Pyrene transformation

Sack, U., Heinze, T.M., Deck,)., Cerniglia, C.E., Cazan, M.C., and Fritsche, W. Novel metabolites inphenanthrene and pyrene transformation by Aspergillusniger, Appl. Environ. Microbiol., 63(7) 2906-2909, 1997. 

Sack, U., T.M. Heinze, J. Deck, C.E. Cerniglia, M.C. Cazau, and W. Fritsche. 1997. Novel metabolites in phenanthrene and pyrene transformations by Aspergillus niger. Appl. Environ. Microbiol. 63 2906-2909. 

Barbisan LF, Mello ML, Russo J, Vidal BC Apoptosis and catastrophic cell death in benzo[a]pyrene-transformed human breast epithelial eells. Mutat Res 1999, 431 133-139. 

Photochemical transformation of pyrene in aqueous media produced the 1,6- and 1,8-quinones as stable end products after initial formation of 1-hydroxypyrene (Sigman et al. 1998). 

Two types of reactions are important in the photochemical transformation of PAHs, those with molecnlar oxygen and those involving cyclization. lllnstrative examples are provided by the photooxidation of 7,12-dimethylbenz[a]anthracene (Lee and Harvey 1986) (Fignre 1.14a) and benzo[a]pyrene (Lee-Ruff et al. 1986) (Figure 1.14b), and the cyclization of CM-stilbene (Figure 1.14c). 

Hu J, X Jin, S Kunikane, Y Terao, T Aizawa (2006) Transformation of pyrene in aqueous chlorination in the presence and absence of bromide kinetics, products, and their aryl hydrocarbon receptor-mediated activities. Environ Sci Technol 40 487-493. 

The transformation of benzene, toluene, naphthalene, biphenyl, and benzo[a]pyrene to the corresponding phenols (Trower et al. 1989) by Streptomyces griseus, and of phenanthrene by Streptomyces flavovirens to ( )tran5 -[95, 105 ]-9,10-dihydrodihydroxyphenanthrene with minor amounts of 9-hydroxyphenanthrene (Sutherland et al. 1990). 

The aryl hydroxylase of Saccharomyces cerevisiae that transforms benzo[a]pyrene to the 3- and 9-hydroxy compounds, and the 7,8-dihydrodiol (King et al. 1984). 

Li X-F, X-C Le, CD Simpson, WR Cullen, KJ Rermer (1996) Bacterial transformation of pyrene in a marine environment. Environ Sci Technol 30 1115-1119. 

FIGURE 8.22 Products produced by fungal transformation of benzo[a]pyrene. (From Neilson, A.H. and Allard, A.-S. The Handbook of Environmental Chemistry, Springer, 1998. With permission.)... 

The metabolism of pyrene and benzo[a]pyrene by C. elegans is increasingly complex. Pyrene is transformed by hydroxylation at the 1-, T and 6-, and 1- and 8- positions, and the bisphenols were glucosylated at the 6- and 8-positions the 1,6- and 1,8-pyrenequinones were also formed (Cerniglia et al. 1986). The same organism transformed benzo[fl]pyrene to the trany-7,8- and trans-... 

A cytochrome P450 has been purified from Saccharomyces cerevisiae that has benzo[a]pyrene hydroxylase activity (King et al. 1984), and metabolizes benzo[fl]pyrene to 3- and 9-hydroxybenzo[fl]pyrene and benzo[fl]pyrene-7,8-dihydrodiol (Wiseman and Woods 1979). The transformation of PAHs by Candida Upolytica produced predominantly monohydroxyl-ated products naphth-l-ol from naphthalene, 4-hydroxybiphenyl from biphenyl and 3- and 9-hydroxybenzo[fl]pyrene from benzo[fl]pyrene (Cerniglia and Crow 1981). The transformation of phenanthrene was demonstrated in a number of yeasts isolated from littoral sediments and of these, Trichosporumpenicillatum was the most active. In contrast, biotransformation of benz[fl]anthracene by Candida krusei and Rhodotorula minuta was much slower (MacGillivray and Shiaris 1993). 

The stereoselected Cda conformation of the BPDE i(-) and Il(-) adducts to N6(a) were chosen for study in a reoriented complex with an externally bound pyrene moiety. In Figure 13, the adduct is shown in its optimum orientation in B-DNA with adenine after an anti - syn transformation for which the non-bonded contacts are poor, and with the normal anti base orientation with favorable contacts. The fit improves for the anti base as ax 30°. The orientation of the pyrene moiety is a(BPDE) =31° and the local helical axis of the DNA is oriented at y(DNA) = 15° Calculations were not performed with externally bound BPDE-DNA adducts to 06(G) and NU(C). Calculations of externally bound BPDE I(-)-N6(a) adducts with kinked DNA with ax + 30° yields an orientation a(BPDE) = 31° in good agreement with experimental results for the externally bound component (51). 

Moreover, oil transformation products such as 3,4-benz(a)pyrene, can migrate even more rapid than the oil itself (Table 2). 

Water-soluble nickel salts enter the cells with relative ease but are less effective than crystalline particulates in the cell transformation assay, when using hamster cells [429, 430]. However, an enhancement of viral transformation of cells has been found [431, 432], In addition, a synergistic effect of cigarette smoke extracts, benzo[a]pyrene and nickel sulphate on the morphological transformation of hamster embryo cells has also been obtained [433], It was suggested that nickel salts are more potent as promoters than they are as initiators [434],... 

Li et al. [323] studied the bacterial transformation of pyrene in an estuarine environment (Kitimat Arm, British Columbia, Canada), where they separated a metabolite (i.e., ris-4,5-dihydroxy-4,5-dihydropyrene) from the sediment and pore waters. The presence of this key metabolite from the dioxygenase-mediated transformation of pyrene [100, 186, 342], along with previous pyrene degradation studies using cultures isolated from the same sediment samples, suggested a possible in situ bacterial transformation of pyrene in the Kitimat Arm environment. 

If PAH-degrading microorganisms use broad-specificity enzymes or common pathways to transform multiple PAHs, then inducers for the metabolism of one PAH substrate might co-induce the transformation of a range of PAHs. Preliminary evidence indicated that the transformation of naphthalene, phenanthrene, fluoranthene, and pyrene by Pseudomonas saccharophila P15 was stimulated by salicylate [132], a known inducer of naphthalene metabolism in pseudomonads [43]. However, Chen and Aitken [181] reported in more detail the inducing effects of salicylate on the transformation of various HMW PAHs by Pseudomonas saccharophila P15 isolated from contaminated soil, including... 

Surface Water. In a 5-m deep surface water body, the calculated half-lives for direct photochemical transformation at 40 °N latitude, in the midsummer during midday were 3.2 and 13 d with and without sediment-water partitioning, respectively (Zepp and Schlotzhauer, 1979). The volatilization half-life of benzo [a] pyrene from surface water (1 m deep, water velocity 0.5 m/sec, wind velocity 1 m/sec) using experimentally determined Henry s law constants is estimated to be 1,500 h (Southworth, 1979). 

Plant. Hiickelhoven et al. (1997) studied the metabolism of pyrene by suspended plant cell cultures of soybean, wheat, jimsonweed, and purple foxglove. Soluble metabolites were only detected in foxglove and wheat. Approximately 90% of pyrene was transformed in wheat. In foxglove, 1-hydroxypyrene methyl ether was identified as the main metabolite but in wheat, the metabolites were identified as conjugates of 1-hydroxypyrene. 

Chemical/Physical. At room temperature, concentrated sulfuric acid will react with pyrene to form a mixture of disulfonic acids. In addition, an atmosphere containing 10% sulfur dioxide transformed pyrene into many sulfur compounds, including pyrene-1-sulfonic acid and pyrenedisulfonic acid (Nielsen et al., 1983). 

Pressure provokes transition of the linear (extended) conformation into the bent (V-like) one. (The V-like form is more compact and occupies a smaller volume.) It is obvious that the V-like form is favorable in respect of intramolecular electron transfer from the donor (the aniline part) to the acceptor (the pyrene part). In the utmost level of the phenomenon, the donor part transforms into the cation-radical moiety, whereas the acceptor part passes into the anion-radical moiety. Such transformation is impossible in the case of the extended conformation because of the large distance between the donor and acceptor moieties. The spectral changes observed reflect this conformational transition at elevated pressures. 

Higher-molecular-weight PAHs, such as pyrene, benzo(a)pyrene, and benzo(e)-pyrene, exhibit a high resistance to biodegradation. PAHs with three or more condensed rings tend not to act as a sole substrate for microbial growth and require cometabolic transformations. Neilson and Allard (1998) report a cometabolic reaction of pyrene, 1,2-benzanthracene, 3,4-benzopyrene, and phenanthrene in the presence of either naphthalene or phenanthrene. However, the cometabolic reactions are very slow in natural ecosystems. 

Photochemical transformation of benzole (e)pyrene (BeP), a polycyclic aromatic hydrocarbon, adsorbed on silica gel and alumina surfaces, is reported by Fioressi and Arce (2005). This study was designed to define the atmospheric degradation of the PAH adsorbed on particulates that originated from wind erosion of the land surface. It can be assumed that similar behavior occurs at the land surface-atmosphere interface. 

Fig. 16.18 Effect of surface nature and loading on the photodegradation rate of adsorbed BeP. The photolysis experiments were carried out in a rotary cell, and the BeP remaining in the sample was determined by HPLC. Uncertainties in measurements are in the range of 4-10% of the absolute values. Reprinted with permission from Fioressi S, Arce R (2005) Photochemical transformation of benzo(e)pyrene in solution and adsorbed on silica gel and alumina surfaces. Environ Sci Technol 39 3646-3655. Copyright 2005 American Chemical Society...

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