PubMed · 4599397
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R Y Stanier, L N Ornston. 1973. The beta-ketoadipate pathway.. https://pubmed.ncbi.nlm.nih.gov/4599397/
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In this work, a complementary experimental and theoretical approach is used to unravel the formation of byproducts in the autoxidation of cyclohexane. The widely accepted vision that cyclohexanone would be the most important precursor of undesired products was found inconsistent with several experimental observations. However, the propagation reaction of cyclohexyl hydroperoxide, which we recently put forward as the missing source of cyclohexanol and cyclohexanone, is now unambiguously identified also as the dominant path leading to byproducts. Indeed, this overlooked reaction produces large amounts of cyclohexoxy radicals, able to ring-open via a beta-C--C cleavage to omega-formyl radicals. The pathway by which these radicals are converted into the observed and quantified byproducts is derived in this work. In this liquid-phase reaction, solvent cages were found very important, steering the fate of nascent species.
OBJECTIVES: Except for polyadipate, which is used as an alternative in polyvinylchloride (PVC) feeding tubes, diethylhexylphthalate (DEHP) is the plasticizer used almost exclusively in PVC medical products. A clear response to the chronic intake of DEHP has been shown in several organ systems from different species. In the present study, we compared the extraction of DEHP and polyadipate from PVC gastric tubes. METHODS: An in vivo setting was simulated. We used 5 cm of PVC nasogastric tubes containing DEHP or polyadipate, which were incubated with gastric juice for 1 week and a feeding solution for 4 weeks. The leakage of these plasticizers was measured daily in the gastric juice group and weekly in the feeding solution group. The amount of plasticizer extracted was compared between groups and days. RESULTS: In the feeding solution group, the extraction of DEHP ranged from 200 to 542 microg after 1 week and from 660 to 1700 microg after 4 weeks. The extraction of polyadipate was 10 times lower than that of DEHP. In the gastric juice group, extracted DEHP ranged from 635 to 1043 microg, whereas the extraction of polyadipate was 100 times lower. CONCLUSIONS: Within 1 week, the extraction of DEHP from a 5-cm PVC tube reaches up to 1 mg. Extrapolated, this represents an in vivo load of up to 4 mg. The load accumulated by a newborn in an intensive care unit can therefore easily reach several milligrams of DEHP per day. Polyadipate nasogastric tubes may therefore be an alternative and help to reduce the daily load of DEHP.
The biodegradation of plasticizers has been previously shown to result in the accumulation of metabolites that are more toxic than the initial compound. The present work shows that the pattern of degradation of di-2-ethylhexyl adipate by Bacillus subtilis can be significantly altered by the presence of biosurfactants, such as surfactin, or synthetic surfactants, such as Pluronic L122. In particular, this work confirms that the monoester, mono-2-ethylhexyl adipate, is a metabolite in the breakdown of the plasticizer. This metabolite was proposed but not observed in earlier studies. Toxicity measurements showed it to be significantly more toxic than the plasticizer. Thus, the effect of the surfactants was to significantly increase the accumulation of one or both of the two most toxic metabolites; i.e., the monoester and 2-ethylhexanol. It was proposed that the most likely cause of the effect of the surfactants was the sequestering of these two metabolites into mixed micelles, resulting in their reduced availability for further degradation.