Phenanthrene transformation

MacGillivray, A. R. Shiaris, M. P. (1994). Relative role of eukaryotic and prokaryotic micro-orgatrisms in phenanthrene transformation in coastal sediments. Applied and Environmental Microbiology, 60, 1154—9. 

By contrast to the thermal process, the photochemistry of 2-vinylbiphenyl (249) and 4-vinylphenan-threne (250) has been widely used in connection with syntheses of polycyclic aromatic compounds, complementing the most commonly used stilbene to phenanthrene transformation/ For example, the product obtained from the ctnirotatory photocyclization of 2-(a-styryl)biphenyl (252) can be trapped by an oxidant to give the phenanthrene (254) or suffers a 1,5-H shift to give the dihydro d)enandiieiie... 

The chloromethylation can be generally employed in aromatic chemistry benzene, naphthaline, anthracene, phenanthrene, biphenyls and many derivatives thereof are appropriate substrates. The benzylic chlorides thus obtained can be further transformed, for example to aromatic aldehydes. Ketones like benzophe-none are not reactive enough. In contrast phenols are so reactive that polymeric products are obtained. ... 

Poly(arylene ether ketone)s can also be modified by introducing the functional groups using similar approaches to polysulfones. For example, poly(arylene ether ketone)s were sulfonated.189 In addition, o-dibenzoylbenzene moieties in the poly(arylene ether)s can be transformed to heterocycles by cyclization with small molecules. These polymers can react with hydrazine monohydrate in the presence of a mild acid in chlorobenzene or with benzylamine in a basic medium.190 Another example of the use of the o-benzyl cyclization strategy is the intramolecular ring closure of poly(arylene ketone)s containing 2,2/-dibenzoylbiphenyl units to form poly(arylene ether phenanthrenes).191... 

The photochemical transformation of phenanthrene sorbed on silica gel (Barbas et al. 1996) resulted in a variety of products including c -9,10-dihydrodihydroxyphenanthrene, phenanthrene-9,10-quinone, and a number of ring fission products including biphenyl-2,2 -dicarboxaldehyde, naphthalene-l,2-dicarboxylic acid, and benzo[c]coumarin. 

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). 

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). 

FIGURE 8.24 Alternative pathways for transformation of phenanthrene by Phanerochaete chrysosporium. (From Neilson, A.H. and Allard, A.-S. The Handbook of Environmental Chemistry, Springer, 1998. With permission.)... 

Samanta SK, AK Chakraborti, RK Jain (1999) Degradation of phenanthrene by different bacteria evidence for novel transformation sequences involving the formation of 1-naphthol. Appl Microbiol Biotechnol 53 98-107. 

Carbazole, A-methylcarbazole, IV-ethylcarbazole, dibenzofuran, dibenzothiophene, fluorene, dibenzo-p-dioxin, phenoxathiin, phenoxazine, phenothiazine, xanthene, biphenyl, naphthalene, phenanthrene, anthracene, and fluoranthene could be transformed by E. coli, [314] which was transformed using a plasmid bearing the carAa, Ac, and Ad genes, and expressing only the carA-encoded proteins. Further work is needed to develop a final biocatalyst and to prove the advantages that this degradative pathway would incorporate in a refining bioprocess. 

The chemical sensitization effect was 0.006 (calculated from the quantum yield of the photochemical transformation of 130 to 131, the yield of 131 obtained with the oxalate/hydrogen peroxide reaction, and the moles of oxalate employed). Higher chemical sensitization efficiencies (about 0.04) were observed when the oxalate/hydrogen-peroxide system was used in the addition of ethyl vinyl ether onto phenanthrene quinone... 

Two other synthetic routes to derivatives of this ring system should be mentioned here, and the transformations are shown in Scheme 54. The phenanthrene-fused fV-aryldihydro[1.2.4]triazine 274 was found to undergo 1,3-dipolar cycloaddition with diarylnitrilimine to give the cycloadduct 275 <1997J(P1)1047. This transformation is entirely analogous to that taking place with a fused oxadiazine derivative, as discussed in Section 11.19.6.1. 

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... 

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. 

Richnow HH, Annweiler E, Koning M, Luth JC, Stegmann R, Garms C, Franke W, MichaeUs W (2000) Tracing the transformation of labeled [1- C] phenanthrene in a soil bioreactor. Environ Pollution 108 91-101... 

In Section 21.1 we discussed the simultaneous influence of transport and transformation processes on the spatial distribution of a chemical in an environmental system. As an example we used the case of phenanthrene in the surface water of a lake. In Fig. 212b two situations were distinguished which differed by the relative importance of the rate of vertical mixing versus the rate of photolysis. Yet, neither was a quantitative method given to calculate the resulting vertical concentration profile (profiles 1 and 2 in Fig. 21.26), nor did we explain how the rates of such diverse mechanisms as diffusion, advection, and photolysis should be compared in order to calculate their relative importance. In this section we will develop the mathematical tools which are needed for dealing with such situations. 

Phenanthrene is transformed to trans-9,10- (major), trans-1,2- (minor), and trans-3,4-dihydrodiol (minor) metabolites via monooxygenase-catalyzed formation of arene oxides, followed by epoxide hydrolase-catalyzed hydration in mammalian liver systems.219-221 In bacterial cultures, phenanthrene is converted to cis-3,4- (major) and cis-1,2- dihydrodiols (minor) through the action of dioxygenase enzymes and molecular oxygen.221,222 Recently, Boyd et al.10 have prepared trons-3,4-dihydroxy-1,2,3,4-tetrahydrophenanthrene (359) and cis-3,4-dihydroxy-1,2,3,4-tetrahydrophenanthrene (360) in optically pure forms. These compounds have made possible the determination of the configurations of the trans- and cis-3,4-dihydrodiol metabolites of phenanthrene (361 and 362) as (-)-(3R,4R) and ( + )-(3S,4R), respectively. 

A common problem at public utilities is soil that becomes contaminated with PCBs near and around transformers. There still are a number of such sites with this problem in the United States. Table 9 gives data from a soil cleanup project from a site in New York State. The soil contained approximately 1200 ppm of PCB (Aroclor 1260) prior to treatment with SET . After treatment, the PCB level was reduced to 1.4 ppm (Table 9). Aroclor 1260 is particularly hard to bioremediate, so this result is significant. Small quantities of PAHs (pyrene and phenanthrene) were also remediated. The total petroleum hydrocarbons increased, which is what should be expected because the initial... 

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