinegar was used to treat the shell surface of boiled eggs. The laccase enhanced the sterilization effect of phenolic compounds contained in the wood vinegar and resulted in prevention of microbial infection of the boiled eggs after storage for 21 days at 40°C and 75% relative humidity. Significant phenoxy radicals, formed by the catalytic reaction of the laccase, could be detected in the shell of the boiled eggs. [source] | |||||||||||||