Polycyclic aromatic hydrocarbons General

During cooxidation, some substrates are activated to become more toxic than they were originally. In some cases substrate oxidation results in the production of free radicals, which may initiate lipid peroxidation or bind to cellular proteins or DNA. Another activation pathway involves the formation of a peroxyl radical from subsequent metabolism of prostaglandin G2. This reactive molecule can epoxidize many substates including polycyclic aromatic hydrocarbons, generally resulting in increasing toxicity of the respective substrates. 

Polycyclic aromatic hydrocarbons undergo electrophilic aromatic substitution when treated with the same reagents that react with benzene In general polycyclic aromatic hydrocarbons are more reactive than benzene Most lack the symmetry of benzene how ever and mixtures of products may be formed even on monosubstitution Among poly cyclic aromatic hydrocarbons we will discuss only naphthalene and that only briefly Two sites are available for substitution m naphthalene C 1 and C 2 C 1 being normally the preferred site of electrophilic attack... 

Unbumed Hydrocarbons Various unburned hydrocarbon species may be emitted from hydrocarbon flames. In general, there are two classes of unburned hydrocarbons (1) small molecules that are the intermediate products of combustion (for example, formaldehyde) and (2) larger molecules that are formed by pyro-synthesis in hot, fuel-rich zones within flames, e.g., benzene, toluene, xylene, and various polycyclic aromatic hydrocarbons (PAHs). Many of these species are listed as Hazardous Air Pollutants (HAPs) in Title III of the Clean Air Act Amendment of 1990 and are therefore of particular concern. In a well-adjusted combustion system, emission or HAPs is extremely low (typically, parts per trillion to parts per billion). However, emission of certain HAPs may be of concern in poorly designed or maladjusted systems. 

The polycyclic aromatic hydrocarbons such as naphthalene, anthracene, and phenan-threne undergo electrophilic aromatic substitution and are generally more reactive than benzene. One reason is that the activation energy for formation of the c-complex is lower than for benzene because more of the initial resonance stabilization is retained in intermediates that have a fused benzene ring. 

In general, the most stable resonance structure for a polycyclic aromatic hydrocarbon is the one with the greatest number of rings that correspond to Kekule formulations of benzene. Naphthalene provides a fairly typical exanple ... 

Dibromofluorene General Procedure for Bromination of Polycyclic Aromatic Hydrocarbons... 

The phosphorescence lifetimes for the p-aminobenzoic acid anion adsorbed on sodium acetate as a function of temperature were evaluated in a manner similar to the one discussed by Oelkrug and coworkers (,28-30) for polycyclic aromatic hydrocarbons adsorbed on y-alumina. In general, the solid-surface phosphorescence lifetime cutrves for the anion of p-aminobenzoic acid followed Equation 2. 

Methods for the synthesis of the biologically active dihydrodiol and diol epoxide metabolites of both carcinogenic and noncarcinogenic polycyclic aromatic hydrocarbons are reviewed. Four general synthetic routes to the trans-dihydrodiol precursors of the bay region anti and syn diol epoxide derivatives have been developed. Syntheses of the oxidized metabolites of the following hydrocarbons via these methods are described benzo(a)pyrene, benz(a)anthracene, benzo-(e)pyrene, dibenz(a,h)anthracene, triphenylene, phen-anthrene, anthracene, chrysene, benzo(c)phenanthrene, dibenzo(a,i)pyrene, dibenzo(a,h)pyrene, 7-methyl-benz(a)anthracene, 7,12-dimethylbenz(a)anthracene, 3-methylcholanthrene, 5-methylchrysene, fluoranthene, benzo(b)fluoranthene, benzo(j)fluoranthene, benzo(k)-fluoranthene, and dibenzo(a,e)fluoranthene. 

By the end of the nineteenth century around 600 fluorescent compounds had been identified [3], including fluorescein (A. von Baeyer, 1871), eosine (H. Garo, 1874), and polycyclic aromatic hydrocarbons (C. Liebermann, 1880) [5], Although it is generally accepted that fluorescence markers are relatively new analytical benefits, it is surprising to note that their chemical synthesis is rather old, such as the fluorescein reported by Baeyer, the 2,5-diphenyloxazole by Fisher in 1896, and the fluorene by Berthelot in 1867 [18],... 

Polycyclic aromatic hydrocarbons (PAHs, sometimes also called polynuclear aromatics, PNA) are a hazardous class of widespread pollutants. The parent structures of the common PAHs are shown in Fig. 4 and the alkylated homologs are generally minor in combustion emissions. PAHs are produced by all natural combustion processes (e.g., wild fires) and from anthropogenic activity such as fossil fuels combustion, biomass burning, chemical manufacturing, petroleum refining, metallurgical processes, coal utilization, tar production, etc. [6,9,15,18, 20,24,131-139]. 

Before we examine the oxidation pathways available to aromatic systems, it is first instructive to review the most notorious role of these compounds in combustion chemistry their propensity to lead to soot formation. Soot is a byproduct of fuel-rich combustion, and soot particles can affect respiration and general health in humans." Soot production is a result of polycyclic aromatic hydrocarbon (PAH) formation in flames as reactive hydrocarbon radical intermediates combine to grow... 

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