Us3919305a process for the preparation of phenylacetic acid. The paa cluster of escherichia coli w involved in the aerobic catabolism of phenylacetic acid pa has been cloned and sequenced. Bacterial phenylalanine and phenylacetate catabolic pathway. Phenylacetic acid 4a and its esters are widely applied as flavors and fragrances. Cometabolic transformation of substituted styrenes was. This molecule is then able to be cleaved into acetyl coa which can enter the tca cycle. The purpose of these studies was to characterize the importance of this.
Accumulation of polyhydroxyalkanoate from styrene and phenylacetic acid by pseudomonas putida ca3. In case of products from hydroxy acetophenones, the products were extracted into ethyl acetate. We previously made a link in burkholderia cenocepacia between pa degradation and. Pdf accumulation of polyhydroxyalkanoate from styrene and. Predicted data is generated using the us environmental protection agencys episuite. Phenylacetic acid paa conjugate base phenylacetate, also known by various synonyms, is an organic compound containing a phenyl functional group and a carboxylic acid functional group.
Microbial metabolism and biotransformations of styrene. The epoxidation of styrene, the rearrangement, and oxidation to phenylacetic acid can be performed in a onepot method using formic acid, aq. In the illicit drug world, phenylacetic acid is often trafficked as a precursor for the bootleg manufacture of methamphetamine, and thus large purchases are monitored by drug enforcement agencies. Because the structure of transition state is similar to that of complex of phenylacetic acid and hemin, we applied phenylacetic acid as the template to form the complex with hemin molecule which is comonomer and provides activity center for synthesized polymers. Ohbutyric acid h balance of fat and cho metabolism.
Ketoglutaric acid h mg b1 b2 b3 succinic acid h iron b2 malic acid h b3. The phenylacetic acid pa degradative pathway is the central pathway by which various aromatic compounds e. Although a phenylacetate metabolic gene cluster had been identified. By the way, the reaction between phenylacetic acid and acetone is claimed to result in phenyl2propanone not bmk, my mistake, with the acetone being regarded as a precursor to acetic acid. The latter enzyme enables the oxidation of the aldehyde to the central metabolite phenylacetic acid 1. Catabolism of phenylacetic acid in escherichia coli. Cometabolic formation of substituted phenylacetic acids by styrene.
The potential for microbial bioremediation of styrene waste has received considerable research attention over the last number of years. It is a metabolite of phenylalanine and is excreted in the urine of patients suffering from diseases like phenylketonuria. The peroxy phenylacetic acid generated was then utilised directly for in situ oxidation of. Styrene, sulfur, liquid ammonia and water into the autoclave, under 165. It has a role as a human metabolite and a mouse metabolite. Methylglutaric acid h coq10 hmgcoa reductase inhibition. Pdf accumulation of polyhydroxyalkanoate from styrene. Bacterial phenylalanine and phenylacetate catabolic. Styrene lower catabolic pathway in pseudomonas fluorescens st. In the lower pathway, phenylacetic acid will be joined to coa to make phenylacetylcoa by a ligase. Phenylacetic acid benzoic acid no reaction substitution elimination oxidation 1b. Gc procedures have been described for the quantitative determination of urinary phenylglyoxylic and mandelic acids, which involve solvent extraction of the.
Catalytical oxidation of styrene by molecularly imprinted. Phenylacetic acid may arise from exposure to styrene plastic or through the consumption of fruits and vegetables. The styrene degradative pathway in pseudmonas putida ca3 has previously been shown to be divided into an upper pathway involving the conversion of styrene to phenylacetic acid and a lower pathway for the subsequent degradation of phenylacetic acid. Synthesizing phenylacetic acid from ethylbenzene, benzyl chloride, benzyl cyanide, mandelic acid, or acetophenone and styrene can be completed in the laboratory or at the industrial level. The immobilised candida antarctica lipase b, novozym 435 was used to catalyse the formation of peroxy acid instantly from hydrogen peroxide h 2 o 2 and phenylacetic acid.
This report describes the isolation, sequencing and analysis of a new chromosomal fragment deriving from. How to prepare phenylacetic acid from 2phenylethanol is to be stated. It is a white crystalline solid that is soluble in water and polar organic solvents. Ppbrxryqalvlmvuhfffaoysan styrene chemical compound. Jul 22, 2004 pseudomonas putida ca3 is capable of converting the aromatic hydrocarbon styrene, its metabolite phenylacetic acid, and glucose into polyhydroxyalkanoate pha when a limiting concentration of nitrogen as sodium ammonium phosphate is supplied to the growth medium. Sciencemadness discussion board p2p from recycled styrene. Process for the preparation of phenylacetic acid rhone. Accumulation of polyhydroxyalkanoate from styrene and.
The peroxy phenylacetic acid generated was then utilised directly for in situ oxidation of alkenes. Pha accumulation occurs to a low level when the nitrogen concentration drops. Mar 22, 2018 this way efficiently transforms styrene into phenylacetic acid as central metabolite. Aug 10, 2010 aromatic compounds constitute the second most abundant class of organic substrates and environmental pollutants, a substantial part of which e. The free phenylacetic acid is precipitated by the addition of conc hcl 3ml, in 92% yield, mp 7676.
I tried this once and had a yield of 7% actually, i did not even bother characterizing it, but it was a carboxylic acid and had the same typical smell as reagent grade phch2cooh. Pha accumulation occurs to a low level when the nitrogen concentration drops below 26. Figures uploaded by kevin edward o connor author content. Research article open access regulation of phenylacetic. Bruker dmx 400mhz data collected by madison metabolomics consortium. Surprisingly, the bacterial catabolism of phenylalanine and phenylacetate remained an unsolved problem. Davidson national high magnetic field laboratory, 1800 east paul dirac dr. The maximum yields for pha from styrene, phenylacetic acid, and glucose are 0. As a commercial chemical, because it can be used in. Styrene degradation via phenylacetic acid was shown for the strains described. Pseudomonas fluorescens st is a styrene degrading microorganism that, by the sequential oxidation of the vinyl side chain, converts styrene to phenylacetic acid. Construction of a recombinant biocatalyst for the production. Evidences of aromatic degradation dominantly via the.
Microbial metabolism of styrene oligomers, 602 styrene is an important industrial chemical and it is also produced naturally, mainly by the decarboxylation of cin namic acid. This pathway of styrene degradation is of potential biotechnological relevance for the production of especially phenylacetic acids. Transcriptional regulation of styrene degradation in. Pseudomonas putidas role in the bioremediation of plastic. Styrene lower catabolic pathway in pseudomonas fluorescens. Citric acid cycle intermediates cisaconitic acid h isocitric acid h b3 mg mn. Escherichia coli living in the animal gut encounters aromatic compounds such as phenylacetic acid pa, 1 phenylpropionic acid, and their hydroxylated derivatives, as a result of the action of intestinal microflora on plant constituents, the amino acids phenylalanine and tyrosine, fatty acids with a terminal phenyl substituent, and some of their metabolites. Apr 22, 2016 this pathway comprises a styrene monooxygenase smo, which oxidizes styrene to styrene oxide, a styrene oxide isomerase soi, which converts styrene oxide into phenylacetaldehyde, and a phenylacetaldehyde dehydrogenase pad. Research article open access regulation of phenylacetic acid uptake is s54 dependent in pseudomonas putida ca3 niall d o leary1,2, mark m o mahony2 and alan dw dobson1,2 abstract background. This method can be improved for pipelining continuous production, styrene. The acid was then taken into 10% nahco 3 solution and was washed with ethyl acetate 3x30 ml, separated the organic layer, and the aqueous layer was acidified with dilute hcl, to yield the pure phenylacetic acid as solid. However, styrene is not a true xenobiotic and microbial pathways for its aerobic assimilation, via an intermediate, phenylacetic acid, have been identified in a diverse range of environmental isolates.
Research article open access regulation of phenylacetic acid. Synthesizing phenylacetic acid from ethylbenzene, benzyl chloride, benzyl cyanide, mandelic acid, or acetophenone and styrene can be completed in the. Furthermore, antibioticsonthe basis of penicillin can be obtained from 4hydroxyphenylacetic acid or nonsubstituted phenylacetic acid 9,11. Finally, phenylacetaldehyde would be oxidized to become phenylacetic acid. Jun 11, 2016 a number of soil bacteria is able to metabolize styrene via initial sidechain oxygenation into the central metabolite phenylacetic acid and harbors corresponding genes. Mandelic acid is an aromatic alpha hydroxy acid with the molecular formula c 6 h 5 chohco 2 h. Cro 3 in acidic solutions oxidize 1 0 alcohols directly into acids and 2 0 alcohols to ketones. As a result it is used as a perfumery and flavoring ingredient phenylacetic acid abr. Chemoenzymatic epoxidation of alkenes and reusability study.
Hydrolysis of chlorinated styrene a new route for the synthesis of phenylacetic acid and aethoxyphenylacetic acid. Although a phenylacetate metabolic gene cluster had been identified, the. Styrene, which is widely used in manufacturing, is both acutely and chronically toxic to mice. This pathway comprises a styrene monooxygenase smo, which oxidizes styrene to styrene oxide, a styrene oxide isomerase soi, which converts styrene oxide into phenylacetaldehyde, and a phenylacetaldehyde dehydrogenase pad. Styrene, the starting material for polystyrene synthesis, is a. Phenylacetic acid is an important metabolite for several pathways and undergoes degradation during a subsequent catabolic route olivera et al. This way efficiently transforms styrene into phenylacetic acid as central metabolite.
A number of soil bacteria is able to metabolize styrene via initial sidechain oxygenation into the central metabolite phenylacetic acid and harbors corresponding genes. The cluster of styrene upper pathway catabolic genes sty genes has been previously localized on a chromosomal region. Here, we focused on a simple enzymatic epoxidation of alkenes using lipase and phenylacetic acid. It is reported here that expression of the regulatory genes stys and styr is essential for transcription of the upper pathway, but not for. Phenylacetic acid is used in some perfumes, possessing a honeylike odour in low concentrations, and is also used in penicillin g production. Endogeneously, it is a catabolite of phenylalanine. Chemoenzymatic epoxidation of alkenes and reusability.
How would you prepare the following compounds from 2. Upper pathways for different aromatic compounds converge at common intermediate phenylacetylcoa pacoa, which is then metabolized to succinylcoa and acetylcoa. Styrene degradation via phenylacetic acid was s hown for the strains described. Styrene oxide is then isomerised into phenylacetaldehyde. Phenylacetic acid via the willgerodt reaction from styrene.
Because of the versatile applications of phenylacetic acids, different chemical strategies for their synthesis have been. The phenylacetic acid paa pathway is an important ring. Pseudomonas putida ca3 is capable of converting the aromatic hydrocarbon styrene, its metabolite phenylacetic acid, and glucose into polyhydroxyalkanoate. Styrene is metabolized by cytochromes p450 to the toxic metabolite styrene oxide, which is detoxified via hydrolysis with microsomal epoxide hydrolase meh playing a major role. As a commercial chemical, because it can be used in the illicit production of phenylacetone used in the. The product 2phenyloxirane is also known as styrene oxide and can be converted by a styrene oxide isomerase soi to obtain phenylacetaldehyde, which can be transformed into the keyintermediate phenylacetic acid by a phenylacetaldehyde dehydrogenase pad. Cometabolic transformation of substituted styre nes was shown.
The willgerodt reaction can also be used to transform acetophenone or styrene to phenylacetic acid. Pseudomonas putida ca3 is capable of converting the aromatic hydrocarbon styrene, its metabolite phenylacetic acid, and glucose into polyhydroxyalkanoate pha when a limiting concentration of nitrogen as sodium ammonium phosphate is supplied to the growth medium. Phenylacetic acid is obtained by oxidation of phenylacetaldehyde with air or oxygen in. Styrene r1, r2 h is transformed to phenylacetic acid through enzymes of sidechain oxygenation by the following steps. The cooled reaction mixture was taken up in chloroform some sulfur remained undissolved and the chloroform solution was washed successively with an equal volume of water. Cometabolic formation of substituted phenylacetic acids by.
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