Degradation products source

Scheme 3 Decision tree for disposition of degradation products. Source Courtesy of Pharmquest Corporation, Mountain View, California, U.S.A.

Figure 5.7 Probable initial decomposition events and identified evolved degradation products. Source Author s own files...

Other components in the feed gas may react with and degrade the amine solution. Many of these latter reactions can be reversed by appHcation of heat, as in a reclaimer. Some reaction products cannot be reclaimed, however. Thus to keep the concentration of these materials at an acceptable level, the solution must be purged and fresh amine added periodically. The principal sources of degradation products are the reactions with carbon dioxide, carbonyl sulfide, and carbon disulfide. In refineries, sour gas streams from vacuum distillation or from fluidized catalytic cracking (FCC) units can contain oxygen or sulfur dioxide which form heat-stable salts with the amine solution (see Fluidization Petroleum). 

In 1933, R. Kuhn and his co-workers first isolated riboflavin from eggs in a pure, crystalline state (1), named it ovoflavin, and deterrnined its function as a vitamin (2). At the same time, impure crystalline preparations of riboflavin were isolated from whey and named lyochrome and, later, lactoflavin. Soon thereafter, P. Karrer and his co-workers isolated riboflavin from a wide variety of animal organs and vegetable sources and named it hepatoflavin (3). Ovoflavin from egg, lactoflavin from milk, and hepatoflavin from Hver were aU. subsequently identified as riboflavin. The discovery of the yeUow en2yme by Warburg and Christian in 1932 and their description of lumiflavin (4), a photochemical degradation product of riboflavin, were of great use for the elucidation of the chemical stmcture of riboflavin by Kuhn and his co-workers (5). The stmcture was confirmed in 1935 by the synthesis by Karrer and his co-workers (6), and Kuhn and his co-workers (7). 

Fatty acids with odd numbers of carbon atoms are rare in mammals, but fairly common in plants and marine organisms. Humans and animals whose diets include these food sources metabolize odd-carbon fatty acids via the /3-oxida-tion pathway. The final product of /3-oxidation in this case is the 3-carbon pro-pionyl-CoA instead of acetyl-CoA. Three specialized enzymes then carry out the reactions that convert propionyl-CoA to succinyl-CoA, a TCA cycle intermediate. (Because propionyl-CoA is a degradation product of methionine, valine, and isoleucine, this sequence of reactions is also important in amino acid catabolism, as we shall see in Chapter 26.) The pathway involves an initial carboxylation at the a-carbon of propionyl-CoA to produce D-methylmalonyl-CoA (Figure 24.19). The reaction is catalyzed by a biotin-dependent enzyme, propionyl-CoA carboxylase. The mechanism involves ATP-driven carboxylation of biotin at Nj, followed by nucleophilic attack by the a-carbanion of propi-onyl-CoA in a stereo-specific manner. 

The first step in the degradation of phosphate and phosphorothioate esters is hydrolysis, and substantial effort has been directed to all groups. Investigations have also been directed to the use of their degradation products as a source of phosphate for the growth of bacteria, and a wide range of phosphates, dialkylphosphates, and phosphorothioates has therefore been examined as sources of phosphorus (Cook et al. 1978). 

Mass spectrometry (MS) coupled with pyrolysis has been a key technique in detecting the thermal degradation products of polymers, and thereby elucidating their thermal decomposition pathways [69]. In pyrolysis-MS, a sample is thermally decomposed in a reproducible manner by a pyrolysis source that is interfaced with a mass spectrometer. The volatile products formed can then be analysed either as a mixture by MS or after separation by GC/MS [70]. 

In a bioanalytical method, analyses of blank samples (plasma, urine, or other matrix) should be obtained from at least six sources. Each blank sample should be tested for the possible interference of endogenous substances, metabolites, or degradation products. The response of the peaks interfering at the retention time of the analyte should be less than 20% of the response of a lower quantitation limit standard, and should be less than 5% of the response of the internal standard that was used [18, 19]. For dissolution studies, the dissolution media or excipients should not give a peak or spot that has an identical Rt or Rf value with the analyte [20]. 

Munro, N.B., S.S. Talmage, G.D. Griffin, L.C. Waters, A.P. Watson, J.F. King, and V. Hauschild. The Sources, Fate and Toxicity of Chemical Warfare Agent Degradation Products." Environmental Health Perspectives 107 (1999) 933-974. 

Methods are also available to measure degradation products of hexachloroethane in environmental samples, but these products (e.g., tetrachloroethylene) are released to the environment from many other sources and are therefore not useful determinants of the environmental impact of this chemical. 

At Cape Cod, USA, a study was carried out by Rudel et al. [18] to investigate the impact of septic systems as a source of APEOs and their degradation products to ground water. In this study NP was detected in all sewage samples at concentrations above 1000 pg L 1. In ground water downgradient of an infiltration bed for secondary treated effluent, NP and OP and ethoxylates were present at about 30 pg L NPEiC and NP/0P(E0)4 were detected in some drinking water wells at concentrations up to 33 pg L-1. 

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